description
stringlengths 2.98k
3.35M
| abstract
stringlengths 94
10.6k
| cpc
int64 0
8
|
|---|---|---|
This is a division, of application Ser. No. 445,639, now U.S. Pat. No. 3,911,592, filed Feb. 25, 1974.
BACKGROUND OF THE INVENTION
This invention relates generally to tilt detection, and more particularly concerns the provision of a tilt detector of improved construction and its use in a system for aligning a sub-sea riser pipe with a stack of sub-sea well head equipment.
There is a continuing need for tilt detection equipment characterized by simplicity, rugged construction, insensitivity of low sensitivity to vibration (enabling use on well drilling equipment), two axis tilt sensitivity, immunity to temperature drift, and capability for operation after inversion despite use of liquid mercury as a pendulum. There is also need for a simple control system for maintaining alignment of a riser pipe with sub-sea well head equipment. No prior equipment meets the above needs in the unusually advantageous manner as will be described herein.
SUMMARY OF THE INVENTION
Basically, the tilt detector of the invention comprises a container; liquid (as for example mercury) in the container having an upper surface tending to remain generally horizontal as the container tilts, and sensors having independently movable members (as for example floats) engaging the liquid at spaced locations to sense the relative levels of the liquid surface at spaced locations and relative to the container during such tilting. As will be seen, the liquid in the container may define pools having restricted intercommunication, the pools respectively engaged by the sensors, thereby to provide reduced sensitivity to vibration; the floats may have upper surfaces which taper upwardly to drain liquid off the floats and into the pools; and the sensors may include plungers carried by the floats (the plungers carrying cores magnetically coupled to differential transformer coils), the plungers having cross sections to form liquid drainage spaces, for return flow to the pools.
It is another object of the invention to provide first and second pools as described, to float first and second floats at opposite sides of an upright axis defined by the detector, and third and fourth pools to float third and fourth floats at opposite sides of that axis, the first and second floats and associated plungers located in 90° relation to the third and fourth plungers and associated plungers, thereby to provide enhanced sensitivity to tilt in two planes, as well as temperature change insensitivity, as will be described.
It is a still further object of the invention to provide two detectors as described, one adjustably carried by a sub-sea stack of well head equipment, and the other adjustably carried by a riser pipe above a ball joint. As will be seen, control means is provided at the ocean surface, as for example on a drilling vessel, and is operatively connected with the circuitry of each sensor on each detector to achieve a visual display corresponding to the absolute tilts of the detectors, as well as the relative tilt therebetween, enabling vessel maneuver to eliminate or reduce such relative tilt, in a simple manner.
These and other objects and advantages of the invention, as well as the details of an illustrative embodiment, will be more fully understood from the following description and drawings, in which:
DRAWING DESCRIPTION
FIG. 1 is a schematic diagram of a sub-sea riser tilt control system;
FIG. 1a is a more complete schematic of the FIG. 1 system;
FIG. 2 is an elevation, in section, showing details of construction of one preferred transducer, as used in FIGS. 1 and 1a;
FIG. 3 is a view like FIG. 2, showing a tilted condition of the FIG. 2 transducer;
FIG. 4 is a section taken on line 4--4 of FIG. 2;
FIG. 5 is an enlarged elevation, partly in section showing the construction of a float as used in the transducer;
FIG. 6 is an end view of the FIG. 5 float;
FIG. 7a is an elevation showing one alignment condition of a sub-sea riser and stack;
FIG. 7b is a top plan view of the drilling vessel shown in FIG. 7a;
FIG. 7c is a view of a surface display panel associated with the FIG. 7a condition;
FIG. 8a is an elevation showing another relative alignment condition of the sub-sea riser and stack first shown in FIG. 7a, and as related to the drilling vessel;
FIG. 8b is a top plan view of the drilling vessel shown in FIG. 8a;
FIG. 8c is a view of the surface display panel indicating stack tilt for FIGS. 8a and 8b;
FIG. 8d is a view of the surface display panel indicating lower riser tilt for FIGS. 8a and 8b.
FIG. 8e is a view of the surface display panel indicating ball joint error for FIGS. 8a and 8b;
FIG. 9a is an elevation showing a further relative alignment condition of the sub-sea riser and stack, as related to the drilling vessel;
FIG. 9b is a top plan view of the drilling vessel shown in FIG. 8a;
FIG. 9c is a view of the surface display panel indicating ball joint error for FIGS. 9a and 9b;
FIG. 10a is an elevation showing a still further relative alignment condition as between the sub-sea riser and stack and the drilling vessel, the relative heading of which has changed from FIG. 9a and 9b;
FIG. 10b is a top plan view of the drilling vessel shown in FIG. 10a;
FIG. 10c is a view of the surface display panel indicating ball joint error for FIGS. 10a and 10b;
FIG. 11 is a view of differential transformer circuitry; and
FIGS. 12-13 are circuit diagrams.
DETAILED DESCRIPTION
Referring first to FIG. 1, two tilt detectors or transducers 10 and 11 are shown in combination with sub-sea well head equipment 12. One detector 10 is carried by the equipment stack 12a, and the other detector 11 is carried by a riser pipe 13 projecting generally upwardly from the stack. A ball joint 12b connects the lower end of the riser pipe 13 with stub casing 14 associated with the stack, allowing the riser to pivot angularly about that joint, as influenced by changes in surface vessel position and/or by underwater currents, without deflecting or displacing the stack. The riser normally protectively contains pipe or tubing extending between the surface and the stack at the ocean floor. Merely as illustrative, the stack may also include a well blow-out preventer 16, well head connectors 17 and 18, a mud valve 19, and other equipment. Also shown are guy wires 20 and guides 21 therefor attached to the stack via bracket arms 22, enabling guided lifted and lowering of the stack between the surface and the ocean floor 23. FIGS. 7a, 7b; 8a and 8b; 9a and 9b; and 10a and 10b also show various relative orientations of a surface vessel, sub-surface stack, and riser pipe extending therebetween, as will be described.
FIG. 1a illustrates, schematically, the detector or transducer 10 carried by the stack 12 as via a mounting and leveling plate 24. The detector may be connected with plate 24 as via a universal pivot connection 25 and three leveling screws 26 having threaded connection with plate 24 may be adjusted as respects their bearing against the underside of the detector to initially align the detector axis 10a in parallel relation with the stack vertical central axis schematically indicated at 27. Similarly, the detector or transducer 11 is carried by the riser pipe 13 as via a mounting or leveling plate 28. Detector 11 may be connected with plate 28 as by universal pivot connection 29, and three leveling screws 30 having threaded connection with plate 28 may be adjusted as respects their bearing against the underside of detector 11 to initially align the detector axis 11a in parallel relation with the axis 28a of the lower end of the riser. Accordingly, means is provided to adjust the angularities of the detectors relative to the stack and to the riser pipe, respectively.
FIG. 1a also shows, schematically, an armored signal cable 29a extending between a cable reel 30a at the surface and the detectors. As seen, a plug connection 31 at the lower end of the cable may fit a socket at 32 associated with transducer or detector 11; and a jumper cable 33 may have plug connection at 34 with a socket 35, and plug connection at 36 with a socket 37. The latter is associated with transducer 10, and the former socket 34 has electrical connection with plug 31 via socket 32. Accordingly, the transducer outputs are transmitted to the surface via series cables 33 and 29a. The upper reeled end of cable 29a has connection with surface display circuitry 38 via a jumper cable 39, the circuitry 38 having an analog output at 40 to a strip chart recorder 41, an output at 42 to an alarm relay 43, and a digital output at 44 to a computer 45.
Referring now to FIGS. 2-6, the tilt detector 10 (which is also representative of detector 11) basically comprises a container; liquid in the container having an upper surface tending to remain generally horizontal as the container tilts; and sensors having independently movable members engaging the liquid at spaced location to sense the relative levels of the liquid surface at such locations and relative to the container, during such tilting. In the example, the container is shown to comprise a receptacle shaped body having a base 134, an annular upper rim 135 defining a bore 136; an inner upwardly facing shoulder 137; and four like recesses or wells 138a-138d sunk downwardly in the body from the inner surface 137.
The container also includes a cap or casing 139 which fits downwardly at 39a into the bore 136 and has a lower end face seating against shoulder 137, there being a central fastener 140 which connects the cap to the body. O-ring seal 142 seals off between the bore 136 and the casing 139, whereby the wells 138a-138d are sealed off from the exterior; however, there are lateral ports 143-146 drilled in the body 133 to restrictively intercommunicate the lower interiors of the wells, as shown, whereby liquid such as mercury in the wells drains from higher to lower wells during tilting of the detector. Such ports dampen or slow changes in mercury level in the wells during changes in detector tilt, so that a more accurate output signal (indicative of tilt) is realized, as will appear.
Pools of mercury or other suitable liquid in the wells are indicated at 47-50.
The movable sensor members referred to above may with unusual advantage comprise plastic floats 51-54 having convex undersides, indicated at 55, to effectively engage the liquid mercury pool surface during various conditions of tilt, as for example as illustrated in FIG. 3; also, the floats have frusto-conically upwardly tapering upper sides 56, to effectively shed mercury wetting such upper sides after return of the detectors to near FIG. 2 upright position following extreme tilt or inversion of the unit. Further, the floats carry plungers 58 movable endwise within bores 70 formed by differential transformer coils 60-62. Magnetic cores 63 carried by the plungers have variable magnetic coupling with the coils, depending on the endwise position of the cores, as is also clear from the FIG. 11 differential transformer circuit. As there shown, the output of oscillator 65 is impressed on coil 61 with which differentially wound coils 60 and 62 are inductively coupled. The DC output at 67 of a demodulator 66 connected with coils 60 and 62 is a function of the endwise position of the core 63. Accordingly, the tilt of the detector determines the core position relative to the coils, which in turn determines DC output of the differential transformer associated with each core. Two such floats such as at 51 and 52 located at 90° angles about the detector axis 10a are sufficient to determine the azimuthal direction of tilt and the degree of such tilt; however, the two additional floats 53-54 and associated circuitry serve to increase the accuracy of the equipment and also provide temperature drift insensitivity. Thus, the outputs of transformers associated with 180° angle related floats 51 and 53 may be added, i.e. differenced, to obtain an analog DC value representative of tilt in one (port and starboard) direction, whereas the outputs associated with 180° related floats 52 and 54 may be added to obtain an analog DC value representative of tilt in another (fore and aft) direction. Temperature change induced changes in mercury level do not affect the "difference" output referred to.
From FIGS. 2-6, it will be seen that the plungers have generally polygonal (as for example generally triangular) cross sections along plunger lengths movable endwise within guide bores 70 surrounded by the coils, thereby to form liquid drainage spaces 71 between the bore and plungers. Accordingly, liquid mercury never collects between the plungers and bores to impede endwise travel of the plungers in the bores, when the detector is in upright position, but rather such mercury freely drains via the spaces 71 back into the pools 47-50 as described.
Referring now to FIG. 12, it will be seen that the "port and starboard" analog output at 80 of the stack transducer 10 may be passed via switch 81 and lead 82 to an analog to digital converter 79 and thence at 83 to a port and starboard digital display; and "fore and aft" analog output at 84 of transducer 10 may be passed via switch 85 and lead 86 to the ADC 79 and thence at 87 to the fore and aft digital display. Alternatively, the "port and starboard" analog output at 88 of the lower riser transducer 11 may be passed via switch 89 and lead 90 to ADC 79 and thence to display 83; and fore and aft analog output at 91 of transducer 11 may be passed via switch 92 and lead 93 to the ADC 79 and thence to display 87. In addition, a so-called port and starboard "ball joint error" analog output at 94 may be obtained by adding at 95 (i.e. differencing) the outputs 80 and 88 of the transducers 10 and 11, and the output 94 may be passed via a switch 96 to the ADC 79 for digital display at 83. Similarly, a so-called fore and aft "ball joint error" analog output at 97 may be obtained by adding at 95 (i.e. differencing) the outputs 84 and 91 of the transducers 10 and 11, and the output 97 may be passed via a switch 99 to ADC 79 for digital display at 87. Finally, an upper riser transducer 201 may be provided with connections similar to those for the lower riser transducer 11. Heading correction equipment 225 may be connected in series with the ADC at the input side thereof, and its use will be described in terms of "correcting" the analog input to the ADC.
FIG. 7c shows a panel having a DEGREES TILT DISPLAY 101 that includes PORT and STARBOARD 2-digit displays 83a and 83b, and FORWARD and AFT 2-digit displays 87a and 87b. In addition, in ZERO TILT display 100 is provided, and includes a FORE and AFT (F/A) section 101a which illuminates when FORE and AFT tilt is zero, and a PORT and STARBOARD section 101b which illuminates when Port and Starboard tilt is zero.
The following examples of Riser/Stack Alignment are provided to give a better understanding of the various situations in which the system can be used. In all of the examples, the DEGREES TILT Display 101 indicates the position of the transducers with respect to true vertical. The "BALL JOINT ERROR" indicates the TILT ERROR difference between the lower riser transducer and the stack transducer. The direction in which the drilling vessel 102 needs to move (as seen in FIG. 7b) in order to align the riser with the stack 12 is opposite from that displayed. In other words, if a starboard ball joint error is indicated, the drilling vessel must move to the port in order to align the riser 13 with the stack.
Example No. 1 (Refer to FIGS. 7a to 7c)
In FIG. 7a the stack 12 is shown perfectly vertical and the drilling vessel 102 is directly over the stack. In this perfect condition, there is "0" ball joint error which is indicated by both sections 100a and 100b of the ZERO TILT Display being illuminated. A display of ball joint error is achieved by depressing switches or pushbuttons 96 and 99. Note: When there is "0" tilt in a plane the two digital displays associated with that plane will be dark. The appropriate section of the ZERO TILT Display will be illuminated.
In FIG. 7c the stack heading has been entered on a STACK HEADING SWITCH 10 3 as 330°. Since the drilling vessel heading in FIG. 7b is identical to the stack heading, a HEADING DEVIATION switch 104 is set to "0". The significance of switches 103 and 104 will be discussed later.
Example No. 2 (Refer to FIG. Nos. 8a, 8b, & 8c)
In FIG. 8c the DEGREES TILT Displays are indicating the tilt registered by the stack transducer. This is accomplished by the operator depressing the "STACK" pushbutton which closes switches 81 and 85 in FIG. 12 for example. In this example the stack has a 9.3° tilt to the port. The Forward/Aft Stack Alignment is perfectly vertical and indicated by the F/A Section 100a of the ZERO TILT Display being illuminated. The stack and vessel are heading due North and are so indicated by the STACK HEADING AND HEADING DEVIATION switches 103 and 104.
FIG. 8d indicates the tilt measured by the LOWER RISER transducer. This is accomplished by the operator depressing the LOWER RISER pushbutton which closes switches 89 and 92 in FIG. 12. In this example we see that the lower riser transducer 11 indicates a 3.1° forward tilt and a 2.4° starboard tilt. If the drilling vessel in FIG. 8b were moved to the port and aft and directly over the stack, the LOWER RISER DEGREES TILT Display would indicate F/A and P/S equal "0" . However, because of the port tilt of the stack, the riser and stack would not yet be correctly aligned.
In FIG. 8e we see displayed the BALL JOINT ERROR which is the difference between the riser and stack angularities relative to vertical. If the drilling vessel is now moved aft and port until the F/A and P/S ZERO Displays 100a and 100b are illuminated, the vessel will be displaced to the port of the stack. However because of the port tilt of the stack, the riser and stack would then be in proper alignment.
Example No. 3 (Refer to FIG. Nos. 9a, 9b, 9c and FIG. Nos. 10a, 10b and 10c)
In FIG. 9a the stack alignment is perfectly vertical. A BALL JOINT ERROR of 4.8° starboard and 2.8° aft is indicated because the drilling vessel in FIG. 9b is horizontally displaced and not directly over the stack. The drilling vessel is heading due North which is the same heading as the stack. In order to obtain proper riser/stack alignment, the vessel must move forward and to the port until it is directly over the stack.
In FIG. 10a the stack and riser angles have not changed; however the drilling vessel is no longer on the same heading as the stack (due North). The new vessel heading of 330° is entered into the display panel by rotating the HEADING DEVIATION switch 104 until the vessel heading is indicated by the COMPASS HEADING Display 120. Without the HEADING DEVIATION adjustment, the BALL JOINT ERROR Display in FIG. 10c would be identical to in FIG. 9c, indicating 4.8° starboard tilt and 2.8° aft tilt. With that indication, if the drilling vessel were to move forward to compensate for the aft tilt of the riser, the vessel would be moving further away from the stack. In this regard, the HEADING DEVIATION switch 104 automatically compensates the BALL JOINT ERROR Display so that the vessel will be moved in the proper direction to achieve perfect riser/stack alignment. The BALL JOINT ERROR Display in FIG. 10c indicates that, because of the 330° heading deviation, the vessel need only move to the port to properly align the riser with the stack.
In FIG. 12, compensation input 225 to the ADC corresponds to the input provided by switch 104.
Certain important advantages of the detectors and system are summarized as follows: the use of a fluid metal pendulum as disclosed to sense vertical eliminates need for mechanical pendulum supports subject to damage under shock loading conditions, it combines low natural frequency with relatively small size, it provides relatively large viscous damping in conjunction with the flow ports between the wells, and its operation remains unaffected following accidental inversions, and it affords high surface tension as well as maximum surface position stiffness to measuring float position errors; the use of lightweight, plastic floats to detect fluid pendulum surface position provides for physical characteristics such as low density, lack of electrical conductivity and absence of magnetic properties, and the positions of the floats are primarily controlled by fluid surface tension rather than float buoyancy to eliminate errors due to fluid contact angle variations with the float surfaces; the float shapes provide independence of fluid contact surface shape from tilt angle, elimination of output non-linearities, and the float upper surfaces promote drainage of fluid after angle overloads, eliminating zero-shifts; and the float plunger shapes eliminate pendulum fluid hold-up or retention in the guides, as described.
Further, the use of differential transformers to detect float positions results in negligible friction or stiffness force application to the floats and plungers, and such transformers are relatively immune to damage due to shock and vibration and they embody no moving electrical components so that wear is not a factor; the use of dual differential transformers enables cancellation of errors due to differential expansions of fluid, case and displacement sensor components; the Cartesian format, decimal angle, display readouts provide for unambiguous and immediate display of error quadrants, error-free readout of cartesian components of angles referred to ship axes, and use of a "zero error angle" target indicator eliminates display ambiguities at zero points. Finally, the provision for manual insertion of ship heading correction eliminates need for operator mental calculation to correct for ship heading changes, and the use of low cost axis transformations allows adequate compensation of the tilt displays, in the range of ± 10° of tilt, by 15° azimuth increments.
FIG. 13 shows typical electrical connections for a differential pair of transducers 248 and 249 in one plane, as for example at the stack, lower riser, or upper riser. Floats 251 and 253 correspond to floats 51 and 53 previously described. Note cross-over connection 254 between the coils of the differentially connected transducers, and the output leads 255 and 256.
From what has been described, as for example in relation to FIG. 12, it will be understood that the riser is typically maintained in aligned azimuthal relation to the stack, by suitable means.
|
A tilt detector is provided especially for use in operating sub-sea drilling equipment including a tool stack at the ocean floor. One such detector is carried by the stack to produce a first output; another detector is carried by a riser pipe near a ball joint interconnecting the stack and pipe to produce a second output, and the outputs are processed to facilitate maneuvering of a drilling vesssel. The detector includes:
A. a container,
B. liquid in the container having an upper surface tending to remain generally horizontal as the container tilts, and
C. sensors having independently movable members engaging the liquid at spaced locations to sense the relative levels of the liquid surface at said locations and relative to the container during said tilting.
| 4
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method of producing a taxane-type diterpene including taxol which is useful as a therapeutic agent for ovarian cancer, mammary cancer, lung cancer and the like.
2. Description of the Prior Art
Taxol, which is useful as a therapeutic agent for ovarian cancer, mammary cancer, lung cancer and the like, is a taxane-type diterpene identified after being isolated from Taxus brevifolia NUTT, which is a plant belonging to genus Taxus, family Taxaceae and has a complex ester group which is related to the above-mentioned pharmacological activity. Taxol can be found in all the parts of the plant body of Taxus brevifolia NUTT, but the bark has been reported to exceed all others in its content of the taxol. At present, taxol is collected from a natural or a cultivated plant body, however, the plant belonging to genus Taxus grows slowly, and it takes more than 10 years to grow to a height of 20 cm above the ground, besides the tree dies after its bark is taken off, thus it has not been easy to obtain a large amount of taxol. It would be advantageous if a taxane-type diterpene such as taxol and/or baccatin III which is a precursor of taxol, can be synthesized by the use of tissue culture, since a large amount of taxol can be easily obtained without cutting down the trees.
As a conventional method of producing taxol by utilizing cultured plant cells, a US patent was issued on a production method utilizing cultured cells of Taxus brevifolia NUTT (U.S. Pat. No. 5,019,504), however, the amount of taxol production described therein is 1-3 mg/l, and that is insufficient for the industrial production. Besides, the production of taxol by the cell culture utilizing the conventional tissue culture technique is unstable and even when a primary cell of high productivity can be obtained by selection, it is difficult to keep its content by subculturing [E. R. M. Wickremesine et al., World Congress on Cell and Tissue Culture (1992)].
On the other hand, as a prior art in the taxol production, a semisynthetic method from baccatin III, which is a precursor in biosynthesis of taxol, is disclosed in the specification of U.S. Pat. No. 5,015,744 issued to Holton et al. By the use of the plant tissue culture, a raw material for the semisynthetic process such as baccatin III can be produced, thus the plant tissue culture can be also utilized for taxol production by the above-mentioned semisynthetic process.
OBJECTS AND SUMMARY OF THE INVENTION
The object of the present invention is to provide a simple method of producing a taxane-type diterpene by plant tissue culture.
As a result of the intensive study, the present inventors found that the productivity of the taxane-type diterpene in the cultures can be improved by carrying out the culture of a cultured cell or a cultured tissue of a plant which produces the taxane-type diterpene, in the presence of coronatines, a bacterium which produces the coronatines, a culture solution or a culture extract of such bacteria, cyclic polysaccharides, fatty acids or an imino or amino derivative of jasmonic acids, and completed the present invention.
Accordingly the present invention is a method of producing a taxane-type diterpene wherein a cell and/or a tissue of a plant which produces a taxane-type diterpene is cultured in the presence of at least one substance selected from the group consisting of coronatines, a bacterium which produces the coronatines, a culture solution or a culture extract of such bacterium, cyclic polysaccharides, fatty acids, and a compound represented by the general formula (X):
[wherein,
Y is hydrogen atom, hydroxyl group, cyano group, NR 28a R 28b (wherein R 28a and R 28b independently represent hydrogen atom, carbamoyl group, acyl group having 1 to 12 carbon atoms, alkyl group having 1 to 12 carbon atoms, aryl group, aryl group having a substituent, arylalkyl group, arylalkyl group having a substituent or alkylsulfonyl group having 1 to 12 carbon atoms), OR 29 (wherein R 29 is acyl group having 1 to 12 carbon atoms, alkyl group having 1 to 12 carbon atoms, aryl group, aryl group having a substituent, arylalkyl group or arylalkyl group having a substituent),—CO—R 30 (wherein R 30 represents hydrogen atom, amino group, alkylamino group having 1 to 12 carbon atoms), alkyl group having 1 to 12 carbon atoms, aryl group, aryl group having a substituent, arylalkyl group, arylalkyl group having a substituent, aminosulfonyl group or alkylsulfinyl group having 1 to 12 carbon atoms;
R 1a , R 1b , R 1c , R 1d , R 1e and R 1f independently represent hydrogen atom, hydroxyl group, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryl group, aryl group having a substituent, arylalkyl group or arylalkyl group having a substituent; R 20 , R 21 , R 22 , R 23 and R 24 independently represent hydrogen atom, hydroxyl group, alkyl group having 1 to 12 carbon atoms, aryl group, aryl group having a substituent, arylalkyl group or arylalkyl group having a substituent;
a side chain consisting of C 1 —C 2 —C 3 —C 4 —C 5 —C 6 may contain one or more double bonds;
R 25 represents hydroxyl group, OM (wherein M is alkaline metal atom, alkaline earth metal atom or NH 4 ), NR 26a R 26b (wherein R 26a and R 26b independently represent hydrogen atom, acyl group having 1 to 12 carbon atoms, alkyl group having 1 to 12 carbon atoms, aryl group, aryl group having a substituent, arylalkyl group, arylalkyl group having a substituent or amino acid residue), OR 27 (wherein R 27 represents alkyl group having 1 to 12 carbon atoms, aryl group, aryl group having a substituent, arylalkyl group, arylalkyl group having a substituent or carbohydrate residue), alkyl group having 1 to 12 carbon atoms, aryl group, aryl group having a substituent, arylalkyl group or arylalkyl group having a substituent;
n is an integer of 1-7;
and in the above-mentioned five-membered ring, a double bond may be formed between the neighboring member carbon atoms],
or represented by the general formula (XI):
[wherein,
R 1a , R 1b , R 1c , R 1d , R 1e , R 1f and R 1g independently represent hydrogen atom, hydroxyl group, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryl group, aryl group having a substituent, arylalkyl group or arylalkyl group having a substituent; R 20 , R 21 , R 22 , R 23 and R 24 independently represent hydrogen atom, hydroxyl group, alkyl group having 1 to 12 carbon atoms, aryl group, aryl group having a substituent, arylalkyl group or arylalkyl group having a substituent;
a side chain consisting of C 1 —C 2 —C 3 —C 4 —C 5 —C 6 may contain one or more double bonds;
R 25 represents hydroxyl group, OM (wherein M represents alkaline metal atom, alkaline earth metal atom or NH 4 ), NR 26a R 26b (wherein R 26a and R 26b independently represent hydrogen atom, acyl group having 1 to 12 carbon atoms, alkyl group having 1 to 12 carbon atoms, aryl group, aryl group having a substituent, arylalkyl group, arylalkyl group having a substituent or amino acid residue), OR 27 (wherein R 27 represents alkyl group having 1 to 12 carbon atoms, aryl group, aryl group having a substituent, arylalkyl group, arylalkyl group having a substituent or carbohydrate residue), alkyl group having 1 to 12 carbon atoms, aryl group, aryl group having a substituent, arylalkyl group or arylalkyl group having a substituent;
n is an integer of 1-7;
R 31a and R 31b independently represent hydrogen atom, hydroxyl group, acyl group having 1 to 12 carbon atoms, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryl group, aryl group having a substituent, arylalkyl group, arylalkyl group having a substituent or amino acid residue;
and in the above-mentioned five-membered ring, a double bond may be formed between the neighboring member carbon atoms], then the taxane-type diterpene is recovered from the resulting cultures.
The taxane-type diterpene, which is an object of the method of the present invention, is not particularly limited to any diterpene as far as it has a taxane skeleton, and the illustrative examples include taxol, 10-deacetyltaxol, 7-epitaxol, baccatin III, 10-deacetylbaccatin III, 7-epibaccatin III, cephalomannine, 10-deacetylcephalomannine, 7-epicephalomannine, baccatin VI, taxane 1a, xylosylcephalomannine, xylosyltaxol, taxol C, 10-deacetyltaxol C, taxicin I, taxicin II, taxine I, taxine II, taxagifine and the like.
Examples of the plant to be used in the present invention which produces the taxane-type diterpene are those belonging to genus Taxus, such as Taxus baccata LINN, Taxus cuspidata SIEB. et ZUCC, Taxus cuspidata SIEB. et ZUCC var. nana REHDER, Taxus brevifolia NUTT, Taxus canadensis MARSH, Taxus chinensis, and Taxus media. Among these plants, Taxus baccata LINN and Taxus media are particularly preferable.
The tissue culture of the said plant is carried out by a conventionally known process except that the culture is carried out in the presence of coronatines, a bacterium which produces the coronatines, a culture solution or a culture extract of such bacterium, cyclic polysaccharides, fatty acids, or a compound represented by the above-mentioned general formulae (X) or (XI) according to the present invention.
Coronatines to be used in the present invention have been found as chlorosis inducing substance produced by Pseudomonas bacterium, and they have activities to induce necrosis of a plant, promotion of ethylene generation or aging of a plant. They also have an activity to promote the thickening growth of the tuber of potato, just like jasmonic acid.
As bacterium which produces coronatines, Pseudomonas bacteria and Xanthomonas bacteria have been known. Illustrative examples of Pseudomonas bacteria include P. syringae (IFO 3310), P. glycinea, P. tabaci (IFO 3508, IFO 14081), P. aptata (IFO 12655), P. coronafaciens, P. phaseolicola (IFO 12656, IFO 14078), P. mori (IFO 14053, IFO 14054, IFO 14055), P. helianthi (IFO 14077) and the like. Illustrative examples of Xanthomonas bacteria include X. campestris (IFO 13303, IFO 13551), X. citri, X. cucurbitae (IFO 13552), X. phaseoli (IFO 13553, IFO 13554), X. pruni (IFO 3780, IFO 13557) and the like.
Examples of coronatines include a compound represented by the general formula (I):
or general formula (II):
[wherein, R 1 represents hydroxyl group, OR 2 (wherein R 2 represents alkyl group having 1 to 6 carbon atoms or carbohydrate residue), OM 1 (wherein M 1 represents alkaline metal atom, alkaline earth metal atom or NH 4 ), or NR 3a R 3b (wherein R 3a and R 3b represent independently hydrogen atom, acyl group having 1 to 6 carbon atoms, alkyl group having 1 to 6 carbon atoms, amino acid residue, or a group represented by the general formula (III):
(wherein R 4 represents hydrogen atom, hydroxyl group, alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms or a group represented by the following formula:
—CO—R 7
(wherein
R 7 represents hydroxyl group, OM 2 (wherein M 2 represents alkaline metal atom, alkaline earth metal atom or NH 4 ), NR 8a R 8b (wherein R 8a and R 8b independently represent hydrogen atom, acyl group having 1 to 6 carbon atoms, alkyl group having 1 to 6 carbon atoms or amino acid residue), or OR 9 (wherein R 9 represents alkyl group having 1 to 6 carbon atoms or carbohydrate residue));
R 5a , R 5b , R 6a and R 6b independently represent hydrogen atom, hydroxyl group, alkyl group having 1 to 6 carbon atoms, or alkoxy group having 1 to 6 carbon atoms);
R 10a , R 10b , R 11a , R 11b , R 12 , R 13 , R 14a , R 14b , R 15a , R 15b , R 16a , R 16b , R 17 and R 19 independently represent hydrogen atom, hydroxyl group, alkyl group having 1 to 6 carbon atoms, or alkoxy group having 1 to 6 carbon atoms;
R 18 represents hydrogen atom, alkyl group having 1 to 6 carbon atoms, or carbohydrate residue;
a double bond may be formed between the neighboring member carbon atoms in the five-membered ring or six-membered ring in the formula].
In the above-mentioned general formulae (I), (II) and (III), illustrative examples of alkyl group having 1 to 6 carbon atoms represented by R 2 , R 3a , R 3b , R 4 , R 5a , R 5b , R 6a , R 6b , R 8a , R 8b , R 9 , R 10a , R 10b , R 11a , R 11b , R 12 , R 13 , R 14a , R 14b , R 15a , R 15b , R 16a , R 16b , R 17 , R 18 or R 19 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, neopentyl, t-pentyl, n-hexyl and isohexyl groups.
In the above-mentioned general formulae (I), (II) and (III), examples of alkoxy group having 1 to 6 carbon atoms represented by R 4 , R 5a , R 5b , R 6a , R 6b , R 10a , R 10b , R 11a , R 11b , R 12 , R 13 , R 14a , R 14b , R 15a , R 15b , R 16a , R 16b , R 17 or R 19 include, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, n-pentyloxy, neopentyloxy, t-pentyloxy, n-hexyloxy and isohexyloxy groups.
When R 1 or R 7 is OM 1 or OM 2 , examples of the alkaline metal atom or alkaline earth metal atom represented by M 1 or M 2 include sodium, potassium and calcium.
When R 1 or R 7 is NR 3a R 3b or NR 8a R 8b , the acyl group having 1 to 6 carbon atoms represented by R 3a , R 3b , R 8a or R 8b may have either a straight chain or a branched chain, and their examples include formyl, acetyl, propionyl, butyryl, valeryl, hexanoyl and acryloyl groups.
When R 1 or R 7 is NR 3a R 3b or NR 8a R 8b , examples of the amino acid residue represented by R 3a , R 3b , R 8a or R 8b include isoleucyl, valyl, glutamyl and lysyl groups.
When R 1 or R 7 is OR 2 or OR 9 , an example of the carbohydrate residue represented by R 2 or R 9 is glucopyranosyl group.
An example of the carbohydrate residue in the above-mentioned general formula (II) represented by R 18 includes glucopyranosyl group.
Preferable examples of the coronatines include coronatine (formula IV) and coronafacic acid (formula V).
Coronatine, which is a compound wherein coronafacic acid and 2-ethyl-1-aminocyclopropane-1-carboxylic acid are linked by amide bond, has the highest activity among those compounds represented by formula (I).
Coronatines to be used in the present invention have various stereoisomers (cis-trans isomers and optical isomers), and each isomer can be used alone or in the form of a mixture.
For adding coronatines, a bacterium which produces the coronatines, a culture solution or a culture extract of such bacteria to the culture medium, the concentration of the coronatines in the culture medium is normally required to be 0.001-1000 μM, and it is particularly preferable, according to the present invention, to control the concentration of the coronatines to be in the range of 0.01 to 100 μM.
By cultivating the cells and/or tissues of the above-mentioned plant by utilizing a culture medium which contains one or more substances selected from the group consisting of coronatines, a bacterium which produces the coronatines, a culture solution or a culture extract of such bacteria, according to the present invention, cultured cells and/or cultured tissues having higher taxane-type diterpene productivity can be obtained compared to the case wherein the substance was not added.
It has been reported that biosynthetic system involved in some secondary metabolism is activated by adding coronatines to plant cell cultures [W. Weiler et al., FEBS Letters 345:1 (1994)], however, there have been no reports on carrying out tissue culture of a plant producing a taxane-type diterpene in the presence of coronatines as a medium additive, and it has been beyond all expectations that the amount of the produced taxane-type diterpene was increased thereby.
A process to increase the productivity of taxane-type diterpene wherein a microorganism or a microorganism culture extract is used as elicitor for cultured cells of a plant belonging to genus Taxus is described in International Publication WO 93/17121 and U.S. Pat. No. 5019504. Though it is specified as elicitor in those publications, the degree of its effect is not given clearly. Besides there is no description regarding the bacteria belonging to genus Pseudomonas or genus Xanthomonas, which are the bacteria producing coronatines to be used in the present invention. Accordingly, it has been beyond all expectations that the amount of the produced taxane-type diterpene was increased by culturing cells of a plant belonging to genus Taxus in the presence of a bacterium which produces coronatines, or a culture solution or a culture extract of such bacteria.
The propagation of a bacetrium which produces coronatines is carried out with a propagation medium for general bacillus or a minimal medium.
An illustrative example of a culture solution of a bacterium which produces coronatines to be used in the present invention includes a culture solution treated by aseptic filtration after it is used for cultivating the bacteria.
Illustrative examples of a culture extract of a bacterium which produces coronatines to be used in the present invention include a culture solution which was autoclaved at 120° C. for 15 minutes after the bacteria had been cultured therein, or an extract of the culture solution of those bacteria which was extracted with an organic solvent such as ethyl acetate under acid conditions, which was optionally further refined with Sephadex LH 20 column and the like to give a partially refined fraction containing coronatine or coronafacic acid.
It is effective to add the coronatines, a bacterium which produces the coronatines, a culture solution or a culture extract of such bacterium, when the cultured cells are in the exponential growth phase through the stationary phase, and it is particularly preferable for the method of the present invention to add them in a transitional period from the exponential growth phase to the stationary phase. For example, when cells are transplanted in every 21 days, the 7th-16th day is the suitable time for addition of the coronatines, a bacterium which produces the coronatines, a culture solution or a culture extract of such bacterium. As for the addition, a predetermined amount of the substance can be added at a time, or they can be successively added in a plurality of parts.
An illustrative example of a cyclic polysaccharide to be used in the present invention includes cyclodextrin, cyclofructan and derivatives thereof.
The cyclic polysaccharide having a cavity inside due to its circular structure, the opening of the cavity and the exterior side showing hydrophilic property, and the interior side of the ring showing hydrophobic property, has clathrate activity to take an oil substance in the cavity. By utilizing this property, it has many uses such as changing a substance which is scarcely soluble in water to a water soluble substance, stabilizing an unstable substance, retaining a volatile substance such as a perfume, and controlling a peculiar odor. Commercially, it has been used for such food as freeze-dried tea, or ham and sausages for controlling the peculiar odor.
Cyclodextrin is a substance in which 6 to 8 glucose units are connected in the form of a donut, and is synthesized from starch by the function of cyclodextrin synthesizing enzyme which is produced by such special microorganism as Bacillus macerans. The cyclofructan is a substance in which 6 to 8 fructose units are connected in the form of a donut, and is synthesized from inulin by the function of cyclofructan synthesizing enzyme which is produced by such special microorganism as Bacillus circulans.
Examples of cyclodextrin and a derivative thereof, which are objects of the present invention, include α-cyclodextrin, βcyclodextrin, γ-cyclodextrin, or a branched dextrin thereof and a partially methylated dextrin thereof, and all of these can be utilized. Examples of the branched cyclodextrin include glycosyl-α-cyclodextrin, maltosyl-α-cyclodextrin, maltotriosyl-α-cyclodextrin, glycosyl-β-cyclodextrin, glycosyl-γ-cyclodextrin, galactosyl-α-cyclodextrin and the like, wherein a saccharide is bonded to the ring as a branch. As cyclofructan or a derivative thereof, a compound in which 6 to 8 fructose units are bonded by β2-1 fructoside bonds, a branched cyclofructan thereof, and partially methylated cyclofructan thereof can be utilized.
The concentration of the above-mentioned cyclic polysaccharides in a culture medium is preferably 0.01-50 mM, and it is more preferable, according to the present invention, to control the concentration of the cyclic polysaccharides to be in the range of 0.1 to 30 mM.
By carrying out the tissue culture of the cells and/or tissues of the above-mentioned plant by utilizing a culture medium to which cyclic polysaccharides are added according to the present invention, cultured cells or cultured tissues having higher taxane-type diterpene productivity can be obtained compared to the case wherein the substance was not added.
There have been no reports on carrying out tissue culture of a taxane-type diterpene producing plant in the presence of cyclic polysaccharides as a medium additive, and it has been beyond all expectations that the secretion of the taxane-type diterpene into the medium was promoted thereby, and the amount of the produced taxane-type diterpene was increased.
Particularly when the cyclic polysaccharide and other productivity improving substance (elicitor) are used together, the effect is heightened. Examples of such productivity improving substance include not only coronatines, a bacterium which produces the coronatines, a culture solution or a culture extract of such bacteria, fatty acids or a compound represented by the general formula (X) or general formula (XI) of the present invention, but also below-mentioned jasmonic acids, alkyl esters thereof, heavy metals, amines and antiethylene agents described in Japanese Patent Application No. 6-252528. It is also particularly effective to combine the use of the cyclic polysaccharides with the cultivation under the atmosphere of a low oxygen concentration described in Japanese Patent Application No. 6-146826.
Examples of fatty acids to be used in the present invention include a synthesized or natural fatty acid wherein the number of the carbon atoms in the main chain is 10-22, among them, the fatty acids having an even number of carbon atoms in its main chain are particularly preferable. These fatty acids can be saturated fatty acids or unsaturated fatty acids having one or more double bonds in its carbon chain. One or more hydrogen atoms bonded to the carbon chain may be substituted by hydrocarbon group having 1 to 6 carbon atoms, hydroxyl group, or amino group. The double bond to be contained in the above-mentioned unsaturated fatty acid can be either cis-form, trans-form or their mixture, however, a fatty acid containing the cis-form double bond is preferable.
Illustrative examples of the above-mentioned fatty acid include straight chain fatty acids such as capric acid, decenoic acid, lauric acid, dodecenoic acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, vaccenic acid, linolic acid, a-linolenic acid, y-linolenic acid, tetraoctadecenoic acid, arachic acid, arachidonic acid, eicosatetraenoic acid, eicosapentaenoic acid, behenic acid, and docosahexaenoic acid, hydroxy fatty acids such as ricinoleic acid, and branched fatty acids such as 14-methylpalmitic acid. Among these, oleic acid, linolic acid, linolenic acid and arachidonic acid are preferable, but particularly preferable is α-linolenic acid.
Among the substituents, examples of a hydrocarbon group having 1 to 6 carbon atoms include methyl, ethyl, propyl, cyclopropyl, butyl, isobutyl, pentyl and hexyl groups.
Among the substituents, examples of amino groups include amino, monomethylamino, and dimethylamino groups.
Fatty acids to be added to the culture medium may be a fatty acid derivative represented by the following general formula (XII):
R 32 —COR 33 (XII)
[wherein
R 32 —CO represents an atomic group derived from the above-mentioned fatty acid;
R 33 represents OR 34 (wherein R 34 represents an alkyl group having 1 to 6 carbon atoms, or a carbohydrate residue), OM (wherein M represents alkaline metal atom, alkaline earth metal atom or NH 4 ), or NR 35a R 35b (wherein R 35a and R 35b independently represent hydrogen atom, alkyl group having 1 to 6 carbon atoms, or amino acid residue)].
In the above-mentioned general formula (XII), examples of alkyl group having 1 to 6 carbon atoms represented by R 34 , R 35a and R 35b include, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, and isohexyl groups.
When R 33 is OM, examples of the alkaline metal atom or alkaline earth metal atom represented by M include, sodium, potassium and calcium.
When R 33 is NR 35a R 35b , examples of the amino acid residue represented by R 35a or R 35b include glycyl, leucyl, glutamyl, lysyl, phenylalanyl, isoleucyl, tyrosyl, and tryptophyl groups.
When R 33 is OR 34 , an example of the carbohydrate residue represented by R 34 is glucopyranosyl group.
Fatty acids and/or a derivative thereof to be used in the present invention are preferably added to the culture medium to give the concentration of 0.01-1000 μM, and it is particularly preferable to control the concentration to be in the range of 0.1 to 500 μM from the view point of the effectiveness in improving the productivity of the taxane-type diterpene (when two or more kinds of fatty acids and/or derivatives are used in combination, the range of the concentration shown above represents the total concentration.)
According to the present invention, a natural oil containing a fatty acid or an enzymatic hydrolysate thereof can be used as well. Examples of a natural oil include vegetable oils such as rapeseed oil, soybean oil, linseed oil and safflower oil, and examples of the enzymatic hydrolysate include those of the above-mentioned vegetable oils decomposed by lipase. The concentration of the above-mentioned natural oil or the enzymatic hydrolysate thereof in the culture medium is preferably in the range of 1 to 1000 mg/l.
In addition to adding the fatty acids from outside of the system, it is also possible to add a lipid decomposing enzyme to the culture medium to partially hydrolyze the lipid such as glycerolipid constituting the said tissue and/or cell, so that the fatty acid is liberated into the medium. Examples of the lipid decomposing enzyme include lipase, phospholipase A 1 , phospholipase A 2 and phospholipase B, and phospholipase A 1 , phospholipase A 2 and phospholipase B having an optimal pH in an acid region are particularly preferable. According to the present invention, the preferable concentration of the above-mentioned enzyme to be added to the culture medium is 0.1-100 milligrams per liter of culture medium.
According to the present invention, the fatty acid, derivative thereof, natural oil, and lipid decomposing enzyme which satisfy the above-mentioned conditions can be used alone, or they can be combined randomly and used together.
These fatty acids or a derivative thereof, natural oil or lipid decomposing enzyme can be added to the culture medium from the initial stage of the cultivation or during the cultivation. It can be added altogether at any time during the cultivation, or they can be added in a plurality of parts.
Illustrative process of adding the above-mentioned fatty acids and natural oils to the culture medium include a process in which they are dissolved in an organic solvent such as ethanol and added, a process in which they are added together with a surfactant such as octyl-β-glucoside, or a process in which they are directly added to the culture medium followed by micelle formation which is carried out by supersonic wave treatment and the like. It is also possible that they are added directly to the medium and cultivation is carried out under the oil-water separated conditions.
Imino or amino derivatives of jasmonic acids to be used in the present invention are the compounds of the general formula (X) or (XI) respectively.
In the above-mentioned general formulae (X) or (XI), examples of the alkyl group having 1 to 12 carbon atoms represented by R 1a , R 1b , R 1c , R 1d , R 1e , R 1f , R 1g , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 28a , R 28b , R 29 , R 26a , R 26b , R 27 , R 31a , R 31b or Y include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups. The alkyl group having 3 or more carbon atoms includes a cyclic alkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups.
In the above-mentioned general formulae (X) or (XI), examples of the alkoxy group having 1 to 12 carbon atoms represented by R 1a , R 1b , R 1c , R 1d , R 1e , R 1f , R 1g , R 31a or R 31b include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy and dodecyloxy groups. The alkoxy group having three or more carbon atoms includes an alkoxy group containing a cyclic alkyl group such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups.
In the above-mentioned general formulae (X) or (XI), the acyl group having 1 to 12 carbon atoms represented by R 28a , R 28b , R 26a , R 26b , R 29 , R 31a or R 31b may have either a straight chain or a branched chain, or it can be an aromatic atomic group, and illustrative examples thereof include formyl, acetyl, propionyl, butyryl, valeryl, hexanoyl, acryloyl, capryloyl, pelargonyl, benzoyl, toluoyl, salicyloyl and cinnamoyl groups.
In the above-mentioned general formulae (X) or (XI), examples of the aryl group or aryl group having a substituent represented by R 1a , R 1b , R 1c , R 1d , R 1e , R 1f , R 1g , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 28a , R 28b , R 29 , R 28b , R 29 , R 26a , R 26b , R 27 , R 27 , R 31a , R 31a , R 31b or Y include phenyl, p-methoxyphenyl, p-chlorophenyl, p-fluorophenyl and naphthyl groups.
In the above-mentioned general formulae (X) or (XI), examples of the arylalkyl group or arylalkyl group having a substituent represented by R 1a , R 1b , R 1 , R 1d , R 1e , R 1f , R 1g , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 28a , R 28b , R 29 , R 26a , R 26b , R 27 , R 31a , R 31b or Y include benzyl, p-methoxybenzyl, p-chlorobenzyl, and p-fluorobenzyl groups.
In the above-mentioned general formulae (X) or (XI), when R 25 is OM, examples of the alkaline metal atom or alkaline earth metal atom represented by M include sodium, potassium and calcium.
In the above-mentioned general formula (X), examples of the alkylsulfonyl group having 1 to 12 carbon atoms represented by R 28a or R 28b include methylsulfonyl, ethylsulfonyl, n-propylsulfonyl and isopropylsulfonyl groups.
In the above-mentioned general formula (X), when R 29 is —COR—R 30 , examples of the alkylamino group having 1 to 12 carbon atoms represented by R 30 include methylamino, ethylamino, n-propylamino and isopropylamino groups.
In the above-mentioned general formula (X), examples of the alkylsulfinyl group having 1 to 12 carbon atoms represented by R 28a or R 28b include methylsulfinyl, ethylsulfinyl, n-propylsulfinyl and isopropylsulfinyl groups.
In the above-mentioned general formulae (X) or (XI), when R 25 is NR 26a R 26b , examples of the amino acid residue represented by R 26a or R 26b and examples of the amino acid residue represented by R 31a or R 31b in the general formula (XI) include isoleucyl, tyrosyl and tryptophyl groups.
In the above-mentioned general formulae (X) or (XI), when R 25 is OR 27 , an example of the carbohydrate residue represented by R 27 is glucopyranosyl group.
In the compounds represented by the general formulae (X) or (XI), a double bond may be formed between the neighboring member carbon atoms in the five-membered ring.
Illustrative examples of the compound represented by the general formula (X) include those shown as follows;
(Compound A)
Y: —OH
R 1a , R 1b , R 1c , R 1d , R 1e , R 1f , R 20 , R 21 , R 22 , R 23 , R 24 : H
A double bond is formed between C 3 and C 4 .
R 25 : —OCH 3
n: 1
(Compound B)
Y: —OCH 3
R 1a , R 1b , R 1c , R 1d , R 1e , R 1f , R 20 , R 21 , R 22 , R 23 , R 24 : H
A double bond is formed between C 3 and C 4 .
R 25 :—OCH 3
n: 1
(Compound C)
Y: —NH 2
R 1a , R 1b , R 1c , R 1d , R 1e , R 1f , R 20 , R 21 , R 22 , R 23 , R 24 : H
A double bond is formed between C 3 and C 4 .
R 25 :—OCH 3
n: 1
(Compound D)
Y: —NHCONH 2
R 1a , R 1b , R 1c , R 1d , R 1e , R 1f , R 20 , R 21 , R 22 , R 23 , R 24 : H
A double bond is formed between C 3 and C 4 .
R 25 :—OCH 3
n: 1
(Compound E)
Y:—NHCHO
R 1a , R 1b , R 1c , R 1d , R 1e , R 1f , R 20 , R 21 , R 22 , R 23 , R 24 : H
A double bond is formed between C 3 and C 4 .
R 25 :—OCH 3
n=1
(Compound F)
Y:—NHSO 2 CH 3
R 1a , R 1b , R 1c , R 1d , R 1e , R 1f , R 20 , R 21 , R 22 , R 23 , R 24 : H
A double bond is formed between C 3 and C 4 .
R 25 :—OCH 3
n=1
(Compound G)
Y:—CN
R 1a , R 1b , R 1c , R 1d , R 1e , R 1f , R 20 , R 21 , R 22 , R 23 , R 24 : H
A double bond is formed between C 3 and C 4 .
R 25 :—OCH 3
n=1
(Compound H)
Y:—SO 2 NH 2
R 1a , R 1b , R 1c , R 1d , R 1e , R 1f , R 20 , R 21 , R 22 , R 23 , R 24 : H
A double bond is formed between C 3 and C 4 .
R 25 :—OCH 3
n=1
An illustrative example of the compound represented by the general formula (XI) is shown as follows;
(Compound I)
R 1a , R 1b , R 1c , R 1d , R 1e , R 1f , R 1g , R 20 , R 21 , R 22 , R 23 , R 24 , R 31a : H
R 31b : OH
A double bond is formed between C 3 and C 4 .
R 25 : —OCH 3
n:1
Compounds to be used in the present invention which are represented by the general formula (X) or (XI) have various stereoisomers, and each isomer can be used alone or the isomers can be used in the form of their mixture. Among the side chains of Compounds A to H, the isopentenyl group and the methoxycarbonylmethyl group are preferably in the cis-configuration.
The compound represented by the general formulae (X) or (XI) can be easily prepared by a process such as addition reaction of jasmonic acids with an ammonia derivative (for example, see “New Experimental Chemistry Course No.14, Synthesis and Reaction of Organic Compounds [III]” edited by The Chemical Society of Japan).
Illustrative examples of the ammonia derivative include hydroxylamine, phenylhydrazine, semicarbazide, O-methylhydroxylamine, O-ethylhydroxylamine, formic hydrazide, methanesulfonyl hydrazide and the like, or a salt thereof. When a salt is used, if necessary, a basic reagent can be liberated from the salt by adding sodium acetate or potassium acetate in the presence of a carbonyl derivative (jasmonic acids).
In the addition reaction, a basic nitrogen compound nucleophilically attacks the carbon in the carbonyl group, and it is preferable for the reaction solution to be controlled to have appropriate acidity.
The imino derivative of jasmonic acids obtained in such a way is further reacted with a complex hydrogen compound such as lithium aluminium hydride, sodium cyanoborohydride and sodium borohydride or a reducing agent such as borane to give an amino derivative of jasmonic acids.
The concentration of the compound represented by the general formulae (X) or (XI) in a culture medium is preferably 0.001-1000 μM, and it is more preferable to control the concentration to be in the range of 0.1 to 500 μM.
Promotion of the production of a specific secondary metabolite by addition of jasmonic acids to plant cell cultures is described in DE 4122208 however, there have been no reports on the production of the taxane-type diterpene. The present inventors have already found that the amount of the produced taxane-type diterpene in the resulting cultures can be increased by addition of jasmonic acids [Japanese Patent Application No. 6-104211, Japanese Patent Application No. 6-104212, Japanese Patent Application No. 7-47580], however, it has been beyond all expectations that imino or amino derivative of Jasmonic acids according to the present invention has higher production promoting effect than that of Jasmonic acids.
It is most effective to add the compound represented by the general formulae (X) or (XI) when the cultured cells are in the exponential growth phase or in the stationary phase, and it is particularly preferable for the method of the present invention to add the compound in a transitional period from the exponential growth phase to the stationary phase. For example, when cells are transplanted in every 21 days, the 7th-14th day is the suitable time for addition of the compound. The addition can be done at a time, or in a plurality of parts.
When a two-step culture is carried out by using a compound represented by the general formulae (X) or (XI), it is also possible that the cells are proliferated in a medium which is free from the compound, in the first culture step and the compound is added in the second culture step. The cells to be inoculated to the second culture step are preferably in the exponential growth phase or in the stationary phase.
According to the present invention, a cell or a tissue is cultured in a culture medium containing at least one substance selected from the group consisting of the above-mentioned coronatines, a bacterium which produces the coronatines, a culture solution or a culture extract of such bacteria, cyclic polysaccharides, fatty acids, and a compound represented by the general formulae (X) or (XI), then the taxane-type diterpene is recovered from the resulting cultures including cultured tissue, cultured cells and culture medium.
Examples of the medium to be used in the present invention include those known media which have been conventionally used for the plant tissue culture, such as medium of Murashige & Skoog (1962), medium of linsmaier Skoog (1965), Woody Plant Medium (1981), Gamborg's B-5 medium and Mitsui's M-9 medium.
A phytohormone, and if necessary a carbon source, an inorganic component, vitamins, amino acids and the like may be added as well to these media.
As the phytohormone, for example, auxins such as indoleacetic acid (IAA), naphthalenacetic acid (NAA), and 2,4-dichlorophenoxy acetic acid (2,4-D), and cytokinins such as kinetin, zeatin and dihydrozeatin can be used.
As the carbon source, a disaccharide such as sucrose, maltose and lactose, a monosaccharide such as glucose, fructose and galactose, starch or a mixture of two or more kinds of such sugar sources mixed at an appropriate ratio can be utilized.
Illustrative examples of the inorganic component include phosphorus, nitrogen, potassium, calcium, magnesium, sulfur, iron, manganese, zinc, boron, copper, molybdenum, chlorine, sodium, iodine and cobalt, and these components can be added in the form of such a compound as potassium nitrate, sodium nitrate, calcium nitrate, potassium chloride, potassium monohydrogenphosphate, potassium dihydrogenphosphate, calcium chloride, magnesium sulfate, sodium sulfate, ferrous sulfate, ferric sulfate, manganese sulfate, zinc sulfate, boric acid, copper sulfate, sodium molybdate, molybdenum trioxide, potassium iodide, cobalt chloride and the like.
Illustrative examples of the vitamins include biotin, thiamine (vitamin B 1 ), pyridoxine (vitamin B 6 ), pantothenic acid, inositol and nicotinic acid.
As the amino acids, for example, glycine, phenylalanine, leucine, glutamine, cysteine and the like can be added.
Generally, the phytohormones in a concentration of about 0.01-about 10 μM, the carbon source in a concentration of about 1-about 30 g/l, the inorganic component in a concentration of about 0.1 μ-about 100 mM, and the vitamins and the amino acids respectively in a concentration of about 0.1-about 100 mg/l are used.
According to the present invention, both a liquid medium and such a solid medium that contains agar and gelan gum normally in an amount of 0.1-1% can be used, however, usually a liquid medium is preferable.
A piece of a tissue or a cell of a root, a growing point, a leaf, a stem, a seed, a pollen, an anther and a calyx and the like of the said plant, or cultured cells which are obtained by the tissue culture thereof with the above-mentioned medium or other conventional medium can be used for the tissue culture of the present invention.
The present invention can also be applied to neoplastic cell and/or hairy-root, obtained by infecting the plant tissue with Agrobacterium tumefaciens or Agrobacterium rhizogenes.
By carrying out the tissue culture of these tissues or cells in the presence of at least one substance selected from the group consisting of coronatines, a bacterium which produces the coronatines, a culture solution or a culture extract of such bacteria, cyclic polysaccharides, fatty acids, and a compound represented by the general formulae (X) or (XI), according to the present invention, cultured tissues or cultured cells having higher taxane-type diterpene productivity can be obtained compared to the case wherein the compound was not added, or no treatment was given.
Taxane-type diterpene can be separated from the cultures such as cultured tissues, cultured cells and culture medium, which are obtained according to the above-mentioned process, by extraction with an organic solvent such as methanol and dichloromethane. It is also possible to recover the taxane-type diterpene continuously by allowing an appropriate adsorbing agent or an organic solvent coexist in the culture medium.
One preferable example of the tissue culture according to the present invention can be illustrated as follows.
A piece of a plant body of a plant belonging to genus Taxus, such as a root, a growing point, a leaf, a stem, a seed and the like is sterilized and placed on Woody Plant Medium solidified with gelan gum, and kept at 10-35° C. for about 14-60 days so that a part of the tissue piece is changed to callus. By subculturing the callus thus obtained, the growing speed is gradually increased and stabilized callus can be obtained. By the stabilized callus, we refer to a callus which remains in callus state during cultivation without showing differentiation into a shoot or a root and the cells of which have uniform growing speed.
Such stabilized callus is inoculated to a liquid medium, suited for the proliferation, such as liquid Woody Plant Medium and proliferated. The growing speed is further increased in the liquid medium. According to the present invention, the stabilized callus or the cells constituting the above-mentioned callus are grown in a solid medium or a liquid medium containing at least one substance selected from the group consisting of coronatines, a bacterium which produces the coronatines, a culture solution or a culture extract of such bacteria, cyclic polysaccharides, fatty acids, and a compound represented by the general formulae (X) or (XI).
The culture temperature for the tissue culture according to the present invention is usually about 10-about 35° C., and preferably it is about 23-about 28° C. due to the high growing speed. As for the culture period, 14-42 days are preferable.
When a liquid medium is used for the culture according to the present invention, the cultured cells can be separated from the culture medium after the cultivation is completed, by such a method as decantation or filtration and the desired taxane-type diterpene can be separated from the cultured cells and/or the culture medium by such a method as extraction with an organic solvent.
The method of the present invention can be used together with a culture method to be carried out in the presence of jasmonic acids, which is disclosed as taxane-type compound production promoting substance in Japanese Patent Application No.7-47580, No. 6-104211, No. 6-104212, and No. 6-104213, to heighten the effect of the present invention.
Illustrative examples of jasmonic acids include jasmonic acid, a salt thereof, an alkyl ester thereof, cucurbic acid, a salt thereof, an alkyl ester thereof, tuberonic acid, a salt thereof and an alkyl ester thereof.
Among these, particularly preferable compounds can be exemplified by jasmonic acid, methyl jasmonate, tuberonic acid, methyl tuberonate, and cucurbic acid or methyl cucurbate from the view point of their high effectiveness in improving the productivity.
Jasmonic acids which can be used in the present invention include all the stereoisomers and the mixtures thereof.
The concentration of the jasmonic acids in a culture medium is 0.01-1000 μM, and it is particularly preferable to control the concentration of the jasmonic acids to be in the range of 0.1 to 500 μM.
It is effective to add jasmonic acids when the cultured cells are in the exponential growth phase or in the stationary phase, and it is particularly preferable to add jasmonic acids in a transitional period from the exponential growth phase to the stationary phase. The same can be said of the timing of the treatment for increasing the amount of the endogenous jasmonic acids to be produced. For example, when cells are transplanted in every 21 days, the 7th-16th day is the suitable time for addition of the jasmonic acids or the treatment to increase the amount of the endogenous jasmonic acids to be produced. The addition of the jasmonic acids or the treatment to increase the amount of the endogenous jasmonic acid to be produced can be done at a time, or in a plurality of parts.
Furthermore, the present invention can be used together with the method disclosed in Japanese Patent Application No.6-146826 wherein the culture is carried out by controlling the oxygen concentration in a gas phase in an culture vessel to less than the oxygen concentration in the atmosphere, from the initial stage of the culture, or by controlling the dissolved oxygen concentration in a fluid medium which is in contact with the tissue or the cell to less than the saturated dissolved oxygen concentration at that temperature from the initial stage of the culture.
Here, by the initial stage of the culture, we refer to from the time when the culture was started through the 7th day after the start of the culture, and the controlling of the oxygen concentration in the gas phase in the culture vessel or the controlling of the dissolved oxygen concentration in the fluid medium which is in contact with the tissue or the cell is preferably done from the beginning of the culture. The controlling period is not particularly limited, and the controlling under the said conditions can be done in the entire culture period, or only in a part of the entire culture period, however, it is preferable to carry out the control at least for 3 days during the entire culture period.
The oxygen concentration in the gas phase in the culture vessel is required to be controlled to 4-15%, and it is particularly preferable to control it to 6-12%. The dissolved oxygen concentration in the fluid medium is required to be controlled to 1-75% of the saturated dissolved oxygen concentration at that temperature and it is particularly preferable to control it to 10-75%.
The present invention can be also used together with the method disclosed in Japanese Patent Laid-Open Publication No.7-135967, Japanese Patent Application No.6-104213, wherein the cells are separated into a plurality of layers according to the difference in their specific gravities, and the cells contained in at least one layer are cultured.
The present invention can be also used together with the method disclosed in Japanese Patent Application No.6-201150, wherein the culture is carried out in the presence of at least one substance selected from the group consisting of compounds containing a heavy metal, complex ions containing a heavy metal and heavy metal ions.
As for the heavy metals, use of a copper group metal represented by silver or an iron group metal represented by cobalt is preferable. It is preferably used in the form of a compound containing the said heavy metal, a complex ion containing the said heavy metal or in the form of the said metal ion. Particularly preferable is silver thiosulfate ion. The concentration of the heavy metal is preferably 10 −8 M-10 −2 M.
The present invention can be also used together with the method disclosed in Japanese Patent Application No.6-201151, wherein the culture is carried out in the presence of amines.
It is preferable to use at least one kind of amine selected from the group consisting of polyamines such as putrescine, spermidine, spermin, ethylene diamine, N,N-diethyl-1,3-propane diamine, diethylene triamine and a salt thereof. The concentration of the amine is preferably 10 −8 M-10 −1 M.
It is also possible to combine the method of the present invention with two or more methods disclosed in the above-mentioned prior patents.
According to the present invention, a large amount of the taxane-type diterpene can be easily obtained by the tissue culture of a plant which produces the taxane-type diterpene using a tissue culture medium containing at least one kind of substance selected from the group consisting of coronatines, a bacterium which produces the coronatines, a culture solution or a culture extract of such bacteria, cyclic polysaccharides, fatty acids or an imino or amino derivative of jasmonic acids.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention will be further illustrated with the following examples, comparative examples, reference examples and synthesis examples, however, these examples are not to be construed to limit the scope of the invention.
EXAMPLE 1
A part of stem of Taxus baccata LINN which had been previously sterilized with 2% antiformin solution or 70% ethanol solution or the like, was placed on solid Woody Plant Medium (containing gelan gum of 0.25% by weight) to which naphthalenacetic acid had been added to give the concentration of 10 −5 M, and static culture was carried out at 25° C. in a dark place to provide callus of Taxus baccata LINN. One gram (fresh weight) of the callus was inoculated to an Erlenmeyer flask containing 20 ml of liquid Woody Plant Medium to which the above-mentioned component was added to give the same concentration and shake culture was carried out with a rotary shaker (amplification of 25 mm, 120 rpm) and the callus was subcultured in every 21 days to accelerate the growth rate thereof.
As the bacterium which produces coronatines, Pseudomonas syringae (IFO 3310) was cultured in a test tube containing 3 ml of bacterial culture medium 802 (Polypepton:1.0%, Yeast extract:0.2%, MgSO 4 .7H 2 O:0.1% , pH 7.0) at 180 rpm, 30° C. for 24 hours to proliferate the bacteria. Then 100 μl of the said culture solution containing the proliferated bacteria was inoculated to an Erlenmeyer flask containing 50 ml of glucose minimal medium (glucose:8.8 g/l, KH 2 PO 4 :2.6 g/l, Na 2 HPO 4 .2H 2 O:6.9 g, NH 4 Cl:2.5 g/l, Na 2 SO 4 :1 g/l, FeSO 4 :0.01 g/l, MnSO 4 :0.01 g/l, MgCl 2 :0.05 g/l, pH 6.8) and further cultured at 30° C. for 24 hours. The culture solution of the bacterium which produces coronatines thus obtained was concentrated to about {fraction (1/20)}, then the pH was adjusted to pH 3 with 2N H 2 SO 4 and extraction with ethyl acetate was carried out. The obtained carboxylic acid fraction was dried under reduced pressure, then dissolved in 2 ml of ethanol and the filtrate obtained by aseptic filtration thereof was used as the culture extract of the bacterium which produces coronatines.
One gram (fresh weight) of the cultured cells of Taxus baccata LINN thus obtained was inoculated to an Erlenmeyer flask containing 20 ml of liquid Woody Plant Medium, and shake culture was carried out at 25° C. for 14 days. On the 14th day after starting the culture, 50 μl of the culture extract of the bacterium which produces coronatines was added to the culture medium and the culture was further carried out for another 7 days.
After completing the culture, cultured cells of Taxus baccata LINN were harvested by filtration and lyophilized, then the dry weight was measured to obtain the yield of the cultured cells per liter of the liquid medium. Taxane-type diterpenes were extracted from the dried callus with methanol or the like, and they were determined by comparing with standard taxol, cephalomannine, and baccatin III using high performance liquid chromatography to measure the yields of the taxane-type diterpenes. The results are shown in Table 1.
Comparative Example 1
Example 1 was repeated except that the culture extract of the bacterium which produces coronatines was not added. The results are shown in Table 1.
EXAMPLE 2
Example 1 was repeated except that 1 ml of a filtrate obtained by aseptic filtration of cultures resulting from culture of Pseudomonas syringae in the minimal medium was added instead of the culture extract of the bacterium and culture was carried out. The results are shown in Table 1.
EXAMPLE 3
Example 1 was repeated except that 1 ml of a liquid obtained by autoclaving the cultures resulting from culture of Pseudomonas syringae in the minimal medium, was added instead of the culture extract of the bacterium and culture was carried out. The results are shown in Table 1.
EXAMPLE 4
Example 1 was repeated except that Xanthomonas campestris (IFO 13551) was used as a bacterium which produces coronatines. The results are shown in Table 1.
EXAMPLE 5
Example 1 was repeated except that Pseudomonas syringae was directly inoculated in the Taxus culture medium as a bacterium which produces coronatines on the 14th day after starting the culture, and the culture was further carried out for another 7 days. After completing the culture, the procedure analogous to that of said Example was carried out. The results are shown in Table 1
EXAMPLE 6
Example 1 was repeated except that Xanthomonas campestris was directly inoculated in the Taxus culture medium as a bacterium which produces coronatines on the 14th day after starting the culture, and the culture was further carried out for another 7 days. After completing the culture, the procedure analogous to that of said Example was carried out. The results are shown in Table 1.
TABLE 1
yield
yield*)
yield*)
of
of
yield*)
of
cultured
baccatin
of
cephalo-
cells
III
taxol
mannine
(g/l)
(mg/l)
(mg/l)
(mg/l)
Comparative
20.2
0.2
2.2
2.4
Example 1
Example 1
19.5
12.2
29.6
3.5
Example 2
19.3
5.3
13.2
2.6
Example 3
18.2
5.0
8.4
2.5
Example 4
19.3
7.9
18.2
2.8
Example 5
17.6
8.7
12.1
3.6
Example 6
14.6
6.9
13.0
4.1
[ *) The yield was calculated based on the total amount of production (in the cell + in the medium.]
EXAMPLE 7
A part of stem of Taxus baccata LINN which had been previously sterilized with 2% antiformin solution or 70% ethanol solution or the like, was placed on solid Woody Plant Medium (containing gelan gum of 0.25% by weight) to which naphthalenacetic acid had been added to give the concentration of 10 −5 M, and static culture was carried out at 25 ° C. in a dark place to provide callus of Taxus baccata LINN. One gram (fresh weight) of the callus was inoculated to an Erlenmeyer flask containing 20 ml of liquid Woody Plant Medium to which the above-mentioned component was added to give the same concentration and shake culture was carried out with a rotary shaker (amplification of 25 mm, 120 rpm) and the callus was subcultured in every 21 days to accelerate the growth rate thereof.
One gram (fresh weight) of the cultured cells thus obtained was inoculated to an Erlenmeyer flask containing 20 ml of liquid Woody Plant Medium to which the above-mentioned component was added to give the same concentration, and shake culture was carried out at 25° C. for 14 days. On the 14th day after starting the culture, 50 μl of coronatine [formula (IV)] was added as coronatines to the culture medium to give the final concentration of 0.001-1000 μM and the culture was further carried out for another 7 days.
After completing the culture, cultured cells of Taxus baccata LINN were harvested by filtration and lyophilized, then the dry weight was measured to obtain the yeild of the cultured cells per liter of the liquid medium. Taxane-type diterpenes were extracted from the dried callus with methanol or the like, and they were determined by comparing with standard taxol, cephalomannine, and baccatin III using high performance liquid chromatography to measure the yields of the taxane-type diterpenes. The results are shown in Table 2.
Comparative Example 2
Example 7 was repeated except that coronatine was not added. The results are shown in Table 2.
EXAMPLE 8
Example 7 was repeated except that 1 μM of N-coronafacoylvaline [formula (IX)] was added as coronatines. The results are shown in Table 2.
EXAMPLE 9
Example 7 was repeated except that 1 μM of methyl ester of coronatine was added as coronatines. The results are shown in Table 2.
EXAMPLE 10
Example 7 was repeated except that 10 μM of coronafacic acid [formula (V)] was added as coronatines. The results are shown in Table 2.
EXAMPLE 11
Example 7 was repeated except that 10 μM of methyl ester of coronafacic acid was added as coronatines. The results are shown in Table 2.
EXAMPLE 12
Example 7 was repeated except that cultured cells of Taxus media, which was obtained in the process analogous to that of said example were used and coronatine was added as coronatines to give the final concentration of 1 μM. The results are shown in Table 2.
Comparative Example 3
Example 12 was repeated except that coronatine was not added. The results are shown in Table 2.
TABLE 2
yield
yield*)
yield*)
concen-
of
of
yield*)
of
tration of
cultured
baccatin
of
cephalo-
coronatines
cells
III
taxol
mannine
(μM)
(g/l)
(mg/l)
(mg/l)
(mg/l)
Comparative
0
20.4
0.2
2.5
2.1
Example 2
Example 7
0.001
20.1
5.0
9.6
3.8
Example 7
0.01
20.2
8.9
15.2
10.2
Example 7
0.1
18.6
18.7
30.1
12.3
Example 7
1
18.4
28.4
60.0
11.4
Example 7
10
17.8
38.5
49.4
8.8
Example 7
100
17.5
44.1
58.0
7.9
Example 7
1000
15.0
13.2
23.1
6.5
Example 8
1
18.1
25.0
51.1
9.2
Example 9
1
19.5
4.6
11.3
6.6
Example 10
10
18.6
12.4
6.2
3.0
Example 11
10
19.2
8.4
S.2
5.1
Comparative
0
20.0
0.4
3.0
4.2
Example 3
Example 12
1
18.6
26.5
65.2
15.1
[*)The yield was calculated based on the total amount of production (in the cell + in the medium.]
EXAMPLE 13
A part of stem of Taxus baccata LINN which had been previously sterilized with 2% antiformin solution or 70% ethanol solution or the like, was placed on solid Woody Plant Medium (containing gelan gum of 0.25% by weight) to which naphthalenacetic acid had been added to give the concentration of 10 −5 M, and static culture was carried out at 25° C. in a dark place to provide callus of Taxus baccata LINN. 0.1 g (fresh weight) of the callus was inoculated to a well having an inner diameter of 18 mm, containing 1 ml of liquid Woody Plant Medium to which the above-mentioned component was added to give the same concentration and shake culture was carried out with a rotary shaker (amplification of 25 mm, 120 rpm) and the callus was subcultured in every 28 days to accelerate the growth rate thereof.
One gram (fresh weight) of the cultured cells thus obtained was inoculated to an Erlenmeyer flask containing 20 ml of liquid Woody Plant Medium to which the above-mentioned component was added to give the same concentration, and shake culture was carried out at 25° C. for 14 days. On the 14th day after starting the culture, β-cyclodextrin was added to give the final concentration of 0.01 mM and the culture was further carried out for another 7 days.
After completing the culture, cultured cells of Taxus baccata LINN were harvested by filtration and lyophilized, then the dry weight was measured to obtain the yeild thereof per liter of the liquid medium. Taxane-type diterpenes were extracted from the dried callus with methanol or the like, and they were determined by comparing with standard taxol, cephalomannine, and baccatin III using high performance liquid chromatography to measure the yields of the taxane-type diterpenes. The results are shown in Table 3.
Comparative Example 4
Example 13 was repeated except that β-cyclodextrin was not added. The results are shown in Table 3.
EXAMPLE 14
Example 13 was repeated except that β-cyclodextrin was added to give the final concentration of 0.1 mM. The results are shown in Table 3.
EXAMPLE 15
Example 13 was repeated except that ,cyclodextrin was added to give the final concentration of 1 mM. The results are shown in Table 3.
EXAMPLE 16
Example 13 was repeated except that β-cyclodextrin was added to give the final concentration of 10 mM. The results are shown in Table 3.
EXAMPLE 17
Example 13 was repeated except that 6-0-β-D-glucosyl-βcyclodextrin was added instead of β-cyclodextrin to give the final concentration of 50 mM. The results are shown in Table 3.
EXAMPLES 18-22
Examples 13-17 were repeated except that further methyl ester of jasmonic acid was added to give the final concentration of 100 μM. The results are shown in Table 4.
Comparative Example 5
Comparative Example 4 was repeated except that further methyl ester of jasmonic acid was added to give the final concentration of 100 μM. The results are shown in Table 4.
EXAMPLE 23
Example 21 was repeated except that ′-cyclodextrin was added instead of β-cyclodextrin to give the final concentration of 10 mM. The results are shown in Table 5.
EXAMPLE 24
Example 21 was repeated except that γ-cyclodextrin was added instead of β-cyclodextrin to give the final concentration of 10 mM. The results are shown in Table 5.
EXAMPLE 25
Example 21 was repeated except that cyclofructan (a compound in which 7 fructose units are connected) was added instead of β-cyclodextrin to give the final concentration of 10 mM. The results are shown in Table 5.
TABLE 3
concentration
yeild
yield*)
yield*)
of
of
of
yield*)
of
β-cyclo-
cultured
baccatin
of
cephalo-
dextrin
cells
III
taxol
mannine
(mM)
(g/l)
(mg/l)
(mg/l)
(mg/l)
Comparative
0
17.3
1.5
3.8
0.6
Example 4
Example 13
0.01
19.0
2.5
4.0
0.7
Examp1e 14
0.1
19.1
3.0
4.2
2.6
Example 15
1
20.1
4.2
6.5
3.0
Example 16
10
20.1
5.0
10.5
2.2
Example 17
50**)
20.5
3.5
8.2
1.3
[*)The yield was calculated based on the total amount of production (in the cell + in the medium.)]
[**)6-O-α-D-glucosyl-β-cyclodextrin was used.]
TABLE 4
concentration
yield
yield*)
yield*)
of
of
of
yield*)
of
β-cyclo-
cultured
baccatin
of
cephalo-
dextrin
cells
III
taxol
mannine
(mM)
(g/l)
(mg/l)
(mg/l)
(mg/l)
Comparative
0
15.4
49.7
25.9
7.3
Example 5
Example 18
0.01
15.6
54.6
28.5
8.0
Example 19
0.1
16.3
62.6
35.4
9.6
Lxample 20
1
15.4
76.0
42.3
10.1
Example 21
10
17.3
54.2
64.4
12.5
Example 22
50**)
17.5
53.0
45.9
11.1
[*)The yield was calculated based on the total amount of production (in the cell + in the medium.)]
[**)6-O-α-D-glucosyl-β-cyclodextrin was used.]
TABLE 5
yield
yield*)
yield*)
kind of
of
of
yield*)
of
cyclic
cultured
baccatin
of
cephalo-
poly-
cells
III
taxol
mannine
saccharides
(g/l)
(mg/l)
(mg/l)
(mg/l)
Example 23
α-cyclodextrin
16.6
55.7
46.0
7.5
Example 24
γ-cyclodextrin
17.5
85.2
45.2
8.5
Example 25
cyclofructan
17.9
51.4
48.9
9.1
[*)The yield was calculated based on the total amount of production (in the cell + in the medium.)]
EXAMPLE 26
A part of stem of Taxus baccata LINN which had been previously sterilized with 2% antiformin solution or 70% ethanol solution or the like, was placed on solid Woody Plant Medium (containing gelan gum of 0.25% by weight) to which naphthalenacetic acid had been added to give the concentration of 10 −5 M, and static culture was carried out at 25° C. in a dark place to provide callus of Taxus baccata LINN. One gram (fresh weight) of the callus was inoculated to an Erlenmeyer flask containing 20 ml of liquid Woody Plant Medium and shake culture was carried out with a rotary shaker (amplification of 25 mm, 100 rpm) and the callus was subcultured in every 21 days to accelerate the growth rate thereof.
Two grams (fresh weight) of the cultured cells thus obtained by liquid culture was inoculated to 20 ml of liquid Woody Plant Medium (contained in an Erlenmeyer flask of 100 ml) to which α-linolenic acid of 0.01-1000 μM (dissolved in ethanol) was added, and shake culture was carried out at 25° C. in a dark place with a rotary shaker (amplification of 25 mm, 100 rpm).
After completing the culture for 14 days, cultured cells were harvested by filtration and lyophilized, then the dry weight was measured to obtain the yield thereof. Taxane-type diterpenes were extracted from the dried callus and the culture medium with methanol or the like, and they were determined by comparing with standard taxol using high performance liquid chromatography to measure the yield of taxol. The results are shown in Table 6.
EXAMPLE 27
Example 26 was repeated except that oleic acid of 100 μM was added instead of α-linolenic acid. The results are shown in Table 7.
EXAMPLE 28
Example 26 was repeated except that linolic acid of 100 μM was added instead of α-linolenic acid. The results are shown in Table 7.
EXAMPLE 29
Example 26 was repeated except that arachidonic acid of 100 μM was added instead of a-linolenic acid. The results are shown in Table 7.
EXAMPLE 30
Example 26 was repeated except that rapeseed oil of 100 mg/l was added instead of α-linolenic acid. The results are shown in Table 7.
EXAMPLE 31
Example 26 was repeated except that species of the plant used was Taxus media (the part used for callus induction was seed). The results are shown in Table 8.
Comparative Example 6
Example 26 was repeated except that α-linolenic acid was not added. The results are shown in Table 6.
Comparative Example 7
Example 31 was repeated except that α-linolenic acid was not added. The results are shown in Table 8.
TABLE 6
concentration
yield of taxane-type
of
diterpenes (mg/l)
α-linolenic
yield of
baccatin
cephalo-
acid (μ M)
cells (g/l)
taxol
III
mannine
Example 26
0.01
20
5
2
2
Example 26
0.1
20
6
2
2
Example 26
1
20
6
2
2
Example 26
10
20
8
3
4
Example 26
100
19
19
6
4
Example 26
500
14
12
4
3
Example 26
1000
12
7
2
2
Comparative
0
20
4
1
1
Example 6
TABLE 7
yield of taxane-type
added fatty
diterpenes (mg/l)
acids or
yield of
baccatin
cephalo-
natural oils
cells (g/l)
taxol
III
mannine
Example 27
oleic acid
20
9
2
4
Example 28
linolic acid
20
7
2
5
Example 29
arachidonic
20
6
2
3
acid
Example 30
rapeseed oil
20
6
2
3
Comparative
none
20
4
1
1
Example 6
TABLE 8
yield of taxane-type diterpenes
(mg/l
yield of
baccatin
cephalo-
cells (g/l)
taxol
III
mannine
Example 31
20
22
10
2
Comparative
20
5
3
1
Example 7
Synthesis Example 1
One gram (4.5 mmol) of methyl jasmonate was dissolved in 50 ml of methanol and cooled with ice, then 0.74 g (4.5 mmol) of hydroxylamine sulfate and 0.88 g (9.0 mmol) of potassium acetate were added thereto to carry out reaction. The reaction mixture was allowed to stand for one night and methanol was removed by evaporation, a saturated aqueous solution of sodium hydrogencarbonate was added and the resulting product was repeatedly extracted with ethyl acetate. The ethyl acetate extracts were collected, and water was removed with anhydrous sodium sulfate, then ethyl acetate was removed by drying under reduced pressure to give Compound A.
Compounds B-I were synthesized in a process analogous to that for Compound A except that the following reagents were employed instead of hydroxylamine sulfate.
Compounds
Reagents
B
O-methylhydroxylamine hydrochloride
C
hydrazine hydrate
D
semicarbazide hydrochloride
E
formic hydrazide
F
methanesulfonyl hydrazide
G
cyanamide
H
sulfamide
Synthesis Example 2
One gram of Compound A synthesized in Synthesis Example 1 was dissolved in 50 ml of methanol, and then a solution of 0.084 g (2.2 mmol) of sodium borohydride in 5 ml of methanol was dropped thereto. After completing of the dropping, the reaction mixture was further agitated for 30 minutes. The solution was concentrated until it became to about 10 ml. To the solution, a saturated solution of sodium hydrogencarbonate was added, and the product was repeatedly extracted with ethyl acetate. The ethyl acetate extracts were collected, and water was removed with anhydrous sodium sulfate, then ethyl acetate was removed by drying under reduced pressure to give Compound I.
EXAMPLE 32
A part of germ of Taxus media which had been previously sterilized with 2% antiformin solution or 70% ethanol solution or the like, was placed on solid Woody Plant Medium (containing gelan gum of 0.25% by weight) to which naphthalenacetic acid had been added to give the concentration of 10 −5 M, and static culture was carried out at 25° C. in a dark place to provide callus of Taxus media. One gram (fresh weight) of the callus was inoculated to an Erlenmeyer flask containing 20 ml of liquid Woody Plant Medium to which above-mentioned component was added to give the same concentration, the and shake culture was carried out with a rotary shaker (amplification of 25 mm, 100 rpm) and the callus was subcultured in every 14 days to accelerate the growth rate thereof.
Two grams (fresh weight) of the cultured cells thus obtained was inoculated to an Erlenmeyer flask containing 20 ml of liquid Woody Plant Medium and Compound A was added as a derivative of jasmonic acids to give the final concentration of 0.01-1000 μM, and the culture was further carried out for another 14 days.
After completing the culture, cultured cells of Taxus media were harvested by filtration and lyophilized, then the dry weight was measured to obtain the yield of the cultured cells per liter of the liquid medium. Taxane-type diterpenes were extracted from the dried callus and the culture medium with methanol or the like, and they were determined by comparing with standard taxol, cephalomannine, and baccatin III using high performance liquid chromatography to measure the yields of the taxane-type diterpenes. The results are shown in Table 9.
Comparative Example 8
Example 32 was repeated except that a derivative of jasmonic acids was not added. The results are shown in Table 9.
Reference Example 1
Example 32 was repeated except that methyl jasmonate of 100 μM was added as a derivative of jasmonic acids. The results are shown in Table 9.
EXAMPLE 33
Example 32 was repeated except that Compound B of 100 μM was added as a derivative of jasmonic acids. The results are shown in Table 9.
EXAMPLE 34
Example 32 was repeated except that Compound C of 100 μM was added as a derivative of jasmonic acids. The results are shown in Table 9.
EXAMPLE 35
Example 32 was repeated except that Compound D of 100 μM was added as a derivative of jasmonic acids. The results are shown in Table 9.
EXAMPLE 36
Example 32 was repeated except that Compound E of 100 μM was added as a derivative of jasmonic acids. The results are shown in Table 9.
EXAMPLE 37
Example 32 was repeated except that Compound F of 100 μM was added as a derivative of jasmonic acids. The results are shown in Table 9.
EXAMPLE 38
Example 32 was repeated except that Compound G of 100 μM was added as a derivative of jasmonic acids. The results are shown in Table 9.
EXAMPLE 39
Example 32 was repeated except that Compound H of 100 μM was added as a derivative of jasmonic acids. The results are shown in Table 9.
EXAMPLE 40
Example 32 was repeated except that Compound I of 100 μM was added as a derivative of jasmonic acids. The results are shown in Table 9.
TABLE 9
concentration
of derivative
yield
yield of taxane-type
of
of
diterpenes (mg/l)*
jasmonic acids
cultured
baccatin
cephalo-
(μM)
cells (g/l)
III
taxol
mannine
Comparative
0
22.2
5.2
14.2
2.1
Example 8
Reference
100
16.8
12.1
48.0
4.2
Example 1
Example 32
0.001
22.0
6.7
16.7
3.2
Example 32
0.01
21.1
6.8
20.2
3.6
Example 32
0.1
20.2
7.5
24.1
4.0
Example 32
1
19.5
8.5
34.5
4.2
Example 32
10
18.3
13.5
56.2
6.3
Example 32
100
16.4
20.1
78.0
9.2
Example 32
1000
14.0
9.3
17.2
3.5
Example 33
100
16.1
18.0
65.3
5.2
Example 34
100
16.7
16.5
55.0
6.6
Example 35
100
15.3
17.2
56.3
5.0
Example 36
100
17.2
18.5
79.5
6.2
Example 37
100
17.1
15.3
73.3
5.9
Example 38
100
14.3
14.5
82.9
5.0
Example 39
100
17.1
19.0
85.0
7.5
Example 40
100
16.2
14.2
73.3
5.5
[*) The yield was calculated based on the total amount of production (in the cell + in the medium.)]
|
The present invention relates to a method of producing a taxane-type diterpene wherein a cell and/or a tissue of a plant which produces the taxane-type diterpene is cultured in the presence of at least one substance selected from the group consisting of coronatines, a bacterium which produces the coronatines, a culture solution or a culture extract of such bacterium, cyclic polysaccharides, fatty acids, and an imino or amino derivative of jasmonic acids, then the taxane-type diterpene is recovered from the resulting cultures.
| 2
|
FIELD OF THE INVENTION
The present invention relates to an apparatus for use by artists and the like for creating unique one-of-a-kind type of works such as paintings and the like.
BACKGROUND OF THE INVENTION
Artists who draw work with a variety of media. There are oil paintings, water colors, pastels and others. Some artists use pen and ink, others use chalk, and still others use brushes. Other artists use non-traditional materials and these materials can be virtually anything that an artist deems appropriate.
One of the most common tools used by a painter is the brush. Paint is typically applied to the brush by dipping the brush into the medium and applying it to the selected surface. Using particular strokes, media and different brushes, different textures can be obtained. Traditionally, the brush is a length of material usually wood that is shaped such that it rests comfortably in the artist's hand. At one end of the brush are a plurality of bristles that are used to apply the paint to a surface. The bristles can be made of a natural or synthetic material. Nylon is one type of synthetic material that can be used in a brush. Other synthetic material can include polyesters, polyamides, polyolefins, etc. A natural material can be the hair of any number of mammals. Squirrel and pig bristles are two materials that are commonly used in brushes.
Artists are frequently seeking a variety of means of expressing themselves in a manner that is unique to themselves. One manner of expression is the type of brush stroke that is employed. When painting with a water color one type of brush stroke is typically employed. When oil paints are used another type of brush stroke can be used. Naturally, different variations of each type of stroke can be used to give texture and other features to the painting.
One concern of many painters is the uniqueness of their work. In addition, many artists are concerned that their works can be readily duplicated by third parties who can reproduce many works of art. Color photocopiers and other modern devices are so sophisticated that it has become very difficult for some people including some artists to discern whether a work is the original or a copy. For some types of works of art, mechanical copying is a real problem. This is less of an issue where the artist uses oil paints and similar media that creates a texture on the surface of the canvas or other surface.
When viewing a series of paintings done by an individual artist, a specific style will emerge. This style is specific to this artist, and is unique only to him or her. By analyzing the artist's brush technique, color palettes, etc., one may be able to generate a replica of an artwork. Thus, an artist's unique style is susceptible to imitation which can generate virtually identical copies of the artist's works. However, if the method of painting is completely random and no two works are the same, then the paintings are unable to be imitated. It has been found that there is a desire among some artists to produce a work that is unique to them and very difficult to reproduce effectively. As a result, there is an increasing amount of interest by painters for producing a work that can not be readily copied.
In addition to artists, patrons of the arts are also desirous of a work that is unique. These persons typically pay top amounts for an individual work or a work in a limited edition. The trust that the work is truly an original or that there work is truly a limited edition is fragile and the market for a work can be destroyed if there are unauthorized or even authorized copies of a work in general circulation.
One artist whose work is of particular interest with respect to the present invention is Jackson Pollock (1912-56) an important figure of the Abstract Expressionist movement. During the 1940's he was painting in a completely abstract manner, and the ‘drip and splash’ style for which he is known was developed in 1947. Instead of using the traditional easel he affixed his canvas to the floor or the wall and poured and dripped his paint from a can; instead of using brushes he manipulated it with ‘sticks, trowels or knives’ (to use his own words), sometimes obtaining a heavy impasto by an admixture of ‘sand, broken glass or other foreign matter’. Pollock's name is also associated with the introduction of the All-over style of painting which avoids any points of emphasis or identifiable parts within the whole canvas and therefore abandons the traditional idea of composition in terms of relations among parts. The design of his painting had no relation to the shape or size of the canvas—indeed in the finished work the canvas was sometimes docked or trimmed to suit the image. Using the apparatus of the present invention it is possible to create paintings that may have some of the attributes of this style of painting popularized by Pollock.
OBJECTS OF THE INVENTION
It is an object of the present invention to provide a device that utilizes the power of the wind to move a brush across a canvas or other surface.
It is another object of the present invention to provide a device that utilize the power and randomness of the wind to manipulate a brush across a canvas to make paint or sketch strokes on the surface of the canvas or other surface.
It is also object of the present invention to provide a device that utilizes the power and randomness of the wind to create unique works such as paintings or sketches
It is a further object of the present invention to provide a device is easy to set-up and works in any location where wind is present.
It is a still further object of the invention to provide an apparatus that creates unique one of a kind works of art.
It is another object of the invention to employ the rotation of the earth to move a brush over a canvas.
SUMMARY OF THE INVENTION
The wind is a powerful force, which flows in generally a random manner. At a given location the force provided by the wind is not always continuous but rather frequently irregular. The present invention uses the wind to provide a driving force to move a paintbrush across a canvas. Since the wind motion is not always in the same direction or with the same force, the wind can be used to produce a sketch or a painting that is unique. The very nature of the painting so created renders it also difficult to copy. The present invention has a stand that supports an implement that may be any suitable drawing device such as a brush, a pen or other device. The implement extends from an upper portion of the stand and is positioned on a string, rope, wire or other suitable material that permits the implement to move at least for a portion of its travel over a canvas or other substrate. In a preferred embodiment the implement is in the form of a pendulum as it travels over at least a portion of its path of travel. Where the implement is traveling in a motion that is like a pendulum, the canvas or other substrate can be curved to receive the strokes of the implement as it is moved. In this manner, each painting or picture created by utilizing the force of the wind will generate a work that is unique to that day, time, weather, etc. And, even if another person were to generate another painting in the same manner, on the same day, at the same time, in the same vicinity as the original was created, the wind pattern would not be the same. Thus, there would be noticeable differences between the two works.
Where paint is to be used on the work there may be one or more reservoirs on the device from supplying paint to the end of the brush. Preferably the device has three such reservoirs. These reservoirs can dispense any color selected by the artist. In the preferred embodiment, the handle of the brush, stylus or other implement is hollow to permit the flow paint to the bristles of the brush. In a preferred embodiment, the brush mechanism is in the form of a tubular member that has a plurality of bristles extending from at least one end of the tubing. The other end of the tubing is connected to the flexible tubing that carries the paint from a paint reservoir to the brush apparatus.
In one embodiment the stand has one or more legs for supporting the device. Supported by the legs may be a generally horizontal member from which a implement is hung. As the writing implement is buffeted by the wind intricate and unique designs are created on a canvas. The uniqueness of the art work so created is further enhanced by anything that is also blown onto the canvas or other substrate by the wind. Thus, for example, if the device is set up at a beach the wind can also blow sand onto the substrate since the amount and placement will vary with the direction and force of the wind each drawing will have a texture that is different from other drawings.
In a still further embodiment of the invention the substrate to be painted can be in an enclosed room where the wind is not present and the brush can be provided with the same motion as a pendulum. If the length of the pendulum is rather long the back and forth motion of the brush can, over a twenty-four hour period cover an entire portion of the substrate not unlike the movement of a Foucault pendulum as it knocks over a circular arrangement of pegs as the pendulum moves back and forth over a twenty-four hour or other period.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of a preferred embodiment of the apparatus of the present invention.
FIG. 2 is an end view of an example of a table having a flat surface for mounting a substrate to be worked on.
FIG. 3 is a side view of an example of another type of table for use with the apparatus of FIG. 1 .
FIG. 4 is an end view of the table of FIG. 3 .
FIG. 5 is a side view of an alternate example of a table for mounting a substrate to be worked on.
FIG. 6 is a side view of a brush that is suitable for use with the present invention
DETAILED DESCRIPTION OF INVENTION
The apparatus 10 of the present invention has a frame 11 from which an applicator mechanism 12 is suspended. The frame may have a generally horizontal member 13 from which one or more generally vertical members 14 and 15 extend. Since the device i subjected to the wind in most instances, a sturdy framework is preferred. The vertical members 14 and 15 have a first end 16 and 17 adjacent to the horizontal member 13 . The opposite ends 18 and 19 of the vertical members may be inserted directly into a support surface such as the ground or they may be provided with a flat base portion (not shown) for resting on a surface such as the ground. The vertical members may alternatively be inserted into two anchor legs 20 and 21 . Each anchor leg may be set into the ground at one end 22 and 23 and open at the other end 24 and 25 for receiving the vertical members. The bottom of the anchor leg 20 and 21 can be dug into the ground or weighted at the surface of the ground as desired. The top end of each anchor leg 24 and 25 is open to allow the vertical members 14 and 15 of the frame to be inserted. Each anchor leg may also be provided with a screw 26 laterally inserted into an orifice 27 in the anchor for securing the vertical members 14 and 15 at the desired height. In one embodiment, the vertical members 14 and 15 are provided with a plurality of orifices 27 along their length for receiving the screw 26 . The plurality of orifices are to secure the vertical members at different heights above the work surface or accommodate different height work surfaces. In another embodiment, when turned, the screw 26 articulates with the frame, and allows for the frame height to be changed. The screw may be replaced by a gear-locking mechanism that will allow the user to push the frame higher and release when the frame is to be lowered.
The frame and anchor leg set-up described above may be replaced by any framing means sufficient to provide support for the device and the necessary height needed for its operation. A-frame type structures may also be used. In the A-frame structure, there are two generally vertical members positioned on each side of the frame. These vertical member join or meet in the vicinity of the horizontal member
Extending downwardly from a member, such as the horizontal member 13 is a connection means 28 for hanging the applicator support 29 A. The connection means 28 is preferably positioned generally in the center of the length of the horizontal member. The connection means may be a ring, or another attachment device that will hold the hanging applicator support 29 A. As shown in FIG. 1 the connection means may be for example a “S” hook. In another embodiment the connection means may be rotatable to permit the apparatus to rotate.
It will be appreciated that the connection means 28 does not have to be in the center of the horizontal member. Also, there need not be a connection means if the hanging applicator member 29 is provided with a rope or cable that may be tied or fastened to the horizontal member 13 . In the embodiment shown in FIG. 1 , The connection means 28 has a chain or cable 29 A attached thereto as the applicator support.
The hanging applicator member 29 preferably has support member 34 of a variable length to be adjusted by the user depending on the height of the frame and the placement of the work surface. Suitable materials for the support member can be a chain, cable rope or other suitable material. The hanging applicator member 29 is provided with one or more reservoirs 30 for storing the paint, ink or other material to be applied to a substrate. Extending from each of the reservoirs are lengths of tubing, preferably hollow. As seen in FIG. 1 there are three lengths of tubing 31 , 32 , 33 for each of three reservoirs. In one embodiment, one or more of the tubes may be provided with a valve means 59 to adjust the flow of paint through the tubes.
The lengths of tubing may be supported by a frame 38 . The frame 38 is preferably a wire frame and may have a first horizontal member 39 and a second horizontal member 40 . The first and second horizontal members are joined by first and second vertical members 41 and 42 . Extending from the junctions 43 and 44 where the second horizontal member 40 connects to the first and second vertical members 41 and 42 respectively, there are preferably a pair of brush members 45 and 46 extending downwardly. Although shown two dimensionally in the Figures, the frame may have three dimensions depending on the number of brushes and the locations chosen for their placement. For example, the frame may be in the form of a generally horizontal triangle with a brush at each corner. Alternatively, the frame may a rectangle or other quadrilateral and have four corners or even other shapes. It is not suggested however, that the number of brushes requires any fixed shape for the frame. For example the frame may only be two dimensioned as seen in FIG. 1 and have additional brushes positioned along second horizontal member 40 at different locations.
The frame may also be rotatable about the support means such as a cable. This permits the brushes to have imparted thereto a rotational motion in addition to the back and forth motion of a pendulum. The wire frame may also have one or more diagonal members 48 and 49 to provide additional support to the frame.
Each of the applicator tubes ends in a brush mechanism. Where there are there three reservoirs of material there will be three brushes present. It may be desired to increase the ability of the wind to power the device. Accordingly, a sail or wind catcher 60 may be present. The sail may be a 0.040 gauge sheet of aluminum or other material. The sail maybe any size or shape desired depending on the wind. The sheet may be secured to the cable, chain or string by ties 61 .
The hanging applicator member 29 moves in response to the force of the wind. For example, in one instance, the applicator member 29 may move like a pendulum's motion between the vertical members of the frame. In other instances, the motion may be completely random. As the hanging applicator member moves, the brushes apply the desired material to the substrate in a random pattern. If the surface of the substrate is considered a plane having X and Y axes, each axes can have a length X 1 , X 2 and Y 1 and Y 2 . Depending on the force of the wind, the length of time the device is operating and the viscosity of the material being applied the brushes can apply the material in a random manner over the surface of the substrate.
In an alternative embodiment, the reservoirs can be positioned any where along the length of the applicator member and can be in the form of container. In one embodiment, the containers can be inverted and inserted into an orifice in a bushing that retains them in position. Valve means can be used to control the flow of the material from the reservoirs. The frame for supporting the brushes may be any shape desired. Although a wire frame is shown, other designs are feasible as long as they are relatively light in weight and can be readily moved by the wind or the motion of a pendulum. In an alternative embodiment, the frame holding the brushes can rotate thereby causing the brushes to have additional motion over and above the back and forth motion usually caused by the wind
As shown in FIG. 1 and FIG. 2 , the substrate may be positioned so that it rests on a table 50 or other flat support surface. The support surface for the substrate may be any suitable means. FIGS. 1 and 2 show a base, support or table 50 having a plurality of legs 51 . Brace 52 may extend from one or more of the legs to another leg to provide additional strength to the support. The substrate 53 may rest on the upper surface of the support or it may be placed on another suitable surface such as a foamed surface 54 . The foamed surface provides a softer surface for the brushes to operate on. In one embodiment, the substrate may be placed on a foamed material which in turn may be paced on a sheet of plastic material 55 such as Lexan. The foamed material absorbs the blows from the wind.
FIG. 3 shows an alternate embodiment of the support of the present invention. In this support there is a curved surface on which the substrate is positioned. The curved surface preferably has the same or similar arc as the motion of the hanging applicator member 29 . In this arrangement, the hanging applicator member covers more of the surface of the substrate than when the substrate lies flat. In other words, a larger substrate may be covered with material when placed in the shape of an arc than when the substrate lies flat. The arc may be provided by a plastic member 55 that is cut and trimmed to mirror the travel of the hanging applicator member 29 .
FIG. 4 shows a side view of the support of FIG. 3 . In this Figure, the substrate rests on the upper surface of the support or other material thereon. Depending on the amount and how continuous is the force supplied by the wind, a support of the type shown in FIG. 5 may be used. In this Figure the support 50 for the substrate is provided with a first height 56 and a second height 57 and the first height 56 is greater than the second height 57 . The upper surface of the support is provided with a curved surface. The arc of the article shown in FIG. 4 is approximately one-half the arc of FIG. 3 .
FIG. 5 shows the preferred brush of the present invention. This brush has a tubular member 70 having a first end 71 and a second end 72 . Extending from the first end 71 are a plurality of bristles 73 . In lieu of bristles, a porous foamed material can be used to apply the paint of other material. In its motion powered by the wind, the brush device will articulate with a canvas or other substrate on a flat or curved palate member. The palate member or base 50 is preferably centered between the anchor legs of the device and underneath the brush portion of the hanging applicator member. In this embodiment, the top surface of the palate member is generally concave, and a substrate such as paper, canvas or a plastic sheet is placed on top of it. The concave surface of the palate member is supported by a rectangular framework. The framework, in one embodiment, is composed of two pieces of wood on its longer sides and two metal stabilizing strips on its shorter sides. Each wood side has a flat bottom side and a concave upper side. Each metal stabilizing strip connects the two wood pieces. The framework positions the concave surface a small distance off the ground. Also, the framework has an attachment means on one of its members. This attachment means holds an anchor member. The anchor member, which may be a weight or fixed to the ground, holds the palate member in a static position.
One of the features of the present invention is the brush. FIG. 6 shows a preferred brush that may be used with the present invention. The brush is made up of a hollow tube portion 71 . The hollow tube portion 71 has a first end 72 and a second end 73 ; The first end is removably connected to the end of the tubing that transports the paint. The connection may be made by inserting the bristles into the open end of the tubular member 31 and securing the two togther by any suitable means such as by tape or other easily removable means so that the tubing may be cleaned. Extending from first end of the hollow tube member are bristles, preferably synthetic bristles 73 that are of the type typically used for latex type paints. These bristles extend into the orifice at the end of the tubing and provide a pathway for the paint to flow into the brush. The bristles transfer paint down the tube into the hollow tube member where it is picked up by the bristles 74 extending from the second end 72 of the hollow tube member. In a preferred embodiment, the bristles my be placed around at least a portion of the exterior surface of the tip or end portion of the tube. These bristles may be either natural bristles if an oil based type paint is used or synthetic brushes if a water based paint is used. Nylon is one type of synthetic material that can be used in the present invention. Other synthetic materials can include polyesters, polyamides, polyolefins, etc. A natural material can be the hair of any number of mammals. Squirrel and pig bristles are two materials that are commonly used in brushes.
The bristles are preferably secured to the outside of the tubes by first applying a layer of flymaker's wax to the second end 72 of the hollow tube. Around the waxed end is wrapped a binding. A cement glue is placed on the binding. The bristles are dipped into a cement glue and placed around the tube. The exterior surface of the bristles where they are positioned on the end of the hollow tube are covered with a varnish and wrapped with a French Tinsel 75 .
|
An apparatus for creating a random image is disclosed. The apparatus has a first support member with a hanging applicator member movably connected thereto. The hanging applicator is provided with at least one reservoir of material to be applied to a substrate. The reservoir has tubing extending from the reservoir for transporting the material to a brush. The brush provides a random pattern of material to a substrate in response to pressure from flowing air.
| 1
|
BACKGROUND OF THE INVENTION
The present invention relates to complexes of 2,6-pyridinebis(imines) with transition metals and their use for polymerizing alpha-olefins.
DISCUSSION OF THE BACKGROUND
It is known that alpha-olefins can be polymerized by means of complexes comprising a transition metal and a tridentate ligand, and an aluminoxane. Patent application WO 99/62967 describes the copolymerization of ethylene with the aid of complexes of iron with 2,6-pyridinebis(imines). However, the catalytic complexes described in that application do not efficiently incorporate propylene during the manufacture of copolymers of ethylene. Patent application WO 99/12981, Britovsek et al. (Chem. Eur., 2000, 6(12), 2221) and Qiu et al. (Polym. Int., 2000, 49(1), 5) report the syntheses of {2,6-bis[1-(1-naphthylimino)methyl]-pyridine-κ 3 : N,N′,N″}FeCl 2 and of {2,6-bis[1-(1-naphthylimino)ethyl]pyridine-κ 3 : N,N′,N″}FeCl 2 and their use for polymerizing ethylene in the presence of methylaluminoxane (MAO). However, the catalytic activity of these complexes and the molecular weights of the polyethylenes obtained are low.
We have now found complexes of a transition metal with 2,6-pyridinebis(imines) for polymerizing alpha-olefins where these do not have the abovementioned disadvantages.
SUMMARY OF THE INVENTION
The present invention therefore provides complexes of a transition metal complying with the general formula (I) in which
M is a transition metal of groups 6 to 12,
T is the oxidation state of M,
each A, which may be identical with or differ from each other, is an atom or an atomic grouping bonded covalently or ionically to the transition metal M,
b is the valency of A,
each R 1 , R 2 , R 3 , R 4 and R 5 is independently a hydrogen atom, an unsubstituted or substituted hydrocarbon group, an unsubstituted or substituted heterohydrocarbon group, or an inert functional group,
R 6 and R 7 are, independently of one another, a polynuclear aromatic hydrocarbon group containing at least two condensed benzene nuclei, substituted with at least one hydrocarbon group.
DETAILED DESCRIPTION OF THE INVENTION
All the references to the Periodic Table of the Elements refer to the version published in CRC Handbook of Chemistry and Physics, 77th Edition, 1996/97; the notation utilized is the new IUPAC notation for the groups.
An “inert functional group” is understood to be an atomic grouping which is not an unsubstituted or substituted (hetero) hydrocarbon group, this group being inert under the conditions of the process using the complex of the present invention, and not coordinating with the transition metal M. Examples which may be mentioned of inert functional groups are halogen atoms and ethers of formula OR in which R is an unsubstituted or substituted hydrocarbon group.
Preferred complexes are those complying with the general formula (I) in which M is Fe, Cr, Co, Ru or Mn. Particular preference is given to Fe. Suitable complexes are those complying with the general formula (I) in which T is 2.
Each A is generally selected from halogen atoms, sulphates, nitrates, thiolates, thiocarboxylates, BF 4 —, PF 6 —, hydrogen atoms, hydrocarbon oxides, carboxylates, unsubstituted or substituted hydrocarbon groups, and heterohydrocarbon groups. Preferred complexes are those complying with the general formula (I) in which A is a halogen atom or a linear or branched alkyl group containing from 1 to 8 carbon atoms. Preference is very particularly given to complexes of the formula (I) in which A is a halogen atom.
Suitable complexes of the invention are those complying with the general formula (I) in which R 1 , R 2 , R 3 , R 4 and R 5 are independently a hydrogen atom or a linear or branched alkyl group containing from 1 to 6 carbon atoms. The complexes in which R 1 and R 5 are independently a linear or branched alkyl group containing from 1 to 6 carbon atoms are particularly preferred, since they have high activity.
R 6 and R 7 are preferably selected independently of each other from groups complying with the formulae (II) or (III) below: in which R 8 to R 21 are independently hydrogen atoms or hydrocarbon groups, such
that at least two thereof can form a ring, with the proviso that at least one of the groups selected from R 8 to R 14 is not a hydrogen atom.
The groups (II) in which R 11 and R 12 , R 12 and R 13 , or R 13 and R 14 together form an unsubstituted or substituted benzene nucleus advantageously give alpha-olefin polymers having high molecular weight. The groups (II) in which R 12 and R 13 together form an unsubstituted or substituted benzene nucleus are particularly suitable. The groups (II) in which at least one of the groups selected from R 12 , R 8 and R 9 represents a linear or branched alkyl group containing from 1 to 8 carbon atoms are preferred because they generally give high catalytic activity. The groups (II) in which R 8 is a linear or branched alkyl group containing from 1 to 8 carbon atoms are particularly preferred. The groups (II) in which R 12 and R 13 together form an unsubstituted or substituted benzene nucleus and R 8 is a linear or branched alkyl group containing from 1 to 8 carbon atoms are particularly preferred because they usually permit alpha-olefin polymers having high molecular weight to be obtained with high activity.
The groups (III) in which R 18 and R 19 , R 19 and R 20 , or R 20 and R 21 together form an unsubstituted or substituted benzene nucleus usually give alpha-olefin polymers having high molecular weight. The groups (III) in which at least one of the groups selected from R 15 and R 16 is a linear or branched alkyl group containing from 1 to 8 carbon atoms are preferred because they generally give complexes having high catalytic activity. The groups (III) in which R 19 and R 20 together form an unsubstituted or substituted benzene nucleus and R 15 or R 16 is a linear or branched alkyl group containing from 1 to 8 carbon atoms advantageously permit alpha-olefin polymers having high molecular weight to be obtained with high activity.
It is preferable to use complexes in which R 6 and R 7 comply with formula (II). The complexes in which R 1 and R 5 are a linear or branched alkyl group containing from 1 to 6 carbon atoms, and R 6 and R 7 comply with the formula (II) in which R 8 is a linear or branched alkyl group containing from 1 to 8 carbon atoms are very particularly preferred. Examples which may be mentioned of abovementioned complexes are {2,6-bis[1-(2-methyl-1-naphthylimino)methyl]pyridine-κ 3 : N,N′,N″}FeCl 2 , {2,6-bis[1-(1-anthracenylimino)methyl]pyridine-κ 3 : N,N′,N″}—FeCl 2 , {2,6-bis[1-(1-anthracenylimino)ethyl]pyridine-κ 3 : N,N′,N″}FeCl 2 and {2,6-bis[1-(2-methyl-1-naphthyl-imino)ethyl]pyridine-κ 3 : N,N′,N″}FeCl 2 .
The complexes of the invention are generally prepared by a first condensation step of Schiff-base type, using amine and unsubstituted or substituted 2,6-bis(carbonyl)pyridine, as described by Britovsek et al. in J. Am. Chem. Soc., 1999, 121, 8728 and Small et al. in J. Am. Chem. Soc., 1998, 120, 4049. This reaction is then followed by addition of the di(imino)pyridine thus obtained to a salt of the transition metal (M) in order to obtain a complex complying with the general formula (I). The condensation reaction is usually carried out by using 2 equivalents of amine to 1 equivalent of 2,6-bis(carbonyl)pyridine. The di(imino)pyridine obtained is preferably added to a halide of the transition metal (M). This complexation reaction may be followed by reaction of the complex obtained with a Grignard reagent of formula AMgBr, in which A is a linear or branched alkyl group containing from 1 to 8 carbon atoms.
The complexes of the invention may be used as catalysts for polymerizing alpha-olefins. The invention therefore also provides a process for polymerizing alpha-olefins by bringing at least one alpha-olefin into contact, under polymerizing conditions, with a catalytic system comprising
(a) a complex of a transition metal from groups 6 to 12 in accordance with the invention and
(b) at least one activator.
The activators are generally selected from organoaluminium compounds. Use is usually made of aluminoxanes or of trialkylaluminium compounds. The preferred aluminoxane is methylaluminoxane (MAO). The trialkylaluminium compounds are advantageously selected from trimethylaluminium (TMA), triethylaluminium (TEA), triisobutylaluminium (TIBAL), and mixtures of these.
The quantity of activator used in the process of the invention is generally such that the atomic ratio of aluminium to the transition metal (M) derived from the complex (a) is from 10 to 20 000. This ratio is preferably at least 30, more particularly at least 50. Good results are obtained when this ratio is at least 100. This ratio is usually not more than 10 000. Ratios of from about 200 to 6000 give particularly good results.
For the purposes of the present invention, alpha-olefins are understood to be terminally unsaturated olefins generally containing from 2 to 20 carbon atoms, preferably from 2 to 8 carbon atoms. Examples of alpha-olefins are ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene. Besides the olefin, it is of course possible for another monomer copolymerizable with the olefin to be used in the process of the invention.
The polymerization process of the invention may be carried out continuously or batchwise, in accordance with any known process, in solution, or in suspension, or even in the gas phase. The polymerization process of the invention is advantageously carried out in suspension in the monomer or in one of the monomers, kept in the liquid state, or in a hydrocarbon diluent, generally selected from aliphatic hydrocarbons containing from 3 to 10 carbon atoms. The diluent is preferably selected from propane, isobutane, hexane, and mixtures of these.
In the process of the invention, the complex of the transition metal (a) is preferably mixed with the activator (b) before it comes into contact with the alpha-olefin. In one advantageous version of the process of the invention, only some of the activator may be used for mixing with the complex, the rest of the activator being introduced directly into the polymerization reactor, optionally in the presence of alpha-olefin. The quantity of activator used in precontact is generally such that the atomic ratio of the aluminium to the transition metal (M) derived from the catalytic complex (a) is from 1 to 10000. This ratio is preferably at least 10, more particularly at least 50. Good results are obtained when this ratio is at least 100. The quantity of activator is usually such that this ratio is not more than 5000. Ratios of from about 300 to 2000 give particularly good results.
The temperature at which the polymerization is carried out is generally from −20 to +150° C., typically from 20 to 115° C.
The total pressure at which the process of the invention is carried out is generally selected between atmospheric pressure and 100×10 5 Pa, more particularly between 5×10 5 and 55×10 5 Pa.
The polymerization process of the invention is advantageously applied to the manufacture of polymers of ethylene, and more particularly to the manufacture of homo- and copolymers of ethylene. Homopolymers of ethylene thus frequently have ethyl and/or butyl branching. The preferred copolymers are those of ethylene with another alpha-olefin containing from 3 to 8 carbon atoms. Particular preference is given to copolymers of ethylene with propylene, with 1-butene and/or with 1-hexene. In the case of copolymerization of ethylene with another alpha-olefin containing from 3 to 8 carbon atoms, the polymerization is preferably carried out in that alpha-olefin in the liquid state, and with a low concentration of ethylene, based on the concentration of alpha-olefin, in the polymerization medium.
The process of the invention can give alpha-olefin polymers with high catalytic activity and can manufacture alpha-olefin polymers of high molecular weight. It can also give branched polyethylenes, or copolymers of ethylene, and more particularly copolymers of ethylene which may contain up to 99% by weight of monomeric units derived from propylene. These polymers are therefore a supplementary subject-matter of the present invention.
EXAMPLES
The examples below serve to illustrate the invention. The methods for measuring the quantities mentioned in the examples and the meaning of the symbols used in these examples are explained below.
IR spectra were recorded on KBr pressings using a Perkin Elmer FTIR 1720X Fourier transform spectrometer. Proton nuclear magnetic resonance spectra ( 1 H NMR) were recorded using a Bruker AMX 500 NMR spectrometer operating at 500 MHz. The significance of the characteristics revealed by 13 C NMR and IR for the compounds synthesized is explained in Spectroscopic Methods in Organic Chemistry, D. H. Williams & I. Fleming. The ethyl and butyl branching in the polyethylenes (expressed as number per 1000 carbon atoms), and the rate of incorporation of 1-hexene or of propylene in the copolymers of ethylene with 1-hexene or propylene, respectively, were determined by 13 C NMR using the same spectrometer. In copolymers of ethylene with propylene, E x P y E z P t is the molar fraction of triads of x monomeric units derived from ethylene (E) followed by y monomeric units derived from propylene (P) followed by z monomeric units derived from ethylene (E) followed by t monomeric units derived from propylene (P), where 0≦x≦3, 0≦y≦3, 0≦t≦3, 0≦z≦3, x+y+t+z=3, and where x, y, z and t are integers and where at least one of x, y, z and t is 0; the molar fractions of the triads are determined by 13 C NMR following the method described by J. C. Randall in J. Macromol Sci, Rev. Macromol. Chem Phys., 1989, 29 (2&3), 201-317.
The melting points (mp) and the enthalpies of fusion (ΔHm) were determined by differential scanning calorimetry in accordance with the standard ISO 3146 (1997).
The symbols C 2 and C 3 have been utilized to indicate, respectively, the monomers ethylene and propylene and the monomeric units derived from ethylene and from propylene.
The weight-average (Mw) and number-average (Mn) molecular weights were obtained by steric exclusion chromatography starting with a 0.5 g/l solution of polymer in trichlorobenzene, by means of a Waters STYRAGEL® HMW 6E polystyrene column. The distribution of molecular weights is expressed by the ratio Mw/Mn.
The standard density (SD), expressed in kg/m 3 , was measured in accordance with the standard ISO 1183-3 (1999).
The productivity is defined as the quantity of polyolefin obtained in kg per mmol of transition metal during one hour of polymerization.
Example 1
Synthesis of {2,6-bis(1-(2-Methyl-1-naphthylimino)ethyl]pyridine-κ 3 :N,N′,N″}FeCl 2 (Compound 1).
a) Synthesis of 1-Amino-2-methylnaphthalene
10 g (53.42 mmol) of 2-methyl-1-nitronaphthalene dissolved in 125 ml of methanol and 0.57 g (0.057 g of Pd, 0.54 mmol) of palladium on activated charcoal were introduced successively into an autoclave.
The suspension was heated to 50° C. during 4 hours under a pressure of 10×10 5 Pa of hydrogen, then filtered at ambient temperature. The solution obtained was evaporated and distilled in vacuo. This gave 6.7 g of 1-amino-2-methylnaphthalene in the form of a yellow oil with a boiling point of between 145 and 150° C. at 133.3 Pa.
1 H NMR (CDCl 3 -300K-500 MHz) δ=2.40 (s, 3H, —C H 3 ), 4.15 (s, broad, 2H, —N H 2), 7.33 (d, 2H, H 3 naphth , 3 J H3-H4 ˜8 Hz), 7.28 (d, 2H, H 2 naphth ), 7.47 (m 2H, H 6-7 naphth ) 7.82 (m, 2H, H 8-5 naphth ) in ppm.
b) Synthesis of 2,6-bis(1-(2-Methyl-1-naphthylimino)ethyl]pyridine.
1.20 g (7.35 mmol) of 2,6-diacetylpyridine dissolved in 25 ml of ethanol were introduced into a 100 ml round-bottomed flask under nitrogen, with stirring.
3.0 g (20.25 mmol) of 1-amino-2-methylnaphthalene dissolved in 10 ml of ethanol were then added dropwise, followed by 0.1 ml of glacial acetic acid. The mixture was heated at reflux for 18 hours, with stirring, then cooled to ambient temperature and dried in vacuo so as to obtain crude 2,6-bis[1-(2-methyl-1-naphthylimino)-ethyl]pyridine, which was dissolved in methylene chloride and neutralized with an aqueous solution of sodium carbonate. The organic phase was separated, and 100 ml of water were added thereto. After dewatering and evaporation of the organic phase, the 2,6-bis[1-(2-methyl-1-naphthylimino)ethyl]pyridine was purified by liquid chromatography on a silica column using a 25/75 v/v AcOEt/n-hexane mixture as eluent. This gave 1.33 g of yellow microcrystalline solid.
1 H NMR (CDCl 3 -300K-500 MHz) δ=2.26 (m, 12H, —C H 3 imine and —C H 3 naphthyl ), 7.45 (m, 6H, H 5-6-7 naphth ), 7.58 (d, 2H, H8 naphth 3 J H7-H8 ˜8 Hz), 765 (d, 2H, H 3 naphth , 3 J H3-H4 ˜8 Hz), 7.85 (d, 2H, H 4 naphth ) 8.06 (t, 1H, H p py , 3 J Hm-Hp ˜8 Hz), 8.68 (d, 2H, H m, py , 3 J Hm-Hp ˜8 Hz) in ppm. FTIR (KBr pressing) ν=1640 (ν C═N ) imine) in cm −1
c) Synthesis of Compound 1.
186 mg (1.467 mmol) of activated ferrous chloride were introduced under nitrogen into a 100 ml round-bottomed flask, followed by 10 ml of anhydrous THF (tetrahydrofuran) and by a solution of 665 mg (1.506 mmol) of 2,6-bis[1-(2-methyl-1-naphthylimino)-ethyl]pyridine in 25 ml of THF.
This last addition caused instantaneous formation. of a blue-grey precipitate. The mixture was then heated at reflux for 18 hours, with stirring.
Once the mixture had been cooled to ambient temperature, the solid was finally filtered under nitrogen, rinsed with hexane and dried in vacuo.
This gave 610 mg of compound 1.
Elemental analysis: C=64.2 (theory (th.) 65.5); N=7.3 (th. 7.4); H=4.9 (th. 4.8); Fe=(th. 9.8); Cl=13.0 (th. 12.5) % w/w.
Example 2
Synthesis of {2,6-bis[1-(2-Methyl-1-naphthylimino)methyl]pyridine-κ 3 :N,N′,N″}FeCl2 (Compound 2).
a) Synthesis of 2,6-bis[(2-Methyl-1-naphthylimino)-methyl]pyridine.
Step b of Example 1 was repeated, but using 1.00 g (7.41 mmol) of 2,6-diformylpyridine and 3.2 g (22.35 mmol) of 1-amino-2-methylnaphthalene dissolved in 20 ml of ethanol, without adding glacial acetic acid during mixing, and purifying with a 20/80 AcOEt/n-hexane mixture as eluent. This gave 890 mg of a golden yellow solid.
1 H NMR (CDCl 3 -300K-500 MHz) δ=2.40 (s, 6H, —C H 3 naphthyl ) 7.42 (m, 6H, H naphth ), 7.62 (d, 2H, H naphth ), 7.85 (m, 4H, H naphth ), 8.11 (t, 1H, H p py , 3 J Hm-Hp ˜7 Hz), 8.62 (d, 2H, H m py , 3 J Hm-Hp ˜8 Hz), 8.80 (s, 2H, H iminoformyl ) in ppm.
b) Synthesis of Compound 2.
Step c of Example 1 was repeated, but using 180 mg of activated ferrous chloride and 600 mg of 2,6-bis[(2-methyl-1-naphthylimino)methyl]pyridine. This last addition was seen to cause instantaneous formation of a beige-coloured precipitate. 630 mg of compound 2 were obtained. Elemental analysis: C=63.8 (th. 64.5); N=7.7 (th. 7.8); H=4.5 (th. 4.3); Fe=(th. 10.3); Cl=12.4 (th. 13.1) % w/w.
Example 3
Synthesis of {2,6-bis[1-(1-Anthracenylimino)ethyl]pyridine-κ 3 :N,N′,N″)FeCl 2 (Compound 3).
a) Synthesis of 2,6-bis[1-(1-Anthracenylimino) Ethyl]-pyridine
0.70 g (4.29 mmol) of 2,6-diacetylpyridine dissolved in 40 ml of ethanol were introduced under nitrogen into a 250 ml round-bottomed flask. The mixture was heated at reflux and stirred.
2.5 g of 1-aminoanthracene (purchased from Aldrich) dissolved in 80 ml of ethanol were then added dropwise, followed by 0.2 ml of glacial acetic acid.
After 60 hours of stirring at reflux, the mixture was cooled to ambient temperature; the solid was filtered and dried in vacuo, giving 2.1 g of 2,6-bis[1-(1-anthracenylimino)ethyl]pyridine in the form of a yellow powder.
1 H NMR (CDCl 3 -300K-500 MHz) δ=2.50 (s, 6H, —C H 3 ), 6.84 (d, 2H, H 2 anthr , 3 J H2-H3 ˜7 Hz), 7.48 (m, 6H, H anthr ), 7.84 (d, 2H, H anthr ), 7.99 (d, 2H, H anthr ), 8.03 (d, 2H, H anthr ), 8.12 (t, 1H, H p py , 3 J Hm-Hp ˜8 Hz), 8.41 (s, 2H, H anthr ), 7.49 (s, 2H, H anthr ), 8.75 (d, 2H, H m py , 3 J Hm-Hp ˜8 Hz) in ppm.
FTIR (KBr pressing) ν=1635 (ν C═N imine) in cm −1 .
b) Synthesis of Compound 3.
240 mg (1.893 mmol) of activated ferrous chloride, 10 ml of anhydrous THF and 50 ml of a solution of 1.00 g (1.948 mmol) of 2,6-bis[1-(1-anthracenylimino)ethyl]pyridine in THF were introduced successively under nitrogen into a 100 ml round-bottomed flask.
This last addition caused an instantaneous change in the colour of the solution, which became green. The mixture was then heated for 3 hours at reflux, with stirring.
Once the mixture had been cooled to ambient temperature and the THF had been evaporated in vacuo, a green residue was obtained, which was suspended in hexane, with stirring; the solid was then filtered under nitrogen, rinsed with hexane and dried in vacuo. This gave 905 mg of compound 3.
Elemental analysis: C=67.6 (th. 69.4); N=6.1 (th. 6.6); H=4.7 (th. 4.2); Fe=(th. 8.7); Cl=10.9 (th. 11.1) % w/w.
Example 4
Synthesis of {2,6-his[1-(1-Anthracenylimino)methyl]pyridine-κ 3 :N,N′,N″}FeCl 2 (compound 4)
a) Synthesis of 2,6-bis[(-1-Anthracenylimino)methyl]pyridine.
0.50 g (3.704 mmol) of 2,6-diformylpyridine dissolved in 25 ml of ethanol were introduced under nitrogen into a 100 ml round-bottomed flask. The mixture was heated to reflux and stirred.
2.15 g (11.11 mmol) of 1-aminoanthracene (provided by Aldrich) dissolved in 45 ml of ethanol were then added dropwise.
After 45 hours of stirring at reflux, the mixture was cooled to ambient temperature; the solid was filtered and dried in vacuo, giving 1.68 g of 2,6-bis[(1-anthracenylimino)methyl]pyridine in the form of a yellow solid.
1 H NMR (CDCl 3 -300K-500 MHz) δ=7.15 (d, 2H, H H 2anthr , 3 J H2-H3 ˜7 Hz), 7.50 (m, 6H, H H anthr ), 7.95 (d, 2H, H H 3anthr ), 8.08 (m, 4H, H anthr ), 8.13 (t, 1H, H p py , 3 J Hm-Hp ˜8 Hz), 8.48 (s, 2H, H 5 or 10 anthr ), 8.65 (d, 2H, H m py , 3 J Hm-Hp ˜8 Hz), 8.90 (s, 2H, H iminoformyl ), 8.95 (s, 2H, H 5 or 10 anthr ) in ppm.
b) Synthesis of Compound 4.
254 mg (2.004 mmol) of activated ferrous chloride and then 10 ml of anhydrous THF followed by a solution of 1.012 g (2.085 mmol) of 2,6-bis[1(1-anthracenylimino)methyl]pyridine in 75 ml of THF were introduced under nitrogen into a 100 ml round-bottomed flask.
This last addition caused instantaneous formation of a mauve-coloured precipitate. The mixture was then heated for 18 hours at reflux, with stirring.
Once the mixture had been cooled to ambient temperature and the THF had been evaporated in vacuo, a mauve residue was obtained, which was then suspended in hexane, with stirring; the solid was finally filtered under nitrogen, rinsed with hexane and dried in vacuo. This gave 1.155 g of compound 4.
Elemental analysis: C=68.4 (th. 68.7); N=6.2 (th. 6.9); H=5.2 (th. 3.8); Fe=(th. 9.1); Cl=10.0 (th. 11.6) % w/w.
Examples 5 to 8
Ethylene Polymerizations
The ethylene polymerization experiments were conducted in a steel autoclave (AC) of 5 litres internal volume. At the outset, the autoclave was charged with MAO (10% by weight solution in toluene, EURECENE® T5010 grade marketed by the company Witco) observing the Al/Fe ratio given in Table 1, and the autoclave was charged with 2.0 litres of isobutane and then heated to 50° C. Ethylene was then introduced into the autoclave until the partial pressure was 10×10 5 Pa.
The quantity mentioned in Table 1 of the complex prepared in Examples 1 to 4 was introduced under anhydrous nitrogen into a 50 ml round-bottomed flask. The quantity of MAO necessary to obtain an atomic ratio Al/Fe of 1000 in precontact was then added to the flask under nitrogen. The catalytic solution was then immediately introduced into the autoclave tube under argon.
0.5 litre of isobutane were then used to drive the catalyst from the tube into the autoclave; stirring of the autoclave was maintained at the specified temperature and pressure for one hour. The polymer was obtained after isobutane degassing
The polymerization conditions and the characteristics of the polymers obtained are found in Table 1 below.
Example 9
Copolymerization of Ethylene with 1-hexene
The operations of Example 7 were repeated, but adding 50 ml of 1-hexene with ethylene to the autoclave, using 5 μmol of the complex prepared in Example 3, and with a total Al/Fe ratio of 2000.
Example 10R (non-Inventive)
The operations of Example 6 or 8 were repeated, but using 5 μmol of the complex {2,6-bis[1-(1-naphthylimino)methyl}pyridine-κ 3 :N,N′,N″}FeCl 2 (DIPNaphthFeCl 2 ). The characteristics of the polyethylene obtained are found in Table 1 below and show that this complex gives both low productivity and low molecular weight.
Example 11R (non-Inventive)
The operations of Example 6 or 8 were repeated, but using 5 μmol of the complex {2,6-bis[1-(2,4,6-trimethyl-1-phenylimino)ethyl}pyridine-κ 3 :N,N′,N″}FeCl 2 (MeDIP2,4,6MePhFeCl 2 ), prepared as described by Britovsek et al. in J. Am. Chem. Soc., 1999, 121, 8728) and n-hexane as solvent. The characteristics of the polyethylene obtained are found in Table 1 below and show that this complex gives polyethylene with no ethyl or butyl branching.
Examples 12 to 20
Ethylene Copolymerizations in Liquid Propylene
The autoclave was charged with the quantity of MAO necessary to attain an atomic Al/Fe ratio of 4000, and after 1.0 liter of liquid propylene had been added at ambient temperature, the autoclave was heated to the specified temperature (30 or 50° C.). Ethylene is introduced at the specified temperature into the autoclave until the molar C 2 /C 3 ratio intended is reached in the gaseous phase. 5 μmol of the complex prepared in Example 1 or 3 were introduced into a 50 ml round-bottomed flask under anhydrous nitrogen. The quantity of MAO necessary to attain an atomic Al/Fe ratio of 1000 in precontact was then added to the flask. The catalytic solution was introduced immediately into the tube of the autoclave, under argon.
0.5 litre of propylene were then used to drive the catalyst from the tube into the autoclave; stirring of the autoclave was maintained at the specified temperature and pressure for one hour, adding ethylene so as to keep the C 2 /C 3 ratio constant. The polymer was obtained after propylene degassing.
The polymerization conditions and the characteristics of the polymers obtained are found in Tables 2 (compound 1) and 3 (compound 3) below.
Examples 21R and 22R (non-Inventive)
The operations of Examples 18 and 20 were repeated, respectively, but using {2,6-bis[1-(2,6-diisopropyl-1-phenylimino)ethyl]pyridine-κ 3 :N,N′,N″)FeCl 2 (MeDIP2,6iPrPhFeCl 2 ), prepared as described in WO98/30612) as complex. The results are given in Table 3 and show that the rate of incorporation of propylene is clearly inferior to that obtained with the complexes of the invention.
TABLE 1
Example
Unit
5
6
7
8
9
10R
11R
Polymerization
Complex (a)
—
Ex. 1
Ex. 2
Ex. 3
Ex. 4
Ex.3
DIPNaphFeCl 2
MeDIP2,4,6,MePhFeCl 2
Complex (a)
μmol
1
5
1
5
5
5
5
Al/Fe
mol/mol
4000
2000
4000
2000
2000
2000
2000
1-Hexene
ml
0
0
0
0
50
0
0
Productivity
kg/mmol
485
9.8
537
3.1
252
2
100
Fe.hour
Characteristics
SD
kg/m 3
971.4
—
—
—
—
—
—
Mw
10 3 daltons
136
121
1.5
68
1.3
2.9
259
mp
° C.
133.7
129.8
116.7
129.8
95.3
112
134
ΔHm
J/g
275
249
151
193
—
148
228
Ethyl
Number/1000 C
<0.5
<0.5
2.7
0.8
2.5
0.9
0
branching
Butyl
Number/1000 C
0
0
0.2
0
1.2
0
0
branching
1-Butene
g/kg
<2
<2
10
3
10
4
0
1-Hexene
g/kg
0
0
0
0
7.13
0
0
TABLE 2
Example
Unit
12
13
14
15
Poly-
merization
Complex (a)
—
Ex.1
Ex.1
Ex.1
Ex.1
Temperature
° C.
50
30
50
30
C 2 /C 3 (AC)
% mol/
8
7
20
24
mol
Productivity
kg/
33.8
50.0
138.8
181.0
mmol
Fe.hour
Charac-
teristics
Mw
daltons
7354
4884
11481
7593
Mw/Mn
—
1.93
1.7
2.17
2.17
Rate of C 3
% w/w
17
30
11
23
incorporation
Molar
fraction of
triads
EEE
+ EEP
—
0.681
0.358
0.779
0.57
PEE —
0.188
0.36
0.138
0.247
PEP
—
0.006
0.019
0.002
0.011
EPE
+ PPE
—
0.077
0.154
0.056
0.108
EPP —
0.043
0.091
0.031
0.053
PPP
—
0.004
0.019
0.005
0.011
TABLE 3
Example
Unit
16
17
18
19
20
21R
22R
Polymerization
Complex (a)
—
Ex. 3
Ex. 3
Ex. 3
Ex. 3
Ex. 3
MeDIP2, 6iPrPhFeCl 2
MeDIP2, 6iPrPhFeCl 2
Temperature
° C.
50
50
30
30
50
30
50
C 2 /C 3 (AC)
% mol/mol
28
14
16
7
8
14
9
Productivity
kg/mmol
45.6
30.6
132.0
95.4
15.2
21.1
6.4
Fe.hour
Characteristics
Mw
daltons
3291
1436
1379
1252
1049
279400
203700
Mw/Mn
—
2.62
1.48
1.42
1.45
1.3
13
18
Rate of C 3
% w/w
12
19
44
54
28
0.6
0.4
incorporation
Molar fraction
of triads
EEE
—
0.742
0.69
0.295
0.179
0.486
—
—
PEE + EEP
—
0.131
0.165
0.323
0.328
0.258
—
—
PEP
—
0.003
0.005
0.008
0.012
0.011
—
—
EPE
—
0.031
0.04
0.067
0.075
0.045
—
—
EPP + PPE
—
0.075
0.095
0.204
0.203
0.192
—
—
PPP
—
0.018
0.005
0.103
0.203
0.008
—
—
|
A complex of a transition metal complying with the general formula (I)
in which
M is a transition metal of groups 6 to 12,
T is the oxidation state of M,
each A, which may be identical with or differ from each other, is an atom or an atomic grouping bonded covalently or ionically to the transition metal M,
b is the valency of A,
each R 1 , R 2 , R 3 , R 4 and R 5 is independently a hydrogen atom, an unsubstituted or substituted hydrocarbon group, an unsubstituted or substituted heterohydrocarbon group, or an inert functional group,
R 6 and R 7 are, independently of one another, a polynuclear aromatic hydrocarbon group containing at least two condensed benzene nuclei, substituted with at least one hydrocarbon group.
| 2
|
FIELD OF THE INVENTION
The invention relates to an optical modulator according to the Mach-Zehnder Interferometer principle, and, more particularly, to the stabilization of the operating point of the modulator with respect to variations of various external parameters.
BACKGROUND
FIG. 1 schematically shows an example of an optical modulator of Mach-Zehnder interferometer type, often called an MZI modulator. An optical wave having a power P 0 arrives through a waveguide to an optical separation unit S 1 , a Y-separator here. The initial wave is separated into two half-power waves, respectively guided in two parallel, upper and lower branches. Each branch comprises, in series, a fast optical phase modulation diode HSPM (“High Speed Phase Modulator”) and a slow optical phase adjusting diode PINPM.
Each of the diodes HSPM and PINPM introduces an adjustable phase delay of the optical wave crossing the diode by producing electric charge in the light path. The HSPM diode operates in reverse bias mode; electric charge is pulled from the junction into the optical path by a junction depletion phenomenon, the junction being offset relative to the optical path. The diode PINPM operates in a forward bias mode. It includes a P-I-N junction, the intrinsic region of which is in the light path and receives electrical charge by an injection phenomenon.
The diode PINPM reacts slowly to changes in its bias, but it has a wide range of phase delay adjustment—it is used to adjust an optimal quiescent phase delay in the branch. Thus, the diodes PINPM of the two branches (PINPM 1 and PINPM 2 ) receive respective constant bias currents depending on the quiescent phase delays to be introduced in the two branches.
The diode HSPM reacts quickly, but has a low phase modulation amplitude—it is used to modulate the phase delay with a digital signal to be transmitted around the quiescent phase delay established by the diode PINPM. Thus, the diodes HSPM of the two branches (HSPM 1 and HSPM 2 ) receive voltage signals that are modulated, based on the digital signal to be transmitted, between 0 and a positive value Vb. The voltage signals applied to the diodes HSPM 1 and HSPM 2 are complementary so as to produce a differential effect in the two branches.
The two branches reach an optical junction unit J 1 , here a directional coupler. The optical waves incident on the two channels of coupler J 1 are shifted by 180° at rest, whereby, in the case of a symmetric coupler, the optical power P 1 , P 2 delivered by each channel of the coupler J 1 is 50% of the input power P 0 of the modulator, the absorption losses in the branches being neglected. Diodes PINPM 1 and PINPM 2 are biased by different currents. For example, the diode PINPM 2 is biased by a zero current introducing theoretically a zero phase delay, and the diode PINPM 1 is biased by a current Ib selected to introduce a phase delay of 180°.
FIG. 2 is a diagram illustrating the variation of the transmission rate P 1 /P 0 of the modulator, measured at the output of the upper channel of the coupler J 1 , as a function of the phase difference between the waves at the inputs of the coupler J 1 . The transmission rate P 2 /P 0 , not shown, at the output of the lower channel, varies inversely.
The initial phase shift of 180° introduced by the diodes PINPM places the operating point of the modulator at the inflection point of a sinusoid, in a region where the linearity is best and the slope is steepest. The diode HSPM 1 causes the phase to vary in a range above 180°, while the diode HSPM 2 causes the phase to vary symmetrically in a range below 180°. By limiting the amplitude of these ranges, the corresponding change in the rate of transmission may be almost linear. For the transmission of digital signals, the linearity is less important, but it may be preferable that the behavior of the modulator remains balanced, which is the case under the conditions of FIG. 2 .
In practice, the bias currents of the diodes PINPM are individually adjusted for obtaining the desired quiescent conditions. However, a drift of the quiescent conditions may be noticeable, particularly as a function of temperature.
SUMMARY
Thus there is a need for compensating the drift in the quiescent conditions of an MZI modulator. It may also be desirable to avoid individual adjustment of the bias currents of modulators in a production environment.
These needs are addressed by an optoelectronic phase comparator configured to provide, in the form of an electrical signal, a measure of a phase difference between two optical waves. The phase comparator comprises an optical directional coupler having two coupled channels respectively defining two optical inputs for receiving the two optical waves to be compared. Two photodiodes are configured to respectively receive the optical output powers of the two channels of the directional coupler. An electrical circuit is configured to supply, as a measure of the optical phase shift, an electrical signal proportional to the difference between the electrical signals produced by the two photodiodes.
An MZI optical modulator may thus comprise an optical separation unit for separating an incoming optical wave into a first and a second optical wave; a first and a second optical phase adjusting diode inserted respectively in the paths of the first and second optical waves; and a first and a second optical directional coupler, each having first and second coupled channels, the first channels being inserted respectively in the paths of the first and second optical waves. The MZI optical modulator may also include an optoelectronic phase comparator as mentioned above, having its optical inputs respectively connected to the second channels of the first and second directional couplers; and a circuit for electrically biasing the phase adjusting diodes, connected in a control loop with the optoelectronic phase comparator.
According to an embodiment, the optical modulator comprises, between one of the optical inputs of the phase comparator and the second corresponding channel of the first or second directional coupler, an intermediate directional coupler connected such that the phase difference between the two optical waves incident on the inputs of the phase comparator is equal to 180°.
According to an embodiment, the optical modulator comprises an optical wave junction unit having two inputs connected respectively to the outputs of the first channels of the first and second directional couplers; and a first and a second optical phase modulation diode respectively inserted in the connections between the junction unit and the first and second directional couplers.
According to an embodiment, the separation unit and the junction unit are directional couplers, and the first and second phase adjustment diodes are biased so that they introduce a 90° phase delay one relative to the other.
According to an embodiment, the separation unit is a directional coupler, the junction unit is a Y-combiner, and the first and second phase adjustment diodes are biased to apply the same phase delay.
BRIEF DESCRIPTION OF THE DRAWINGS
Other advantages and features will become more clearly apparent from the following description of particular embodiments provided for exemplary purposes only and represented in the appended drawings, in which:
FIG. 1 , previously described, schematically shows an exemplary Mach-Zehnder interferometer (MZI) modulator as in the prior art.
FIG. 2 is a graph illustrating the transmission rate of the modulator of FIG. 1 as a function of the phase difference between the optical waves of the two branches.
FIGS. 3A through 3D represent different configurations of an MZI modulator combining different types of optical separation and junction units according to the invention.
FIG. 4 shows an embodiment of an optoelectronic regulation circuit adapted to a first MZI modulator configuration according to the invention.
FIG. 5 shows an alternative embodiment of the optoelectronic regulation circuit adapted to another MZI modulator configuration according to the invention.
FIG. 6 shows a detailed example of an optoelectronic regulation circuit according to the invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
A P-I-N diode of an MZI modulator, even if its bias current is zero, causes a nonzero optical phase delay, a residual phase shift. This residual phase shift depends on the characteristics obtained after manufacture, such as doping and dimensions. If the two PIN diodes of the modulator could be matched, they would provide the same residual phase shift, which would be offset by the differential structure of the modulator. However, the diodes PINPM, which are formed in optical waveguides, are large compared to diodes used for plain electronic functions, and located far apart from each other at the scale of a semiconductor chip. As a result, it is difficult to match these “optical” diodes, and unpredictable offsets that are too great to be neglected are generally observed between the residual phase shifts of the two diodes PINPM.
Despite an accurate adjustment of the bias currents, even in modulator configurations where the two diodes PINPM may have the same phase setting, the quiescent conditions drift with temperature. This drift may be explained by the fact that the rate of change of the phase shift as a function of temperature depends on the operating conditions of the diode PINPM. These operating conditions are generally not identical initially for the two diodes, whereby the phase shifts of the two diodes diverge when the temperature varies.
The HSPM diodes are also subject to difficulties in matching, but their structure is inherently less sensitive to variability of manufacturing processes. It is noted that the offset between the residual phase shifts of the two HSPM diodes, even after thermal drift, may remain within acceptable limits to be neglected.
FIGS. 3A through 3D show configurations of MZI modulators differing by combinations of separation and junction units requiring different bias conditions for the diodes PINPM. The structures of the two branches of the modulators are unchanged from FIG. 1 .
FIG. 3A corresponds to the configuration of FIG. 1 , already described. The separation unit S 1 is a Y-separator and the junction unit J 1 is a symmetric directional coupler. Separator S 1 maintains the phase of the input optical wave on both outputs, whereas the coupler J 1 requires a phase difference of 180° to be in the center of its dynamic range, the desired quiescent condition. Thus, diodes PINPM 1 and PINPM 2 are biased to introduce an initial phase shift of 180° between the inputs of the coupler J 1 .
The two waves exiting the coupler J 1 are in phase quadrature, but their phase difference with respect to the input waves is variable depending on the characteristics of the input waves.
In FIG. 3B , the output directional coupler J 1 has been replaced by a Y-combiner J 2 . Such a combiner transmits 50% of the optical power when the waves at its two inputs are in phase quadrature. The two waves arriving at the diodes PINPM being in phase, the diodes PINPM are biased to introduce the desired phase difference of 90° between the two waves. E.g. the diode PINPM 1 is biased to introduce a phase delay of 90° and the diode PINPM 2 receives a zero current, corresponding theoretically to a null phase delay. In practice, the diode PINPM 2 introduces a residual phase delay at zero bias current, which is difficult to predict, for example 1°. In that case, the diode PINPM 1 is biased for introducing a phase delay of 90+1=91°.
The configuration of FIG. 3B may be preferred to that of FIG. 3A , because the diode PINPM 1 causes less absorption losses than in FIG. 3A . Indeed, a greater phase delay is obtained in FIG. 3A by injecting more charge in diode PINPM 1 , and absorption losses increase with the number of charges.
In FIG. 3C , the Y-separator S 1 of FIG. 3A has been replaced by a symmetrical directional coupler S 2 . The input optical wave is applied to one of the channels of the coupler, for example the lower one. In that case, the wave exiting the upper channel of the coupler is delayed by 90° relative to the wave exiting the lower channel. The output coupler J 1 requiring a phase difference of 180° to operate in the desired quiescent conditions, it is sufficient that the diode PINPM 1 introduce a phase delay of 90° that is added to the delay of 90° introduced by the upper channel of the input coupler S 2 .
The absorption losses of the configuration of FIG. 3C are similar to those of FIG. 3B .
In FIG. 3D , the output directional coupler J 1 of FIG. 3C has been replaced by a Y-combiner J 2 . The input coupler S 2 directly produces the phase quadrature desired for the quiescent conditions, between the waves input to the combiner J 2 . Thus, the diodes PINPM need not introduce additional phase delay. In this case, the two diodes PINPM may be biased at zero current, in theory. This configuration therefore provides the best performance in terms of absorption losses.
Because the two diodes PINPM operate in similar conditions, this configuration also offers the best performance in terms of thermal drift.
In practice, the diode PINPM having the highest residual phase delay may be biased at zero current, while the other diode PINPM is biased with a current sufficient to balance the residual phase delay. As it is difficult to know in advance which of the two diodes PINPM has the highest residual phase delay, it is preferred to bias both diodes with non-zero currents, one fixed and one adjustable.
FIG. 4 shows an embodiment of an optoelectronic circuit for regulating the quiescent conditions of an MZI modulator. The MZI modulator has a configuration similar to that of FIG. 3D . With respect to FIGS. 3A to 3D , the positions of the diodes PINPM have been interchanged with those of the HSPM diodes, so that the diodes PINPM are the first elements in the two branches of the modulator, and are part of a control loop. The HSPM diodes are not included in the loop—as mentioned earlier, the drifts of the HSPM diodes may be neglected.
The optoelectronic regulation circuit, whose principles may be applied to various MZI modulator configurations, such as those illustrated in FIGS. 3A to 3D , measures the optical phase difference between the waves in the two branches of the modulator, and provides the error relative to a desired value in the form of optical power received by photodiodes PD 1 , PD 2 . The electrical signals provided by the photodiodes are exploited to vary the bias currents of the diodes PINPM in a direction tending to reduce the error.
The measurement of the phase difference may be achieved using a symmetrical optical directional coupler DC 0 receiving, on its two channels, optical waves derived from the two branches of the modulator. The paths of the derived optical waves are configured so that the phase difference at the input of the coupler DC 0 equals 180° when the phase difference between the derived optical waves corresponds to that desired at the input of the junction unit. Under these conditions, the coupler DC 0 outputs at each of its channels 50% of the total optical power received. If the phase difference is not equal to 180°, one of the channels provides more than 50% of the power, while the other channel provides the complement. The optical waves at the outputs of the two channels of the coupler are provided to two respective photodiodes PD 1 , PD 2 . Thus, the difference between the electrical signals generated by the photodiodes represents the optical phase error.
In FIG. 4 , more specifically, the optical outputs of diodes PINPM 1 and PINPM 2 are provided to the first channels of two respective asymmetric directional couplers DC 1 and DC 2 . The outputs of these first channels are provided to diodes HSPM 1 and HSPM 2 respectively.
The couplers DC 1 and DC 2 are asymmetrical in that the optical power received in the first channel is distributed asymmetrically between the outputs of the first and second channels, for example 98% at the output of the first channel, and 2% at the output of the second channel. The fraction of the output power in the second channel is chosen to be detectable by a photodiode in good conditions.
The optical waves output by the second channels of the couplers DC 1 and DC 2 have respective phase delays of 180° and 90° relative to the optical wave input to the modulator (each of the couplers DC 1 and DC 2 introduces a phase delay of 90° as the wave passes from the first channel to the second). The phase difference between these waves is thus 90° while the coupler/comparator DC 0 requires 180°. A symmetrical directional coupler DC 3 is provided to add the missing 90° phase delay to the 180° optical wave. The coupler DC 3 receives in its first channel the 180° wave and provides a 270° wave from its second channel to the upper channel of coupler/comparator DC 0 .
A directional coupler DC 4 is provided to equalize the optical paths leading to the coupler/comparator DC 0 . Its first channel connects the coupler DC 2 to the lower channel of the coupler DC 0 , without introducing a phase delay.
The outputs of the first and second channels of the coupler/comparator DC 0 are respectively sensed by the photodiodes PD 1 and PD 2 . These photodiodes are part of an electrical control circuit 10 configured to adjust the bias currents of the diodes PINPM according to the difference between the sensed optical powers. In this modulator configuration, the bias currents are substantially the same, since the diodes PINPM are designed to introduce the same phase delay (as close to 0° as possible.)
The regulator circuit of FIG. 4 is also usable, as is, in the modulator configuration of FIG. 3B .
FIG. 5 shows an alternative of the optoelectronic regulation circuit, integrated with an MI modulator of the type of FIG. 3C . The same elements as in FIG. 4 are designated by the same references. The diode PINPM 1 is biased here for introducing a phase delay of 90°, so that the second channel of the coupler DC 1 provides an optical wave delayed by 270°. The second channel of the coupler DC 2 still provides a wave delayed by 90°. The phase difference between these waves is 180°, whereby the two waves may be directly applied to the inputs of the coupler/comparator DC 0 .
The configuration of FIG. 5 is simpler than that of FIG. 4 in that it uses two directional couplers less.
The regulator circuit FIG. 5 is also usable, as is, in the modulator configuration of FIG. 3A .
FIG. 6 shows a detailed example of electronic circuitry of the optoelectronic regulation circuit 10 . The photodiodes PD 1 and PD 2 are reverse biased by two resistors R 1 and R 2 . The cathodes of diodes PD 1 and PD 2 are connected respectively to a non-inverting input and an inverting input of a differential transconductance amplifier 20 . The diodes PINPM 1 and PINPM 2 are forward biased by respective constant current sources Ib 1 and Ib 2 . The anodes of diodes PINPM 1 and PINPM 2 are connected to forward and reverse outputs of the amplifier 20 .
The currents Ib 1 and Ib 2 are set by design to the typical values required to introduce the quiescent phase difference corresponding to the modulator configuration (180° for FIG. 3A , 90° for FIGS. 3B and 3C , and 0° for FIG. 3D ). In theory, one of the currents (Ib 2 ) may be zero. In practice, the two currents are non-zero, so that each has a margin of adjustment. Current Ib 2 is selected, for example, to introduce a phase delay of 5°. Then, the current Ib 1 is selected to introduce a phase delay of 185° in FIG. 3A , 95° in FIGS. 3B and 3C , and 5° in FIG. 3D .
When the phase difference between the input waves of coupler/comparator DC 0 is 180°, each of the photodiodes PD 1 and PD 2 receives the same optical power, 50% of the power received by the coupler/comparator DC 0 . If the photodiodes are matched, which is easier to achieve than for diodes PINPM, their cathode voltages stand at identical values. Thus, the amplifier 20 sees a zero input voltage and does not influence the bias currents of the diodes PINPM.
If the phase difference between the input waves of coupler/comparator DC 0 drops below 180°, it means that the delay introduced by the diode PINPM 1 decreases or the delay introduced by the diode PINPM 2 increases. The optical power received by photodiode PD 1 increases, and the optical power received by the photodiode PD 2 decreases. The cathode voltage of the photodiode PD 1 increases and that of the photodiode PD 2 decreases. The amplifier 20 sees its differential input become positive—it injects a proportional current in the diode PINPM 1 and subtracts a proportional current from the diode PINPM 2 . The diode PINPM 1 increases its phase delay while the diode PINPM 2 decreases its phase delay.
A symmetrical behavior is obtained when the phase shift between the waves becomes greater than 180°.
An automatic correction is thus obtained for the quiescent phase errors in the modulator. This correction is independent of the nature of the error—the error may be due to a temperature drift, a poor matching between the diodes PINPM, a poor initial choice of the bias currents, or any other cause. The accuracy of the correction depends on the open loop gain of the control loop, which may be easily adjusted by way of amplifier 20 .
The accuracy also depends on the parasitic offset referred to the input of the amplifier, caused for instance by a mismatch between the photodiodes or a lack of precision in the coupling coefficient of each of couplers DC 0 , DC 1 and DC 2 . Such an offset may be compensated electrically by techniques known in the field of differential amplifiers.
|
An optical modulator uses an optoelectronic phase comparator configured to provide, in the form of an electrical signal, a measure of a phase difference between two optical waves. The phase comparator includes an optical directional coupler having two coupled channels respectively defining two optical inputs for receiving the two optical waves to be compared. Two photodiodes are configured to respectively receive the optical output powers of the two channels of the directional coupler. An electrical circuit is configured to supply, as a measure of the optical phase shift, an electrical signal proportional to the difference between the electrical signals produced by the two photodiodes.
| 6
|
This application is a divisional of Ser. No. 08/932,893 filed on Sep. 18, 1997, now U.S. Pat. No. 6,011,160.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to crosslinked polymers of vinyl pyrrolidone, and, more particularly, to crosslinked copolymers of vinyl pyrrolidone and a monomer derived from 1-vinyl-3-(E)-ethylidene pyrrolidone (EVP).
2. Description of the Prior Art
Crosslinked polyvinylpolypyrrolidone (PVPP) is widely employed as a clarifying agent in the industrial purification of wine and beer solutions, particularly for the removal by adsorption of organic impurities such as polyphenols, tannins and anthrocyanins which may be present in the aqueous solution. However, this polymer is incapable of removing heavy metal ions, in particular, copper and iron ions, which also contribute to the toxicity and cloudiness of such solutions.
PVPP is made by popcorn or proliferous polymerization of vinyl pyrrolidone (VP) in the presence or absence of added crosslinking agents, as described in U.S. Pat. Nos. 3,277,066; 3,306,888; 3,759,880; 3,933,766; 3,992,562; and 5,391,668, and by F. Haaf et al. in Polymer J. 1701), p. 143-152 (1985), entitled "Polymer of N-Vinyl Pyrrolidone: Synthesis, Characterization and Uses".
Controlled modification of the properties of PVPP may be accomplished by the introduction of comonomers with vinyl pyrrolidone which contain functional or ligand groups capable of preferential binding of copper or iron ions. For example, U.S. Pat. No. 5,094,867 described a copolymer of vinyl pyrrolidone containing 50-99.5% of a ligand-containing comonomer, particularly N-vinyl imidazole, (NVI), which is an amine-containing comonomer, to remove such heavy metal ions. However, the NVI comonomer in this system must be used in very high concentrations to achieve the desired binding effect. In addition, the vinyl pyrrolidone content of this copolymer is much less than for PVPP alone, which reduces the useful properties of the copolymer as a clarifying agent.
Accordingly, it is an object of the present invention to provide a new and improved PVPP copolymer for use in the industrial clarification of aqueous solutions.
Another object herein is to provide a crosslinked PVPP copolymer which includes a heavy metal chelating comonomer for vinyl pyrrolidone, which comonomer is present in small amounts but is effective in completing and removing traces of heavy metals such as copper and iron ions present in aqueous solutions.
A particular object herein is the provision of a vinyl pyrrolidone copolymer which contains a monomer derived from 1-vinyl-3-(E)-ethylidene pyrrolidone (EVP).
Still another object herein is to provide a vinyl pyrrolidone copolymer which contains 3-(2-aminoethyl)-α-aminoethyl-N-vinyl pyrrolidone (AEAEVP) as comonomer therein.
A further object herein is to provide a proliferous polymerization process for making such copolymers.
These and other objects and features of the invention will be made apparent from the following more particular description of the invention.
SUMMARY OF THE INVENTION
A crosslinked PVPP copolymer is provided herein which contains predominately vinyl pyrrolidone (VP) monomer, and, in small amounts, a heavy metal chelating comonomer derived from 1-vinyl-3-(E)-ethylidene pyrrolidone (EVP) having the formula: ##STR1## where Y is ##STR2## Q is H, lower alkyl or ##STR3## R 1 , R 2 and R 3 are independently H, lower alkyl, alkylene carboxylate, alkylene phosphonate or alkylene sulfonate, or 2-ethyl (3-N-vinyl pyrrolidonyl);
X is alkylene, arylene, cycloalkylene or a heterocylic metal chelating group, and
n is 1-10.
Preferably, R 3 is H and R 1 and/or R 2 is ##STR4## where M is H or monovalent alkali metal; and n is 1-6.
A typical derivatized EVP for use as a comonomer for polymerization with VP is 3-(2-aminoethyl)-α-aminoethyl-N-vinyl pyrrolidone (AEAEVP).
A typical crosslinked PVPP copolymer of the invention comprises, by weight, about 80-90% VP, about 5-15% AEAEVP and about 1-5% EVP.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the invention, a new and improved crosslinked polyvinylpolypyrrolidone (PVPP) copolymer is provided herein which contains a comonomer in small amounts which can effectively chelate with and remove traces of copper and iron cations present in aqueous solutions.
A suitable comonomer is 3-(2-aminoethyl)-α-aminoethyl-N-vinyl pyrrolidone (AEAEVP), which is made by a Michael addition reaction between one mole of 1-vinyl-3-(E)-ethylidene pyrrolidone (EVP) (U.S. Pat. No. 5,391,668) and one mole of ethylenediamine (EDA). The comonomer may be generated in situ during the course of proliferous polymerization of vinyl pyrrolidone, or obtained independently of the polymerization, and added to the vinyl pyrrolidone monomer to form the polymerization reaction mixture. Excess EVP present in the reaction product of the Michael addition reaction may be used as the crosslinker in the polymerization process. The Michael addition reaction proceeds as follows: ##STR5##
The EVP reactant is a white, needle-shaped crystalline solid having a melting point of 59-61° C.
The AEAEVP monomer also may be generated in situ from a polymerization charge of EVP and EDA, and VP. Similarly, EVP itself may be generated in situ from the VP reactant, as described in U.S. Pat. No. 5,391,668.
While the use of EDA as a reactant is used to illustrate the formation of a suitable monomer for proliferous polymerization with VP and EVP, it will be understood that the equivalents of EDA may be used as well. For example, diethylene triamine (DETA), triethylenetetramine (TETA), etc. may be used in place of EDA, as illustrated in the following examples. Similarly, alkylene-substituted amines including such substituents with aryl, cycloalkyl or alkylene carboxylic groups may be considered equivalents of EDA. Those groups which enhanced the overall chelation abilities of the resultant polymer are considered as preferred equivalents of the simple EDA. Such materials can operate at an acid pH which may be desirable in beer and wine clarification processes.
The invention will now be described in more detail in the following examples.
EXAMPLES 1-2
Preparation of AEAEVP Monomer (EVP/EDA--1:1 Mole Ratio)
Example 1
25 g of EVP (MW 137) and 10.95 g of EDA (MW 60) were charged into a 150 ml pressure vessel, and, after a nitrogen purge, was sealed at 110° C. and allowed to react overnight. The contents then were analyzed by GC measurements. The results are shown in Table 1 below.
TABLE 1______________________________________Time (hrs) Wt. % EVP Wt. % EDA______________________________________ 0 69.54 30.4616 13.75* 7.73*Wt. % Reacted 55.79% 22.73%______________________________________Mole ratio of EVP/EDA reacted:(55.79/137)/22.73/60 = 1.07.______________________________________ *GC/MS analysis of the reaction product indicated the presence of the desired AEAEVP monomer. The proton (.sup.1 H) and .sup.13 C NMR spectral data was consistent with a 1:1 addition product.
Test Procedure
*GC Method:
% EVP remaining in the mixture was calculated using 2-dodecanol as an internal standard; and
% EDA remaining was calculated using several concentrations of EDA as an external standard.
Example 2
14.251 g of EVP was charged into a 150 ml pressure vessel equipped with a 2-hole metal plate. The system was purged with nitrogen for 30 minutes using 2 syringe needles, one for the N 2 purge and the other to relieve the air pressure in the bottle. Then 6.37 g of EDA was added by means of a syringe needle while opening the other hole to relieve the air pressure. Then the contents were heated to 100° C. under reflux while stirring magnetically. After about 12 hours cessation of reflux of the high vapor pressure reactants was observed, which was an indication of formation of the reaction product and of completion of the reaction. The reaction vessel then was cooled to room temperature. The product was a clear, yellow liquid containing AEAEVP monomer.
Example 3
A 150 ml pressure bottle equipped with a magnetic stirrer was charged with 30 g of EVP and sealed with a two-hole rubber gasket metal cap. Nitrogen was purged through the bottle using a 12 inch syringe needle for half an hour. Using a 50 ml syringe, 72.26 g of ethylene diamine (EDA) was introduced into the pressure bottle, and at the same time, the nitrogen purge was disconnected. The reaction bottle then was placed in an oil bath at 110° C. and held there for 16-24 hours with constant stirring. Then the reaction bottle was cooled to room temperature and discharged. The AEAEVP monomer was formed in excess EDA. Residual EVP in the solution mixture was determined by GC as being <1%.
Thereafter excess EDA was stripped off by vacuum distillation (<0.5 mm Hg) at a temperature below 50° C. The AEAEVP monomer obtained had a purity in excess of 97%; its chemical structure was confirmed by GC/MS, 1 H and 13 C NMR analysis.
EXAMPLES 4-5
Proliferous Polymerization of VP/EVP/AEAEVP Reaction Mixtures
Example 4
The reaction product of Example 1 (12.27 g), which contained 1.35% EVP and 8-9% AEAEVP, and 112.73 g VP (89%), in 31.25 g distilled water, were heated to 120° C. in a Buchi reactor, held at that temperature for 2 hours, and then cooled to 100° C., at which temperature proliferous polymerization occurred over a period of one hour. The resultant product was the desired crosslinked copolymer of VP and AEAEVP including EVP as crosslinker in proportions of the starting reactants.
Example 5
The reaction product (20.27 g) of the Michael addition of 30 g of EVP and 13.14 g of EDA having a 1:10 ratio of EVP/EDA, and containing 2.2% EVP and 14% AEAEVP, with 104.73 g of VP, and 31.25 g of water were heated in a Bucchi reactor to 100° C. A proliferous polymerization reaction then took place over a period of one hour. A similar copolymer product as in Example 4 was obtained.
Example 6
Proliferous Polymerization of Diethylenetriamine (DETA) with EVP
Reactant: 1:1 mole ratio of EVP/DETA
10 g of EVP were charged into a 150 ml reaction vessel and purged with nitrogen. Then 7.52 g of DETA were introduced and the reactants were heated at 110° C. for 16 hrs. The reaction proceeded as follows:
______________________________________Time Wt. % EVP Wt. % DETA (MW 103)______________________________________Start 57.08% 42.92%16 Hrs. 10.13% 12.00%Wt. % reacted 46.95% 30.92%______________________________________Mole Ratio of EVP/EDA Reacted:(46.95/137):(30.92/103) = 1.14______________________________________Popcorn Copolymer of the reaction products:______________________________________2.2% EVP 16.0 grams of the above reactant83.78% VP 107.87 grams of VP monomerapprox. 14% comonomer 31.25 grams of distilled water 1.1292 grams of EVP crystals Heated in Bucchi reactor to 100° C. for proliferous polymerization.______________________________________
The product is a white slurry; the first washing of the mother liquid contains the unreacted VP and EVP-adduct comonomer.
Example 7
Proliferous Polymerization of Triethylenetetramine (TETA) with EVP
Reactant: 1:1 mole ratio of EVP/TETA
10 g of EVP in 150 ml reaction bottle, nitrogen purged, then introduced 10.66 g of TETA (60%) and heated at 110° C. for 15 hrs.
______________________________________Time Wt. % EVP Wt. % TETA (MW 146)______________________________________Start 48.38% 51.67%15 Hrs. 17.93% 27.85%Wt. % reacted 30.50% 23.75%______________________________________Mole Ratio of EVP/EDA Reacted:(30.50/137):(23.75/146) = 1.37______________________________________Popcorn Copolymer of the reaction products:______________________________________2.2% EVP 15.0 grams of the above reactant88% VP 110.0 grams of VP monomerapprox. 9% comonomer 31.25 grams of distilled water Heated in Bucchi reactor to 100° C. for proliferous polymerization.______________________________________
Reaction is fast. The product is white solid.
Example 8
Dimethylethylenediamine (DMEDA) with EVP
Reactant: 1:1 mole ratio of EVP/DMEDA
10 g of EVP (Mwt. 137) in 6.42 gm of DMEDA (Mwt. 88) in 150 ml of pressure bottle. (Nitrogen purged, 110° C. overnight).
______________________________________Time Wt. % EVP Wt. % DMEDA)______________________________________To 60.90% 39.10%T24 29.78% 20.62%Wt. % reacted 31.12% 18.48%______________________________________Mole Ratio of EVP/DMEDA Reacted:(31.12/137):(18.48/88) = 1.08______________________________________
The product is mainly DMAEAEVP monomer. Its chemical structure is confirmed by GC/MS.
Example 9
Copper Removal by Polymers
The crosslinked polymer of Example 4 was introduced separately at 5 g/l into 5, 10 and 20 ppm aqueous Cu ++ solutions of copper sulfate and pentahydrate. The mixture was stirred for a total contact time of 20 minutes. An aliquot of each solution was withdrawn and passed through a glass fiber filter to remove any adhering polymer. The aliquot then was analyzed for residual copper ions by atomic absorption spectroscopy. The percent copper removal was calculated by subtraction of the final copper concentration from the initial copper concentration. A total of 94% Cu was removed from the 5 ppm solution, 94% Cu was removed from the 10 ppm solution, and 79% Cu was removed from 20 ppm solution.
While the invention has been described with particular reference to certain embodiments thereof, it will be understood that changes and modifications may be made which are within the skill of the art. Accordingly, it is intended to be bound only by the following claims, in which:
|
What is described herein is a crosslinked polyvinylpyrrolidone (PVPP) copolymer of vinyl pyrrolidone (VP) and monomer derived from 1-vinyl-3-(E)-ethylidene pyrrolidone (EVP).
| 2
|
CLAIM OF PRIORITY
[0001] This application claims priority under 35 USC §119(e) to U.S. Provisional Application Ser. No. 61/514,216, filed on Aug. 2, 2011 and U.S. Provisional Application Ser. No. 61/521,461 filed on Aug. 9, 2011, the entire contents of which are hereby incorporated by reference.
TECHNICAL FIELD
[0002] This disclosure relates to material separations, including recycling plastics from streams of waste plastics and other materials.
BACKGROUND
[0003] Products made from or incorporating plastic are a part of almost any work place or home environment. Generally, the plastics that are used to create these products are formed from virgin plastic materials. That is, the plastics are produced from petroleum and are not made from existing plastic materials. Once the products have outlived their useful lives, they are generally sent to waste disposal or a recycling plant.
[0004] Recycling plastic has a variety of benefits over creating virgin plastic from petroleum. Generally, less energy is required to manufacture an article from recycled plastic materials derived from post-consumer and post-industrial waste materials and plastic scrap (collectively referred to in this specification as “waste plastic material”), than from the comparable virgin plastic. Recycling plastic materials obviates the need for disposing of the plastic materials or product. Further, less of the earth's limited resources, such as petroleum and polymers, are used to form virgin plastic materials.
[0005] When plastic materials are sent to be recycled, the feed streams rich in plastics may be separated into multiple product and byproduct streams. Generally, the recycling processes can be applied to a variety of plastics-rich streams derived from post-industrial and post-consumer sources. These streams may include, for example, plastics from office automation equipment (printers, computers, copiers, etc.), white goods (refrigerators, washing machines, etc.), consumer electronics (televisions, video cassette recorders, stereos, etc.), automotive shredder residue (the mixed materials remaining after most of the metals have been sorted from shredded automobiles and other metal-rich products “shredded” by metal recyclers), packaging waste, household waste, building waste and industrial molding and extrusion scrap.
[0006] Different types of plastic parts are often processed into shredded plastic-rich streams. The variety of parts can vary from a single type of part from a single manufacturer up to multiple families of part types. Many variations exist, depending on at least the nature of the shredding operation. Plastics from more than one source of durable goods may be included in the mix of materials fed to a plastics recycling plant. This means that a very broad range of plastics may be included in the feed mixture. Some of the prevalent polymer types in the waste plastic materials derived from the recycling of end-of-life durable goods are acrylonitrile-butadiene-styrene (ABS), high impact polystyrene (HIPS), polypropylene (PP), polyethylene (PE) and polycarbonate (PC), but other polymers may also be present.
[0007] Mixtures of recycled plastic materials can sometimes contain residual organic materials such as petroleum derived liquids (e.g. gasoline or diesel fuel, various lubricating oils, brake fluids, windshield washing fluids and other fluid residues) and polychlorinated biphenyls (PCBs). Such contaminants can occur on the surface and interior of the plastic pieces. These organic materials can result in problems with the end products, such as odors, difficulties with melt processing and environmental concerns.
[0008] End users require products meeting their requirements for odor, volatiles emissions and limits for PCBs, but market and legislative forces are encouraging manufacturers to incorporate post-consumer plastics into their products.
[0009] In order to satisfy these requirements, it is important to identify and implement appropriate methods to reduce the content of residual organic materials in plastics recovered from mixtures of post-consumer durable goods.
[0010] In the following, methods are described for the selective reduction of the content of organic contaminants in mixtures of plastic flakes.
SUMMARY
[0011] Methods are described for reducing the content of residual organic substances in mixtures of plastics from durable goods. A process for reducing the content of residual organic substances in mixtures of plastics from durable goods can include separating a feed stream into two or more mixtures of flakes and preforming a cleaning process to remove a portion of one or more of the absorbed organic substances from one or more of the mixtures. Each mixture can contain one or more plastic types and at least one organic substance absorbed into the one or more plastic types. The flakes in the mixtures can have an average particle diameter of less than 10 millimeters.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 —Thermogravimetric analysis of pellets extruded from flake and from flake milled to smaller than 800 microns
DETAILED DESCRIPTION
[0013] This application describes methods for reducing the content of residual organic materials in recycled plastics. In some embodiments, the organics can be removed in a single step using a single system or device. In some embodiments, these methods, systems, and devices can be used in multiple locations in the process.
[0014] Accordingly, in the following, we describe methods, systems and devices for the removal of residual organic materials from plastic flakes.
[0015] A recycling plant for the recovery of plastics from durable goods typically includes a number of process steps. For example, U.S. Pat. No. 7,802,685 describes various sequences of various process steps for the removal of non-plastics and the separation of the various plastic types from streams containing mixtures of plastics from durable goods. The methods, systems, and devices described herein can be used in sequence with or in substitution for the various process steps described in U.S. Pat. No. 7,802,685, which is hereby incorporated by reference. Theses sequences of processes apply to both streams derived from durable goods and to streams of packaging materials, bottles or other mixtures rich in plastics. The process can include the use of one or more size reduction steps performed on a plastics-rich mixture from durable goods. The feed mixture can be shredded material from which some metal has been removed. The durable goods themselves can be size reduced two or more times prior to extrusion.
[0016] A mixture rich in plastic material can be processed through size reduction equipment one or more times. The size reduction steps may include rotary grinding, a hammermill, shredding, granulation, or any other size reduction processes known by those skilled in the art.
[0017] The mixture rich in plastic flakes can be processed through one or more density separation processes. These density separation processes can occur in water at a density cut point of 1.0, or in aqueous salt solutions or aqueous suspensions of solid particles with density cut points greater than 1.0, for example as described in U.S. Pat. No. 7,802,685. The plastic-rich mixture may also contain rubber, wood and other non-plastics. The flakes can range in size from around 1 mm to around 50 mm, although the process works best when the particles are between about 2 mm and about 10 mm. Size reduction, in some embodiments, can precede the density separation processes. In other embodiments, size reduction can also follow the density separation process to create a final flake size between about 2 mm and about 10 mm.
[0018] The density separations may be carried out in any of the types of density separation equipment. For example, hydrocyclones can efficiently separate materials of different densities based on the high centrifugal forces present in the liquid slurry swirling inside a cyclone.
[0019] An appropriate rinsing step can be used after elevated density separations. The rinsing step may contain, for example, small water jets that are designed to rinse the majority of the salt solution or suspended particles off the materials in the plastic-rich flake mixture.
[0020] The mixtures can also be dried in a controlled manner after the density separations. Flake materials tend to adhere to surfaces if they are overly damp or wet, and this can result in poor separation performance for some of the processes described herein.
[0021] Two product streams can be recovered from each density separation process. One or both of these product streams may be further processed to recover high purity plastics. Each product from the density separation often contains two or more types of plastics and small amounts of non-plastics. Such a product therefore requires further purification steps, as described in U.S. Pat. No. 7,802,685. These purification steps typically include processes relying on a narrow surface to mass distribution which are preceded by surface to mass control operations.
[0022] After purification of the plastics by type (and also sometimes grade), the material can be melt compounded. The flake to be melt compounded can be blended prior to extrusion in order to improve product uniformity. The product from melt compounding can be pellets, sheet or other profile shape (e.g. a board).
[0023] Plastics recovered from mixtures of durable goods can contain residual organic materials that should ideally be removed from the flakes prior to their formation into pellets or molded part. Such residual organics can include, for example, residual fuels from automobile fuel tanks, residue from radiators, residue from windshield wiper fluid containers, adhesives, or polychlorinated biphenyls (PCBs).
[0024] Automobile fuel tanks are often made of plastics and can contain layers of high density polyethylene (HDPE) along with barrier materials such as ethylene vinyl alcohol (EVOH, which is a copolymer containing ethylene and vinyl alcohol repeat units), polyamides or other barrier materials, and adhesives to attach the barrier material to the HDPE. The plastics from fuel tanks can contain gasoline and diesel fuels on the plastic surface as well as gasoline and diesel fuels that have absorbed into the plastic over the life of the automobile.
[0025] Plastics from durable goods, especially those derived from streams of end-of-life vehicles (ELV), can contain PCBs at concentrations higher than allowed by some customers or by the legislation of some countries. PCBs can be found in these streams because automobile shredders sometimes process electrical transformers or other equipment that can contain small amounts of PCBs.
[0026] Other undesirable organic materials may also be present in the recovered plastics. For example, aldehydes, ketones or carboxylic acids produced by oxidation of additives or residual monomers in the plastic can result in undesirable odors in the end product. Because of the long lifetime and multiple heat histories of the recovered plastic pieces, the amounts of these compounds and the resulting odors can be much stronger than found in virgin plastics.
[0027] In addition to odors or environmental concerns about organic contaminant molecules in recovered plastics, the contaminants can also cause difficulties during the extrusion step itself. During the extrusion of HDPE recovered from ELVs, for example, residual fuels in the HDPE fuel tanks can vaporize resulting in bubble formation in pellets or other extrusion products. These bubbles result in large and low density pellets, and end products manufactured from these pellets (e.g. by injection molding or blow molding) can have a poor surface appearance and can contain voids that result in mechanical failures.
[0028] The processes described herein can be used to reduce the levels of organic contaminants in the recovered plastic flakes. Such methods include heating the plastics to volatilize the organic contaminants, extraction of organic contaminants with solvents (including supercritical fluids), cleaning the organic contaminants from the polymer surface using aqueous surfactant solutions, cleaning the organic contaminants from the polymer surface using commercial cleaning equipment with or without surfactants, or heating the organic contaminants using microwaves or other radiation that preferentially heats the organic contaminants compared with the plastic itself.
[0029] Methods of heating the plastic can include heating the plastic flakes under vacuum or with a continuous flow of air or nitrogen to ensure that volatiles are efficiently removed. Heating of the material can be in a sealed container (if under vacuum) in batches, in a continuous operation where the flakes are conveyed in a blending operation using hot air to convey the flakes, or in a fluidized bed with hot air.
[0030] Processes to remove residual organic contaminants can be improved by increasing the surface area to mass ratio of the plastic material. The smallest size plastic flakes just prior to extrusion (typically between about 2 mm and about 10 mm) have a greater surface to mass ratio than larger sized plastic flakes directly after shredding.
[0031] Methods such as milling the flakes to under about 1 mm can greatly increase the surface area as well as provide heating of the material. Such processes should therefore be considered as a method to remove residual organics from plastics recovered from durable goods. Example 1 provides an example of such a process.
[0032] In addition to its utility in driving off volatiles, milling can liberate small fragments of metal, glass or sand that have embedded in the plastic flakes. These liberated fragments can then be separated from the plastic. Milling may also benefit the recycling process by a large increase in surface to mass which may enable more efficient purification in an electrostatic separator, high pressure dense medium, and under the force of a magnet. Milling can also create stratification of different materials in different size ranges. Low density polyethylene (LDPE) will generally remain as larger particles after milling compared with HDPE. HIPS and ABS can become much smaller than LDPE or HDPE because they are more brittle.
[0033] Milling can also facilitate the removal of EVOH, polyamides or other barrier materials, and adhesives that attach the barrier material to the HDPE in fuel tanks. These barrier layers and adhesives can cause problems for the product quality of the HDPE after extrusion if they are not separated from the HDPE. Milling can liberate a portion of the HDPE from the barrier layers and adhesives, though, and the milled materials (smaller than about 1 mm) can be separated from each other using methods such as density separation or electrostatic separation.
[0034] Density separation may be useful for the separation of HDPE from the barrier materials because the specific gravity of HDPE is well below 1.0 while the specific gravities of EVOH (1.1 to 1.2, depending on the ethylene content) and polyamides (approximately 1.14 for PA66 or PA6) are well above 1.0. Density separation in systems capable of processing small particles may therefore be suitable for separating HDPE from the barrier layers, with HDPE floating in water and pieces rich in the barrier layers sinking in water.
[0035] Electrostatic may also be useful for the separation of HDPE from the barrier materials. Polyamides tend to charge positive relative to HDPE, and EVOH should also charge quite differently from HDPE, so it should be possible to easily separate these materials. This is especially true since the surface area per mass of the milled particles is so large.
[0036] The removal of organic contaminants from recovered plastics preferentially occurs after the plastic type has been separated from other plastics. The reasons for this are that 1) each type of plastic can contain different levels and types of problematic organic contaminants and 2) each type of plastic has different thermal or chemical properties that can affect the selection of the method and process parameters for the removal of organic contaminants. In other embodiments, the organic contaminants are removed prior to the full separation of different plastic types or on mixtures of two or more plastic types
[0037] Each type of plastic recovered from mixtures of durable goods can contain a different assortment of residual organic contaminants. Contaminant residues are preferentially found in some plastics prior to shredding, for example, whereas other plastic types contain fewer or different contaminant types. Processes and methods used to remove organic contaminants can be quite expensive, so it is desirable for the processes to be employed primarily for plastics that require the removal of contaminants. Some plastics may not need such processing, whereas others may need two or more different types of processing to remove different types of contaminants. It is therefore often better to employ the contaminant removal process after plastics have been separated rather than on the entire mixture of plastics.
[0038] Processes to remove organic contaminants can sometimes be carried out at high temperatures in order to increase the volatility of the residual organic contaminants. In some embodiments, flakes or pellets are dried out at temperatures below the melting temperature (for semicrystalline polymers) or glass transition temperature (for amorphous polymers) of the plastic flakes or pellets in order to avoid agglomeration of the flakes or pellets. The maximum temperature of such processes can be limited to the lowest glass transition or melting temperature of flakes in a mixture of several plastic types, so it is desirable to perform such operations after the separation of plastic flakes into individual plastic types. After such a separation, some streams can be heated to temperatures higher than others.
[0039] The chemical nature of different plastics also allows for different behaviors of the plastic under the influence of solvents. Solvents can be used to dissolve the organic contaminants to extract them from the plastics, but the flake mixture will be difficult or impossible to convey to downstream processes if the solvent dissolves any plastic flakes or pellets. Separating the plastic flakes into pure streams of each plastic type can enable the use of solvents selected for their ability to dissolve the contaminants without greatly affecting the plastic itself.
[0040] The chemical nature of the surfaces of the different plastics means that different levels of organic contaminants may be present on the surfaces of different plastic types. Solvents or aqueous surfactant solutions that can solubilize organic contaminants on the plastic surface may be employed on streams of plastic flakes where higher levels of the surface contaminants exist.
[0041] Solvents that can be useful for removing contaminants can include, but are not limited to, biodegradable bio-derived solvents such as alkyl lactates (e.g. ethyl lactate), common solvents such as hexane, acetone, tetrahydrofuran, xylene, liquid or supercritical CO 2 , or combinations of solvents used at the same time or sequentially. The one or more solvents selected should dissolve and remove the contaminant without dissolving the plastic.
[0042] Surfactants that can be useful for removing contaminants can include, but are not limited to, certain grades of Triton™ RW series alkylamine ethoxylates (Dow Chemical Company, Midland, Mich., USA), nonionic surfactants such as some of the Tergitol™ alcohol ethoxylates (Dow Chemical Company, Midland, Mich., USA), and others. The surfactant should be selected to best remove the organic contaminants of interest. The chemical nature of different plastics also allows for different behaviors of the plastic under the influence of electromagnetic radiation. Microwaves or other electromagnetic radiation may preferentially excite residual organic molecules, heating the residual organic molecules instead of the polymer itself. If several polymer types are present, though, the radiation is likely to interact with some of the polymer types. Interaction of radiation such as microwaves can heat the polymer to temperatures above their melting temperature (for semicrystalline polymers) or glass transition temperature (for amorphous polymers). Separating the plastic flakes into pure streams of each plastic type can enable the use of electromagnetic wavelengths selected for their ability to heat up the contaminants without heating the plastic itself.
[0043] Some of the organic contaminants are present at higher concentrations near the polymer surface, so it is possible to reduce their concentrations by intensive washing. The washing may be carried out in water alone, in water containing surfactants, or in solvents capable of dissolving the organic contaminants found on the plastic surface. The washing may be accomplished by mechanical agitation in equipment such as screw conveyors or rotating drums, in centrifuges, or in systems using ultrasonic cleaning
[0044] Having several process lines to remove organic contaminants for multiple types of plastics might be more costly than such a process for a larger volume of mixed plastics, though, so it may be possible to perform a cleaning step on particular intermediate flake mixtures. This is especially true if the mixtures have similar thermal or chemical properties and if they contain similar organic contaminants. It might make sense to process mixtures of ABS and HIPS in a thermal drying process, for example, since they have similar glass transition temperatures.
[0045] Organic contaminants can also be removed during the extrusion step by the use of vacuum devolatilization equipment commonly used in the plastics industry. The molten plastic in a section of the extruder screw with a low pressure is made into a thin film exposed to a vacuum. The vacuum extracts residual moisture along with any organic contaminants of sufficient volatility at the melt temperature in this zone of the extruder. Since this melt temperature is well above the melting temperature (for semicrystalline polymers) or glass transition temperature (for amorphous polymers) of the plastic, this provides a good opportunity to reduce the concentration of semi-volatile organics from the plastic.
[0046] Other equipment designed to remove monomers to very low levels, such as wipe film evaporators, can also be employed to remove as much residual organic contamination as possible from the molten plastic during the extrusion step.
[0047] After the extrusion step and formation of pellets, residual organic materials can be further removed from the plastic by operations such as thermal treatment, treatment with microwave or other radiation to preferentially heat and remove the residual organics, or extraction of the organics with solvents (especially supercritical fluids).
[0048] The various processes to reduce the levels of residual organic contaminants in plastics recovered from durable goods can be accomplished in one or more steps. Because a single process step is unlikely to remove all of the contaminants, multiple steps of the same process or combinations of processes can be used until marketing or environmental targets are achieved.
[0049] Organic contaminants can be removed in at least three steps using the following sequence of processes. In the first step, a solvent is added to dissolve the organic contaminant. In the second step, most, but not all of the solvent and organic contaminant are removed from the polymer. The second step can include screening to drain off the solvent, or drying in a device such as a spin drier. The amount of solvent remaining is greater than 0.1% by weight of the mixture of flakes. In some embodiments, the amount of solvent remaining is greater than 1% by weight of the mixture of flakes. In other embodiments, the amount of solvent remaining is greater than 2% by weight of the mixture of flakes. In the this step, the product flakes with some residual solvent may then be melt compounded with vacuum devolatilization to remove the solvent and the organic contaminant. The presence of the solvent in the melt can improve the removal of the organic contaminant from the melt compared with vacuum devolatilization in the absence of a solvent.
[0050] Organic contaminants can be removed in at least three steps using the following sequence of processes. In the first step, an aqueous surfactant solution is added to remove the organic contaminant from the polymer surface. In the second step, most, but not all of the aqueous surfactant solution and organic contaminant are removed from the polymer. The second step can include screening to drain off the aqueous solution, or drying in a device such as a spin drier. The amount of aqueous solution remaining is greater than 0.1% by weight of the mixture of flakes. In some embodiments, the amount of aqueous solution remaining is greater than 1% by weight of the mixture of flakes. In other embodiments, the amount of aqueous solution remaining is greater than 2% by weight of the mixture of flakes. In the third step, the flake product with some residual aqueous surfactant may then be melt compounded with vacuum devolatilization to remove the surfactant, water vapor and the organic contaminant. The presence of the surfactant and water vapor in the melt can improve the removal of the organic contaminant from the melt compared with vacuum devolatilization in the absence of these components.
[0051] In cases where odors cannot be completely removed to the desired end point, it is possible to melt compound into the plastic activated carbon or molecular sieves to reduce the odor of the plastic product. The organic contaminant still remains in the plastic, but it is trapped such that it cannot be easily detected during the normal use of the plastic.
[0052] The following examples illustrate various methods for reducing the amount of organic contaminants in recovered plastics.
EXAMPLES
[0053] The following examples demonstrate the effectiveness of methods for reducing the organics content of plastic-rich mixtures derived from durable goods.
Example 1
Milling of HDPE Flakes to Reduce the Level of Volatiles
[0054] A mixture of primarily HDPE flakes from a source of ELVs was milled to a top size less than 800 microns. The temperature of the powdered material during the milling process reached approximately 85-95° C. The powdered material was then extruded and pelletized.
[0055] FIG. 1 shows results from the thermogravimetric analysis (TGA) of these pellets compared with pellets produced from flakes that had not undergone the milling process. At temperatures near the extrusion temperature (200-230° C.), the pellets produced from the milled flakes have less than half of the volatiles of pellets extruded from flakes.
Example 2
Levels of PCBs in Different Plastics
[0056] Three types of flake products were recovered from a single European automobile recycler's shredder residue (ABS, HIPS and a blend of PP and HDPE). After extrusion, we determined that the levels of PCBs in the products were different for each plastic type, as shown in Table 2.1.
[0057] If the maximum allowable concentration of PCBs in plastic products is 2 ppm, then, at least for this particular example, only the PP/HDPE blend would need to be processed using a method suitable for removing the PCBs. The ABS and HIPS products would not require such processing.
[0000]
TABLE 2.1
Levels of PCBs in plastics recovered from shredded ELVs
Plastic type
PCB concentration (ppm)
ABS
0.2
HIPS
0.1
PP/HDPE blend
7.2
|
A process for reducing the content of residual organic substances in mixtures of plastics from durable goods can include separating a feed stream into two or more mixtures of flakes and preforming a cleaning process to remove a portion of one or more of the absorbed organic substances from one or more of the mixtures. Each mixture can contain one or more plastic types and at least one organic substance absorbed into the one or more plastic types. The flakes in the mixtures can have an average particle diameter of less than 10 millimeters.
| 1
|
CROSS REFERENCE TO RELATED APPLICATIONS AND CLAIM OF PRIORITY
This application is a divisional of application Ser. No. 13/357,052, filed on Jan. 24, 2011, which is a continuation of application Ser. No. 13/069,925 filed Mar. 23, 2011 each of which is incorporated herein in its entirety.
FIELD OF THE INVENTION
The present invention relates to machines used to separate particulate materials or mixed recyclable materials into difference fractions, and more particularly, to a disc assembly for a disc screen that allows its discs to be more easily removed and replaced.
RELATED ART
Disc screens have long been used to separate particulate materials such as wood chips into difference fractions, according to size. More recently disc screens have been used to separate or classify mixed recyclable materials into respective streams of similar materials such as broken glass, containers, mixed paper and newspaper.
A disc screen typically includes a frame in which a plurality of rotatable shafts are mounted in parallel relationship. A plurality of discs are mounted on each shaft and a chain drive rotates the shafts in the same direction. The discs on one shaft interleave with the discs on each adjacent shaft to form screen openings between the peripheral edges of the discs. The size of the openings determines the dimension (and thus the type) of material that will fall through the screen. Rotation of the discs, which have an irregular outer contour, agitates the mixed recyclable materials to enhance classification. The rotating discs also propel the larger articles which are too big to fall between the discs across the screen. The general flow direction extends from an input area where the stream of material pours onto the disc screen to an output where the larger articles pour off of the disc screen. The smaller articles fall between the discs onto another disc screen or a conveyor, or into a collection bin.
The discs of a disc screen normally have a central opening or bore that allows them to be slid over the end of a shaft which may have a round or square cross-section. See for example U.S. Pat. No. 4,836,388 of Bielagus granted Jun. 6, 1989. Over time, the discs wear out and must be replaced. It is not practical to re-surface or repair damaged or worn discs without removing them from the shafts of the disc screen. However, it is tedious to dismount the ends of the shafts of a disc screen from their respective bearings so that the old discs can be removed and replaced by sliding the discs off the ends of the shafts. Moreover, if only single disc is worn out or broken, it is usually necessary to remove several discs before the damaged or broken disc can be slid off the shaft. In order to alleviate these problems, a split disc was developed by CP Manufacturing, Inc. of National City, Calif. See U.S. Pat. No 6,318,560 of Robert M. Davis granted Nov. 20, 2001. The split disc is comprised of two identical halves which are assembled around a shaft and tightly held together by a pair of bolt assemblies which clamp the disc to the shaft. Each disc half is made of an outer rubber portion which is stiffened with a rigid internal metal frame embedded inside the rubber portion.
While the split disc design is beneficial in removing particular discs without disturbing other discs on the shaft, typical disc screens may employ 600 or more discs. With so many discs, the process of replacing one disc at a time may still be too-time consuming. In order to alleviate these problems, multi-disc assemblies have been developed as demonstrated in U.S. Pat. No. 7,261,209 to Duncan, et. al. The multi-disc assemblies compfise multiple discs that can be replaced at the same time, reducing the amount of effort in servicing a disc screen. However, the multi-disc assembly of Duncan involves a complex mounting arrangement involving a securing hub and mounting plate between the multi-disc assembly and the shaft. Thus, it would be desirable to provide a multi-disc assembly that is even more convenient to remove and install.
SUMMARY
In accordance with an embodiment of the present invention, a multi-disc assembly for releasable attachment to the shaft of a disc screen is provided. The multi-disc assembly includes a multi-disc hub of elastomeric material including multiple discs configured for use in the disc screen. The hub has a through bore configured for direct engagement over a shaft of the disc screen. The hub has a longitudinal separation plane which splits the hub into two separate multi-disc hub halves. The longitudinal separation plane defines first and second radial end faces in each hub half which extend along opposite sides of the through bore and oppose corresponding first and second radial end faces in the other hub half. Each hub half has at least one first connecting portion extending up to the first radial end face and at least one second connecting portion extending up to the second radial end face. The multi-disc assembly also includes a first rigid insert between the opposing first radial end faces and a second rigid insert between the opposing second radial end faces. The multi-disc assembly also includes at least two fastener devices configured to releasably secure the hub halves together around the shaft. The fastener devices include a first fastener device configured to extend through the first connecting portions of the hub halves and the first rigid insert and a second fastener device configured to extend through the second connecting portions of the hub halves and the second rigid insert.
Other features and advantages of the present invention will become more readily apparent to those of ordinary skill in the art after reviewing the following detailed description and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an exploded perspective view of a multi-disc assembly and a shaft of a disc screen;
FIG. 2 is a perspective view of a multi-disc hub half and rigid inserts;
FIG. 3 is perspective view of a multi-disc assembly;
FIG. 4 is a top plan view of a multi-disc hub;
FIG. 5 is a side elevation view of one multi-disc hub half;
FIG. 6 is a cross sectional view of the hub half on the lines 6 - 6 of FIG. 5 ;
FIG. 7A is a bottom plan view of a multi-disc hub half;
FIG. 7B is a cross-sectional view of the hub half on the lines 7 B- 7 B of FIG. 7A ;
FIG. 7C is a cross-sectional view of the hub half on the lines 7 c - 7 c of FIG. 7A ; and
FIG. 8 is a top plan view of a rigid insert.
DETAILED DESCRIPTION
FIGS. 1 to 8 illustrate one embodiment of a multi-disc assembly 10 . In FIG. 1 , a multi-disc assembly 10 is positioned about a hollow rectangular shaft 24 with radial corners. While shown in an exploded view in FIG. 1 , the multi-disc assembly 10 is configured for direct engagement with the shaft 24 when assembled as shown in FIG. 3 . Only a portion of the shaft 24 is shown in FIG. 1 . The shaft would typically be long enough to support more multi-disc assemblies. The ends of the shaft 24 are supported by bearing assemblies (not illustrated) of a disc screen (not illustrated) such as those disclosed in U.S. Pat. No. 6,250,478 of Robert M. Davis granted Jun. 26, 2001 and U.S. Pat. No. 6,648,145 of Robert M. Davis et al. granted Nov. 18, 2003, and co-pending U.S. patent application Ser. No. 10/044,222 of Robert M. Davis filed Nov. 21, 2005, the entire disclosures of which are incorporated herein by reference.
The multi-disc assembly 10 is basically two opposing multi-disc hub halves 12 , a pair of rigid inserts 32 located between the hub halves 12 , and fasteners 36 which secure the hub halves and inserts around the shaft 24 , as described in more detail below. The hub halves 12 are positioned on opposing sides of the shaft 24 . Each hub half 12 has a plurality of integrally formed discs 18 with spacers 20 positioned between adjacent pairs of the discs 18 . The discs 18 are specially configured for use in classifying mixed recyclable materials. In particular, the discs 18 are configured for engaging materials to be classified (not illustrated) and propelling the materials in a conveying direction when the multi-disc assembly 10 is rotated. For example, if the multi-disc assembly 10 is rotated clock-wise in FIG. 1 the materials would be propelled to the right. A through bore 26 in multi-disc assembly 10 is configured for direct engagement with the shaft 24 . In one embodiment, the through bore 26 is rectangular with radial corners. The through bore 26 interfaces with the shaft 24 in order to maintain the multi-disc assembly 10 in a fixed relationship with respect to the shaft 24 . In alternative embodiments, multi-disc assemblies may be provided with through bores of different shapes, such as circular or other shapes for engaging around shafts of corresponding shape.
A longitudinal separation plane 16 (see FIG. 3 ) divides the two hub halves 12 . The longitudinal separation plane defines radial end faces 34 of the hub halves 12 . The radial end faces 34 extend on opposites sides of the through bore 26 on each hub half 12 . The radial end faces 34 of one hub half 12 oppose the radial end faces 34 in the opposing hub half 12 .
Connecting portions 14 extend up to the radial end faces 34 of the hub halves 12 as best illustrated in FIGS. 2 , 3 , and 7 B. In one embodiment, the connecting portions 14 are formed in on or more of the spacers 20 . The connecting portions 14 include bores 28 . The bores 28 in the corresponding connecting portions 14 of opposing hub halves 12 are aligned. Fastener devices 36 releasably secure opposing hub halves 12 about the shaft 24 . The fastener devices 36 extend through the bores 28 in the connecting portions 14 of opposing hub halves 12 . In one embodiment, the radial end faces 34 each have an elongate recess 38 .
Rigid inserts 32 are shown in FIGS. 2 and 8 . The rigid inserts 32 may be made of metal, such as cast Aluminum and have holes 30 configured for alignment with the bores 28 in the connecting portions 14 . Rigid inserts 32 include bores 30 . In one embodiment, the rigid inserts 32 are configured to interface with the radial end faces 34 . In another embodiment, the rigid inserts 32 are configured to be received in elongate recesses 38 in the opposing radial end faces 34 . In the illustrated embodiment, the rigid inserts 32 are embedded in the body of the hub half 12 proximate the radial end faces 34 , as illustrated in FIGS. 6 and 7A . The holes 30 align with the bores 28 in the connecting pieces 14 of the hub halves 12 . Each securing device 36 extends through the bores 28 in the connecting portions 14 and through the aligned hole 30 of the respective rigid insert 32 . In one embodiment, the securing device is a stainless steel bolt or threaded fastener that extends through the bore in the bores 28 in the connection portions 14 and the bore 30 through the rigid insert 32 . The male end is screwed into a female threaded nut. Other forms of securing means can be utilized, such as ancillary collars, clamps, brackets and/or sleeves for indirectly attaching the hub halves 12 in releasable fashion.
Referring to FIG. 3 , a multi-disc assembly 18 is shown. Longitudinal separation plane 16 separates the two hub halves 12 . Each of the discs 18 has a major and a minor axis. The major axes of adjacent discs 18 may be out of alignment by a predetermined angle. In one embodiment, the major axes of each pair of adjacent discs 18 on the multi-disc assembly 18 is out of alignment by approximately 90 degrees. Other angles may also be used While five discs 18 are illustrated, often multi-disc hubs may have a greater or smaller number of integral discs. In one embodiment, the spacers 20 are circular and have a diameter approximately equal to the size of the minor axis of the discs 18 . The connecting portions 14 are formed as flanges in portions of the spacers 20 .
In one embodiment, the hub half 12 is molded from an elastomeric material. Each disc 18 has an inner surface 40 that defines a portion of an interior cavity 44 as shown in FIGS. 1 , 3 , and 5 . The interior cavity 44 may be larger in a radial dimension than the through bore 26 in some areas, with inner surfaces 40 of at least some discs fitting closely about the shaft. Accordingly, the hub half 12 may contact the shaft 24 along less than entire length of the hub half 12 . In one example, the hub half 12 contacts the shaft 24 in two areas near the end portions 13 of the hub half 12 . Advantageously, this allows a sturdy connection between the hub half 12 and the shaft 24 while also allowing the hub half 12 to be formed of a smaller amount of material. In one embodiment, the hub half 12 is formed of an elastomeric material, i.e. a rubber-like synthetic polymer such as silicone rubber or polyurethane
FIG. 7A is a bottom view of one hub half 12 which is broken away to reveal the embedded rigid insert 32 adjacent one radial end face 34 . In this embodiment, a rigid insert 32 is positioned within the hub half 12 parallel with the radial end face 34 . The holes 30 through the rigid insert 32 are aligned with the bores 28 through the two connecting portions 14 . As shown in FIG. 7 b the spacer 20 has an inner surface 46 that defines part of interior cavity 44 . Thus, hub half 12 has rigid inserts embedded adjacent each radial end face 34 . The opposing hub half may have similarly located rigid inserts or inserts may be located in only one hub half
The hub halves 12 may be integrally molded as one unitary piece of elastomeric material in a mold (not illustrated), then separated into two halves along the separation plane 18 . In one embodiment, the molding occurs after the rigid inserts 32 have been positioned within the mold. The use of synthetic rubber, polyurethane or other similar durable elastomeric materials ensures that the discs 18 will have high friction impacting surfaces to maximize their propelling. The use of elastomeric material also minimizes the likelihood that glass containers be broken.
The multi-disc assembly 10 is easier to dismount and mount than prior multi-disc assemblies because it attaches directly to the shaft 24 without any intervening securing hubs or mounting plates.
While I have described alternate embodiments of my invention, variations and modifications will occur to those skilled in the art. For example, the through bore need not be rectangular, but could be circular, triangular, oval, etc. to accommodate shafts having matching outer cross-sections. The multi-disc assembly could also be made entirely of metal for the purpose of crushing glass. Therefore, the protection afforded my invention should only be limited in accordance with the scope of the following claims.
|
A multi-disc assembly for releasable attachment to the shaft of a disc screen is provided. The multi-disc assembly includes a multi-disc hub of elastomeric material including multiple discs configured for use in the disc screen. The hub has a through bore configured for direct engagement over a shaft of the disc screen. A disc screen comprising the multi-disc assembly and method of using the multi-disc assembly are also provided.
| 8
|
This application is a continuation of application Ser. No. 07/386,912, filed Jul. 27, 1989, now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to preparing composites.
Various processes exist for dispersing solid fillers (e.g., fibrous or particulate fillers) in solid or liquid matrices. These processes include compounding the filler-matrix mixture using blade mixers, high shear Waring-type blenders, roll mills, dough mixers, or internal Brabender-type mixers.
Carbon fibrils are carbon filaments having diameters less than 500 nanometers. Examples of particular carbon fibrils and methods for preparing them are described in Snyder et al., U.S. Ser. No. 149,573 ("Carbon Fibrils") filed Jan. 28, 1988, now abandoned; Tennent, U.S. Pat. No. 4,663,230 ("Carbon Fibrils Method for Producing Same and Compositions Containing Same"); Tennent et al., U.S. Ser. No. 871,676 filed Jun. 6, 1986 ("Novel Carbon Fibrils, Method for Producing Same and Compositions Containing Same"), now U.S. Pat. No. 5,165,909; Tennent et al., U.S. Ser. No. 871,675 filed Jun. 6, 1986 ("Novel Carbon Fibrils, Method for Producing Same and Encapsulated Catalyst"), now abandoned; Mandeville et al., U.S. Ser. No. 285,817 filed Dec. 16, 1988 ("Fibrils"), now abandoned; and McCarthy et al., U.S. Ser. No. 351,967 filed May 15, 1989 ("Surface Treatment of Carbon Microfibers"), now abandoned, all of which are assigned to the same assignee as the present application and are hereby incorporated by reference in their entirety.
SUMMARY OF THE INVENTION
In general, the invention features a compounding process for preparing a composite that includes the steps of introducing one or more fillers and a matrix material into a stirred ball mill, and subjecting the fillers and matrix material to a combination of shear and impact forces under reaction conditions including reaction time sufficient to reduce the size of agglomerates formed by the fillers to a value below a pre-determined value to disperse the fillers throughout the matrix material.
In preferred embodiments, the pre-determined value of the agglomerate size is no greater than 1000 times the size of the filler, more preferably no greater than 100 times, even more preferably no greater than 10 times. One or more of the characteristic dimensions of the filler (which is a measure of its size) preferably is less than 1 μm, more preferably less than 0.1 μm.
A viscosity modifier (i.e. a material that modifies the intrinsic viscosity of the matrix-filler mix to facilitate dispersion) is preferably added to the stirred ball mill. Preferred viscosity modifiers include both materials that are removed following the dispersion step, e.g., solvents, and materials that are retained following the dispersion step; an example of the latter type of viscosity modifier is a reactive diluent that chemically reacts with the matrix material. In additional preferred embodiments, one or more milling media (i.e. a particulate material that facilitates dispersion by supplying additional impact force) is added to the stirred ball mill.
Preferred fillers include whiskers (i.e. single crystal fibers), discontinuous fibers, particulate fillers, and carbon fibrils. The fibrils preferably are tubes having graphitic layers that are substantially parallel to the fibril axis. One aspect of substantial parallelism is that the projection of the graphite layers on the fibril axis extends for a relatively long distance in terms of the external diameter of the fibril (e.g., at least two fibril diameters, preferably at least five diameters), as described in Snyder et al., U.S. Ser. No. 149 573, now abandoned. These fibrils preferably are also free of a continuous thermal carbon overcoat (i.e. pyrolytically deposited carbon resulting from thermal cracking of the gas feed used to prepare the fibrils). The fibrils preferably have diameters between 3.5 and 75 nanometers, inclusive, and a length to diameter ratio of at least five. Also preferred are fibrils having this morphology in which the outer surface of the graphitic layers is bonded to a plurality of oxygen-containing groups (e.g., a carbonyl, carboxylic acid, carboxylic acid ester, epoxy, vinyl ester, hydroxy, alkoxy, isocyanate, or amide group), or derivatives thereof (e.g., a sulfhydryl, amino, or imino group).
Preferred matrix materials include metal powder, ceramic powder (e.g., glass powder), thermoplastic resins, thermoset resins, and elastomers, and matrix materials which are in the form of liquids. Preferred thermoplastic resins include thermoplastic polyester (e.g., polyethylene terephthalate), polyurethane, polyether ether ketone, polyether sulfone, polyether imide, polyamide (e.g., nylon), and polyurea resins. Preferred thermoset resins include phenolic, epoxy, thermosetting polyurethane, thermosetting polyester (e.g., alkyd), polyimide, bismaleimide, polycyclopentadiene, and vinylacrylimide (such as the Arimix resins commercially available from Ashland Chemical Co., Columbus, Ohio). Preferred elastomers include styrene-butadiene rubber, natural rubber, ethylene-propylene-diene monomer (EPDM) rubber, silicone rubber, polybutadiene (both cis and trans 1,4 and 1,2-polybutadiene), polyisoprene, neoprene, chloroprene, fluoroelastomers (e.g., fluorinated polyethylene), and urethane elastomers.
When the matrix material is a thermoplastic resin, the compounding process preferably includes cooling the contents of the stirred ball mill to a temperature at which the matrix material becomes brittle prior to the dispersion step, and maintaining that temperature throughout the dispersion step.
The invention also features a composite prepared according to the above-described process.
The invention creates composites in which the filler is substantially uniformly dispersed throughout the matrix material, even when the mean filler diameter is on the order of a micron or less, leading to improved composite properties, e.g., electrical, optical, mechanical, and magnetic properties. The degree of uniformity (as measured by the size of the filler agglomerates) can be tailored to the particular application for which the composite is intended by adjusting the milling time.
The invention also makes it possible to co-disperse a variety of fillers having different diameters and/or shapes in a matrix. Moreover, the invention obviates the need for pre-treating the filler surface or adding chemical dispersants to achieve good filler dispersion throughout the matrix.
Other features and advantages will be apparent from the following description of the preferred embodiments thereof, and from the claims.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Composites are preferably prepared by introducing the matrix material and one or more fillers into a stirred ball mill of the type conventionally used for powder comminution. In the mill, these materials are subjected to both shearing forces due to the stirring action of a mechanical rotor and impact forces due to particulate milling media of the type conventionally used for powder comminution which are added to the mill during stirring; these particulates are removed once the milling operation is over. In the case of metal and ceramic matrices, however, it is not necessary to add separate milling media because the matrices themselves (which are added in the form of powders) are capable of supplying the impact force.
A viscosity modifier is added to viscous matrix-filler mixes to lower the intrinsic viscosity to a value sufficiently low to permit easy milling. Viscosity modifiers are particularly useful when the matrix material is a high molecular weight thermoplastic or a partially cured thermoset resin. Examples of suitable viscosity modifiers include solvents such as water, toluene, acetone, methyl ethyl ketone (MEK), isopropanol, or mineral oil. Following the milling operation the solvent is removed, e.g., by vacuum drying, steam stripping, or freeze drying. The viscosity modifier may also be a material which becomes part of the matrix or filler once milling is complete. Examples of such modifiers include monomers called reactive diluents (e.g., styrene, triallyl cyanurate, diallycyanurate, multi-functional acrylates, and divinylbenzene) which chemically react with the matrix material during milling. The viscosity modifier may also be built into the matrix. In such cases, the viscosity modifier may be present during manufacture of the matrix, e.g., in solutions of solution-polymerized SBR and solutions of thermoplastics obtained from the polymerization reaction.
Suitable fillers include discontinuous fibers (e.g., chopped glass or carbon fibers), whiskers (e.g., carbon or silicon carbide whiskers), particulate fillers (e.g., silica or carbon black), carbon fibrils, or a combination of any or all of these fillers. Preferably, the mean filler diameter (i.e. the diameter of the individual grains or fibers making up the filler) is on the order of a micron or less. Preferred fibrils have small diameters (preferably between 3.5 and 75 nanometers), graphitic layers that are substantially parallel to the fibril axis, and are substantially free of a continuous thermal carbon overcoat, as described in Tennent, U.S. Pat. No. 4,663,230; Tennent et al.; U.S. Ser. No. 871,675; Tennent et al., U.S. Ser. No. 871,676; Snyder et al., now U.S. Pat. No. 5,165,909, U.S. Ser. No. 149,573; and Mandeville et al., U.S. Ser. No. 285,817, now abandoned. These fibrils are prepared as described in the aforementioned patent and patent applications. The fibrils may also be treated to introduce oxygen-containing functional groups onto the fibril surface, as described in McCarthy et al., U.S. Ser. No. 351,967, now abandoned.
Preferred matrix materials include metal and ceramic (e.g., glass) powders, and organic matrices, e.g., thermoplastic, thermoset, and elastomer resins, as described in the Summary of the Invention, above. The preparation of carbon fibril-filled elastomers is described in Barber et al., U.S. Ser. No. 859,611 entitled "Fibril-Filled Elastomers", now abandoned, filed concurrently with the present application and assigned to the same assignee as the present application, and is hereby incorporated by reference in its entirety. In the case of thermoplastic resins, the composites are preferably prepared by introducing the resin and fillers into the stirred ball mill, and then adding dry ice to the mill to cool the contents to a temperature at or near which the resin is transformed into a brittle solid. In this form, the resin is more easily broken up during milling, leading to more uniform dispersions. The dry ice evaporates during milling so that none is retained in the final dispersion.
The milling time determines the final size of the filler agglomerates and thus the degree of dispersion, which in turn is a function of the end use for which the composite is targeted. For example, electrical applications, which rely on interparticle contact to establish a conductive network, can tolerate larger agglomerates than mechanical applications, where the agglomerates act as strength-lowering defects.
A composite in which carbon fibrils (prepared as described above) were dispersed in a styrene butadiene rubber (SBR) matrix was prepared using the above-described stirred ball milling procedure and its properties compared to a fibril-reinforced SBR matrix prepared using conventional internal mixing and roll milling compounding techniques. The results, which are shown in Table I, demonstrate that the composite prepared using the stirred ball mill exhibits superior properties.
TABLE I______________________________________Property Roll Mill Ball Mill______________________________________Ultimate Tensile 6.7 10.1Strength (MPA)Elongation at Break (%) 255 395Modulus at Elongation(MPa)100% 2.8 3.1200% 5.2 5.4300% -- 7.5Hardness (IRHD) 64 64Trouser Tear (KN/M) 5.4 6.0Ring Fatigue 12 40(Kilocycles to failureDIN Abrasion:Loss (mm.sup.3) 203 189Index 95 102Heat Build-up (°C.) 70 65Resistivity (Ω cm) 2190 42______________________________________
Other embodiments are within the following claims.
For example, the compounding method can be used to prepare prepregs for hybrid composites as described in Creehan et al., U.S. Ser. No. 386,822 entitled "Hybrid Composites" now pending, filed concurrently with the present application and assigned to the same assignee as the present application, and is hereby incorporated by reference in its entirety.
|
A compounding process for preparing a composite that includes introducing one or more fillers and a matrix material into a stirred ball mill and subjecting the fillers and the matrix material to a combination of shear and impact forces under reaction conditions including reaction time sufficient to reduce the size of agglomerates formed by the fillers to a value below a pre-determined value to disperse the fillers throughout the matrix material.
| 8
|
BACKGROUND OF THE INVENTION
Thermoplastic polyamides, such as nylon 6,6, are a class of materials which possess a good balance of properties comprising strength and stiffness which make them useful as structural materials. However, for a particular application, a thermoplastic polyamide may not offer the combination of properties desired, and therefore, means to correct this deficiency are of interest.
One major deficiency of thermoplastic polyamides is their poor resistance to impact, especially when dry. A particularly appealing route to achieving improved impact resistance in a thermoplastic is by blending it with another polymer. It is well known that stiff plastics can often be impact modified by addition of an immiscible low modulus rubber. However, in general, physical blending of polymers has not been a successful route to toughen thermoplastic polyamides. This is due to the poor adhesion immiscible polymers typically exhibit with each other. As a result, interfaces between blend component domains represent areas of severe weaknesses, providing natural flows which result in facile mechanical failure.
It is well known to those skilled in the art that hydrogenated block copolymers of styrene and butadiene possess many of the properties which are required for impact modification of plastics. They have a low glass transition, low modulus rubber phase which is required for toughening. Because they contain little unsaturation, they can be blended with high temperature processing temperature plastics without degrading. In addition, they are unique compared to other rubbers in that they contain blocks which are micorphase separated over application and processing conditions. This microphase separation results in physical crosslinking, causing elasticity in the solid and molten states. Such an internal strength mechanism is often required to achieve toughness in the application of plastic impact modification. In addition, melt elasticity of the block copolymer during processing can, under the right conditions, enable it to be finely dispersed with another polymer in a stable interpenetrating co-continuous phase structure. A stable, fine dispersion is desirable in a rubber modified plastic.
Proof that hydrogenated block copolymers of styrene and butadiene are useful plastic impact modifiers can be seen in their widespread use for modifying polyolefins and polystyrene. For these blends, interfacial adhesion is great enough to achieve toughening.
Although the hydrogenated block copolymers do have many of the characteristics required for plastic impact modification, they are deficient in modifying many materials which are dissimilar in structure to styrene or hydrogenated butadiene. Blends of the hydrogenated block copolymer with dissimilar plastics are often not tough due to a lack of interfacial adhesion.
A route to achieve interfacial adhesion between the hydrogenated block copolymer and a dissimilar material is by chemically attaching to the block copolymer functional moieties which interact with the dissimilar material. Such interactions include chemical reaction, hydrogen bonding, and dipole-dipole interactions.
Epstein in U.S. Pat. No. 4,174,358 discloses a broad range of low modulus polyamide modifiers. However, this patent does not disclose or suggest the use of modified block copolymers of styrene and butadiene.
It has been previously proposed to increase the impact strength of polyamides by addition of a modified block copolymer. Hergenrother et al in U.S. Pat. No. 4,427,828 and Shiraki et al in International Kokai Application No. W083/00492 disclose blends of thermoplastic polyamide with a modified block copolymer. Specifically, the block copolymer is a partially hydrogenated monovinyl aryl/conjugated diene to which is attached anhydride moieites by the so-called "ENE reaction". Such modified block copolymers contain functional moieties only in the diene block, unlike the present invention. In addition, such modified block copolymers are deficient because the ENE reaction depends on unsaturation in the base polymer for reaction sites. A reasonable amount of residual unsatauration must be present in order to obtain an advantageous degree of functional moeities onto the base polymer. Since the ENE reaction cannot be carried out so that all double bonds on the base polymer are scavenged, the result of such a process is a modified block copolymer which contains too high a level of unsatauration for successful impact modification of high processing temperature thermoplastic polyamides.
The `ENE` process as described in the prior art results in a modified polymer product which is substituted at a position on the polymer backbone which is allylic to the double bond. The reaction can be shown for maleic anhydride as follows: ##STR1## wherein (a) represents addition across a double bond in the main chain of the base polymer and (b) represents addition across a double bond occuring in a side chain. After addition and isomerization the substitution is positioned on a carbon allylic to the double bond.
The allylically substituted polymers are prone to thermal degradation due to their thermal instability. It is known in the art that allylic substituents can undergo what has been referred to as a retro-ENE reaction, see B. C. Trivedi, B. M. Culbertson, Maleic Anhydride, (Plenum Press, New York, 1982) pp. 172-173.
Further, because the ENE reaction requires a reasonable amount of unsaturation in the precursor base polymer, as discussed previously, the resulting functionalized copolymer product will have a significant amount of residual unsaturation and will be inherently unstable to oxidation.
SUMMARY OF THE INVENTION
According to the present invention, there is provided an impact resistant blend of a thermoplastic polyamide and a thermally stable modified selectively hydrogenated high 1,2 content monovinyl aromatic/conjugated diene block copolymer wherein at least one functional group is grafted to the block copolymer primarily in the vinyl aromatic block. Examples of such modified block copolymers are described in U.S. patent application Ser. No. 766,217, filed Aug. 16, 1985, which is incorporated herein by reference. Said patent application describes the preparation of modified block copolymers by metallation, a process which does not require a base polymer with an undesirably high level of residual unsaturation.
More particularly there is provided an impact resistant polymeric composition comprising
(a) from 50 to 97 percent by weight of a polamide having a number average molecular weight of a least 5000; and
(b) from 3 to 50 percent by weight of a functionalized selectively hydrogenated block copolymer of the formula B n (AB) o A p where n=0,1, o=1,2 . . . ; p=0,1 to which has been grafted at least one electrophilic graftable molecule or electrophile wherein substantially all of said graftable molecules are grafted to the block copolymer in the vinylarene block.
DETAILED DESCRIPTION OF THE INVENTION
Polyamides
The polyamide matrix resin of the toughened compositions of this invention is well known in the art and embraces those semi-crystalline and amorphous resins having a molecular weight of at least 5000 and commonly referred to as nylons. Suitable polyamides include those described in U.S. Pat. Nos. 2,071,250; 2,071,251; 2,130,523; 2,130,948; 2,241,322; 2,312,966; 2,512,606; and 3,393,210. The polyamide resin can be produced by condensation of equimolar amounts of a saturated dicarboxylic acid containing from 4 to 12 carbon atoms with a diamine, in which the diamine contains from 4 to 14 carbon atoms. Excess diamine can be employed to provide an excess of amine end groups over carboxyl end groups in the polyamide. Examples of polyamides include polyhexamethylene adipamide (nylon 66), polyhexamethylene azelaamide (nylon 69), polyhexamethylene sebacamide (nylon 610), and polyhexamethylene dodecanoamide (nylon 612), the polyamide produced by ring opening of lactams, i.e., polycaprolactam, polylauric lactam, poly-11-aminoundecanoic acid, bis(paraaminocyclohexyl) methane dodecanoamide. It is also possible to use in this invention polyamides prepared by the copolymerization of two of the above polymers or terpolymerization of the above polymers or their components, e.g., for example, an adipic isophthalic acid hexamethylene diamine copolymer. Preferably the polyamides are linear with a melting point in excess of 200° C. As great as 99 percent by weight of the composition can be composed of polyamide; however, preferred compositions contain from 60 to 99 percent, and more narrowly 80 to 95 percent, by weight of polyamide.
Modified Block Copolymers
The modified block copolymers according to the present invention are grafted or substituted in the vinylarene block as shown in the exemplary reactions given below: ##STR2##
The structure of the substituted block copolymer specifically determined by the location of the functionality on the polymer backbone in the vinylarene block gives the block copolymer a substantially greater degree of thermal stability.
Selectively Hydrogenated Block Copolymer Base Polymer
Block copolymers of conjugated dienes and vinyl aromatic hydrocarbons which may be utilized include any of those which exhibit elastomeric properties and those which have 1,2-microstructure contents prior to hydrogenation of from about 7% to about 100%. Such block copolymers may be multiblock copolymers of varying structures containing various ratios of conjugated dienes to vinyl aromatic hydrocarbons including those containing up to about 60 percent by weight of vinyl aromatic hydrocarbon. Thus, multiblock copolymers may be utilized which are linear or radial symmetric or asymmetric and which have structures represented by the formulae A-B, A-B-A, A-B-A-B, B-A, B-A-B, B-A-B-A, (AB).sub. 0,1,2 . . . BA and the like wherein A is a polymer block of a vinyl aromatic hydrocarbon or a conjugated diene/vinyl aromatic hydrocarbon tapered copolymer block and B is a polymer block of a conjugated diene.
The block copolymers may be produced by any well known block polymerization or copolymerization procedures including the well known sequential addition of monomer techniques, incremental addition of monomer technique or coupling technique as illustrated in, for example, U.S. Pat. Nos. 3,251,905; 3,390,207; 2.598,887 and 4,219,627. As is well known in the block copolymer art, tapered copolymer blocks can be incorporated in the multiblock copolymer by copolymerizing a mixture of conjugated diene and vinyl aromatic hydrocarbon monomers utilizing the difference in their copolymerization reactivity rates. Various patents describe the preparation of multiblock copolymers containing tapered copolymer blocks including U.S. Pat. Nos. 3,251,905; 3,265,765; 3,639,521 and 4,208,356 the disclosures of which are incorporated herein by reference.
Conjugated dienes which may be utilized to prepare the polymers and copolymers are those having from 4 to 8 carbon atoms and include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Mixtures of such conjugated dienes may also be used. The preferred conjugated diene is 1,3-butadiene.
Vinyl aromatic hydrocarbons which may be utilized to prepare copolymers include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinylanthracene and the like. The preferred vinyl aromatic hydrocarbon is styrene.
It should be observed that the above-described polymers and copolymers may, if desired, be readily prepared by the methods set forth above. However, since many of these polymers and copolymers are commercially available, it is usually preferred to employ the commercially available polymer as this serves to reduce the number of processing steps involved in the overall process. The hydrogenation of these polymers and copolymers may be carried out by a variety of well established processes including hydrogenation in the presence of such catalysts as Raney Nickel, noble metals such as platinum, palladium and the like and soluble transition metal catalysts. Suitable hydrogenation processes which can be used are ones wherein the diene-containing polymer or copolymer is dissolved in an inert hydrocarbon diluent such as cyclohexane and hydrogenated by reaction with hydrogen in the presence of a soluble hydrogenation catalyst. Such processes are disclosed in U.S. Pat. Nos. 3,113,986 and 4,226,952, the disclosures of which are incorporated herein by reference. The polymers and copolymers are hydrogenated in such a manner as to produce hydrogenated polymers and copolymers having a residual unsaturation content in the polydiene block of from about 0.5 to about 20 percent of their original unsaturation content prior to hydrogenation.
Graftable Compounds
In general, any materials having the ability to react with the base polymer, are operable for the purposes of this invention.
In order to incorporate functional groups into the base polymer, monomers capable of reacting with the base polymer are necessary. Monomers may be polymerizable or nonpolymerizable, however, preferred monomers are nonpolymerizable or slowly polymerizing.
The class of preferred electrophiles which will form graft polymers within the scope of the present invention include reactants from the following groups carbon dioxide, ethylene oxide, aldehydes, ketones, carboxylic acid salts, their esters and halides, epoxides, sulfur, boron alkoxides, isocyanates and various silicon compounds.
These electrophiles may contain appended functional groups as in the case of N,N-dimethyl-p-amino benzaldehyde where the amine is an appended functional group and the aldehyde is the reactive electrophile. Alternatively, the electrophile may react to become the functional site itself; as an example, carbon dioxide (electrophile) reacts with the metalated polymer to form a carboxylate functional group. By these routes, polymers could be prepared containing grafted sites selected from one or more of the following groups of functionality type carboxylic acids, their salts and esters, ketones, alcohols and alkoxides, amines, amides, thiols, borates, and functional groups containing a silicon atom.
These functionalities can be subsequently reacted with other modifying materials to produce new functional groups. For example, the grafted carboxylic acid described above could be suitably modified by esterifying the resulting acid groups in the graft by appropriate reaction with hydroxy-containing compounds of varying carbon atom lengths. In some cases, the reaction could take place simultaneously with the grafting process but in most examples it would be practiced in subsequent post modification reaction.
The grafted polymer will usually contain from 0.02 to 20, preferably 0.1 to 10, and most preferably 0.2 to 5 weight percent of grafted portion.
The block copolymers, as modified, can still be used for any purpose for which an unmodified material (base polymer) was formerly used. That is, they can be used for adhesives and sealants, or compounded and extruded and molded in any convenient manner.
Preparation of the Modified Block Copolymers
The polymers may be prepared by any convenient manner one of which is described in copending U.S. application Ser. No. 766,622, filed Aug. 19, 1985, now abandoned, which is herein incorporated by reference.
An example of a method to incorporate functional groups into the base polymer primarily in the vinylarene block is metalation.
Metalation is carried out by means of a complex formed by the combination of a lithium component which can be represented by R'(Li) x with a polar metalation promoter. The polar compound and the lithium component can be added separately or can be premixed or pre-reacted to form an adduct prior to addition to the solution of the hydrogenated copolymer. In the compounds represented by R'(Li) x` , the R' is usually a saturated hydrocarbon radical of any length whatsoever, but ordinarily containing up to 20 carbon atoms, and can be an aromatic radical such as phenyl, napthyl, tolyl, 2-methylnaphthyl, etc., or a saturated cyclic hydrocarbon radical of e.g. 5 to 7 carbon atoms, a mono-unsaturated cyclic hydrocarbon radical of 5 to 7 carbon atoms, an unconjugated, unsaturated aliphatic hydrocarbon radical of 1 to 20 carbon atoms, or an alkyllithium having one or more aromatic groups on the alkyl group, the alkyl group containing 1 to 20 carbon atoms. In the formula, R'(Li) x x is an integer of 1 to 3. Representative species include, for example: Methyllithium, isoporpyllithium, sec-butyllithium, n-butyllithium, t-butyllithium, n-dodecyllithium, 1,4-dilithiobutane, 1,3,5-trilithiopentane, and the like. The lithium alkyls must be more basic than the product metalated alkyl. Of course, other alkali metal or alkaline earth metal alkyls could be used but the lithium alkyls are preferred due to their ready commercial availability. In a similar way, metal hydrides could be employed as the metalation reagent but the hydrides have only limited solubility in the appropriate solvents. Therefore, the metal alkyls are preferred and their greater solubility which makes them easier to process.
Lithium componds alone usually metalate copolymers containing aromatic and olefinic functional groups with considerable difficulty and under high temperatures which may tend to degrade the copolymer. However, in the presence of tertiary diamines and bridgehead monoamines, metalation proceeds rapidly and smoothly. Some lithium compounds can be used alone effectively, notably the menthyllithium types.
It has been shown that the metalation occurs at a carbon to which an aromatic group is attached, or in an aromatic group, or in more than one of these positions. In any event, it has been shown that a very large number of lithium atoms are positioned variously along the polymer chain, attached to internal carbon atoms away from the polymer terminal carbon atoms, either along the backbone of the polymer or on groups pendant therefrom, or both, in a manner depending upon the distribution of reactive or lithiatable positions. This distinguishes the lithiated copolymer from simple terminally reactive polymers prepared by using a lithium or even a polylithium initiator in polymerization thus limiting the number and the location of the positions available for subsequent attachment. With the metalation procedure described herein, the extent of the lithiation will depend upon the amount of metalating agent used and/or the groups available for metalation. The use of a more basic lithium alkyl such as tert-butyllithium alkyl may not require the use of a polar metallation promoter.
The polar compound promoters include a variety of tertiary amines, bridgehead amines, ethers, and metal alkoxides.
The tertiary amines useful in the metalation step have three saturated aliphatic hydrocarbon groups attached to each nitrogen and include, for example:
(a) Chelating tertiary diamines, preferably those of the formula (R 2 ) 2 N--C y H 2y ----N(R 2 ) 2 in which each R 2 can be the same or different straight- or branched-chain alkyl group of any chain length containing up to 20 carbon atoms or more all of which are included herein and y can be any whole number from 2 to 10, and particularly the ethylene diamines in which all alkyl substituents are the same. These include, for example: tetramethylethylenediamine, tetraethylethylenediamine, tetradecylenediamine, tetraoctylhexyienediamine, tetra-(mixed alkyl) ethylene diamines, and the like.
(b) Cyclic diamines can be used, such as, for example, the N,N,N',N'-tetraalkyl 1,2-diamino cyclohexanes, the N,N,N',N'-tetraalkyl 1,4-diamino cyclohexanes, N,N'-dimethylpiperazine, and the like.
(c) The useful bridgehead diamines include, for example, sparteine, triethylenediamine, and the like.
Tertiary monamines such as triethylenediamine are generally not as effective in the lithiation reaction. However, bridgehead monoamines such as 1-azabicyclo[2.2.2] octane and its substituted homologs are effective.
Ethers and the alkali metal alkozides are presently less preferred than the chelating amines as activators for the metalation reaction due to somewhat lower levels of incorporation of functional group containing compounds onto the copolymer backbone in the subsequent grafting reaction.
In general, it is most desirable to carry out the lithiation reaction in an inert solvent such as saturated hydrocarbons. Aromatic solvents such as benzene are lithiatable and may interfere with the desired lithiation of the hydrogenated copolymer. The solvent/copolymer weight ratio which is convenient generally is in the range of about 5:1 to 20:1. Solvents such as chlorinated hydrocarbons, ketones, and alcohols, should not be used because they destroy the lithiating compound.
Polar metalation promotors may be present in an amount sufficient to enable metalation to occur, e.g. amounts between 0.01 and 100 or more preferably between 0.1 to about 10 equivalents per equivalent of lithium alkyl.
The equivalents of lithium employed for the desired amount of lithiation generally range from such as about 0.001-3 per vinyl arene unit in the copolymer, presently preferably about 0.01-1.0 equivalents per vinyl arene unit in the copolymer to be modified. The molar ratio of active lithium to the polar promoter can vary from such as 0.01 to 10.0. A preferred ratio is 0.5.
The amount of alkyl lithium employed can be expressed in terms of the Li/vinylarene molar ratio. This ratio may range from a value of 1 (one lithium alkyl per vinylarene unit) to as low as 1×10 -3 (1 lithium alkyl per 1000 vinylarene units).
The process of lithiation can be carried out at temperatures in the range of such as about -70° C. to +150° C., presently preferably in the range of about 25° C. to 60° C., the upper temperatures being limited by the thermal stability of the lithium compounds. The lower temperatures are limited by considerations of production cost, the rate of reaction becoming unreasonably slow at low temperatures. The length of time necessary to complete the lithiation and subsequent reactions is largely dependent upon mixing conditions and temperature. Generally the time can range from a few seconds to about 72 hours, presently preferably from about 1 minute to 1 hour.
Grafting Step
The next step in the process of preparing the modified block copolymer is the treatment of the lithiated hydrogenated copolymer, in solution, without quenching in any manner which would destroy the lithium sites, with a species capable of reacting with a lithium anion. These species must contain functional groups capable of undergoing nucleophilic attack by a lithium anion. Such species contain functional groups including but not limited to
______________________________________ ##STR3## carboxyl CNR.sub.2 AmineCOH hydroxyl ##STR4## AmideCOR ether CSH Thiol ##STR5## ketone CB(OR).sub.2 Borane Containing ##STR6## aldehyde ##STR7## Silicon Containing______________________________________
The process also includes further chemistry on the modified block copolymer. For example, converting of a carboxylic acid salt containing modified block copolymer to the carboxylic acid form can be easily accomplished.
Preparation of the Final Compositions
The toughened compositions of this invention can be prepared by melt blending, in a closed system, a polyamide and at least one modified block copolymer into a uniform mixture in a multi-screw extruder such as a Werner Pfleiderer extruder having generally 2-5 kneading blocks and at least one reverse pitch to generate high shear, or other conventional plasticating devices such as a Brabender, Banbury mill, or the like. Alternatively, the blends may be made by coprecipitation from solution, blending or by dry mixing together of the components followed by melt fabrication of the dry mixture by extrusion.
The modified polyamide resin may be prepared by melt-blending from about 50 percent to about 97 percent by weight preferably from about 70 percent to about 95 percent or more preferably 75 percent to about 90 percent of the polyamide, and from about 3 percent to about 50 percent by weight preferably from about 5 percent to about 30 percent or more preferably 10 percent to about 25 percent functionalized block copolymer.
The compostions of the invention may be modified by one or more conventional additives such as stablizers and inhibitors of oxidative, thermal, and ultraviolet light degradation; lubricants and mold release agents, colorants including dyes and pigments, fibrous and particulate fillers and reinforcements, nucleating agents, plasticizers, etc.
The stablizers can be incorporated into the composition at any stage in the preparation of the thermoplastic composition. Preferably the stabilizers are included early to preclude the initiation of degradation before the composition can be protected. Such stabilizers must be compatible with the composition.
The oxidative and thermal stabilizers useful in the materials of the present invention include those used in addition polymers generally. They include, for example, up to 1 percent by weight, based on the weight of polyamide of Group I metal halides, e.g., sodium, potassium, lithium with cuprous halides, e.g., chloride, bromide, iodide, hindered phenols, hydroquinones, and varieties of substituted members of those groups and combinations thereof.
The ultraviolet light stabilizers, e.g., up to 2.0 percent, based on the weight of polyamide, can also be those used in addition polymers generally. Examples of ultraviolet light stabilizers include various substituted resorcinols, salicylates, benzotriazoles, benzophenones, and the like.
Suitable lubricants and mold release agents, e.g., up to 1.0 percent, based on the weight of the composition, are stearic acid, stearic alcohol, stearamides, organic dyes such as nigrosine, etc., pigments, e.g., titanium dioxide, cadmium sulfide, cadmium sulfide selenide, phthalocyamines, ultramarine blue, carbon black, etc. up to 50 percent, based on the weight of the composition, of fibrous and particulate fillers and reinforcements, e.g., carbon fibers, glass fibers, amorphous silica, asbestos, calcium silicate, aluminum silicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, fildspar, etc.; nucleating agent, e.g., talc, calcium fluoride, sodium phenyl phosphinate, alumina, and finely divided polytetrafluoroethylene, etc.; plasticizers, up to about 20 percent, based on the weight of the composition, e.g., dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, N-normal butyl benzene sulfonamide, ortho and para toluene ethyl sulfonamide, etc. The colorants (dyes and pigments) can be present in an amount of up to about 5.0 percent by weight, based on the weight of the composition.
It is to be understood that in the specification and claims herein, unless otherwise indicated, when in connection with melt-blending, the amount of the polyamide or block copolymer is expressed in terms of percent by weight it is meant percent by weight based on the total amount of these materials which is employed in the melt-blending.
EXAMPLES
To assist those skilled in the art in the practice of this invention. the following Examples are set forth as illustrations, parts and percentages being by weight unless otherwise specifically noted. The molded bars were tested using the following test procedures in the dry-as-molded state:
Notched Izod toughness: at each end ASTM D-256-56
Example 1: Preparation of Modified Block Copolymer
The base polymer used was a styrene-ethylene/butylene-styrene block copolymer which contained 29 wt % styrene and had a molecular weight of 66,000. 2270 gm of this polymer were dissolved in 15 gallons of cyclohexane. This mixture was placed in a 20 gallon stainless steel pressurized reaction vessel and pressurized to about 25 psi. 0.8 meq/gm polymer of tetramethylethylene diamine was then added to the vessel. A small amount, 0.5 ml of 1-1 diphenylethylene (an indicator), was then added to the reactor. Sec-butyllithium was then added incrementally until a yellow color was obtained, indicating the absence of impurities.
The reactor contents were then heated to 60° C. Next, 0.4 meq/gm polymer of additional sec-butyllithium was added to the reactor. After 2 1/2 hours reaction time, the contents of the vessel were transferred to another vessel which contained a stirring mechanism. This second vessel contained 2-3 lbs of dry ice (solid CO 2 ), 10 gallons of tetrahydrofuran, and 5 gallons of diethylether. The solution was stirred for 30 minutes. Next, 85 grams of acetic acid in an isopropanol solution was added to the reactor. This solution was stirred for 16 hours. The modified block was then recovered by steam stripping.
Infrared analysis of the polymer showed the presence of both bound carboxylic acid at 1690 cm -1 and bound lithium carboxylate salt at 1560-1600 cm -1 . By colorimetric titration with 0.01N KOM in methanol using a phenothalein indicator, it was found that the level of bound acid was 0.3 wt % COOH. After repreated washings of the polymer with alcoholic hydrochloric acid, infrared showed that complete conversion of salt to acid took place. Titration of the washed polymer have a bound acid level of 0.4 wt % COOH.
Example 2
The thermoplastic polyamide used in this example was a commercial nylon 6,6, Zytel 101, a molding grade obtained from Dupont. Prior to all processing steps, the nylon 6,6 and its blends were dried at 120° C. for 4 hours under vacuum with a nitrogen purge.
Blends of nylon 6,6 with both unmodified and modified block copolymer were prepared in a 30 mm diameter corotating twin screw extruder. The blend components were premixed by tumbling in polyethylene bags, and then fed into the extruder. The extruder melt temperature profile varied from 270° C. in the feed zone to 285° C. at the die. A screw speed of 300 rpm was used. The extrudate was pelletized and injection molded into test specimens. The formulations and physical properties are shown in Table 1.
TABLE 1______________________________________Composition (parts by weight) 1 2 3 4 5 6 7______________________________________Nylon 6,6 100 90 80 70 90 80 70Unmodified Block Copolymer -- 10 20 30 -- -- --Modified Block Copolymer -- -- -- -- 10 20 301/8" Dry as Molded Room 0.8 0.9 1.0 1.2 1.0 2.0 5.4Temperature Notched Izod(ft. lb./in.)______________________________________
The above example shows that the compositions according to this invention exhibit an unexpected improvement in impact strength over the thermoplastic polyamide or blends of the thermoplastic polyamide with unmodified block copolymer.
The foregoing embodiments are intended to illustrate but not to limit the invention. Various modifications can be made in the invention without departing from the spirit and scope.
|
The present invention relates to an impact resistant polymeric composition comprising a polyamide and a thermally stable modified selectively hydrogenated high 1,2 content block copolymer wherein at least one graftable functional molecule is grafted to the block copolymer in the vinylarene block.
| 2
|
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This is a division of U.S. application No. 09/082,205, filed May 20, 1998, which was a continuation of copending international application PCT/DE97/02139, filed Sep. 22, 1997, which designated the United States.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention relates to a wavelength-converting casting composition based on a transparent epoxy casting resin which is mixed with a luminous substance, for an electroluminescent component having a body that emits ultraviolet, blue or green light.
[0004] 2. Description of the Related Art
[0005] A component of that type has become known, for instance, from German published, non-prosecuted patent application DE 38 04 293. The reference describes an arrangement with an electroluminescent diode or laser diode, in which the emissions spectrum emitted by the diode is shifted toward longer wavelengths, by means of a plastic element mixed with a fluorescing, light-converting, organic colorant. The light emitted by the arrangement as a result has a different color from what the light emitting diode emitted. Depending on the type of colorant added to the plastic, it is possible to produce LED arrays that light up in different colors with one and the same type of light-emitting diode (LED).
[0006] In many potential applications for LEDs, such as in display elements in motor vehicle dashboards, illumination in aircraft and automobiles, and in LED displays capable of showing full color, there is an increasing demand for LED arrays with which mixed color light and in particular white light can be generated.
[0007] However, the prior art casting compositions of the type referred to at the outset with organic luminous substances exhibit a shift in the color location, that is, the color of the light emitted by the electroluminescent component, under temperature and temperature/humidity stresses.
[0008] Japanese patent disclosure JP-07 176 794-A describes a white-light-emitting planar light source, in which two diodes that emit blue light are disposed on one face end of a transparent plate and emit light into the transparent plate. The transparent plate is coated on one of the two opposed main sides with a fluorescing substance that emits light when it is excited with the blue light of the diodes. The light emitted by the fluorescing substance has a different wavelength from the blue light emitted by the diodes. In this known component, it is especially difficult to apply the fluorescing substance in such a way that the light source emits homogeneous white light. Moreover, replicability and mass production presents major problems, because even slight fluctuations in the layer thickness of the fluorescing layer, for instance from irregularities of the surface of the transparent plate, cause a change in the white of the light emitted.
SUMMARY OF THE INVENTION
[0009] It is accordingly an object of the invention to provide a wavelength-converting casting mass, which overcomes the above-mentioned disadvantages of the prior art devices and methods of this general type and with which electroluminescent components can be produced that emit homogeneous mixed-colored light, and which enables mass production at reasonable engineering effort and expense and with maximally replicable component characteristics. The emitted light should be color-stable even under temperature and temperature/humidity stresses. It is a further object to specify a use for the casting mass and a method for producing the composition.
[0010] With the foregoing and other objects in view there is provided, in accordance with the invention, a wavelength-converting casting composition, for converting a wavelength of ultraviolet, blue or green light emitted by an electro-luminescent component, comprising:
[0011] a transparent epoxy casting resin;
[0012] an inorganic luminous substance pigment powder dispersed in the transparent epoxy resin, the pigment powder comprising luminous substance pigments from a phosphorus group having the general formula A 3 B 5 X 12 :M;
[0013] the luminous substance pigments having grain sizes ≦20 μm and a mean grain diameter d 50 ≦5 μm.
[0014] In accordance with an added feature of the invent-ton, the mean grain diameter d 50 of the luminous substance pigments is between one and two micrometers.
[0015] Inorganic/mineral luminous substances are extremely stable with regard to temperature and temperature/humidity stresses.
[0016] In accordance with an additional feature of the invention, the composition includes the following parts:
[0017] a) epoxy casting resin ≧60% by weight;
[0018] b) luminous substance pigments >0 and ≦25% by weight;
[0019] c) thixotropic agent >0 and ≦10% by weight;
[0020] d) mineral diffusor >0 and ≦10% by weight;
[0021] e) processing adjuvant >0 and ≦3% by weight;
[0022] f) hydrophobic agent >0 and ≦3% by weight; and
[0023] g) adhesion promoters >0 and ≦2% by weight.
[0024] Suitable epoxy casting resins are described for instance in German published, non-prosecuted patent application 26 42 465 (pp. 4-9, in particular examples 1-4), and in European patent disclosure EP 0 039 017 (pp. 2-5, in particular examples 1-8). The disclosures of those documents are hereby expressly incorporated by reference.
[0025] Pyrogenic silicic acid is for instance used as the thixotropic agent. The thixotropic agent is used to thicken the epoxy casting resin, so as to reduce the sedimentation of the luminous substance pigment powder. The flow and wetting properties are also adjusted for processing the casting resin.
[0026] CaF 2 is preferably used as a mineral diffusor for optimizing the luminous pattern of the component.
[0027] Glycol ether is for instance suitable as a processing adjuvant. It improves the compatibility between the epoxy casting resin and the luminous substance pigment powder and is thus used to stabilize the dispersion of luminous substance pigment powder and epoxy casting resin. To that end, surface modifiers based on silicone can also be employed.
[0028] The hydrophobic agents such as liquid silicone wax, is also used to modify the pigment surface; in particular, the compatibility and wettability of the inorganic pigment surface is improved with the organic resin.
[0029] The adhesion promoter, such as functional alkoxysiloxane, improves the adhesion between the pigments and the epoxy resin in the cured state of the casting composition. A; a result it is attained that the boundary face between the epoxy resin and the pigments will not rupture, for instance in response to temperature fluctuations. Gaps between the epoxy resin and the pigments would cause light losses in the component.
[0030] The epoxy casting resin, preferably with a reactive triple oxiran ring, preferably includes a monofunctional and/or multifunctional epoxy casting resin system (≧80% by weight, such as bisphenol-A-diglycidyl ether), a reactive diluent (≦10% by weight, such as aromatic monoglycidyl ether), a multifunctional alcohol (≦5% by weight), a degassing agent based on silicone (≦1% by weight), and a decolorizing component to adjust the color number (≦1% by weight).
[0031] In accordance with another feature of the invention, the luminous substance pigments are substantially spherical particles or flakelike particles. The tendency to clumping of such pigments is advantageously very slight. The H 2 O content is below 2%.
[0032] In the production and processing of epoxy casting resin components with inorganic luminous substance pigment powders, in general not only wetting but also sedimentation problems occur. Especially luminous substance pigment powders with d 50 ≦5 μm have a strong tendency to clumping. In the last-named composition of the casting composition, the luminous substance pigments, with the above-indicated particle size, can advantageously be substantially free of clumps and can be dispersed homogeneously in the epoxy casting resin. This dispersion is stable even under long-term storage of the casting composition. Essentially no problems of wetting and/or sedimentation occur.
[0033] In accordance with a further feature of the invention, the luminous substance pigments are particles of Ce-doped garnets, such as, particularly, YAG:Ce particles. An advantageous dopant concentration is 1%, for example, and an advantageous luminous substance concentration is 12%, for example. The preferred high-purity luminous substance pigment powder also advantageously has an iron content of ≦5 ppm. A high iron content leads to high light losses in the component. The luminous substance pigment powder is highly abrasive. The iron content in the casting composition can therefore rise considerably during production. Iron contents in the casting composition <20 ppm are advantageous.
[0034] The inorganic luminous substance YAG:Ce has the particular advantage, among others, that this involves insoluble color pigments with an index of refraction of approximately 1.84. As a result, along with the wavelength conversion, dispersion and scattering effects occur that lead to good mixing of blue diode emissions with yellow converter radiation.
[0035] It is also especially advantageous that the luminous substance concentration in the epoxy resin when inorganic luminous substance pigments are used is not limited by the solubility, as is the case for organic colorants.
[0036] For further reduction of clumping, the luminous substance pigments may advantageously be provided with a silicone coating.
[0037] With the above and other objects in view there is also provided, in accordance with the invention, a method of producing a wavelength-converting casting composition, for converting a wavelength of ultraviolet, blue or green light emitted by an electroluminescent component, the method which comprises:
[0038] providing a base of transparent epoxy casting resin;
[0039] providing a luminous substance pigment powder of luminous substance pigments from a phosphorus group having the general formula A 3 B 5 X 12 :M;
[0040] tempering the luminous substance pigment powder at: a temperature of ≦200° C. and subsequently mixing the tempered pigment powder with the epoxy casting resin.
[0041] Tempering is preferably effected for approximately ten hours. As a result, again the tendency to clumping can be reduced.
[0042] As an alternative or in addition for this purpose, the luminous substance pigment powder, before being mixed with the epoxy casting resin, can be slurried in a higher-boiling alcohol and subsequently dried. A further possibility for reducing clumping is to add a hydrophobic silicone wax to the luminous substance pigment powder before the powder is mixed with the epoxy casting resin. Surface stabilization of the phosphors by heating the pigments in the presence of glycol ethers, for instance for 16 hours at T>60° C., is especially advantageous.
[0043] To avoid problematic contamination upon dispersal of the luminous substance pigments, caused by abrasion, reaction vessels, agitators and dispersing devices as well as rolling mechanisms of glass, corundum, carbide and nitride materials as well as especially hardened types of steel are used. Clump-free luminous substance dispersions are also obtained by ultrasonic methods or by the use of screens and glass ceramic frits.
[0044] An especially preferred inorganic luminous substance for producing optoelectronic components that light up white is the phosphorous YAG:Ce (Y 3 Al 5 O 12 :Ce 3+ ). This phosphorous can be especially simply mixed with transparent epoxy casting resins conventionally used in LED technology. Also conceivable as luminous substances are other garnets, doped with rare earths, such as Y 3 Ga 5 O 12 :Ce 3+ , Y(Al,Ga) 5 O 12 :Ce 3+ , and Y(Al,Ga) 5 O 12 :Tb 3+ .
[0045] To generate mixed-colored light, the thiogallates doped with rare earths are moreover especially suitable, examples being CaGa 2 S 4 :Ce 3+ and SrGa 2 S 5 :Ce 3+ . Once again, the use of aluminates doped with rare earths, such as YAlO 3 :Ce 3+ , YGaO 3 :Ce 3+ , Y(Al,Ga)O 3 :Ce 3+ , and orthosilicates doped with rare earths, M 2 SiO 5 :Ce 3+ (M:Sc,Y,Sc), such as Y 2 SiO 5 :Ce 3+ is conceivable. In all the yttrium compounds, the yttrium can in principle also be replaced with scandium or lanthanum.
[0046] Therefore, in the phosphorous group A 3 B 5 X 12 :M, the variables may stand for the following exemplary elements: A=Y, Ca, Sr; B=Al, Ga, Si; X=O, S; and M=Ce 3+ , Tb 3+ .
[0047] Preferably, the casting composition according to the invention is used in a radiation-emitting semiconductor body, in particular with an active semiconductor layer or semiconductor layer sequence of Ga x In 1-x N or Ga x Al 1-x N, which in operation emits an electromagnetic radiation of the ultraviolet, blue and/or green spectral range. The luminous substance particles in the casting composition convert some of the radiation originating in this spectral range into radiation with a longer wavelength, in such a way that the semiconductor component emits mixed radiation, and in particular mixed-colored light comprising this radiation as well as radiation from the ultraviolet, blue and/or green spectral range. This means for instance that the luminous substance particles spectrally selectively absorb some of the radiation emitted by the semiconductor body and emit in the longer-wave range. Preferably, the radiation emitted by the semiconductor body has a relative maximum intensity at a wavelength lambda λ≦520 nm, and the wavelength range spectrally selectively absorbed by the luminous substance particles is outside this maximum intensity.
[0048] It is also advantageously possible for a plurality of different kinds of luminous substance particles, which emit at different wavelengths, to be dispersed in the casting composition. This is preferably achieved by means of different doping in different host lattices. This advantageously makes it possible to generate manifold color mixtures and color temperatures of the light emitted by the component. This is especially of interest for LEDs capable of emitting full color.
[0049] In a preferred use of the casting composition of the invention, a radiation-emitting semiconductor body (such as an LED chip) is at least partly enclosed by the casting composition. The casting composition is preferably simultaneously used as a component envelope (housing). The advantage of a semiconductor-component in accordance with this embodiment is essentially that conventional production lines used to make conventional LEDs (such as radial LEDs) can be used to produce it. For the component envelope, instead of the transparent plastic used for this purpose in conventional LEDs, the casting composition can simply be employed.
[0050] With the casting composition of the invention, it is possible in a simple way, with a single colored light source, particularly an LED with a single semiconductor body that emits blue light, to create mixed-colored and in particular white light. For instance to generate white light with a semiconductor body that emits blue light, some of the radiation emitted by the semiconductor body is converted out of the blue spectral range into the yellow spectral range, which is complementary in color to blue, by means of inorganic luminous substance particles.
[0051] The color temperature or color location of the white light can be varied by a suitable choice of the luminous substance, its particle size, and its concentration. In addition, luminous substance mixtures can also be employed, and as a result advantageously the desired tonality of the color of the emitted light can be adjusted very precisely.
[0052] Especially preferably, the casting composition is used in a radiation-emitting semiconductor body in which the emitted radiation spectrum has a maximum intensity at a wavelength between 420 nm and 460 nm, and in particular at 430 nm (examples being semiconductor bodies based on Ga x In 1-x N) or 450 nm (such as semiconductor bodies bsed on Ga x In 1-x N). With such a semiconductor component, nearly all the colors and mixed colors in the CIE chromaticity diagram can advantageously be generated.
[0053] Instead of the radiation-emitting semiconductor body of electroluminescing semiconductor material, however, some other electroluminescing material may be used, such as polymer material.
[0054] With the objects of the invention is view there is further provided, in accordance with the invention, a light-emitting semiconductor component, comprising:
[0055] a semiconductor body formed of a semiconductor layer sequence and being capable, during an operation of the semiconductor component, of emitting electromagnetic radiation in at least one of an ultraviolet, blue, and green spectral range;
[0056] a wavelength-converting casting composition disposed in a vicinity of the semiconductor body, the casting composition being formed of a transparent epoxy casting resin and an inorganic luminous substance pigment powder dispersed in the transparent epoxy resin, the pigment powder comprising luminous substance pigments from a phosphorus group having the general formula A 3 B 5 X 12 :M and having grain sizes ≦20 μm and a mean grain diameter d 50 ≦5 μm;
[0057] the luminous substance pigments converting a portion of the radiation originating from the ultraviolet, blue and green spectral range into radiation of a higher wavelength, such that the semiconductor component emits mixed radiation including the higher-wavelength radiation and radiation from at least one of the ultraviolet, blue and green spectral range.
[0058] In other words, the casting composition is especially suitable for a light-emitting semiconductor component (for instance an LED), in which the electroluminescing semiconductor body is disposed in a recess of a prefabricated housing, optionally already provided with a leadframe, and the recess is provided with the casting composition. This kind of semiconductor component can be produced in great numbers on conventional production lines. All that is needed, after mounting of the semiconductor body in the housing, is to fill the recess with the casting composition.
[0059] A semiconductor component that emits white light can be produced with the casting composition according to the invention advantageously by choosing the luminous substance in such a way that a blue radiation emitted by the semiconductor body is converted into complementary wavelength ranges, in particular blue and yellow, or additive color triads, such as blue, green and red. The yellow or green and red light is generated via the luminous substances. The color tonality (color location in the CIE chromaticity diagram) of the white light thus produced can then be varied by means of a suitable choice of the luminous substance or luminous substances in terms of their mixture and concentration.
[0060] To improve the mixing of the radiation emitted by an electroluminescing semiconductor body with the radiation converted by the luminous substance and thus to improve the homogeneity of color of the light emitted by the component, in an advantageous feature of the casting composition according to the invention a blue-luminescing colorant, which attenuates a so-called directional characteristic of the radiation emitted by the semiconductor body. The term “directional characteristic” is understood to mean that the radiation emitted by the semiconductor body has a preferential emission direction.
[0061] A semiconductor component according to the invention that emits white light, with an electroluminescing semiconductor body emitting blue light, can be especially preferably achieved by admixing the inorganic luminous substance YAG:Ce (Y 3 Al 5 O 12 :Ce 3+ ) with the epoxy resin used for the casting composition. Some of the blue radiation emitted by the semiconductor body is shifted by the inorganic luminous substance (Y 3 Al 5 O 12 :Ce 3+ ) into the yellow spectral range and thus into a wavelength range that is complementary in color to the color blue. The color tonality (color location in the CIE chromaticity diagram) of the white light can then be varied by means of a suitable choice of the colorant concentration.
[0062] In addition, light-scattering particles, so-called diffusers, can be added to the casting composition. As a result, the color impression and the emission characteristics of the semiconductor component can advantageously be still further optimized.
[0063] With the casting composition of the invention, advantageously an ultraviolet radiation emitted by an electroluminescing semiconductor body along with the visible radiation can advantageously be converted into visible light. This markedly increases the brightness of the light emitted by the semiconductor body.
[0064] A particular advantage of semiconductor components according to the invention that emit white light, and in which YAG:Ce is used in particular as the luminescence-converting colorant, is that this luminous substance on excitation with blue light causes a spectral shift of approximately 100 nm between absorption and emission. This leads to a substantial reduction and reabsorption of the light emitted by the luminous substance and thus to a higher light yield. Moreover, YAG:Ce advantageously has high thermal and photochemical (such as UV) stability (substantially higher than organic luminous substances) so that even white-emitting diodes for outdoor use and/or high temperature ranges can be produced.
[0065] YAG:Ce has by now proved itself to be the best-suitable luminous substance in terms of reabsorption, light yield, thermal and photochemical stability, and processability. However, the use of other Ce-doped phosphors, in particular Ce-doped types of garnet, is also conceivable.
[0066] The wavelength conversion of the primary radiation is determined by the crystal field cleavage of the active transition metal centers in the host lattice. By substituting Gd and/or Lu for Y, or Ga for Al in the Y 3 Al 5 O 12 garnet lattice, the emission wavelengths can be shifted in various ways, and this can also be done by the type of doping. By substituting Eu 3+ and/or Cr 3+ for Ce 3+ centers, corresponding shifts can be brought about. Corresponding dopings with Nd 3+ and Er 3+ even make it possible, because of the greater ion radii and thus reduced crystal field cleavage, to make components that emit infrared (IR) light.
[0067] Other features which are considered as characteristic for the invention are set forth in the appended claims.
[0068] Although the invention is illustrated and described herein as embodied in a wavelength-converting casting composition, its use, and method for its production, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
[0069] The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0070] [0070]FIG. 1 is a schematic sectional view of a first semiconductor component with a casting composition according to the invention;
[0071] [0071]FIG. 2 is a schematic sectional view of a second semiconductor component with a casting composition according to the invention;
[0072] [0072]FIG. 3 is a schematic sectional view of a third semiconductor component with a casting composition according to the invention;
[0073] [0073]FIG. 4 is a schematic sectional view of a fourth semiconductor component with a casting composition according to the invention;
[0074] [0074]FIG. 5 is a schematic sectional view of a fifth semiconductor component with a casting composition according to the invention;
[0075] [0075]FIG. 6 is a graph of an emission spectrum of a semiconductor body that emits blue light, with a layer sequence on the basis of GaN;
[0076] [0076]FIG. 7 is a graph of the emissions spectra of two semiconductor components with a casting composition according to the invention, which emit white light; and
[0077] [0077]FIG. 8 is a graph of the emissions spectra of further semiconductor components that emit white light.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0078] Reference is now had to the figures of the drawing in which elements that are identical or that function identically are identified by the same reference numerals throughout.
[0079] In the light-emitting semiconductor component of FIG. 1, the semiconductor body 1 is secured by its back-side contact 11 to a first electrical terminal 2 by means of an electrically conductive joining means such as a metal solder or an adhesive. The front-side contact 12 is joined to a second electrical terminal 3 by means of a bond wire 14 .
[0080] The free surfaces of the semiconductor body 1 and portions of the electrical terminals 2 and 3 are enclosed directly by a hardened, wavelength-converting casting or potting composition 5 . The casting composition preferably has the following: epoxy casting resin 80 to 90% by weight, luminous substance pigments (YAG:Ce)≦15% by weight, diethylene glycol monomethyl ether ≦2% by weight, Tegopren 6875-45≦2% by weight, Aerosil 200≦5% by weight.
[0081] The exemplary embodiment of a semiconductor component according to the invention shown in FIG. 2 differs from that of FIG. 1 in that the semiconductor body 1 in portions of the electrical terminals 2 and 3 are enclosed not by a wavelength-converting potting mass but by a transparent envelope 15 . The transparent envelope 15 does not cause any change in the wavelength of the radiation emitted by the semiconductor body 1 and for instance comprises an epoxy, silicone or acrylate resin conventionally used in LED technology, or some other suitable radiation-permeable material, such as inorganic glass.
[0082] A layer 4 is applied to the transparent envelope 15 . The layer 4 comprises a wavelength-converting casting composition and, as shown in FIG. 2, covers the entire surface of the envelope 15 . It is equally conceivable for the layer 4 to cover only a portion of the surface. The layer 4 for instance comprises a transparent epoxy resin which is mixed with luminous substance particles 6 . Once again, for a semiconductor component that emits white light, YAG:Ce is preferred as the luminous substance.
[0083] [0083]FIG. 3 illustrates a particularly advantageous and preferred embodiment of the invention. The first and second electrical terminals 2 , 3 are embedded in an opaque, and optionally prefabricated, basic housing 8 that has a recess 9 . The term “prefabricated” is understood to mean that the basic housing 8 is already finished at the terminals 2 , 3 , for instance by means of injection molding, before the semiconductor body is mounted on the terminal 2 . The basic housing 8 , by way of example, is formed of opaque plastic, and in terms of its form the recess 9 is embodied as a reflector 17 for the radiation emitted by the semiconductor body in operation (the reflection optionally being achieved by means of suitable coating of the inside walls of the recess 9 ). Such basic housings 8 are used in particular for LEDs that are surface-mounted on printed circuit boards. They are applied, before mounting of the semiconductor body, to a conductor strip (lead frame) that has the electrical terminals 2 , 3 , the application for instance being done by injection molding.
[0084] The recess 9 is filled with a casting composition 5 , whose composition is equivalent to that given above in conjunction with the description of FIG. 1.
[0085] [0085]FIG. 4 shows a so-called radial diode. Here, the electroluminescing semiconductor body 1 is secured, for instance by soldering or adhesive bonding, in a part 16 , embodied as a reflector, of the first electrical terminal 2 . Such housing constructions are known in LED technology and therefore require no further description here. The free surfaces of the semiconductor body 1 are covered directly by a casting composition 5 containing luminous substance particles 6 , and the casting composition in turn is surrounded by a further transparent housing envelope 10 .
[0086] It will be appreciated by those skilled in the art that, in the construction of FIG. 4 as well, analogously to the component of FIG. 1, an integral envelope comprising hardened casting composition 5 with-luminous substance particles 6 , may also be used.
[0087] In the exemplary embodiment of FIG. 5, a layer 4 (see the list of materials given above) is coated directly on the semiconductor body 1 . The semiconductor body 1 and portions of the electrical terminals 2 , 3 are enclosed by a further transparent housing envelope 10 . The latter causes no change in wavelength of the radiation that has passed through the layer 4 , and it is made for instance from a transparent epoxy resin that is usable in LED technology, or from glass.
[0088] Such semiconductor bodies 1 provided with a layer 4 and without an envelope can naturally advantageously be used in all the housing constructions known from LED technology (such as SMD housings, and radial housings; see FIG. 4).
[0089] In all the components described above, in order to optimize the color impression of the light emitted and to adapt the emission characteristics, the casting composition 5 , optionally the transparent envelope 15 , and/or optionally the further transparent envelope 10 may have light-scattering particles, advantageously so-called diffusers. Examples of such diffusers are mineral fillers, in particular CaF 2 , TiO 2 , SiO 2 , CaCO 3 , or BaSO 4 , or organic pigments. These materials can easily be added to epoxy resins.
[0090] FIGS. 6 - 8 illustrate emissions spectra. FIG. 6 refers to a semiconductor body that emits blue light (luminescence maximum at λ˜430 nm) and FIGS. 7 and 8 refer to semiconductor components that emit white light. In each case, the wavelength λ is plotted in nm on the abscissa, and a relative electroluminescence (EL) intensity is plotted on the ordinate.
[0091] Of the radiation emitted by the semiconductor body in FIG. 6, only some is converted into a longer-wavelength range, so that white light is created as the mixed color. The dashed line 30 in FIG. 7 represents an emissions spectrum of a semiconductor component which emits radiation comprising two complementary wavelength ranges (blue and yellow) and thus emits combined white light. The emissions spectrum here has one maximum each at wavelengths between approximately 400 and approximately 430 nm (blue) and between approximately 550 and 580 nm (yellow). The solid line 31 represents the emissions spectrum of a semiconductor component that mixes the color white from three wavelength ranges (additive color triad comprising blue, green and red). The emissions spectrum here has one maximum each for the wavelengths of approximately 430 nm (blue), approximately 500 nm (green) and approximately 615 nm (red).
[0092] [0092]FIG. 8 shows an emissions spectrum of a white-emitting semiconductor component, which is provided with a semiconductor body that transmits an emissions spectrum as shown in FIG. 6 and in which TAG:Ce is used as the luminous substance. Of the radiation shown in FIG. 6 emitted by the semiconductor body, only some is converted into a longer-wavelength range, so that white light is created as a mixed color. The variously dashed lines 32 - 33 of FIG. 8 represent emissions spectra of semiconductor components according to the invention, in which the epoxy resin of the casting composition 5 has different YAG:Ce concentrations. Each emissions spectrum has one maximum intensity between lambda=420 nm and lambda=430 nm (i.e., in the blue spectrum), and between lambda=520 nm and lambda=545 nm (i.e., in the green spectrum) . The emission bands having the longer-wavelength maximum intensity are predominantly located in the yellow spectral range. The graph of FIG. 8 shows that in the semiconductor component of the invention, the CIE color location of the white light can be varied in a simple way by varying the luminous substance concentration in the epoxy resin.
[0093] While the foregoing specification refers specifically to a semiconductor body, for example LED chips or laser diode chips, the invention is not in the least restricted to these embodiments. The term may also be understood to mean a polymer LED, for instance, that emits an equivalent radiation spectrum.
|
The wavelength-converting casting composition is based on a transparent epoxy casting resin with a luminous substance admixed. The composition is used in an electroluminescent component having a body that emits ultraviolet, blue or green light. An inorganic luminous substance pigment powder with luminous substance pigments is dispersed in the transparent epoxy casting resin. The luminous substance is a phosphororous group of the general formula A 3 B 5 X 12 :M, and the luminous substance pigments have particle sizes ≦20 μm and a mean grain diameter d 50 ≦5 μm.
| 7
|
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to the field of printed wiring boards and their manufacture. More particularly, it relates to the production of double-sided printed wiring boards. The present invention relates to a method for an improved reliability surface finishing process.
[0003] 2. Discussion of Related Art
[0004] In the manufacture of printed circuit boards, also called printed wiring boards, it is now commonplace to produce circuitry on both sides of a rigid or flexible substrate. Multilayer printed wiring boards consist of alternating layers of insulating substrate material and conductive metal. The exposed outer surfaces, as well as the innerlayers, of the structure are provided with circuit patterns. The most common metallurgy selected for the circuit patterns is copper.
[0005] In double-sided and multilayer PWBs, it is necessary to provide surfaces for subsequent assembly processing. The most common surface finish is the application of a solder mask onto some circuit patterns and an organic surface protection (OSP) onto others. The OSP serves two purposes; the first being to delay the oxidation of the surface metallurgy to extend the shelf-life of the panel between shipping and assembly so that additional cleaning or oxidation removal steps are prevented; the second is that the OSP improves the wettability of the metal surface for subsequent soldering operations. Other surface metallurgies can be applied to the PWB depending upon the components to be assembled. These metallurgies include gold and palladium generally with an underlying layer of nickel that provides a diffusion barrier layer between the copper and surface metal. While these metallurgies can also be used for a solderable surface, they are more suited to providing a highly conductive surface for subsequent connector systems. Of particular interest for this invention is the method for providing these additional metallurgies.
[0006] The surface finish metallurgies are generally applied by plating processes. Most common in the industry are electroless and electrolytic plating. Electroless plating is done without electricity. The advantage of an electroless process is that circuit patterns can be formed onto a PWB and immersed into the electroless solutions to deposit metal onto exposed circuit patterns. To prevent deposition on undesired areas, photolithographic processes or masking can be used.
[0007] To provide an electrolytic metal deposition, one needs a commoning layer on the surface to be metallized to provide electrical contact. If the PWB had been fabricated using electrolytic plating processes, a commoning layer is generally present, is used for all subsequent plating, and is removed during one of the final steps. A disadvantage to this method is that as dissimilar metals are applied, the final commoning layer etch exposes these dissimilar metals in contact with each other to an electrolyte solution. When this happens, a galvanic cell is generated that accelerates the etch rate of the less noble metal. In this case, the circuit pattern would etch faster than the surface finish metal. This can produce an undercut of the surface metallurgy causing it to produce metal overhanging the underlying circuit pattern, which can flake off and contact adjacent circuit patterns causing an electrical short. The industry refers to this phenomenon as “slivering”.
[0008] For a PWB fabricated using an electrolytic double-sided plating process, a commoning layer is provided on both surfaces of the PWB substrate. In the industry, this method is performed by first electrolytically pattern plating a first copper layer over a commoning layer. A photoresist is then applied after the commoning layer is formed. While leaving the pattern photoresist on the panel, subsequent electrolytic metallizations can take place. However, in some operations, the process is a full panel plate with subtractive etching to form the circuit traces. As a result, there is no commoning layer on the panel's surfaces as the copper is etched to the laminate substrate surface.
[0009] The two primary methods in the industry for pattern plating are pattern electroplate and pattern electroless plating.
[0010] In pattern electroplate, holes are drilled through or into a copper clad dielectric substrate to form through holes (extending from one planar surface of the substrate to the other) or vias (extending in from one surface but terminating within the substrate) followed by plating a commoning layer of copper onto the surface of the board. A commoning layer is an electroless copper applied over a PdSn catalyst layer. For one such process, the substrate is copper clad on at least one of its surfaces and the process employed would be a subtractive process whereby the unwanted copper is removed by chemical etching or laser ablation. The substrate typically is nonconductive, and may be provided with through holes or vias.
[0011] Because the holes extend into or through the dielectric, which is an insulator, a continuous electrical connection is first created by putting a thin metallization of copper in the holes. A photoresist is applied over the commoning layer and a pattern is formed in the photoresist through known photolithographic techniques (expose, develop) such that the open channels in the photoresist are the places where circuit traces will be formed. The substrate is then electroplated with copper, and metallization build-up only occurs in the open channels to form circuit traces. A layer of tin/lead is plated over the copper traces, followed by stripping of the photoresist and etching of the commoning layer with the copper traces protected by the tin/lead during the etch. Then the tin/lead is etched off. The result is a PWB with copper circuit traces onto which a solder mask is later placed.
[0012] It should be observed that the copper clad substrate can be any thickness, limited only to the handling capability of the fabricator. Very thin cores (approx. 5-8 mils) with laser drilled holes and vias up to multilayer boards (MLB) composites or 300+ mils and mechanically drilled holes and vias can be processed if equipment permits. The commoning layer is generally thin, about 100 microinches, and is usually applied with an electroless strike. It can also be applied by sputter coating. The photoresist can be any of the many available for copper plating in the industry. Likewise, the expose and develop chemistries are industry known. The subsequent copper plating can be direct current (DC) or pulse plated. Pulse plating provides the advantage of a more even distribution, less thieving area needed and better ‘throw’ into the drilled holes. DC is the most common, but has the drawbacks of non-uniform plating on isolated features and not very good throw in high aspect ratio (length to diameter) holes. Once the panel has been pattern electroplated, the commoning layer is still present under the photoresist and opens up several finishing options:
[0013] 1. If tin/lead (solder) is desired on certain areas of the board, then prior to etching off the tin/lead in the last step, a photoresist/mask is applied to protect those areas during the tin/lead etch process. The mask is then removed
[0014] 2. If gold is desired, for instance, on the land grid array pads, then after copper plate and tin/lead plate, a second photoresist/mask is applied, leaving open the features to be gold plated bearing in mind that the first pattern plate resist is still on the board. The tin/lead is etched off the pads, leaving a copper surface. Then the board is electrolytically nickel/gold plated, the second photomask is stripped, the first photomask is stripped either simultaneously or subsequently, the commoning layer is etched off, creating the galvanic cell phenomenon seen by the industry as slivering, and then the tin/lead is etched off.
[0015] 3. These steps can be extended further. For example, if tin/lead areas are needed on a board with gold, another photomask operation is carried out. If there are requirements that the gold be thick in one place and thin in another, again, masking and plating operations are performed as long as the base commoning layer is still present.
[0016] A similar pattern plate option is practiced called ‘semi-additive’, the difference being that, instead of an electrolytic plating to create the traces in the patterned resist, a full-build electroless process is used. Since the commoning layer is still present, all of the aforementioned finishing processes can be carried out.
[0017] Still another pattern plate process is a full-build electroless process. In this process, there is no base copper clad panel and no commoning layer. The substrate surface is catalyzed with a palladium seed, and the photoresist is applied directly to this surface and patterned. The electroless plating builds up additively to create the traces. Since there is no commoning layer, if it is desired to continue with precious metal or tin/lead plating, this plating also has to be electroless.
[0018] Electroless gold is advantageous for wire bonding, but is not good for LGA pads or connector fingers where a ‘hard’ gold is needed. Solder paste can be used for places that need tin/lead.
[0019] The other method to create a PWB is the standard ‘print and etch’ process. In this process, the drilled substrate is plated with copper, a negative photoresist is applied and patterned, the panel is then etched such that the areas opened in the photoresist are etched away and the covered areas are protected. Again, there is no commoning layer, so to finish a board with hard gold requires a method, such as personalizing one side of the substrate only, so that the other side is left copper clad. The copper clad side acts as a commoning layer for a single sided gold plate. The gold plated side is then subsequently covered with a photoresist and the copper clad side is patterned and etched.
[0020] The problem with the first ‘base process’ is that the nickel and gold are plated onto the copper with the photoresist in place. Hence, the process is ‘non-conformal’ in that it does not plate the sidewalls of the copper features. When the commoning layer is etched, the more noble nickel/gold layer will not be etched but the underlying copper features and commoning layer will. When two dissimilar metals are in contact with one another, a galvanic cell is created upon exposure to an ionic solution. In this galvanic cell, the less noble metal (copper) acts like the anode and is preferentially etched while the more noble metals (nickel and gold) are the cathode. This is the same analogy as the rivets in the hull of a ship. If the rivets are a different metal than that of a ship hull, the rivets will corrode when exposed to seawater. In the circuit board, the galvanic etch acts to undercut the copper feature leaving a nickel/gold overhang which can subsequently break off and form a ‘sliver’. This sliver of conductive metal can then cause shorting of the circuits on the PWB.
[0021] Various techniques for PWB manufacture are described in the following patents.
[0022] U.S. Pat. No. 4,790,912 describes a selective plating process where, after a photolithographic process produces electrical tracings of copper, then tin/lead alloys may be coated upon at least part of the copper tracings.
[0023] U.S. Pat. No. 5,028,513 describes a process for producing a printed circuit board by pattern plating wherein, after copper traces are formed, additional metal such as solder, copper, nickel, gold, or other metal is deposited on the tracings.
[0024] U.S. Pat. No. 5,262,041 describes additive plating wherein a flash metal is deposited onto a substrate, followed by application of a resist. Windows are left open in the resist to the flash metal after which additional metal is deposited within the windows.
[0025] U.S. Pat. No. 5,985,124 describes nickel or nickel alloy electroplating wherein at least a partially masked electrical circuit has nickel metal deposited hereon. This may be followed by plating with gold or other precious metal.
[0026] U.S. Pat. No. 6,221,229 describes a method for forming metal conductor patterns. After metal circuit lines are formed and any excess metal is removed by laser ablation, additional metals are electrolytically deposited onto at least a portion of the circuit lines.
BRIEF DESCRIPTION OF THE INVENTION
[0027] An objective of the present invention is to meet customer needs for a printed wiring board (PWB) with electrolytic gold and other multiple surface finishes.
[0028] Another objective is a printed wiring board that does not require a non-metallic conductive coating.
[0029] Yet another objective is a pattern plated structure having a layer of hard gold electrodeposited on the circuit pattern.
[0030] In this novel invention, a method is used to provide the desired electrolytic metallizations and obtain a novel structure.
[0031] Still another objective is the use of a conductive commoning layer that is applied on top of a preformed circuitry without the need to be customized for each different circuit pattern, which is applied after the solder mask and not before, and which can be applied in very thin layers, being independent of the thickness of the circuitized layer.
[0032] These and other objects and advantages, which will become readily apparent, are achieved in the manner herein described.
[0033] The invention relates to a method of making a printed wiring board without forming slivers, comprising the following steps. The board is provided having thin circuit lines thereon. A thin conductive commoning layer is applied over the board substrate and over the thin circuit lines on the surfaces of the substrate. This layer may be a flash plate of a metallic layer, typically copper, having a thickness of between about 15 and about 200μ inches. A photoresist is then applied over the thin commoning layer after which the photoresist is removed from the commoning layer over the circuit lines. Preferably, the openings in the photoresist are sufficiently wide to expose the sidewalls of the circuit lines as well as the top surface. A thin layer of a noble metal is electrodeposited as a conforming layer over the exposed commoning layer. This more noble metal can comprise a first electrodeposit of nickel followed by a gold layer applied over the nickel in precise registry therewith. Instead, other metals, such as platinum, cobalt, silver, tin and its alloys may be applied over the commoning layer. Prior to the application of the commoning layer over the substrate and the thin circuit lines, a solder mask may be applied over any portion or portions of the circuit lines on which the thin conductive layer is not required. This is followed by the step of applying a seed catalyst layer over the solder mask and over the surfaces of the substrate that are not covered by the solder mask.
[0034] The invention also relates to a method of manufacturing a printed wiring board having a circuitized metal electrodeposit on both sides thereof. The method comprises the following steps. At least one continuous metallization layer is formed on each side of the printed wiring board. This metallization layer may be copper or a tin/palladium colloid depending on whether the circuit traces are to be formed by electrolytic pattern plating or by a full build electroless pattern plating process. Further, the conductive circuit traces may be created on each metal layer by removing unwanted metal, for example by etching. Then, any traces not requiring a selective layer of a more noble metal are masked over with a solder mask. A seed catalyst layer is applied over the entire surface, including the areas that are masked, after which a commoning layer of copper is plated to a thickness of between about 15 and about 200μ inches over the seed catalyst layer. The adhesion between the solder mask and the seed catalyst can be enhanced by roughening the surface of the mask before applying the seed catalyst. The commoning layer is then exposed over the circuit traces to be plated followed by electroplating of a conforming layer of a more noble metal over the exposed commoning layer over the circuit traces. The more noble metal can be a first layer of nickel, and a layer of gold electroplated over the nickel. Other more noble metals, such as platinum, cobalt, silver, tin and its alloys may be applied over the commoning layer instead of the nickel/gold. This is followed by stripping the photoresist layer and etching away the commoning layer between the traces. The commoning layer is exposed by applying a photoresist film over the layer and then exposing and developing the film to create openings through the film to the commoning layer over traces to be plated. Etching, as with a laser beam or other radiation, exposes the openings through the film. The photoresist is then stripped off and the commoning layer that is not protected by the nickel/gold is removed as by etching.
[0035] The invention also relates to a printed wiring board prepared according to the following steps: a) providing a substrate having thin circuit lines thereon; b) applying a thin conductive commoning layer on the substrate and the thin circuit lines; c) applying a photoresist over the commoning layer; d) processing the photoresist to expose only the commoning layer over the circuit lines to be processed; and e) applying a more noble metal over the exposed commoning layer. The panel is circuitized by any of the methods previously discussed but only to the point at which there are copper features on the panel. Then a solder mask is applied on those features that will remain SMOBC (solder mask over bare copper). This is followed by a thin commoning layer over the entire panel and the solder mask. The commoning layer is copper deposited by electroless plating or by sputter coating. A photoresist is applied to the panel and those features needing gold plating are exposed. Care must be taken not to make the opening too wide to avoid plating onto the commoning layer between copper features, while still fully exposing the features that are to be plated. This can be achieved by using a laser to ablate or develop the resist over the features inside of an expose machine. The more noble metal, typically nickel/gold, is then plated in the openings. Multiple finishes again require multiple photolithography steps. When finished, the photoresists are stripped off and the exposed commoning layer is etched.
[0036] The invention also relates to a circuit trace deposited onto a printed wiring board or a multiple layer wiring board. The circuit trace comprises copper having a rectangular or a trapezoidal cross sectional shape and having a layer of a more noble metal deposited thereon and conforming to the surface thereof. The copper comprises a laminate of a copper foil on the wiring board, a copper flash, copper electrodeposit and a commoning layer. The commoning layer has a thickness of between about 15μ inches and about 200μ inches. Typically, the commoning layer is deposited by electroless plating or sputter coating. The more noble metal comprises a nickel electrodeposit on the copper commoning layer and a gold electrodeposit on the nickel. Alternatively, the more noble metal can comprise other metals, such as platinum, cobalt, silver, tin and its alloys.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] [0037]FIG. 1 is a cross-sectional view of a printed wiring board with a full panel plate;
[0038] [0038]FIG. 2 shows a printed wiring board (PWB) after printing and etching;
[0039] [0039]FIG. 3 shows a solder mask in place;
[0040] [0040]FIG. 4 shows a commoning layer applied over the solder mask and over all exposed circuit patterns of FIG. 3;
[0041] [0041]FIG. 5 shows a patterned photoresist;
[0042] [0042]FIG. 6 shows a plate of noble metal on the circuit traces;
[0043] [0043]FIG. 7 shows the PWB with the photoresist stripped off;
[0044] [0044]FIG. 8 shows the commoning layer etched away; and
[0045] [0045]FIG. 9 is a cross sectional view of a circuit trace of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0046] A number of procedures may be used to prepare a PWB substrate which is used as the starting structure for the present invention. One such procedure utilizes full panel plating and subtractive etching. In this procedure, the substrate comprises an inner plane or multiple planes if the substrate is a multiple layer board (MLB). The inner plane is sandwiched between dielectric layers, generally of the FR-4 family of epoxy resins. The top and bottom surfaces of the substrate are covered with a copper foil laminated to the substrate using heat and pressure. One or more holes are drilled into and through the layer to form, respectively, vias and through holes. A metallization layer of, e.g., copper, is then applied over the foil and along the side of each hole. This is achieved by a combination of one or more cycles of electroless flash plating and electroplating. Following this, a photoresist is applied over the metallized surface, also covering the holes and vias. Portions of the resist are then exposed to light, actinic radiation, or a laser beam and are developed to form a pattern of covered areas in the resist conforming to the circuit patterns or traces, and open spaces between the traces. The metallized layer and foil are then removed by etching or other suitable means from the exposed surfaces of the substrate where the photoresist had previously been removed. Then the remaining photoresist is stripped off to leave a pattern of copper circuit traces.
[0047] Turning now to the drawings, FIG. 1 shows a conventionally prepared substrate 10 comprising an inner plane 12 sandwiched between layers 14 a , 14 b of a dielectric material, such as a cured epoxy resin that can be fiber glass filled, particle filled or non-glass fiber filled, polytetrafluorethylene, or other organic materials known to the industry. It is understood that for a multilayer board, the substrate 10 shown in FIG. 1 would have multiple inner planes and dielectric layers. The substrate 10 is clad in copper 22 on the top surface and copper 24 on the bottom surface. The copper cladding is typically a thin foil that is laminated to the substrate by procedures which are well-known in the art. A hole 30 is shown extending between the top and bottom surfaces. It is understood that the substrate can have a plurality of holes. Because the dielectric material in the drilled holes is nonconductive, it is necessary to provide an electrical connection for plating. At this point, the surface of substrate 10 and hole 30 are metallized with a thin coating of the copper layer 32 . A thicker layer of copper 28 is electrodeposited on top of the foil as well as the interior side walls of hole 30 .
[0048] [0048]FIG. 2 shows a PWB substrate after performing print and etch operations wherein portions of the copper has been etched away to form a plurality of circuit traces 40 . These circuit traces 40 are present on the top and bottom surface with no commoning layer. Although the structure is shown having circuit traces with a rectangular shape, it is understood that this is a representation for the figures; however, a PWB made from a full build electroless copper process would exhibit rectangular circuit traces. For the etching process used, the circuit traces have a trapezoidal shape as known in the industry rather that the “apple core” shape that results from pattern plating. Although not shown in the figures, the circuit traces also exhibit the intermediate plating steps of the plater whereas the pattern plater would not have these. Up to this point, the processing steps are conventional, and are well-known in the art.
[0049] [0049]FIG. 3 shows a solder mask 42 applied over some but not all of the circuit traces 40 on the top and bottom surfaces of the PWB. The selection as to which traces are to be covered and which are not to be covered is within the discretion of the circuit board designer. Typically, the solder mask is used to encapsulate all surfaces of the panel on which the commoning layer is not desired. A preferred solder mask is an organic high molecular weight resist layer. The layer is an acid resistant, negative photoresist, such as a photopolymerizable compound having an ethylenically unsaturated terminal bond, including compounds such as acrylic esters and methacrylic esters of polyhydric alcohols. If a universal plate is desired, the solder mask step is omitted.
[0050] It is now desired to create a conductive layer over the entire panel surface to be used as a commoning layer for subsequent electroplating. A catalyst layer (not shown) is applied over the solder mask as well as any surfaces that are not covered by solder mask. The solder mask may be roughened prior to the catalyst deposition to improve the adhesion of the catalyst to the underlying surface. The catalyst typically is a tin/palladium colloid prepared by the reduction of the palladium metal in an acid medium. The colloid is applied by immersion of the PWB or the MLB in the catalyst medium for a period from 1-10 minutes at a temperature from ambient to 150° C. to allow adsorption of the catalyst. It is understood that ionic catalyst chemistries can be used as well as other methods such as Cr sputter.
[0051] A very thin layer of copper, between about 15 and about 200μ inches in thickness, flash plated or otherwise plated over the top and bottom surfaces of the panel, is shown in FIG. 4. The flash layer covers the entire surface of the board that is covered by the catalyst, including the solder mask. This layer of copper now forms the commoning layer.
[0052] It is also understood that a commoning metallization layer can also be deposited by other techniques well known in the industry, such as sputtering, mag-ion, or other similar methods. For the embodiment being discussed, commoning layer thicknesses of 15-25 microinches was used due to the fine circuitization requirements. The highest benefit of this invention is derived by the ability to plate a very thin commoning layer so that subsequent etching of the commoning layer removes the thin layer rapidly. For most metallization methods used for the commoning layer, there is a minimum thickness that must be used to achieve a continuous electrical layer. For methods most common in the industry, this occurs at approximately 15μ inches, but is affected by the topography and planarity of the substrate. For substrates having a varied topography because of the circuit patterns and solder mask areas, or because of excessive board warpage, a thicker commoning layer may have to be used to achieve a continuous electrical layer. It is understood that, as the technology advances, it may be possible to achieve a continuous electrical layer with a thinner commoning layer. Such thinner layers are contemplated as being within the scope of the present invention.
[0053] The next step involves applying a photoresist/mask over the surfaces of the commoning layer, leaving open any copper features that are to be subsequently plated. This feature is shown in FIG. 5. In this figure, the photoresist/mask 50 is applied to both surfaces of the substrate over the commoning layer 46 . Any of the copper covered features 48 that are to be subsequently plated are intentionally left uncovered.
[0054] Turning now to FIG. 6, a layer of a more noble metal 60 than that of the commoning layer is deposited upon the exposed portions 48 of the copper traces. When copper is used as the commoning layer, any of the more noble metals disclosed in prior art patents, such as U.S. Pat. No. 4,377,448, including zinc, cadmium, chromium, nickel, cobalt, gold, silver, palladium, platinum, ruthenium, and alloys with each other and with tin and lead, may be used. Although FIG. 6 shows one layer of the noble metal 60 , it is understood that there may be at least two distinct layers. In one embodiment, the first layer is electrolytic nickel 62 , and a second layer of electrolytic gold 64 is deposited thereon. An intermediate thin layer of electroless gold can also be deposited immediately after the nickel to prevent oxidation of the nickel and to enhance the adhesion of the gold electrodeposit to the nickel. Note that registration is critical so extra fiducials can be placed about the panel for precise alignment. It is desired not to plate on the commoning layer at the laminate surface but, instead, only on the circuit traces or other patterns. The advantage of this invention becomes evident at this point. The openings in the photoresist are such that the sidewalls of the circuit patterns are exposed as well as the top surface. By providing openings in this manner, subsequent plating on the circuit patterns will be conformal to the sidewalls as well as the top, eliminating potential reliability risks due to slivers and galvanic etch.
[0055] Turning now to FIG. 7, the photoresist/masks 50 are removed. If desired, additional surface finish metallization layers can be added. Optionally, another layer of photoresist may be applied over the surfaces, again leaving exposed any areas that need a second type of metallization. Clearly, this removal and reapplication can be carried out a number of times to achieve the objective of applying different metallization layers on different portions of the printed wiring board. The difference could be in the type of the metal, the method of application, or the thickness.
[0056] [0056]FIG. 8 shows the last step in this process. In this step, the commoning layer 46 is removed by suitable means, such as by etching, typically using an ammonical etch which is the most common one used in the industry. The etching step preferentially attacks and dissolves the exposed copper surfaces without attacking the nickel/gold or tin lead on the circuit patterns. The advantage of a conformal metallization layer is evident at this processing step. This provides additional protection to the circuit traces and is particularly useful in preventing undercutting of the precious metal layer, as previously mentioned with the prior art processes.
[0057] The nickel can be plated from a conventional Watts bath of NiSO 4 and NiCl 2 , or from a nickel sulfamate bath. The plating bath can also include cobalt ions so as to deposit a nickel/cobalt alloy. Buffers, such as boric acid, and brighteners, such as saccharin, can be included as needed.
[0058] The gold can be electroplated as a bright or a matte finish from alkaline cyanide or a neutral cyanide bath. Typical plating baths are disclosed in numerous publications, including the Metal Finishing Guidebook and Directory published on an annual basis by Elsevier Science Publishing Co. The noble metal electroplating baths typically do not have high throwing ability. Therefore, the through holes and vias are plated with copper, but remain relatively free of these more noble metals.
[0059] The photoresist is then stripped off the panel using a suitable organic solvent. The flash layer of copper is then etched off by chemical etching using an ammoniacal etchant, cupric chloride, ferric chloride or a sulfuric acid/peroxide etchant, being careful to avoid etching the substrate. If, prior to etching the copper commoning layer, a plurality of surface finishes is desired, one need only apply additional layers of photoresist over the areas to protect or to plate.
[0060] In FIG. 9, the structural features of the circuit traces prepared by the present invention are shown. In this figure, the completed circuit lines of the present invention are shown as trapezoidal, but it is also understood that they can be rectangular instead. The substrate 10 is shown with a cross section of a circuit trace 40 comprising a first layer of copper foil 20 . The second layer comprises copper electrodeposit 28 over the foil. Next is the commoning layer 46 representing a flash copper layer having a thickness of 0.2 mils or less. This is followed sequentially by the nickel layer 62 and the gold layer 64 . Significantly, the nickel and gold layers form a conformal layer that covers the top and extends down the sides of the trace at least to the point at which the commoning layer is intersected. This provides a more robust circuit trace and serves to preclude undermining of the nickel/gold layer during the subsequent copper etch step.
[0061] Contrasted with this cross-section are those formed by the typical additive processes of the prior art. These are somewhat parabolic in shape, and have the layers of nickel and gold on the top only. Thus, the traces tend to be structurally weaker than those made according to the present invention. And undercutting and slivering is commonplace during the step of etching the commoning layer.
[0062] The printed wiring board useful in the teaching of the present invention typically comprises a non-conductive glass-epoxy laminate in the form of a double-sided board. The board contains a high-density pattern of circuits formed according to techniques that are well established in the art. Typical of such boards are the PWBs being used for high end server, backpanel or other mother board applications. However, all printed wiring boards produced by fabricators from cellular phone applications to the aforementioned high end server boards can utilize this process.
[0063] The specific details of PWBs and their use are known to persons of ordinary skill in the art and do not comprise a part of the present invention, except to the extent that these details and uses have been modified to become part of the present invention, and to interengage with other components of an overall system. Specific details, including the programming of individual computers or processors in which the printed wiring board of the present invention is used, are not deemed to comprise a part of the present invention. The process of this invention has been found to be particularly useful when using tooling of the type generally described as a full panel plate followed by subtractive etching to form circuit traces.
[0064] While the invention has been described in combination with embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing teachings. Accordingly, the invention is intended to embrace all such alternatives, modifications and variations as fall within the spirit and scope of the appended claims.
|
A PWB or multilayer board with circuit traces is treated by a process that serves to reduce the incident of failure of the board. The process includes the steps of applying a thin commoning layer of copper onto a catalyzed surface of the board substrate and the circuit lines. A photoresist is then applied over the commoning layer after which the photoresist is removed only from the commoning material over the circuit lines. A thin layer of a more noble metal, such as nickel, is electrodeposited over the exposed conductive layer. This is followed by a gold layer electrodeposited over the nickel in close registry therewith. The process provides the traces with a conforming nickel/gold layer that extends down the side of the traces. This reduces the tendency of a subsequent copper etch step from undercutting the nickel/gold, thereby causing slivers that could cause short circuiting between adjacent circuit patterns.
| 2
|
[0001] This application is a continuation of U.S. Ser. No. 09/633,156 filed on Aug. 4, 2000, the contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to pharmaceutical compositions, and particularly pharmaceutical compositions incorporating compounds that are capable of affecting nicotinic cholinergic receptors. More particularly, the present invention relates to compounds capable of activating nicotinic cholinergic receptors, for example, as agonists of specific nicotinic receptor subtypes. The present invention also relates to methods for treating a wide variety of conditions and disorders, and particularly conditions and disorders associated with dysfunction of the central and autonomic nervous systems.
[0003] Nicotine has been proposed to have a number of pharmacological effects. See, for example, Pullan et al. N. Engl. J. Med. 330:811-815 (1994). Certain of those effects may be related to effects upon neurotransmitter release. See for example, Sjak-shie et al., Brain Res. 624:295 (1993), where neuroprotective effects of nicotine are proposed. Release of acetylcholine and dopamine by neurons, upon administration of nicotine, has been reported by Rowell et al., J. Neurochem. 43:1593 (1984); Rapier et al., J. Neurochem. 50: 1123 (1988); Sandor et al., Brain Res. 567: 313 (1991) and Vizi, Br. J. Pharmacol. 47: 765 (1973). Release of norepinephrine by neurons, upon administration of nicotine, has been reported by Hall et al., Biochem. Pharmacol. 21: 1829 (1972). Release of serotonin by neurons, upon administration of nicotine, has been reported by Hery et al., Arch. Int. Pharmacodyn. Ther. 296: 91 (1977). Release of glutamate by neurons, upon administration of nicotine, has been reported by Toth et al., Neurochem Res. 17: 265 (1992). In addition, nicotine reportedly potentiates the pharmacological behavior of certain pharmaceutical compositions used for the treatment of certain disorders. See, Sanberg et al., Pharmacol. Biochem. & Behavior 46: 303 (1993); Harsing et al., J. Neurochem. 59: 48 (1993) and Hughes, Proceedings from Intl. Symp. Nic. S 40 (1994). Furthermore, various other beneficial pharmacological effects of nicotine have been proposed. See, Decina et al., Biol. Psychiatiy 28: 502 (1990); Wagner et al., Pharmacopsychiatry 21: 301 (1988); Pomerleau et al., Addictive Behaviors 9: 265 (1984); Onaivi et al., Life Sci. 54(3): 193 (1994); Tripathi et al., JPET 221: 91-96 (1982) and Hamon, Trends in Pharmacol. Res. 15: 36.
[0004] Various nicotinic compounds have been reported as being useful for treating a wide variety of conditions and disorders. See, for example, Williams et al. DN & P 7(4): 205-227 (1994), Arneric et al., CNS Drug Rev. 1(1): 1-26 (1995), Arneric et al., Exp. Opin. Invest. Drugs 5(1): 79-100 (1996), Bencherif et al., JPET 279: 1413 (1996), Lippiello et al., JPET 279: 1422 (1996), Damaj et al., Neuroscience ( 1997), Holladay et al., J. Med. Chem 40(28): 4169-4194 (1997), Bannon et al., Science 279: 77-80 (1998), Japan Patent 7061940 to Kozo et al., PCT WO 94/08992, PCT WO 96/31475, PCT WO 96/40682, PCT WO 97/11072, U.S. patent application Ser. No. 09/210,113, filed on Dec. 11, 1998 and Ser. No. 09/327, 141, filed Jun. 7,1999, and U.S. Pat. No. 5,583,140 to Bencherif et al., U.S. Pat. No. 5,597,919 to Dull et al. U.S. Pat. No. 5,604,231 to Smith et al., U.S. Pat. Nos. 5,817,679, 5,852,041 to Cosford et al. and U.S. Pat. No. 6,060,473 to Shen et al. Nicotinic compounds are reported as being particularly useful for treating a wide variety of Central Nervous System (CNS) disorders.
[0005] CNS disorders are a type of neurological disorder. CNS disorders can be drug induced; can be attributed to genetic predisposition, infection or trauma; or can be of unknown etiology. CNS disorders comprise neuropsychiatric disorders, neurological diseases and mental illnesses; and include neurodegenerative diseases, behavioral disorders, cognitive disorders and cognitive affective disorders. There are several CNS disorders whose clinical manifestations have been attributed to CNS dysfunction (i.e., disorders resulting from inappropriate levels of neurotransmitter release, inappropriate properties of neurotransmitter receptors, and/or inappropriate interaction between neurotransmitters and neurotransmitter receptors). Several CNS disorders can be attributed to a cholinergic deficiency, a dopaminergic deficiency, an adrenergic deficiency and/or a serotonergic deficiency. CNS disorders of relatively common occurrence include presenile dementia (early onset Alzheimer's disease), senile dementia (dementia of the Alzheimer's type), Parkinsonism including Parkinson's disease, Huntington's chorea, tardive dyskinesia, hyperkinesia, mania, attention deficit disorder, anxiety, dyslexia, schizophrenia and Tourette's syndrome.
[0006] It would be desirable to provide a useful method for the prevention and treatment of a condition or disorder by administering a nicotinic compound to a patient susceptible to or suffering from such a condition or disorder. It would be highly beneficial to provide individuals suffering from certain disorders (e.g., CNS diseases) with interruption of the symptoms of those disorders by the administration of a pharmaceutical composition containing an active ingredient having nicotinic pharmacology and which has a beneficial effect (e.g., upon the functioning of the CNS), but which does not provide any significant associated side effects. It would be highly desirable to provide a pharmaceutical composition incorporating a compound which interacts with nicotinic receptors, such as those which have the potential to effect the functioning of the CNS, but which compound when employed in an amount sufficient to effect the functioning of the CNS, does not significantly effect those receptor subtypes which have the potential to induce undesirable side effects (e.g., appreciable activity at skeletal muscle sites).
SUMMARY OF THE INVENTION
[0007] The present invention relates to compounds in which an aromatic ring is bridged with an ethylenic or acetylenic unit to an azabicyclic moiety. Of particular interest are compounds such as (E)-5-(2-(7-azabicyclo[2.2.1]hept-2-yl)ethenyl)isoxazole and (E)-2-(2-(3-pyridyl)ethenyl)-7-azabicyclo[2.2.1]heptane. The present invention also relates to prodrug derivatives of the compounds of the present invention.
[0008] The present invention also relates to methods for the prevention or treatment of a wide variety of conditions or disorders, and particularly those disorders characterized by disfunction of nicotinic cholinergic neurotransmission including disorders involving neuromodulation of neurotransmitter release, such as dopamine release. The present invention also relates to methods for the prevention or treatment of disorders, such as central nervous system (CNS) disorders, which are characterized by an alteration in normal neurotransmitter release. The present invention also relates to methods for the treatment of certain conditions (e.g., a method for alleviating pain). The methods involve administering to a subject an effective amount of a compound of the present invention.
[0009] The present invention, in another aspect, relates to a pharmaceutical composition comprising an effective amount of a compound of the present invention. Such a pharmaceutical composition incorporates a compound which, when employed in effective amounts, has the capability of interacting with relevant nicotinic receptor sites of a subject, and hence has the capability of acting as a therapeutic agent in the prevention or treatment of a wide variety of conditions and disorders, particularly those disorders characterized by an alteration in normal neurotransmitter release. Preferred pharmaceutical compositions comprise compounds of the present invention.
[0010] The pharmaceutical compositions of the present invention are useful for the prevention and treatment of disorders, such as CNS disorders, which are characterized by an alteration in normal neurotransmitter release. The pharmaceutical compositions provide therapeutic benefit to individuals suffering from such disorders and exhibiting clinical manifestations of such disorders in that the compounds within those compositions, when employed in effective amounts, have the potential to (i) exhibit nicotinic pharmacology and affect relevant nicotinic receptors sites (e.g., act as a pharmacological agonist to activate nicotinic receptors), and (ii) elicit neurotransmitter secretion, and hence prevent and suppress the symptoms associated with those diseases. In addition, the compounds are expected to have the potential to (i) increase the number of nicotinic cholinergic receptors of the brain of the patient, (ii) exhibit neuroprotective effects and (iii) when employed in effective amounts do not cause appreciable adverse side effects (e.g., significant increases in blood pressure and heart rate, significant negative effects upon the gastrointestinal tract, and significant effects upon skeletal muscle). The pharmaceutical compositions of the present invention are believed to be safe and effective with regards to prevention and treatment of a wide variety of conditions and disorders.
[0011] The foregoing and other aspects of the present invention are explained in detail in the detailed description and examples set forth below.
DETAILED DESCRIPTION OF THE INVENTION
[0012] The compounds of the present invention include compounds having the structure represented by the formula:
[0013] In the structure, Cy represents a suitable 5 or 6 member aromatic ring, and exemplary ring systems are set forth hereinafter. B′ represents a suitable bridging moiety, such as a bridging moiety having a length of two carbon atoms (e.g., an ethylenic or acetylenic moiety). When the bridging moiety is ethylenic, the compound can have a Z (cis) or E (trans) form, but preferably the E (trans) form. Q is (CH 2 ) m , Q′ is (CH 2 ) p , and Q″ is (CH 2 ) q where m is 1, 2, 3 or 4 (preferably 1, 2 or 3), p is 0,1, 2 or 3 (preferably 0, 1 or 2), and q is 0, 1 or 2 (preferably 0 or 1). In addition, the values of m, p and q are selected such that the azabicyclic ring contains 6 members, or 7 members, or 8 members, or 9 members. Z J represents a suitable non-hydrogen substituent group, and exemplary groups are set forth hereinafter. In addition, j is an integer from 0 to 5, preferably 0 or 1. At the point of attachment of B′ to the azabicyclic ring system, the stereochemistry of the compound can be either endo or exo. Z′ is either hydrogen or lower alkyl(C 1-8 ), and Z′ can be positioned at any location within the azabicyclic ring.
[0014] For representative compounds of the present invention, Cy includes the following:
[0015] Cy can be a five member heteroaromatic ring, such as one of those described in U.S. Pat. No. 6,022,868 to Olesen et al., the disclosure of which is incorporated by reference in its entirety, which may bear suitable non-hydrogen substituent species as set forth hereinafter. Thus, as used herein, the terms “5 or 6 member aromatic ring” and “five or six member heteroaromatic ring” refer to aromatic ring systems wherein the structure of the ring is composed of either 5 or 6 members (e.g., carbon atoms, or carbon and nitrogen atoms); and those 5 or 6 member rings can possess suitable substituent moieties. Each of X, X′ and X″ are individually nitrogen, nitrogen bonded to oxygen (e.g., an N-oxide or N—O functionality) or carbon bonded to a substituent species characterized as having a sigma m value greater than 0, often greater than 0.1, and generally greater than 0.2, and even greater than 0.3; less than 0 and generally less than −0.1; or 0; as determined in accordance with Hansch et al., Chem. Rev. 91: 165 (1991). When any of X, X′ and X″ are carbon bonded to a substituent species, those substituent species typically have a sigma m value between about −0.3 and about 0.75, frequently between about −0.25 and about 0.6; and each sigma m value individually can be 0 or not equal to zero. In addition, A and A′ individually are either hydrogen or suitable non-hydrogen substituent species; and typically those substituent species have a sigma m value between about −0.3 and about 0.75, frequently between about −0.25 and about 0.6; and each sigma m value individually can be 0 or not equal to zero. Preferably, 1 or 2 of X, X′ and X″ are nitrogen or nitrogen bonded to oxygen. In addition, it is highly preferred that not more than one of X, X′ and X″ be nitrogen bonded to oxygen; and it is preferred that if one of those species is nitrogen bonded to oxygen, that species is X″. Typically, X′ is CH, CBr, CR′, or COR′, where R′ (defined hereinafter) preferably is benzyl, methyl, ethyl, isopropyl, isobutyl, tertiary butyl, cycloalkyl (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl), or an unsubstituted or substituted, five or six membered, aromatic or heteroaromatic ring. Most preferably, X″ is nitrogen. For certain other preferred compounds X″ is C—NR′R″, COR′ or CNO 2 , typically CNH 2 , CNHCH 3 or CN(CH 3 ) 2 , with CNH 2 being preferred. In certain preferred circumstances, both X′ and X″ are nitrogen. Typically, X is carbon bonded to a substituent species, and it is typical that X is carbon bonded to a substituent species such as hydrogen. Adjacent substituents of X, X′, A′, X″ and A (when adjacent X, X′ and X″ each are carbon bonded to a respective substituent component) can combine to form one or more saturated or unsaturated, substituted or unsubstituted carbocyclic or heterocyclic rings containing, but not limited to, ether, acetal, ketal, amine, ketone, lactone, lactam, carbamate, or urea functionalities.
[0016] The substituents of either X, X′ or X″ (when each respective X, X′ and X″ is carbon), the substituents A, A′ and Z, and the substituents attached to five member heteroaromatic ring representatives of unit Cy can include alkyl, substituted alkyl, alkenyl, substituted alkenyl, heterocyclyl, substituted heterocyclyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, alkylaryl, substituted alkylaryl, arylalkyl, substituted arylalkyl, halo (e.g., F, Cl, Br, or I), —NR′R″, —CF 3 , —OH, —CN, —NO 2 , —C 2 R′, —SH, —SCH 3 , —N 3 , —SO 2 CH 3 , —OR′, —SR′, —C(═O)NR′R″, —N R′C(═O)R′, —C(═O)R′, —C(═O)OR′, —(CH 2 ) x OR′, —OC(═O)R′, —(CR′R″) x OCH 2 C 2 R′, —(CR′R″) x C(═O)R′, —O(CR′R″) x C(═O)R′, —C 2 (CR′R″) x O R′, —(CR′R″) x NR′R″, —OC(═O)NR′R″ and —NR′C(═O)OR′ where R′ and R″ are individually hydrogen or lower alkyl (e.g., straight chain or branched alkyl including C 1 -C 8 , preferably C 1 -C 5 , such as methyl, ethyl, or isopropyl), an aromatic group-containing species or a substituted aromatic group-containing species, and x is an integer from 1 to 6. R′ and R″ can be straight chain or branched alkyl, or R′ and R″ can form a cycloalkyl functionality. Representative aromatic group-containing species include pyridinyl, quinolinyl, pyrimidinyl, phenyl, and benzyl (where any of the foregoing can be suitably substituted with at least one substituent group, such as alkyl, hydroxyl, alkoxy, halo, or amino substituents). Other representative aromatic ring systems are set forth in Gibson et al., J. Med. Chem. 39: 4065 (1996). The substituents of X, X′ and X″, the substituents A and A′, and the substituents attached to five member heteroaromatic ring representatives of unit Cy individually can include hydrogen.
[0017] When B′ is ethylenic, B′ can be represented as —CE′=CE″-, where E′ and E″ individually represent hydrogen or a suitable non-hydrogen substituent (e.g., alkyl, substituted alkyl, halo substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocyclyl, substituted heterocyclyl, aryl, substituted aryl, alkylaryl, substituted alkylaryl, arylalkyl or substituted arylalkyl), preferably lower alkyl (e.g., straight chain or branched alkyl including C 1 -C 8 , preferably C 1 -C 5 , such as methyl, ethyl, or isopropyl) or halo substituted lower alkyl (e.g., straight chain or branched alkyl including C 1 -C 8 , preferably C 1 -C 5 , such as trifluoromethyl or trichloromethyl). Generally, both of E′ and E″ are hydrogen; or one of E′ or E″ is non-hydrogen (e.g., alkyl, such as methyl) and the other is hydrogen.
[0018] Compounds of the present invention can, depending on their structure, occur as stereoisomers (e.g., E/Z isomers about a double bond or R,S isomers about a chiral center). Both the bicyclic ring system and the bridging moiety (B′) can be sources of stereoisomerism. The present invention relates to mixtures of stereoisomers, such as racemates, as well as single stereoisomer compounds.
[0019] As employed herein, “alkyl” refers to straight chain or branched alkyl radicals including C 1 -C 8 , preferably C 1 -C 5 , such as methyl, ethyl, or isopropyl; “substituted alkyl” refers to alkyl radicals further bearing one or more substituent groups such as hydroxy, alkoxy, mercapto, aryl, heterocyclo, halo, amino, carboxyl, carbamyl, cyano, and the like; “alkenyl” refers to straight chain or branched hydrocarbon radicals including C 1 -C 8 , preferably C 1 -C 5 and having at least one carbon-carbon double bond; “substituted alkenyl” refers to alkenyl radicals further bearing one or more substituent groups as defined above; “cycloalkyl” refers to saturated or unsaturated, non-aromatic, cyclic ring-containing radicals containing three to eight carbon atoms, preferably three to six carbon atoms; “substituted cycloalkyl” refers to cycloalkyl radicals further bearing one or more substituent groups as defined above; “aryl” refers to aromatic radicals having six to ten carbon atoms; “substituted aryl” refers to aryl radicals further bearing one or more substituent groups as defined above; “alkylaryl” refers to alkyl-substituted aryl radicals; “substituted alkylaryl” refers to alkylaryl radicals further bearing one or more substituent groups as defined above; “arylalkyl” refers to aryl-substituted alkyl radicals; “substituted arylalkyl” refers to arylalkyl radicals further bearing one or more substituent groups as defined above; “heterocyclyl” refers to saturated or unsaturated cyclic radicals containing one or more heteroatoms (e.g., O, N, S) as part of the ring structure and having two to seven carbon atoms in the ring; “substituted heterocyclyl” refers to heterocyclyl radicals further bearing one or more substituent groups as defined above.
[0020] Of particular interest are compounds of the formulas set forth hereinbefore wherein preferably j is 0, and Z′ is hydrogen or lower alkyl; preferably m is 1, 2 or 3, q is 0 or 1, and the sum of m and q is 3 or less; preferably p is 1 or 2; preferably each of E′ and E″ is hydrogen or methyl, but most preferably each of E′ and E″ is hydrogen; preferably Cy is 3-pyridyl (unsubstituted or substituted in the 5 and/or 6 position(s) with any of the aforementioned substituents), 5-pyrimidinyl (unsubstituted or substituted in the 2 position with any of the aforementioned substituents), or 3- or 5-isoxazolyl (unsubstituted or substituted in the 4 and/or 5 and 3 and/or 4 positions respectively).
[0021] Representative compounds of the present invention include the following:
[0022] (E)- and (Z)-5-(2-(7-azabicyclo[2.2.1]hept-2-yl)ethenyl)isoxazole
[0023] (E)- and (Z)-5-(2-(7-azabicyclo[2.2.1]hept-2-yl)ethenyl)-3-methylisoxazole
[0024] (E)- and (Z)-5-(2-(8-azabicyclo[3.2.1]oct-6-yl)ethenyl)isoxazole
[0025] (E)- and (Z)-5-(2-(8-azabicyclo[3.2.1]oct-6-yl)ethenyl)-3-methylisoxazole
[0026] (E)- and (Z)-5-(2-(8-azabicyclo[3.2.1]oct-2-yl)ethenyl)isoxazole
[0027] (E)- and (Z)-5-(2-(8-azabicyclo[3.2.1]oct-2-yl)ethenyl)-3-methylisoxazole
[0028] (E)- and (Z)-5-(2-(9-azabicyclo[4.2.1]non-2-yl)ethenyl)isoxazole and
[0029] (E)- and (Z)-(2-(9-azabicyclo[4.2.1]non-2-yl)ethenyl)-3-methylisoxazole.
[0030] The following compounds also are representative compounds of the present invention:
[0031] (E)- and (Z)-2-(2-(3-pyridyl)ethenyl)-7-azabicyclo[2.2.1]heptane
[0032] (E)- and (Z)-2-(2-(5-methoxy-3-pyridyl)ethenyl)-7-azabicyclo[2.2.1]heptane
[0033] (E)- and (Z)-2-(2-(5-ethoxy-3-pyridyl)ethenyl)-7-azabicyclo[2.2.1]heptane
[0034] (E)- and (Z)-2-(2-(5-isopropoxy-3-pyridyl)ethenyl)-7-azabicyclo[2.2.1]heptane
[0035] (E)- and (Z)-2-(2-(5-isobutoxy-3-pyridyl)ethenyl)-7-azabicyclo[2.2.1]heptane
[0036] (E)- and (Z)-2-(2-(5-phenoxy-3-pyridyl)ethenyl)-7-azabicyclo[2.2.1]heptane
[0037] (E)- and (Z)-2-(2-(5-benzyloxy-3-pyridyl)ethenyl)-7-azabicyclo[2.2.1]heptane
[0038] (E)- and (Z)-2-(2-(5-methoxymethyl-3-pyridyl)ethenyl)-7-azabicyclo[2.2.1]heptane
[0039] (E)- and (Z)-2-(2-(5-phenyl-3-pyridyl)ethenyl)-7-azabicyclo[2.2.1]heptane
[0040] (E)- and (Z)-2-(2-(5-hydroxy-3-pyridyl)ethenyl)-7-azabicyclo[2.2.1]heptane
[0041] (E)- and (Z)-2-(2-(5-pyrimidinyl)ethenyl)-7-azabicyclo[2.2.1]heptane
[0042] (E)- and (Z)-2-(2-(3-pyridyl)ethenyl)-8-azabicyclo[3.2.1]octane
[0043] (E)- and (Z)-6-(2-(3-pyridyl)ethenyl)-8-azabicyclo[3.2.1]octane and
[0044] (E)- and (Z)-2-(2-(3-pyridyl)ethenyl)-9-azabicyclo[4.2.1]nonane.
[0045] The following compounds also are representative compounds of the present invention:
[0046] 2-(2-(3-pyridyl)ethynyl)-7-azabicyclo[2.2.1]heptane
[0047] 2-(2-(5-methoxy-3-pyridyl)ethynyl)-7-azabicyclo[2.2.1]heptane
[0048] 2-(2-(5-ethoxy-3-pyridyl)ethynyl)-7-azabicyclo[2.2.1]heptane
[0049] 2-(2-(5-isopropoxy-3-pyridyl)ethynyl)-7-azabicyclo[2. 2.1]heptane
[0050] 2-(2-(5-isobutoxy-3-pyridyl)ethynyl)-7-azabicyclo[2.2.1]heptane
[0051] 2-(2-(5-phenoxy-3-pyridyl)ethynyl)-7-azabicyclo[2.2.1]heptane
[0052] 2-(2-(5-benzyloxy-3-pyridyl)ethynyl)-7-azabicyclo[2.2.1]heptane
[0053] 2-(2-(5-methoxymethyl-3-pyridyl)ethynyl)-7-azabicyclo[2.2.1]heptane
[0054] 2-(2-(5-phenyl-3-pyridyl)ethynyl)-7-azabicyclo[2.2.1]heptane
[0055] 2-(2-(5-hydroxy-3-pyridyl)ethynyl)-7-azabicyclo[2.2.1]heptane
[0056] 2-(2-(5-pyrimidinyl)ethynyl)-7-azabicyclo[2.2.1]heptane
[0057] 2-(2-(3-pyridyl)ethynyl)-8-azabicyclo[3.2.1]octane
[0058] 6-(2-(3-pyridyl)ethynyl)-8-azabicyclo[3.2.1]octane and
[0059] 2-(2-(3-pyridyl)ethynyl)-9-azabicyclo[4.2.1]nonane.
[0060] The manner in which arylethenyl- and arylethynyl-substituted 7-azabicyclo[2.2.1]heptane compounds of the present invention are synthetically produced can vary. Ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate can be utilized as a key intermediate in the synthetic pathway. Treatment of tropinone with ethyl chloroformate provides ethyl 8-aza-3-oxobicyclo[3.2.1]octane-8-carboxylate which is readily converted to ethyl 8-aza-2-bromo-3-oxobicyclo[3.2.1]octane-8-carboxylate upon treatment with bromine and 30% hydrogen bromide in acetic acid. Subsequent Favorski ring contraction using freshly prepared sodium ethoxide in ethanol provides ethyl 7-aza-2-(ethoxycarbonyl)bicyclo[2.2.1]heptane-7-carboxylate, as reported by Daly et al. Eur. J. Pharmacol. 321:189-194 (1997). Di-isobutylaluminum hydride reduction of the ester functionality provides ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate in modest overall yield. Horner-Wadsworth-Emmons reaction between diethyl(5-isoxazolylmethyl)phosphonate and ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate provides a mixture of ethyl(E)-5-(2-(7-azabicyclo[2.2.1]hept-2-yl)ethenyl)isoxazole carboxylate and ethyl(Z)-5-(2-(7-azabicyclo[2.2.1]hept-2-yl)ethenyl)isoxazole carboxylate. The two isomers are readily separated by chromatography. Diethyl(5-isoxazolylmethyl)phosphonate is prepared according to the method described in Deshong et. al. J. Org. Chem. 53: 1356-1364 (1988). Deprotection of the amine functionality of ethyl(E)-5-(2-(7-azabicyclo[2.2.1]hept-2-yl)ethenyl)isoxazole carboxylate using hydrochloric acid affords (E)-5-(2-(7-azabicyclo[2.2.1]hept-2-yl)ethenyl)isoxazole. The synthesis of this compound is described as Example 1. Alternatively, the treatment of ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate with 5-(lithiomethyl)isoxazole and dehydration of the resulting alcohol as described in U.S. Pat. No. 6,022,868 to Olesen et. al. followed by removal of the ethyl carbamate protecting group will provide (E)- and (Z)-5-(2-(7-azabicyclo[2.2.1]hept-2-yl)ethenyl)isoxazole.
[0061] Compounds of the present invention include those in which the isoxazole ring is substituted (e.g., on the 3 and 4 position) with moieties that are stable to the processes used in their generation. For instance, treatment of ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate with the anion of 5-diethylphosphonylmethyl-3-methylisoxazole will provide (E) and (Z)-5-(2-(7-azabicyclo[2.2.1]hept-2-yl)ethenyl)-3-methylisoxazole in a similar manner to that described for Example 1. 5-Diethylphosphonylmethyl-3-methylisoxazole can be prepared as described in Lee et. al. Synthetic Commun. 29: 3621-3636 (1999) and Lee et. al. Synthesis 2027-2029 (1999). Alternatively, treatment of 3-methyl-5-(trimethylsilyl(lithiomethyl))isoxazole with of ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate followed by removal of the carbamate protecting group will provide (E)- and (Z)-5-(2-(7-azabicyclo[2.2.1]hept-2-yl)ethenyl)-3-methylisoxazole. Techniques such as those described in U.S. Pat. No. 6,022,868 to Olesen et al. can be used. Arylethenyl-substituted azabicyclic compounds containing other five-membered heterocycles can using Horner-Wadsworth-Emmons reaction chemistry as described in U.S. Pat. No. 6,022,868 to Olesen et al. Alternatively, condensation of ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate with a 5-membered (heterocyclyl)methyllithium followed by dehydration of the resulting alcohol will provide the desired compounds. Representative examples of 5-membered (heterocyclyl)methyllithium species are described by Micetich et al. Can. J. Chem. 48: 2006-2015 (1970). Other five-membered heterocycle ethenyl azabicyclic compounds can be synthesized from the trimethylsilylmethyl derivatives of 5-membered ring heterocycles. Thus, condensation of chlorotrimethylsilane with 5-membered (heterocyclyl)methyllithiums gives trimethylsilylmethyl-substituted heterocycles, which can be deprotonated with n-butyllithium. For example see Nesi, et al. J. Organomet. Chem. 195: 275-283 (1980). Treatment of the these carbanions with ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate, followed by deprotection as described previously, will lead to the desired compounds of the present invention.
[0062] Compounds of the present invention include those in which the heterocycle is a six membered ring containing at least one nitrogen atom. For example these heterocycles represented in PCT WO 97/11072 to Olesen et al. The treatment of ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate with 3-picolyllithium followed by dehydration and deprotection of the secondary amine will provide (E)-and (Z)-2-(2-(3-pyridyl)ethenyl)-7-azabicyclo[2.2.1]heptane. Alternatively, the treatment of ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate with the anion of bis(dimethylamino)phosphonylmethylpyridine followed by de-protection of the carbamate protected amine will provide (E)- and (Z)-2-(2-(3-pyridyl)ethenyl)-7-azabicyclo[2.2.1]heptane. Bis(dimethylamino)phosphonylmethylpyridine can be synthesized according to the method by Tarasenko et al. Tett. Lett. 41: 1611-1613 (2000). (E) and (Z)-2-(2-(3-pyridyl)ethenyl)-7-azabicyclo[2.2.1]heptane may also be prepared by reaction of the lithio derivative of 3-trimethylsilylmethylpyridine with ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate followed by deprotection. Trimethylsilylmethylpyridine can be prepared as described in Tamao et al. Tetrahedron 38: 3347 (1987).
[0063] Arylethenyl-substituted azabicyclic compounds of the present invention can also be produced using palladium catalyzed coupling between an alkene and an aromatic ring. For instance, ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate can be treated with methylenetriphenylphosphorane to provide ethyl 7-aza-2-ethenylbicyclo[2.2.1]heptane-7-carboxylate. Palladium-catalyzed coupling reaction of a 3-bromopyridine or 3-iodopyridine with ethyl 7-aza-2-ethenylbicyclo[2.2.1]heptane-7-carboxylate followed by de-protection of the carbamate protected amine will afford (E)-2-(2-(3-pyridyl)ethenyl)-7-azabicyclo[2.2.1]heptane. Reaction conditions employing palladium(II) acetate, tri-o-tolylphosphine, and triethylamine, similar to those described by Frank et. al., J. Org. Chem. 43 (15): 2947-2949 (1978) and Malek et. al., J. Org. Chem. 47: 5395 (1982) can be used.
[0064] Arylethynyl-substituted azabicyclic compounds of the present invention can be produced in a similar manner using palladium catalyzed coupling between an alkyne and an aromatic ring. Thus, the coupling ethyl 7-aza-2-ethynylbicyclo[2.2.1]heptane-7-carboxylate with a 5-substituted 3-halo pyridine (i.e. 3-bromo-5-isopropoxypyridine) under Sonagashira reaction conditions, followed by removal of ethyl carbamate protecting group, will provide 2-(2-(3-(5-isopropoxypyridyl))ethynyl)-7-azabicyclo[2.2.1]heptane. Typically, the types of procedures set forth in K. Nakamura et. al. Synlett 549 (1999), J. W. Tilley et. al. J. Org. Chem. 53: 386 (1988) and S. Thornrad et. al. J. Org. Chem. 63: 8551 (1998), involving the palladium and copper(I) catalyzed coupling of an alkyne and a halo-substituted pyridine or benzene, are used. Ethyl 7-aza-2-ethynylbicyclo[2.2.1]heptane-7-carboxylate can be prepared by treatment of ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate with triphenylphosphine and carbon tetrabromide followed by n-butyllithium. This can be performed as described in Eymery et al. Synthesis: 185-213 (2000).
[0065] Compounds of the present invention include those in which the pyridine ring is substituted (e.g., on the 5 position) with moieties that are stable to the processes used in their generation. For instance, a variety of 5-alkoxy, 5-aryloxy and 5-aryl substituents can be accommodated by the reactions described previously for the assembling of the ethenyl and ethynyl linkage between the pyridine ring and the azabicyclic unit. The 5-alkoxy- and 5-aryloxy-3-bromopyridines required for the production of these compounds can be made in various ways. In one method, 3,5-dibromopyridine is heated with an excess of sodium alkoxide or sodium aryloxide in N,N-dimethylformamide (with or without copper powder catalyst). Techniques such as those described in D. L. Comins et al., J. Org. Chem. 55: 69-73 (1990) and H. J. den Hertog et al., Recl. Trav. Chim. Pays - Bas 74:1171-1178 (1955) can be used for this purpose. The 5-alkoxy- and 5-aryloxy-3-bromopyridines thus produced can be coupled with ethyl 7-aza-2-ethenylbicyclo[2.2.1]heptane-7-carboxylate or ethyl 7-aza-2-ethynylbicyclo[2.2.1]heptane-7-carboxylate, using palladium (II) catalysis. Alternatively, 5-alkoxy-3-bromopyridines can be generated from 5-bromonicotinic acid as follows: (i) 5-Bromonicotinic acid is converted to 5-bromonicotinamide by sequential treatment with thionyl chloride and aqueous ammonia. (ii) The resulting 5-bromonicotinamide, previously described by C. V. Greco et al., J. Heteocyclic Chem. 7(4): 761 (1970), is subjected to Hofmann degradation by treatment with sodium hydroxide and a 70% solution of calcium hypochlorite. (iii) The resulting 3-amino-5-bromopyridine, previously described by C. V. Greco et al., J. Heteocyclic Chem. 7(4): 761 (1970), can be converted to 5-alkoxy-3-bromopyridines by diazotization (with isoamyl nitrite under acidic conditions) in the presence of alcohols.
[0066] 5-Aryl-3-bromopyridines, generated from Suzuki coupling of 3,5-dibromopyridine and arylboronic acids, can also be used in the palladium catalyzed reactions previously described. For instance, 5-phenyl-3-bromopyridine can be made by treatment of 3,5-dibromopyridine with phenylboronic acid in the presence tetrakis(triphenylphosphine)palladium(0). Procedures such as those described by N. Miyaura and A. Suzuki, Chem. Rev. 95: 2457-2483 (1995) can be used. Subsequent palladium catalyzed reaction with ethyl 7-aza-2-ethenyl bicyclo[2.2.1]heptane-7-carboxylate or ethyl 7-aza-2-ethynylbicyclo[2.2.1]heptane-7-carboxylate (as previously described for 3-bromopyridine), followed by deprotection will provide the substituted pyridylethenylazabicycle or substituted pyridylethynylazabicycle. For example, palladium (II) catalyzed coupling of ethyl 7-aza-2-ethenylbicyclo[2.2.1]heptane-7-carboxylate and 5-phenyl-3-bromopyridine (followed by hydrolytic removal of the ethyl carbamate) will produce (E)-2-(2-(3-(5-phenylpyridyl))ethenyl)-7-azabicyclo[2.2.1]heptane.
[0067] Other 2-(2-(3-(5-substitutedpyridyl))ethenyl)-7-azabicyclo[2.2.1]heptanes and 2-(2-(3-(5-substitutedpyridyl))ethynyl)-7-azabicyclo[2.2.1]heptanes can be generated from commercially available 3,5-dibromopyridine, using techniques known to those skilled in the art of organic synthesis. Thus, coupling of 3,5-dibromopyridine to ethyl 7-aza-2-ethenylbicyclo[2.2.1]heptane-7-carboxylate or ethyl 7-aza-2-ethynylbicyclo[2.2.1]heptane-7-carboxylate will provide the 5-bromo derivatives, which can be used as precursors for other 5-substituted compounds. For instance, (E)-2-(2-(3-(5-bromopyridyl))ethenyl)-7-azabicyclo[2.2.1]heptane can be converted into (E)-7-tosyl-2-(2-(3-(5-bromopyridyl))ethenyl)-7-azabicyclo[2.2.1]heptane by the action of toluenesulfonyl chloride as described by S. Ji, et al., J. Amer. Chem. Soc. 89: 5311-5312 (1967). (E)-7-Tosyl-2-(2-(3-(5-bromopyridyl))ethenyl)-7-azabicyclo[2.2.1]heptane can then be heated with aqueous ammonia and cupric sulfate to generate the corresponding 5-amino substituted material, (E)-7-tosyl-2-(2-(3-(5-aminopyridyl))ethenyl)-7-azabicyclo[2.2.1]heptane. Such a method is reported by C. Zwart et al., Recueil Trav. Chim. Pays - Bas 74: 1062-1069 (1955). 5-Alkylamino substituted compounds can be prepared in a similar manner. 5-Ethynyl-substituted compounds can be prepared from the 5-bromo compound by palladium catalyzed coupling using 2-methyl-3-butyn-2-ol, followed by base (sodium hydride) catalyzed removal of the acetone unit, according to the general techniques described in N.D.P. Cosford et al., J. Med. Chem. 39: 3235-3237 (1996). The 5-azido substituted analogs can be prepared from the 5-bromo compound by reaction with lithium azide in N,N-dimethylformamide. 5-Alkylthio substituted analogs can be prepared from the 5-bromo compound by reaction with an appropriate sodium alkylmercaptide(sodium alkanethiolate), using techniques known to those skilled in the art of organic synthesis. The tosyl protecting group may be removed by reductive desulfonation using sodium naphthalide, as described by S. Ji, et al., J. Amer. Chem. Soc. 89: 5311-5312 (1967).
[0068] A number of other analogs, bearing substituents in the 5 position of the pyridine ring, can be synthesized from (E)-7-tosyl-2-(2-(3-(5-aminopyridyl))ethenyl)-7-azabicyclo[2.2.1]heptane (the synthesis of which is described above) via the 5-diazonium salt intermediate. Among the other 5-substituted analogs that can be produced from 5-diazonium salt intermediates are: 5-hydroxy analogs, 5-alkoxy analogs, 5-fluoro analogs, 5-chloro analogs, 5-bromo analogs, 5-iodo analogs, 5-cyano analogs, and 5-mercapto analogs. These compounds can be synthesized using the general techniques set forth in C. Zwart et al., Recueil Trav. Chim. Pays - Bas 74:1062-1069 (1955). For example, 5-hydroxy substituted analogs can be prepared from the reaction of the corresponding 5-diazonium salt intermediates with water. 5-Alkoxy analogs can be made from the reaction of the diazonium salts with alcohols. 5-Fluoro substituted analogs can be prepared from the reaction of the 5-diazonium salt intermediates with fluoroboric acid. 5-Chloro substituted analogs can be prepared from the reaction of the 5-amino compounds with sodium nitrite and hydrochloric acid in the presence of copper chloride. 5-Cyano substituted analogs can be prepared from the reaction of the corresponding 5-diazonium salt intermediates with copper cyanide. Appropriate 5-diazonium salt intermediates can also be used for the synthesis of mercapto substituted analogs using the general techniques described in J. M. Hoffman et al., J. Med. Chem. 36: 953-966 (1993). The 5-mercapto substituted analogs can in turn be converted to the 5-alkylthio substituted analogs by reaction with sodium hydride and an appropriate alkyl bromide. 5-Acylamido analogs of the aforementioned compounds can be prepared by reaction of the corresponding 5-amino compounds with an appropriate acid anhydride or acid chloride using techniques known to those skilled in the art of organic synthesis.
[0069] 5-Hydroxy substituted analogs of the aforementioned compounds can be used to prepare corresponding 5-alkanoyloxy substituted compounds by reaction with the appropriate acid, acid chloride, or acid anhydride. 5-Cyano substituted analogs of the aforementioned compounds can be hydrolyzed to afford the corresponding 5-carboxamido substituted compounds. Further hydrolysis results in formation of the corresponding 5-carboxylic acid substituted analogs. Reduction of the 5-cyano substituted analogs with lithium aluminum hydride yields the corresponding 5-aminomethyl analogs. 5-Acyl substituted analogs can be prepared from corresponding 5-carboxylic acid substituted analogs by reaction with an appropriate alkyl lithium using techniques known to those skilled in the art.
[0070] 5-Carboxylic acid substituted analogs of the aforementioned compounds can be converted to the corresponding esters by reaction with an appropriate alcohol and acid catalyst. Compounds with an ester group at the 5-pyridyl position can be reduced with sodium borohydride or lithium aluminum hydride to produce the corresponding 5-hydroxymethyl substituted analogs. These analogs in turn can be converted to compounds bearing an ether moiety at the 5-pyridyl position by reaction with sodium hydride and an appropriate alkyl halide, using conventional techniques. Alternatively, the 5-hydroxymethyl substituted analogs can be reacted with tosyl chloride to provide the corresponding 5-tosyloxymethyl analogs. The 5-carboxylic acid substituted analogs can also be converted to the corresponding 5-alkylaminoacyl analogs by reaction with thionyl chloride and the appropriate alkylamine.
[0071] 5-Tosyloxymethyl substituted analogs of the aforementioned compounds can be converted to the corresponding 5-methyl substituted compounds by reduction with lithium aluminum hydride. 5-Tosyloxymethyl substituted analogs of the aforementioned compounds can also be used to produce 5-alkyl substituted compounds via reaction with an alkyllithium. 5-Hydroxy substituted analogs of the aforementioned compounds can be used to prepare 5-N-alkylcarbamoyloxy substituted compounds by reaction with N-alkylisocyanates. 5-Amino substituted analogs of the aforementioned compounds can be used to prepare 5-N-alkoxycarboxamido substituted compounds by reaction with alkyl chloroformate esters, using techniques known to those skilled in the art of organic synthesis.
[0072] The synthesis of arylethenyl-substituted 8-azabicyclo[3.2.1]octanes and arylethynyl-substituted 8-azabicyclo[3.2.1]octanes are accomplished in a manner similar to that described for arylethenyl-substituted 7-azabicyclo[2.2.1]heptanes and arylethynyl-substituted 7-azabicyclo[2.2.1]heptanes. Treatment of pseudopelletierine(N-methyl-9-azabicyclo[3.3.1]nonan-3-one) as described earlier for tropinone (Daly et al. Eur. J. Pharmacol. 321:189-194 (1997)) will generate ethyl 8-aza-6-(ethoxycarbonyl)bicyclo[3.2.1]octane-8-carboxylate. Pseudopelletierine is made according to Howell et al., Org. Syn. Coll. Vol IV: 816-819 (1963). Reduction of ethyl 8-aza-6-(ethoxycarbonyl)bicyclo[3.2.1]octane-8-carboxylate with diisobutylaluminum hydride and subsequent reaction of the 6-formyl derivative with diethyl(5-isoxazolylmethyl)phosphonate and n-butylithium will provide mixture of ethyl(E)- and (Z)-5-(2-(8-azabicyclo[3.2.1]oct-6-yl)ethenyl)isoxazole-8-carboxylate. Separation of the isomers followed by deprotection will provide (E)-5-(2-(8-azabicyclo[3.2.1]oct-6-yl)ethenyl)isoxazole and (Z)-5-(2-(8-azabicyclo[3.2.1]oct-6-yl)ethenyl)isoxazole. The other methods described previously for the preparation of five-membered heterocycle analogues of ethenyl-substituted 7-azabicyclo[2.2.1]heptanes may be applied similarly.
[0073] The palladium catalyzed reaction of ethyl 8-aza-6-ethenylbicyclo[3.2.1]octane-8-carboxylate (prepared by Wittig methylenation of the aldehyde) with 3-bromopyridine followed by deprotection of the amine will provide (E)- and (Z)-6-(2-(3-pyridyl)ethenyl)-8-azabicyclo[3.2.1]octane. Sonagashira reaction between ethyl 8-aza-6-ethynylbicyclo[3.2.1]octane-8-carboxylate (prepared by reaction of the aldehyde with triphenylphosphine and carbon tetrabromide followed by n-butyllithium) and 3-bromopyridine, then hydrolytic deprotection will provide 6-(2-(3-pyridyl)ethynyl)-8-azabicyclo[3.2.1 octane. Other olefinic and acetylenic derivatives can be made from 5-substituted-3-bromopyridines using methods previously described.
[0074] The synthesis of arylethenyl-substituted 9-azabicyclo[4.2.1]nonanes is accomplished in a similar manner. For instance, 9-p-toluenesulfonyl-9-aza-2-(methoxycarbonyl)bicyclo[4.2.1]non-2-ene, the synthesis of which is described by B. Trost and J. Oslob, J. Amer. Chem. Soc. 121: 3057-3064 (1999), serves as a suitable precursor. Reduction with diisobutylaluminum hydride will provide of 9-p-toluenesulfonyl-9-aza-2-formylbicyclo[4.2.1]nonane. Reaction of this aldehyde with diethyl(5-isoxazolylmethyl)phosphonate and n-butyllithium, then subsequent transformation as previously described, will produce (E)- and (Z)-9-p-toluenesulfonyl-5-(2-(9-azabicyclo[4.2.1]non-2-yl)ethenyl)isoxazole. Deprotection of the amine by reductive desulfonation (using sodium naphthalide, as described by S. Ji, et al., J. Amer. Chem. Soc. 89: 5311-5312 (1967) will provide (E)- and (Z)-5-(2-(9-azabicyclo[4.2.1]non-2-yl)ethenyl)isoxazole.
[0075] The palladium catalyzed reaction, of 9-p-toluenesulfonyl-9-aza-2-ethenylbicyclo[4.2.1]nonane (prepared by Wittig methylenation of the corresponding aldehyde) with 3-bromopyridine followed by deprotection of the amine will provide (E)- and (2)-2-(2-(3-pyridyl)ethenyl)-9-azabicyclo[4.2.1]nonane. Sonagashira reaction 9-p-toluenesulfonyl-9-aza-2-ethynylbicyclo[4.2.1]nonane (prepared by reaction of the aldehyde with triphenylphosphine and carbon tetrabromide followed by n-butyllithium) and 3-bromopyridine, then reductive desulfonation (using sodium naphthalide, as described by S. Ji, et al., J. Amer. Chem. Soc. 89: 5311-5312 (1967)) will provide 2-(2-(3-pyridyl)ethynyl)-9-azabicyclo[4.2.1]nonane. Other olefinic and acetylenic derivatives can be made from 5-substituted-3-bromopyridines using methods previously described.
[0076] Other aryl ethylene substituted azabicyclic systems and aryl acetylene substituted azabicyclic systems can be generated using similar methods. For instance, the previously described ethyl 8-aza-3-oxobicyclo[3.2.1]octane-8-carboxylate (see Daly et al. Eur. J. Pharmacol. 321:189-194 (1997)) provides an entry into the 3-substituted 8-azabicyclo[3.2.1]octane system. Treatment with the methoxymethylene Wittig reagent will convert ethyl 8-aza-3-oxobicyclo[3.2.1]octane-8-carboxylate into ethyl 8-aza-3-formylbicyclo[3.2.1]octane-8-carboxylate. A similar use of this Wittig reagent is described by L. Jenneskens et al., J. Org. Chem. 51: 2162-2168 (1986). Ethyl 8-aza-3-formylbicyclo[3.2.1]octane-8-carboxylate can then be transformed, using the techniques described previously, into 3-(2-(8-azabicyclo[3.2.1]oct-6-yl)ethenyl)isoxazole or substituted versions thereof. The aldehyde can also be transformed into the corresponding alkene or alkyne and coupled to 3-bromopyridine using palladium catalysis to provide (E)-3-(2-(3-pyridyl)ethenyl)-8-azabicyclo[3.2.1]octane or 3-(2-(3-pyridyl)ethynyl)-8-azabicyclo[3.2.1]octane.
[0077] The present invention relates to a method for providing prevention of a condition or disorder to a subject susceptible to such a condition or disorder, and for providing treatment to a subject suffering therefrom. For example, the method comprises administering to a patient an amount of a compound effective for providing some degree of prevention of the progression of a CNS disorder (i.e., provide protective effects), amelioration of the symptoms of a CNS disorder, and amelioration of the recurrence of a CNS disorder. The method involves administering an effective amount of a compound selected from the general formulae, which are set forth hereinbefore. The present invention relates to a pharmaceutical composition incorporating a compound selected from the general formulae, which are set forth hereinbefore. Optically active compounds can be employed as racemic mixtures or as enantiomers. The compounds can be employed in a free base form or in a salt form (e.g., as pharmaceutically acceptable salts). Examples of suitable pharmaceutically acceptable salts include inorganic acid addition salts such as hydrochloride, hydrobromide, sulfate, phosphate, and nitrate; organic acid addition salts such as acetate, galactarate, propionate, succinate, lactate, glycolate, malate, tartrate, citrate, maleate, fumarate, methanesulfonate, p-toluenesulfonate, and ascorbate; salts with acidic amino acid such as aspartate and glutamate; alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; ammonium salt; organic basic salts such as trimethylamine salt, triethylamine salt, pyridine salt, picoline salt, dicyclohexylamine salt, and N,N′-dibenzylethylenediamine salt; and salts with basic amino acid such as lysine salt and arginine salt. The salts may be in some cases hydrates or ethanol solvates., Representative pharmaceutically acceptable salts and the properties thereof are set forth in Berge et al., J. Pharm. Sci., 66: 1-19 (1977) and Anderson et al., In: The Practice Medicinal Chemistry, Ch. 34: 739-754 (1996). Representative salts of nicotinic compounds can include those organic or inorganic acid addition salts of the type set forth in U.S. Pat. No. 5,597,919 to Dull et al., U.S. Pat. No. 5,616,716 to Dull et al. U.S. Pat. No. 5,663,356 to Ruecroft et al.; U.S. Pat. No. 5,861,423 to Caldwell et al. and U.S. Pat. No. 5,986,100 to Bencherif et al., the disclosures of which are incorporated herein by reference in their entirety. See, also, U.S. Pat. No. 3,952,050 to Price and U.S. Pat. No. 5,326,782 to Barriere et al., as well as U.S. Pat. Nos. 5,962,737 to 4,803,207 to White et al. and U.S. Pat. No. 4,528,290 to Wong et al.
[0078] Compounds of the present invention are useful for treating those types of conditions and disorders for which other types of nicotinic compounds have been proposed as therapeutics. See, for example, Williams et al. DN & P 7(4): 205-227 (1994), Arneric et al., CNS Drug Rev. 1(1): 1-26 (1995), Arneric et al., Exp. Opin. Invest. Drugs 5(1): 79-100 (1996), Bencherif et al., JPET 279: 1413 (1996), Lippiello et al., JPET 279: 1422 (1996), Damaj et al., Neuroscience (1997), Holladay et al., J. Med. Chem 40(28): 4169-4194 (1997), Bannon et al., Science 279: 77-80 (1998), PCT WO 94/08992, PCT WO 96/31475, and U.S. Pat. No. 5,583,140 to Bencherif et al., U.S. Pat. No. 5,597,919 to Dull et al., and U.S. Pat. No. 5,604,231 to Smith et al the disclosures of which are incorporated herein by reference in their entirety. Compounds of the present invention can be used as analgesics, to treat ulcerative colitis, to treat a variety of neurodegenerative diseases, and to treat convulsions such as those that are symtematic of epilepsy. CNS disorders which can be treated in accordance with the present invention include presenile dementia (early onset Alzheimer's disease), senile dementia (dementia of the Alzheimer's type), HIV-dementia, multiple cerebral infarcts, Parkinsonism including Parkinson's disease, Pick's disease, Huntington's chorea, tardive dyskinesia, hyperkinesia, mania, attention deficit disorder, anxiety, depression, mild cognitive impairment, dyslexia, schizophrenia and Tourette's syndrome. Compounds of the present invention also can be used to treat conditions such as syphillis and Creutzfeld-Jakob disease.
[0079] The pharmaceutical composition also can include various other components as additives or adjuncts. Exemplary pharmaceutically acceptable components or adjuncts which are employed in relevant circumstances include antioxidants, free radical scavenging agents, peptides, growth factors, antibiotics, bacteriostatic agents, immunosuppressives, anticoagulants, buffering agents, anti-inflammatory agents, anti-pyretics, time release binders, anaesthetics, steroids, vitamins, minerals and corticosteroids. Such components can provide additional therapeutic benefit, act to affect the therapeutic action of the pharmaceutical composition, or act towards preventing any potential side effects which may be posed as a result of administration of the pharmaceutical composition. In certain circumstances, a compound of the present invention can be employed as part of a pharmaceutical composition with other compounds intended to prevent or treat a particular disorder.
[0080] The manner in which the compounds are administered can vary. The compounds can be administered by inhalation (e.g., in the form of an aerosol either nasally or using delivery articles of the type set forth in U.S. Pat. No. 4,922,901 to Brooks et al., the disclosure of which is incorporated herein in its entirety); topically (e.g., in lotion form); orally (e.g., in liquid form within a solvent such as an aqueous or non-aqueous liquid, or within a solid carrier); intravenously (e.g., within a dextrose or saline solution); as an infusion or injection (e.g., as a suspension or as an emulsion in a pharmaceutically acceptable liquid or mixture of liquids); intrathecally; intracerebro ventricularly; or transdermally (e.g., using a transdermal patch). Although it is possible to administer the compounds in the form of a bulk active chemical, it is preferred to present each compound in the form of a pharmaceutical composition or formulation for efficient and effective administration. Exemplary methods for administering such compounds will be apparent to the skilled artisan. For example, the compounds can be administered in the form of a tablet, a hard gelatin capsule or as a time-release capsule. As another example, the compounds can be delivered transdermally using the types of patch technologies available from Novartis and Alza Corporation. The administration of the pharmaceutical compositions of the present invention can be intermittent, or at a gradual, continuous, constant or controlled rate to a warm-blooded animal, (e.g., a mammal such as a mouse, rat, cat, rabbit, dog, pig, cow, or monkey); but advantageously is preferably administered to a human being. In addition, the time of day and the number of times per day that the pharmaceutical formulation is administered can vary. Administration preferably is such that the active ingredients of the pharmaceutical formulation interact with receptor sites within the body of the subject that effect the functioning of the CNS. More specifically, in treating a CNS disorder administration preferably is such so as to optimize the effect upon those relevant receptor subtypes which have an effect upon the functioning of the CNS, while minimizing the effects upon muscle-type receptor subtypes. Other suitable methods for administering the compounds of the present invention are described in U.S. Pat. No. 5,604,231 to Smith et al.
[0081] The appropriate dose of the compound is that amount effective to prevent occurrence of the symptoms of the disorder or to treat some symptoms of the disorder from which the patient suffers. By “effective amount”, “therapeutic amount” or “effective dose” is meant that amount sufficient to elicit the desired pharmacological or therapeutic effects, thus resulting in effective prevention or treatment of the disorder. Thus, when treating a CNS disorder, an effective amount of compound is an amount sufficient to pass across the blood-brain barrier of the subject, to bind to relevant receptor sites in the brain of the subject, and to activate relevant nicotinic receptor subtypes (e.g., provide neurotransmitter secretion, thus resulting in effective prevention or treatment of the disorder). Prevention of the disorder is manifested by delaying the onset of the symptoms of the disorder. Treatment of the disorder is manifested by a decrease in the symptoms associated with the disorder or an amelioration of the reoccurrence of the symptoms of the disorder.
[0082] The effective dose can vary, depending upon factors such as the condition of the patient, the severity of the symptoms of the disorder, and the manner in which the pharmaceutical composition is administered. For human patients, the effective dose of typical compounds generally requires administering the compound in an amount sufficient to activate relevant receptors to effect neurotransmitter (e.g., dopamine) release but the amount should be insufficient to induce effects on skeletal muscles and ganglia to any significant degree. The effective dose of compounds will of course differ from patient to patient but in general includes amounts starting where CNS effects or other desired therapeutic effects occur, but below the amount where muscular effects are observed.
[0083] Typically, the effective dose of compounds generally requires administering the compound in an amount of less than 5 mg/kg of patient weight.
[0084] Often, the compounds of the present invention are administered in an amount from less than about 1 mg/kg patent weight, and usually less than about 100 ug/kg of patient weight, but frequently between about 10 ug to less than 100 ug/kg of patient weight. For compounds of the present invention that do not induce effects on muscle type nicotinic receptors at low concentrations, the effective dose is less than 5 mg/kg of patient weight; and often such compounds are administered in an amount from 50 ug to less than 5 mg/kg of patient weight. The foregoing effective doses typically represent that amount administered as a singlee dose, or as one or more doses administered over a 24 hour period.
[0085] For human patients, the effective dose of typical compounds generally requires administering the compound in an amount of at least about 1, often at least about 10, and frequently at least about 25 ug/24 hr./patient. For human patients, the effective dose of typical compounds requires administering the compound which generally does not exceed about 500, often does not exceed about 400, and frequently does not exceed about 300 ug/24 hr./patient. In addition, administration of the effective dose is such that the concentration of the compound within the plasma of the patient normally does not exceed 500 ng/ml, and frequently does not exceed 100 ng/ml.
[0086] The compounds useful according to the method of the present invention have the ability to pass across the blood-brain barrier of the patient. As such, such compounds have the ability to enter the central nervous system of the patient. The log P values of typical compounds, which are useful in carrying out the present invention are generally greater than about −0.5, often are greater than about 0, and frequently are greater than about 0.5. The log P values of such typical compounds generally are less than about 3, often are less than about 2, and frequently are less than about 1. Log P values provide a measure of the ability of a compound to pass across a diffusion barrier, such as a biological membrane. See, Hansch, et al., J. Med. Chem. 11: 1 (1968).
[0087] The compounds useful according to the method of the present invention have the ability to bind to, and in most circumstances, cause activation of, nicotinic dopaminergic receptors of the brain of the patient. As such, such compounds have the ability to express nicotinic pharmacology, and in particular, to act as nicotinic agonists. The receptor binding constants of typical compounds useful in carrying out the present invention generally exceed about 0.1 nM, often exceed about 1 nM, and frequently exceed about 10 nM. The receptor binding constants of certain compounds are less than about 100 uM, often are less than about 10 uM and frequently are less than about 5 uM; and of preferred compounds generally are less than about 2.5 uM, sometimes are less than about 1 uM, and can be less than about 100 nM. Receptor binding constants provide a measure of the ability of the compound to bind to half of the relevant receptor sites of certain brain cells of the patient. See, Cheng, et al., Biochem. Pharmacol. 22: 3099 (1973).
[0088] The compounds useful according to the method of the present invention have the ability to demonstrate a nicotinic function by effectively activating neurotransmitter secretion from nerve ending preparations (i.e., synaptosomes). As such, such compounds have the ability to activate relevant neurons to release or secrete acetylcholine, dopamine, and other neurotransmitters. Generally, typical compounds useful in carrying out the present invention provide for the activation of dopamine secretion in amounts of at least one third, typically at least about 10 times less, frequently at least about 100 times less, and sometimes at least about 1,000 times less, than those required for activation of muscle-type nicotinic receptors. Certain compounds of the present invention can provide secretion of dopamine in an amount which is comparable to that elicited by an equal molar amount of (S)-(−)-nicotine.
[0089] The compounds of the present invention, when employed in effective amounts in accordance with the method of the present invention, are selective to certain relevant nicotinic receptors, but do not cause significant activation of receptors associated with undesirable side effects at concentrations at least greater than those required for activation of dopamine release. By this is meant that a particular dose of compound resulting in prevention and/or treatment of a CNS disorder, is essentially ineffective in eliciting activation of certain ganglia-type nicotinic receptors at concentration higher than 5 times, preferably higher than 100 times, and more preferably higher than 1,000 times, than those required for activation of dopamine release. This selectivity of certain compounds of the present invention against those ganglia-type receptors responsible for cardiovascular side effects is demonstrated by a lack of the ability of those compounds to activate nicotinic function of adrenal chromaffin tissue at concentrations greater than those required for activation of dopamine release.
[0090] Compounds of the present invention, when employed in effective amounts in accordance with the method of the present invention, are effective towards providing some degree of prevention of the progression of CNS disorders, amelioration of the symptoms of CNS disorders, an amelioration to some degree of the reoccurrence of CNS disorders. However, such effective amounts of those compounds are not sufficient to elicit any appreciable side effects, as demonstrated by increased effects relating to skeletal muscle. As such, administration of certain compounds of the present invention provides a therapeutic window in which treatment of certain CNS disorders is provided, and certain side effects are avoided. That is, an effective dose of a compound of the present invention is sufficient to provide the desired effects upon the CNS, but is insufficient (i.e., is not at a high enough level) to provide undesirable side effects. Preferably, effective administration of a compound of the present invention resulting in treatment of CNS disorders occurs upon administration of less than ⅕, and often less than {fraction (1/10)} that amount sufficient to cause certain side effects to any significant degree.
[0091] The pharmaceutical compositions of the present invention can be employed to prevent or treat certain other conditions, diseases and disorders. Exemplary of such diseases and disorders include inflammatory bowel disease, acute cholangitis, aphteous stomatitis, arthritis (e.g., rheumatoid arthritis and ostearthritis), neurodegenerative diseases, cachexia secondary to infection (e.g., as occurs in AIDS, AIDS related complex and neoplasia), as well as those indications set forth in PCT WO 98/25619. The pharmaceutical compositions of the present invention can be employed in order to ameliorate may of the symptoms associated with those conditions, diseases and disorders. Thus, pharmaceutical compositions of the present invention can be used in treating genetic diseases and disorders, in treating autoimmune disorders such as lupus, as anti-infectious agents (e.g, for treating bacterial, fungal and viral infections, as well as the effects of other types of toxins such as sepsis), as anti-inflammatory agents (e.g., for treating acute cholangitis, aphteous stomatitis, asthma, and ulcerative colitis), and as inhibitors of cytokines release (e.g., as is desirable in the treatment of cachexia, inflammation, neurodegenerative diseases, viral infection, and neoplasia), The compounds of the present invention can also be used as adjunct therapy in combination with existing therapies in the management of the aforementioned types of diseases and disorders. In such situations, administration preferably is such that the active ingredients of the pharmaceutical formulation act to optimize effects upon abnormal cytokine production, while minimizing effects upon receptor subtypes such as those that are associated with muscle and ganglia. Administration preferably is such that active ingredients interact with regions where cytokine production is affected or occurs. For the treatment of such conditions or disorders, compounds of the present invention are very potent (i.e., affect cytokine production and/or secretion at very low concentrations), and are very efficacious (i.e., significantly inhibit cytokine production and/or secretion to a relatively high degree).
[0092] Effective doses are most preferably at very low concentrations, where maximal effects are observed to occur. Concentrations, determined as the amount of compound per volume of relevant tissue, typically provide a measure of the degree to which that compound affects cytokine production. Typically, the effective dose of such compounds generally requires administering the compound in an amount of much less than 100 ug/kg of patient weight, and even less than 10 ug/kg of patient weight. The foregoing effective doses typically represent the amount administered as a single dose, or as one or more doses administered over a 24 hour period.
[0093] For human patients, the effective dose of typical compounds generally requires administering the compound in an amount of at least about 1, often at least about 10, and frequently at least about 25 ug/24 hr./patient. For human patients, the effective dose of typical compounds requires administering the compound which generally does not exceed about 1, often does not exceed about 0.75, often does not exceed about 0.5, frequently does not exceed about 0.25 mg/24 hr./patient. In addition, administration of the effective dose is such that the concentration of the compound within the plasma of the patient normally does not exceed 500 pg/ml, often does not exceed 300 pg/ml, and frequently does not exceed 100 pg/ml. When employed in such a manner, compounds of the present invention are dose dependent, and as such, cause inhibition of cytokine production and/or secretion when employed at low concentrations but do not exhibit those inhibiting effects at higher concentrations. Compounds of the present invention exhibit inhibitory effects upon cytokine production and/or secretion when employed in amounts less than those amounts necessary to elicit activation of relevant nicotinic receptor subtypes to any significant degree.
[0094] The following examples are provided to illustrate the present invention, and should not be construed as limiting the scope thereof. In these examples, all parts and percentages are by weight, unless otherwise noted. Reaction yields are reported in mole percentages.
EXAMPLE 1
[0095] Sample No.1 is (E)-5-(2-(7-azabicyclo[2.2.1]hept-2-yl)ethenyl)isoxazole, which was Prepared in Accordance with the Following Techniques:
Ethyl 8-aza-3-oxobicyclo[3.2.1]octane-8-carboxylate
[0096] Under a nitrogen atmosphere, ethyl chloroformate (35 mL) was added drop-wise to a stirred solution of tropinone (7.00 g, 50.3 mmol) in dry tetrahydrofuran (70 mL). The reaction mixture was stirred overnight, then neutralized with a saturated aqueous sodium bicarbonate (200 mL) solution and extracted with ethyl acetate (3×50 mL). The combined ethyl acetate extracts were dried over anhydrous potassium carbonate, which was subsequently filtered off. Removal of the ethyl acetate on a rotary evaporator gave ethyl 8-aza-3-oxobicyclo[3.2.1]octane-8-carboxylate (7.70 g, 77.7%) as a light yellow, viscous oil (Daly, et al., Euro. J. Pharmacol. 32: 189-194 (1997)).
Ethyl 8-aza-2-bromo-3-oxobicyclo[3.2.1]octane-8-carboxylate
[0097] Under a nitrogen atmosphere, a mixture of bromine (0.95 mL, 18 mmol) and 30% hydrogen bromide in acetic acid (12 mL) was added drop-wise to a stirred solution of ethyl 8-aza-3-oxobicyclo[3.2.1]octane-8-carboxylate (3.63 g, 18.4 mmol) in dry dichloromethane (100 mL) at −10° C. The mixture was stirred for 45 min, neutralized with a saturated aqueous sodium bicarbonate solution and then extracted with dichloromethane (3×25 mL). The combined dichloromethane extracts were dried over anhydrous sodium sulfate, filtered and concentrated by rotary evaporation, to give a mixture of ethyl 8-aza-2-bromo-3-oxobicyclo[3.2.1]octane-8-carboxylate and a dibrominated derivative. Chromatography on a Merck silica gel 60 (70-230 mesh) column, with ethyl acetate: hexane (1:1) as eluant, provided a pure sample of ethyl 8-aza-2-bromo-3-oxobicyclo[3.2.1]octane-8-carboxylate (2.95 g, 58.1%) and a sample (2.00 g) that was a mixture of the desired compound and the dibromo derivative.
Ethyl 7-aza-2-(ethoxycarbonyl)bicyclo[2.2.1]heptane-7-carboxylate
[0098] To a stirred solution of ethyl 8-aza-2-bromo-3-oxobicyclo[3.2.1]octane-8-carboxylate (2.90 g,10.5 mmol) in anhydrous ethanol (20 mL), sodium (0.32 g, 14 mmol) dissolved in anhydrous ethanol (20 mL) was added, and the mixture stirred at room temperature for 45 min. Saturated aqueous ammonium chloride solution (40 mL) was added, and the mixture was extracted with ethyl acetate (4×25 mL). The combined ethyl acetate extracts were dried over anhydrous sodium sulfate, filtered, and concentrated on a rotary evaporator, leaving a light brown, viscous oil (2.40 g). Chromatography on a Merck silica gel 60 (70-230 mesh) column, with ethyl acetate: hexane (1:3) as eluant, gave ethyl 7-aza-2-(ethoxycarbonyl)bicyclo[2.2.1]heptane-7-carboxylate (1.56 g, 75.4%) as a clear viscous oil.
Ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate
[0099] Diisobutylaluminum hydride (4.14 mL of 1.5 M solution in toluene, 6.2 mmol) was added over a period of five minutes, drop-wise, to a stirred solution of ethyl 7-aza-2-(ethoxycarbonyl)bicyclo[2.2.1]heptane-7-carboxylate (1.50 g, 6.22 mmol) in dry toluene (20 mL) under a nitrogen atmosphere at −78° C. After 4 h at -78° C, the reaction was quenched with saturated aqueous ammonium chloride solution (10 mL) and extracted with ethyl acetate (5×15 mL). The ethyl acetate extracts were combined, dried over anhydrous magnesium sulfate, filtered, and rotary evaporated to give a light brown oil (1.0 g). Column chromatography on Merck silica gel 60 (70-230 mesh), using ethyl acetate: hexane (3:1) as eluant, afforded ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate (750 mg, 61.0%) as a brown oil.
5-(Bromomethyl)isoxazole
[0100] N-bromosuccinimide (21.4 g, 120 mmol), 5-methylisoxazole (9.97 g, 120 mmol) and benzoyl peroxide (2.91g, 12.0 mmol) in carbon tetrachloride (250 mL) were heated at 80° C. for 6 h, filtered then concentrated. Distillation at reduced pressure (bp 55-60° C./1 mm Hg) provided pure product as a colorless oil (14.0 g, 72.0%).
Diethyl(5-isoxazolylmethyl)phosphonate
[0101] 5-(Bromomethyl)isoxazole (5.38 g, 33.2 mmol) was stirred at 0° C. as triethylphosphite (5.7 mL, 33.2 mmol) was slowly added. The mixture was stirred at room temperature for 48 h, heated under reflux for 24 h, then concentrated. Purification by distillation at reduced pressure (bp 109-115° C./0.04 mm Hg) provided pure product as a colorless oil (6.75 g, 92.7%).
Ethyl(E)- and (Z)-5-(2-(7-azabicyclo[2.2.1]hept-2-yl)ethenyl)isoxazole -7-carboxylate
[0102] n-Butyllithium (1.52 mL of 2.5 M in hexanes, 3.8 mmol,) was added to a stirred solution of diethyl-5-isoxazolylmethyl)phosphonate (0.834 g, 3.80 mmol) in dry tetrahydrofuran (10 mL) at 0° C. The mixture was stirred for 30 min, and then a solution of ethyl 7-aza-2-formylbicyclo[2.2.1]heptane-7-carboxylate (0.500 g, 2.53 mmol) in dry tetrahydrofuran (10 mL) was added. The mixture was stirred for 12 h, and was then poured onto saturated ammonium chloride solution and extracted using methylene chloride (2×50 mL). The combined methylene chloride extracts were dried (sodium sulfate) and concentrated. Purification by chromatography on Merck silica gel 60 (70-230 mesh), using ethyl acetate: hexane (1:9) as eluent, provided pure (E)-product as a colorless oil (0.103 g, 16%), pure (Z)-product as a colorless oil (0.172 g, 26%) and a mixture of (E)- and (Z)-product as a colorless oil (0.103 g, 16%)
(E)-5-(2-(7-Azabicyclo[2.2.1]hept-2-yl)ethenyl)isoxazole
[0103] Ethyl(E)-5-(2-(7-azabicyclo[2.2.1]hept-2-yl)ethenyl)isoxazole-7-carboxylate (0.173 g, 0.659 mmol) and concentrated aqueous hydrochloric acid (2 mL) were heated at reflux for 8 h. The mixture was partitioned between methylene chloride (20 mL) and water (10 mL). The aqueous portion was adjusted to pH 12 using 10% aqueous sodium hydroxide solution and extracted with methylene chloride (3×25 mL). The extracts were dried using sodium sulfate and concentrated to an oil. Purification by chromatography on Merck silica gel 60 (70-230 mesh) using methanol : chloroform (1:9) provided the desired product as a yellow oil (0.050 g, 40% yield).
EXAMPLE 2
[0104] Determination of Binding to Relevant Receptor Sites
[0105] Binding of the compounds to relevant receptor sites was determined in accordance with the techniques described in U.S. Pat. No. 5,597,919 to Dull et al. Inhibition constants (Ki values), reported in nM, were calculated from the IC 50 values using the method of Cheng et al., Biochem, Pharmacol. 22:3099 (1973). Low binding constants indicate that the compounds of the present invention exhibit good high affinity binding to certain CNS nicotinic receptors. The compound of Example 1 exhibits a Ki of 80 nM.
|
Pharmaceutical compositions incorporate compounds that are capable of affecting nicotinic cholinergic receptors. A wide variety of conditions and disorders, and particularly conditions and disorders associated with dysfunction of the central and autonomic nervous systems can be treated using pharmaceutical compositions incorporating compounds in which an aromatic ring is bridged with an ethylenic or acetylenic unit to an azabicyclic moiety.
| 2
|
RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent application Ser. No. 12/564,600, filed Sep. 22, 2009, which is a continuation of U.S. patent application Ser. No. 12/103,790, filed Apr. 16, 2008, the specification and drawings of both of which are fully incorporated by reference herein.
BACKGROUND OF THE INVENTION
[0002] Wire and cable for installation in residences and buildings typically comes on cable reels. The types of wire and cable so provided are numerous, and include 110V three-conductor wire, “Romex”, and many different kinds of low-voltage, multiconductor insulated communications cable, such as that used for setting up Ethernet networks, intercom systems, entertainment systems and the connection of security sensors and devices. A new building under construction will need many kinds of these cables, and several reels of cable will be used by an installer on-site.
[0003] One known technique is to provide coils of such cable in boxes, and to create a hole in a front or top panel of the (typically cardboard) box for pulling out a desired length of cable. This conventional method has a drawback in that the cable may kink inside of the box or otherwise resist being pulled out of the box to such an extent that a cable installer or technician finds that he or she is pulling the box across the floor. Oftentimes the installer has to install several different lengths of cable on a single run. To do this, the installer has had to identify which kinds of cable he or she needs, individually pull cable out of separate boxes and estimate as best as he or she can the amount of cable so pulled.
[0004] These boxes of cable are heavy and it takes some effort to move them around. In complex jobs it is easy for one needed box of cable to become physically dissociated from one or more other boxes of cable that will supply lengths of different cable for the same run. A need therefore persists for more efficient methods and apparatus for dispensing cable.
SUMMARY OF THE INVENTION
[0005] One aspect of the invention provides a container for the dispensing of electrical or communications cable wound on a cable reel. The container includes a carton having a bottom panel with left and right sides, an upstanding left panel of the carton joined to the left side of the bottom panel, and an upstanding right panel joined to the right side of the panel. A cable reel is disposed in the carton and includes an elongate spindle on which electrical or communications cable is wound. The spindle has opposed left and right ends and is adapted to rotate around a horizontal axis that is spaced from and parallel to the bottom panel of the carton.
[0006] A left support extends from the bottom panel for rotatably supporting the left end of the cable spindle to be off of the bottom panel of the carton. Similarly, a right support extends from the bottom panel for rotatably supporting the right end of the cable spindle. A continuous axial passageway is formed through the left panel of the carton, the left support, the spindle, the right support and the right panel of the carton, such that the container may be affixed to another structure by means of inserting an elongate connecting rod through the axial passageway.
[0007] Containers according to the invention may be assembled together and attached to carts, or wheel trucks, from which lengths of several different cables may be withdrawn at the same time. The containers may include pass-through slots in the top and bottom panels, which allow cable to be passed vertically from a lower container and through an upper container. This facilitates the installation of the cables in overhead areas.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] Further aspects of the invention and their advantages can be discerned in the following detailed description, in which like characters denote like parts and in which:
[0009] FIG. 1 is an isometric view of a single container or carton according to the invention, in which an outer carton wall is shown in phantom to reveal internal components;
[0010] FIG. 2 is an exploded view of a cable reel and support caddies used in the container shown in FIG. 1 ;
[0011] FIG. 2A is a detail of FIG. 2 showing a preferred caddy bushing;
[0012] FIG. 3 is an exploded isometric view of a first mobile cable dispensing system according to the invention, made up in part of cartons similar to those shown in FIGS. 1 and 2 ;
[0013] FIGS. 4A-4D are variations on the system shown in FIG. 3 , in which the size and number of joined cartons is varied;
[0014] FIG. 5 is an isometric view of a second mobile cable dispensing system according to the invention, as including a cart;
[0015] FIG. 6 is a rear end view of the cart shown in FIG. 5 ;
[0016] FIG. 7 is a detail of the front of the cart shown in FIG. 5 ;
[0017] FIG. 7A is a detail sectional view taken substantially along line 7 A- 7 A of FIG. 7 ;
[0018] FIG. 8 is an isometric view of the cart shown in FIG. 5 , in a folded or “broken down” condition in which it can be easily transported or stored;
[0019] FIG. 9 is an isometric view of two stacked cartons according to an further embodiment of the invention, showing the function of vertical cable pass-through;
[0020] FIG. 10 is an isometric view of two-wheeled hand truck or dolly for use with the cartons shown in FIG. 9 ;
[0021] FIG. 11 is an exploded isometric view of the hand truck shown in FIG. 10 , showing the loading of a single stack of cartons; and
[0022] FIG. 12 is an isometric view from another angle of the hand truck shown in FIG. 10 , as shown with two stacks of cartons.
DETAILED DESCRIPTION
[0023] FIGS. 1 and 2 show a cable reel carton indicated generally at 10 , which in turn forms the exterior components of a cable reel container 11 . Carton 10 is preferably formed of a single sheet of corrugated cardboard and includes a front panel 12 having a bottom side 14 , a left side 16 , a top side 18 and a right side 20 . The front panel 12 preferably has, in a lower portion thereof, an elongate die-cut cable dispensing or payout slot 22 through which cable or wire may be pulled. The slot 22 is elongate in a direction parallel to a cable reel axis X and is long enough to permit cable to come off the reel at right angles to the reel axis and through the slot 22 , no matter where on the reel the cable is presently being unspooled. Preferably the length of the slot 22 is selected to be at least roughly the same as the distance between the internal surfaces of the two cable reel flanges (described below).
[0024] Carton 10 also includes a left panel 24 which extends rearwardly from side 16 and at right angles to the front panel 12 , and a top panel 26 which extends rearwardly from top side 18 and at right angles to the front panel 12 and left panel 24 . The carton 10 is completed by a bottom panel 27 , a rear panel 29 and a right panel 31 , the last of which is a mirror image of the left panel 24 . An arbor hole 28 is formed in left panel 24 around the horizontal axis X, axis X being a predetermined distance h from an upper surface of the carton bottom panel 27 . The cable payout slot 22 is preferably positioned well below the axis X in order to better approximate the point of departure of the cable from the reel, which will be at some nonzero radius from the axis X. Alternatively the cable payout or dispensing slot 22 could be positioned above axis X. Payout slot 22 may be defined by a closed line of perforations in corrugated cardboard front panel 12 . In this instance, container 11 would be shipped with the payout slot 22 closed. At the installation site, the installer would open slot 22 by punching out the perforation.
[0025] Conveniently, handholes 34 may be die-cut into the cardboard panels 12 , 26 , 29 for ease in handling. In alternative embodiments the cable payout slot 22 can be repeated in top panel 26 and/or rear panel 29 , so as to give the user some flexibility in arranging the cartons in the mobile unit or on the cart (later described) and some ability to select how the cable will exit the carton 10 . An embodiment in which the carton has elongate pass-through slots in both the top and bottom panels is described in conjunction with FIG. 9 .
[0026] The interior components of container 11 are shown in exploded view in FIG. 2 . A preferably spoked left caddy 200 is, in use, disposed interiorly adjacent an inner surface of the left carton panel 24 . Caddy 200 may be injection-molded from a tough plastic that at the least is capable of suspending half of the weight of a full cable reel 202 without buckling A right caddy 204 can be formed from the same mold as the one which makes left caddy 200 . In use, the right caddy or reel support member 204 is positioned interiorly adjacent an inner surface of the right carton panel 31 .
[0027] As best seen in FIG. 2A , each caddy 200 , 204 has a substantially cylindrical bushing 206 which extends axially from a general plane in which the remainder of caddy 200 , 204 is formed toward the other caddy. The bushing 206 could be formed from a surface of rotation other than a straight cylinder; it could, for example, have a terminal lip of increased radius that would run in an annular groove (not shown) in the reel flange central hole 208 . Such a departure from a straight cylinder could allow the caddies 200 , 204 to be snapped to the cable reel 202 . In the illustrated embodiment the bushing surface 206 is slightly tapered toward its free end and has a terminal curved or rounded surface. For the purpose of defining the surface of bushing 206 as “substantially cylindrical”, these departures from a perfect mathematical cylinder are to be included in the definition. The taper and terminal curved or rounded surface aid in registering the bushing 206 within the reel flange central holes 208 .
[0028] Since caddies 200 , 204 are preferably molded of a hard plastic, the surfaces of bushings 206 tend to have a low amount of friction and can be used without augmentation. In alternative embodiments, the bushings 206 can be either coated or sleeved to present surfaces which have an even lower coefficient of friction relative to the cable reel which is rotatably mounted between them. On the other hand, some resistance to rotation of the reel 202 around axis X is desirable, as this mitigates against the spinning of the reel 202 in the absence of tension on the cable being withdrawn. Were reel 202 to continue to spin a long time without such tension, the cable 220 could spool off of the reel 202 inside of the carton 10 .
[0029] The caddies or cable reel support members 200 , 204 have bodies which generally conform in two dimensions to the interior of the carton 10 into which they are designed to be placed, and in general will be of slightly smaller dimension than, but will conform to the shape of, left box panel 24 and right box panel 31 . To save weight it is preferred that the caddies 200 , 204 be spoked instead of be solid plates. The caddies 200 , 204 suspend between them a reel 202 of cable that can weigh many dozens of pounds. Accordingly it is preferred that each caddy 200 , 204 have a horizontal base member 210 which is meant to rest on an upper surface of bottom carton panel 27 . A central, vertically oriented spoke 212 can be formed to extend from the base member 210 to a central portion 214 , from which in turn bushing 206 extends. The spokes 212 will bear most of the weight of the reel 202 . Preferably each caddy has a top rail or horizontal member 215 which in use is disposed adjacent an internal surface of top panel 26 of the carton 10 . The top rail 215 can in turn be supported by side rails 217 and angled spokes 219 . The top rail 215 is useful in accepting a columnar load imposed by other reel containers 11 placed on top of the particular reel container 11 of which the caddies 200 , 204 are a part. Such container stacking occurs in the use of the cart illustrated in FIGS. 5 and 6 and described below, and also in the embodiment discussed in conjunction with FIGS. 9-12 . In one embodiment (not shown) the spoke 212 is duplicated in a vertical spoke collinear with it which extends from axis X to the top rail 215 .
[0030] Preferably the panels of carton 10 , the caddies 200 , 204 , the cable reel 202 and the bushings 206 are so sized that the carton interior prevents the reel 202 from coming off of the bushings 206 . The carton 10 will have an internal length L in between the internal surfaces of side panels 24 and 31 . Most of the distance L will be occupied by the reel 202 , which has a predetermined length R between external surfaces of the reel flanges 222 , 224 . Each caddy 200 , 204 will have a general body thickness T. The bushings 206 extend inwardly from the general interior surfaces of the caddies 200 , 204 by a distance D. Preferably, the dimensions of these components are selected such that 2T+R is slightly less than L. On the other hand, 2T+R+2D should be somewhat greater than L, such that the cable reel 202 is forced to ride on the bushings 206 while the caddies 200 , 204 and the reel 202 are inside of the carton 10 . This dimensioning would not be necessary in those embodiments in which the caddies are snapped or otherwise affixed to the reel 202 prior to the insertion of all three components into a carton or box 10 . Further, there will be variations in reel lengths according to the amount and kind of cable wound thereon. In at least many cases, the caddies 200 , 204 will be used in many different carton sizes, so that dimension L of the carton 10 should closely follow cable reel length R.
[0031] The cable reel 202 is preselected to have a flange radius r which is smaller than axis height h. This will ensure that the reel 202 can rotate freely inside of carton 10 on bushings 206 .
[0032] Each caddy 200 , 204 has a central hole 216 sized to receive an axial support rod (later described) therethrough. Each reel 202 has an axial passageway 221 that joins together reel flange central holes 208 . Conveniently this axial passageway 221 can be formed by an interior volume of a tube which also bears the wound cable 220 on its exterior surface. As assembled and in the condition shown in FIG. 1 , each carton 10 therefore has a free passageway all the way along axis X from one side of the box 10 to the other, including a left arbor hole 28 , central hole 216 in caddy 200 , central hole 208 in left cable reel flange 222 , a central passageway between left cable reel flange 222 and right cable reel flange 224 , a central hole 216 in right caddy 204 , and an arbor hole 28 in the right carton panel 31 .
[0033] In many instances a user or installer will wish to pull the same length of different kinds of cable at the same time, usually to be installed along the same run. FIG. 3 illustrates a first cart or vehicle 300 which makes this very convenient to do. The center or backbone of the cart 300 is made up by a rigid support rod or pipe 302 that can be formed of tubular steel and in any event is strong enough to withstand buckling when supporting a hundred pounds or more of weight. The support rod 302 is threaded through the arbor holes 28 , central caddy holes 216 and reels 202 of each of a plurality of cartons 10 , 304 and 306 (three shown in FIG. 3 ). The unit 300 can be formed of containers having different lengths in an axial direction. The length of the axial rod 302 used is preselected to be a little longer than the combined exterior axial length of cartons 10 , 304 and 306 , which are arranged along rod 302 to abut each other and preferably to present front faces or panels 12 in the same direction (although one or more could be reversed). After the user or cable supplier selects cartons 10 , 304 , 306 which are to be combined, they can be taped together with tape 305 or the like to better unify them such that they will not rotate around axis X independently of each other.
[0034] A base end 308 of the rod 302 is preferably threaded and is received into a hole 310 in a wheel truck or base 312 . An upstanding panel 314 of the wheel truck 312 is affixed between a left panel 24 of an end carton 10 and a cap 316 , which screws onto the base end 308 of the rod 302 . In an alternative embodiment (not shown), rod 312 may have opposed holes drilled through the sidewall of rod 302 , at right angles to and intersecting rod 302 's axis, near base end 308 . These holes would receive a cotter pin or clevis of the kind described elsewhere herein. The wheel truck 312 , which conveniently can be fabricated of a single piece of sheet steel, further has at least one horizontal panel 317 (in the illustrated embodiment, there are two such panels 317 and 318 ) which receive a lower left corner 323 of the leftmost carton 10 . Separate casters 320 , 322 may be affixed by welding or riveting to lower surfaces of the horizontal panels 317 and 318 . Once carton 10 has been received by horizontal panels 317 and 318 , the three cartons 10 , 304 and 306 will be prevented from rotating around axis X.
[0035] A front end 324 of the axial rod 302 is fitted with or formed to have an ell 326 which may be internally threaded. The ell 326 threadably accepts a vertical member 328 of a handle 330 which may have a horizontal member 332 at its top end. After assembly, an installer can move unit 300 from place to place by pulling up on handle 330 . Half of the weight of the unit 300 will be borne by wheel truck 312 . The installer may set down the unit 300 such that axial rod 302 is at about right angles to the direction of cable pull. Casters 320 , which preferably are of the nonturning type (that is, they stay in alignment with axis X), and the forward corner 334 of carton 306 will exhibit enough friction with the floor surface that the unit 300 will resist being drawn in the direction of the cable pull.
[0036] FIGS. 4A-4D show variations on how integrated mobile multicontainer units 400 , 402 , 404 and 406 may be assembled. Unit 400 is composed of just two containers 408 , 410 . The containers 408 and 410 may be of different lengths, as would be the case where cable of smaller length or thickness was being stored in container 410 than in container 408 . A relatively short axial support rod 412 is selected for assembling the unit 400 . In contrast, unit 402 ( FIG. 4B ) is assembled from four reel containers 414 - 420 and a longer axial support rod 422 . A five-container unit 404 is shown in FIG. 4C , as composed of containers 424 - 432 and an even longer axial support rod 434 . FIG. 4D shows a unit 406 in which containers 436 - 440 are assembled together as supported by axial support rod 446 , while additional containers 442 , 444 are mounted on top of containers 436 - 440 .
[0037] FIGS. 5-8 show a four-wheeled cart 500 to which containers 502 - 520 can be mounted in up to three parallel rows, one each for respective axial support rods 522 , 524 and 526 . The support rods 522 - 526 are preferably parallel to but vertically spaced apart from each other so as to each be coaxial with a respective row of containers through which they are inserted. FIG. 5 shows cart 500 in a use configuration; when not in use it may be collapsed to a storage configuration, as explained in conjunction with FIG. 8 . The cart 500 is built on an elongate rectangular frame 528 which has a bottom plate 530 , left and right side panels or plates 532 and 534 which extend upwardly from the longitudinal edges of bottom panel 530 and which are preferably orthogonal to panel 530 , and front and rear panels 536 and 538 which extend upwardly from the transverse edges of bottom panel 530 and preferably are orthogonal to plates 530 - 534 and parallel to each other. Panels 530 - 538 can be formed from a single blank of sheet steel and together form a shallow box sized to receive the first row of reel containers 502 - 508 . The height of left side panel 532 is chosen to be somewhat less than the height of cable payout slots 22 above the bottom panels of the containers 502 - 508 , such that the cables being withdrawn from slots 22 will not be occluded or abraded by the side panel 532 . The height of right side panel 534 can be preselected to be taller than this, or can be the same height, in case that the installer chooses to face the slots 22 (or even just some of them) the opposite way.
[0038] A vertical, elongate, preferably flat front support rod holder 540 can have its lower end 542 affixed as by riveting or welding to front panel 536 . The front support rod holder more preferably is affixed to the front panel 536 by flat-headed studs 543 formed to extend from a front flat surface of holder 540 and keyed slots 545 formed in panel 536 which have top openings sized and shaped to receive therethrough a head of a respective stud 543 , and a slot depending from this opening which accepts only a shaft of the stud 543 . Other user-operable fasteners such as pins or nuts and bolts could alternatively be employed. As assembled to cart 500 , the front support rod holder 540 extends upwardly from the front panel 536 at least beyond the horizontal level of the third and highest support rod 526 . Holes 544 , 546 , 548 are made in support rod holder 540 to be sized and positioned to slidably receive ends of respective ones of the axial support rods 522 , 524 , 526 . The support rods 522 - 526 are preferably straight and have through-holes drilled through their sidewalls near their ends, so as to received clevis pins (not shown; see FIG. 8 ) after insertion of the rods through respective holder holes 544 - 548 . In an alternative embodiment (not shown); see FIG. 3 ) the rods are threaded on the ends, so as to threadably receive female threaded caps after insertion through respective holder holes 544 - 548 .
[0039] Similarly, in a use configuration a vertical elongate rear support rod holder 600 ( FIG. 6 ) has a lower end 602 affixed to rear plate 538 as by riveting, welding or (preferably) user-operable fasteners such as studs 543 received into respective keyed slots 545 . The rear support rod holder extends upwardly from the rear panel 538 at least beyond the horizontal level of the third support rod 526 . Holes 604 , 606 and 608 are made in support rod holder 600 and are sized and positioned to slidably receive rear ends of the respective ones of the axial support rods 522 , 524 and 526 . Clevis pins (not shown; see FIG. 8 ) may be inserted through diametrically opposed holes drilled in the sidewalls of the rods near their ends in order to fasten the rods in place. Alternatively caps (not shown; see representative cap 316 in FIG. 3 ) may be threaded onto the (in this instance, threaded) rear ends of the support rods 522 - 526 so as to secure the reel containers 502 - 520 between rod holders 540 and 600 .
[0040] In a preferred embodiment, the front panel 536 and the rear panel 538 extend upwardly beyond the level of the lowest axial support rod 522 . Holes 551 , 650 are made in the front and rear panels 536 , 538 to slidably receive therethrough the axial support rod 522 . Extending the front and rear panels 536 , 538 upwardly in this manner obviates any transverse deflection of the support rod holders 540 , 600 at this height, and enhances the resistance to such deflection at locations higher up on the support rod holders 540 , 600 . The upward extension of front and rear panels 536 , 538 also permits the formation of holes 551 , 650 therein to receive the lowest support rod 522 therethrough while the cart 500 is in a storage configuration, as will be hereinafter described.
[0041] The bottom panel 530 of the cart 500 has affixed thereto, as by riveting or welding, two front casters 550 which turn on their vertical axes, and two rear casters 552 which don't. In one embodiment some or all of the casters 550 - 552 may be of the type which are equipped with foot-actuated brakes (not shown), so that the cart 500 may be parked in one place.
[0042] At the front corner of left panel 532 and front panel 536 there is provided a left socket 554 , which may be joined to left panel 532 and front panel 536 by welding. Similarly, at the front corner of right panel 532 and front panel 536 there is provided a right socket 556 . Sockets 554 and 556 are vertical cylindrical sleeves meant to slidably receive respective left and right legs 558 , 560 of a handle 562 .
[0043] As shown in the detail of FIG. 7 , the left and right legs 558 , 560 of the handle 562 can be affixed to respective sockets 554 , 556 by means of cotter or clevis pins 700 , 702 . A shaft of each clevis pin 700 , 702 is inserted into a hole in a respective socket 554 or 556 , a hole in a respective handle leg 558 , 560 , a hole in the opposite wall of handle leg 558 or 560 (which conveniently can be formed of tubular steel), and finally through an inboard hole in a respective socket 554 or 556 . Another, curved leg of each clevis pin 700 , 702 meanwhile fits around the curved external surface of socket 554 or 556 , thereby locking the pin 700 or 702 in place.
[0044] FIG. 7 also provides a close-up view of left and right storage holes 704 , 706 which are not used when the cart 500 is loaded with cartons, but which are used to receive ends of support rods 524 , 526 when the cart 500 is being separately transported or stored.
[0045] FIG. 8 shows cart 500 in a “knocked down” condition. The support rod holders 540 , 600 are stored on the left and right sides of the cart interior. Keyed storage slots 800 are formed in sides 532 , 534 so as to receive studs 543 of the support rod holders 540 , 600 , affixing them in place in a storage configuration. Support rods 526 , 528 are threaded through storage holes 704 , 706 , and like storage holes in the rear panel 538 , and affixed in place as by means of cotter or clevis pins, so they don't slide out. The legs 558 , 560 of cart handle 562 are removed from respective sockets 554 , 556 and laid into the interior of the cart 500 . The lowest support rod 522 is reattached in the same position that it takes when cartons are mounted to it, but is now used as a handle to carry the cart 500 .
[0046] Returning to FIGS. 5 and 6 , cart 500 permits the stacking of containers 502 - 520 three rows high, and in alternative embodiments (not shown) a fourth or even more rows could be added, as long as the entire cart 500 is not in danger of tipping over. The containers 502 - 520 have a lessened danger of tipping over when cable is pulled from them than they otherwise would, as during a cable pull the cable is being pulled off of rotating spools 202 internal to the cartons 502 - 520 . The rotation of spools in the cartons 502 - 520 around their respective axes relieves most of the tension caused by pulling the cables, and as such the shear force experienced by the whole structure will be less than it otherwise would be. The combination of the cart 500 and the containers 502 - 520 create a wall or two-dimensional array of reels from which cable may be pulled.
[0047] In use, the installer installs one, two or three rows of containers 502 - 520 on cart 500 , employing one, two or three axial support rods 522 - 526 . If only one row of containers 502 - 508 is to be used, the support rod holders 540 and 600 aren't necessary and don't have to be installed. Otherwise the support rod holders 540 and 600 are bolted on or otherwise fastened to the front and rear plates 536 and 538 , preferably in advance of loading a first row of reel containers 502 - 508 onto the bottom plate 530 . The lowest support rod 522 is then threaded through plate 536 , support rod holder 540 , containers 502 - 508 , rear plate 538 and rear support rod holder 600 , and is fastened in place by means of threaded end caps (not shown) or clevis pins. Then, a second row of containers 510 - 514 is installed in a similar manner, using second support rod 524 . If needed, a third row of containers 516 - 520 is installed using third support rod 526 . Legs 558 , 560 of the handle 562 are then installed in respective sleeves 554 and 556 .
[0048] The cart 500 is then rolled to a desired location and is parked (as by setting its caster brakes) such that its long axis (and therefore the axes of the support rods) is at a substantial angle (such as a right angle) to the direction of cable pull. The combined mass of cart 500 and its payload provides a massive anchor against which cable can be pulled out of containers 502 - 520 through slots 22 .
[0049] FIGS. 9-12 depict an embodiment permitting the dispensing of cable from each reel in a vertical stack of containers 900 A, 900 B. Each container 900 A,B is like container 10 ( FIG. 1 ) in most respects and each such container 900 A, 900 B houses a reel 202 A, 202 B of cable as supported by reel caddies or mounting plates (omitted from FIGS. 9-12 for clarity). Each container 900 A,B has an arbor hole 28 A or 28 B in each of its side panels and a clear passageway between them, as before. Each container 900 A,B further has a front panel cable dispensing slot 22 .
[0050] The containers 900 A,B are different from containers 10 in that each additionally has an elongate top pass-through slot 902 A or 902 B in a top panel 904 thereof, and an elongate bottom pass-through slot 906 A, 906 B in a bottom panel 908 thereof. The top pass-through slot 902 A, 902 B should be positioned in top panel 904 in a way which is similar to the positioning of bottom pass-through slot 906 A, 906 B in bottom panel 908 . This is so a top pass-through slot 902 A in one container 900 A will communicate with a bottom pass-through slot 906 B in the container 900 B immediately on top of it. As in front slots 22 , it is preferred that top and bottom slots 902 A,B, 906 A,B be offset from the middle of the panel and to be parallel to but offset from the vertical plane which the reel axes will tend to occupy. Said another way, a plane containing the centers of all pass-through slots 902 - 906 in the stack will be parallel to but spaced from the plane containing the reel axes in the stack.
[0051] The pass-through slots 902 A,B, 906 A,B permit cables from different reels to exit out the top one of the slots 902 B in common. By way of example, in FIG. 9 a first cable 910 originates from a lower cable reel 202 A. The cable 910 is fed through a pass-through slot 902 A prior to the upper container 900 B being placed all the way onto the lower container 900 A. The cable 910 is fed through the bottom pass-through slot 906 B in the upper container 900 B, and thence out the top pass-through slot 902 B. A cable 912 originates from an upper reel 202 B, and is simply threaded out of the top slot 902 B. The wide extent of the slots 902 A,B, 906 A,B allows multiple cables 910 , 912 (only two such shown here) to be pulled out of the top of the stack with little resistance and with little interference with each other.
[0052] FIG. 10 shows a two-wheeled dolly or hand truck 1000 adapted to receive and hold at least one vertical stack of the containers 900 A,B. The hand truck 1000 has a bottom shelf 1002 which will receive most or all of the weight of the containers, wheels 1004 , a left vertical frame member 1006 and a right vertical frame member 1008 , both extending upwardly from the shelf 1002 . The left and right vertical frame members 1006 , 1008 may be terminated at their upper ends by a handle 1010 which may, as shown, join together the vertical frame members 1006 , 1008 .
[0053] The hand truck 1000 further includes horizontally disposed cross members 1012 , 1014 , 1016 each of which join together and bridge vertical frame members 1006 and 1008 . The elevations of the cross members 1012 , 1014 and 1016 are chosen to be at about the centers of the first, second and third containers stacked on the shelf 1002 ; the containers (such as containers 900 A,B in FIG. 9 ) should therefore be of uniform height, even if they can be of different widths. In the center of each elongate horizontal cross member 1012 - 1016 there is formed a hole 1018 A, 1018 B, 1018 C for the receipt of a respective support rod, as will be described below.
[0054] Preferably at the same elevations as horizontal cross members 1012 - 1016 are left and right side retaining plates 1020 , 1022 . Each side retaining plate 1020 or 1022 is joined to one of the vertical frame members 1006 and 1008 , has a flat and vertical inwardly facing surface, and extends forwardly therefrom in a direction orthogonal to the plane in which cross members 1012 - 1016 reside. The retaining plates 1020 , 1022 help keep the containers mounted the cart 1000 from sliding off in a transverse direction.
[0055] FIG. 11 shows cart 1000 as holding a single stack of the containers 900 A- 900 C. For this use a set of relatively short support rods 1100 , 1102 and 1104 are used to mount the containers 900 A- 900 C to the cart 1000 . First, a container 900 A is placed on shelf 1002 . If vertical dispensing is desired from this stack, a cable 910 from container 900 A is threaded through a top pass-through slot such as 902 A in FIG. 9 , and thence into a bottom slot 906 B in container 900 B. Container 900 B is then stacked on container 900 A. A cable or conductor 912 is threaded through a top pass-through slot 902 B together with cable 910 . Then both cables 910 , 912 are fed through a bottom pass-through slot (not shown; similar to slots 906 A,B) in a third container 900 C. Container 900 C is then placed on top of container 900 B. Cables 910 and 912 , respectively originating from containers 900 A and 900 B, are joined by a further cable or conductor 1106 and all are threaded through a top pass-through slot 902 C.
[0056] To firmly secure the containers 900 A-C to the hand truck 1000 , rod 1100 is inserted through arbor hole 28 A, rod 1102 is inserted through arbor hole 28 B and rod 1104 is inserted through arbor hole 28 C. The rods 1100 - 1104 continue to be inserted through the caddy holes, reel flange holes, and communicating reel passageways to and through the opposing carton sides and into and through respective cross member holes 1018 A, 1018 B and 1018 C. The inserted ends of the rods 1100 - 1104 may be drilled to receive respective clevis pins (not shown) to prevent their withdrawal. At the other end thereof, each of the rods 1100 - 1104 has an enlargement 1106 (such as a disk) that is large enough to not be admitted into a respective arbor hole 28 A-C, and which is also large enough to sufficiently distribute some of the weight of the loaded container (which the rod enlargement 1106 may experience if the hand truck 1000 is tipped forwardly) throughout its disk area without tearing or “perforating through” the typically cardboard carton panel which will be pressing against it.
[0057] FIG. 12 shows hand truck 1000 as loaded with two stacks of containers 900 A-C and 900 D-F. The reel axis inside of container 900 A should be substantially coaxial with the reel axis inside of container 900 D, and this coaxial pairing should also take place for containers 900 B, 900 E and 900 C, 900 F. This will create a continuous straight passageway for an axial rod 1200 , 1202 or 1204 from a cross member hole 1018 A-C, through all intervening carton walls, caddies, reel flanges and reel passageways, and out an arbor hole 28 located on the remote side of the remoter one 900 D-F (with respect to the cross member) of the two containers. Axial rods 1200 - 1204 , which are in general similar to axial rods 1100 - 1104 but longer, can be inserted through respective ones of these continuous horizontal passageways. A remote end of each of the axial rods 1200 - 1204 will have an enlargement like enlargement 1107 on rods 1100 - 1104 , and a near end of the axial rods 1200 - 1204 will be drilled to receive a respective clevis pin 1206 after the near end has been inserted through a respective one of the cross member holes 1018 A-C.
[0058] The cables from the reels inside of containers 900 A-C may be fed through a top pass-through slot 902 C, after being threaded through zero, one or two intervening pairs of pass-through slots in the containers 900 A-C, depending on the identity of the reel from which the cable is being paid off. Alternatively, the cables from respective containers 900 A-C may be threaded in parallel out respective front slots 22 A, 22 B, 22 C. Cable from containers 900 D-F may similarly all be drawn through top pass-through slot 902 F, or alternatively through the front slots 22 D, 22 E and 22 F thereof. The way in which cable is drawn from each stack may be the same as the way used for the other stack, or intentionally may be chosen to be different.
[0059] The pass-through-slotted containers 900 A-F may also be used with the four-wheeled cart 500 , with cables drawn out of top pass-through slots in the top row of containers affixed together by top support rod 526 .
[0060] In summary, a cable container has been provided in which a reel of cable rotates freely on caddies inside of a carton as cable is being drawn out of an offset elongate slot provided for this purpose. With the aid of an axial support rod threaded through multiple ones of these containers, two or more such containers can be combined into a single mobile cable pulling unit. For larger jobs, a cart is provided by which multiple rows of such containers are secured to the cart by respective axial support rods. A dolly or hand truck is also provided to create one or two stacks of these containers, and pass-through slots may be formed in the stacked containers to permit the pulling of all cables in the stack in a vertical direction out of one top slot.
[0061] While illustrated embodiments of the present invention have been described and illustrated in the appended drawings, the present invention is not limited thereto but only by the scope and spirit of the appended claims.
|
A container for the dispensing of electrical or communications cable has an external carton which receives a reel of cable and is supported by left and right supports. A continuous axial passageway through the container extends through the left panel of the carton, the left support, the spindle of the reel, the right support, and the right panel of the carton so that an elongate connecting rod may be passed through the container.
| 1
|
This application claims the benefit of U.S. Provisional Patent Application No. 60/743,106 filed Jan. 9, 2006, the entirety of which is incorporated herein by reference.
BACKGROUND
This invention relates generally to refiners for removing contaminants from fiber materials, such as recycled or recovered paper and packaging materials. In particular, the present invention relates to teeth on refiner plates and especially to the leading sidewall surfaces and leading edges of such teeth.
Refiner plates are used for imparting mechanical work on fibrous material. Refiner plates having teeth (in contrast to plates having bars) are typically used in refiners which role is to deflake, disperge or mix fibrous materials with or without addition of chemicals. The refiner plates disclosed herein are generally applicable to all toothed plates for dispergers specifically and refiners in general.
Disperging is primarily used in de-inking systems to recover used paper and board for reuse as raw material for producing new paper or board. Disperging is used to detach ink from fiber, disperse and reduce ink and dirt particles to a favorable size for downstream removal, and reduce particles to sizes below visible detection. The disperger is also used to break down stickies, coating particles and wax (collectively referred to as “particles”) that are often in the fibrous material fed to refiner. The particles are removed from the fibers by the disperger, become entrained in a suspension of fibrous material and liquid flowing through the refiner and are removed from the suspension as the particles float or are washed out of the suspension. In addition, the disperger may be used to mechanically treat fibers to retain or improve fiber strength and mix bleaching chemicals with fibrous pulp.
There are typically two types of mechanical dispergers used on recycled fibrous material: kneeders and rotating discs. This disclosure focuses on disc-typed disperger plates that have toothed refiner plates. Disc-type dispergers are similar to pulp and chip refiners. A refiner disc typically has mounted thereon an annular plate or an array of plate segments arranged as a circular disc. In a disc-type disperger, pulp is fed to the center of the refiner using a feed screw and moves peripherally through the disperging zone, which is a gap between the rotating (rotor) disk and stationary (stator) disk, and the pulp is ejected from the disperging zone at the periphery of the discs.
The general configuration of a disc-type disperger is two circular discs facing each other with one disc (rotor) being rotated at speeds usually up to 1800 ppm, and potentially higher speeds. The other disc is stationary (stator). Alternatively, both discs may rotate in opposite directions.
On the face of each disc is mounted a plate having teeth (also referred to as pyramids) mounted in tangential rows. A plate may be a single annular plate or an annular array of plate segments mounted on a disc. Each row of teeth is typically at a common radius from the center of the disc. The rows of rotor and stator teeth interleave when the rotor and stator discs are opposite each other in the refiner or disperger. The rows of rotor and stator teeth intersect a plane in the disperging zone that is between the discs. Channels are formed between the interleaved rows of teeth. The channels define the disperging zone between the discs.
The fibrous pulp flows alternatively between rotor and stator teeth as the pulp moves through successive rows of rotor and stator teeth. The pulp moves from the center inlet of the disc to a peripheral outlet at the outer circumference of the discs. As fibers pass from rotor teeth to stator teeth and vice-versa, the fibers are impacted as the rows of rotor teeth rotate between rows of stator teeth. The clearance between rotor and stator teeth is typically on the order of 1 to 12 mm (millimeters). The fibers are not cut by the impacts of the teeth, but are severely and alternately flexed. The impacts received by the fiber break the ink and toner particles off of the fiber and into smaller particles, and break the stickie particles off of the fibers.
Two types of plates are commonly used in disc-type dispergers: (1) a pyramidal design (also referred to as a tooth design) having an intermeshing toothed pattern, and (2) a refiner bar design. A novel pyramidal tooth design has been developed for a refiner plate and is disclosed herein.
FIGS. 1 a , 1 b and 1 c show an exemplary pyramidal plate segment having a conventional tooth pattern. An enhanced exemplary pyramidal toothed plate segment is shown in commonly-owned U.S. Patent Application Publication No. 2005/0194482, entitled “Grooved Pyramid Disperger Plate.” For pyramidal plates, fiber stock is forced radially through small channels created between the teeth on opposite plates, as shown in FIG. 1 c . Pulp fibers experience high shear, e.g., impacts, in their passage through dispergers caused by intense fiber-to-fiber and fiber-to-plate friction.
With reference to FIGS. 1 a , 1 b and 1 c , the refiner or disperger 10 comprises disperger plates 14 , 15 which are each securable to the face of one of the opposing disperger discs 12 , 13 . The discs 12 , 13 , only portions of which are shown in FIG. 1 c , each have a center axis 19 about which they rotate, radii 32 and substantially circular peripheries.
A plate may or may not be segmented. A segmented plate is an annular array of plate segments typically mounted on a disperger disc. A non-segmented plate is a single piece, annular plate. Plate segment 14 is for the rotor disc 12 and plate segment 15 is for the stator disc 13 . The rotor plate segments 14 are attached to the face of rotor disc 12 in an annular array to form a plate. The segments may be fastened to the disc by any convenient or conventional manner, such as by bolts (not shown) passing through bores 17 . The disperger plate segments 14 , 15 are arranged side-by-side to form plates attached to the face of the each disc 12 , 13 .
Each disperger plate segment 14 , 15 has an inner edge 22 towards the center 19 of its attached disc and an outer edge 24 near the periphery of its disc. Each plate segment 14 , 15 has, on its substrate face concentric rows 26 of pyramids or teeth 28 . The rotation of the rotor disc 12 and its plate segments 14 apply a centrifugal force to the refined material, e.g., fibers, that cause the material to move radially outward from the inner edge 22 to the outer edge 24 of the plates. The refined material predominantly move through the disperging zone channels 30 formed between adjacent teeth 28 of the opposing plate segments 14 , 15 . The refined material flows radially out from the disperging zone into a casing 31 of the refiner 10 .
The concentric rows 26 are each at a common radial distance (see radii 32 ) from the disc center 19 and arranged to intermesh so as to allow the rotor and stator teeth 28 to intersect the plane between the discs. Fiber passing from the center of the stator to the periphery of the discs receive impacts as the rotor teeth 28 pass close to the stator teeth 28 . The channel clearance between the rotor teeth 28 and the stator teeth 28 is on the order of 1 to 12 mm so that the fibers are not cut or pinched, but are severely and alternately flexed as they pass in the channels between the teeth on the rotor disc 12 and the teeth on the stator disc 13 . Flexing the fiber breaks the ink and toner particles on the fibers into smaller particles and breaks off the stickie particles on the fibers.
FIGS. 2 a and 2 b show a top view and a side perspective view, respectively, of a standard tooth geometry 34 used in disperging. The tooth 34 has a pyramidal design including strait sidewalls 36 that taper to the top 38 of the tooth. The sidewalls are planar and flat. The sidewalls of the conventional tooth are each substantially parallel to a radius of the plate.
A primary role of the disperger plate is to transfer energy pulses (impacts) to the fibers during their passage through the channels between the discs. The widely accepted toothed plate has generally incorporated the square pyramidal tooth geometry with variations in edge length and tooth placement to achieve desired results.
Refiner material passing through the channels on the plates can erode teeth. Each tooth has a leading edge that faces the pulp flow resulting from the rotation of the rotor plate. The leading edge is formed by the intersection of the front tooth surface and a leading tooth sidewall. The tooth sidewalls are planar, i.e., flat, on conventional teeth. Further, the corner of the sidewall and front surface of a conventional tooth is typically 90°. The leading edges of the teeth wear and become rounded due to the erosion.
Disperger plates are replaced typically because their teeth become rounded and lose their efficiency for disperging or refining the pulp and lose the ability to feed the pulp through the refining or disperging zone. The rounding of the teeth often results in taking the disperger or refiner offline to replace plate segments. This reduces the efficiency of the disperger and refiner. There is a long felt demand for teeth designs that extend the life of plate segments and reduce the wear on teeth.
SUMMARY
A toothed refiner plate has been developed having teeth with a leading sidewall, wherein the surface of the sidewall on the radially innermost part of the tooth forms an angle with the surface of the leading sidewall on the radially outermost part of the tooth. This angle in the leading sidewall may be formed by a V-shaped sidewall surface, a curvilinear sidewall surface, or other sidewall surface that yields an angle between the radially inward portion of the surface and the radially outward portion of the surface.
The angle between the radially inward portion of the sidewall surface and the radially outward portion may be in a range of 170 degrees to 75 degrees, and preferably in a range of 165 degrees to 90 degrees. Further, the angle in the sidewall surface results in portions of the sidewall surface forming angles with respect to a radial line of the plate. Preferably, the portions of the sidewall surface form an angle in a range of 0 degrees to 60 degrees with respect to a radial line, and preferably in a range of 5 degrees to 45 degrees.
A refiner plate is disclosed comprising: a generally planar surface having annular rows of teeth arranged concentrically on the plate, and at least one of said rows includes teeth having a leading edge corner angle of less than 90 degrees. The leading edge corner is formed by a front surface of each tooth and the leading sidewall of the tooth. The interior angle between the leading sidewall and the front surface is the leading edge corner angle. The leading sidewall faces the direction of plate rotation. The front tooth surface may be substantially tangential to its row on the plate.
The leading sidewall (at least the radially inward portion of the sidewall adjacent the leading corner) forms an angle of 0° to 60° with respect to a radial of the plate and may be in a narrow angular range of 5° to 45°. The leading sidewall may also have a radially outward portion slanted in a direction opposing the rotation of the plate. Further, the leading sidewall may form a V-shape in which a radially inward surface has an edge forming the leading edge corner. The angle of the V-shape may be in a range of 170° to 75° and more narrowly in a range of 165° to 90°.
The trailing sidewall of the tooth (which is opposite to the leading sidewall) may be symmetrical to the leading sidewall, e.g., includes a V-shape, such that a gap between the trailing side wall and the leading sidewall of the adjacent tooth is substantially constant across the length of the two teeth. Further, the radially outer row of the teeth may include teeth having rear walls normal to a substrate of the plate and front walls that slope upward from the substrate.
In another embodiment, the disperger plate may comprise: rows of teeth wherein the rows are concentrically arranged; the teeth each include a leading sidewall facing a rotational direction of the plate or of another plate rotating with respect to the plate, and the leading sidewall comprises a V-shape having a radially inner section with a leading edge and a radially outward section slanted with respect to a radial of the disc in a direction opposing the disc rotation. The angle of the V-shape is in a range of 170° to 75° and may be in a narrower range of 165° to 120°. The leading edge may be formed by an intersection of a front surface of the tooth and the leading sidewall, wherein an angle between the front surface and leading sidewall is in a range of 0° to 60° or in a narrower range of 5° to 45°.
A method has been developed of refining pulp material with opposing discs comprising: feeding the pulp material to an inlet of at least one of the discs, wherein the inlet is at or near a center axis inlet; rotating one disc with respect to the other disc while pulp material is moved between the discs due to centrifugal force; refining the pulp material by subjecting the material to impacts caused by the rows of teeth on the rotating disc intermeshing with the rows of teeth on the other disc, wherein refining further includes feeding the pulp into successive rows of teeth on the discs, wherein at least one of the rows on at least one of the discs includes teeth having a leading edge corner formed by a front tooth surface and a leading sidewall having an angle therebetween of less than 90 degrees. The method may further include deflecting pulp passing through the at least one of the rows on the at least one of the discs with a radial outward surface of the leading sidewall that is slanted in a direction opposing the rotation of at the disc. Further, the leading sidewall may form a V-shape wherein a radially inward edge of the sidewall is the leading edge corner.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1( a ) and 1 ( b ) are a front view and side view, respectively, of a pyramidal toothed plate segment conventionally used in disc-type dispergers.
FIG. 1( c ) is a side partially cross-sectional view of a stator and rotor disperger plates with a gap therebetween.
FIGS. 2 a and 2 b are a top down view and a side perspective view, respectively, of a conventional tooth geometry for a disperger plate segment.
FIGS. 3 a and 3 b are a top down view and a side perspective view, respectively, of an angled tooth for a disperger plate segment.
FIGS. 4 a and 4 b are a front plan view and a side cross-sectional view, respectively, of a disperging rotor plate segment having double angled teeth.
FIGS. 5 a and 5 b are a front plan view and a side cross-sectional view of a disperging stator plate segment having double-angled teeth.
DETAILED DESCRIPTION
A novel arrangement of teeth for toothed refiner plates has been developed in which the teeth have sidewalls that are angled to form a V-shape. The V-shaped teeth have a double-angled geometry. In particular, the surface of at least a leading sidewall of a tooth has an inner portion that forms an angle with respect to a radially outward portion. The V-shaped can be applied to the teeth of plate segments for any type of disperger and refiner plate segments with teeth. The V-shaped sidewalls can be applied to teeth located on either or both the rotor and stator plate portions of a disperger or refiner. In a preferred embodiment, both the rotor and stator plate segments include teeth with V-shaped sidewalls.
FIGS. 3 a and 3 b show a top view and a side perspective view, respectively, of an angled stator tooth 40 where the sides of the tooth are angled to form a V-shape. At least the leading sidewall 42 of the tooth 40 has a V-shape geometry. The trailing sidewall 43 may have a V-shape. While the sidewalls 42 , 43 as shown taper towards the top 46 of the tooth, it is not necessary that the teeth are tapered from the substrate to their top and it may be preferable that there be no taper from the substrate to the top. The base 48 of the tooth is at the substrate of the plate. The front wall 50 of the tooth faces radially inward and the rear wall 52 of the tooth faces radially outward. The front and rear walls may each be substantially perpendicular to a radial of the plate. The front and rear walls may also slope towards the top of the tooth.
Each V-shape tooth has a leading sidewall 42 that faces the pulp flow resulting from the rotation of the rotor plate. The leading sidewall has an inner surface 54 that is radially inward of an outer surface 56 . The inner and outer surfaces of the leading sidewall are not planar and together form a V-angle that is preferably in a range of 170° to 75°, and more preferably in the range of 165° to 120°. The angle of the V-shaped leading wall 42 is selected depending on disperging and feeding needs. The opposite (trailing) sidewall 43 preferably also has an inverted V-shape that forms a complementary angle to the leading sidewall, such as an angle of from 190° to 285°. A row of teeth with complementary leading and trailing sidewalls may have constant width gaps between the teeth.
Alternatively, the trailing sidewall may have a sidewall with a convex profile, e.g. a continually curved bulging profile, and have complementary angles to the angles of a convex (continually curved with a bowel profile) profile leading sidewall. A row of teeth having a concave leading sidewall and convex trailing sidewall (in which the angles of the leading and trailing sidewalls are complementary) may have constant width gaps between the teeth in the row.
The trailing sidewall 43 may or may not have a similar surface geometry to the leading sidewall 42 . The surface profile of the leading sidewall need not be complementary to the surface profile of the trailing sidewall. For example, the trailing sidewall may be entirely planar and straight. Further, a concave surface profile on both leading and trailing sidewalls of all teeth allows a plate to perform equally in both directions of rotation and provides for a reversible plate.
Further, the V-shaped leading sidewall may have a curved cup shape from the leading edge to a radially outward edge. The angle of the sidewall should change by at least 10° from the leading edge to the radially outward edge. Further, the V-shaped sidewall teeth may be confirmed to one or a few rows of teeth on the rotor or stator plates, or may be on all teeth rows in the rotor or stator plates.
The V-shaped angle of the leading sidewall 42 forms a concave surface facing the direction of rotation 57 on the rotor plate. The first and second sidewall surfaces 54 , 56 preferably each form an angle with respect to a radial of the plate. The angles are preferably in a direction opposite to the rotation of the rotor disc. For example, the first and second sidewall surfaces 54 , 56 may be each at an angle of 0° to 60° with respect to a radial 32 ( FIG. 1 a ). In a preferred embodiment, the first and second 54 , 56 surfaces may be each at an angle of 5° to 45° with respect to a radial. While the first and second sidewall surfaces 54 , 56 may each have the same magnitude of angle, they may alternatively have different angles with respect to a radial 32 . For example, the first sidewall surface 54 may form an angle of 7.5° and the second sidewall surface 56 may form an angle 35° with respect to a radial. The angle of the first surface 54 and a radial is a feeding angle.
The leading edge 60 of the corner of a disperger tooth 40 may be formed by an front edge of the first surface 54 (radially inward) and a leading edge of the front wall of 50 . The angle may be less than 90° between the first surface 54 of the sidewall and the front wall 50 . For example, the leading edge 60 of the tooth may have an angled of 85° to 30° , and more preferably 82.5° to 65° . The leading edge is sharp as compared to the 90° corners of traditional disperger teeth. The sharp leading corners should retain a sharp edge better as they wear, as compared to traditional 90° edges.
The second surface 56 may have an angle and length such that it deflects refiner material particle moving radially between the teeth. The deflection slows the refined material radially flowing between the teeth. Slowing refined material reduces the erosion of the leading edges of teeth because the impact against the leading edge is lessened by the slower refined material. The angle and length of the second surface 56 may be such that its length perpendicular to a radial is at least a width of the gap between the tooth and an adjacent tooth. The angle of the second surface 56 to a radial is the holdback angle. Any combination of feeding and holdback angles may be employed depending on the desired dispersing effects.
The transition 62 between the surfaces 54 , 56 of the sidewall 42 of the tooth can either be a sharp corner or a radius which may have the same width as the upper surface of the tooth (as shown in FIG. 3 b ), so that the angle across the whole height of the tooth edge is constant. A smooth radius across the whole sidewall surface (collectively 54 , 56 and 62 ) would also achieve the same overall goals of a sharp leading edge and a holdback surface, even if the angle at the leading edge is not constant.
The described rotor plate design can be used with a stator plate with a standard tooth. On the other hand, the stator plate may also have V-shaped sidewalls. The stator design may present the same sharp crossing corner angle, e.g., greater than 90°, to the process to maintain better wear characteristics. The crossing angle is from a tangent line extending in front of the tooth edge and back to the surface of the sidewall adjacent the edge. The stator plate segments may include double-angle teeth having the convex sidewalls that face the rotation, so that the angle of the tooth edge at the crossing interface would be greater than 90°. A crossing angle of greater than 90° is not perceived as a problem for stator wear, because edge rounding mostly occurs on the rotor teeth. It may be desirable to for the crossing angles of rotor and stator tooth surfaces to vary to improve disperging efficiency and feed transfer through the interface of rotor and stator teeth.
FIGS. 4 a and 4 b are a front plan view and a side-cross-sectional view, respectively, of an exemplary disperger rotor plate segment 70 that is to be mounted on a disc and in opposition to a stator plate. The rotational direction for the rotor plate is counter clock-wise as indicated by arrow 72 .
The disperger plate segment 70 includes rows 74 , 76 , 78 , 80 , 82 and 84 of teeth 86 . The rows of teeth may be each at a respective radius 88 of the disc, but may also be slanted with respect to the radius. Similarly, the stator plate ( FIGS. 5 a and 5 b ) has rows of teeth that interleave with the rows of rotor teeth, when the plates are arranged in the disperger.
To promote feeding and retention of the pulp into the disperging zone, the rotor may include at least one inner row (see row 74 ) of disperging teeth 86 . The stator is not limited to the inlet for feeding and may include disperging teeth, feeding inlets (such as the feed injectors disclosed in U.S. Pat. No. 6,402,071), breaker bars and other features. These inlet features may be selected for a particular disperger plate depending on the disperging requirements for the plate.
FIGS. 5( a ) and 5 ( b ) show a top down view and a side cross-sectional view, respectively, of an exemplary stator disperger plate segment 100 employing the double angle geometry teeth 102 arranged in rows 104 , 106 , 108 , 110 , 112 and 114 . The stator disperger plate segment (when arranged in a plate) is intended to be opposite the rotor plate 70 such that the respective rows of the rotor and stator plates intermesh. The stator plate 100 includes an outermost row 114 of disperger teeth in holdback to prevent wear of the inner portion of the refiner casing. The rear wall of teeth in the outer row 114 may be perpendicular to the substrate of the plate and not tapered as is the near wall of the inner rows of teeth. The holdback angle is the angle with respect to a radial formed by the second section 116 (which is radially outward) of the sidewall of the tooth. The holdback angle may be at least as great as the holdback angle of the last row of teeth 84 on the rotor plate 60 . The angles of the teeth sidewalls of the rows of the stator plate segment 100 are show as being similar to the sidewall angles for corresponding rows on the rotor plate segment 70 . However, the sidewall angles on the stator plate segment need not necessarily correspond to the sidewall angles of the rows of rotor teeth.
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 refiner plate including a generally planar surface having annular rows of teeth arranged concentrically on the plate, and at least one of said rows includes teeth including a leading edge corner angle of less than 90 degrees. These teeth may include a leading sidewall having a radially outward portion slanted in a direction opposing the rotation of the plate.
| 3
|
[0001] This application is a continuation of U.S. patent application Ser. No. 14/733,322 filed Jun. 8, 2015 which is a continuation of U.S. patent application Ser. No. 14/516,024 filed Oct. 16, 2014 and is related to Provisional Patent Application Ser. No. 61/891,614 filed on Oct. 16, 2013 and is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a golf cart enclosure, and more particularly, to a sliding panel golf cart enclosure to be used during inclement weather to protect persons within the enclosure from such weather. Specifically, the present invention relates to a sliding panel golf cart enclosure wherein the golf cart is equipped with panel mounting rails where each rail is adapted to slidably carry a panel through a swivel fastener.
BACKGROUND OF THE INVENTION
[0003] Golf carts are generally designed to carry two persons (golfers) within a cabin portion of the cart while a platform positioned behind the cabin portion carries each person's golf bag and golf clubs. Many golf carts are further outfitted with a roof and a windshield. Golf carts, however, are generally designed to have no doors or other impediments along the sides of the cart. This lack of doors is intentional as it allows for quick and easy ingress into and egress from the cabin while playing a round of golf. One drawback to this open design, however, is the inability to control or limit golfer exposure to inclement weather and/or insects. Thus, numerous systems exist in the art which retrofit golf carts to be more weather/insect repellant. Each of these systems, unfortunately, suffers from a number of setbacks.
[0004] One example of a system for weather- and/or insect-proofing a golf cart includes the provision of a roll-up barrier. These roll-up systems generally include a vinyl or other clear plastic panel fixedly secured to the frame structure of the golf cart which supports the roof. When in use, the panel drapes downwardly to cover the open sides of the golf cart passenger cabin. When not in use, the panels are rolled upwardly to be collected and secured to the roof frame so as to allow quick and easy access to the passenger cabin. A significant drawback to these roll-up systems, however, is the entrapment of moisture within the panel when in the rolled condition. This moisture leads to the buildup of mildew.
[0005] Alternative systems have been developed to overcome the mildew problems associated with roll-up panels. These alternative systems generally employ one or more panels which slide horizontally along a track situated above, and in some cases below, the side openings of the golf cart's passenger cabin. When not in use, these panels slide laterally towards the back of the golf cart where they are then secured from closing unintentionally. One example of a horizontally sliding enclosure includes clear panels constructed of relatively thick plastic. This example can be thought of as being similar to conventional shower doors where a first panel passes in front of (or behind) a second panel. Another similar example of a sliding enclosure includes a generally thin panel of clear plastic. This example is generally similar to a conventional shower curtain which can be displaced laterally by bunching the plastic panel together. In each of these examples, however, ease of admission to the passenger cabin of the golf cart is restricted by the presence of the panel when the panel is not in use. One attempt to alleviate the bunching of a thin panel has been to split the panel into thin strips with successive strips splined together via rigid vertical members. In this manner, the constructed panel is able to fold compactly so as to minimize obstruction of the cabin opening. However, when in an extended position, such as during inclement weather, the vertical members obstruct the view of the cart driver and pose a safety hazard. Further, the provision of the vertical members and spline increases cost of production while increasing points of possible enclosure failure through stress and wear.
[0006] As such, there is a need for a golf cart enclosure which provides protection from the elements when needed but that also retracts to a generally compact bundle when not in use. There is a need for a golf cart enclosure that provides maximum viewability to the occupants of the golf cart when the enclosure is being employed but that also retracts compactly so as not to hinder ingress into or egress from the golf cart passenger cabin when the enclosure is unneeded.
BRIEF SUMMARY OF THE INVENTION
[0007] In general, one embodiment the present invention is directed to a golf cart enclosure that provides a barrier along the sides and back of a golf cart passenger cabin. The golf cart enclosure generally consists of a number of clear plastic panels which drape from a support structure situated proximate the roof frame of the golf cart. In further embodiments, the enclosure may consist of a number of two-part panels wherein the lower portion of each panel is constructed of a durable fabric, such as marine grade canvas while the upper portion is constructed of a clear plastic material such as polyethylene or vinyl sheeting. The enclosure is selectively retractable along the support structure such that one or more panels can be withdrawn from covering the door opening to the passenger cabin and/or the back “window” above the seat bench. The panels are mounted to the support structure by swiveling rollers such that the retracted panel does not impede ingress into or egress from the passenger cabin.
[0008] Accordingly, in one embodiment of the present invention, a golf cart enclosure system for a golf cart having a passenger cabin, a roof mounted on a frame for covering the passenger cabin and a front windshield is disclosed. The system comprises a guide rail secured to the frame proximate the roof and a panel of a length sufficient to extend from the guide rail to the golf cart passenger cabin below. A plurality of swivel rollers is provided, wherein a first end of the swivel roller rollably engages the guide rail and wherein a second end of the swivel roller is fastened to the panel. The panel slidably moves along the guide rail from a closed position where the panel is fully extended to an open position where the panel is retracted.
[0009] The embodiments of the present invention are well-suited to provide protection from inclement weather and/or insects when deployed while also compactly stowing when not in use so as not to hinder access to the golf cart passenger cabin.
[0010] Additional objects, advantages and novel features of the present invention will be set forth in part in the description which follows, and will in part become apparent to those in the practice of the invention, when considered with the attached figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The accompanying drawings form a part of this specification and are to be read in conjunction therewith, wherein like reference numerals are employed to indicate like parts in the various views, and wherein:
[0012] FIG. 1 is a perspective view of a golf cart with an employed golf cart enclosure according to an embodiment of the present invention;
[0013] FIG. 2 is a perspective view of a golf cart with a retracted side panel of a golf cart enclosure according to second embodiment of the present invention;
[0014] FIG. 3 a perspective view of a golf cart with a retracted side panel and retracted back panel of a golf cart enclosure according to an embodiment of the present invention;
[0015] FIG. 4 is an expanded view of a panel fastener used with a golf cart enclosure according to an embodiment of the present invention;
[0016] FIG. 5 is an expanded view of a front guide rail bracket used with a golf cart enclosure according to an embodiment of the present invention;
[0017] FIG. 6 is an expanded view of a rear guide rail bracket with panels in the extended position;
[0018] FIG. 7 is an expanded view of a rear guide rail bracket with a panel in the retracted position;
[0019] FIG. 8A is an detailed cross sectional view of a swivel roller used with a golf cart enclosure according to an embodiment of the present invention;
[0020] FIG. 8B is an expanded view of a swivel member used with a golf cart enclosure according to an embodiment of the present invention; and
[0021] FIGS. 9-17 are simplified views showing alternate embodiments of guide rails and associated panel sliding mechanisms.
DETAILED DESCRIPTION OF THE INVENTION
[0022] Referring to the drawings in detail, and specifically to FIGS. 1-3 , a golf cart 10 is equipped with an embodiment of a golf cart enclosure 100 in accordance with the present invention. Golf cart 10 generally includes a passenger compartment 20 equipped with a bench for seating of passengers, as well as operational controls (steering wheel, brake pedal, acceleration pedal, etc.) to operate the golf cart. To the rear of the passenger compartment 20 is a platform area 40 for securing a golf bag and clubs for use during a round of golf. Optionally, platform area 40 may include a further bench to provide additional passenger seating. Many golf carts also include a frame 12 for mounting a roof 50 (see FIGS. 5-7 ). Further included may be a windshield 30 mounted to frame units 12 .
[0023] As explained above, golf carts are not typically constructed to have an enclosed passenger compartment, but are rather open-sided and open-backed. Thus, during inclement weather, or should insects be particularly bothersome, passengers in the passenger compartment 20 are left open to the adverse environment. Golf cart enclosure 100 is designed and mounted so as to minimize, if not eliminate altogether, the negative effects of poor environmental conditions.
[0024] Golf cart enclosure 100 is generally comprised of one or more panels 110 , 120 , 130 which have sufficient length to extend from the roof to the body of the golf cart. As shown in perspective, side panel 110 generally covers the left hand side of the cart and may incorporate rear panel 120 to form a continuous single panel unit. Similarly, and not referenced by a reference numeral, a right side panel generally covers the right hand side of the cart and may incorporate rear panel 130 into a single panel unit. Panel unit 110 A may also be included to compensate for the angle created by the forward frame while creating a generally perpendicular rear edge with respect to the roofline/cart floor. An optional canopy 150 may also be included which is intended to cover the hardware associated with the golf cart enclosure which will be discussed in more detail with reference to FIGS. 5-7 .
[0025] As can be seen by FIGS. 1 and 2 , side panel 110 is configured to cover the left hand side of golf cart 10 . When in a closed position ( FIG. 1 ) side panel 110 extends generally from rear frame member 12 forward to the perpendicular edge created by panel 110 A. Retraction of side panel 110 ( FIG. 2 ) exposes passenger compartment 20 allowing for efficient ingress into or egress out of the compartment. When retracted, side panel 110 may be releasably secured by fastener 112 . Fastener 112 may be any suitable fastener, such as clips, snaps, hook and loop material, and is preferably a tie-back strap or toggle strap. As further shown in FIG. 2 , side panel 110 may be manufactured as a two piece construction. The two piece construction includes a generally clear plastic top portion 110 ′ and a robust fabric bottom portion 110 ″. Top portion 110 ′ is preferably a clear plastic such as vinyl or polyethylene. Bottom portion 110 ″ is preferably a marine grade canvas material which would resist tearing and puncturing such as from multiple retractions and extensions of the panel or from abuse from passengers, such as from golf spikes or driving the cart through wooded areas were limbs may impinge upon the panel.
[0026] With reference to FIG. 3 , rear panel 120 is shown in a retracted position. As discussed above with regard to side panel 110 , rear panel 120 may be secured in an open position by any suitable fastener, such a toggle strap 122 . Rear panel 120 is also provided with one or more fasteners 125 which mate with fastener 135 of rear panel 130 . Thus, when both rear panels 120 and 130 are in a closed position ( FIGS. 1 and 2 ) the mating fasteners 125 / 135 serve to secure to two panels together. Examples of suitable fasteners include respective male and female counterparts of clips, snaps, buttons, hook and loop, and zippers, with said fasteners preferably being hook and loop fasteners. As described above, rear panel 120 may be incorporated with side panel 110 to form one continuous panel unit. Rear panel 130 may similarly form a continuous panel with the right side panel (not enumerated). Alternatively, rear panels 120 and 130 may each be distinct panel units apart from the side panels, or further, rear panels 120 and 130 may be manufactured as a single continuous rear panel thereby obviating the need for mating fasteners 125 / 135 .
[0027] FIG. 4 is a representative view of a mechanism for mounting the forward edge of panel 110 A to a golf cart frame unit 12 . Panel 110 A is equipped with a fastener 115 which removably mounts the panel to the frame. In a preferred embodiment, fastener 115 is a double D-ring strap having a first strap with D-rings fixedly secured to the panel 110 A. A second strap is similarly secured to the panel with its free end passing through and around the two D-rings so as to cinch the panel to the frame. While preferably a double D-strap fastener, it would be appreciated by those skilled in the art that any suitable fastener may be employed. It should also be stated, for purposes of clarification, that fastener 115 is generally located on the lower portion of the panel and is meant to prevent lifting of the panel from the bottom. The top portion of each panel is secured to a guide rail as will be discussed in greater detail with regard to FIGS. 5-7 . Also, while shown and described as mounting panel 110 A to a front frame member 12 , similar fasteners are positioned at suitable locations on the remainder of the panels as desired or required.
[0028] FIG. 5 shows an expanded view of the mounting of the forward end of a guide rail 160 utilized in the golf cart enclosure 100 of the present invention. Guide rail 160 is generally mounted proximate roof 50 of the golf cart. Roof 50 is typically mounted to frame unit 12 through roof strap 55 . Bent bracket 170 is secured to frame member 12 , preferably by bolts or lag screws 171 . Bent bracket 170 is configured to have a flat portion 170 ′ which rests against and is secured to frame member 12 . A generally perpendicular bend portion 170 ″ extends outwardly from frame member 12 and is selected to have a length equal to or slightly larger than the width of guide rail 160 . Finally, bent bracket 170 includes a further portion 170 ″′ which extends upwardly in a plane generally parallel with flat portion 170 ′ but displaced outwardly from frame member 12 by the length of 170 ″. In this manner, guide rail 160 is constrained in the x-direction between bent bracket portion 170 ″ and roof 150 and between bent bracket portion 170 ″′ and frame unit 12 in the z-direction. Travel in the y-direction is prevented through friction between the guide rail and the bent bracket 170 . Optionally, guide rail 160 may be secured in the z-direction by fastening it to the bent bracket or frame unit by a suitable fastener, such as a screw or bolt. Side panel 110 A is mounted within the guide rail and allowed to drape downwardly as shown in FIGS. 1-3 . In an alternate embodiment, 172 is omitted and the bars 160 and 162 are attached to each other directly
[0029] FIGS. 6 and 7 are detailed views of the guide rails used for retracting and extending the panels. As can be seen in FIGS. 6 and 7 , by way of example, with such discussion meant to encompass each guide rail employed by the present invention, guide rail 162 has a generally square c-shaped cross section. Guide rail 162 has generally parallel opposing sides 162 ′ and bottom members 162 ″ and 162 ″′ forming a groove 163 therebetween. Swivel rollers 180 are rotatably secured within the guide rail 162 and include a portion which extends through groove 163 , with such portion fastened to a panel 110 / 120 / 130 .
[0030] Further shown in FIGS. 6 and 7 is a mounting bracket 172 used to secure guide rails 160 and 162 to the golf cart at a rear frame member 12 . Mounting bracket 172 is a generally T-shaped bracket wherein a portion of one horizontal arm of the T is bent at a generally 90° angle. The vertical portion of the T-shaped mounting bracket 172 is secured to the frame member 12 . As shown, the left hand horizontal arm of the T-shaped bracket extends into the interior opening of guide rail 160 where the arm secures the guide rail against the frame member 12 . The bent portion 173 of the right hand horizontal arm secures guide rail 162 to the frame. Bracket 172 is positioned on the frame member 12 such that bent portion 173 engages the open portion of guide rail 162 and impinges a side wall 162 ′ against frame member 12 , thereby constraining movement in the y-direction. The width of the horizontal arms of bracket 172 is selected to be slightly smaller than the width W of guide rail 162 such that bracket 172 fits snugly within the guide rail. This snug fit, in conjunction with the roof 50 , prevent guide rail displacement in the x-direction. While not shown or described, the opposing side of the golf cart is similarly equipped with guide rails and brackets as discussed with above with regard to FIGS. 5-7 . Thus, the two rear T-shaped brackets, in combination serve to prevent movement of the guide rail 162 in the z-direction. Panels 110 / 120 / 130 are draped from the guide rails by swivel rollers 180 . Optional canopy 150 is mounted to the roof and serves to hide or obscure the guide rails and swivel rollers 180 from casual view.
[0031] Turning now also to FIGS. 8A and 8B , swivel rollers 180 of the present invention generally comprise a tab 182 having a top end 182 ′ and a bottom end 182 ″. A pair of roller bearings 184 ′ and 184 ″ is rotatably mounted on an axle 183 . Axle 183 extends through the tab 182 proximate the top end 182 ′ with roller bearing 184 ′ situated on one side of the tab 182 and roller bearing 184 ″ located on the other side of tab 182 . Swivel member 185 is situated below the tab 182 with the swivel member 185 being attached to the tab by way of a tang 185 ′. Swivel member 185 further includes a tang 185 ″ which is attached to a respective panel 110 / 120 / 130 . Preferably, each tang 185 ″ may be attached to its respective tab or panel through use of a rivet 186 , for example. The number and location of swivel rollers 180 positioned along the top of a panel may vary and is selected to control the size of the bundled panel when in the open position as well as the width of each fold of that bundle. More swivel rollers leads to a shorter width of each fold but a wider resultant bundled panel.
[0032] Roller bearings 184 ′ and 184 ″ rest upon and are rotatably moveable across the inner surface of guide rail bottom members 162 ″′ and 162 ″, respectively. Ideally, the total width of roller bearings 184 ′, 184 ″, axle 183 and tab 182 is such that lateral movement of the swivel roller in the y-direction is minimized. The roller bearings minimize friction to ensure quiet and essentially effortless sliding of a panel between an open or closed position requiring the use of only a single finger to slide it along. Swivel member 185 allows the panel to swivel with respect to the roller elements and further allows the panel to compact into a tight bundle when the panel is retracted to an open condition allowing golfer ingress and egress to and from the cart. This compact bundle afforded by the swivel member provides greater accessibility to the passenger cabin 20 when a side panel is open as compared to panels generally known in the art.
[0033] FIGS. 9-14 are simplified views illustrating alternate embodiments of guide rails “R” and associated sliding mechanisms “SM” which may be attached to the panels.
[0034] Although the present invention has been described in considerable detail with reference to certain aspects thereof, other versions are possible. For example, and not by way of limitation, the framework which attaches to the cart may be modified as desired. Therefore, the spirit and scope of the appended claims should not be limited to the description of the aspects contained herein.
[0035] All features disclosed in the specification, including the claims, abstract, and drawings, and all the steps in any method or process disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. Each feature disclosed in the specification, including the claims, abstract, and drawings, can be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
|
A golf cart enclosure system for a golf cart having a passenger cabin, a roof mounted on a frame for covering the passenger cabin and a front windshield. The system comprises a guide rail secured to the frame proximate the roof and a panel of a length sufficient to extend from the guide rail to the golf cart passenger cabin below. A plurality of swivel rollers is provided, wherein a first end of the swivel roller rollably engages the guide rail and wherein a second end of the swivel roller is fastened to the panel. The panel slidably moves along the guide rail from a closed position where the panel is fully extended to an open position where the panel is retracted.
| 1
|
This is a divisional application of application Ser. No. 08/441,253, filed May 15, 1995, now U.S. Pat. No. 5,781,772, which was a continuation of application Ser. No. 08/016,659, filed Feb. 10, 1993 now abandoned, which was a continuation of application Ser. No. 07/378,718, filed Jul. 12, 1989 now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to prefix matching in database searches.
A database associates sets of strings, or keys, with stored information. Databases are frequently used to search for particular information associated with a given input string or key.
Some applications also require the retrieved information be associated with the best matching prefix, if any, of the input string. For example, if the string "CART" is the input string to a database, and the database holds information associated with the strings "C", "CA", and "CARL", the best matching prefix to "CART" is the string "CA", and the information associated with "CA" should be returned. Note that "C" is also a prefix of "CART", but "CA" is a better (i.e. longer) prefix than "C".
Best matching prefix searching is typically performed by a database having a hierarchical, tree-like structure. This type of database is often called a trie. A trie database allows both exact matching (i.e. searching for a string that is exactly equal to the input string) as well as best prefix matching.
Referring to FIG. 1, a trie consists of a number of nodes 32 each of which contain pointers to other nodes. Each node has an array of n pointers, one pointer corresponding to each of n possible characters that can occur in a character of the input string. The trie also has a single node 33 called the root, at which the search begins.
To look up a string, e.g. "CAD", a search starts at the root node of the trie and uses the first character "C" to index into the array of pointers at the root node. The "C" pointer 34 will point to a section of the trie that contains information for all strings that begin with "C". The search travels to this new node, and uses the next character in the input string, "A", to index into the array of stored pointers. The "A" pointer 35 yields the root of another section of the trie that contains information for all strings that of all strings that begin with "CA". Finally, the search uses the last character "D" to index into the array to obtain the actual entry corresponding to "CAD".
The storage requirement of a trie can be calculated, and is roughly proportional to the product of: (1) the number of entries in the database, (2) the number of distinct characters, (3) the average number of characters in a word, and (4) the storage size of a pointer. Thus for a 50,000 entry directory database having (2) 26 possible characters, (3) up to 20 characters per entry, and (4) 4 byte pointers, the amount of storage required is around 2K bytes per entry, or 100 Mbytes.
Despite this storage requirement, the trie is attractive for fast look up and prefix matching. Some useful applications include directory look ups in a telephone context, on-line dictionaries, spelling checkers, and looking up social security numbers.
A computer network consists of a number of computers that are connected together by devices called routers, such that any computer can send messages, called packets, to any other computer. By analogy, the routers are post offices, and the packets correspond to letters. Each packet carries a destination address, and each router computes the best path towards that destination address. Each router along this path is responsible for "forwarding" the packet to the next router on the path. This forwarding process continues until the packet reaches its destination. When a packet arrives at a router, the router searches for the destination address in a forwarding database. The forwarding database consists of a list of destination addresses and the next router in the path toward each such address.
Since the postal system is too large, it is impossible for each post office to store a database containing entries for every address in the world. Instead, to route a letter to WHITEHALL-LONDON-ENGLAND, it is first sent to the destination country (England), then to the city (London) and finally to the street address (Whitehall) in the destination city. Thus we could describe the postal system addresses as having three levels of hierarchy: Level 0 is the street address, Level 1 is the city, and Level 2 the country. For the same reason, destination addresses in very large computer networks are also divided hierarchically and have several levels of hierarchy.
One method for constructing very large networks that is described by the Internation Standards Organization (ISO) Routing Standard. This is soon to be a worldwide standard which will be used to build large global networks. According to the ISO standard, each router does not store routing information for every possible address in the network. Rather, it stores routing information for partial addresses.
For example, a router might store the best ways to forward a packet to the partial addresses DEC-READING-ENGLAND, ENGLAND, and LONDON-ENGLAND. Suppose the router now gets a packet addressed to WHITEHALL-LONDON-ENGLAND. The ISO Standard states that the router should send the packet to the best matching partial address it has in its database. Thus, in the above example, since the router knows how to forward packets to LONDON-ENGLAND, the packet should be sent there. In this scheme, each time a packet is forwarded it gets closer to its destination.
The ISO Routing Standard for worldwide networks specifies that each router in the network maintain a database of partial addresses. When a packet arrives at the router, the router must search through the database and retrieve the entry corresponding to the destination address in the packet or, failing that, retrieve the entry corresponding to the best matching prefix of the destination address.
A ISO routing standard of particular interest is the open Systems Interconnection (OSI) standards, such as ISO 8348 Addendum 2 (ISO 8348/AD2), as promulgated by the International Organization for Standardization. Under this standard, the administration of sub-spaces of an OSI address has been delegated to various internationally recognized organizations. Each of these organizations has been allocated a unique initial address octet (typically eight bits) indicating the delegated administration. The individual organizations are responsible for allocating further portions of the address, as identified by unique initial parts of a length specific to the organization, for administration and allocation by other organizations. This process can iterate many times, but guarantees that specific assigned node addresses are globally unique.
An OSI network address (NSAP) format is shown in FIG. 2A. It includes an initial domain part IDP 60 and a domain specific part DSP 70. The format and length of the IDP 60 is standardized. It consists of two parts, the AFI 62 (authority and format identifier) and the IDI 64 (initial domain identifier). These elements each require a specified number of bits, counted by octets (eight bits) or semi-octets (four bits). The digits in the AFI and IDI are binary coded decimal digits. Each decimal digit is represented by a semi-octet value in the range of 0000 (decimal 0) to 1001 (decimal 9).
The AFI 62 is standardized as two semi-octets (i.e. two binary coded decimal digits) long and is used to specify the authority responsible for allocating IDI values, and for defining the format of the IDI. The IDI 64 identifies the subdomain from which DSP values are allocated, and the authority responsible for allocating the values. Depending upon the IDI format, the actual number of digits in the IDI field 64 may be fewer than the number of semi-octets which are allocated to the IDI field. The Preferred Binary Encoding specified by ISO 8348/AD2 specifies that the IDI be padded with leading digits, if necessary, to obtain the maximum IDP length specified by the AFI. Thus the IDI field may contain some digits 66 which convey address information, and other fill digits 65 which do not convey information. The useful IDI digits 66 are right-justified in the IDI field, and the remainder of the IDI field contains the fill digits 65. The value of the AFI be used to determine the IDP length and to locate the useful IDI digits 66, as will be fully discussed below.
IDI formats specified in the ISO 8348/AD2 standard include those promulgated by a number of different authorities, including the following:
X.121 (Public data network numbering)
ISO DCC (Geographic address assignment under ISO control)
F.69 (Telex numbering)
E.163 (Telephone numbering)
E.164 (ISDN numbering)
ISO ICD (Non-geographic address assignment under ISO control)
Local (IDI is null; address is not necessarily unique).
The IDI 64 identifies the authority which administers the DSP. The specific format of the DSP 70, except for its maximum length, is not presently prescribed by ISO but rather is left to the indicated authority. The DSP may use a binary coded decimal syntax similar to the IDP, or may use a straight binary syntax. Where the DSP uses a binary syntax, the DSP value is represented directly as binary octets. Where the DSP uses a decimal syntax, each decimal digit is represented by a semi-octet in the range of 0000 to 1001 (as in the IDP). In the latter case, where necessary, the semi-octet value of 1111 is used as a pad after the last semi-octet of the DSP to round the entire address length to an integral number of octets.
FIGS. 2B and 2C are tables indicating the AFI values and maximum lengths required for IDP, DSP and entire NSAP address corresponding to each IDI format. (Note that in NSAP addresses in ISO 8348/AD2 format, the IDI is padded to the maximum length.) Where two values are given for the AFI, the first identifies an IDI which is padded to maximum length with zero (0000) leading digits, while the second identifies an IDI which is padded with non-zero leading digits (the non-zero padding digits must have the value 0001). Non-zero leading digits are used to alleviate confusion when the first digit of the actual IDI value is equal to 0000. Therefore, if non-zero padding digits are used in the IDI, the first zero digit in the IDI must be the first non-fill digit. FIG. 2B applies to cases where the DSP syntax is binary, whereas FIG. 2C applies to cases where it is decimal.
As an example, a two semi-octet BCD AFI value of thirty-six indicates that: (1) the destination system is using an X.121 public network address, (2) the IDI 64 consists of up to fourteen significant decimal digits identifying a subdomain authority, and (3) the DSP 70 semi-octets, if present, will represent a destination device in Binary Coded Decimal syntax.
In the current version of the DECnet Phase V addresses for the Digital Network Architecture (DNA), as promulgated by Digital Equipment Corporation, Maynard, Mass., for example, the DSP 70 has binary syntax, and the last nine octets of the NSAP (the last seven of which must be in the DSP) are partitioned into several fields as shown in FIG. 2A. (Those fields in FIG. 2A which are specific to DNA are marked with an asterisk (*))
LOC-AREA 72 is a field defined for backward compatibility with former versions of DNA and for possible future enhancements. The LOC-AREA 72 is defined as the first two octets of the last nine octets of the NSAP.
Level-1 ID 74 is a six octet field which uniquely identifies the destination system within a DECnet area. Correct operation of the DNA Network Routing Layer requires only that the ID 74 field be unique within a DECnet area (except for Level-2 routers, where the Level-1 ID of the Level-2 router is typically unique within the whole private network). However, the ID field is usually chosen from the IEEE 802 address space, in which case it is guaranteed to be globally unique. If an 802 address is used, it may correspond to the actual Data Link address of the node on an 802 LAN, but this correspondence is not assumed or required by the routing algorithms.
SEL 76 is a one octet field at the end of a DECNET Phase V address. SEL acts as a selector for the module which is to receive the packet once it reaches its destination. The concatenation of the IDP 60 and the leading portion of the DSP (i.e., if it exists, the portion of the DSP preceding the last nine octets) is called the PRE-LOC-AREA 80. The concatenation of the PRE-LOC-AREA and LOC-AREA is known as the Area Address 90. (Thus the Area Address is all but the last seven bytes of the NSAP). If a packet has an Area Address 90 which exactly matches that of the local area, then the packet's destination is local to the area and is routed by Level-1 routing, using the Level-1 ID field 74. Otherwise, it is routed by Level-2 routing. Level-2 routing acts on prefix portions of the area address, directing the packet to that area whose area address has the maximum exact match with the packet address.
Other, non-DNA nodes need not follow DNA addressing conventions or requirements. However, routers designed for DNA address syntax will interoperate with non-DNA nodes and non-DNA networks if certain requirements are met. There are several possible modes of interoperation:
In one mode, a non-DNA End System is operating in the DNA Level-2 network, and an adjacent Level-2 router is manually configured to forward packets to the End System via a DNA "Reachable Address Entry". The only requirement of the address of the non-DNA End System is that every prefix of the End System's address, formed by removing at most 14 trailing semi-octets, must be distinct from all Area Addresses in the Level-2 network.
As an End System in a particular DNA area, the address of the non-DNA node is subject to the restriction that the leading octets, prior to the last 7 octets, must be equal to the Area Address of the area in which the node resides. Additionally, the leading 6 octets of the last seven octets must constitute a unique Level-1 ID within the area. Configuration of the adjacent router occurs manually, or, automatically via the ES/IS (ISO 9542) protocol.
Finally, a DNA network will interoperate with autonomous networks of non-DNA nodes via Reachable Addresses, using address prefixes.
Routing in a network is based on a forwarding database. In a forwarding database, each listed destination address is cross-referenced with the next link, and the address on that link, of the routing path a packet should take to reach its destination.
The database may be divided into two parts: (i) a part which maps network addresses onto internal indices, and (ii) a part which maps the internal indices onto sets of links and link address elements.
A network router obtains the destination address information from the header of a received packet, accesses the database to determine the best next link through which to route the packet and the data Link address on that link, and forwards the packet accordingly.
Known database formats affect the rate at which packets are forwarded, and the storage requirements of the database may be large.
SUMMARY OF THE INVENTION
According to the invention, a routing database requires less space than prior art databases for identical function. In addition, routing information is located more quickly using less expensive computing hardware.
One aspect of the invention is a method of conducting a search along a search path of reduced length. A node which would otherwise occur between a previous and a following node in the search path is eliminated, and information is stored as to whether, had said eliminated node been present, the search would have proceeded to the following node. During the search, a search argument is compared with the stored information, and the search effectively progresses from the previous node directly to the following node if the comparison is positive.
Preferred embodiments include the following features. Some nodes provide result values for the search. A node is eliminated only if its presence would not affect the result value for the search. The information to be compared is stored in the following node. The search has first and second modes, the first mode including processing nodes along the search path. The eliminated node is one that, if present, would either cause the search to progress to the following node, or cause the search to enter the second mode. The search argument comprises a series of search segments, some values of segments of said argument corresponding to nodes along the search path, some other values of the segments relating to the second mode of the search. The stored information is a sequence of said search segments. Indicators are associated with nodes, each indicator indicating the segments corresponding to the second mode. The search path is searched by processing successive search segments, the processing including inspecting the indicator associated with each node, and proceeding to the second search mode if the indicator indicates that the segment relates to the second mode. The second mode of the search comprises terminating said search. The search argument comprises a system address in a network.
Another aspect of the invention is a method of conducting a two mode search of reduced length. For a first mode of the search, nodes along a search path are provided, at least some of the nodes including one or more pointers pointing to other nodes. A search argument comprising a series of search segments is provided, some values of segments of the argument corresponding to nodes along the search path, some other values of the segments relating to a second mode of the search. Indicators associated with nodes are provided, each indicator indicating the segments corresponding to the second mode. The search path is searched by processing successive search segments by inspecting the indicator associated with each node, and proceeding to the second search mode if the indicator indicates that the segment relates to the second mode.
Preferred embodiments include the following features. If the indicator does not indicate that said segment corresponds to the second search mode, the indicators and the segment are examined to determine one pointer, and the search is continued to a subsequent node. Each indicator is a bit in a sequence of bits associated respectively with a plurality of the segment values. The second mode of the search comprises terminating the search. The search argument comprises a system address in a network.
Another aspect of the invention is a method of hierarchically searching a search path. A hierarchy of nodes along the search path is provided, at least some of the nodes including one or more pointers indicating other nodes at different hierarchical levels. A search argument comprising a series of search segments is provided, successive segments of the argument corresponding to successive nodes along the search path. The path is searched by processing successive search segments in the nodes, including inspecting the pointers, and proceeding to the indicated nodes if the search argument satisfies a validation condition.
Preferred embodiments include the following features. The validation condition comprises counting the number of processed or unprocessed segments. The search arguments are system addresses for a computer network in accordance with ISO 8348/AD2. The search comprises a Level-2 routing search at a first hierarchical level and a Level-1 routing search at a second hierarchical level. The search comprises a IDP search at a first hierarchical level and a DSP search at a second hierarchical level.
Another aspect of the invention is a method of parsing a search argument of segments, some segments having predetermined values. Nodes along a search path are provided, at least some of the nodes including one or more pointers indicating subsequent nodes, each pointer corresponding to one possible value of a segment. The pointers corresponding to the predetermined segment values are directed to indicate the node storing the pointer as the subsequent node.
Preferred embodiments include the following features. The search argument is a network address in accordance with ISO 8348/AD2, and the predetermined values are the values of fill digits.
Another aspect of the invention is an apparatus for storing a trie shaped routing database for computer network routing, nodes of the trie storing data of various types. The apparatus includes a plurality of memory devices having differing access times and power requirements, each device storing data of a particular type for more than one node. The memory devices are chosen in order to store data types requiring rapid access in memory devices with low access times, and otherwise store data types requiring less rapid access in memory devices with low power consumption.
The invention saves storage space, processing time, and hardware.
Other advantages and features will become apparent from the following description of the preferred embodiment and from the claims.
DESCRIPTION OF THE PREFERRED EMBODIMENT
We first briefly describe the drawings.
FIG. 1 is a diagram of a trie database.
FIG. 2A is a diagram of an OSI network address format.
FIGS. 2B and 2C are tables of IDI formats.
FIG. 3 is a block diagram of a router having a recognition engine.
FIG. 4 is a diagram of an uncompressed routing database structure.
FIG. 5 is a diagram of a pointer-compressed routing database structure.
FIG. 5A is a diagram of a pointer-compressed node structure.
FIG. 6 is ia diagram of a path-compressed routing database structure.
FIG. 7 is a diagram of a partial database structure illustrating the provisions for IDI, DSP and Level-1 processing.
FIG. 8 is a diagram of the datapaths of a recognition engine.
FIG. 9 is a table illustrating the locations of node data in the memories of FIG. 8.
STRUCTURE AND OPERATION
Tries are an appropriate candidate for maintaining the a database of partial addresses in ISO routers. Tries support a best matching prefix search of a destination address easily. In addition, tries are appropriate for searching large and variable length strings such as ISO partial addresses. However, the storage requirements of tries can make the use of tries in practical routers infeasible. Also, to apply a trie to ISO addresses, the trie search method must be adapted to the particular characteristics of ISO addresses, such as the variable-length fields and fill digits discussed above.
The invention reduces the storage requirements of a trie database, and also adapts a trie search to ISO addresses. The storage reductions accomplished by the invention are detailed later in the disclosure.
The methods for reducing trie storage requirements are applicable to tries in a wide variety of contexts outside of the preferred embodiment; the methods for adapting trie searches to ISO addresses can also be useful in other contexts.
Referring to FIG. 3, in the primary operation of a router 10 a packet 11 is received at a receive unit 12. Receive unit 12 presents the packet to a forwarding engine 14. The forwarding engine 14 processes the packet header, extracting the destination network address and transferring it to a recognition engine 20. A logic unit 22 provides the logic signals used by forwarding engine 14 to interface with recognition engine 20. Recognition engine 20 uses the destination address to recover an index from a database stored in memory 50. This index is returned to the forwarding engine 14, which uses the value to access a forwarding database (not shown). The forwarding database consists of sets of link references and link addresses. Forwarding engine 14 then uses the link reference to direct packet 11 to one of several transmit units 26A through 26D (four being shown for illustrative purposes). Transmit units 26A through 26D are responsible for queuing packets and sending them via the network communications links 16 to other routers or destination systems.
In address recognition engine 20, a fetch unit 30 receives the packet destination address from forwarding engine 14 and presents the address, or specific fragments of the address, to a search unit 40. Search unit 40 uses the address or address fragments presented by fetch unit 30 to directly access memory 50. Intermediate results fetched from memory 50 are processed by search unit 40 and are used, in conjunction with the address presented by fetch unit 30, to access further intermediate results and ultimately the final result. The final result is returned by search unit 40 to forwarding engine 14 which uses the result as an index into the forwarding database (not shown).
In other modes of operation, the database may be used by a management engine 18. Management engine 18 as detailed later in the disclosure is responsible for creating and maintaining the database stored in memory 50. Management engine 18 receives information about the current network connectivity on a continuous basis, through paths which are not shown. Management engine 18 presents address fragments, generated from network connectivity information, to search unit 40. The result of this search is returned to management engine 18, which uses the result to learn about the current information in the database. If it is necessary to update the database, so that it correctly represents the current network connectivity, management engine 18 directly accesses memory 50 to effect the changes.
As mentioned in the background to the invention, router 10 must be capable of performing Level-1 and Level-2 routing. Level-1 routing requires that an exact match of the network destination address presented by fetch unit 30 be located in the database. There are many known database structures that allow an exact match to be realized. Level-2 routing, however, requires that if an exact match cannot be found, then the entry in the database which is the longest prefix of the network destination address should be located. This requirement limits the number of different database structures that may be used.
In the invention, the database stored in memory 50 is a particular type of tree structure known as a TRIE. FIG. 4 is an example of a fragment of such a TRIE structured database. Each node 110 of the TRIE may contain an array of sixteen pointers 105 to other nodes 110. A transition from the root of the TRIE to other nodes 110 is made by fragmenting the search argument (e.g a network destination address) into a sequence of segments (e.g. semi-octets); at each node in the TRIE, the next semi-octet in the sequence, having a value from zero through fifteen, is used to select one of the sixteen pointers.
Referring to FIG. 3, the Current Node Register 41 points in turn to the nodes of the TRIE that are traversed during a search. When a search is initiated, the Current Node Register 41 is set to point at the root of the TRIE. In the fragmentation of the search argument into semi-octets, the semi-octets formed correspond to the constituent digits of the NSAP discussed earlier.
Referring to FIG. 4, nodes 110 with pointers are called parent nodes; the targets of the pointers are child nodes. Nodes in the trie which do not contain pointers to other nodes (e.g nodes 110-8, 110-9 and 110-11) are called "terminal nodes". When the search reaches a terminal node, the search terminates. The search will also terminate if the pointer 105 selected by the next semi-octet points to a NIL node 115. (Although several nodes of FIG. 3 contain nil result values, for clarity, many other nil nodes have been omitted.)
If a terminal node is reached by using all of the semi-octets in the search argument, then an exact match has been located in the database, and the terminal node holds a result value 120 which corresponds to the search argument. If, however, a NIL node 115 is reached, or a terminal node (e.g 110-8) is reached before all of the sequence of semi-octets has been used, then an exact match of the search object is not contained in the database.
It is possible that a prefix of the search object is contained in the database; if this is the case, then at least one of the nodes traversed during the search will hold a result value 120. If no traversed node contains a result value (e.g. a search ending at node 110-13) then no such prefix exists in the database. If multiple nodes holding a result value are traversed, then multiple prefixes of the search object are contained in the database: the first such node traversed holds a result corresponding to the shortest prefix, while the last such node traversed holds a result corresponding to the longest prefix. The result corresponding to the longest prefix is returned as the result of the search.
In many cases, the result value 120 for a child node and its parent node would be identical. In these cases (e.g., nodes 110-5 and 110-7), the child node does not hold a result value 120. If the search terminates at a child node which does not contain a result value 120, the result value 120 of the most-recently-traversed prior node which has a result value is returned. In this way, a prefix stored in the database has its corresponding result value entered at only one node, simplifying maintenance.
The preceding outlines how a TRIE structured database can be used to enable a search process to locate an exact match or the best-prefix match of a given search argument. Two forms of database compression are used in preferred embodiments of the invention to reduce the amount of memory required to support the TRIE structure. These are known as pointer compression and path compression.
Referring to FIG. 5, pointer compression is achieved by eliminating all of the nil nodes and all of the pointers to nil nodes from the trie. This is done by associating a pointer bit mask 115 with each parent node in the trie. The bit mask indicates which of the child nodes are nil, i.e. which of the pointers 105 point to nil nodes. Each bit in the mask corresponds to one of the parent node's pointers, and is set if that pointer's target node is non-nil; otherwise it is cleared.
For example, the root node 100 is associated with bit mask 115-0. Two non-nil child nodes 110-1, 110-2 exist below the root node 100. Thus; the root node bit mask 115-0 contains two "1" bits, one for each of the non-nil child nodes. All other bits of the mask are "0", indicating that all other child nodes of the root node are nil nodes.
By comparing FIG. 5 to FIG. 4 it can be seen that the location of these two "1" bits correspond exactly to the location of the two pointers. In operation, before moving to a child node, the search unit 40 checks the parent bit mask 115 to determine that the new node is non-nil. If the new node is nil, then the search immediately terminates without moving to the new node.
Thus, referring to FIG. 5A all nil nodes (and the pointers which indicate nil nodes) are eliminated from the trie, saving storage space. Since it would be necessary to store only one nil node for the entire TRIE, the memory savings are a result of the elimination of the pointers to the nil node or nodes. With pointer compression, the memory requirements for a TRIE structured database may be reduced, but the calculation of current node addresses is more complex. To determine the address of new nodes, the search unit 40 must reference the parent's bit mask 115 to determine the number and distribution of pointers 105. If the bit mask indicates that the pointer corresponding to the next semi-octet in sequence is; present, the bit mask is used to determine the location of the required pointer 115 in the list of pointers stored in the parent node.
To introduce path compression, we first note that pointer compression has eliminated nil nodes and pointers to nil nodes, but has not reduced the path length (i.e. the number of nodes) from the root node to any given result node. Path compression is used to achieve such reductions.
Path compression eliminates each node in the database that has: (1) only one child node, and (2) no result value or the same result value as its parent node. Node 110-7 of FIG. 5 meets these requirements. Referring to FIG. 6, after path compression, node 110-7 has been eliminated, and node 110-11 is directly below node 110-2.
In the preferred embodiment of the invention, the semi-octets corresponding to the (one or more) eliminated nodes is stored as a path-compression digit string 125. (In FIG. 6, the string is just one digit in length.) In operation, search unit 40 compares each digit of the path compression digit string 125 against successive semi-octets of the search object. All comparisons must indicate equality in order to proceed to the next node. If any of the comparisons fail, the search terminates at the node traversed immediately prior to the path compression digit string 125. By implementing path compression in this way, the TRIE database may be used to locate the best prefix for a search object. This would not be possible if the skipped semi-octets were not processed.
In preferred embodiments, the path digit string is stored at the child node. If a string is present at a child node, the string must successfully be matched against subsequent semi-octets of the search object in order to arrive at the child node. If the string match fails, the failure is treated as though a nil pointer were selected at the parent node.
This process is indicated diagrammatically in FIG. 6 by the interjection of the path digit string 125 between nodes 110-2 and 110-11. The existence of a path digit string in a node is indicated by a flag bit at that node. If this flag is set, the node has an associated path digit string; if not set, the node contains no such string. As can be seen in FIG. 6, flag bits have been included with each of the nodes 110.
Thus, pointer compression and path compression result in reduced memory requirements for a TRIE structured database while allowing exactly the same functionality as an uncompressed database.
The optimized TRIE structure described above requires some enhancements to allow it to properly process an OSI network destination address (NSAP) in the context of DECNET Phase-V routing. The mechanisms described so far provide for searches capable of finding exact matches and of finding maximal length prefix matches of the input address. These mechanisms must be enhanced in order to: (i) allow stored address prefixes which are shorter than the IDP to match addresses whose leading significant IDI digits are identical to the significant IDI digits of the stored prefix; and (ii) allow recognition of area addresses, prompting a transition to a Level-1 database (since network addresses are variable in length, it is possible for a stored area address to match the leading semi-octets of an input address without the input address meeting the requirement that it have precisely fourteen semi-octets remaining after the matching area address).
As an example to illustrate the requirement for the first enhancement, consider a prefix 37-123 stored in the database. In this example, the AFI "37" indicates that the IDP length is 16 digits (i.e. the IDI length is 14 digits). The digits that follow the hyphen, namely "123" are the leading significant digits of the IDI. Every address presented, for example by fetch unit 30, whose AFI is equal to "37" and whose leading significant IDI digits are equal to "123" should traverse a node in the TRIE that indicates a recognition of the prefix 37-123. Consider the following three addresses, as presented by fetch unit 30:
(i) 37000000000123456789abcdef
(ii) 3700000000000123456789ab
(iii) 37000000000000123456789abcdef
The first address has significant IDI digits equal to "12345". The second address has significant IDI digits equal to "123". The third address has significant IDI digits equal to "12". Thus the first and second addresses contain the prefix 37-123 but the third does not. Because there can be any number of padding digits in the IDI (between zero and eleven) in an address containing the above prefix 37-123, an unmodified address recognition tries would have twelve different branches for the prefix 37-123, each representing a different number of pad digits (in the range 0 through 11) and each leading to a distinct node labelled with the result corresponding to prefix 37-123. However, this structure is both inelegant and memory intensive.
A preferred way to store the prefix 37-123 is to treat all IDI pad digits; as discardable. Then the node storing the result corresponding to the prefix 37-123 is reached after the semi-octet sequence 3,7,1,2,3. In preferred embodiments, pad digits are easily discarded, without changing the basic operation of the TRIE. Pad digits are discarded by arranging the TRIE such that IDI pad digits select pointers 105 that point back to the parent node, rather than to a different child node. (As a consequence of this self-referencing, a node which corresponds to the first digit of the IDI cannot have an associated path compression digit string).
Without further modification, the third address in the example list above, once the IDI padding digits are discarded, will also travel along the path 3,7,1,2,3, and falsely indicate that it contains the prefix 37-123. To overcome this, two mechanisms are added to the basic TRIE: (i) a counter, the Remaining IDI Length Counter 43 (FIG. 3) which maintains a count of the remaining IDI digits of the input search address; and (ii) a seventeenth pointer, called the DSP pointer, which points from a parent node representing a digit of the IDI to a child node representing the first digit of the DSP. The seventeenth pointer is accessed when the IDI Length Counter is decremented to zero.
In operation, during a search of a network destination address, nodes in the TRIE reached after processing the second semi-octet of the address store the corresponding IDI lengths. That an IDI length is stored is indicated by an additional flag bit. Search unit 40 recognizes that the flag is set, reads the IDI length stored at the node and transfers it to the IDI Length Counter 43. Each time that a semi-octet is processed by search unit 40 (including the padding digits of the IDI), the IDI Length Counter 42 is decremented by one. When the IDI length is decremented to zero, the entire IDI has been processed. At this point, the seventeenth (i.e. DSP) pointer will be selected at the current node. Note that if the AFI value is 48 or 49, then there is no IDI; thus nodes in the database corresponding to these AFI values must provide an indication that the IDI Length is zero and must also provide a seventeenth pointer for immediate transition into the DSP domain of the database.
Another example illustrates the need for a second enhancement of the basic TRIE, relating to recognition of area addresses. Consider that a router is operating in a DECNET area defined by the area address 47123400000000abcd. By referring to FIGS. 2A and 2B, distinct fields of this area address can be recognized, as shown
______________________________________AFI IDI DSP lead LOC-AREA______________________________________47 1234 00000000 abcd______________________________________
Next, consider that the following three network destination addresses are presented to search unit 40 by fetch unit 30 (having been extracted from packets traversing the network):
(i) 47123400000000abcd0123456789ab00
(ii) 47123400000000abcd0123456ff
(iii) 47123400000000abcd01234567ff89ab00
The leading digits of the first address exactly match the area address of the area in which the router resides. The remaining digits can be interpreted as two fields: (a) a 12 semi-octet field 0123456789ab which is the DECNET Level-1 ID part of the address and (b) a two semi-octet field 00 which is the DECNET SEL field. Thus the packet from which the first address was extracted should be regarded as destined for an End System within this area, and should be routed by DECNET Level-1 routing. An exact match for the Level-1 ID part must be found in the database so that the packet may be forwarded to the correct End System.
The leading digits of the second address also exactly match the area address of the area in which the router resides. When the remaining digits are examined, there are nine. Thus, the remaining digits cannot be interpreted as a Level-1 ID part plus a SEL part; accordingly, the packet containing the specified destination address is not destined for an End System within the area in which the router resides. The incidental match between the leading digits of the destination address and the area address must be discounted; the longest prefix of the entire address should be sought in the Level-2 database, and the packet routed by Level-2 routing.
Similarly, the leading digits of the third example address exactly match the area address. Here again, the match must be discounted because the remaining digit string would be too long to interpret as a Level-1 ID part plus a SEL part. Again, the longest prefix of the entire address should be sought in the Level-2 database, and the packet routed by Level-2 routing.
When a search of the above three addresses is effected in a TRIE database, it is clear that they will all follow the same path until and beyond the node in the database corresponding to a match with the area address. As explained above, it is necessary for the first address to follow a different path once a match with the area address has occurred--at this point, a branch should be made to a subtrie which is a logically separate database holding all Level-1 addresses.
To allow for branches from the Level-2 database into the Level-1 database, a further, eighteenth, pointer is added to each TRIE node. In order to use the eighteenth, or "Level-1", pointer, two additional mechanisms are added to the basic TRIE: (i) a counter and comparator in a Current Remaining Length register (CRL 42 in FIG. 3), which indicate that there are exactly 14 semi-octets of the search object remaining; and (ii) an additional flag bit stored at each node, which is set only at the node or nodes in the TRIE that are reached after an exact match against the area address (i.e. the area address of the area in which the router resides). This flag bit will be referred to as the "Level-1 transition possible" bit.
The CRL register 42 is loaded with the length of the entire search object (i.e. number of constituent semi-octets) when it is first presented by the forwarding engine 14 to the fetch unit 30. Although not part of the address per se, the length of the address is included in the packet header as specified in ISO 8348/AD2. The CRL register 42 is decremented by one each time that a semi-octet is processed by search unit 40.
Only when the Level-1 transition possible bit is set and the CRL register indicates that there are exactly fourteen semi-octets remaining, will the eighteenth pointer be selected. The child node of the eighteenth pointer will be the root node of the Level-1 database. Note that the next semi-octet from the search object will not be consumed until after the transition into the Level-1 database.
In operation, if a transition into the Level-1 database takes place during a search of a network destination address, then the packet containing the address is destined for an End System within the area in which the router resides. As explained above, an exact match must be found in the Level-1 database for the Level-1 ID part of the destination address. That is, any former "best prefix" results that may have been acquired during the initial traversal of the Level-2 database are irrelevant once a transition into the Level-1 database has taken place. If an exact match cannot be found in the Level-1 database, the packet must be discarded since its destination address does not exist. Results returned from a search in the Level-1 database must therefore correspond to exact matches; otherwise, a nil result should be returned.
Referring to FIG. 7, four nodes of a partial database are illustrated, and will be used as an example of the progression of a search through a database in accordance with the invention. In the example, path compression has been used, but pointer compression has not.
The search progresses as follows. An address search arrives at node 110-A. The Path String and IDI flags are checked upon arrival. Since both flags are not set ("0") in node 110-A, node 110-A does not require special processing. Therefore, the search uses the next semi-octet to index the array of pointers and proceeds to a child node. In the example, the fetched semi-octet has a value of 7, so the search unit 40 uses pointer seven to move to node 110-B.
Upon arrival at node 110-B, the search unit 40 sees that the Path String flag is "0", and thus node 110-B has no associated path digit strings. However, the "IDI" flag is "1". This indicates that node 110-B contains IDI information 130 which contains the length of the IDI field. (It can be assumed, therefore, that in all probability the semi-octet "7"that was just processed was the second AFI digit.) The search unit 40 retrieves this information, and loads the value into the IDI length register. This register will then be decremented by one every time a semi-octet is processed. The next semi-octet (the first digit of the IDI field) is fetched, and the search progresses.
In the example search, the AFI for the search path specifies that the IDI fill digits equal the decimal value 0. To ignore fill bits, the pointer in node 110-B corresponding to a semi-octet value of 0000 points to node 110-B. Therefore, as long as IDI fill digits are processed and the IDI length register is not decremented to zero, the search does not leave node 110-B. The search ordinarily leaves the node only after a non-fill (non 0000) digit is parsed.
In one path the search could subsequently follow, it would arrive at node 110-D, whose Path String flag is set. This indicates that node 110-D contains a path digit string 125. Before further processing at node 110-D, the search unit retrieves the path digit string 125 and compares the elements of the string with the subsequent semi-octets presented to the search unit. Only after the entire digit string has been successfully compared does the search unit further process node 110-D.
During further processing, the search unit discovers that the result field contains the value xyz, indicating that the semi-octets processed so far are a prefix having associated routing information (the prefix is associated with the result value xyz). The result value xyz is stored by the search unit. If no further result is encountered during the search, then the value xyz will be returned as the search result, indicating that the associated prefix is the best one stored in the database for this particular search argument.
Subsequently, the search unit discovers that the DSP flag is set. This indicates that node 110-D has a non-nil seventeenth pointer which points into the DSP domain of the database. (In an actual implementation, the DSP flag bit may be implemented by the use of nil and non-nil DSP pointers rather than with an explicit bit.) If and only if the IDI Length register has been decremented to exactly zero can this seventeenth pointer be accessed. If this is the case, the search will continue in the DSP domain of the database. If the IDI Length has not been decremented to zero, the next semi-octet of the search object is used to select one of the first sixteen pointers at node 110-D.
In another path the search could follow, it would arrive at node 110-C. At node 110-C, the Level-1 flag is set. This indicates that the semi-octets of the search argument that have been processed so far exactly match the Area Address of the area in which the router resides (i.e. the router that this database is contained within). If, at this point, there are exactly fourteen semi-octets of the search argument remaining, then the search argument will be regarded as an address of an End System within this DECnet Area; accordingly, the eighteenth pointer will be selected at node 110-C and the search will resume in the Level-1 subtrie.
Thus, each node contains several flags and possible pieces of information. Each node may contain (where pointer compression is used) an 18 bit pointer bit mask, 16 pointers to subsequent nodes (or to itself), a DSP pointer, a Level-1 pointer, a path compression string and an indication of its length, result information, and IDI length information.
DETAILED DESCRIPTION
A specific implementation of a search unit is described here. The design is driven by the desire to use a minimal number of readily available components and to minimize the power consumed.
The desire to use a minimal number of readily available components must be stressed. We have described above minimizing the use of memory through the techniques of path compression and pointer compression. By looking at these techniques from an implementation viewpoint, it may be decided that path compression should be implemented but pointer compression should not. Although pointer compression allows a reduction in the amount of memory required, it also requires that the memory be segmented into small pieces that are managed by some memory management process. Additional overhead includes extra logic to read and decode the bit mask, multi-level hardware adders to accumulate the significant bits of the mask and additional adders to then add this accumulation onto the address of the block of compressed vectors.
This overhead not only requires the use of extra control logic, but also reduces the potential cycle time of the machine because the extra logic is in the critical path of every cycle. By dispensing with pointer compression, the control logic is greatly simplified and the cycle time improved. The addition of more memory does not increase the component count to what it would be with pointer compression in effect. Different implementation requirements, especially those with larger databases, may make memory usage the greater consideration. Under these different requirements, pointer compression may be used effectively.
The recognition engine here is designed to fit into a "Widget-2"system. This system has a small 3-slot backplane, one slot of which is intended for some form of address recognition engine (ARE). The backplane bus is essentially that of a host 68020 Motorola microprocessor, but with only 24 rather than 32 address bits. The timing of the bus has been slowed down relative to the CPU in order to simplify bus interface logic. It is still possible to guarantee no more than two wait states (200 ns cycles) when the CPU accesses the ARE if performance requirements mandate this.
To permit maximum flexibility, the implementation supports eight different root nodes for initiating searches. The proper root node may be selected for searching different address formats or performing various types of generalized searches.
Central Components
Referring to FIG. 3, there are four basic components implementing memory 50 of recognition engine 20, and a number of registers and elementary state machines operating concurrently (collectively known as the search engine 40). The four central memory components are described below.
DRAM Pointer Memory
The core of the recognition engine 20 consists of the node pointer memories and the "current node+current digit→next node" search unit 40. Referring to FIG. 8, the pointer memories are implemented by an array of DRAM memories 200 supported by a small amount of control logic. A 16-bit state vector (i.e. the node address carried by lines 202) and a 4-bit digit (carried by lines 204) requires a DRAM memory 200 organized as 1M×16 (20 bits×16 bits) and allows 64K states (or nodes) to be implemented. This allows at least 32K addresses to be recognized; in fact, by asserting that there are 32K nil nodes (with no "next state" child nodes) and 32K non-terminal nodes with next states, then only half as much physical memory is required, i.e. only one Megabyte (organized as 512K×16). A DRAM array 200 of this size requires only eight (256K×4) chips, or (looking ahead in memory technology) only four (1M×4) chips.
The basic machine cycles DRAM array 200 at the highest possible speed, and this speed largely dictates the search time for any given address (assuming that there is time to generate the DRAM address for the next cycle after the data for the current cycle has become valid; this can easily be managed, as the next DRAM address is essentially a concatenation of the 16-bit pointer data with the 4-bit digit).
A node is thus defined by a 16-bit address carried on lines 202. If the most significant bit of the address is equal to zero, the node is defined (in this implementation) to be terminal (with no next-node pointers), but is non-terminal (i.e. has next-node pointers) otherwise.
Fast Static RAM
All 64K nodes must provide the extra information (in addition to the pointers to next nodes) that has been alluded to earlier. To supply this information, a fast 64K×16 static RAM 210 is accessed concurrently with DRAM pointer array 200. The static RAM provides the following information about the current node:
NIL Flag: set if node is NIL (and processing should halt);
Path String: if a path string stored at the node, a non-zero length is stored in SRAM;
Result Flag: set if node contains a new result value;
IDI Flag: set if AFI done (and node contains IDI length);
Level-1 Flag: Level-1 transition possible (DECnet area recognized at this node).
The mapping of this information into physical memory will be more fully discussed later, under the heading "Memory Map".
Path Digit String Memory
The Path Digit String Memory 220 is accessed concurrently with the DRAM pointer array 200. String storage space is allocated for each of the 64K nodes. The number of digits stored at each node is indicated by the string-length field that is stored in the fast static RAM 210. The maximum number of digits that can be stored at a node is determined by the address of the node. There are three different maxima: 48 digits, 16 digits, or zero digits. The node address on lines 202 determines which maximum is in effect; the assignment is partly hard-wired and partly logic-programmable and is designed to minimize the amount of physical memory.
The implementation supports 48 digits of storage at 4K nodes and 16 digits of storage at 52K nodes. 8K nodes have no string storage space. The total memory required is 1M digits which is 512K octets or four (1M*1) chips. Again, with next generation 4 Mbit DRAMs, only one chip is required.
According to the invention, techniques are used to map the node address (16 bits) and the value of the string-digit-counter (6 bits) onto the 1M*4 DRAM address lines (20 bits). In effect, the mapping changes as a function of the node address lines. This will also be further detailed in the section entitled "Memory Map" below.
DSP Pointer Memory
The DSP Pointer Memory 230 is also accessed concurrently with the DRAM pointer array 200. Only 32K of the nodes, known as "transition nodes" (where the node address MSB is equal to one) can access this memory. The memory requirement is thus 32K*16, equating to only two chips. The DSP pointer accessed at a node will only be used when the end of the IDP is recognized; i.e. after an IDI search when the CRL counter is decremented to zero.
Control Logic
Central components of the control logic for the ARE are described below:
The timing generator (not shown) is responsible for the correct sequencing of the memory arrays; e.g. RAS and CAS control, refresh timing, cycle-to-cycle control, etc.
The fetch unit 280, 290 is responsible for supplying semi-octets of the address to the search unit on a demand basis. The semi-octets are extracted in order from the search address as supplied (in this case) by the host CPU to a register file 270. The semi-octets are presented to the search engine and are synchronized to its timing generator. Interlock is provided, in that if the search engine requires a semi-octet that the host CPU has not yet supplied, then the search engine is stalled until the semi-octet is ready.
There are three digit-counters that are capable of concurrent operations:
The current remaining length (CRL) counter 240 is loaded with the semi-octet length of the entire search argument when it is first presented by the CPU to the recognition engine. The counter is decremented by one whenever a digit is consumed (processed) by the search engine. If the count reaches zero, it is an indication that the search must terminate.
The CRL counter 240 also provides a signal on line 310 to the Cycle Controller (not shown, see description under Cycle Controller, below) that exactly fourteen digits of the search argument remain, for the purpose of making a Level-1 transition.
The Remaining-IDI-length IDIL counter 250 is loaded with the length of the IDI that is dictated by the AFI value (as specified in the DECNET Phase-V routing specification). The loading takes place under command of a control bit set at a node (the node immediately following the second AFI digit). This counter is also decremented by one whenever a digit is consumed by the search engine; if the count reaches zero, then the next machine cycle must be a DSP transition cycle. The value of the IDIL counter is reset to -64 each time a new search starts. The value -64 indicates "length not loaded".
Note that the ARE may be used to search arbitrary words in an arbitrary database; it is not necessary to load the IDIL counter (if it is not loaded, then a DSP transition cannot and will not be made).
String-digit-counter 260 is always reset to zero upon entering any node. The counter is incremented at the end of every machine cycle that is a string-digit comparison cycle; thus this counter will remain reset to zero until a node is reached at which a constant string is stored. If a string of length N digits is stored at a node, then the string digit counter will increment from the value zero through N minus one, as N string digit comparison cycles take place (assuming that the comparisons are successful). When the string-digit-counter reaches the value N, no further comparisons take place; the counter is reset to zero in the next machine cycle.
The cycle controller (not shown) might be regarded as the central intelligence of the search engine. It sees status information about the current machine cycle and control information from the Node Control Word on bus 330. The cycle controller decides how to continue with the present cycle (i.e. whether to compare a string digit, select a pointer for another cycle, or stop); whether to start another machine cycle, and, if so, whether to use a new digit and/or a new node address. The cycle controller also generates signals to various registers and counters.
Status registers 245, 248 are used to save the node address of the most recently traversed prefix (i.e. the best prefix so far), and to save useful past history; in particular, whether DSP and/or Level-1 transitions have taken place, whether the "best prefix so far" has ever been loaded, whether the remaining-IDI-length register 250 has been loaded.
Host CPU access transceivers 252, 254, 256, 258, 262 allow the host CPU to access the internal memories of the ARE for maintenance purposes. The concurrent operation employed by the search engine is disabled for this purpose; the memories collectively appear to the host CPU as a single database with what is intended to be a "programmer friendly" structure and address map. In this structure, all of the data associated with a particular trie node appears within a uniformly organized data structure.
Functional Interfaces to the ARE
There are basically three functional interfaces to the ARE. These are:
1. Search interface--packet forwarding;
2. Search interface--maintenance;
3. Maintenance interface.
The first of these is straightforward; it may be considered as the primary reason for constructing an ARE. In this mode, forwarding addresses (and/or other addresses, e.g. datalink addresses) that have been extracted from packets traversing the network are presented to the ARE. The ARE performs a look-up on the addresses and returns forwarding information to a forwarding engine (in this case, the forwarding engine is the host CPU).
The second and third functions are both concerned with maintenance. The search interface for maintenance is very similar to the search interface for packet forwarding. In this case though, addresses presented to the ARE are not necessarily complete addresses. Typically, address fragments are presented in order to determine what structural changes to the database are required to add, delete or modify entries. A slight modification to the operational behavior of the ARE is used for maintenance searches, to cope with the subtle differences of the address semantics.
The maintenance interface involves no searching; indeed, the search engine is inhibited from operating in this mode. The address, data and control paths within the ARE are completely restructured so that the internal memories of the ARE are made visible to the host CPU. Each memory component of the ARE is then accessed by decoding the CPU address lines, rather than by a search engine.
The CPU interface to the ARE for the purpose of performing a search is functionally the same, whether the search is for the purpose of forwarding a packet or of inspecting the database. The interface is supported by direct memory mapped control, status and data registers. The control registers allow the mode of operation of the ARE to be controlled, while the status registers allow the operation of the ARE to be monitored. The data registers provide a means of presenting an address to the ARE and of reading a search result.
The control registers provide control of the following:
1. Select search mode or maintenance mode;
2. Select address format mode (influences the interpretation of results);
3. Inhibit: Level-1 transitions (for maintenance searches);
4. Inhibit: IDP to DSP transitions (maintenance searches);
5. Select poll or stall until search result complete;
6. Control parity protection of ARE memories.
The status registers allow the following to be monitored:
1. State of search engine (reset, searching, halted);
2. State of address input to search engine.
The data registers are broken into eight blocks. Each block corresponds to a search initiation at one of eight root nodes, but otherwise the blocks are functionally identical. (Some of the eight root nodes may begin databases used for different types of searches, others may correspond to the start of, for example, Level-1 branches of an address search database.) A register block is 64 bytes in size; the second 32 bytes being an alias of the first 32 bytes (i.e. using the same physical memory). Of the 32 physical bytes in a block, up to 24 bytes may be used to write an address to the ARE that is to be searched. The first byte must be a length indication of the entire length of the address to be supplied. (Note that this format allows direct extraction from ISO 8348/AD2 packets traversing the network). The choice of which alias to write the address into determines whether the length byte will be interpreted as the length of the address measured in octets or measured in semi-octets. An octet length allows direct extraction from a ISO 8348/AD2; a semi-octet length allows arbitrary length prefixes to be searched, which is particularly useful for maintenance searches. The maximum length address that can be searched (in the current implementation) is 23 octets or 46 semi-octets.
The search operation will start as soon as the first four octets of the search address are written. An interlock mechanism prevents the search engine from using octets five through eight until these also have been written by the CPU. Similarly, the interlock is provided for the remaining octets in groups of four. Note that four octets may be written with one write operation, as the ARE has a 32 bit data interface. Note also that the search address, including the length byte, must be padded out with arbitrary data if necessary to be a multiple of four octets in total length.
The search result will be written by the search engine into the same block that the search address was written into by the CPU. The status of the search engine can be monitored by the CPU (using status registers 248) to determine when the search result is valid; or, alternatively, an interlock can be enabled so that the CPU is stalled when reading the result until the result is valid.
The search result is a group of eight bytes. The group is broken up into the following fields:
1. Summary (1 byte);
2. Result-so-far (2 bytes);
3. Got-so-far (2 bytes);
4. Internal counter values (3 bytes).
The summary byte provides rapid detection of search success or failure. In the case of a search success, in packet forwarding mode, the result-so-far provides an index into a remote table (i.e. external to the recognition engine) that provides all the necessary forwarding information. In the case of search failure, particularly in maintenance searches, the summary indicates the reason for failure. The other fields provide sufficient information to allow the ARE database to be easily and rapidly updated by the CPU if desired. Further details on these registers and their interpretation is provided later in the disclosure.
The CPU can put the search engine into "maintenance" mode (rather than "search" mode) by writing to a bit in the control register.
When in maintenance mode, the search engine does not function and all previously acquired status (except for the database) is lost. In this mode, all of the internal memory of the ARE is mapped into some part of the CPU address space. This part of the address space is not accessible unless the search engine is in maintenance mode. (This greatly simplifies arbitration for the internal memories and buses, and is consistent with the goal of minimum parts count).
Memory Map
The mapping is organized as 64 K of consecutive nodes; each node is 256 octets in size. Thus the total virtual space spanned by the memories is 16 Mbytes. The memory map of each node is shown in FIG. 9; the physical memory parts making up various fragments are shown in parentheses.
In this memory mapping scheme, a resource within a node N that has an offset (as shown in FIG. 9) of m is addressed with the CPU-supplied address:
N*2 8+m; i.e. the concatenation of N followed by m.
Some hard rules are enforced with the mapping scheme of FIG. 9. The rules are:
1. All nodes with address less than 8000 hex are terminal nodes. A path digit string may be stored at some terminal nodes, but a transition to another node is strictly not allowed at any terminal node.
2. There are 4K of nodes with provision for up to 48 semi-octets of path digit string storage. Half of these nodes are terminal nodes (Nodes 7800-7fff hex) and the other half are transition nodes (Nodes f800-ffff hex). These nodes are provided primarily for storing Level-2 entries in the database.
3. There are 52K of nodes with provision for up to 16 semi-octets of path digit string storage. Half of these nodes are terminal nodes (Nodes 1000-77ff hex) and the other half are transition nodes (Nodes 9000-f7ff hex). These nodes are provided for storing Level-1 entries, datalink addresses and other entities of total length not exceeding 16 semi-octets in the database.
4. There are 8K of nodes with no provision for path digit string storage; this is a consequence of giving up what would be storage for 16 semi-octets and allocating the memory to the 4K of nodes with 48 semi-octet storage. These nodes can be used, however, for example for those nodes where an IDP count is located within a node (and string storage is thus not allowed) or for any node where a constant string is not present.
5. There is only one Level-1 pointer. It is accessible at all transition nodes. The pointer should be set to point to the root of the Level-1 branch of the database.
Theory of Operation for ARE
The basic theory of operation for a search according to the invention is described here. It is assumed that the CPU will have built a valid database trie structure before searching starts.
Referring to FIG. 8, a register file 270 is used to provide the necessary memory for holding the search address that the CPU provides to the ARE, and for holding the result to be returned to the CPU. The register file 270 is dual ported, allowing concurrent access by the ARE and the CPU. This improves performance and obviates the need for arbitration control logic.
Searching is initiated when the CPU writes the search argument into the register file 270. In particular, when the CPU writes to the third octet of a longword entry (this will usually be concurrent with writing the whole longword) a hardware flag is set that indicates that the associated longword contains valid data. At the same time, the block chosen is remembered for the purpose of starting the search at the correct root node; and the alias used within the block is remembered so that the first octet can be properly interpreted as an octet or a semi-octet length.
There are six "ready" flags, one for each of the first six longwords in a block. The flags are cleared in one of two ways: either the CPU explicitly clears them by issuing a maintenance mode command (and by subsequently returning the mode to search mode); or the CPU overwrites the search argument with a new search argument. Overwriting the first longword will generate an ARE system reset but will leave the first longword "ready" flag set. The latter method allows multiple searches to be performed with little or no control overhead.
Control logic 290 around the register file 270 tests the flags and routes the longwords (when they are ready, i.e. valid) to a multiplexer 280 built in a couple of programmable logic arrays. The multiplexer 280 output feeds semi-octets of data to the search engine on bus 204 and generates a "data ready" indication. If "data ready" is stalled (because the CPU cannot fill the file as quickly as the search engine can empty it) then the search engine will also stall. The register file control logic 290 looks for a "next digit" signal on line 282 from the search engine whereupon it will drive the next semi-octet onto the multiplexer 280 output bus. Synchronization of the "ready" flags occurs in parallel with the serialization of each longword into eight semi-octets; this pipelining technique allows the overhead of synchronization to be completely recovered.
The first octet in a register file block (i.e. the octet with the lowest address) is routed to the CRL register 240. If the length is to be interpreted as an octet-length (rather than a semi-octet length), then its value is doubled so that the CRL register 240 always holds a semi-octet count. The second and subsequent octets are all routed to semi-octet multiplexer 280. For each octet entering multiplexer 280, the most significant four bits will be output first, followed by the least significant four bits. When each semi-octet is valid on the semi-octet bus 204, control logic 290 signals "ready" on line 292. If and when the Next Digit signal on line 282 is asserted, the CRL register 240 is decremented by one and a semi-octet is consumed. After all of the semi-octets have been output onto the semi-octet data bus (lines 204), the semi-octet generator logic will still indicate "ready" on line 292 to the search engine even though there are no more semi-octets. If "next digit" is asserted on line 282 to the control logic 290, undefined data will be driven onto the semi-octet data lines 204. However, the data will be qualified with an indication that the "remaining length is zero" (RLEQ0) on line 284.
As soon as "data ready" is indicated for the first semi-octet on semi-octet data bus 204, the first machine cycle starts. The cycle starts by driving a valid digit onto the semi-octet data bus 204 and a valid node address onto the node address bus 202. The node address used for the first machine cycle (i.e. the root node address) will be one of the eight values 8000 through 8007 (hexadecimal) as determined by which of blocks zero through seven was loaded with the search address.
A machine cycle is equal (in time) to a DRAM cycle. The master crystal oscillator frequency is selected to minimize the cycle time but also guarantee proper DRAM operation under worst case conditions. This time is approximately 208 nanoseconds per machine cycle.
A general case machine cycle will be considered. This general case includes the very first machine cycle. Machine cycles will execute back-to-back with no delay, unless there is a delay in obtaining the next digit (indicated by "data ready" being negated), caused by an unduly slow load of the register file. Approximately every 15 microseconds, a machine cycle will be donated to the cause of refreshing the DRAM arrays; no search progress is made during these refresh cycles.
At the beginning of the machine cycle, the current node address is driven onto the node address bus and the current search address digit is driven onto the digit data bus. Concurrent access is made to the following memories:
1. A next-node pointer is fetched from pointer DRAM array 200;
2. A DSP pointer is fetched from DSP pointer static RAMs 230;
3. A next string digit is fetched from path digit string DRAM array 220;
4. String/IDI length and control bits fetched from fast static RAMs 210.
The next-node pointer and the DSP pointer both contend for node data bus 206, as does the Level-1 pointer data register 340. Control logic will decide which contender is enabled onto the bus (see below).
The next string digit is enabled onto bus 208, and is compared with the current search digit on bus 204 (even if there is no string digit). The comparison is made by comparator 300. The comparison status, indicated by the "digit match" signal on line 302, is made available to the control logic.
The control information fetched from the fast static RAMs is available relatively early in the machine cycle, after approximately 60 ns. By this time, additional status information is available from registers and control circuits within the search engine. This additional status includes:
1. CRL=14 (line 310): 14 semi-octets remain, Level-1 transition possible.
2. CRL=0 (line 284): last digit has been used.
3. IDIL=0 (line 312): IDIL has been decremented to, or is being loaded with zero.
4. "IDI loaded" (line 314): prevents IDI reloading at a fill digit looping node.
5. "string exhausted" (line 316): indicates that the value in string digit counter 260 is equal to the "string length" field from the fast static RAM (carried on bus 320)--both values are 0 if there is no string stored.
The setting of the above status bits together with the Node Control Information carried on bus 330 from fast static RAM 210 determines what will happen the second half of this machine cycle. Basically, the machine cycle will be one of four types:
1. String digit comparison cycle (string cycle);
2. Level-1 transition cycle (Level-1 cycle);
3. IDP to DSP transition cycle (DSP cycle);
4. Normal next-node pointer cycle (pointer cycle).
Types 2, 3 and 4 may be collectively referred to as a "normal cycle"; there is nothing abnormal about a "string cycle" other than that the search engine does not progress to a new node.
The following description of how the cycle type is decided is given in a sequential form; the search engine however makes all these decisions concurrently:
If "load IDI length" (a node control bit on bus 330) is asserted and "IDI loaded" (on line 314) is false, then the IDI length will be loaded into this register and "IDI loaded" will be asserted. "IDI length=0"(on line 312) will be asserted whenever the register contents are zero and "IDI loaded" is asserted.
If "load IDI length" is negated, string comparison may be called for. If "string exhausted" (on line 316) is asserted, this is a "normal cycle"; otherwise, this machine cycle will be a path string digit comparison cycle. In the latter case, the next-digit and DSP pointers are ignored. The machine waits until the "digit match" flag (on line 302) is valid (after about 180 ns) and then, if it is negated, a string mismatch is declared and the machine stops. If "digit match" is asserted, then "next digit" (on line 282) is requested from the semi-octet generator; string count register 260 is incremented; IDI length register 250 and CRL register 240 are decremented. The machine ends the current cycle and starts the next cycle without changing the value on node address bus 202.
String comparison cycles will continue to take place until there is a digit mismatch or until "string exhausted" is asserted on line 316, indicating that all digits have successfully been matched, or until "CRL=0"is asserted on line 284 by CRL counter 240 (considered also to be a mismatch). Whenever "string exhausted" is asserted on line 316, string count register 260 will be reset to zero in the next machine cycle (even if it is already zero).
A "string cycle" will not take place if "string exhausted" is asserted during the machine cycle, because "string exhausted" is only asserted when (1) there is no path digit string at the node; or (2) the string at the current node has already been successfully matched. A "string cycle" will not take place if "load IDI length register" is asserted, because there can be no string if there is an IDI length stored at the node (because only one field in memory is provided for storing length information--when an IDI transition occurs, this field stores the IDI length and thus cannot store string lengths).
A "normal cycle" will select one of three potential next node addresses from three sources: the next-node pointer, the DSP pointer and the Level-1 pointer. The selection will be made according to the following rules:
(a) If "IDI length=0" is asserted on line 312, and "IDI loaded" is asserted on line 314, and DSP transitions are globally enabled, then a "DSP cycle" is selected. The value of the DSP pointer accessed from memory 230 becomes the address of the next node. Only one "DSP cycle" is allowed during the search operation, which prevents the search engine from being stuck in infinite loops.
(b) If (a) does not apply, if "CRL=14"is asserted by counter 240 on line 310, and if the "Level-1 transition" flag is set at the current node, then, if Level-1 transitions are globally enabled, the Level-1 pointer accessed from register 340 will be the source of the next node address. In this case, the cycle is a "Level-1 cycle". Again, only one "Level-1 cycle" is allowed per search operation.
If either (a) or (b) apply, then the next machine cycle will be run without fetching a "next digit" from the semi-octet generator. That is, the same digit will be re-examined once the Level-1 or the DSP transition has been made. If neither (a) nor (b) apply, then the "next node pointer" accessed from pointer DRAM array 200 will be the source of the next node address--i.e. this machine cycle will be a "pointer cycle". In this case, "next digit" will be asserted on line 282 to semi-octet generator 290 so that the next digit is available at the beginning of the next machine cycle. CRL register 240 and IDIL register 250 are both decremented.
For any "normal cycle", the following rules also apply: If the most significant node address bit is equal to zero, or if the "NIL node" flag is set, then this machine cycle will be the last for the current search argument (i.e., current network address being searched). If the "save current node address" flag is set, then the node address of the current cycle will be saved in "result so far" register 295 (only if this is not a nil node), overwriting any former value.
For a "string cycle", or for a "pointer cycle" (i.e. any machine cycle that absorbs a search digit), the current machine cycle will be the last if "CRL=0"is asserted on line 284. In the case of a "string cycle", a string mismatch is declared. In the case of a "pointer cycle", the current node is declared to represent the greatest progress that can be made on the search address. If the signal "CRL=0"is asserted during a "DSP cycle" or a "Level-1 cycle", then the appropriate transition can still be made since it does not require a valid semi-octet to be present on semi-octet data bus 204.
Errors in the database may be recognized by the machine, causing premature error termination. The following errors will be recognized:
1. A parity error between the current semi-octet and the current path digit string, as detected by parity check element 300;
2. A parity error in pointer DRAM array 200, as detected by parity check element 302, if the error occurs during a "pointer cycle" (i.e. when data from this memory is to be used as the next node address);
3. When string length counter 260 has been incremented beyond the legal range during a "string cycle".
Once the machine has stopped cycling, the "BUSY" status bit is cleared and the result of the search can be read by the CPU. Appendix B details the format and interpretation of the search result.
Performance prediction for ARE
Search time
The performance of the ARE is relatively easy to predict. The search time will be roughly equal to the number of digits in the search argument multiplied by the machine cycle time. Some overhead must be added to this estimate.
Once every 15 microseconds, a machine cycle will be run to refresh DRAMs 200, 220. Only one such "extra" cycle can be expected per search. Additionally, there may be two other machine cycles where a digit is not absorbed: a "DSP cycle" and a "Level-1 cycle". According to the invention, as discussed above, intrinsic hardware interlocks prevent more than one of each transition cycle per search argument, even with corrupted databases.
Thus, if the maximum length of a search argument is forty digits, then it will take at most 44 machine cycles to process the argument. (This includes one final "dummy" machine cycle, run with no valid semi-octet on semi-octet data bus 204). To this must be added the overhead of loading the input and reading the output registers. This calculation is difficult, especially when the data write and data read cycles are referenced to the instructions that cause them.
The CPU register load cycles can all run with at most two wait states. The first machine cycle can start as soon as the first register file load cycle is detected. This time is of the order 300 ns measured from the start of S0 of the CPU write cycle to the start of the first machine cycle. For reading the result, CPU DSACK signals can be asserted (or rather, the blocking of them can be released) coincidentally with the end of the last machine cycle. The end of S5 of the CPU read cycle will then occur within 150 ns.
The CPU will typically transfer six longwords (up to 46 digits, only up to the first 40 being significant) to the register file. The time measured from the start of the first transfer to the end of the read cycle reading the result will be, for a 208 ns machine cycle:
300 ns+44*208 ns+150 ns=9.6 μs.
To give a more accurate figure for the available spare CPU time, the transfer time of six longwords should be subtracted from this figure (6*200 ns=1.2 μs). This gives a result of 8.4 μs.
The look up time of a Level-1 address or IEEE 802.3 datalink address is much less. If the CPU prepends the address with an octet of value "12", and then transfers the result to register file 270, two longword writes will be required (the last octet of which is ignored). By making use of the fact that data in register file 270 is not overwritten, one of the eight input blocks (and, correspondingly, one of the eight root nodes) may be dedicated to Level-1 look ups--once the first octet is written with the value "12", it will stay there. In this way, the Level-1 address can be written directly to the file. This will still require two write operations, but at least three CPU bus cycles will be run by the interface hardware because of the misalignment.
The root node for Level-1 look up will (presumably) be the same as the initial node in the Level-1 branch of the database; no domain transitions can be expected. If a refresh cycle happens during the look up, the look up time will be 12 digits+refresh+dummy:
300 ns+14*208 ns+150 ns=3.4 μs.
Subtracting the time for (probably 3) write cycles gives an effective look up time of 2.8 μs.
Database capacity.
The database capacity of the inventive ARE presented here is relatively easy to calculate. Two database types are considered to coexist in the ARE: those allowing addresses up to 16 semi-octets in total length to be recognized; and secondly, those allowing addresses up to 40 (potentially 46) semi-octets to be recognized. A total of up to eight different databases can coexist, limited by the number of root nodes.
The former databases are used for recognizing Level-1 addresses, datalink addresses and router-IDs amongst others. Given that there are 52K of nodes with up to 16 semi-octet constant string storage at each node, of which 26K are terminal, it follows that a combined total of up to 26K entries for these databases can be guaranteed. (In the worst case, each transition node will have at most two next-node pointers; thus the trie becomes a binary trie with as many transition nodes as final nodes.)
Since there are 4K of nodes storing constant strings up to 48 semi-octets in length (of which 2K are terminal), at first it seems reasonable to suppose that up to 2K entries can be guaranteed for searching these longer addresses. However, in the worst case, extra transition nodes may be required--these extra nodes having one exit only, namely the DSP pointer exit. (The DSP transition cannot be stored as part of the constant string.) Under these conditions, only 1K entries can be guaranteed. Note that it is possible to redefine the ARE so the DSP transitions are allowed from terminal nodes--then the guarantee increases to 1.3K entries in the worst case. Note also that it is possible to steal nodes from the other databases and "chain" together the nodes with smaller constant string capacities. In fact, the current maximum length IDP defined is only 18 digits in length--hence, even the 16-digit capacity nodes can be used for holding IDP digits without fear that constant string storage length with exceed node capacity. (If the maximum length IDP is 18 digits, then the maximum length IDI will be two less--AFI digits are not ordinarily stored as part of a constant string.)
For packet forwarding purposes, note that the Level-2 database is branched to the Level-1 database through the Level-1 pointer. Thus it may be stated that a database can be built that guarantees recognition of up to 26K addresses that are in-area (and will be routed by Level-1 routing) and up to 1K addresses that are out-of-area (and will be routed according to longest prefix).
Other embodiments are within the scope of the claims that follow the disclosure.
For example, the invention may be used for searches of any large database that contains strings of (possibly widely) varying length. Such databases are common: examples include directory look ups in a telephone context, on-line dictionaries, spelling checkers, looking up social security numbers, etc. In any such context, where the directory look up is performed using a search trie, the invention would be applicable. Although the word "node" has been used here to describe an element in a hierarchical tree structure, the invention applies to any tree structure search, whether or not the word "node" is used to describe the tree structure.
ARE Memory Map
The ARE is mapped into a 16 MB space in the Widget memory map, between addresses 0800 0000 and 08ff ffff.
The 16 MB ARE space is divided into 64K "nodes", where each node is 256 octets in size. Thus, an ARE address (consisting of eight hexadecimal digits) may be broken up into three fields, as shown:
08|nnnn|aa
Were the first two digits, "08", select the ARE; the next four digits, "nnnn" select one of 64K nodes; and the final two digits, "aa" select a subspace within a node.
The allowable subspaces that can be accessed at each node are defined in FIG. 9.
Description of resources
Node Control Word
The node control word is a byte-addressable 16-bit word supported at every node. Not all bits are interpreted by the search engine, but all bits are implemented to facilitate ARE maintenance (e.g. by chaining free nodes). The format and explanation of this word is given below
______________________________________NIL SR IC L1 d11 d10 d9 d8 d7 d6 <--LENGTH-->______________________________________
NIL (Nil Node): If this bit is set, then this node is interpreted by the search engine as a nil node. At a nil node, the setting of any other control bits is irrelevant. Immediately upon entering a Nil Node, the search engine will stop, indicating "Nil Node" as the reason for stopping. Any string stored at a Nil Node is ignored. The address of the Nil Node is not reported in any result returned by the search engine.
NOTE: All nodes whose address MSB is equal to zero (i.e. nodes 0000 through 7fff) are Terminal Nodes. During a search operation, if at Terminal Node is encountered the search engine will stop rather than to make a transition from the node.
SR (Save Result): During a search operation, all nodes encountered that have this bit set will be saved in Result So Far register 245. This single word register 245 will always contain the address of the node most recently encountered with the SR bit set. The SR bit will not be examined by the search engine until any constant string present has been successfully matched against the search key; string mismatch (which includes premature exhaustion of the search key digits) will result in the node NOT being saved, despite the condition of the SR bit. The node address will not be saved if the node is NIL.
IC (IDP Count present): If this bit is set, then the value of the "length" field will be interpreted by the search engine as the length of an IDP. This bit should be set at the first node following the second digit of the AFI. The length field should be set to the appropriate IDP length that is indicated by the relevant AFI. Only one such value will be loaded during a search operation. The IC bit will be ignored if the node is NIL.
NOTE: A constant string cannot be stored (and will be ignored) at any node with the IC bit set.
L1 (Level-1 transition possible): This bit will be examined by the search engine only when it has exactly fourteen digits of the search key remaining and it has successfully matched any constant string present against the search address. If this is the case, and the L1 bit is set, then the search engine will use the value of the Level-1 pointer as the address of the next node.
d11,d10, . . . ,d6: These bits are not used by the search engine.
LENGTH (5 bits): This field is interpreted in one of two ways:
1. If IC is set, and NIL is not set, then this field is interpreted as the length of an IDP (as explained above).
2. If IC is not set, and NIL is not set, then this field is interpreted as the length of a constant string stored at the node. The constant string will be matched against the digits of the search key until there is a mismatch or until either source is exhausted.
String storage spaces
String storage space is provided to store constant strings of variable length at a node. The string is stored as a succession of digits, one digit per byte. (The four most significant bits of each byte are ignored on a write and always read as zero.) The length of the string (number of digits stored) is indicated in the Node Control Word. The maximum number of digits that may be stored is a function of the node address, as shown below:
Transition Nodes:
f800<=Node Address<=ffff--maximum 48 digits.
9000<=Node Address<=f7ff--maximum 16 digits.
8000<=Node Address<=8fff--no storage allowed.
Terminal Nodes:
7800<=Node Address<=7fff--maximum 48 digits.
1000<=Node Address<=77ff--maximum 16 digits.
0000<=Node Address<=0fff--no storage allowed.
("x<=y" means x is less than or equal to y)
When the search engine encounters a node at which a path digit string is stored, the string will be compared against the remaining search address digits until either source of digits is exhausted or until there is a mismatch.
Next Node Pointers
Eighteen "next node" pointers are provided for all 32K Transition Nodes. (Pointer compression has not been implemented.) The first 32K nodes are "Terminal Nodes" and no transitions can be made from them.
A next-node pointer will be selected by the search engine if a string match has been successfully completed (where relevant), if the node is not a terminal or NIL node, and if there are search address digits remaining. The selection is made according to the following rules (refer to Theory of Operation, above):
1. If an IDI length has been loaded into the IDIL register 250 and that length has been decremented to exactly zero (or, if not, and the current node is loading a total IDP length of 2 into IDIL)--i.e. if the search engine believes that the next search key digit to be processed is the first digit of the DSP--then the DSP Pointer will be selected. The DSP Pointer can be selected at most once during a search operation. Selection of the DSP Pointer does not consume the current search key digit--it will be used in the next machine cycle. 2. Otherwise, if there are exactly fourteen search key digits remaining and the L1 bit is set in the Node Control Word at this node, then the Level-1 Pointer will be selected. The Level-1 Pointer can be selected at most once during a search operation. Selection of the Level-1 Transition Pointer does not consume the current search key digit--it will be used in the next machine cycle.
NOTE: If both (1) and (2) apply, the conditions for (2) will be re-examined after (1) has been effected.
3. Otherwise, the next digit of the search key will be used to select one of the first sixteen next-node pointers. For example, if the digit is zero, then the pointer at address 40 will be used. (Pointer address offset is 40, refer to FIG. 9).
Search Address Storage Area
32 bytes of storage space are provided at each of nodes 8000 through 8007. Of these 32 bytes, the first 24 bytes are used for loading a new search address; the result of the search is written by the search engine into the last eight bytes. Up to eight search contexts are supported--but note that a new search should not be initiated until the current one is complete (because this will abort the current search). When a search is initiated, the node used to load the search address will be the root node used by the search engine. The format of the search address must be as follows:
First byte (address 80/a0): length of search address.
Subsequent bytes: search address, length as defined in first byte.
The length information written to the first byte is interpreted in one of two ways: If the byte is written to address 80, it is interpreted as an octet length, i.e. the number of digits provided is twice the value of the length byte; if the length byte is written to address a0 , it is interpreted as a semi-octet length, explicitly indicating the number of digits in the search key. Address space a0-bf is otherwise an alias of address space 80-9f. (NOTE: the current ARE implementation regards a semi-octet length in excess of 40 (decimal) or equal to zero as an error).
More digits can be written to the search key area than are implied by the length octet; at most 32 octets in total should be written or else the thirty-third octet will either reinitialize the search or cause a bus error. If more than 24 octets are supplied, the excess octets will be overwritten with the search result at the time that it becomes available. If fewer octets are supplied than the length field indicates, then the search engine will wait indefinitely for them to be supplied unless it terminates the search prematurely.
Search Result Information
The result of a search is available at addresses 98-9f (equally b8-bf) at the same node in which the search key was loaded (i.e. one of nodes 8000 through 8007). The format of the result is as follows:
______________________________________Offset Interpretation______________________________________98 or b8 Summary status byte.99 or b9 Remaining semi-octet length of search address at termination of search. [byte]9a-9b or Most recent node encountered with SR bit setba-bb [unsigned word].9c or bc Remaining semi-octet length of IDI at termination of search [signed byte].9d or bd Value of string digit counter at termination of search. [byte]9e-9f or Node most recently encountered during searchbe-bf (except if this is a NIL node). [unsigned word]______________________________________
Refer below to appendix B for detailed information on interpreting the result information.
Control and Status Registers
Parity Control and Status register 0 Address
______________________________________format: PES PEP EPS EPP 0 0 0 0reset state: 0 0 0 0 0 0 0 0______________________________________
Status register 0 provides parity control and status for CPU accesses to the database memories that are implemented with DRAMs.
PES: Set whenever parity error is detected on CPU read of string storage memory. Reset by CPU overwriting with a one.
PEP: Set whenever parity error is detected on CPU read of next-node pointers. Reset by CPU overwriting with a one.
EPS: Read/write by CPU. When zero, use odd parity (generate and check) on string storage memory; when set to one, use even parity.
EPP: Read/write by CPU. When zero, use odd parity (generate and check) on next-node pointer memory; when set to one, use even parity.
______________________________________Control Register 1 - Address 080000c1______________________________________format: SM NSAP IL1 IDSP SDK d2 d1 d0reset state: 0 0 0 0 0 0 0 0______________________________________
There is one control register for the entire ARE. The bits are defined below:
SM (Search Mode): When SM=0 (="maintenance mode"), Search Mode is inhibited and search result information is invalid; the search engine is reset. This mode must be selected before the CPU can access any resource below address 7f. When SM=1, Search Mode is enabled. This mode must be selected before a search key is loaded, and must be maintained until the result has been read. In this mode, all resources below address 7f are inaccessible.
NSAP (NSAP mode): This bit influences only the setting of the success/failure bit in the result summary octet at the end of a search, as detailed later in the disclosure.
IL1 (Inhibit Level-1 transitions): If this bit is set, then during any search a Level-1 transition will not be made.
IDSP (Inhibit DSP transition): If this bit is set, then during any search, a DSP transition will not be made.
SDK (Stall DSACK): If this bit is set, then reading the search result information (defined under Search Result Information above) will result in a possibility extended bus cycle that will be stalled until the result is available; this eliminates the need to check if the result is available. This is applicable to every context, but only in Search Mode.
d2,d1,d0--not used by the ARE.
______________________________________Search Status Register 2 - address 080000c2 (read only)______________________________________format: BCNT RT2 RT1 RTO 0 0 0 0reset state: u u u u 0 0 0 0______________________________________
The four status bits available from this register are provided primarily for diagnostic purposes. The bits are valid only when the search engine is either HALTed or BUSY (as defined in status register 3).
BCNT: This bit is set when the search engine is assuming that the first byte of the search address is a octet-wise length count; if BCNT is cleared, then a semi-octet (digit) count is assumed.
RT2.0: These three bits are equal to the three least significant bits of the root address that the search engine is using for the purpose of reading the search argument.
______________________________________Search Status Register 3 - address 080000c3 (read only)______________________________________format: BUSY HALT f5 f4 f3 f2 f1 f0reset state: 0 0 0 0 0 0 0 0______________________________________
This status register provides search engine status for application and diagnostic use.
BUSY: This bit is set when the search engine is processing nodes or is loading the result.
HALT: This bit: is set when the search engine has stopped processing nodes.
The above two bits should be decoded as a pair.
______________________________________BUSY HALT Interpretation______________________________________0 0 Search engine is reset.1 0 Search engine is searching.1 1 Result is being loaded (short transitional state).0 1 Result is available for reading.______________________________________
f5 . . . f0: These bits are set by writing components of the search key into the register file, and are used by the search engine as an indication that valid data is present.
All bits of register 3 are reset whenever the machine is in maintenance mode (bit 7 of control register 1 is zero). Bits f5 through f1 are reset whenever the CPU writes to the last byte of the first longword of the search key; at the same time, bit f0 is set (if search mode is enabled). Bit f1 is set, in search mode, when the CPU writes to the last byte of the second longword of the search key; and bits f2 through f5 are similarly set on writing the last byte of the third through sixth longwords.
______________________________________ARE Status Register 4 - address 080000c4 (read only)______________________________________format: s7 s6 s5 s4 s3 s2 s1 s0reset state -- -- -- -- -- -- -- --______________________________________
This status register allows the CPU to read the positions of eight switches in the on-board switchpack.
Decoding the Search Result from the ARE
The result of a search is available at addresses 98-9f (equally b8-bf) at the same node in which the search key was loaded; i.e., one of nodes 8000 through 8007. If the control bit "SDK" is set (bit 3 in control register 1), then the result may be read at any time after loading the search key--the CPU will be stalled by hardware until valid data can be returned. If the "SDK" bit is not set, then the CPU must poll status register 3 to determine when search result status is valid.
The format of the result is as follows; minimum delay will be incurred if the result is read as two longwords.
______________________________________address field contents(* = 0..7)08800*98 <--summary-> <-Rem. Len.-> <-Result So Far->08800*9C <-Rem. IDI-> <-Str. Cnt.-> <---Got So Far-->Field Size Interpretation______________________________________Summary byte Summary status byte (see below).Rem. Len. byte Number of remaining search key digits not processed by the search engineResult So Far word Most recent node in TRIE traversed by search engine that had "save result" bit set.Rem. IDI. byte Number of remaining IDI digits in search key not processed by search engine (value may be negative).Str.Cnt byte String Counter value -- provides information in cases of string mismatch search termination.Got So Far word Node being processed by search engine at time.of termination (except if this is a NIL Node)______________________________________
Summary Status Byte.
The summary status byte is provided so that the host CPU can rapidly determine whether a search was successful or not; and if not, the reason for the search failure.
The encoding depends upon whether the database is deemed by the search engine to be corrupted or not; and is further influenced by the "NSAP mode" bit in Control Register 1.
The two cases are dealt with separately below:
Case 1: database corrupted.
For a corrupted database, the encoding of the output will be:
______________________________________1 1 0 ISC PEP PES L1ND L1DE______________________________________
where
ISC=Illegal String Count reached (the CPU indicated that there were more string digits present than the maximum allowed at a node)
PEP=Parity Error on Pointer memory
PES=Parity Error on String memory
L1ND=Level-1 transition made but no DSP transition made (NSAP mode only)
L1LDE=Level-1 transition made and source digits exhausted (NSAP mode only)
The setting of bits ISC, PEP and PES is mutually exclusive.
If ISC is set, then the search engine attempted to run a string comparison cycle with a digit pointer that exceeded the maximum string length allowed at a node. The "Got So Far" field contains the node at which the string is stored; the "String Count" field contains the string digit pointer which is too large.
If PEP is set, then a transition was made from a node through one of the sixteen "next node" pointers. The address indicated for the next node contained a parity error. The "Got So Far" field contains the node at which the corrupted "next node" pointer is stored. The "Remaining Length" field indicates how many digits of the search key remain to be processed by the search engine; the first of these remaining digits is the one immediately following the digit that was used to select the corrupted "next node" pointer.
If PES is set, then a string comparison cycle was run but the stored string digit contained a parity error. The "Got So Far" field contains the node at which the corrupted string is stored. The "String Count" field points to the digit after the one at which a parity error was detected.
The setting of the L1ND and L1DE bits is independent of the ISC, PEP and PES bits. At the termination of the search, for whatever reason, the L1ND bit will be set if NSAP mode is selected, and a Level-1 transition has been made but not a DSP transition. The L1DE bit will be similarly set if a Level-1 transition has been made and there are no remaining search key digits--the search engine expects that there will normally be at least two remaining digits at the termination of an NSAP search if a Level-1 transition has been made (these two digits are the SEL field).
Case 2: database not corrupted.
If the database is not considered to be corrupted, then the encoding of the bits in the Summary Status Byte will be:
______________________________________F 0 RL NIL SM DE L1 DSP______________________________________
where
F=search Failure (0=success). This bit is influenced by the NSAP Mode bit.
RL="Result So Far" field is valid.
NIL=NIL Node reached
SM=String Mismatch occurred
DE=Source Digits Exhausted
L1=Level-1 transition made
DSP=DSP transition made
The F bit is 0 when the search is successful. A successful search is defined as one in which the database is not corrupted, the supplied length is in the range 1 to 40 semi-octets, and, in addition, in NSAP mode either a) a Level-1 transition has not been made and the Result-So-Far register has been loaded at least once; then the encoding of the summary status byte will be: 001X XX0X--or b) a Level-1 transition has been made, there has been no string-mismatch, a terminal node has been reached at which the SR bit is set, and (implicitly) a DSP transition has been made and not all of the search key digits have been used. The encoding of the summary status byte in this case will be: 0010 0011.
In non-NSAP mode a successful search is where the database is not corrupted, the search address length is in the prescribed length, all of the search address digits have been used, there has been no string mismatch (and the search address digits did not become exhausted during a string match), and the final node reached (which is not a NIL Node) has the SR bit set. The final node may or may not be a Terminal Node--if it is a Terminal Node, then the "DE" bit will be zero (even though the digits are exhausted). The encoding of the Summary Status Byte will be: 0010 0XXX
The RL bit is set after the "Result So Far" field is loaded with a node address during a search. This bit indicates that the "Result So Far" field contains valid data; if RL equals zero, then the value of the "Result So Far" field is undefined (in preferred embodiments, it will contain the root node).
The setting of the L1 bit depends upon whether the control bit "IL1" in control register 1 is set or not. If it is not set, then Level-1 transitions are enabled, and the L1 status bit will be set only if a Level-1 transition was made during the search. Otherwise, if the "IL1" bit is set, then Level-1 transitions are inhibited; in this case, the L1 status will be set if, at any time during the search, a transition was made from a node (not a DSP transition) at which the node control bit "Enable Level-1 Transition" was set.
The DSP bit will be set if and only if a DSP transition was made during the search. If the control bit "IDSP" is set in control register 1, then DSP transitions are inhibited and the DSP (transition made) status bit will always be zero.
The NIL, SM, DE bits encode the reason why the search engine stopped in the case where the database is not corrupted. Each case is dealt with in detail below; note that, as explained above, the "Result So Far" field is only valid if the RL bit is set.
a) NIL, SM, DE=000: This encoding means that a terminal node was reached by the search engine. The "Got So Far" field contains the terminal node. The "Result So Far" field contains the node most recently traversed that had the "SRSF" node control bit set; if "SRSF" is set at the terminal node, then "Result So Far" will be equal to "Got So Far". The "Remaining Length" field indicates how many search key digits were not used by the search engine; the value may be zero, indicating that the very last digit was responsible for taking the search engine to the terminal node.
b) NIL, SM, DE=001: This encoding means that the search engine stopped because it ran out of search key digits; it would otherwise have made a transition from the node at which it came to rest. The "Got So Far" field contains the node reached by the search engine when the digits ran out. This node is neither NIL nor a terminal node. If there is a string stored at the node, then it will have been successfully matched. If the "SR" bit is set at this node, then the "Result So Far" will be equal to "Got So Far"; otherwise, it will contain the node most recently traversed that had the "SR" bit set. Note that a Level-1 or a DSP transition can be made from node even when the search address digits are exhausted; thus, neither a DSP nor a Level-1 transition can be made from the final node reached as indicated by "Got So Far".
c) NIL, SM, DE=010: This encoding means that the search engine stopped because it detected a mismatch between a constant string digit and the next digit of the search key. The "Got So Far" field contains the node at which the constant string is stored. The "String Count" field points to the string digit after the one which mismatched. The "Remaining Length" field indicates how many search key digits have not been processed by the search engine; the first of these remaining digits immediately follows the digit that was mismatched against the constant string digit.
The "Result So Far" field contains the node most recently visited (before the one at which the search terminated) that had the "SRSF" bit set.
d) NIL, SM, DE=011: This encoding means that the search engine stopped because it could not perform the string digit comparison cycle that it was tasked with. This occurred because either: (i) the digits in the search argument became exhausted, or (ii) specifically, the IDP digits of the search argument became exhausted while comparing against a path digit string storing only IDP digits. The "Got So Far" field contains the node at which the string is stored. The "String Count" field points to the string digit that would have been compared against (i) the next search key digit, or (ii) the next IDP digit, had there been one.
The "Result So Far" field contains the node most recently visited (before the one at which the search terminated) that had the "SR" bit set.
e) NIL, SM, DE=100: This encoding means that the search engine reached a NIL node. The "Got So Far" field contains the node most recently visited before the NIL Node; similarly, the "Result So Far" field contains the node most recently visited (before the NIL Node) at which the "SR" bit was set.
The transition to the NIL node was made by using a search key digit to leave the node indicated in the "Got So Far" Field. This digit is the last that was used by the search engine; it is not included in the "Remaining Length" or "Remaining IDI length" counts.
f) NIL, SM, DE=110: This encoding also means that the search engine reached a NIL node. In this case, the transition was made by using either a DSP or the Level-1 pointer to leave the node indicated in the "Got So Far" field. In the usual case, the Level-1 pointer will not point to a NIL Node and so it can be assumed that a DSP transition was made to the NIL Node.
Note that, even though the DSP transition was to a NIL Node, the status bit "DSP Transition Made" will be set; the value of the "Remaining IDI length" will be zero. The value of the "Remaining length" field will be equal to the entire DSP length of the supplied search key.
g) NIL, SM, DE=111: This encoding means that an illegal search key length was supplied to the search engine; i.e., zero or more than forty digits. In this case, the search engine makes no progress at all on the search key.
Overview of maintenance support required
Maintenance engine 18 inserts a new entry into the database by first presenting it as a search argument to search unit 40. Search unit 40 attempts to locate the search argument in the database; if it fails, it will, at least, report the longest prefix of the search argument that exists in the database. (This longest prefix will not necessarily be associated with "result" in the database).
At most two new nodes will be inserted in the database; one new node will be added to differentiate the new entry from all existing entries--this node will be inserted at the point where the search unit located the longest prefix of the new entry; one additional new node will be added, and will contain a path compression string equal to all of the remaining digits of the new entry beyond the prefix match with the database.
The differentiation node only needs to be added where the new entry was being compared against a path compression string the database, and a mismatch occured during one of the comparisons. In this case, the path compression string must be broken in two at the point of mismatch. The part which compared successfully against the new entry is stored in a new node (the differentiation node), which will have two non-nil pointers. One pointer points to the node which originally held the path compression string (the original path compression string is replaced by the part of it which mismatched against the new entry). The second pointer points to the new node which holds the path compression string (if any) of the remaining digits of the new entry.
The inverse process is used for deletion.
Memory Savings of Pointer and Path Compression
The analysis presented here shows roughly how much physical memory can be saved by applying the techniques of path compression and pointer compression to a TRIE based database. For the analysis, it will be assumed that there are up to sixteen pointers at a node, corresponding to four-bit characters (semi-octets) of the search argument processed at each node. For different sizes of characters, the analysis should be performed with a parameter substituted for the fixed size of sixteen pointers assumed here. Additionally, the idiosyncrasies of ISO and DECnet Phase-V addresses are not considered.
The analysis will consider the memory requirements for storing a worst-case database with a given number of entries. Firstly, path compression will be considered, followed by the application of pointer compression in addition to path compression.
Consider a TRIE based database that is required to store up to N entries. Let the entries be of variable length up to a maximum of L semi-octets. Each node in the TRIE will contain sixteen pointers. In the worst case, a maximal number of nodes is required to hold these N entries.
The worst case will occur when all distinctions between the entries are made at nodes as close to the root as possible. In the way, every entry will have associated with it a large chain of nodes each using only one non-nil pointer pointing to the next link in the chain. The depth of TRIE required to specify all N entries will be Log 16 N. The total number of nodes used up to this level will be (N-1)/15.
Nodes that are used within the long chains make up the bulk of the total number of nodes required. There will be N chains. If every entry in the database is L semi-octets long, then every chain will be of length (L-log 16 N), the end of each chain pointing to a terminal node for which no storage requirement will be assumed.
Thus, the total number of nodes required will be:
(N-1)/15+(L-log.sub.16 N)*N (1)
each of size 16 pointers. To a good first approximation, this can be simplified to
L*N nodes. (2)
Now consider that path compression is implemented. Long chains of nodes will now be collapsed into terminal nodes or into nodes with at least two pointers. The greatest amount of memory will be required when there are as many (non-terminal) nodes as possible. This is the case when every non-terminal node has exactly two pointers (for example, a binary trie). The total number of non-terminal nodes will be N-1. Terminal nodes will require no storage for pointer; thus the memory requirement for pointers will be (with sixteen pointers per node)
(N-1)*16 pointers (3)
There is also some memory requirement for the path compression strings. The distribution of the strings amongst the nodes can vary widely; but if there are N entries in the database each of length L semi-octets, the total storage requirement cannot exceed (N*L) semi-octets. If a pointer is equated to four semi-octets, then adding the requirement of equation (3) gives a total memory requirement of
(N-1)*64+(N*L)=N*(64+L) semi-octets (4)
to a good approximation. When compared with the storage requirement for the same sized database without path compression, equation (2), the ratio of (2) to (4) is
(64*L)/(64+L) (5)
which is bounded by the limits of 1 (for small L) and 64 (for large L). In the case of ISO 8348/AD2 network addresses, for which L=40, the reduction factor is 24.6, representing a very significant savings in physical memory.
Note that an implementation may want to allocate enough memory for a maximum length path compression string at every node, in order to make memory management easier. In this case, approximately twice as much memory is required to store the path compression strings, and equation (5) is modified to
(32*L)/(32+L) (6)
which has an upper bound of 32, and the reduction factor for the case of ISO addresses is 17.8, still very significant.
Next consider adding pointer compression to a path compressed TRIE. The worst case storage requirement for a path compressed TRIE without pointer compression is given by equation (4). When pointer compression is introduced, the worst case occurs when as many actual (i.e. non-nil) pointers as possible are used. Since each non-nil pointer points to a node, this occurs when as many nodes as possible are used. Thus the worst case occurs for the same binary trie structure used in the non pointer compressed case above. The size of each non-terminal node will be two pointers plus a bit mask. The bit mask is sixteen bits wide, essentially the same size as a pointer. Thus the storage requirement for the path compressed and pointer compressed TRIE is, in the worst case,
(N-1)*3 pointers+(N*L) semi-octets= (7)
N*(12+L) semi-octets (8)
to a good approximation. By comparison with the storage requirement for path compression alone, equation (4), there is a further reduction in memory requirement by a factor of
(64+L)/(12+L) (9)
having a value between 1 and 5. For the case of ISO addresses, where L=40, the reduction factor is 2.
The overall reduction factor for a path compressed and pointer compressed database, compared to a database with no compression, is the product of equations (5) and (9). This is
(64+L)/(12+L) (10)
which is bounded by the limits of 5 for small L and 64 for large L. For the case of ISO addresses, the overall reduction factor is 49.
|
Aspects of the invention include a method of conducting a reduced length search along a search path. A node which would otherwise occur between a previous and a following node in the search path is eliminated, and information is stored as to whether, had said eliminated node been present, the search would have proceeded to the following node. During the search, a search argument is compared with the stored information, and the search effectively progresses from the previous node directly to the following node if the comparison is positive. In preferred embodiments, some nodes provide result values for the search, and a node is eliminated only if its presence would not affect the result value for the search. In another aspect, the invention features a method of conducting a two mode search of reduced length. For a first mode of the search, nodes along a search path are provided, at least some of the nodes including one or more pointers pointing to other nodes. A search argument comprising a series of search segments is provided, some values of segments of the argument corresponding to nodes along the search path, some other values of the segments relating to a second mode of the search. Indicators associated with nodes are provided, each indicator indicating the segments corresponding to the second mode. The search path is searched by processing successive search segments by inspecting the indicator associated with each node, and proceeding to the second search mode if the indicator indicates that the segment relates to the second mode.
| 8
|
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to European Patent Application No. 03405339.7 filed May 16, 2003, the entire text of which is specifically incorporated by reference herein.
FIELD OF THE INVENTION
[0002] The present invention relates to a method and system for delivering electronic information anonymously from a first party to a user, in particular to the delivery of advertisement via the Internet.
BACKGROUND
[0003] Unsolicited commercial e-mail, referred to herein as UCE, is already a major problem on the Internet and is steadily growing worse. It is estimated that 45 percent of the overall e-mail traffic is unwanted bulk e-mail (The Economist, Apr. 26th 2003, page 54). With approximately one billion e-mail users, the Internet is an irresistibly attractive means of delivering advertising. In general, there seem to be four main channels for providing and delivering advertisements over the Internet:
[0004] 1) UCE or “spam”, where unsolicited commercial e-mail is sent to vast numbers of mostly unwilling recipients. Despite the strong negative connotation, this is an attractive option to advertisers since nearly all the cost is shifted to the customer and his or her Internet Service Provider.
[0005] 2) Sponsored links such as those found in search engines such as Google.com. For example, in response to a search, Google offers a related sponsored link to the advertiser.
[0006] 3) Banners used on many portals and Web-sites. Banners have not been very successful economically so far.
[0007] 4) “Admediation”, wherein one voluntarily becomes a member of a group and as a result receives advertising e-mail for a broad product category. These schemes use gimmicks such as contests, earning points and lotteries to attract customers.
[0008] Both advertisers, i.e. sellers, and admediators are potential sources of spam or leaks of a user's personal information (e-mail address and other information) and preferences. In general, no service exists allowing users to register for receiving exactly the advertisements he or she wants and for as long as he or she wants, without danger of being spammed based on non-existing or old preferences.
SUMMARY OF THE INVENTION
[0009] The present invention address the above-referenced limitations of conventional Internet advertising by introducing a new service for the delivery of electronic information, referred to as an “anonymediary” service. The anonymediary service fulfills the function of an admediary in that it delivers advertisements from different advertisers or sellers to potential customers in a way which allows customers to receive only the advertisements they are interested in, i.e. by matching a customer's profile or preferences against that of advertisements, and for a customer-specified period of time, while remaining anonymous to the sellers. Such a scheme or service can allow users to register to it, state preferences as to which advertisements the user is interested in, decide (and be able to enforce) how long this registration should last (1 day, 1 month, 1 year, etc.), and ideally would not give any personal information, including e-mail or other location or reachability information, to advertisers or admediaries. Such a service, if successful, may substantially decrease the amount of spam transmitted on the Internet. The anonymediary's service could be advertised via a pop-up window on a Web portal, for example.
[0010] Thus, one embodiment of an anonymediary service contemplated by the present invention puts the user in control and guarantees the user's anonymity. The user specifies not only what material he or she is interested in receiving, but also for how long. The anonymediary service can be realized by adding only one anonymediary entity, or by two separate entities: an anonymizing entity (or infrastructure) and an admediary entity. The term anonymediary is used regardless of how the invention is implemented: the admediary offering the anonymized service, whether in the one-entity setting by playing both roles, or in the two-entity setting by allowing anonymous access.
[0011] The anonymediary service is most likely financed by advertisers, but a model where users register for a fee is also conceivable. In the more likely scheme, the anonymediary receives either a fixed payment or a per-enquiry payment from the advertisers. The advertiser might want proof that payments to the anonymediary are effective. Since the potential customer remains unknown to the advertiser as well as to the anonymediary, the potential customer or user could be given a unique certificate entitling the customer to a discount on an actual purchase. Receipts of these certificates in the course of a sale would indicate the degree of success of the anonymediary.
[0012] In accordance with the present invention, there is provided a method for delivering electronic information anonymously from a first party via a second party to a third party as user. The method is performed by the admediary, also referred to as fourth party, and comprises the steps of providing the information received from the first party and receiving a preference request from the user via the second party comprising a session key and a request that applies the session key. In response to the request and in the event that the request matches with the provided information, a response comprising a matching information that applies the session key is provided to the third party.
[0013] The method can comprise the step of registering the user with a preference and a time limit. This allows the user to register anonymously for a limited time and to receive advertisements from specific advertiser(s) mating the preferences within the registered time frame.
[0014] The request can comprise preferences of the user. This preferences allow to register exactly to the users needs. The preferences of the user can be encrypted by using the session key. This has the advantage that the preferences can only be read by the user itself and the recipient, that is the admediary.
[0015] If the information is advertisement provided by the first party with an expiration value, then the admediary always provides up-to-date information for interested customers. This may also reduce storage such as to use it efficiently.
[0016] The response with the matching information can be sent directly to the user whenever matching information is identified. This applies to a “push” approach or model described in more detail below. By doing so, the user is always up-to-date and will be delivered with the newest information. However, it is also possible that the response with the matching information is only sent to the user upon another request by said user. This applies to a “pull” approach or model described in more detail below. By doing so, the user has it in its hands when information is received. This allows the user a flexible control of the information that is provided for him or her.
[0017] In accordance with another aspect of the present invention, there is provided a system for delivering electronic information anonymously. This arrangement comprise a first party for providing the information, i.e. the advertisement, a third party as user who requests the information with a preference request comprising a session key and a request that applies the session key, a fourth party that in response to the request provides to the third party a response comprising a matching information that applies the session key, and a second party for concealing the traffic between the third party and the fourth party.
[0018] Yet another exemplary embodiment of the invention includes a computer program product embodied in a tangible media. The computer readable program codes are coupled to the tangible media for delivering electronic information anonymously, and are configured to cause the program to receive a preference request from a user over a network, match advertising information from at least one advertiser with the preference request, and provide the advertising information to the user in response to the preference request without revealing user information to the advertiser.
[0019] The foregoing and other features, utilities and advantages of the invention will be apparent from the following more particular description of various embodiments of the invention as illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Preferred embodiments of the invention are described in detail below, by way of example only, with reference to the following schematic drawings.
[0021] [0021]FIG. 1 shows an exemplary environment embodying the present invention.
[0022] [0022]FIG. 2 shows a schematic illustration of an overall scenario to support the understanding of the figures and the description.
[0023] [0023]FIG. 3 shows a schematic illustration of information flow according to one embodiment of the present invention.
[0024] [0024]FIG. 4 shows a schematic illustration of a further information flow.
[0025] The drawings are provided for illustrative purpose only and do not necessarily represent practical examples of the present invention to scale.
DETAILED DESCRIPTION OF THE INVENTION
[0026] [0026]FIG. 1 shows an exemplary environment embodying the present invention. It is initially noted that the environment shown is presented for illustration purposes only, and is representative of countless configurations in which the invention may be implemented. Thus, the present invention should not be construed as limited to the environment configurations shown and discussed herein.
[0027] In one configuration of the invention, the environment includes a user 10 , an anonymizer 20 , an admediary 30 , and advertisers 40 , 50 coupled to a network 60 . The network 60 may be any network known in the art for effecting communications between the entities in the environment. Thus, the network 60 can be a local network (LAN), a wide area network (WAN), or a combination thereof. It is contemplated that the network 60 may be configured as a public network, such as the Internet, and/or a private network, and may include various topologies and protocols known in the art.
[0028] [0028]FIG. 2 illustrates how the various environment entities interact with each other. It is understood that the parties are represented by computer, computer devices, or system that are able to communicate or exchange data. Within this description the advertisers 40 , 50 are also referred to as first parties or advertisers Z and X. The anonymizer 20 is also referred to as second party. The user 10 is also called third party or user U. Moreover, the admediary 30 is also referred to as fourth party or admediary A. The anonymizer 20 and the admediary 30 together can from a single unit 60 .
[0029] The user 10 or user U is a person or other entity who wants to receive only the electronic information, in particular advertisement, that the user U is interested in.
[0030] The anonymizer 20 , also referred to as anonymizing entity, is contemplated as a service that conceals the identity of the user U to the other parties with which the user U interacts through the anonymizer.
[0031] The admediary 30 is contemplated as a service that stores the electronic information received from the advertisers 40 , 50 in order to deliver the information to the interested users 10 . There are many possible realizations of this service. For example, one can distinguish between models where the service is operated by one entity, or by two entities playing the role of anonymizer and admediary. Other distinguishing factors can be the service model assumptions, e.g., “push” models could be considered where the user 10 registers once and receives e-mail advertisements; or “pull” models could be considered where the admediary 30 does not keep any information about the user's registration, but where the user 10 periodically pulls new advertisements based on his or her current registration preferences. For this “pull” model the user 10 will typically use a specialized local application that supports the user 10 in managing his or her preference profile. For pulling advertisement information the user 10 then sends preference information or a preference request and receives as a response the desired information. The “pull” model has the advantage that the user 10 can manage his or her profile locally. Therefore, the user 10 does not need to trust an intermediary party.
[0032] A one-entity model, where anonymizer 20 and admediary 30 from a unity as anonymediary 60 requires a large amount of trust in the anonymediary 60 . The anonymediary 60 knows the address, e.g. e-mail, or IP, preferences, etc., of the user 10 or customer. For the one-entity model to work it is generally essential that users trust the anonymediary more than they would trust the advertisers 40 , 50 they want to receive electronic information from. In order to make this more secure, i.e. against eavesdropping outsiders on the customer-admediary communication channel, the traffic on this channel can be protected by encryption. In the one-entity model, implementing a push model is easy and does not restrict the security or anonymity one could achieve. This is because in the one-entity model, it is assumed that even in the pull model the anonymediary can map an address or, equivalently, the user to preference and registration information.
[0033] The two-entity model, as herein described, allows a realization with optimal trust guarantee and separation of knowledge; the anonymizer 20 does not know the user's preferences or registration data, and the admediary 30 does not know any name or addressing information about the user 10 .
[0034] The advertisers 40 , 50 provide electronic information, usually as advertisement, to the admediary 30 .
[0035] In the following, a most secure embodiment is described in detail with reference to FIG. 3 and FIG. 4.
[0036] In general, there are many users U, many advertisers X, Z, . . . , and the admediary A, i.e. the admediary service 30 . A user U registers with the system for a limited time period, e.g. until a time Tmax, with a set of preferences pref(U). During that time, until Tmax, the user U will receive advertisements from admediary A that match pref(U). After time Tmax, the user U may re-register with the same or different preferences and a new time Tmax. Advertisers X and/or Z send new advertisements adv(Z, T) at times T to admediary A (periodically, or whenever they have new advertisements). The admediary A has a function or algorithm match(pref, adv) returning a subset of adv which matches pref., that is the user's preferences.
[0037] This embodiment realizes this functionality in the two-entity model where users pull information. Generally, the user U does not need to trust any entity or service to respect the chosen time limits for this registration. In order to realize this pull functionality, the existence of a software client at the user's computer is assumed.
[0038] The embodiment takes advantage of an anonymizing service 20 , hereafter the Anonymizer 20 , such as Anonymizer: www.anonymizer.com. The separation of knowledge is achieved as follows:
[0039] The Anonymizer 20 acts as a proxy for HTTP requests, and hides the user's address and other information from the Admediary A.
[0040] The actual requests/replies for which the Anonymizer 20 acts as a proxy are encrypted with a key shared between the user U and Admediary A, that is the session key K. Thus, the Anonymizer 20 only sees encrypted preferences and advertisements.
[0041] In the example scenario, Advertiser Z publishes its current set of advertisements to Admediary A at time Tl, and Advertiser X publishes its current set of advertisements to Admediary A at time T2. Thus, adv(Z, T1) and adv(X,T2) replace any previous adv(Z, Tz) or adv(X,Tx).
[0042] Then, the user U registers (pref(U), Tmax) to the system. In this example, registration is local-only: U's local software client will keep track of this registration and will periodically, e.g., once per day until Tmax, pull for new advertisements matching pref(U) by sending an HTTP request to the admediary 30 through the anonymizer 20 . In FIG. 3, two such “pulls” are shown: “first advert request” and “second advert request”.
[0043] Admediary A has a public/private decryption/encryption key pair (SK_A, PK_A). For each advertisement request, the user U creates a session key, here K 1 for the first request, which will be used to encrypt this request/response pair. The user U communicates the session key to the Admediary A by encrypting it with A's public encryption key and sending E_A(K 1 ) together with the encrypted request.
[0044] The request comprises pref(U) and optionally a parameter adv_from 1 indicating that the user U is only interested in advertisements newer than a certain date. It is assumed that each advertisement is time-stamped by its advertiser such that A's matching function matcho can take adv_from as an additional parameter. Other means to ensure that the user U receives the same advertisement only once are described below.
[0045] The response comprises the advertisements matching pref(U), and optionally adv_from, from the different advertisers. After the first advertisement request, Advertizer Z updates its advertisements (adv(Z,T3)). The user's second request, here encrypted with a new session key K 2 , will now be matched against adv(Z,T3) and adv(X,T2).
[0046] With the presented scheme, a separation of knowledge of address and knowledge of user preferences can be achieved. Because of the encryption with K 1 or K 2 , the Anonymizer 20 cannot find out anything about the user's preferences and the Admediary A cannot find out the user's address.
[0047] The trust of the user in anonymity and unlinkability is concentrated in the Anonymizer 20 . Also, if the Admediary A is malicious, it can, even without help from Anonymizer 20 , try to trace the Anonymizer's incoming/outgoing traffic in order to determine where a request comes from. Both the concentration of trust in the Anonymizer 20 and the traffic tracing can be avoided by replacing the Anonymizer 20 with a mix network, which is described in a paragraph below.
[0048] The user U may have several sets of preferences, e.g. each with their own Tmax, in which case the above procedure is executed for each of the user's preference sets. Separating a user's preferences in multiple sets has the additional advantage that the Admediary A cannot link these multiple preference sets to each other. This additional unlinkability provides for more protection against the Admediary's being able to trace slightly varying full preference sets over time and ultimately identifying the user U based on knowledge of his or her full preferences over time.
[0049] A local software client can be installed on the user's system which can keep track of a user's registration(s) and deal with the encryption process. This software may but need not be provided by the Admediary A. In either case, it needs to be loaded/initialized with the Admediary's public key PK_A.
[0050] If the software is provided by the Admediary A, the Admediary A could also provide a tool that interactively helps the user U to formulate one or several preference sets pref(U).
[0051] The adv_from parameter is one of many possible ways of avoiding that the user U gets the same advertisement multiple times. However, it may facilitate additional linking between different requests by the user U, e.g. adv_from, most probably, corresponds to the time of the user's last request with possibly the same preferences. A more secure way would be as follows. It is assumed that each advertisement has an expiration time and a serial number, and that the user client keeps track of a list of tuples (advertiser, serial_nr, expiration). The user client's list is periodically pruned to delete expired entries. When the user U sends an advertisement request, the matching result in the response only contains a similar tuple list of non-expired matching advertisements, e.g., match(pref(U), adv(Z,T3))={(Z, 101, 2002/09/17), (Z, 105, 2002/09/31)}.
[0052] At this point, the user client can decide of which serial_nr to really request the contents. This is additional overhead for the user client. But, other than solving the problem of requests using adv_from being linked, it has the additional advantage that the individual ‘sub-requests’ again cannot be linked, especially if the sub-requests are spread over time and each of the sub-requests uses a different session key K 1 ′, K 1 ″, etc. The procedure for the first advertisement request is indicated in FIG. 4. The exchange runs as shown in the figure.
[0053] The previous embodiment describes a procedure of achieving anonymous registration. Moreover, one can add the functionality of allowing the Advertiser Z, X to have proof that a customer-transaction is based on an advertisement delivered through the Admediary A. This can be achieved by the Advertiser Z, X encoding in the advertisement a reference, e.g., rA. This could be part of a coupon or another incentive for a customer or user to refer to the advertisement. By giving the customer an incentive to mention rA when making a purchase from the Advertiser Z, X, the Advertiser Z, X can recognize the specific advertisement, e.g., an advertisement made through Admediary A.
[0054] A mix network, mentioned above, allows for the realization of anonymous synchronous or asynchronous communication. It is implemented by a number of servers or routers, called mixes, relaying messages or a data stream between parties such that the receiving party cannot trace the origin of traffic or messages. Also, observing third parties (such as parties listening on network links) cannot read messages or data as traffic is encrypted on all the links between mixes, as well as between originator and mix network, as well as between mix network and receiver. More strongly, as mixes buffer and “mix” traffic on different originator-recipient paths, an observing third party cannot even observe which originator is communicating with which recipient. In the most secure implementations, trust requirements on the different mixes are minimized such that, e.g., anonymity requirements are fulfilled as long as one of the mixes is trustworthy.
[0055] Mix-based anonymous synchronous communication is the equivalent of a TCP connection between an originator and a receiver, with the feature that the recipient cannot trace the originator; that the communication is encrypted towards any external observer; that none of the relevant mixes sees the content of the communication; and that no external observer (including the recipient) can derive the fact that the originator is communicating with the observer.
[0056] Mix-based anonymous asynchronous communication is the equivalent of an originator sending one (or a set of) request e-mail(s) to a recipient, and is able to receive reply e-mail to those e-mails (the number of reply e-mails can be set by the originator), with the feature that the recipient never sees the originator's real e-mail address; that the e-mail content is encrypted on any link of the mix network; that none of the mixes (except the egress mix) sees the content of the e-mail; that none of the mixes (except the ingress mix) ever sees the originator's real e-mail address; and that no external observer (including the recipient) can derive the fact that this originator sends or receives e-mail to/from this recipient. Both types (synchronous or asynchronous) anonymous communication were achieved by the first version of the ZeroKnowledge Freedom network, currently only the synchronous (anonymous version) is offered commercially.
[0057] Computer program means or computer program in the present context mean any expression, in any language, code or notation, of a set of instructions intended to cause a system having an information processing capability to perform a particular function either directly or after either or both of the following a) conversion to another language, code or notation; b) reproduction in a different material form.
[0058] Any disclosed embodiment may be combined with one or several of the other embodiments shown and/or described. This is also possible for one or more features of the embodiments.
[0059] The foregoing description of the 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 disclosed, and other modifications and variations may be possible in light of the above teachings. The embodiments disclosed were chosen and described in order to best explain the principles of the invention and its practical application to thereby enable others skilled in the art to best utilize the invention in various embodiments and various modifications as are suited to the particular use contemplated. It is intended that the appended claims be construed to include other alternative embodiments of the invention except insofar as limited by the prior art.
|
A method, system and computer program product for delivering electronic information anonymously from a first party to a user, in particular to the delivery of advertisement via the Internet. The method for delivering electronic information anonymously from the first party via a second party to a third party as user includes the operations of providing the information received from the first party, receiving a preference request from the user via the second party comprising a session key and a request that applies the session key, and responsive to the request and in the event that the request matches with the provided information, providing to the third party a response comprising a matching information that applies the session key.
| 6
|
CROSS REFERENCES TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent application Ser. No. 10/781,267 filed Feb. 17, 2004, which is a continuation of U.S. patent application Ser. No. 10/177,920, now U.S. Pat. No. 6,691,483, filed Jun. 21, 2002, both of which are herein incorporated by reference in their entirety.
BACKGROUND OF THE INVENTION
[0002] The present invention relates generally to panel doors, and more particularly to panel pet doors for insertion into sliding glass doors.
[0003] Panel pet doors for sliding glass doors are pet doors designed to fit in the space that results when a sliding glass door is partially opened (or, also, the resulting space when a stationary panel is moved to one side). The advantage to this type of pet door is that it does not require cutting a hole through, and thereby ruining, a door.
[0004] There are three dimensions that are critical to accommodating the animal(s) that will be using a panel pet door: width of a flap opening, height of the flap opening and, just as important, rise. The rise is defined as the height of a bottom edge of the flap above a base of the panel door. For a most comfortable fit, the top edge of the flap should be about the same height as the pet at the top of the withers (top of the shoulder). Customarily, panel pet door flaps have not been designed to be that height. Rather, the flap is raised up off the ground (the rise) so as to get the flap opening about even with the trunk of the pet's body. Short dogs would prefer a shorter rise and taller dogs need a higher rise. For example, currently a pet door company manufactures a “large” pet door with a flap that measures 10×15 inches with a 5 inch rise. They also offer a “large/tall” pet door using the same flap, but with a 9 inch rise.
[0005] It would be beneficial to a consumer to offer the largest sizes in at least three or four different rises and for medium and small/medium sizes to be offered in at least two rises. It would also be beneficial to offer customers ways to change the size of the flap door and/or rise, such as when a dog changes size over time, e.g., grows from a puppy into a mature dog. Heretofore, the only way a manufacturer could offer multiple rise options was by building and maintaining an inventory of separate panel pet door sizes for each rise option.
[0006] It would also be beneficial to offer customers ways to change the size of the flap door in addition to adjusting the height of the rise, all without replacing the entire panel pet door. Common circumstances which would make this desirable occur when, for example, the owner of a taller dog acquires a short dog (desiring to preserve the height of the present flap, but shorten the rise.), or vice versa. Also, if an owner's dog becomes injured the dog may benefit from a lower rise and/or a taller flap.
[0007] There is thus a need in the art for a panel pet door that provides a way to offer customers different height and rise combinations of the pet door flap without having to manufacture a separate panel pet door for each combination, and provides a way for customers to adjust the rise and height of the pet door flap without having to replace an entire panel pet door.
SUMMARY OF THE INVENTION
[0008] The present invention advantageously addresses the needs above as well as other needs by providing a panel door and method of adjusting the panel door.
[0009] In one embodiment, the invention can be characterized as a panel door assembly comprising a panel door frame, an entrance portal assembly mounted on the panel door frame that is vertically slidable on the panel door frame and a spacer panel mounted on the panel door frame that is vertically slidable on the frame.
[0010] In another embodiment, the invention can be characterized as a the panel door assembly described above further comprising at least one additional spacer panel mounted on the panel door frame that is vertically slidable on the panel door frame, a total number of spacer panels mounted on the panel door frame comprising a plurality of vertically slidable spacer panels.
[0011] In another embodiment, the invention can be characterized as a method of adjusting an entrance of a panel door assembly comprising the steps of sliding vertically at least one spacer panel and an entrance portal assembly out of a panel door frame of the panel door assembly and sliding vertically at least one spacer panel and the entrance portal assembly into the panel door frame in a configuration such that the entrance portal is at a different height from a bottom of the panel door frame.
[0012] In another embodiment, the invention can be characterized as a method of adjusting an entrance of a panel door assembly comprising the steps of sliding vertically at least one spacer panel and a first entrance portal assembly out of a panel door frame of the panel door assembly and sliding vertically a second entrance portal assembly of a different height than the first into the panel door frame.
[0013] In yet another embodiment, the invention can be characterized as a method of adjusting an entrance of a panel door assembly comprising the steps of sliding vertically a first entrance portal assembly out of a panel door frame of the panel door assembly and sliding vertically a second entrance portal assembly of a different height than the first and at least one spacer panel into the panel door frame.
[0014] A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description of the invention and accompanying drawings which set forth an illustrative embodiment in which the principles of the invention are utilized.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The above and other aspects, features and advantages of the present invention will be more apparent from the following more particular description thereof, presented in conjunction with the following drawings wherein:
[0016] FIG. 1 is a front elevation view of a fixed rise/height panel pet door;
[0017] FIG. 2 is a front elevation view of another fixed rise/height panel pet door;
[0018] FIG. 3 is a front elevation view of a panel pet door according to an embodiment of the present invention;
[0019] FIG. 4 is a partial top cross sectional view of the panel pet door of FIG. 3 ;
[0020] FIG. 5 is a partial top cross sectional view of an alternative embodiment of the panel pet door of FIG. 3 ;
[0021] FIG. 6 is a partial top cross sectional view of a further alternative embodiment of the panel pet door of FIG. 3 ;
[0022] FIG. 7 is a front perspective view of the entrance portal assembly according the embodiment of the present invention shown in FIG. 3 ;
[0023] FIG. 8 is a front perspective view of a stepwise assembly of an alternative embodiment of an entrance portal assembly according to the present invention.
[0024] FIG. 9 is a side cross sectional view of a spacer panel according to an embodiment of the present invention;
[0025] FIG. 10 is a side cross sectional view of taller spacer panel than that of FIG. 9 according to an embodiment of the present invention;
[0026] FIG. 11 is a side cross sectional view of an alternative embodiment of a spacer panel according to the present invention;
[0027] FIG. 12 is a front perspective view of the panel pet door of FIG. 3 according to the present invention, using a different number, size and configuration of spacer panels;
[0028] FIG. 13 is a partial side cross sectional view of the panel pet door of FIG. 12 ;
[0029] FIG. 14 is a close-up partial side cross sectional view of the panel pet door of FIG. 12 ;
[0030] FIG. 15 is a front elevation view of the panel pet door of FIG. 3 installed in a sliding glass door frame;
[0031] FIG. 16 is a front perspective view of the-panel pet door of FIG. 15 installed in a sliding glass door frame; and
[0032] FIG. 17 is a side cross sectional view of the panel pet door in a sliding door of FIG. 16 .
[0033] Corresponding reference characters indicate corresponding components throughout the several views of the drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0034] The following description of the presently contemplated best mode of practicing the invention is not to be taken in a limiting sense, but is made merely for the purpose of describing the general principles of the invention. The scope of the invention should be determined with reference to the claims.
[0035] Referring to FIGS. 1 and 2 , shown are front elevation views of examples of panel pet doors with fixed, i.e., single, rise and height dimensions. In FIG. 1 , a fixed door flap 100 has a rise equal to the height of a cross member 105 . To make the rise higher, a separate panel door ( FIG. 2 ) is built with the door flap 200 raised higher and a first additional fixed cross piece 210 attached permanently below a second additional cross piece 215 below the door flap 200 and above cross member 205 . One difficulty with this approach is that it results in a great many stocking units (SKU's), i.e., a great deal of panel pet door inventory, and an increase in raw materials inventory to support manufacturing. Also, production efficiency is decreased as there are many small production runs for each of a large number of rise options for each flap size. For example, in the event a panel pet door is available in four standard height adjustment ranges, three frame colors and, counting each size/rise combination as separate, 16 size/rise combinations, a total of 192 SKU's are required, i.e., a total of 192 different panel pet door models must be maintained in inventory.
[0036] Referring to FIGS. 3 and 4 , shown in FIG. 3 is a front elevation view of a panel pet door 300 according to an embodiment of the present invention and in FIG. 4 shown is a partial top cross sectional view of the panel pet door of FIG. 3 . Shown in FIG. 3 are the panel door frame 301 having two vertical stiles 302 , 303 , and a top horizontal frame cross piece 304 . Also shown are a glass pane 305 , a top fixed cross piece 310 a movable top spacer panel 315 , a movable entrance portal assembly 316 (having a movable frame 320 and a door flap 325 ), two movable riser spacer panels 330 , 335 , and a bottom fixed cross piece 340 . In FIG. 4 shown is the movable top spacer panel 315 and stile 302 of FIG. 3 along with a vertical track 400 in the stile 302 .
[0037] The panel door frame 301 is a solid frame of wood, metal, plastic or vinyl (preferably metal). The two stiles 302 , 303 are fixedly attached to the top horizontal frame cross piece 304 and may be formed integral with the two vertical stiles 302 , 303 . A pane 305 (preferably of glass) is attached in the interior of the top portion of the frame 301 above the top fixed cross piece 310 that extends horizontally between the two stiles 302 , 303 .
[0038] Directly below the top fixed cross piece 310 is the movable top spacer panel 315 . This panel 315 fits into and is movable vertically along a vertical track 400 in each stile 302 , 303 (shown in FIG. 4 ) located on the interior of the two stiles 302 , 303 . The top spacer panel 315 is located above and rests on the movable entrance portal assembly 316 (preferably a movable door flap assembly 316 ). The movable door flap assembly 315 is also movable along vertical tracks 400 (shown in FIG. 4 ) located on the interior of the two stiles 302 , 303 .
[0039] The door flap assembly 316 has a movable frame 320 that fits into the tracks 400 of the stiles 302 , 303 (shown in FIG. 4 ) like the movable top spacer panel 315 .
[0040] Preferably, two vertical frame members 321 , 322 of the movable frame 320 fit into the tracks 400 of the stiles 302 , 303 (as in FIG. 4 ). The door flap 325 is preferably flexible and is hingedly attached to the movable frame 320 to allow the passage of pets through the flap 325 .
[0041] Located below the door flap assembly 316 in the panel door frame 301 are two movable riser spacer panels 330 , 335 that are also movable along the tracks 400 of the two stiles 302 , 303 (shown in FIG. 4 ). Located below the two riser spacer panels is the bottom fixed cross piece 340 . The bottom fixed cross piece is fixedly attached between the bottom of the two stiles 302 , 303 , and is preferably removable and thus not formed integral with the panel door frame 303 .
[0042] The spacer panels 315 , 330 , 335 and the door flap assembly 316 can be slid out of the panel door frame 301 through an opening in the bottom of the frame 301 by removal of the bottom fixed cross piece 340 from the panel door frame 301 . This is to allow removal and replacement of the spacer panels 315 , 330 , 335 and the door flap assembly 316 . Replacement of the spacer panels 315 , 330 , 335 into the panel door frame 301 in a different configuration and/or with spacer panels of a different size effects a change in the rise (the distance between the bottom of the door flap 325 and bottom of the panel door 300 ). For example, to increase the rise to a degree equal to the height of the top spacer panel 315 , first remove the bottom cross piece 340 and then remove spacer panels 315 , 330 , 335 and the door flap assembly 316 by sliding them out through the bottom of the panel door frame 301 . Next, slide in the door flap assembly 316 into the panel door frame and then slide the same spacer panels 315 , 330 , 335 below the door flap assembly 316 into the panel door frame 301 . Finally, replace the bottom fixed cross piece by reattaching it between the bottom of the two stiles 302 , 303 . Now all the spacer panels 315 , 330 , 335 are located below the door flap assembly 316 , thus increasing the rise of the door flap 325 .
[0043] A removable bottom crosspiece 340 may be attached to the stiles 302 , 303 by reusable means such as screws or a locking mechanism (preferably screws).
[0044] Also, replacement of the spacer panels 315 , 330 , 335 with a spacer panel (or panels) of a different height or heights can also effect a change in the rise. The height of the door flap assembly 316 in the panel door 300 may also be changed by sliding out the door flap assembly 316 in the manner previously described and replacing it with a door flap assembly of a different height. Optionally, this may be done in combination with changing the rise as described above.
[0045] It is important to note that the area between the top fixed cross piece 310 and the bottom fixed cross piece 340 may be filled with a door flap assembly 316 of any selected height and any combination of spacer panels of various optional heights, either above or below the door flap assembly 316 .
[0046] Referring next to FIG. 5 , shown is a partial top cross sectional view of an alternative embodiment of the panel pet door of FIG. 3 . Shown is the stile 302 of FIG. 4 having a vertical track 400 and an alternative embodiment of the movable top spacer panel 315 having a vertical track 500 in the spacer 315 .
[0047] The vertical track 500 is located on each side of the spacer 315 (one side shown in FIG. 5 ) and is representative of an alternative way for spacers and door flap assemblies to fit in the panel door frame 301 . The track 500 is slightly wider than the depth of the stile 302 such that the stile 302 fits into the vertical track 500 and allows the spacer 315 to slide vertically along the stile 302 .
[0048] Referring next to FIG. 6 , shown is a partial top cross sectional view of an alternative embodiment of the panel pet door of FIG. 3 . Shown is the stile 302 of FIG. 4 having a vertical track 4 . 00 and an alternative embodiment of the movable top spacer panel 315 having a vertical tracks 610 , 615 in the spacer 315 .
[0049] The vertical tracks 600 , 605 are located on each side of the spacer 315 (one side shown in FIG. 6 ) and is representative of an alternative way for spacers and door flap assemblies to fit in the panel door frame 301 . The tracks 600 , 605 are slightly wider than the depth of walls 610 , 615 of the track 400 in the stile 302 . Thus, the track walls 610 , 615 fit respectively into the vertical tracks 600 , 605 of the spacer 315 and allow the spacer 315 to slide vertically along the stile 302 .
[0050] Referring next to FIG. 7 , shown is a front perspective view of the entrance portal assembly 316 (a door flap assembly in this case) according to the embodiment of the present invention shown in FIG. 3 . Shown are the door flap frame 320 , the two vertical frame members 321 , 322 of the door flap frame 320 and the door flap 325 .
[0051] The door flap assembly frame 320 has guides 323 , 324 on the exterior of the vertical frame members that fit into the vertical stiles 302 , 303 (shown in FIG. 3 ) of the panel door frame 302 that allow the door flap assembly 316 to slide vertically along the panel door frame 301 as a single unit. Located on the top and bottom of the door flap frame are projections 326 , 327 that allow the door flap assembly 316 to nest into the bottom and top of spacer panels 315 , 330 , respectively (shown in FIG. 3 ).
[0052] Referring next to FIG. 8 , shown is a front perspective view of a stepwise assembly of an alternative embodiment of an entrance portal assembly 1000 according to the present invention. Shown is a door flap frame 1002 and a standard (wall or door mounted) pet door 1005 with a flap 1010 . The flap frame 1002 is a carrier onto which the pet door 1005 is mounted. The perimeter of the completed door flap assembly 1000 fits into the panel door frame 301 and spacer panels 315 , 330 (shown in FIG. 3 ) in the same manner as the door flap assembly 316 of FIG. 7
[0053] Referring next to FIGS. 9, 10 and 11 , shown are side cross sectional views of a spacer panel, a taller spacer panel and an alternative embodiment of a spacer panel according to the present invention, respectively.
[0054] FIGS. 9 and 10 show spacer panels 916 , 920 having vertical protrusions 930 at the top and bottom of the panels 916 , 920 that allow nesting of the panels 916 , 920 . The protrusions 930 at the bottom of the panels 916 , 920 fit over the protrusions 930 at the top of the panels below them. The protrusions 930 are sufficiently long to allow clearance 940 for screw heads, other fastening means, and weather stripping to fit between the panels 916 , 920 . The spacer 920 of FIG. 10 is taller to replace two or more “single size” spacers. The spacer 925 of FIG. 11 has a protrusion 935 on top of the spacer with a cross member to shed water more efficiently, but leaves no gap for screw heads.
[0055] Referring next to FIG. 12 , shown is a front perspective view of the panel pet door 300 of FIG. 3 according to the present invention, using a different number, size and configuration of spacer panels.
[0056] Shown in FIG. 12 is the panel door frame 301 having two vertical stiles 302 , 303 , and a top horizontal frame cross piece 304 . Also shown are a glass pane 305 , a top fixed cross piece 310 nested movable spacer panels 945 , a movable entrance portal assembly 316 , and a bottom fixed cross piece 340 . Note in FIG. 12 that in this configuration the spacer panels 945 are all above the entrance portal assembly 316 , thus lowering the rise of the entrance portal assembly.
[0057] Referring next to FIG. 13 , shown is a partial side cross sectional view of the panel pet door 300 of FIG. 12 . Shown in FIG. 13 is the top fixed cross piece 310 nested movable spacer panels 945 , the movable entrance portal assembly 316 (showing the door flap assembly frame 320 and flap 325 ), and a bottom fixed cross piece 340 .
[0058] Note how the spacers 945 nest together, one on top of the other, and also into the bottom of the top fixed cross piece 310 . Also, the door flap assembly frame 320 nests into the spacers panels 945 above it and into the bottom fixed cross piece below it.
[0059] Referring next to FIG. 14 , shown is a close-up partial side cross sectional view of the panel pet door 300 of FIG. 12 . Shown in FIG. 13 is the top fixed cross piece 310 , nested movable spacer panels 945 and the top part of the movable entrance portal assembly 316 (showing the top of the door flap assembly frame 320 and flap 325 ). Shown in detail are the protrusions 930 on the top and bottom of the spacers 945 that nest together 950 . Also note the clearance 940 between the spacer panels 945 for weather stripping, screws and other hardware.
[0060] Referring next to FIGS. 15 and 16 , shown are front elevation and front perspective views, respectively, of the panel pet door 300 of FIG. 3 installed in a sliding glass door 700 . Shown in FIGS. 15 and 16 are the panel door 300 and sliding glass door 700 , a sliding glass door frame 705 , a top horizontal frame member 715 , a bottom horizontal frame member 710 and a glass door 720 . Shown in FIG. 16 are horizontal tracks 800 , 805 of the sliding glass door frame 705 .
[0061] The panel pet door 300 fits as an insert into the frame 705 of the sliding glass door 700 . The panel door frame 301 is of sufficient height to fit inside the sliding glass door frame 705 onto the respective tracks 800 , 805 of the top and bottom frame members 715 , 710 , of the sliding glass door frame 705 (as shown in detail in FIG. 17 ).
[0062] Referring next to FIG. 17 , is a side cross sectional view of the panel pet door 300 in the sliding door 700 of FIG. 16 . Shown is the vertical stile 302 and top and bottom cross pieces 304 , 340 of the panel door frame 301 of the panel door 300 . Also shown are the top and bottom tracks 800 , 805 of the sliding glass door frame 705 , a spring mechanism 900 having a spring 905 and a rail 901 , and a thumb screw 910 .
[0063] The spring mechanism 900 is located on the top of the top horizontal frame cross piece 304 of the panel door frame 301 . The spring 905 supports the rail 901 which is inserted into top track 800 of the sliding glass door 700 . The thumb screw is located on the interior side of the panel door frame 301 and is operably connected to the spring mechanism such that the spring mechanism is locked in place when the thumb screw is tightened and unlocked when loosened. The bottom cross piece 340 of the panel door frame 301 has a horizontal channel 915 that allows the bottom cross piece 340 to fit into the bottom outside track 805 of the sliding glass door frame 705 .
[0064] The panel pet door frame 301 is inserted into the sliding glass door frame 705 by first loosening the thumb screw 910 , then inserting the spring mechanism 900 into the top track 800 . Then, while pushing up against the spring mechanism 900 , the bottom of the panel door frame 301 is swung onto the bottom rail 805 . The thumb screw 910 is then tightened to lock the spring mechanism 900 and thus the panel door frame 301 in place.
[0065] 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.
|
An adjustable panel door comprises a panel door frame having a top cross piece and a bottom cross piece. A portal assembly provides access through the panel door. The portal assembly is positioned between the top cross piece and the bottom top piece. At least one spacer panel is adjustably positioned on the panel door frame adjacent to the portal assembly. The position of the portal assembly is adjustable by altering a position of the at least one spacer panel along the panel door frame.
| 4
|
BACKGROUND AND SUMMARY
This invention relates to hand tools, and more particularly to a device, commonly known as a level, for indicating the angular relationship of a substantially flat work surface to level, plumb, or other datum.
A spirit level generally consists of a frame providing flat horizontal top and bottom surfaces adapted for placement on a work surface. One or more spirit vials are mounted to the frame in a predetermined orientation relative to the top and bottom surfaces of the level. In a typical application, three vials are mounted to the frame. The central vial is oriented such that its longitudinal axis is parallel to the planes of the top and bottom surfaces. One of the end vials is oriented such that its longitudinal axis is oriented perpendicular to the planes of the top and bottom surfaces. The other end vial may have an orientation similar to that of the first-mentioned end vial, or it may be positioned such that its longitudinal axis is oriented 45° to the plane of the top and bottom surfaces.
It is known to provide an opening in the top surface of the level to extend the range of positions from which the level-indicating vial can be viewed. This topreading feature is shown in Johnson U.S. Pat. No. 4,011,660 issued Mar. 15, 1977; Mayes U.S. Pat. No. 4,492,038 issued Jan. 8, 1985, and Rawlings et al U.S. Pat. No. 4,765,061 issued Aug. 23, 1988.
It is an object of the present invention to provide an improvement to a top-reading feature associated with a level, such as is exemplified in the noted patents. Specifically, the present invention has as its object to provide magnification of the level vial when viewed through the opening formed in the top surface of the level, to enhance the advantages provided by the top-reading feature. It is a further object of the invention to provide a top-reading level, with magnification of the vial, in which the magnifying element is secured within the opening in an advantageous manner.
The invention is employed in combination with a level of conventional construction, which typically comprises horizontal top and bottom surfaces, with an interposed body portion in which a cavity is formed. A vial is located within the cavity for providing an indication of the relationship to level, or other datum, of the work surface when the bottom surface is placed thereon. In accordance with one aspect of the invention, an opening is formed in the top surface of the level, and is in visual communication with the cavity to allow the vial to be viewed through the opening. A transparent magnifying element is located between the vial and the opening for providing magnification of the vial when viewed through the opening. In one form of the invention, the level consists of a frame having upper and lower horizontal flanges with a vertical web disposed therebetween, with the cavity in the level body portion comprising a vial-receiving opening formed in the web. A pair of vial covers are located one on either side of the web, defining an internal cavity within which the vial is located. Each vial cover defines a window opening for providing visual access to the vial therethrough. A transparent lens is located within each window opening, and is positioned between one of the vial covers and a side of the web. The magnifying element is formed integrally with a first one of the lenses. The first lens includes a laterally extending upper portion, and the magnifying element is defined by the first lens upper portion. Each of the lenses includes structure which engages the underside of the upper flange adjacent the opening, for sealing the internal cavity defined by the vial covers within which the vial is located. Each of the lenses is provided with an upper portion extending above the upper surface of its associated vial cover, and the lens upper portions are provided with mating structure for interlocking the lenses together. The mating structure preferably comprises a tongue-and-groove arrangement. In addition, a connection arrangement is provided for securing each lens to its associated vial cover. The connection arrangement consists of one or more locking tabs located adjacent the window opening formed in each vial cover, and engagement structure, in the form of protrusions, provided on each lens for engagement with the locking tabs to secure the lenses to the vial covers.
The invention further contemplates an improvement in a level, and a method of making a level, substantially in accordance with the foregoing summary.
Various other objects, features and advantages of the invention will be made apparent from the following description taking together with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The drawings illustrate the best mode presently contemplated of carrying out the invention.
In the drawings:
FIG. 1 is an isometric view of a level incorporating the top-reading magnification feature of the invention;
FIG. 2 is a partial exploded isometric view showing the pair of vial covers, the lenses secured to the vial covers, the vial, and a portion of the level frame which includes the opening within which the vial is positioned;
FIG. 3 is a partial exploded isometric view showing one of the vial covers and the lens adapted to be secured thereto, with the lens including the transparent magnifying element defined by its upper portion;
FIG. 4 is a section view taken generally along line 4--4 of FIG. 1;
FIG. 5 is a section view taken generally along line 5--5 of FIG. 4;
FIG. 6 is a partial section view taken generally along line 6--6 of FIG. 5; and
FIG. 7 is a partial section view taken generally along line 7--7 of FIG. 5.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, a level 10 generally consists of an I-shaped metal frame 12 having an upper horizontal flange 14, a lower horizontal flange 16, and a vertical web 18 extending between and interconnecting flanges 14, 16. A series of vials shown at 20, 22 and 24 are mounted within stamped openings formed in web 18. As shown in FIG. 2, a stamped opening 25 is formed in web 18, and includes notches, such as shown at 26 and 28, which are adapted to receive the ends of vial 22. Similar stamped openings are formed in web 18 for vials 10 and 24. This manner of mounting vials to the web of a level frame is known in the art.
As further shown in FIG. 2, a pair of vial covers 30, 32 are adapted for placement one on either side of web 18, for enclosing vial 22 and maintaining it in engagement with the notches, such as 26, 28, formed in web 18. Similarly, vial 20 is enclosed by a pair of vial covers, one of which is shown in FIG. 1 at 34, and vial 24 is enclosed by a pair of vial covers, one of which is shown in FIG. 1 at 36.
Referring to FIGS. 1 and 2, an opening 38 is formed in top flange 14. Opening 38 is in communication with stamped opening 25 in web 18 within which vial 22 is located. In this manner, vial 22 can be viewed through opening 38.
As shown in FIGS. 2 and 3, vial cover 30 has a transparent lens assembly 40 secured thereto. Vial cover 30 is provided with a window opening 42 and a cut-out 44 in its upper surface 46. Lens assembly 40 is injection molded of a transparent plastic material, and provides a lens panel 48, a pair of lens side walls 50 and 52, and a lower wall 54. Lens assembly 40 further includes an upper portion, shown generally at 56, which includes an elongated convex magnifying element 58. Magnifying element 58 is of a shape and size, viewed in plan, substantially identical to the interior shape defined by opening 38 in upper flange 14. Upper portion 56 further includes a C-shaped shoulder 60 which partially surrounds magnifying element 58. A pair of spaced projections 62, 64 extend laterally from the side of magnifying element 58 opposite the long central portion of C-shaped shoulder 60. The facing ends of spaced projections 62, 64, in combination with the edge of magnifying element 58, cooperate to define a slot.
Lens side walls 50, 52 are provided with arcuate recesses 66, 68, respectively. In addition, lens side wall 50 is provided with a pair of locating tabs 70, 72 and a pair of locking projections 74, 76. Lens side wall 52 is similarly provided with pairs of locating tabs 70, 72 and locking projections 74, 76.
Vial cover 30 includes a pair of locking tabs 78, 80 extending inwardly from the front wall of vial cover 30 and located adjacent one edge of window opening 42. A facing pair of locking tabs 82, 84 are provided adjacent the opposite edge of window opening 42. Locking tabs 78-84 each include inwardly-facing protrusions, such as shown at 86, 88 with respect to locking tabs 78, 80, respectively.
Lens assembly 40 is assembled to vial cover 30, to attain the assembled position as shown in FIG. 2, by means of a push-on motion. Proper alignment of lens assembly ing tabs, such as 70, 72, engaging the upper edge of locking tab 82 and the lower edge of locking tab 84, respectively, during push-on engagement of lens assembly 40 with vial cover 30. The locking projections, such as 74, 76, engage the protrusions, such as 86, 88 provided on the locking tabs 78-84, which deflect outwardly until the locking projections, such as 74, 76 pass the protrusions, such as 86, 88, on the locking tabs 78, 84. Upon continued push-on engagement of lens assembly 40 with vial cover 30, the locking tabs, such as 78-84, return to their undeflected position so that the protrusions, such as 86, 88 are positioned over the locking projections, such as 74, 76, to secure lens assembly 40 in position on vial cover 30. When so secured, the upper portion 56 of lens assembly 40 extends above upper surface 46 of vial cover 30, in a manner as is shown in FIG. 2. Lens panel 48 is positioned within window opening 42.
A second lens assembly, shown generally at 90 in FIG. 2, is secured to vial cover 32 in the same manner as described with respect to lens assembly 40 and vial cover 30. Lens assembly 90 includes an upper portion 92 which defines a pair of end walls 94, 96, a central projection 98, and a pair of recesses 100, 102. Upper portion 92 extends above the upper surface 104, of vial cover 32. Lens assembly 90 further includes a lens panel 106, a pair of lens side walls 108, 110, and a lower wall 112. An arcuate notch 114 is formed in side wall 108, and a similar notch 116 is formed in side wall 110.
Vial covers 30, 32, with lens assemblies 40, 90, respectively, connected thereto in the manner described, are assembled to level frame 10 by positioning each vial cover and lens assembly one on either side of web 18 after vial 22 is engaged with web 18, such as at notches 26, 28. When the vial covers and lens assemblies are in their assembled position, a pair of projections 118, 120 (FIG. 3) which extend rearwardly from the front wall of vial cover 30, extend into a pair of openings 122, 124 (FIG. 2) provided in a pair of bosses extended rearwardly from the front wall of vial cover 32. A pair of screws, such as shown at 126 in FIG. 2, are inserted through openings 122, 124 to threadedly engage openings formed in projections 118, 120, to secure vial covers 30 and 32 to each other, with web 18 sandwiched therebetween. A recess, shown in FIG. 2 at 128, is formed in web 18 to accommodate projections 118, 120 extending through web 18.
Notches 66, 68 in side walls 50, 52, respectively.of lens assembly 40 accommodate vial 22 and serve to maintain vial 22 in engagement with the notches, such as 26, 28 associated with opening 25 in web 18. In a similar manner, notches 114, 116 in side walls 108, 110, respectively, of lens assembly 90 accommodate the opposite side of vial 22 to maintain vial 22 in position on web 18.
FIG. 4 illustrates, in section, vial covers 30, 32 and lens assemblies 40, 90 assembled to web 18 of level frame 12. As shown in FIG. 4, C-shaped shoulder 60 provided on upper portion 56 of lens assembly 40 engages the underside of upper flange 14 of level frame 12 adjacent opening 38. Magnifying element 58, which is convex in cross-section to provide magnification, extends upwardly into opening 38, with the upper surface of magnifying element 58 being disposed below the upper surface of upper flange 14. Spaced projections 62 provided on upper portion 56 of lens assembly 40 also engage the underside of upper flange 14 adjacent opening 38. Between projections 62 and 64, central projection 98 provided on upper portion 92 of lens assembly 90 engages the underside of upper flange 14 adjacent opening 38. End walls 94, 96 provided on upper portion 92 of lens assembly 90 also engage the underside of upper flange 14 adjacent the end portions of opening 38. With this arrangement, the internal cavity defined by vial covers 30, 32 in combination with lens assemblies 40, 90 is sealed so as to prevent dirt or other foreign material from entering the cavity where it could obstruct the viewing of vial 22.
With magnifying element 58 disposed within opening 38 formed in upper flange 14, vial 22 is magnified by magnifying element 58 when viewed through opening 38 in upper flange 14. This feature allows the position of the bubble within vial 22 to be ascertained with greater clarity than without magnification.
Vial covers 30, 32 are preferably injection molded.plastic components formed of any satisfactory thermoplastic material such as ABS or the like. Lens assemblies 40, 90 are preferably injection molded components formed of a transparent acrylic material. Other satisfactory clear plastic materials, such as polycarbonate, could be employed.
Various alternatives and embodiments are contemplated as being within the scope of the following claims particularly pointed out and distinctly claiming the subject matter regarded as the invention.
|
A level is provided with a top-reading feature, allowing a vial to be viewed through the upper flange of the level. A magnifying element is disposed between the vial and an opening formed in the upper flange, to magnify the vial when it observed from the top of the level. The magnifying element is preferably formed integrally with a transparent lens, which is retained between a vial cover and a side of the web of the level frame. Complementary structure is provided on the lens on the opposite side of the web, for sealing the internal cavity defined by the vial covers, in combination with the lenses, to prevent entry of dirt or other foreign material into the cavity.
| 6
|
RELATED APPLICATIONS
[0001] This application is a continuation of PCT International Patent Application No. PCT/EP2005/006905, filed Jun. 27, 2005, which claims priority to U.S. Provisional Patent Application No. 60/583,227, filed Jun. 25, 2004, the disclosures of each of which are incorporated herein by reference in their entirety.
BACKGROUND
[0002] The present invention is directed to a method of producing spider dragline and/or flagelliform proteins. The invention is further directed to a method of producing spider threads and to a dragline/flagelliform protein or dragline/flagelliform protein thread produced by these methods. The invention further provides the use of these proteins/threads in the field of biotechnology and/or medicine, in particular in the manufacture of wound closure or coverage systems, suture materials and in the manufacture of replacement materials, preferably artificial cartilage or tendon materials, as well as in other commercial applications.
[0003] Spider dragline silk has extraordinary properties ( 1 ) originating in its composition as a semi crystalline polymer ( 2 ) that contains crystalline regions embedded in an amorphous matrix. X-ray diffraction and NMR show the crystalline regions to consist of pleated beta sheets of polyalanine stretches which are giving strength to the thread ( 3 , 4 ), while the predominant secondary structure of the amorphous matrix is a glycine rich 3 1 helix providing elasticity ( 5 ). Freshly secreted silk proteins are stored at high concentrations ( 6 ) as a liquid crystalline dope ( 7 , 8 ) that is altered by changes in ionic composition, pH (from pH 6.9 to 6.3) ( 9 , 10 ) and water extraction ( 10 , 11 ) during its passage through the spinning duct to be finally converted into a solid thread induced by extensional flow ( 12 ).
[0004] All dragline silks studied so far consist of at least two different proteins with molecular masses of up to several hundred kDa ( 13 ). The individual contribution of the two major dragline silk proteins of Araneus diadematus , ADF-3 and ADF-4, to dragline thread assembly and structure has not been determined so far. Analyzing the primary structures revealed that ADF-3 and ADF-4 ( 14 , 15 ) have similar proline contents and polyalanine motifs, but they differ in glutamine and serine content as well as in length of the glycine-rich regions. Importantly, the properties of silk threads cannot be inferred from the underlying protein sequences. Although the quality of a silk thread is based on the primary structure of the involved proteins, it further depends on the silk assembly process ( 8 ), which necessitates experimental analysis of structural and assembly properties.
[0005] Scientific and commercial interest initiated the investigation of industrial scale manufacturing of spider silk. Native spider silk production is impractical due to the cannibalism of spiders, and artificial production has encountered problems in achieving both sufficient protein yield and quality thread-assembly. Bacterial expression yielded low protein levels ( 16 ), likely caused by a different codon usage in bacteria and in spiders. Synthetic genes with a codon usage adapted to the expression host led to higher yields ( 13 , 17 ), but the proteins synthesized thereof showed different characteristics in comparison to native spider silks. Expression of partial dragline silk cDNAs in mammalian cell lines did yield silk proteins (e.g. ADF-3) that could be artificially spun into ‘silken’ threads, albeit as yet of inferior quality ( 18 ).
[0006] WO03060099 relates to methods and devices for spinning biofilament proteins into fibers. This invention is particularly useful for spinning recombinant silk proteins from aqueous solutions and enhancing the strength of the fibers and practicality of manufacture such as to render commercial production and use of such fibers practicable. Therein, it is disclosed to express spider silk proteins in mammalian cells, e.g. transgenic goat mammary gland cells.
SUMMARY
[0007] Therefore, it is an object of the present invention to provide an improved method for the manufacture of spider silk proteins in high yield and superior quality. It is a further object to provide an improved expression system to be used in said method. Additional objects are to simplify the manufacturing process for spider silk proteins/threads and the provision of new proteins/threads and further materials based on spider silk proteins for use in biotechnology and medicine.
[0008] These objects are solved by the subject-matter of the independent claims. Preferred embodiments are set forth in the dependent claims.
[0009] Regarding the drawbacks of the prior art methods, which are related to the production of spider silk proteins and threads derived therefrom, a different and more efficient route to synthesize authentic spider silk proteins was achieved by the inventors.
[0010] Spider dragline silk, which exhibits extraordinary strength and toughness, is primarily composed of two related proteins whose role in thread assembly and whose contribution to the mechanical properties of dragline threads is largely unknown.
[0011] In order to elucidate this role, a baculovirus expression system was used by the inventors to produce recombinant ADF-3 and ADF-4, the two major dragline silk proteins of the garden spider Araneus diadematus , in host insect cells. It was shown that ADF-4, but not ADF-3 readily self-assembled into filaments in the cytosol of the cells. These ADF-4 filaments displayed the exceptional chemical stability typical for authentic spider dragline silk threads. As a result, the properties of ADF-4 show its role as the structural key player in dragline silk.
[0012] Thus far, little is known about the structure, function and possible interplay between the two major protein components of spider dragline silk threads. The inventors observed that, despite their similarities in primary structure, ADF-3 and ADF-4 display surprisingly different properties. Whilst, ADF-3 represents an intrinsically soluble protein, ADF-4 is virtually insoluble under the experimental conditions employed and forms filamentous aggregates in the cytoplasm of Sf9 cells with a chemical stability comparable to natural dragline threads. The similarities between ADF-4 filaments and native dragline silk threads suggest that ADF-4 is the structural ‘key player’ in dragline threads providing its chemical and physical strength. Since thread formation has to be fast at natural reeling speeds of 1-10 cm/s ( 19 ), an easily assembling compound, such as ADF-4, is mandatory for silk formation. However, the tendency of ADF-4 to aggregate implies that other factors within the spinning dope are likely required to keep it from premature polymerization in the gland. These factors are likely to be post-translational modifications such as phosphorylation and glycosylation. Additionally, ADF-4's solubility could be influenced by proteins that are co-secreted and also stored in the dope. Although ADF-3 did not influence solubility of ADF-4 within the cytosol of the insect cells, it may still play an important role in regulating ADF-4 solubility during or after secretion from the spider gland. The specific conditions present in the secretory pathway of the spider gland cells as well as in the glands' lumen may lead to interactions between ADF-3 and ADF-4, which regulates silk thread assembly.
[0013] Spider silks can be regarded as the benchmarks for future polymer design not only due to their superb quality but are also preferred since they could be produced economically and in an environment-friendly way from aqueous solvents under ambient temperatures and pressures. However, major barriers remain our ability to match the native silk fiber production process. The inventors hereby provide an ideal system for large-scale production of spider silk proteins. Further, the results provided herein constitute the essential basis for elucidating the function and interplay of the two major components of spider silk dragline proteins, e.g. of Araneus dragline silk, ADF-3 and ADF-4. Such knowledge is essential for spinning silk threads from recombinant proteins and for production of a new generation of fibrous materials.
[0014] Therefore, the present invention provides according to a first aspect, a method of producing spider silk dragline proteins derived from the major ampullate gland and/or proteins derived from the flagelliform gland, comprising the following steps:
a) providing a nucleic acid sequence coding for one or more spider dragline and/or flagelliform proteins, b) introducing the nucleic acid sequence(s) provided in a) into an insect cell, c) expressing the dragline and/or flagelliform proteins; and d) recovering said dragline and/or flagelliform proteins.
[0019] Thus, as mentioned above, one of the major advantages offered by the method of the present invention resides in the provision of a novel expression system for spider silk dragline proteins, i.e. the expression in insect cells. It surprisingly turned out that, as explained above, the expression of those proteins in insect cells is superior to the expression in other cells, as, for example, bacterial cells and mammalian cells. This improvement equally affects the quality, i.e. mechanical properties and the like, as well as the yield of spider silk dragline proteins, which can be obtained by the method of the present invention.
[0020] As an example, according to the method of ref. 16, 4 mg/l of cells were obtained, which could not be spun into threads; in ref. 18, 25 mg/l of cells (threads were obtained, however, had poor quality). In the present invention, >30 mg/l of cells could be obtained (self-assembling, stabile thread).
[0021] The dragline/flagelliform proteins encoded by the nucleic acid sequence provided in step a) of the above method are preferably selected from dragline and/or flagelliform proteins of orb-web spiders (Araneidae).
[0022] More preferably, the dragline proteins and/or flagelliform proteins are derived from one or more of the following spiders: Arachnura higginsi, Araneus circulissparsus, Araneus diadematus, Argiope picta , Banded Garden Spider ( Argiope trifasciata ), Batik Golden Web Spider ( Nephila antipodiana ), Beccari's Tent Spider ( Cyrtophora beccarii ), Bird-dropping Spider ( Celaenia excavata ), Black-and-White Spiny Spider ( Gasteracantha kuhlii ), Black-and-yellow Garden Spider ( Argiope aurantia ), Bolas Spider ( Ordgarius furcatus ), Bolas Spiders—Magnificent Spider ( Ordgarius magnificus ), Brown Sailor Spider ( Neoscona nautica ), Brown-Legged Spider ( Neoscona rufofemorata ), Capped Black-Headed Spider ( Zygiella calyptrata ), Common Garden Spider ( Parawixia dehaani ), Common Orb Weaver ( Neoscona oxancensis ), Crab-like Spiny Orb Weaver ( Gasteracantha cancriformis ( elipsoides )), Curved Spiny Spider ( Gasteracantha arcuata ), Cyrtophora moluccensis, Cyrtophora parnasia, Dolophones conifera, Dolophones turrigera , Doria's Spiny Spider ( Gasteracantha doriae ), Double-Spotted Spiny Spider ( Gasteracantha mammosa ), Double-Tailed Tent Spider ( Cyrtophora exanthematica ), Aculeperia ceropegia, Eriophora pustulosa , Flat Anepsion ( Anepsion depressium ), Four-spined Jewel Spider ( Gasteracantha quadrispinosa ), Garden Orb Web Spider ( Eriophora transmarina ), Giant Lichen Orbweaver ( Araneus bicentenarius ), Golden Web Spider ( Nephila maculata ), Hasselt's Spiny Spider ( Gasteracantha hasseltii ), Tegenaria atrica, Heurodes turrita, Island Cyclosa Spider ( Cyclosa insulana ), Jewel or Spiny Spider ( Astracantha minax ), Kidney Garden Spider ( Araneus mitificus ), Laglaise's Garden Spider ( Eriovixia laglaisei ), Long-Bellied Cyclosa Spider ( Cyclosa bifida ), Malabar Spider ( Nephilengys malabarensis ), Multi-Coloured St Andrew's Cross Spider ( Argiope versicolor ), Ornamental Tree-Trunk Spider ( Herennia ornatissima ), Oval St. Andrew's Cross Spider ( Argiope aemula ), Red Tent Spider ( Cyrtophora unicolor ), Russian Tent Spider ( Cyrtophora hirta ), Saint Andrew's Cross Spider ( Argiope keyserlingi ), Scarlet Acusilas ( Acusilas coccineus ), Silver Argiope ( Argiope argentata ), Spinybacked Orbweaver ( Gasteracantha cancriformis ), Spotted Orbweaver ( Neoscona domiciliorum ), St. Andrews Cross ( Argiope aetheria ), St. Andrew's Cross Spider ( Argiope Keyserlingi ), Tree-Stump Spider ( Poltys illepidus ), Triangular Spider ( Arkys clavatus ), Triangular Spider ( Arkys lancearius ), Two-spined Spider ( Poecilopachys australasia ), Nephila species, e.g. Nephila clavipes, Nephila senegalensis, Nephila madagascariensis and many more (for further spider species, see also below). Araneus diadematus is most preferred.
[0023] According to one preferred embodiment, the dragline proteins produced by the method of the present invention are the dragline proteins are wild type ADF-3, ADF-4, MaSp I, MaSp II and the flagelliform protein is FLAG. The term ADF-3/-4 is used in the context of MaSp proteins produced by Araneus diadematus (Araneus diadematus fibroin-3/-4). Both proteins, ADF-3 and 4 belong to the class of MaSp II proteins (major ampullate spidroin II).
[0024] In a further embodiment, the nucleic acid sequence provided in step a) is ADF-3 (SEQ ID NO:1) and/or ADF-4 (SEQ ID NO:2), or a variant thereof.
[0025] It is noted that two different kinds of ADF-3 and ADF-4 coding sequences are contemplated in this invention: first, the already published sequence of ADF-3 and ADF-4 (herein: “wild type” sequence) and, second, a variant thereof, encoded by SEQ ID NO: 1 (ADF-3) and 2 (ADF-4). The wild type sequences were already published and are available under the accession numbers U47855 and U47856 (SEQ ID NO: 3 and 4).
[0026] As explained above, the silk fiber has crystalline regions of β-sheets interspersed with elastic amorphous segments similar to liquid crystalline polymers. These two segments are represented by two different proteins, MaSp I (major ampullate spidroin I) and MaSp II (major ampullate spidroin II) coded by different genes.
[0027] The nucleic acid sequence provided in step a) of the method of the present invention is preferably ADF-3, ADF-4 (SEQ ID NO: 1 and 2) or a variant thereof. SEQ ID NO: 3 and 4 are showing the corresponding amino acid sequences of the wild type sequences.
[0028] Further spider silk proteins, which can preferably be produced by the method of the present invention (i.e. alone or in combination with further proteins) and their database accession numbers are:
[0000] spidroin 2 [Araneus bicentenarius]gi|2911272
[0000] major ampullate gland dragline silk protein-1 [Araneus ventricosus ]gi|27228957
[0000] major ampullate gland dragline silk protein-2 [Araneus ventricosus ]gi|27228959 ampullate spidroin 1 [Nephila madagascariensis ]gi|13562006
[0000] major ampullate spidroin 1 [Nephila senegalensis ]gi|13562010
[0000] major ampullate spidroin 1 [Latrodectus geometricus ]gi|13561998
[0000] major ampullate spidroin 1 [Argiope trifasciata ]gi|13561984
[0000] major ampullate spidroin 1 [Argiope aurantia ]gi|13561976
[0000] dragline silk protein spidroin 2 [Nephila clavata ]gi|16974791
[0000] major ampullate spidroin 2 [Nephila senegalensis ]gi|13562012
[0000] major ampullate spidroin 2 [Nephila madagascariensis ]gi|13562008
[0000] major ampullate spidroin 2 [Latrodectus geometricus ]gi|13562002
[0029] The invention also encompasses a spider dragline protein, which is encoded by the nucleic acid sequence of SEQ ID NO. 1 or 2, or variants of those nucleic acid sequences. These variants are each defined as having one or more substitutions, insertions and/or deletions as compared to the sequence of SEQ ID NO. 1 or 2, provided that said variants hybridize under moderately stringent conditions to a nucleic acid which comprises the sequence of SEQ ID NO. 1 or 2, or provided that said variants comprise nucleic acid changes due to the degeneracy of the genetic code, which code for the same or a functionally equivalent amino acid as the nucleic acid sequence of SEQ ID NO. 1 or 2.
[0030] The term “nucleic acid sequence” refers to a heteropolymer of nucleotides or the sequence of these nucleotides. The terms “nucleic acid” and “polynucleotide” are used interchangeably herein to refer to a heteropolymer of nucleotides.
[0031] Stringency of hybridization, as used herein, refers to conditions under which polynucleotide duplexes are stable. As known to those of skill in the art, the stability of duplex is a function of sodium ion concentration and temperature (see, for example, Sambrook et al., Molecular Cloning: A Laboratory Manual 2 nd Ed. (Cold Spring Harbor Laboratory, (1989)). Stringency levels used to hybridize can be readily varied by those of skill in the art.
[0032] As used herein, the phrase “moderately stringent conditions” refers to conditions that permit DNA to bind a complementary nucleic acid that has about 60% identity, preferably about 75% identity, more preferably about 85% identity to the DNA; with greater than about 90% identity to said DNA being especially preferred. Preferably, moderately stringent conditions are conditions equivalent to hybridization in 50% formamide, 5×Denhart's solution, 5×SSPE, 0.2% SDS at 42° C., followed by washing in 0.2×SSPE, 0.2% SDS, at 65° C.
[0033] According to a preferred embodiment, the method of the present invention provides spider silk proteins consisting of a polymer, the building blocks thereof being defined as one or more of the proteins as defined above or a variant of said proteins. The amino acid sequences of the proteins of the present invention also encompass all sequences differing from the herein disclosed sequences by amino acid insertions, deletions, and substitutions.
[0034] Preferably, amino acid “substitutions” are the result of replacing one amino acid with another amino acid having similar structural and/or chemical properties, i.e., conservative amino acid replacements. Amino acid substitutions may be made on the basis of similarity in polarity, charge, solubility, hydrophobicity, hydrophilicity, and/or the amphipathic nature of the residues involved. For example, nonpolar (hydrophobic) amino acids include alanine, leucine, isoleucine, valine, proline, phenylalanine, tryptophan, and methionine; polar neutral amino acids include glycine, serine, threonine, cysteine, tyrosine, asparagine, and glutamine; positively charged (basic) amino acids include arginine, lysine, and histidine; and negatively charged (acidic) amino acids include aspartic acid and glutamic acid.
[0035] “Insertions” or “deletions” are typically in the range of about 1 to 5 amino acids, preferably about 1, 2 or 3 amino acids. Amino acid additions typically are not more than 100, preferably not more than 80, more preferably not more than 50, most preferred not more than 20 amino acids, which are added on and/or inserted into the proteins of the present invention. It is noted that only those additions are contemplated in this invention, which do not negatively affect the mechanical and further characteristics of the proteins disclosed herein.
[0036] The variation allowed may be experimentally determined by systematically making insertions, deletions, or substitutions of amino acids in a protein using recombinant DNA techniques and assaying the resulting recombinant variants for activity. This does not require more than routine experiments for the skilled artisan.
[0037] According to a preferred embodiment, one or more of the nucleic acid sequences defined above are contained in a vector. Preferably, this vector is an expression vector, which comprises the nucleic acid sequence coding for one or more dragline proteins and/or flagelliform proteins as defined above and one or more regulatory sequences. Such regulatory sequences may preferably comprise promoters p 10 and/or polyhedrin, but other late and very late baculoviral promoters can be used as well.
[0038] The vector is more preferably a viral vector, most preferably a baculovirus vector system or a vaccinia virus vector system. Further viral vector systems may also be used in this invention. From case to case, a modification of the vector may be needed. Examples for further viral vectors are adenoviruses and all negative-strand RNA-viruses, e.g. rabies, measles, RSV, etc.
[0039] As insect cells, Lepidoptera insect cells may preferably be used, more preferably cells from Spodoptera frugiperda and from Trichoplusia ni . Most preferably, the insect cell is a Sf9, Sf21 or high five cell.
[0040] One advantage of insect cell expression system, for example regarding bacterial systems, resides in the fact that the proteins produced are glycosylated, thereby being a target for degradation by microorganisms. This characteristic may be of importance, for example, in the field of medicine, whenever the silk proteins are intended for an in vivo use, in which biological degradation is desired. This characteristic may in particular find application in suture materials and wound closure and coverage systems.
[0041] According to a further preferred embodiment, the only dragline protein expressed is wild type ADF-4 or ADF-4 encoded by SEQ ID NO: 2.
[0042] The inventors surprisingly found out that, in contrast to the conviction of the prior art, only one of the two known major dragline proteins is needed for the manufacture and assembly of a dragline silk thread. Therefore, the already known approaches for the manufacture of dragline silks can be considerably simplified by using only one component for preparing the dragline silk instead of two, as it is known in the art.
[0043] Class MaSp I can be distinguished from MaSp II by the content of amino acid proline. Within the class of MaSp II, no further official subranges are existing. However, ADF-3 and ADF-4 are differing from each other by their content of amino acid glutamine and in the spacing and length of the poly-alanine regions. Therefore, one of skill in the art can easily determine those regions in MaSp II, which are corresponding to ADF-3 and ADF-4, respectively.
[0044] Preferably, the expression of said dragline and/or flagelliform proteins occurs by secretory expression. For further explanation, see chapter Examples. Alternatively, the expression occurs by cytoplasmatical production. As it is shown in the Examples, the conditions, which are present in the insect cells used for expression led to the surprising result that—as mentioned above—spider silk proteins were expressed in high yield an good quality and, moreover, a self-assembly of those proteins to threads occurred already in the cytoplasm without any further production step.
[0045] In a second aspect, the present invention provides a method for producing spider dragline and flagelliform protein threads, comprising the following steps:
a) expressing spider dragline proteins and/or flagelliform proteins as defined above, b) recovering said proteins, and c) spinning said proteins into threads by a suitable method.
[0049] In step c), spinning methods may be used, which are per se known in the art. For example, a dope solution of spider silk protein is extruded through a spinneret to form a biofilament. The resulting biofilament can be drawn or stretched. Whenever both crystalline and amorphous arrangements of molecules exist in biofilaments, drawing or stretching will apply shear stress sufficient to orient the molecules to make them more parallel to the walls of the filament and increase the tensile strength and toughness of the biofilament.
[0050] The dope solution may contain a mixture of silk proteins from one or more spider species, or silk proteins from different silk-producing genera, for example, a mixture of silk proteins from spiders and B. mori . In the most preferred embodiments, the silk proteins are dragline and/or flagelliform silks from N. clavipes or A. diadematus , particularly the proteins MaSpI, MaSpII, ADF-3, and ADF-4. In alternate embodiments, the dope solution contains a mixture of silk proteins and one or more synthetic polymers or natural or synthetic biofilament proteins.
[0051] Preferably, the dope solution is at least 1%, 5%, 10%, 15% weight/volume (w/v) silk protein. More preferably, the dope solution is as much as 20%, 25%, 30%, 35%, 40%, 45%, or 50% w/v silk protein. In preferred embodiments, the dope solution contains substantially pure spider silk protein. In preferred embodiments, the dope has a pH of approximately 6.9.
[0052] By “dope solution” is meant any liquid mixture that contains silk protein and is amenable to extrusion for the formation of a biofilament or film casting. Dope solutions may also contain, in addition to protein monomers, higher order aggregates including, for example, dimers, trimers, and tetramers. Normally, dope solutions are aqueous solutions of pH 4.0-12.0 and having less than 40% organics or chaotropic agents (w/v). Preferably, the dope solutions do not contain any organic solvents or chaotropic agents, yet may include additives to enhance preservation, stability, or workability of the solution.
[0053] By “filament” is meant a fiber of indefinite length, ranging from microscopic length to lengths of a mile or greater. Silk is a natural filament, while nylon and polyester as an example are synthetic filaments.
[0054] By “biofilament” is meant a filament created (e.g., spun) from a protein, including recombinantly produced spider silk protein.
[0055] Further information regarding how to spin spider silk protein fibers may be found in WO03060099 (Karatzas et al.), published Jul. 24, 2003, which is incorporated herein by reference.
[0056] According to a third aspect, a spider dragline protein or flagelliform protein/thread is provided, which is obtainable by the methods as defined herein.
[0057] The invention further encompasses a spider dragline protein or thread, comprising an amino acid sequence encoded by the nucleic acid of SEQ ID NO: 1 and/or 2; or a variant thereof.
[0058] In a preferred embodiment, the spider dragline protein/thread only comprises wild type ADF-4 or an amino acid encoded by the nucleic acid of SEQ ID NO: 2 as a dragline protein.
[0059] A vector, which comprises a nucleic acid coding for wild-type ADF-4 as only dragline protein or which comprises the nucleic acid of SEQ ID NO: 1 and/or SEQ ID NO: 2 is provided in the present invention as a fourth aspect.
[0060] In a fifth aspect, a baculovirus vector is provided, which comprises a nucleic acid coding for one or more dragline and/or flagelliform proteins, preferably for the dragline proteins ADF-3, ADF-4 (wild type) and/or for the flagelliform protein FLAG, ADF-3 (SEQ ID NO:1) and/or ADF-4 (SEQ ID NO:2).
[0061] As already explained above, the proteins/threads as defined herein may be used in the field of biotechnology and/or medicine, preferably for the manufacture of wound closure or coverage systems, suture materials for use in neurosurgery or ophthalmic surgery.
[0062] Furthermore, the proteins/threads may preferably be used for the manufacture of replacement materials, preferably artificial cartilage or tendon materials.
[0063] Additionally, the threads/fibers of the invention can be used in the manufacture of medical devices such as medical adhesive strips, skin grafts, replacement ligaments, and surgical mesh; and in a wide range of industrial and commercial products, such as clothing fabric, bullet-proof vest lining, container fabric, bag or purse straps, cable, rope, adhesive binding material, non-adhesive binding material, strapping material, vehicle covers and parts, construction material, weatherproofing material, flexible partition material, sports equipment; and, in fact, in nearly any use of fiber or fabric for which high tensile strength and elasticity are desired characteristics. Adaptability and use of the stable fiber product in other forms, such as a dry spray coating, bead-like particles, or use in a mixture with other compositions is also contemplated by the present invention.
[0064] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
[0065] The invention is now further illustrated by Examples and the accompanying drawings, which are showing the following:
BRIEF DESCRIPTION OF THE DRAWINGS
[0066] FIG. 1 Expression of adf-3 and adf-4 in Sf9 cells. (A) Solubility of ADF-3 and ADF-4 after synthesis. Soluble (S) and insoluble components (P) of cell lysates were separated by sedimentation. Proteins were detected by immunoblotting with an anti-His 6 antibody. (B) Filament in adf-4 expressing cell, as seen with light microscopy (upper panel) and with fluorescence microscopy after immunocytochemistry (middle panel). An additional confocal fluorescence image after immunocytochemistry of another cell is shown in the lower panel. Scale bars: 10 μm. (C) Solubility of co-synthesized ADF-3 and ADF-4. Soluble (S) were separated from insoluble (P) cell components by sedimentation. ADF-3 was detected with S-protein-peroxidase conjugates after western blotting and ADF-4 with anti-T7-tag antibodies. (D) Sf9 cells in suspension were infected with the mel-His 6 -adf-4 virus. At the indicated times (in days post infection) aliquots equivalent to 6×10 4 cells were taken from the culture media, centrifuged to remove cells and subjected to SDS-PAGE followed by immunoblotting. (E) Cells infected for 3 days with the mel-his 6 -adf-4 virus were subjected to immunofluorescence. Secretion vesicles on the cell surface could be clearly detected. Scale bar 10 μm.
[0067] FIG. 2 Morphology of ADF-4 filaments and aggregates. (A) Scanning electron microscopy on purified filaments. Scale bar: 5 μm (B) Transmission electron microscopy on purified filaments. Scale bar: 500 nm (C) Immunoelectron microscopy on purified filaments using mouse anti-His 6 antibodies followed by gold-conjugated anti-mouse antibodies. Scale bar: 500 nm (D, E) Atomic force microscopy (AFM): (D) height image (E) deflection image. The height of the filament is 0.7 μm. Scale bar 5 μm.
[0068] FIG. 3 Chemical stability of ADF-4 filaments and of dragline silk threads. (A) ADF-4 filaments were denatured as indicated. Undissolved filaments and aggregates did not enter the gel. Dissolved ADF-4 was detected by immunoblotting using an anti-His 6 antibody. Samples treated with 6M GdmSCN were also silver stained (GdmSCN/S). (B) Air dried ADF-4 filaments on mica and dragline silk threads on polypropylene were incubated for 30 seconds with ˜0.1 μl of each solution as indicated. After rinsing with water samples were examined by light microscopy. Scale bar 25 μm.
[0069] FIG. 4 (A) Filaments of ADF-4 without His 6 -tag formed within Sf9 cells were visualized by light microscopy. (B) The morphology of filaments obtained after dual expression of adf-3 and adf-4 was investigated by scanning electron microscopy. (C) adf-3 expressing Sf9 cell were imaged by light microscopy. (D) Cellular localization of ADF-3. Cells infected for 3 days with adf-3 viruses were subjected to immunofluorescence analysis. (E) ADF-4 aggregates formed after renaturation in vitro visualized by scanning electron microscopy. (F) Chemical stability of ADF-4 aggregates formed in vitro. After treatment with denaturants, as indicated, solubilized ADF-3 was detected by immunoblotting. Scale bars 5 μm (B,E) and 10 μm (A,C,D).
DETAILED DESCRIPTION
Examples
[0070] The improvement provided herein was based on the idea to express and study the two major protein constituents of Araneus diadematus dragline silk simultaneously. Since insects belong to the same phylum as spiders, the inventors chose the insect cell line Sf9 (derived from the fall armyworm Spodoptera frugiperda ), for the expression of adf-3 and adf-4 using baculoviruses as vectors. Recombinant baculoviruses were generated containing partial cDNAs of adf-3 and adf-4 ( 14 ). In order to monitor synthesis, both proteins were provided with a His 6 -Tag. To exclude artificial influences caused by the tag, versions without His 6 -Tag were also employed.
[0071] The recombinant viruses were used to infect Sf9 cells for production of the spider silk proteins in the cytoplasm. After 3 days of incubation, infected cells were lyzed by sonification and insoluble cell contents were separated from soluble material by sedimentation. The sediment was dissolved in guanidinium thiocyanate (GdmSCN) prior to analysis by immunoblotting.
[0072] While a large fraction of ADF-3 was found to be soluble, ADF-4 was almost entirely insoluble three days after infection under the conditions employed ( FIG. 1A ) and independent from the presence of the His 6 -Tag ( FIG. 4A ). Surprisingly, investigating the aggregates in adf-4 expressing cells revealed filaments that coiled throughout the cytoplasm, whereby most of the cells contained only one or few filaments of a uniform width ( FIG. 1B ). In contrast, cells infected with control viruses or the adf-3 encoding virus never produced such filaments ( FIG. 4C , D). Immunofluorescence performed on the infected cells using anti-His 6 antibodies showed specific staining of the filaments thus confirming that the filaments were composed of ADF-4 ( FIG. 1B ).
[0073] Next, the inventors investigated whether ADF-3 and ADF-4 can co-assemble into filaments. The inventors generated a recombinant baculovirus containing both adf-3 and adf-4 under different and independent promoters, using the pFastbacDUAL donor plasmid. Infection of Sf9 cells with this virus resulted in synthesis of both proteins and the formation of protein filaments that showed similar appearance in comparison to the filaments formed by synthesis of ADF-4 alone ( FIG. 4B ). Interestingly, filaments assembled in the DUAL expression system were entirely formed by ADF-4 with no incorporated or stably associated ADF-3 ( FIG. 1C and data not shown).
[0074] In order to study whether the apparent self-assembly is solely based on properties of ADF-4 or whether additional factors or modifications are involved, the inventors created a recombinant baculovirus coding for a secreted form of His 6 -ADF-4. Infection of cells with this virus led to accumulation of ADF-4 in the culture media of the cells ( FIG. 1D ). Immunofluorescence revealed the abundance of ADF-4 containing secretory vesicles at the cell surface of the infected cells ( FIG. 1E ). Strikingly, the inventors did not observe any formation of ADF-4 filaments neither in compartments of the host cells nor in the culture media.
[0075] Silk thread formation generally depends on the protein concentration as well as on additional factors. Interestingly the intracellular pH 6.3 of Sf9 cells corresponds to the pH in the spinning dope prior to silk thread assembly ( 19 ). Further factors required for ADF-4 filament assembly in the cytosolic environment remain elusive. Investigating the self-assembling properties of ADF-4 in vitro stressed the importance of additional factors. Soluble ADF-4 was readily obtained by dissolving filaments in 6 M GdmSCN. Dissolved ADF-4 rapidly aggregated upon removal of GdmSCN by dialysis or dilution.
[0076] However, the ADF-4 aggregates formed in vitro showed neither fibrillar structures nor did they display the chemical stability of ADF-4 filaments formed inside the Sf9 cells (see below and FIG. 4E , F). The above findings indicate the importance of the specific cytosolic environment, which may include additional, so far unresolved, cytoplasmatic factors important for controlled self-assembly.
[0077] Next the inventors characterized the morphology of ADF-4 filaments. The diameters of filaments ranged from 200 nm to 1 μm, however for each single filament the diameter was found to be constant. Furthermore, the filaments showed lengths up to 100 μm and often terminated in knots, branches or formed closed circles ( FIG. 2A , D, E). Filaments displayed a smooth surface and were often associated with nanofibers (diameter˜5 nm) and other protein aggregates ( FIG. 2 ). Immunoblotting, and immunoelectron microscopy indicated that filaments and associated assembly forms were composed of ADF-4 ( FIG. 2C, 3A ). Besides ADF-4 no other abundant protein could be detected in filaments as visualized by SDS-PAGE analysis followed by silver staining ( FIG. 3A ). The low number of filaments per cell and the recruitment of almost the entire cellular ADF-4 into the aggregates indicated that self-assembly of ADF-4 in Sf9 cells is likely to be a nucleated process, which previously has been also suggested for the silk spinning process of Bombyx mori ( 20 ).
[0078] The size of the filaments formed in the Sf9 cells seemed to be constrained by the volume of the cells making them too short for mechanical force measurements typically performed with silk threads ( 21 ). However, the inventors were able to analyze the chemical stability of wet and dry ADF-4 filaments in comparison to natural dragline silk threads of A. diadematus . Dragline threads have been reported to be insoluble in many denaturing agents ( 22 ). Application of 2% sodium dodecylsulfate (SDS) and 8 M urea apparently had no effect on the structure of ADF-4 filaments and dragline threads after 30 s of exposure ( FIG. 3 and data not shown). Immersion of the filaments in 6 M guanidinium chloride (GdmCl) did not lead to solubilization of either ADF-4 filaments or dragline threads, although it did lead to swelling of dragline silk. Such swelling is likely caused by fibre supercontraction ( 21 ) which has previously been described for spider silks immersed in aqueous solutions and which results from reformation of hydrogen bonds in the amorphous matrix ( 21 ). In contrast to the denaturants mentioned above, a small drop of 6 M GdmSCN completely dissolved ADF-4 filaments as well as dragline threads within seconds ( FIG. 3 ). In consequence the inventors conclude that both structures share molecular interactions, which are responsible for chemical resistance to specific denaturants.
[0000] Methods
[0000] Plasmid Construction.
[0079] The partial cDNAs of adf-3 and adf-4 (gi|1263286; gi|1263288 in pBluescriptSK+) were kindly provided by John Gosline (Vancouver, Canada). The cDNAs were cloned into pFastBac™ donor plasmids from Invitrogen. Sequences coding for peptide tags were provided 5′-terminal to the gene fragments. For His 6 -tagged proteins, genes were excised from the host vector using SpeI/XhoI and ligated with equally digested pFastBac™HTa. For T7-taged ( 23 ) proteins, genes were first cloned into pET21 from Novagen using XhoI and EcoRI. The insert including the T7-Tag coding region was then excised with BglII and XhoI and ligated with pFastBac™1 digested with BamHI/XhoI. For co-expressing adf-3 and adf-4, both genes were cloned into pFasBac™DUAL and provided with sequences coding for T7- and S-Tags ( 24 ). The adf-4 gene was excised from pET21-adf-4 with BglII/XhoI and ligated with pFasBac™DUAL cleaved with NheI/BamHI. Two synthetic oligonucleotides (MWG Biotech) were annealed to provide an S-Tag coding sequence, which resulted in double stranded DNA with NheI/BamHI-compatible single strand extensions:
(SEQ ID NO: 5) 5′-CTAGCCCGGGATGAAAGAAACCGCTGCTGCTAAATTCGAACGCCAGC ACATGGACAGCGGTCGG-3′ (SEQ ID NO: 6) 5′-GATCCCGACCGCTGTCCATGTGCTGGCGTTCGAATTTAGCAGCAGCG GTTTCTTTCATCCCGGG-3′
[0080] pET21-adf-3 was digested with NheI/BamHI to remove the T7-Tag coding region. The vector was then ligated with the S-tag encoding DNA. The S-tagged adf-3 was cloned into pFasBac™DUAL-adf-4 using XhoI/XmaI. In the dual construct, adf-3 and adf-4 were under the control of the independent p 10 ( 25 ) and Polyhedrin ( 26 ) promoters. The sequence coding for the secretion signal of Honeybee melittin was amplified by PCR using the pMIB/V5-HisA vector (Invitrogen) as template and the following primers containing CpoI restriction sites:
5′-CCTTCC CGGTCCG CCATGAAATTCTTAGTCAAC (SEQ ID NO: 7) 5′-CCTTCC CGGACCG GGCATAGATGTAAGAAAT (SEQ ID NO: 8)
The resulting PCR product was cut with CpoI and ligated into pFastBac™HTa-adf-4 digested likewise. Positive clones were checked for orientation and correctness by sequencing.
Cell Culture
[0081] Sf9 ( Spodoptera frugiperda ; ATCC#: CRL-1711) cells were propagated at 27° C. in BIOINSECT-1 serum-free insect cell culture medium (Biological Industries). Sf9 cells were grown either as monolayers on cover slips in 6 well plates or in shaker flasks agitated at 80 rpm.
[0000] Production of Recombinant adf-3 and adf-4 Containing Baculovirus
[0082] Competent E. coli DH10BAC cells, containing bacmid (baculovirus shuttle vector plasmid) and a helper plasmid, were used to generate recombinant bacmids according to the manufacturer's protocol (Invitrogen). Insertion of the gene into the bacmid was verified by PCR. Sf9 cells were transfected with recombinant bacmid DNA using ESCORT transfection reagent (Sigma-Aldrich) in 6-well plates. The cells were incubated for 5 h at 27° C., rinsed, and incubated for another 72 h. Media were harvested, centrifuged, and the virus-containing supernatant was tittered by plaque assays.
[0000] Expression of adf-3 and adf-4
[0083] Sf9 cells (3×10 6 cells/ml) were infected with the recombinant viruses at various MOIs (multiplicity of infection) ranging from 0.1 to 10. Three days post infection (PI), cells were harvested by centrifugation at 500×g for 5 min.
[0000] Detection and Solubility of ADF-3 and ADF-4
[0084] Cells were resuspended at 1.2×10 7 cells/ml in 100 mM NaCl, 20 mM N-(2-hydroxyethyl)piperazine-N′-(2-ethanesulfonic acid) (HEPES), pH 7.5 and lyzed by sonification. Soluble and insoluble components were separated by centrifugation at 125,000×g for 30 min. For further analysis, pellets were resuspended in 6 M GdmSCN and dialyzed against 8 M Urea. Supernatant and pellet derived from 1.5×10 5 cells were loaded on 10% Tris-Glycine polyacrylamide gels under reducing conditions and blotted onto PVDF membranes (Millipore). Spider silk proteins were detected using a mouse anti-His 6 monoclonal antibody (Sigma-Aldrich, 1:10,000) or a mouse anti-T7 monoclonal antibody (Novagen, 1:10,000) and anti-mouse IgG peroxidase conjugate (Sigma-Aldrich, 1:5,000) as secondary antibody. An S-Protein peroxidase conjugate (Novagen, 1:5,000) was used to directly detect S-tagged ADF-3.
[0000] Immunocytochemistry
[0085] Cells grown on cover slips at 50% confluency were infected with adf-3 or adf-4 containing recombinant viruses at MOI=10. Three days PI cells were fixed with methanol at −20° C. Cover slips were incubated with mouse anti-His 6 monoclonal antibody (Roche) at a 1:300 dilution followed by Texas Red conjugated anti-mouse secondary IgG at 1:500 dilution. Cells were observed with an Olympus BX51 fluorescence microscope and images were taken with a Magnafire SP camera or analyzed by confocal microscopy.
[0000] ADF-4-Thread Purification
[0086] Cells were resuspended at 1.2×10 7 cells/ml in 100 mM NaCl, 20 mM HEPES, pH 7.5 and lyzed by adding 2% w/v sodium dodecylsulfate followed by incubation at 95° C. for 5 min. Threads were sedimented at 5,000×g followed by washing with 8 M urea and water bidest .
[0000] Atomic Force (AFM), Scanning Electron (SEM) and Transmission Electron Microscopy (TEM)
[0087] Purified filaments were resuspended in water bidest and incubated for 3 min on freshly cleaved mica (AFM) or loaded on Thermanox® plastic cover slips (Nalgene Nunc) (SEM). For AFM, samples were rinsed with water bidest four times and air-dried prior to contact mode imaging using a Multimode SPM (Veeco). For SEM, samples were air dried after removal of the solution, vacuum coated with a gold layer and analyzed with a JSM-5900LV (JEOL Ltd.) at 20 kV. For TEM (JEOL Ltd.) analysis, filaments were adsorbed onto formvar coated grids and negatively stained with uranyl acetate. For immunostaining, fibers were incubated with mouse anti-His 6 antibodies followed by labeling with 18 nm gold-conjugated goat anti mouse IgG.
[0000] Thread Formation of ADF-4 without His 6 -tag
[0088] To rule out possible influences of the His 6 -tag on filament formation, T7-tagged ADF-4 was synthesized in Sf9 cells. The filament formation of T7-tagged ADF-4 was apparently indistinguishable to that of His 6 -tagged ADF-4 ( FIG. 4A ).
[0000] Thread Formation in adf-3 and adf-4 Co-Expressing Cells
[0089] In Sf9 cells co-expressing adf-3 and adf-4, filaments could be detected that displayed an apparently indistinguishable morphology in comparison to filaments formed in cells producing only ADF-4 ( FIG. 4B ).
[0000] Expression of adf-3 in Sf9 Cells
[0090] Although immunocytochemistry revealed fluorescent foci in adf-3 expressing cells, filament-like structures could not be observed ( FIG. 4C ,D). Importantly, ADF-3 synthesized in Sf9 cells was largely soluble. Therefore foci formation represented sub-cellular accumulation rather than protein aggregation.
[0000] In Vitro Assembly of ADF-4
[0091] ADF-4 aggregated upon removal of denaturants by dialysis or after dilution into aqueous buffers. The resulting aggregates did not display any fibrillar morphology ( FIG. 4E ). Testing chemical stability revealed that in contrast to ADF-4 filaments, formed in the cytosol, the aggregates formed in vitro were soluble in 2% SDS or 8 M Urea ( FIG. 4F ).
REFERENCES
[0000]
1. J. M. Gosline, P. A. Guerette, C. S. Ortlepp, K. N. Savage, J. Exp. Biol. 202 Pt 23, 3295-3303 (1999).
2. J. Warwicker, J. Mol. Biol. 2, 350-362 (1960).
3. A. H. Simmons, E. Ray, L. W. Jelinski, Macromolecules 27, 5235-5237 (1994).
4. A. D. Parkhe, S. K. Seeley, K. Gardner, L. Thompson, R. V. Lewis, J. Mol. Recognit. 10, 1-6 (1997).
5. J. D. van Beek, S. Hess, F. Vollrath, B. H. Meier, Proc. Natl. Acad. Sci. U.S.A 99, 10266-10271 (2002).
6. D. H. Hijirida et al., Biophys. J. 71, 3442-3447 (1996).
7. K. Kerkam, C. Viney, D. Kaplan, S. Lombardi, Nature 349, 596-598 (1991).
8. D. P. Knight and F. Vollrath, Proc. R. Soc. Lond. 519-523 (1999).
9. D. P. Knight and F. Vollrath, Naturwissenschaften 88, 179-182 (2001).
10. F. Vollrath, D. Knight, X. W. Hu, Proc. R. Soc. Lond B Biol. Sci. 265, 817-820 (1998).
11. E. K. Tillinghast, S. F. Chase, M. A. Townley, J. Insect Physiol. 30, 591-596 (1984).
12. D. P. Knight, M. M. Knight, F. Vollrath, Int. J. Biol. Macromol. 27, 205-210 (2000).
13. S. Winkler and D. L. Kaplan, J. Biotechnol. 74, 85-93 (2000).
14. P. A. Guerette, D. G. Ginzinger, B. H. Weber, J. M. Gosline, Science 272, 112-115 (1996).
15. J. Gatesy, C. Hayashi, D. Motriuk, J. Woods, R. Lewis, Science 291, 2603-2605 (2001).
16. S. Arcidiacono, C. Mello, D. Kaplan, S. Cheley, H. Bayley, Appl. Microbiol. Biotechnol. 49, 31-38 (1998).
17. J. Scheller, K. H. Guhrs, F. Grosse, U. Conrad, Nat. Biotechnol. 19, 573-577 (2001).
18. A. Lazaris et al., Science 295, 472-476 (2002).
19. V. Vachon, M. J. Paradis, M. Marsolais, J. L. Schwartz, R. Laprade, Biochemistry 34, 15157-15164 (1995).
20. G. Li et al., Eur. J. Biochem. 268, 6600-6606 (2001).
21. Z. Shao, R. J. Young, F. Vollrath, Int. J. Biol. Macromol. 24, 295-300 (1999).
22. S. Lombardi and D. Kaplan, J. Arachnol. 18, 297-306 (1990).
23. Kroll, D. J. et al. DNA Cell Biol. 12, 441-453 (1993).
24. Kim, J. S. & Raines, R. T. Protein Sci. 2, 348-356 (1993).
25. Knebel, D., Lubbert, H. & Doerfler, W. EMBO J. 4, 1301-1306 (1985).
26. Smith, G. E., Summers, M. D. & Fraser, M. J. Mol. Cell. Biol. 3, 2156-2165 (1983).
|
The present invention is directed to a method of producing spider dragline and/or flagelliform proteins. The invention is further directed to a method of producing spider threads and to a dragline/flagelliform protein or dragline/flagelliform protein thread produced by these methods. The invention further provides the use of these proteins/threads in the field of biotechnology and/or medicine, in particular in the manufacture of wound closure or coverage systems, suture materials and in the manufacture of replacement materials, preferably artificial cartilage or tendon materials.
| 3
|
FIELD
Embodiments of the present invention relate generally to the field of wireless telephony networks, and more particularly to a subscriber identity module having a plurality of subscriber identities to be used in devices of said wireless networks.
BACKGROUND
Mobile telephony may provide for wireless voice communication by mobile equipment used in a public land mobile network (PLMN). A user may utilize a mobile station to communicate with other entities that belong to the PLMN or another network that is coupled to the PLMN. The PLMN may itself, contain a number of different network domains. As the station travels from one network domain to another, so must the call handling responsibilities. The number and types of existing network domains continually increase with each one having associated capabilities and standards of communicating designed to match the objectives of the particular domain. Roaming between these different domains and utilization of their particular capabilities and standards may present a variety of challenges for handling calls of a mobile station.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the invention are illustrated by way of example and not by way of limitation in the figures of the accompanying drawings, in which like references indicate similar elements and in which:
FIG. 1 illustrates a mobile communication system in accordance with an embodiment of this invention;
FIG. 2 illustrates a station in accordance with an embodiment of this invention;
FIG. 3 illustrates a subscriber identity module in accordance with an embodiment of this invention;
FIG. 4 illustrates a subscriber identity registration in accordance with an embodiment of this invention;
FIG. 5 illustrates a subscriber identity registration in accordance with another embodiment of this invention;
FIG. 6 illustrates the mobile communication system in accordance with another embodiment of this invention;
FIG. 7 illustrates the mobile communication system in accordance with another embodiment of this invention; and
FIG. 8 illustrates the mobile communication system in accordance with another embodiment of this invention.
DETAILED DESCRIPTION
Embodiments of the present invention may provide a method, article of manufacture, apparatus, and system for utilization of a subscriber identity module (SIM) having a plurality of subscriber identities.
Various aspects of the illustrative embodiments will be described using terms commonly employed by those skilled in the art to convey the substance of their work to others skilled in the art. However, it will be apparent to those skilled in the art that alternate embodiments may be practiced with only some of the described aspects. For purposes of explanation, specific devices and configurations are set forth in order to provide a thorough understanding of the illustrative embodiments. However, it will be apparent to one skilled in the art that alternate embodiments may be practiced without the specific details. In other instances, well-known features are omitted or simplified in order not to obscure the illustrative embodiments.
Further, various operations will be described as multiple discrete operations, in turn, in a manner that is most helpful in understanding the present invention; however, the order of description should not be construed as to imply that these operations are necessarily order dependent. In particular, these operations need not be performed in the order of presentation.
The phrase “in one embodiment” is used repeatedly. The phrase generally does not refer to the same embodiment; however, it may. The terms “comprising,” “having,” and “including” are synonymous, unless the context dictates otherwise.
In providing some clarifying context to language that may be used in connection with various embodiments, the phrase “A/B” means “A or B.” The phrase “A and/or B” means “(A), (B), or (A and B).” The phrase “A, B, and/or C” means “(A), (B), (C), (A and B), (A and C), (B and C) or (A, B and C).” The phrase (A) B means “(B) or (A and B),” that is, A is optional.
As used herein, reference to a “component” may refer to a hardware, a software, and/or a firmware component employed to obtain a desired outcome. Although only a given number of discrete components may be illustrated and/or described, such components may nonetheless be represented by additional components or fewer components without departing from the spirit and scope of embodiments of the invention. The term “element” may be used interchangeably with “component.”
FIG. 1 illustrates a communication system 100 in accordance with an embodiment of this invention. The mobile communication system 100 may include a mobile network device, e.g., a station 104 , coupled to a voice-call continuity (VCC) server 108 of a mobile telephony network 112 (hereinafter “network 112 ”). VCC, as used herein, may refer to services that allow for a handover of an existing voice call from one network access domain to another without interrupting the call. A handover may also be referred to as a handoff.
The station 104 may include a network interface, e.g., a wireless network interface card (WNIC) 116 designed to use an antenna structure 118 to allow the station 104 to communicate with entities of the network 112 via wireless connection with a network access device 120 . The station 104 may also communicate with entities of other networks, e.g., Internet 122 and/or public switched telephone network (PSTN) 126 , that are coupled to the network 112 .
The station 104 may include a SIM 124 having an identity manager 128 to cooperate with the WNIC 116 to register one or more of a plurality of subscriber identities 132 with the VCC server 108 , more particularly, with a database 136 of the VCC server 108 . The VCC server 108 may also include a service manager 140 and a network interface 144 to communicatively couple the VCC server 108 to other network entities, e.g., network access device 120 . The VCC server 108 may provide functionality to receive and process mobile application part (MAP) transactions and messages among the entities of the network 112 .
The registered subscriber identities may be utilized to access various information on the station 104 stored in the database 136 . The service manager 140 may also use the registered subscriber identities as indicia of a requested level of service, which will be discussed in further detail below. In various embodiments the database 136 may be a home location register (HLR) and/or a home subscriber station (HSS).
The subscriber identities 132 , which may be, e.g., international mobile subscriber identities (IMSIs), mobile identification numbers (MINs), etc., may be unique numbers that are associated with the station 104 . The subscriber identities 132 may each be mapped to the same mobile phone number, e.g., mobile station international subscriber directory number (MSISDN). A subscriber identity may be, e.g., a 15-digit number with the first three digits indicating a country code, the next two or three digits indicating a network code, and the remaining digits indicating a unique subscriber number within the network's customer base.
In various embodiments, the station 104 may be any type of device capable of wirelessly communicating with entities of the network 112 . For example, the station 104 may be, but is not limited to, a mobile phone, mobile personal computer, personal digital assistant, or a smart phone. In various embodiments, the antenna structure 118 may include one or more directional antennas, which radiate or receive primarily in one direction (e.g., for 120 degrees), cooperatively coupled to one another to provide substantially omnidirectional coverage; or one or more omnidirectional antennas, which radiate or receive equally well in all directions.
The network 112 may be a network such as a public land mobile network (PLMN) with the entities communicating according to any of a variety of mobile communication standards such as those developed by the 3rd Generation Partnership Project (3GPP), e.g., the Global System for Mobile Communication (GSM) standard. The mobile telephony network 112 may include a variety of mobile access domains. For example, in an embodiment, the network 112 may include a packet-switched Internet Protocol (IP) Multimedia Subsystem (IMS) access domain to provide both mobile and fixed multimedia services for the station 104 . The mobile telephony network 112 may also include circuit-switched (CS) mobile access domain.
In an embodiment, the station 104 may have VCC capabilities that allow for a voice call to be handed-over between heterogeneous access domains, e.g., between an IMS domain and a CS domain. When the VCC enabled station 104 communicates over networks supporting a VCC call a seamless handover between these access domains may occur without a noticeable disruption to the voice call. A network domain providing VCC support may be referred to as an intelligent network (IN) utilizing, e.g., Customized Applications for Mobile Networks Enhanced Logic (CAMEL), operating on a GSM core network.
While VCC services may allow for seamless handover of a voice call, there may be instances in which a VCC call may not be desirable and/or possible. For example, when the call termination and origination points are both in a CS domain providing, or attempting to provide, a VCC call may introduce unnecessary inefficiencies. These inefficiencies may include a high number of control signals being transmitted if VCC support is not found in order to downgrade the service to a non-VCC call. This may be the case if, e.g., a VCC server in the home network domain (e.g., VCC server 108 ) attempts to inform a non-IN, visited network domain using CAMEL procedures that a CS procedure is to be followed. These inefficiencies may result in a call-failure or service delay.
In an embodiment, selective registration of the one or more of the subscriber identities 132 by the identity manager 128 may indicate to the VCC server 108 a preference of the station 104 with respect to VCC services. For example, the station 104 may register a particular subscriber identity to indicate a request for VCC services, e.g., the station 104 can and wishes to receive VCC calls. This may be referred to as a VCC subscriber identity. The station 104 may register another subscriber identity to indicate that VCC services are not requested, e.g., the station 104 is not able to and/or does not wish to receive VCC calls. This may be referred to as a non-VCC subscriber identity.
In various embodiments, the identity manager 128 may determine call-continuity parameters to decide which of the subscriber identities to register. In various embodiments, call-continuity parameters may include any data relevant to determining whether or not a VCC call is possible and/or desirable. Examples of call-continuity parameters will be discussed in greater detail below with respect to various embodiments.
FIG. 2 illustrates the station 104 in accordance with an embodiment of this invention. In this embodiment, the station 104 may receive a SIM card 200 in a port 204 to implement the SIM 124 . The SIM card 200 may be a smart card, e.g., a universal integrated circuit card (UICC), designed to securely store information related to, e.g., identities, subscriptions, security mechanisms, user preferences, etc. The station 104 may include a host 208 communicatively coupled to the SIM card 200 and the WNIC 116 via input/output drivers 212 .
The identity manager 128 may include a SIM application toolkit (SAT) to provide a standardized execution environment to provide interoperability between the SIM card 200 and a large number of stations, regardless of the type or manufacturer of the station. The SAT may allow for the components on the SIM card 200 to utilize certain functions of the station 104 .
FIG. 3 illustrates the SIM card 200 in accordance with an embodiment of this invention. The SIM card 200 may include a processor 304 , memory 308 , storage 312 , and an input/output module 316 coupled to each other via a bus 320 , as shown. The SIM card 200 may also include an input/output module 316 to interface with the port 204 and I/O drivers 212 .
Memory 308 and storage 312 may include in particular, temporal and persistent copies of ID-manager logic 324 , respectively. The ID-manager logic 324 may include instructions that when accessed by the processor 304 result in the SIM card 200 performing operations or executions described in conjunction with the SIM 124 in accordance with embodiments of this invention. In particular, the accessing of the ID-manager logic 324 by the processor 304 may facilitate subscriber-identity selection and registration operations of the identity manager 128 as described herein in connection with various embodiments. The instructions implementing the ID-manager logic 324 may be provided to memory 308 and storage 312 from a machine-accessible medium.
The storage 312 may also include copies of the subscriber identities 132 and other subscriber information. In various embodiments, the storage 312 may store this information in flash memory or some other type of non-volatile storage medium.
In various embodiments, storage 312 may be a storage resource physically part of the SIM card 200 or it may be accessible by, but not necessarily a part of, the SIM card 200 . For example, the storage 312 may be accessed by the station 104 over the network 112 .
In various embodiments, the memory 308 may include RAM, dynamic RAM (DRAM), static RAM (SRAM), synchronous DRAM (SDRAM), etc.
In various embodiments, the processor 304 may include one or more single-core processors, multiple-core processors, controllers, application-specific integrated circuits (ASICs), etc.
In various embodiments, SIM card 200 may have more or less elements, and/or different architectures.
FIG. 4 illustrates a subscriber identity registration in accordance with an embodiment of this invention. In this embodiment, the identity manager 128 may detect a registration event, block 404 . A registration event may be, e.g., a power-on of the station 104 , an initial connection to the network 112 , a location update event (e.g., when the station 104 detects a different area code), etc.
The identity manager 128 may then communicate with the host 208 and/or the network 112 to determine call-continuity parameters, block 408 . In various embodiments, this may include capabilities of the network 112 (and in particular the access domain to which the station 104 is connected), capabilities of the station 104 , and/or settings of the station 104 .
The identity manager 128 may then select one or more appropriate subscriber identities from the subscriber identities 132 , based at least in part on determined call-continuity parameters, and cooperate with the WNIC 116 , either directly or through the host 208 , to register the selected subscriber identities, block 412 .
FIG. 5 illustrates a subscriber identity registration in accordance with another embodiment of this invention. In this embodiment, similar to the above embodiment, the registration may be initiated with a detection of a registration event, block 404 . As discussed above, the SIM card 200 may be compatible with a wide variety of stations, including legacy stations. Therefore, the identity manager 128 may communicate with the host 208 to determine if the station 104 is VCC capable, block 504 . In an embodiment, this may be determined based at least in part on the type of identity request posted to the SIM card 200 from the host 208 . For example, if the VCC flag is set in the identity request from the host 208 , then the identity manager 128 may determine that the station 104 is VCC capable. If the station 104 is not VCC capable, the identity manager 128 may select and register the non-VCC subscriber identity, block 508 .
If the station 104 is VCC capable, the identity manager 128 may determine if the network 112 (and in particular, an access domain to which the station 104 is connected) can support a VCC call, block 512 . Whether the access domain can support a VCC call may be indeterminable by the station 104 . If this is the case, then the identity manager 128 may select and register both the VCC subscriber identity and the non-VCC subscriber identity, block 516 . If it is determined that the access domain cannot support a VCC call, the identity manager 128 may select and register the non-VCC subscriber identity, block 508 .
In some embodiments, the identity manager 128 may be able to determine if the access domain can support a VCC call. For example, if the access domain is the home domain, the identity manager 128 may conclude there is sufficient VCC support. If it is determined that the access domain can support a VCC call, the identity manager 128 may determine whether the station 104 desires VCC calls, block 520 . If the station 104 desires VCC calls, the identity manager 128 may select and register the VCC subscriber identity, block 524 .
The figures to be discussed below may present some examples of specific scenarios in which the station 104 may be deployed in accordance with embodiments of this invention. Other scenarios are within the scope of the teachings of embodiments of this invention.
FIG. 6 illustrates the mobile communication system 100 in accordance with an embodiment of the present invention. In this embodiment the network 112 may be a (visited) home domain 604 . That is, the station 104 may be coupled to a home domain directly, or indirectly through a visited domain. The home domain may be the domain to which the station 104 subscribes and therefore has the primary responsibility for provisioning services to the station 104 and managing billing functions. If the station 104 is roaming in an area not serviced by the home domain it may still connect to the network 112 through a visited network domain that has a subscription agreement with the home domain.
In this embodiment, the identity manager 128 may determine that the station 104 is a legacy station without VCC capability. Therefore, the identity manager 128 may select and register the non-VCC subscriber identity with the VCC server 108 . Communication between the station 104 and other network entities may be transmitted through a router and/or switch 608 (hereinafter “mobile switching center (MSC) 612 ”), which may be coupled to, or integrated with, the network access device 120 shown in FIG. 1 .
An incoming call may be directed to the station 104 from the PSTN 124 through the use of a telephone number, e.g., an MSISDN. This call may be received at a gateway MSC (GMSC) 612 , of the (visited) home domain 604 . The GMSC 612 may transmit a query to the VCC server 108 to determine the location of the station 104 . Information about the station 104 associated with the registered subscriber identity may be returned to the GMSC 612 . This information may include routing information that includes directives consistent with a non-VCC call. The GMSC 612 may then connect a non-VCC call to the station 104 , e.g., by using standard CS call setup procedures.
If the (visited) home domain 604 includes a visited domain, a visiting MSC (VMSC) may be employed in the visited domain to facilitate communications between the station 104 and the home domain.
The VCC server 108 may also use the non-VCC subscriber identity for outgoing calls in this embodiment.
FIG. 7 illustrates the mobile communication system 100 in accordance with another embodiment of this invention. In this embodiment the network 112 may include a visited domain 704 and a home domain 708 . The station 104 may be roaming and therefore may be connected to the mobile communication system 100 through a visited MSC (VMSC) 712 . The identity manager 128 may be unable to determine whether the visited domain 704 has VCC capabilities, e.g., does not know if the visited domain 704 is a CAMEL network. Therefore, the identity manager 128 may select and register both the VCC subscriber identity and the non-VCC subscriber identity.
The VCC server 108 may be able to determine the VCC capabilities of the visited domain 704 , e.g., determine if the visited domain 704 is a CAMEL network. Therefore, the VCC server 108 may be in a position to determine whether to use the VCC subscriber identity or the non-VCC subscriber identity for purposes of call routing. The VCC server 108 may respond with the appropriate subscriber identity when it receives an identity request from the GMSC 612 , in response to the GMSC 612 receiving an incoming call from the PSTN 124 . If the non-VCC subscriber identity is used, the GMSC 612 may use standard CS call setup procedures.
It may be noted that in this embodiment, the selection and registration of the VCC and the non-VCC subscriber identities may be done if the identity manager 128 is unaware of the VCC capabilities of the visited domain 704 and desires VCC services. If the identity manager 128 is unaware of the VCC capabilities of the visited domain 704 and does not desire VCC services, just the non-VCC subscriber identity may be selected and registered.
FIG. 8 illustrates the mobile communication system 100 in accordance with another embodiment of this invention. In this embodiment, the network 112 may include a home domain 708 and the station 104 may be coupled directly to the MSC 608 .
In an embodiment, the identity manager 128 may determine that the station 104 does not desire (e.g., for charging reasons) VCC service or cannot support VCC service (e.g., the station 104 is a legacy device). This determination may be based at least in part on settings of the host 208 , which may be configurable by a user of the station 104 . Therefore, in this embodiment the identity manager 128 may select and register its non-VCC subscriber identity. As a result, the VCC server 108 may return routing information associated with a non-VCC call to the GMSC 612 in response to an identity request. All calls may be routed without VCC service using normal CS call setup procedures.
Although the present invention has been described in terms of the above-illustrated embodiments, it will be appreciated by those of ordinary skill in the art that a wide variety of alternate and/or equivalent implementations calculated to achieve the same purposes may be substituted for the specific embodiments shown and described without departing from the scope of the present invention. Those with skill in the art will readily appreciate that the present invention may be implemented in a very wide variety of embodiments. This description is intended to be regarded as illustrative instead of restrictive on embodiments of the present invention.
|
Embodiments of apparatuses, articles, methods, and systems for utilizing a subscriber identity module having a plurality of subscriber identities for communications within wireless networks are generally described herein. Other embodiments may be described and claimed.
| 7
|
BACKGROUND OF THE INVENTION
This invention relates to a cassette for storing an inked ribbon in which the cassette may be operated in a first mode when a single "color" ribbon is used, and a second mode when a "bi-color" ribbon is used so as to obtain, for example, bi-color printing capability.
Some of the problems with prior art ribbon shifting mechanisms which are used to obtain bi-color printing capability are that they are generally complex, expensive to manufacture, and have a large mass which must be shifted. Some prior art ribbon shifting mechanisms are shown in U.S. Pat. Nos. 3,897,867, 3,904,016 and 3,904,017.
The present invention obviates the problems mentioned in the previous paragraph in addition to realizing the usual benefits derived from ribbon cassettes, ie. low cost, ease and cleanliness of changing ribbons, etc. The cassette of this invention may be used with various business machines like accounting machines, printers, etc.
SUMMARY OF THE INVENTION
This invention relates to a ribbon cassette having a body portion, means for supporting a ribbon in an operating plane, and first and second means connecting the supporting means with the body portion. The second means is removable to enable the cassette to be operated in first and second modes. When operated in the first mode, the supporting means is fixed relative to the body portion for use with single "color" inked ribbons. Upon the removal of the second means, the cassette is enabled to permit the supporting means to shift or pivot relative to the body portion on the first means to obtain bi-color printing capability.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a general, exploded view, in perspective, of a ribbon cassette made according to the principles of this invention, showing a body portion, ribbon supporting means for supporting a ribbon in an operating plane, and a cover portion for the cassette;
FIG. 2 is a plan view of the body portion of the cassette, and first and second means connecting the ribbon supporting means to the body portion; and
FIG. 3 is a cross-sectional view, taken along the line 3--3 of FIG. 2, to show additional details of the first and second connecting means, and the means for connecting the cassette to a utilization device like a printer.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a general, exploded view, in perspective, of a ribbon cassette designated generally as 10 and made according to the principles of this invention. The cassette 10 includes a body portion designated generally as 12, a ribbon supporting means 14, and a cover portion 16.
The body portion 12 (FIG. 1) includes a chamber 18 for storing a ribbon 20, which in the embodiment shown, is an endless ribbon which contains random convolutions or folds when stuffed into the chamber 18. The ribbon 20 exits from the chamber 18 around a post 22, is guided around the ribbon supporting means 14 (as will be described in detail hereinafter) and is returned to the chamber 18 via a feed means including a conventional drive wheel 24 and an idler wheel 26 which is resiliently biased into engagement with the drive wheel 24 by a cantilever type resilient lever spring 28. The drive wheel 24 is rotatably supported in arcuately shaped supports 30, and similarly, idler wheel 26 is rotatably supported in arcuately shaped supports 32 located on the free end of lever spring 28. The drive wheel 24 has a splined driving hole 34 therein which is aligned with a hole 36 in the body portion 12 to enable the drive wheel 24 to be driven by an external driving shaft (not shown) which is associated with the machine with which the cassette 10 is used. When the drive wheel 24 is rotated in a clockwise direction as viewed in FIG. 1, the ribbon 20 is pulled out of the chamber 18 at post 22, is pulled through the ribbon supporting means 14, and is pushed or stuffed back into the storage chamber 18.
The ribbon supporting means 14 (FIG. 2) is connected to the body portion 12 by a first means or hinge means including bar segments 38 and 40, and a second means which is a fracturable segment 42. The ribbon supporting means 14 has wall segments 44, 46 extending therefrom, and the bar segments 38 and 40 are integrally formed therewith as is best shown in FIG. 3. The opposite ends of the bar segments 38 and 40 are integrally formed with walls 48 and 50 which are part of the body portion 12. The fracturable segment 42 is planar, having a reduced, cross-sectional area 52 (FIG. 1), where it is joined to a connecting section 54, and also having a reduced, cross-sectional area 56 where it is joined to a connecting edge 58 of a joining section 60 on the body portion 12.
The ribbon supporting means 14 has channels formed on opposed sides thereof to enable the ribbon 20 to be guided to an operating plane (formed by the spaced, parallel edges 62, 64) as is best seen in FIG. 1. The channels are formed by laterally displaced walls 66, 68 (FIG. 1) and similar, laterally-displaced walls 70, 72 (FIG. 2) to enable the ribbon 20 to pass therebetween as is best shown in FIG. 2. The walls 68, 72 have lip portions 74, 76 respectively, extending slightly therefrom to support the lower edge of the ribbon 20 as it is pulled around the edges 62, 64 of these walls 68, 72 by the drive and idler wheels 24, 26. The connecting section 54 has similar lip portions 78, 80 (FIG. 1) extending from opposed sides thereof to similarly retain the upper edge of ribbon 20. The path of the ribbon 20 from post 22 in FIG. 2 is such that it passes around a post 82 (in which wall 46 terminates), inside wall 70, outside of wall 72, around the edges 64 and 62 (forming the operating plane where the ribbon 20 is supported in operative or printing relationship with a utilization device like a print means 84 and platen 86 as shown in FIG. 3), outside wall 68, inside wall 66, and around a post 88 (in which wall 66 terminates) and is then routed to the drive and idler wheels 24, 26.
The body portion 12, ribbon supporting means 14, bar segments 38 and 40 (forming the hinge means) and the fracturable segment 42 are integrally formed from a plastic material like phenelyene oxide into a single piece construction by conventional injection moulding techniques. Phenelyene oxide is a tough plastic which is manufactured, for example, by The General Electric Company and is sold under that company's trademark "Noryl"; it is a tough and flexible material without being brittle. Another satisfactory plastic material which may be used is a polycarbonate plastic which is sold under the trademark "Lexan".
The cover portion 16 (FIG. 1) is shaped to cover the body portion 12 and thereby retain the ribbon 20 in the cassette 10. In the embodiment shown, the body portion 12 has an opening 90 therein to receive the print means 84 (FIG. 3) and the cover portion 16 has an arcuately shaped section 92 formed therein for the same reason. The cover portion 16 also has holes 94 and 96 therein which are aligned with the tubular posts 98, 100, respectively, which are integrally formed with the body portion 12 to enable a "U"-shaped member 102 to secure the cover portion 16 to the body portion 12 and to a mounting plate 104 (FIG. 3). The "U"-shaped member 102 has legs 106, 108 which are received by the holes 94, 96, and by tubular posts 98, 100 (located in the body portion 12) to detachably lock the cassette 10 to the mounting plate 104 when assembled thereon. The lower ends of the tubular posts 98, 100 have sections 110, 112 which pass through matching holes 105 in the plate 104. When the "U"-shaped member 102 is inserted in the tubular posts 98, 100, the lower ends of the legs 106, 108 (which have trapezoidally shaped sections 107, 109 thereon) cause the sections 110, 112 (FIG. 3) associated with each of the tubular posts 98, 100 to expand and detachably lock the cassette 10 to the plate 104.
The cover portion 16 also has resilient means extending therefrom which means is a cantilever type leaf spring 114. The leaf spring 114 (FIG. 1) is integrally formed with the cover portion 16 and biases the ribbon supporting means 14 in a downward direction (as viewed in FIG. 1) when the fracturable segment 42 is removed.
The cassette 10 can be operated in first and second modes. In the first mode, the fracturable segment 42 is not removed, and therefore, the ribbon supporting means 14 remains fixed relative to the body portion 12 as shown in FIG. 3. Usually, a single colored inked ribbon is installed in the cassette 10 when the cassette 10 is to be operated in the first mode.
When the cassette 10 is to be operated in the second mode, a bi-colored ribbon 20 is installed in the cassette 10 and the fracturable segment 42 is removed by fracturing it. When the segment 42 is removed, the ribbon mounting means 14 is enabled to pivot on the bar segments 38, 40 between first and second positions relative to the body portion 12. The leaf spring 114 biases the ribbon supporting portion 14 in a downward direction (as viewed in FIG. 3) to bring the top half 20A or first color of the ribbon 20 into operative proximity with the print means 84 (which may be a wire matrix printer for example). When it is desired to operate the ribbon supporting means 14 in the second position to utilize the bottom half 20B or second color of the ribbon 20, the ribbon supporting means 14 is merely pushed upwardly (as viewed in FIG. 3) by an external member like a solenoid 116. When the solenoid 116 is energized, its operating plunger 118 engages a contact area 120 on the underside of the ribbon supporting means 14 to push it upwardly. In the embodiment shown, the ribbon supporting means 14 is biased downwardly below the center line 122 to the first position by an angle of about 7 degrees, and is pushed above the center line 122 to a second position by an angle of about 3 degrees by the solenoid 116. The movement of the ribbon supporting means 14 in the downward direction (as viewed in FIG. 3) is limited by the lower end of wall 46 abutting against the lower end of wall 50. The upward pivoting movement of the ribbon supporting means 14 is correspondingly limited.
While the cassette 10 has been described with regard to an inked ribbon 20, it is conceivable that the cassette 10 may store other ribbon like materials like magnetic tape or film whenever shifting is required to obtain the benefits of this invention. Also, while a ribbon cassette 10 of the stuffed ribbon type is selected to portray the invention, reel type cassettes or cassettes employing mobius loops may be employed by simply conventionally adjusting the storage chamber 18 of the cassette 10.
|
A ribbon cassette having a body portion and a nose portion which pivots with respect to the body portion to obtain bi-color printing capability. The cassette also includes hinges and a fracturable member interconnecting the body portion and the nose portion. The fracturable member retains the nose portion in fixed relationship with respect to the body portion; however, upon removing the fracturable member, the nose portion is free to pivot between first and second positions with respect to the body portion and thereby present first and second colors of inked ribbon to an associated print means.
| 1
|
BACKGROUND OF THE INVENTION
1. The field of this invention
is oil well production and servicing.
2. Description of the Prior Art.
The Panhandle of Texas and many other oil fields produce paraffin-base oil, while while other fields produce asphalt-base oil. Paraffin-base oil causes a problem and is expensive to produce because the oil derived continues to release paraffin inside the wells' walls, adhering to tubing, rods, paddles, etc. A sticky, gummy, substance, known as paraffin rather quickly clogs the tubing, thus reducing the efficiency of the energy used for production.
When a well's temperature at oil formation is below 160 degrees fahrenheit, the well is subject to increased paraffin deposit problems. Wells in the Panhandle of Texas have a temperature ranging between 80-85 degrees Fahrenheit, which means that in such wells, a steady build-up of paraffin on the interior within the walls of the wells' tubing occurs as a result of such comparatively low temperatures, which affects the pumping equipment notwithstanding use of rotating paddles.
With the wearing of pump parts, the pump will no longer pump fluids into the above ground storage tanks. This requires the pulling of the pump to the surface to be overhauled or replaced with a pump that will lift properly.
When the pump piston and sucker rods attached thereto are now pulled by conventional practices from the pump's seat, which is initially precisely in the center of the tubing, in returning to the surface the pump piston does not remain in the center of the tubing but scrapes the sides of the interior wall of the tubing string while creating unequal deposits of paraffin on the tubing walls.
This occurs because when the pump has been pulled from its seat and dragged against the tubing wall to the surface, it changes direction as it moves and scrapes the sides of the tubing and paraffin deposit on the wall in some places, leaving a 1/2 inch thick accumulation in others. The bare tubing and 1/2" paraffin patches within the wall create a zig-zag, off-set puzzle which made re-entry of the pump against a maze of friction too great a risk for practical relible economic use.
Producers have ceased the practice of using standing valves, (those valves left in the tubing below the pump which retain the fluids in the tubing when the pump and rods are pulled). This, in turn, causes the fluids to flow back into the well. The reason usually offered for not using a standing valve is the great risk incurred in trying to re-run the pump and rods back into the tubing, as such a practice creates a build-up of paraffin in and on the pump that results in stoppage prior to achieving seating, whereupon the pump and rods must be pulled again. In addition, the tubing must be pulled and steam-cleaned.
The dumping of the fluids back into a well's pay formation is a prime factor in reducing the well's capacity to produce at maximum level and causes much expense later in cleaning the formation with heat, chemicals, or tools. It requires a significant amount of energy to refill the tubing, and the delay in the resumption of production adds to the total loss. Accordingly, by conventional practices, the repair or changing of the pump in order to resume production causes much waste of time, energy, and pre-depletion of the tubing.
SUMMARY OF THE INVENTION
In this system and process pump and rods are lifted in combination with other paraffin deposit removing tools in such a manner to enable the pump and rods to remain substantially in the exact center of the tubing all the way to and from the surface and remove accumulated paraffin from the tubing wall while the tubing remains full of fluid.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic vertical longitudinal overall sectional view of a well and the well tubing and stripper unit 80 therein in an operative position.
FIG. 2 is a diagrammatic vertical longitudinal overall sectional view of a well and a heater unit 30 in a state of operation of that heater unit while supported on a wire line 220.
FIG. 3 is a diagrammatic vertical longitudinal sectional view of heater unit 30 along plane 3A--3A of FIG. 4 and an emptying receptacle therefor.
FIG. 4 is a diagrammatic transverse sectional view of heater unit 30 along broken or stepped section 4A--4A of FIG. 3.
FIG. 5 is an enlarged scale view of apparatus components shown in zone 5B of FIG. 1 and shows the stripper unit 80 in side view with tubing 22 broken away and shown in longitudinal diametral section along plane 5A--5A of FIG. 6.
FIG. 6 is a transverse sectional scale view along plane 6A--6A of FIG. 5 to illustrate the relations of parts of unit 80 as seen from above and to show the diametral opposite position of each member of the sets of blades such as 61 and 62, 63 and 64, 65 and 66, 67 and 68 and the overlapping circumferential relations of the blades of the array 91.
FIG. 7 is an enlarged sectional view of zone 7A of FIG. 5 along plane 7A--7A of FIG. 8 (and plane 5A--5A of FIG. 6) and showing the stripping blade 61 in the position thereof when the stripper unit 80 is moving upwards of the tubing wall 89.
FIG. 8 is a transverse composite sectional view along the broken or stepped section 8A--8A of FIG. 7.
FIG. 9 is a vertical longitudinal sectional view at same scale as FIGS. 7 and 8 along a plane which corresponds to the plane 7A--7A in FIG. 8 and illustrates the position of parts when the stripper unit is moving downward of the tubing wall. Here the blade 61 is out of contact with the interior surface 89 of the tubing 22.
FIG. 10 is a transverse sectional view taken along te plae 10A--10A of FIG. 9.
FIG. 11 is a side view of cutter assembly 180 along direction of arrow 11A of FIGS. 12 and 13.
FIG. 12 is a longitudinal sectional view of cutter assembly 180 along the plane 12A--12A of FIG. 13.
FIG. 13 is a bottom view of assembly 180 along direction of arrow 13A of FIG. 11.
FIG. 14 is an enlarged sectional view along plane 14A--14A of FIG. 13.
FIG. 15 is a diagrammatic vertical longitudinal diametral sectional view of the lower portion, as zone 15A of FIG. 1, of a well as 20 during operation using the trowel 250 and centralizer apparatus 281.
FIG. 16-A is an enlarged diagrammatic view of zone 16A of FIG. 15.
FIG. 16-B is a transverse diagrammatic cross sectional view along plane 16B--16B of FIG. 15.
FIG. 17 is a diagrammatical vertical longitudinal sectional view of a swab 260 in its longitudinally extended and radially contracted position of parts.
FIG. 18 is a view as in FIG. 7 in the longitudinally retracted and radially extended position of parts of swab 260.
FIG. 19 is a perspective view of the resilient sleeve element 231 of the swab 260 in its longitudinally extended and radially contracted position.
FIG. 20 is a top diagrammatic sectional view of portions of stripper unit 80 along plane 20A--20A of FIG. 21.
FIG. 21 is the side view of only the array of the stripper blades of the cutter assembly relative to the nipple; more details of the stripper unit are shown in FIG. 5.
FIG. 22 is a diagrammatic showing of a trowel and the swab 260 in operative position.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The apparatuses described herein operate in a well 20 comprising a casing 21 and string of tubing 22 reaching to a pay formation 23 and provided with a surface rig 24 on surface 25 for raising and lowering well tools on a sucker rod string 120 or on a wire line 220.
The tubing string 22 has at its bottom a conventional pump 26 and a standing valve 27. The conventional pump with a plunger 28 and a traveling valve 29 are supported on the sucker rod string 120. The well is one that develops a typical paraffin deposit layer shown as 19 on the interior wall of the tubing. It is such deposits that are removed by the apparatuses and processes disclosed herein.
The tools described herebelow, by choice, can be used for different procedures, all of which will accomplish the desired result with significant savings, especially in the Panhandle area of Texas where most of the wells are 3,000 feet deep at the pay formations. The top 1,000 feet provides most (about 95%) of the paraffin deposits. These procedures are necessary until all pumps and tubing are adjusted to make possible a withdrawal that retains the pump in the exact center of the tubing. The procedures described comprise the following, all of which are performed while the tubing 22 is full of liquid:
(1) A radial heater 30 is run to liquify paraffin, making possible a smooth re-entry of pump plunger and rods.
(2) One paraffin scraper 180 is used to release paraffin from the top down and
(3) A second scraper 80 is used to release paraffin on moving upwards. The paraffin will float and cause no impediment to re-entry of pump plunger and rods.
(4) An expandible swab 260 is passed downward through the tubing and expands upon pulling upward.
(5) A trowel 250, 1/4 inch larger in diameter than the pump plunger moves down in the exact center of the tubing and
(6) A centralizer unit 281 that guides a pump and thereto attached apparatuses through the tubing.
On pump renewal according to the processes of this invention there are approximately 31/2 barrels of paraffin on the tubing walls, rods, and paddles which are recovered and will be pumped into above ground storage tanks and may be sold as good oil.
The processes described herein will take much better care of a well's ability to produce its natural best and correct usual costly waste of time and energy and are simple and practical; they provide that the standing valve is put in the well to stay and the tubing stays in the well while pump and rods are returned to proper seating. Thereby the paraffin-base well can now compete economically with an asphalt-base well.
THE HEATER UNIT 30
The heater unit 30 comprises a rigid hollow cylindrical shell 31, an upper check valve unit 32, a lower check valve unit 33, and, within shell 31, an upper reservoir chamber 39, an intermediate reaction chamber 51, a lower chamber 46, and a conduit channel 42.
The, cylindrical side wall of shell 31 is imperforate and the shell is joined firmly at its top to the bottom of the upper check valve unit 32 and, at its bottom, to the top of the lower check valve unit 33. An upwardly extending bail or hanger 34 is attached to the top of the shell 31.
The upper check valve unit comprises a conventional valve ball 35 in a seat 36 and is provided with a perforate cage 37. A rigid cylindrical bushing as 38 has a shoulder 38A which shoulder is firmly yet releasably attached to the top of the shell 31 in a water-tight and gas-tight manner, as by threads 38B and the seat 36 and the cage 37 are firmly attached to bushing 38.
The upper chamber 39 is ended or defined at its bottom by a perforated horizontal upper chamber floor plate 40 which has a large lateral opening 41. Hole 41 is located adjacent to the an upwardly extending channel or conduit 42. The channel 42 is separated from chamber 39 by an imperforate curved vertical plate 43 the sides of which plate join the shell wall.
The intermediate reaction chamber 51 extends downward from chamber 39 to plate 47 at the top of the lower chamber 46. The lower chamber 46 is bounded at its top by a rigid perforated rod support plate 47. A mass 53 of loosely packed aluminum rods, as 53A, 53B, and 53C has each rod supported on and extending vertically from the plate 47 and each rod of substantially equal length and diameter as the other rods of mass 53. The rods are 1/4 to 1/2 inch in diameter and 6 to 20 feet long.
Plate 47 has many small holes as 47A and 47B therein. Each hole is smaller in diameter than the diameter of the rods to allow liquor 59 to quickly pass upward therethrough; the conduit 42 extends from its upper opening 42A through opening 50 in the plate 47 to side opening 41 in the plate 40 and the lower end 48 of conduit 42 extends centrally of the shell wall 31 to lower conduit opening 48A so that the upper chamber space 45 and the lower chamber 46 are thereby connected for fluid flow therebetween.
The plate 40 has many small evenly spaced holes therein equal or greater in number then the number of rods of mass 53 to equalize bubble distribution and hold the loose rods below the liquor surface. Plate 40 is loosely attached to shell 31 and may be readily removed therefrom; the rods may be removed from shell 31 by removing bushing 38 and inverting the heater 30.
A heat-producing liquid to which the steel shell 31 is passive or inactive, such as 25% caustic in water, is located in part in conduit 42 and in part in chambers 46, 51, and 39 and extends to an chamber upper liquid surface 44. A space 45 for gas is located between the upper liquid surfaces 44 and 49 and the bottom of the valve 32.
The reaction liquor 59 fills the lower part of the upper chamber 39, all of the interior of conduit 42, and all of the lower chamber 46 and also fills the spaces as 54 between the rods in the intermediate or reaction chamber 51. In the conduit 42 the liquor 59 extends to an upper conduit surface 49.
The lower check valve unit 33 comprises a valve ball 55, a lower valve seat 56, and valve ball cage 57. Unit 33 normally seals the bottom of the lower chamber 46. The seat 56 and the cage 57 are firmly attached to a lower nipple or bushing 58 and the lower valve is normally also closed by a removable external threaded cap 60.
The bushing shoulder is releasably attached as by threads 38B to corresponding threads on shell 31 to allow removal of the bushing 38 from the shell to provide access to the interior of shell 31 to place liquor 59 and the rods in chamber 51 as well as replace such rods; liquor replacement is below described.
In operation of the heater 30, the heater is run into the tubing 22 by a wire line 220 to a location in the tubing 22 below the level of the paraffin deposit 19 to dissolve paraffin and salt crystals that adhere to the interior surface of the tubing 22. The heater heats by circulating 25% caustic soda water solution in contact with and through the aluminium tubing held in chamber 51. Each pound of aluminium generates 18,200 B.T.U.; the chamber 51 may be 29 feet long. The total length of the shell 31 is 30 feet.
The structure of the heater 30 provides that, in operation of apparatus 30 liquid 59 is warmed by the reaction in chamber 51 with the aluminum tubing and generates hot hydrogen gas bubbles as 50A and 50B and 50C. Such bubbles provide for forming with liquid 59 a liquid-gas mixture which mixture flows upward of chambers 51 and 39 to the upper liquid surface 44. The liquid component of that mixture flows over the top of plate 43 to surface 49 and thence down conduit 42 to the horizontally directed opening 48A at the lower end 48 of conduit 42 while the hot hydrogen gas of that mixture first gathers in space 45 and then escapes through valve 32 into the liquid in the tubing 22 above the heater and the heater wall 31 warms the adjacent liquor within the tubing 22. The hot hydrogen gas provides turbulence and also heat to assist in melting the paraffin deposits on the tubing wall adjacent to and above the heater 30. Five gallons of Coal oil are also added to the top of the liquor in the well tubing and in a layer on top of the well liquor in the well tubing. Such coal oil layer dissolves the paraffin scraped off the tubing wall and prevents such scraped paraffin from re-depositing on the tubing wall or on the pump barrel when the pump barrel is subsequently run back into the well tubing to its downhole pumping location. The operation of the heater 30 also causes the salt crystals to dissolve within the water in the well as well as causing the paraffin deposits to become liquid and to float to the top of the water in the tubing 22. The pump and rods may thereafter be put in place with no trouble.
The heater is designed with safety features for its loading, draining, and reloading. The heater starts its reaction slowly from the cold (60-80 degrees Fahrenheit) caustic. After the heater is at location needed in the tubing it takes about 15 minutes before its action is visible at surface as determined from its release of hydrogen gas. When such gas is no longer seen all of the aluminum has been reacted or dissolved; then operator pulls the heater 30 to the surface to drain and refill. If not clean, the chambers 46, 51 and 39 are cleaned by running water through the heater.
To drain the heater 30, the cap 60 is taken off and the opening at the bottom of the valve 33 placed over a receptacle as a 10 gallon pail 142 provided with a top opening 143 and a rigid sloped plate 140 inside of and firmly fixed to a wall of the container 142 below the opening 143. The plate 140 supports a upwardly projecting rigid pin 141 sufficiently thin to fit into the valve seat 56 and such reaches to the level of the opening 143. The opening 143 is of larger internal diameter and size than the external diameter and size of the bushing 58 of lower valve unit 33. With the cap 60 removed, pin 141 is placed in contact with the ball 55 and, on upward movement of the pin, the pin moves the ball upwardly, allowing the spent liquid in chambers 46 and 39 and 51 to safely and completely drain therefrom to the receptacle.
THE STRIPPER UNIT 80
The stripper unit 80 comprises an array of stripping blades 61-68, an upper centralizer 83, a lower centralizer 88, and a support assembly 92. Unit 80 operates in combination with collars 100 and 101. The array of stripping blades comprises a plurality of like sets of stripper blades 93, 94, 95, and 96. Each set of blades (93-96) comprises a pair of circumferentially spaced apart like cutting blades as 61 and 62 in set 93, and like blades 67 and 68 for set 94, like blades 65 and 66 for set 95, and like blades 67 and 68 for set 96. Each cutting blade as 61 has an external cylindrical surface 77 with a radius of curvature the same as the radius of curvature of the interior wall or surface 89 of the tubing, and an upper horizontal cutting edge 111, and a lower horizontal bevelled edge 112, and parallel straight side edges as 151 and 161.
The support assembly 92 comprises a nipple 69, and like pivotal support assemblies as 70 for each of the like blades as 61-68. The centralizers 83 and 88 are directly connected to and supported on the nipple 69. The nipple 69 is formed of two like rigid portions 79 and 78 each semi-cylindrical in shape and firmly joined to each other. Each such portion as 79 and 78 has an exterior chordal portion, 81 on piece 79, 82 on piece 78 for each of the stripper blade sets 93-96. In this particular embodiment shown the nipple is 1 foot long and 3/4 inch in interval diameter to smoothly but slidably embrace the cylindrical center portion 102 of the sucker rod 90.
The sets of blades 93-96 are longitudinally spaced apart from each other along the length of nipple 69 in sequence. Thus, the set of blades 94 is sufficiently spaced below set 93 so that any movement of any one or more blade member as 63 and 64 thereof upwardly to its contracted or raised position, (as shown in FIGS. 9 and 10 for blade 61) that the blades as 63 or 64 will not engage or contact any member of the set of blades 93 thereabove. Similarly, the set of blades 95 is sufficiently spaced below the set of blades 94 so that on movement of any one or more blade member as 65 or 66 thereof upwardly to its raised or contracted position, (as shown in FIGS. 9 and 10 for blade 61) that such blade members as 65 or 66 of set 95 will not contact or engage any member of the set of blades 94 thereabove. The set of blades 96 is sufficiently spaced below the set of blades 95 so that on movement of any one or more blade member as 67 or 68 thereof upwardly to its raised or contracted position, (as shown in FIGS. 9 and 10 for blade 61) that such blade movement as 67 or 68 of set 96 will not contact or engage any member of the set of blades 95 thereabove.
An upper centralizer 84 is formed with four curved flat radially equispaced springs as 84, 85, 86, (and one not shown) to hold the nipple and the attached blades in the center of the tubing. The springs of the centralizers are firmly attached at their ends to the nipple 69 in conventional manner.
The centralizers are slightly oversize, measured across the diameter of the tubing, so as to fit the tubing tightly and hold the nipple and the blades attached thereto from sideways movement transverse to the length of the tubing.
The support assembly 70 which connects each blade as 61 with the nipple 69 is composed of a pair of rigid parallel, laterally or radially projecting ears 71 and 71A, an arm 75 and a pin 73. Each of the ears as 71 has a elongated hole 72 therein for a rigid cylindrical pivot pin as 73. The pivot pin 73 fits into the hole 72, the hole 72 is not circular but is rounded at its ends with the same height as the diameter of the pivot pin and is longer than the diameter of the pin 73 and provides a space 74 for shifting of the pin and blade 61 relative to the nipple 69. The arm 75 is rigid and firmly attaches to the interior surface 76 of the blade 61 below its upper cutting edge 111 while the exterior surface 77 is of the same internal diameter and curvature as the interior surface 89 of the tubing 31.
Each of the bases as 107 of each of the ears 71 and 71A is firmly welded to a chordal portion as 81 of the sleeve or nipple portion 79; a chordal portion 82 of the sleeve or nipple portion 78 is similarly provided with a support assembly 70A like link assembly 70 for blade 62. The rigid steel pivot pin 73 provides for a hinging or pivoting action of the arm 75 about ears 71 and 71A.
A soft rubber C-shaped shim 174 fits in and fills the space 74 between the holding eye or hole 72 and pin 73 to provide elastic yield of the pin in the radial direction to so accomodate for "drift" or change in diameter of the tubing as to avoid interference therefrom during upward and downward travel of the unit 80 with its blades 61-68 through the tubing. The blades 61-68 also are beveled at their top and bottom to freely pass the recesses of the tubing in the vicinity of the collars therefor.
Each of the blades of set 61-68 as 61 have straight vertical sides as 151 and 161 and is in the shape of a cylindrical sector with a square or rectangular outline. The blades 61-68 are formed by cutting a piece of 1/8 inch thick walled stainless steel cylindrical, 2 inch outside diameter, tubing to form 8 like cylindrical sector blanks or pieces each having side edges 11/2 inch long parallel to the central longitudinal axis of the tubing and 11/2 inch wide along the upper and lower edges thereof transverse to the longitudinal axis of the tubing. Thereby the blanks for the stripper blades as 61-68 are formed each with an curved exterior surface of one inch radius of curvature, which matches the inner surface of the tubing wall curvature. The upper blank edge is sharpened and the lower edge bevelled before firmly attaching to a steel arm as 75 by welding.
In the cutting position of parts of the unit 80 the portion of the interior cylindrical surface 89 of the tubing 22 contacted by the cutting edges of the blades of the set of blades 93 overlap the edges of the portions of the interior cylindrical tubing surface 89 contacted by the cutting edges of the blades of the neighboring set of blades 94 as shown in FIGS. 5 and 6. In the cutting position of parts of the unit 80 the portions of the interior cylindrical surface 89 of the tubing 22 contacted by the cutting edges of the set of blades 94 overlap the portions of the interior cylindrical surface 89 contacted by the cutting edges of the blades of the set of blades 95 as shown in FIGS. 5 and 6. Also, in the cutting position of parts of the unit 80 the portions of the interior cylindrical surface 89 of the tubing 22 contacted by the cutting edges of the blades of the set of blades 95 overlap the edges of the portions of the interior cylindrical surface contacted by the cutting edges of the blades of the set of blades as 96 as shown in FIG. 5 and 6. In the cutting position of parts of the unit 80 the portions of the interior cylindrical surface 89 of the tubing 22 contacted by the cutting edges of the blade of the set of blades 96 overlap the edges of the portions of the interior cylindrical surface 89 contacted by the cutting edges of the blades of the set of blades 93.
The blade 61 is symmetrical about a vertical center plane 160 (the same plane as 5A--5A in FIG. 6) and extends circumferentially for 60 degrees from a counterclockwise side edge 161 to a clockwise side edge 151 (shown in FIG. 6) and has a center plane of symmetry which passes through arm 75 as shown in FIG. 6 at zero (0) degrees to plane 5A--5A as shown in FIG. 6 and 8. Blade 68 also extends circumferentially for 60 degrees, but its center plane is 45 degrees counter-clockwise from plane 160. Blade 68 extends clockwise located blade side edge 158 located 15 degrees counter-clockwise of the center plane 160 of blade 61 to a counter-clockwise blade side edge located 75 degrees counter-clockwise of the center plane 160 of blade 61.
The cutting edge of the blade 63 also extends circumferentially for an arc of 60 degrees from a counterclockwise blade side edge 163 located 15 degrees clockwise from the center plane 160 of blade 61 to a clockwise blade side edge 153 which is located 285 degrees (measured counter-clockwise) from the center plane 160 of blade 61. The relations of the other blade side edges and cutting edges and the centers of those blades are as set out in Table 1 below, and are illustrated, insofar as shown, in FIGS. 5 and 6.
As shown in FIGS. 5 and 6 and as set out in Table 1 the clockwise blade side edge 151 of the cutting edge of blade 61 extends angularly clockwise of the counter-clockwise side edge 163 of the cutting edge of blade 63 and the counter clockwise side edge 161 of the cutting edge of blade 61 is located in the counter-clockwise direction of the clockwise edge of the blade 68 in the set of blades 96. Thereby the cutting edge of each of the blades as 61 overlap the circumferentially neighboring cutting edges of the blades (as 63 and 68) of the totality of remaining sets of blades of the array of blades 91.
In the preferred embodiment shown, the radial length of the arm 75 of the set of blades 93, and the radial length of the like arm 175 of the set of blades 94 are offset from each other at an angle of 45 degrees; similarly the arms as 75 (for blade 61) of all of the blades 61-68 are arrayed with equal angular spacing between such arms (and blades) between angularly (although not longitudinally ) neighboring arms (and blades) as shown in FIG. 6 and set out in Table 1.
The blades 61-68 each extend for 60 degrees circumferentially adjacent the inner surface 89 of the wall 22 from the blade clockwise side edge to the blade counter-clockwise side edge. Thus the side edge to side edge circumferential extent or distance or arc (60 degrees) covered by the cutting edge as 116 is greater than the amount of (45 degrees) offset or angle between the center planes of each such blade and the center plane of the most circumferentially proximate or neighboring blade (as 63 and 68). Thereby the cutting edges of the blades of the array of sets of blades 91 overlap each other circumferentially although those blades are spaced apart along the length of the nipple or sleeve 69 sufficiently so that none of the blades can contact each other or mechanically engage with each other especially during the pivoting movement of such blades from their lowered and laterally or radially extended paraffincutting position (as in FIGS. 7 and 8 for blade 61) to their raised and contracted or centrally located or released position (as shown in FIGS. 9 and 10 for blade 61).
TABLE 1______________________________________Blade CC P CL______________________________________61 (161) 30 0 330 (151)63 (163) 345 315 300 (153)65 (165) 300 270 240 (155)67 (167) 255 225 195 (165)62 (162) 210 180 150 (152)64 (164) 165 135 105 (154)66 (NS) 120 90 65 (156)68 (NS) 75 45 15 (158)______________________________________
CC=counterclockwise position of blade edge shown in parenthesis.
CL=clockwise position of blade edge shown in parenthesis.
P =position of center line of blade.
NS=not shown.
In the array 91, the central longitudinal axis of each cylindrical pivot pin as 73 is located below the lower edge as 112 of the corresponding blade as 61 and the bottom edge of each arm 75 is supported on the top edge of a rigid support plate as 110 firmly attached to the nipple 69 when the blade 61 is in its lowered or extended cutting position, as shown in FIGS. 7 and 8. In the position of parts shown in FIGS. 7 and 8 the upper, cutting, edge 116 is close to the interior surface 89 of the tubing 22 except for a very narrow surface 117 (to avoid catching on edges of tubing near the recesses thereof). Upper cutting edge 111 is bevelled inward and downward at a wide (1/8 inch wide) central frustoconical surface 115. A sharp cutting edge 116 is located at the junction of a vary narrow (1/64 inch to 0.01 inch) upper lateral outwardly and downwardly bevelled frustoconical surface edge portion 117 and surface 115.
Each sucker rod 90 of the sucker rod string 120 has a central cylindrical portion 102, an upper connector end portion 103 and a bottom connector end portion 107. The upper end portion 103 has a lower frustoconical portion 104 and an upper square in transverse section portion 105. The upper portion 105 has a threaded connector as 106 attached thereto for attachment to an adjacent sucker rod as 131 in the string 120. The bottom connector portion 107 has a upper frustoconical portion 108 and an enlarged square in transverse section portion 109.
A first, lower, cylindrical rigid collar 101 of which the right half is shown in diametral longitudinal section in FIG. 5 and left half is shown in side view has an upper flat surface 121 and a lower central generally frustoconical surface 122 and a cylindrical outer surface. The collar 101 slidably embraces the cylindrical portion 102 of the sucker rod 90 and makes a smooth fit over the frustoconical portion 108 at the junction of the upper end of the lower connector portion 107 of the sucker rod and the lower part of the cylindrical portion 102 of the sucker rod 90.
A second, upper, collar 100, shown in diametral longitudinal section in FIG. 5 has a lower flat surface 125 and a upper generally frustoconical interior surface 126. That upper frustoconical surface slidably embraces the cylindrical portion 102 of rod 90 and makes a smooth fit over the lower generally frustoconical surface 104 at the junction of the lower end of the upper connector portion 103 and the upper end of the cylindrical portion 102 of that sucker rod 90. The upper flat surface 121 of the lower collar 101 and the lower flat surface 125 of the upper collar 100 both are attached to and surround and slidably fit over the sucker rod cylindrical portion 102 and prevent the stripper unit sleeve or nipple 69 from jamming on the frustoconical surfaces 104 and 108 usually found at the lower and upper end portions of the sucker rod as 90. The combination of collars as 100 and 101 and stripper unit structure permit that the sucker rod upon which the stripper unit 80 is supported may move upward and downward during the pumping operation of the sucker rod string with the nipple 69 of the unit 80 sliding on the central cylindrical portion 102 of the sucker rod 90. Thereby, when the movement of the sucker rod 90 would tend to result in movement of the collars adjacent to or past the position of the stripper unit 80 the lower surface of the upper collar (or the upper surface of the lower collar) nudges and engages and moves the adjacent top or bottom) edge of the sleeve 69 of the unit 80 and thereby moves the unit 80 downward (or upward respectively) until such unit 80 is moved to a position whereat further reciprocation of the sucker rod does not further move the unit 80. However, on upward movement of the sucker rod and pump barrel during removal of the pump, the blades 61-68 of the stripper unit 80 move to their wall-contacting position as in FIGS. 7 and 8 and the entire unit 80 is urged and moved upward while supported by the engagement of the lower collar 101 with the enlarged portion 107 of the sucker rod as 90 without wedging thereon.
The nipple 69 is made of two semi-cylindrical mating portions 78 and 79 each with one half of the stripper blades, support arms therefor, and centralizers firmly attached thereto. The two halves of the nipple and associated parts of the stripper 80 are joined together as by welding while located on the sucker rod portion as 102 to which the stripper unit is to be slidably attached.
To operate the stripper 80, it is attached to the portion as 102 of a sucker rod as 90 to be located in the tubing string 32 below the level of paraffin formation, as 19. Thereby the exterior surfaces of the cutter blades 61-68 may initially directly contact and rest upon a portion of the interior surface of the well tubing that is free of paraffin. Thereby, the cutter blades may be readily moved to their expanded position, shown in FIG. 6, by jogging the rod string or applying downward impact thereto, which will move the cutter blades to their expanded cutting position as shown in FIG. 6 if such blades are not already in such position. Such positioning of the cutter blades is effected and retained immediately after raising the sucker rod string and removing the pump barrel upward of the pump a short distance for replacement thereof and before the stripper unit 80 reaches the level of paraffin formation. When the stripper unit is moved downward with the sucker rod string to its proposed position (below the level of paraffin formation) it moves with the blades 61-68 in their retracted position (shown in FIGS. 8 and 9) due to the friction of the fluid in the well acting against the arms as 75. When the stripper units is so moved any paraffin remaining on the tubing wall and contacted thereby will locate on the inner surfaces of the cutter blades, not on the outer surface thereof, and so will not inhibit the outer surfaces of the cutting blades from making contact with the inner wall of the tubing, as is necessary for the cutter blades to subsequently effect their paraffin-removing action.
A straight line from the center of each pivot pin 72 to the geometrical center of each cutter blade as 61 in apparatus 80 is substantially at 45 degrees to the horizontal (when the sucker rod extends vertically). FIGS. 5 and 6 are drawn to scale to better illustrate the dimensions of a particular embodiment of apparatus 80 in a 2 inch internal diameter tubing 22.
On downward movement of the sucker rod string when the pump is being replaced in the well, with the stripper unit 80 attached to a rod as 90 in the string 120, the lower surface 125 of the upper collar 100 engages the upper edge of nipple 69 of the stripper unit 80 and moves that unit 80 downward with the sucker rod as 90 to which that collar is attached until the sucker rod string is in its operative pumping position. Reciprocation of the sucker rod string may cause the collar 100 to engage the sleeve 69 of the unit and move it downward to such a position that further reciprocatory movement of the sucker rod string does not further move the unit 80 and the unit 80, held by the centralizers thereof, stays fixed in location while the sucker rod moves up and down until such time as the rod string is withdrawn from the tubing. At that time the upper flat surface 121 of the lower collar 101 engages the bottom end of the sleeve or nipple 69 and forces the stripper unit 80 upward of the tubing while the stripper blades 61-68 engage and then remove paraffin adjacent the tubing walls. Thereby, although each sucker rod as 90 has an upper frustoconical connector portion 104 and a lower frustoconical connector portion 108 (which releasably yet firmly connect with adjacent upper and lower sucker rods 131 and 132 by threaded connections as 106 in such enlarged portions) the collars as 100 and 101 prevent the sleeve or nipple 69 of the stripper unit 80 from wedging and/or jamming on the frustoconical portions of the sucker rods.
When the well is pumping, the rod portion 102 travels inside the nipple 69 and the stripper unit 80 is stationary.
There is more than ample cross section area for the well fluids to travel through the spaces as 128 between parts of the stripper unit 80 when the stripper 80 is raised either by a wire line or by attaching of the stripper to the sucker rod string. The stripper paraffin comes to the surface of the well fluid and does not interfere with the pump re-entry inasmuch as the paraffin deposits as 19 are usually located at about 1,000 feet below the surface of the ground and the pump is located another 1,000 or 2,000 feet below that location.
CUTTER ASSEMBLY 180
A cutter assembly 180 is provided for operation with the system herein provided to remove paraffin deposits as 19 from well tubing walls as 22 and allow the pump plunger 28 to be withdrawn and reinserted in operative position in the pump barrel 26 at the bottom of the well tubing. The cutter assembly 180 comprises a tooth support ring, 181, ring support arms 182, 183, and 184 and a support rod 185. The support rod is a rigid steel rod, 5/8 inch in diameter, attached to a connector 106 such as used on a sucker rod. The rod 185 has an upper socket 188 for connection as by coupling 186 to another sucker rod as 187, as 90, in a rod string as 120.
The tooth support ring is a solid rigid tubular element 3" long with an upper set of teeth 190 and a lower set of teeth 194 and 17/8" outside diameter. The upper set of teeth 190 comprises a set of upper peripheral teeth 191 and an upper central set of teeth 192. The lower set of teeth 194 comprises a lower peripheral set of teeth 195 and a lower central set of teeth 196. Each of the teeth of the lower peripheral set, as 197, comprises an inwardly and upwardly sloped surface 198 with a terminal or peripheral cutting edge 199 lying in the outer surface 193 of ring 181. Each tooth, as 200, of the lower central set comprises an oblique upwardly and inwardly directed flat oblique surface 201 with a terminal cutting edge 202 lying in the outer surface 193 of ring 181.
The teeth of the upper peripheral set of teeth comprise an oblique inwardly and downwardly sloped surface 203 with a terminal cutting edge as 204 lying in the outer surface 193 of ring 181. Each of the teeth in the upper central set of teeth comprises an oblique downwardly and inwardly sloped surface 205 with a terminal cutting edge 206. The edges of the lower peripheral set of teeth lie in a first flat plane and the edges of the lower central set of teeth lie in a second flat plane above or longitudinally spaced away from the first plane. The upper central teeth cutting edges lie in a third flat plane above the second plane and the upper peripheral teeth cutting edges lie in a fourth flat plane above or spaced longitudinally of the ring 181 from the third plane.
These first, second, third, and fourth flat planes are all parallel to each other and are all perpendicular to the central longitudinal axis of the cylindrical outer surface 193 of the ring 181.
In a preferred embodiment the ring 181 is three inches long from its top edge to bottom edge, i.e. from the first plane to fourth plane and there is 18 inches from the first plane to connector 106.
In operation of tool 180 in a well in which the tubing walls are already coated with paraffin deposits, when the pump is "pulled", and some paraffin remains on the walls of the well tubing, the tool 180 is then moved downward of the well tubing on the sucker rod string and scrapes paraffin from the tubing walls. The space 209 between arms 182 and 183 and space 208 between arm 183 and 184 and the space 207 between arms 182 and 184 is large enough to permit free passage of the scraped paraffin therethrough without accumulation or blockage. The scraped-off paraffin floats to the top of the well fluid and is preferably caught or dissolved in a layer as 210 of coal oil added to the well fluid. The tool 180 thus serves to clear paraffin accumulations from well tubing in wells which have an accumulation thereon when treatment by this system starts. When the well wall is cleaned before the pump is added the stripper tool 80 is particularly effective in operation and cleaning of a paraffin producing well.
THE TROWEL
According to this invention a solid firm cylindrical mass 250, 4 inches long and 15/8 inch o.d. composed of 11/2 lb. barite, 11/4 lb. soap, and 11/4 lb. soda is attached to the gas nipple at the bottom of the pump plunger 28 as shown in FIG. 15 prior to passing the plunger through the tubing string to the seat therefor, as 251 while that plunger is attached to the sucker rod string. The mass has a hardness on the mho scale of 2 to 3 and has the hardness of a cake of hand soap. It develops a sufficiently slippery surface when in the well fluids to allow the pump barrel to slide freely thropugh the tubing and is sufficiently mechanically strong to support the 11/2 inch diameter pump barrel in position spaced away from the tubing walls while the barrel is moving down the tube against the friction resistance of the tubing wall contacted thereby and has a frustoconical lower end.
The trowel 250 loosely fits the interior wall 89 of tubing 22 (2 inch internal diameter) and so serves to push before it any small amount of remaining paraffin adherent to the walls of the tubing and spread it on the tubing wall in a sufficiently thin layer that such paraffin does not contact nor adhere to the pump barrel. The mass 250 is thus sufficiently mechanically stable to space and protect the barrel surface from contact with the sides of the tubing; this spacing action avoids contact of the barrel with small accumulations of paraffin on the sides of the pump and valves associated therewith as might interfere with the subsequent pumping action of the pump. Not only does the trowel serve to protect the pump from paraffin accumulation thereon while passing to its seat but also it serves to centralize the pump plunger and locate it in the pump seat therefor. After the plunger has reached its seat the trowel mass 250 may be readily and reliably disintegrated by striking that mass against the pump seat because the trowel mass has insufficient compressive strength to withstand such stress and then crushes and is dissolved in the well fluid and permits the pump barrel to be located in its seat free of any accumulations thereon.
SWAB 260
The swab 260 comprises a rigid shaft 261, an upper, movable, rigid, weight sleeve unit 271, and a resiliently expansible sleeve unit 231.
The shaft unit 261 comprises a central rigid cylindrical rod 262 having substantially the same external diameter as the cylindrical portion of the sucker rods of the sucker rod string. The unit 261 also comprises a lower conical end 264 which conical end has a pointed lower end 254A and an upwardly extending skirt portion 265. The skirt portion 265 has an internal threaded portion 266 which matches with and is joined to the threaded shaft portion 263. The upper edge 267 of the skirt 265 has a frustoconical surface which extends downwardly and inwardly from its exterior surface to the exterior surface of the shaft 262.
The shaft 262 is provided with a plurality of transverse notches 268 and 269 which extend transversely of the length of the shaft 262. These notches are chordal in shape and provide for engaging holding members as below described. These chordal notches are equal in size and shape and spaced along the length of the shaft 262 near the junction of sleeve end 279 with the exterior surface of the shaft 262. The cylindrical surface 262 and the exterior surface of the skirt portion and the conical portion 264 of the unit 261 are coaxial with each other.
The resilient and expansible sleeve unit 231 comprises a solid mass of oil resistant rubber which is located between the upper weight sleeve unit 271 and the conical end portion 264 of the shaft unit 261 and peripheral to the outer surface of the rod 262.
The unit 231 has a cylindrical outer surface 232, which, in its contracted stable state, is of the same outer diameter as the outer surface of the sleeve 272 which is also the same outer diameter as the maximum diameter of the conical end 264 of the shaft unit 262. The unit 231 also has a top frustoconical surface 234 which is sloped outwardly and radially or outwardly and downwardly and matches the outward and downwardly directed frustoconical surface 275 at the bottom of the sleeve 272. The unit 231 also has a bottom frustoconical surface 235 which matches and has the same slope as the frustoconical surface 267 at the upper edge of the skirt 265 at the end 264 of the shaft unit 261. In the longitudinally contracted and radially expanded position of parts of the swab 260 the outer surface 232 expands to the position shown in FIG. 18 to meet and slidably engage the wall of the tubing. The expansion is controlled so there is a sliding and swabbing action rather than a locking action of the sleeve unit 231 with the interior wall 89 of the tubing 22. Such dimensional control is achieved by the relationship of the notches as 268 with the locking element on the sleeve unit 271. The sleeve unit 271 is provided with resilient locking means such as lock washers or wires, as 277 and 278, which engage the notches as 268 and 269 and firmly hold the unit 231 in its expanded position.
The shaft 262 freely slides within the cylindrical hollow of the cylindrical surface 233 of the sleeve unit 231 as well as within the inner surface 274 of the weight sleeve 272.
The upper movable rigid weight sleeve unit 271 comprises a rigid cylindrical sleeve 272 which is coaxial with the shaft 262, which shaft also is coaxial with the frustoconical portion 264. The sleeve 272 has an outer surface 273 and an inner cylindrical surface 274 both coaxial with each other and with the shaft 262. The inner surface 274 forms a readily slidable fit with the exterior surface of the shaft 262. The sleeve has a bottom edge 267 which is frustoconical in shape and slopes upwardly and inwardly at an angle of about 45 degrees to the central longitudinal axis of the shaft 262.
The sleeve 272 is firmly attached to releasable locking means 277 or 278 which are designed to be engageable with the notches 268 and 269 on the shaft 262.
In the diametrically extended longitudinally contracted position of the swab 260 as shown in FIG. 18 the sleeve 271 is moved downwardly of the shaft 262 and the flexible sleeve 231 is expanded to an outer diameter that resiliently yet slidably contacts the inner wall 89 of the tubing 22.
The flexible sleeve 231 bows out on its interior surface 233 as well as on its exterior surface 232 when it is compressed longitudinally as shown in FIG. 18. When so compressed longitudinally the channels 315-317 in the upper sleeve 271 and groove 319 in the rod 261 provide communication of the fluid 314 in the tubing above that sleeve with sleeve interior surface 233 to apply the fluid pressure of such fluid above the flexible sleeve to such interior surface. As the interior diameter of the tubing is only two inches and the shaft 262 is usually 3/4 inch diameter the sleeve only needs to expand from 11/4 inch outside diameter (or 11/2 inch if such size is used) to 2 inch outside diameter or a maximum of 3/8 inch expansion on each side of the rod 261. Accordingly only a small longitudinal displacement of the upper weight sleeve 271 is required for the flexible sleeve to forcefully contact the interior surface of the tubing and effect its swabbing action on the paraffin deposit on the interior surface of the tubing 22. Thus a 1/2 inch longitudinal displacement for a sleeve 271 with 11/2 inches between outer portion of lower edge 275 of sleeve 271 and outer portion of upper edge 267 of skirt 265 provides for a cylindrical or flattened area of contact between the outer surface of sleeve 232 and the interior surface 89 of the tubing 22 as shown in FIG. 18 at 323.
In operation of the swab, the swab 260 is lowered down the tubing 22 by a wire line as 220. On jogging or on sharp impact applied to the swab 260 as by following a small but sharp lowering of the wire line the weight sleeve 271 moves to its lowered position as shown in FIG. 18 and the sleeve 231 expands to contact the inner wall 89 of the tubing 22 and so remove, on movement longitudinally of the tubing, to remove paraffin therefrom and/or to even out the deposits of paraffin on that tubing so that the pump may pass through that tubing without difficulty.
The sleeve 271 is held in position relative to the conical end 264 of the shaft 262 by engagement of the notches as 268 and 269 on the shaft 262 with the holding means or lock washers as 277 and 278 on the sleeve unit 271. The unit 260 is held on a rod string or on a wire line by a welded attachment as 380 to a connector as 186 to a wire line or a connector to a tubing string as desired by the operator.
Further, the swab may be provided with a hinged connection locating it at the bottom of a separate trowel as in FIG. 22. The flexible connection allow pulling up of the swab in the center of the tubing.
The swab 260 is used in a combination 320, with a trowel 322 as in FIG. 21. A joint 321 between the trowel 322 and swab 260 is a flexible joint so that the two tools may traverse irregularities in the interior surface of accumulations of paraffin deposits on the interior surface of the tubing. The trowel is 11/4 inch outside diameter and 14 inches long and weighs 121/2 pounds. The swab 260 is 10 to 14 inches long.
CENTRALIZER
A centralizer apparatus 281 is attached to the bottom end and top end of the pump 26 to provide that the pump 26 may come to the surface 25 while traveling in the center portion of the tubing 22. Usually, the pump has an outside diameter of 11/2 inch. The centralizer apparatus 281 comprises a pair of like centralizer units upper unit 282 and lower unit 283. Each centralizer unit as 282 comprises a cuff 284, a blanket 285, and an array of pins 286. Each cuff is a thin curved steel plate formed into a C-shape which closely and firmly fits the outside of the pump 26. The array of pins comprises three like sets of pins as 287, 288 and 289. Each set as 287 comprises a set of three like member pins as 290 and 291 and 292. The member pins as 290, 291, and 292 of each set of pins as 287 are located in a straight line parallel to the length of the pump--which length is parallel to the central longitudinal axis of the tubing string 22 in which the centralizer apparatus 281 operates. Each set of pins as 287 comprises three like rigid pins 290, 291, and 292. Each pin extends radially from the central longitudinal axis of the cylindrical pump 26 and each pin is firmly attached at its central end to the cuff 284. The three pins as 290, 291, and 292 of each set are arranged with the middle pin, as 291, halfway between the upper pin 290 and lower pin 292 of such set. Each set of the array, as 287, is located 120 degrees from the neighboring set, as 288, and each set has the same longitudinal spacing of the member pins thereof. The middle pin of all three sets of pins lie in the same flat plane transverse to the length of the tubing string in which the pump is located.
Each cuff, as 284 (and 284' in centralizer unit 283) is formed of rigid sheet steel about 0.010 inch thick. The blanket 285, is a sheet of soft steel screening located and compressed between the pump 26 outer surface and the cuff as 284 inner surface to provide improved frictional engagement between the pump outer surface and the inner surface of the cuff. Each cuff and screen are firmly held to the pump by a plurality of steel wires as 293 and 294 the ends of each of which wires are tightly twisted together and folded as at 295 and 296 to be located in the space 297 between the ends 298 and 299 of the cuff as 284. The components of unit 283 have same referent numerals as in unit 282 but with addition of a prime (') as 284' and 285'.
The radial edges of the pins are bevelled or rounded as hemispheres and extend to a circle of 17/8 inch diameter, which circle is co-axial with the central longitudinal axis of the cylindrical pump 26, to which the units as 282 and 283 are attached.
The sets of pins serve to bridge over the spaces as 301 between tubing units as 302 and 303 of the tubing string 22 which tubing units are joined by collars as 304.
Each pin as 288 of the array of pins 286 comprises a rigid large diameter thin steel head portion 306 and a thin (1/16" to 1/8") and 3/16" long rigid steel shaft 307. The pin shaft 307 is firmly affixed to and extends perpendicularly to the flat head portion therefor, as 306. The shaft portion of each pin extends through a hole therefor in the cuff as 284 and extends in a radial direction from the central longitudinal axis of the cylindrical exterior surface of the pump. Each of the pins is sufficiently stiff and thin to pass through any usual paraffin deposit on the tubing wall but not jam or wedge on the wall so that the array of pins serves to locate the pump in the center of the tubing during travel of the pump along the length of the tubing when in the vicinity of paraffin deposits on the interior wall of such tubing.
Each blanket as 285 is a layer of soft wire screening and has a plurality of cut-out areas as 310, 311, 312, 313. Such cut-out areas encircle the heads as 306 of each pin as 288 in the array of pins on each centralizer unit as 282. Such cut-out areas serve to locate the pin heads as 306 and also avoids concentration of pressure between cuff and pump barrel surface near the pin head and causes the screening to engage evenly with the cuff and pump surface and hold each cuff and the pins held by such cuff in a firm fixed location on the pump barrel.
The centralizer unit 280 formed by the pump 26 and centralizer apparatus 281 may support the swab 260 and may be supported and manipulated by a wire line or rod string in the tubing 22.
FIG. 20 is a simplified top diagrammatic view of parts of the stripper assembly; it shows only a single stripper blade showing its pivotal connection to the nipple and its relations to the well tubing 22; more details of the array of blades are shown in FIG. 6. FIG. 21 is a side view of the array of the stripper blades only relative to the nipple; more details of the stripper unit are shown in FIG. 5.
Resilient spring means attached to and extending between each cutter blade as 61 and the support as 110 therefor or nipple 69 may be used to positively urge each blade as 61 to its operative position as shown in FIG. 7 at 113.
In the cutter assembly 180, the ring 181 may be cut through at a narrow (1/21") gap 381--about the width of a saw blade. The arms 181, 182 and 183 resiliently support the ring in position adjacent the inner tubing wall. The ring thereby may be contracted to accomodate to drift (i.e. dimensional irregularities) of the tubing so the outer surface of the ring hugs the wall while the cutting edges of the cutter assembly shave paraffin off the tubing wall.
|
In the systems and processes pump and rods are lifted in combination with other paraffin deposit removing tools in such a manner to enable the pump to remain substantially in the exact center of the tubing all the way to and from the surface and remove accumulated paraffin from the tubing wall while the tubing remains full of fluid.
| 4
|
FIELD OF THE INVENTION
[0001] The present invention is generally directed to an electronic device that is used in a health care setting, such as a hospital, nursing home, clinic, or similar environment. By way of example, the electronic device may be a hand-held pillow speaker kept at a patient's bedside for remotely controlling a television, room lights, or other electronic items in the room, and for communicating with nursing staff or other personnel.
BACKGROUND OF THE INVENTION
[0002] Many electronic control and/or or communication devices, including prior art pillow speakers found in hospital rooms, have a rigid enclosure assembly for physical protection and electrical isolation. For manufacturability, it is commonplace to create the rigid enclosure assembly by providing two complementary rigid shells, and screwing, clipping or gluing the shells together with a printed circuit board (PCB) and any other electronic components inside the rigid enclosure assembly.
[0003] Where the electronic device has user control buttons, these are typically incorporated into the device by a switch membrane mounted on one of the shells. A typical switch membrane either comprises the entire switch assembly and a wire harness to drive the signals to the PCB, or it includes the metal domes within its confines and adheres the domes to the PCB to create a normally open switch.
[0004] Electronic devices used in health care settings are used on a daily basis, and they are cleaned and disinfected often to prevent the spread of germs. They must be reliable for patient safety reasons. Consequently, they require service and repair more frequently than electronic devices used under less demanding circumstances.
[0005] Electronic devices formed according to the prior art are susceptible to damage not only from normal use, but also from liquid cleaning and disinfecting agents. Oftentimes, it is the switch membrane that is damaged, and the entire switch membrane must be removed and replaced, even though an outer graphic overlay of the switch membrane or metal switch domes of the switch membrane may be in perfect condition.
[0006] Switch membranes of the prior art, wherein the switch domes are attached to the overlay material, give the electronic device a tactile performance that is less than ideal due to the resistance to movement introduced by the overlay material.
[0007] What is needed is an improved electronic device assembly that is easier and less expensive to manufacture, allows for more efficient and less wasteful servicing, and responds better from a tactile standpoint to a user's pushbutton touches.
SUMMARY OF THE INVENTION
[0008] In a first aspect of the invention, an electronic device for use in a health care setting generally comprises a rigid shell defining an interior space and an opening communicating with the interior space, and a rigid PCB fixed to the shell to cover the opening. The rigid PCB includes electronic circuitry for operation of the device. The shell and PCB cooperate with one another to form a rigid enclosure assembly for the electronic device, thereby avoiding the need for a two-piece shell to enclose a separate PCB.
[0009] In a second aspect of the invention, an electronic device for use in a health care setting is improved by providing a physically separate dome layer and overlay. The dome layer may be fixed to an outward surface of the PCB and include a nonconductive sheet and a switch dome attached to the nonconductive sheet, wherein the switch dome is operable to close a switch trace on the PCB. The overlay may be arranged adjacent to the dome layer and fixed to a housing shell containing the PCB and/or to the outward surface of the printed circuit board, but the overlay is unattached to the dome layer. The overlay includes a switch graphic at a location corresponding to the switch dome.
[0010] The present invention extends to methods of making and servicing electronic devices embodying one or both of the aspects summarized above.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] In the drawings:
[0012] FIG. 1 is an exploded perspective view of an electronic device formed in accordance with an embodiment of the present invention;
[0013] FIG. 2 is a top plan view showing a printed circuit board, a dome layer, and an overlay of the electronic device in greater detail;
[0014] FIG. 3 is a top plan view of the dome layer adhered to the printed circuit board;
[0015] FIG. 4 is a plan view of an internal surface of overlay; and
[0016] FIG. 5 is a top plan view of the overlay adhered to the printed circuit board overtop the dome layer.
DETAILED DESCRIPTION OF THE INVENTION
[0017] FIG. 1 shows, in exploded view, a pillow speaker 10 formed in accordance with an embodiment of the present invention. Pillow speaker 10 is an electronic device for use in a health care setting, such as a hospital, nursing home, clinic, or similar environment. While the present invention is described with respect to a pillow speaker, it will be understood that other types of electronic devices used in health care settings may be constructed as taught herein. Examples of other types of electronic devices to which the present invention may be applied include, without limitation, handheld pendants, bed rails, wall plates, and call cords where a user interface is required.
[0018] Pillow speaker 10 generally comprises a rigid shell 12 , a rigid PCB 14 , a dome layer 16 , and an overlay 18 . Shell 12 defines an interior space 15 and an opening 30 communicating with the interior space. Shell 12 may include a plurality of fastener receptacles 20 , a cord passageway 26 through which wires may pass to reach interior space 15 , a speaker mount 28 for receiving an audio speaker (not shown), a support surface 32 for supporting PCB 14 , an inner surface 33 generally orthogonal to support surface 32 in the region of the support surface, and a rim surface 34 around opening 30 . Shell 12 may also include a retainer tab 35 protruding from rim surface 34 overtop support surface 32 .
[0019] In the embodiment shown in FIG. 1 , shell 12 is manufactured from a first shell portion 12 A and a second shell portion 12 B. The first and second shell portions 12 A, 12 B may each be molded of plastic, and then attached to one another to form rigid shell 12 . It is advantageous that the shell be free of small openings through which moisture may penetrate. Shell portions 12 A and 12 B may be ultrasonically welded together, as evidenced by weld seam 13 , to form rigid shell 12 . Alternatively, a moisture sealing adhesive may be used to bond the shell portions together. Rigid shell 12 may also be formed in unitary fashion as a single piece of molded plastic.
[0020] Rigid PCB 14 is fixed to shell 12 by fasteners 24 extending through respective fastener holes 22 through PCB 14 and engaging fastener receptacles 20 . Fasteners 24 may be threaded fasteners, and fastener receptacles 20 may be internally threaded to mate with a corresponding fastener 24 . PCB 14 covers opening 30 and includes electronic circuitry (not shown) for operation of pillow speaker 10 . In accordance with a first aspect of the present invention, shell 12 and PCB 14 cooperate with one another to form a rigid enclosure assembly for pillow speaker 10 .
[0021] PCB 14 includes an inward surface 38 contacting support surface 32 of shell 12 . As shown in Fig. I, support surface 32 may be recessed relative to rim surface 34 , such that a peripheral edge 40 of PCB 14 opposes inner surface 33 of the shell 12 . In this arrangement, PCB acts as a rigid member providing structural integrity to the rigid enclosure assembly. For example, if pillow speaker 10 is subjected to an impact force as may happen if pillow speaker 10 is dropped to the floor, inwardly directed force applied to the outside of shell 12 may be opposed by rigid PCB 14 . Applicants have found that a PCB thickness of 3.5 mm or greater will provide the rigid enclosure assembly with suitable structural integrity to withstand forces commonly encountered during normal use of the pillow speaker device. However, it will be understood that thickness is but one dimension of PCB 14 , and PCB's that are less than 3.5 mm in thickness may be suitable for some applications. The word “rigid,” as used herein to modify PCB, is intended to distinguish from flexible PCBs now on the market, and does not imply a minimum thickness requirement.
[0022] In the embodiment of FIG. 1 , retainer tab 35 is arranged to engage a recessed portion 37 of an outward surface 36 of PCB 14 . Retainer tab 35 and recessed portion 37 may be at corresponding longitudinal ends of shell 12 and PCB 14 , respectively, whereby the retainer tab pushes down on the end of the circuit board such that an axial tension force is created in fasteners 24 when the fasteners are tightened.
[0023] Referring also now to FIGS. 2 and 3 , it will be seen that outward surface 36 of PCB 14 may include one or more switch traces 54 associated with pushbutton control switches enabling a user to enter commands to the device. Dome layer 16 is arranged adjacent outward surface 36 of PCB 14 . Dome layer 16 includes a nonconductive sheet 42 and at least one conductive switch dome 56 attached to the sheet. Sheet 42 may be a thin polyester layer with adhesive only on its inward surface 44 ( FIG. 1 ) to adhere the sheet to outward surface 36 of PCB 14 as shown in FIG. 3 . Each switch dome 56 is applied to adhesive surface 44 of sheet 42 and positioned to register with a corresponding switch trace 54 on the PCB, wherein the switch dome is operable to close the switch trace by applying pressure to the switch dome.
[0024] Overlay 18 is arranged adjacent dome layer 16 and covers the dome layer to provide switch button embossing, switch graphics, and electrical isolation. Overlay 18 may be a polyester layer having an external surface 48 and an internal surface 50 ( FIG. 1 ). Overlay 18 may have an electrical insulation voltage rating greater than 25 kV, however this property is subject to design choice depending upon the specific application. Overlay 18 includes a switch graphic 58 on external surface 48 at a location corresponding to an associated switch dome 56 of the dome layer. The switch graphic 58 may indicate a function of the switch button to the user, and may include alphanumeric characters or a word. In a commercial embodiment of the invention, the overlay 18 is embossed in the region of each switch graphic 58 and switch dome 56 to provide a more user-friendly tactile push button. The embossing may include Braille characters to assist blind patients.
[0025] As seen in FIG. 4 , the internal surface 50 of overlay 18 may include an adhesive portion 50 A and a non-adhesive portion 50 B. Adhesive portion 50 A adheres to shell 12 and/or PCB 14 , but does not adhere to dome layer 16 . Dome layer 16 is covered by non-adhesive portion 50 B, such that overlay 18 and dome layer 16 remain unattached to one another. Accordingly, overlay 18 may be fixed to the outward surface 36 of PCB 14 by adhesive at a portion of outward surface 36 not covered by dome layer 16 . As represented in FIG. 5 , adhesive portion 50 A may extend beyond a peripheral region of PCB 14 so that it adheres to both the peripheral region of the PCB and to the rim surface 34 of shell 12 .
[0026] The present invention extends to a method of making electronic device 10 . The method generally comprises the steps of providing rigid shell 12 defining interior space 15 and opening 30 communicating with the interior space; providing rigid PCB 14 including electronic circuitry for operation of the device; and fixing the PCB to the shell such that the PCB covers the shell opening, wherein the shell and the PCB cooperate with one another to form a rigid enclosure assembly for the electronic device. A peripheral edge of the PCB may be arranged to oppose an inner surface of the shell.
[0027] According to another aspect of the inventive method, PCB 14 includes outward surface 36 having switch trace 54 thereon, and the inventive method further comprises the steps of providing dome layer 16 including nonconductive sheet 42 and switch at least one dome 56 attached to the sheet; fixing dome layer 16 to outward surface 36 of PCB 14 such that the switch dome is operable to close the switch trace; providing overlay 18 overlay including at least one switch graphic 58 ; and fixing overlay 18 to at least one of the shell 12 and the outward surface 36 of PCB 14 such that the switch graphic 58 is at a location corresponding to the switch dome 56 , wherein the overlay 18 is unattached to dome layer 16 . The dome layer 16 and the overlay 18 may be fixed to the outward surface 36 of PCB 14 by adhesive at different portions of the outward surface 36 . Overlay 18 may also be fixed to shell 12 by adhesive. The steps mentioned in this paragraph also represent an improved method of making electronic device 10 for a health care setting, independently of the steps for constructing the rigid enclosure assembly described in the immediately preceding paragraph.
[0028] The present invention eliminates the need for a second rigid piece to form an enclosure assembly by using the PCB for structural function in addition to electronic function.
[0029] Moreover, the use of a dome layer and an overlay that are unattached to one another reduces cost, improves tactile feel of the buttons, and facilitates servicing of the device. Cost is reduced due to the fact that the dome layer 16 carries only the metal switch domes 56 , whereby the dome layer may be configured for use with a large number of corresponding overlays 18 . This reduces the number of different part numbers for manufacturing specifications. Tactile feel is improved because the user feels the entire tactile feel of the metal dome 56 itself, which was not the case with prior art switch membranes where the overlay and switch dome were physically coupled to one another. Serviceability is improved because only the overlay 18 needs to be discarded and replaced when the device is opened up, and the dome layer 16 including costly metal domes 56 can remain and be reused.
[0030] With regard to serviceability, the present invention is further embodied by an improved method for servicing an electronic device of a type comprising a PCB including a switch trace, a switch dome operable to close the switch trace, and an overlay including a switch graphic at a location corresponding to the switch dome. The servicing method of the present invention comprises the steps of removing the overlay 18 from the device 10 without removing the switch dome 56 from the device 10 ; performing a service operation; and fixing a replacement overlay different from the removed overlay on the device overtop the original switch dome 56 .
[0031] Modifications and other embodiments of the inventions set forth herein will be apparent to one skilled in the art to which these inventions pertain in light of teachings presented in the present specification. Therefore, the inventions are not to be limited to the specific embodiments disclosed, and modifications and other embodiments are intended to be included within the scope of the appended claims.
PARTS LIST
[0000]
10 Electronic device (pillow speaker)
12 Shell
12 A First shell portion
12 B Second shell portion
13 Ultrasonic weld seam
14 Printed circuit board (PCB)
15 Interior space of shell
16 Dome layer
18 Overlay
20 Fastener receptacles
22 Fastener holes through PCB
24 Fasteners
26 Cord passageway
28 Speaker mount
30 Shell opening
32 Support surface for PCB
33 Inner surface of shell
34 Rim surface of shell
35 Retainer tab
36 Outward surface of PCB
36 A Portion of outward surface of PCB not covered by dome layer
38 Inward surface of PCB
40 Peripheral edge of PCB
42 Nonconductive sheet of dome layer
44 Adhesive surface of nonconductive sheet
46 Cut-out regions of nonconductive sheet
48 External surface of overlay
50 Internal surface of overlay
50 A Adhesive portion of internal surface of overlay
50 B Non-adhesive portion of internal surface of overlay
54 Switch traces on outward surface of PCB
56 Switch domes of dome layer
58 Switch graphics of overlay
|
An electronic device for use in a health care setting has a rigid enclosure assembly formed by a rigid shell and a rigid printed circuit board carrying circuitry for operating the device. A switch dome layer and an overlay are independently attached to the device but not to each other, whereby the overlay may be removed without disturbing the dome layer and a better tactile response is achieved.
| 8
|
This application is a continuation of application Ser. No. 07/709,204, filed Jun. 3, 1991 now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method for controlling a compressor in an air conditioner, and more particularly to a method for controlling a compressor in an air conditioner so as to reduce the difference between discharge pressure and suction pressure in the compressor.
2. Description of Prior Art
Referring to FIG. 1 , there is shown an example of conventional air conditioners. In the air conditioner, room temperature is sensed by a room temperature sensor 10; an outdoor heat exchanger temperature is sensed by a temperature sensor 1'; an indoor heat exchanger temperature is sensed by a temperature sensor 2'. An invertor 8 controls amount of circulating refrigerant through a compressor 5 to reverse the operation of compressor 5 from the cooling mode to the heating mode, or vice versa. At this time, invertor 8 outputs as high a frequency voltage as possible, in order to shorten the operation mode reversal time in each reversal of the operation mode. Thus, high speed rotation of compressor 5 could be possible, thereby reducing operation mode reversal times for cooling, heating and defrosting operations.
However, although reducing the operation mode reversal time, the high speed rotation of compressor 5 resulted from the above-mentioned high frequency voltage outputted from invertor 8 causes a considerably high pressure difference between discharge pressure and suction pressure in the compressor. As a result, refrigerant of high pressure returns to compressor 5, thereby generating high pressure noise. If such high pressure refrigerant flows into compressor 5 at this time, the compressor may be damaged.
A representative example of attempts to solve the above-mentioned problems is disclosed in Japanese Patent Laid-open Publication No. 57-150763. A heat exchanger temperature sensor and a room temperature sensor sense heat exchanger temperature and room temperature and supply signals corresponding to the sensed temperatures to a temperature control circuit, respectively. When a difference between the two temperatures is no more than a predetermined value the temperature control circuit applies a signal to a switch for a compressor drive circuit, which switch then turns on. A first timer which is connected to the switch in series via a contact of a second relay produces conducting time. As the first timer counts a predetermined time, a first timer switch turns on, so that the second relay connected to the first timer switch in series via a second timer switch can conduct. Conducting of the second relay makes the other contact of second relay turn off, so that the contact of first relay turns off, thereby causing the compressor connected thereto in series to stop. Such conventional device thus involves stopping the compressor for a predetermined time before the reversal of operation mode .
SUMMARY OF THE INVENTION
An object of the invention is to solve the above mentioned problems encountered in the prior art and to provide a method for reducing the difference between discharge pressure and suction pressure in a compressor by driving the compressor at low speed just before the reversal of the operation mode.
In order to accomplish the object, a control method of the present invention comprises counting a predetermined time by the timer when an operation mode reversal signal has been sensed by a sensor attached to a heat exchanger. When the predetermined time elapses, an invertor outputs alternating current (AC) voltage of low frequency so that the difference between discharge pressure and suction pressure in the compressor is reduced. After a predetermined time elapses during the driving of compressor under the condition that the difference between discharge pressure and suction pressure is maintained low, the reversal of operation mode is carried out.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and the other objects, features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic block diagram of a conventional air conditioner;
FIG. 2 and 2A is a schematic block diagram of an embodiment according to the present invention;
FIG. 2A is a fragmentary view of FIG. 2 after the reversing valve has been reversed;
FIG. 3 depicts a first operation characteristic curve when using the invention of FIG. 2 to switch between heating and defrosting modes;
FIG. 4 depicts a second operation characteristic curve when using the invention of FIG. 2 to switch between heating and cooling modes;
FIG. 5 is the flow chart illustrating the process of FIG. 3;
FIG. 6 is a flow chart illustrating a modified version of the FIG. 3 process; and
FIG. 7 is a flow chart illustrating the process of FIG. 4.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 2 there is shown an air conditioner in accordance with the present invention which includes an indoor heat exchanger 2, a compressor 5, a four-way reversing valve 4 and an outdoor heat exchanger 1, the four components being intercoupled in series via refrigerant tubes to form a refrigeration circuit. Temperature sensors 2, and 1, are attached to indoor and outdoor heat exchangers 2 and 1 respectively. Temperature sensors 1' and 2' sense temperatures and supply temperature signals to a microprocessor 12, respectively. To microprocessor 12, a room temperature sensor 10, a timer 11 and an invertor 8 are connected, which invertor 8 is also connected to compressor 5.
FIG. 5 is a flow chart illustrating a process for controlling compressor in the heating operation mode in accordance with an embodiment of the present invention. The air conditioner is initially reset by receiving electric power. Thereafter, as the air conditioner is driven in its heating operation mode, compressor 5 is driven in its heating operation mode by high frequency voltage outputted from invertor 8, while maintaining the difference PO between the pressure of discharge-side DS and the pressure of suction-side SS in compressor 5 (step 501).
At this time, refrigerant is introduced into R-side of a four-way reversing valve 4, discharged from B-side of the valve and then compressed in compressor 5. After being compressed, the refrigerant of high pressure and high temperature gaseous state is introduced into A-side of a four-way reversing valve 4, discharged from P-side of the valve and then condensed in an indoor heat exchanger 2. As condensed, the refrigerant emits heat into the room to warm atmosphere of the room. Then, the refrigerant flows into an outdoor heat exchanger 1 via a capillary tube 3. In outdoor heat exchanger 1, the refrigerant is changed into gas of low pressure by absorbing heat from outside atmosphere. If the heat absorption is not efficiently carried out due to frosting of outdoor heat exchanger 1, the temperature of outdoor heat exchanger 1 cannot be lower than a predetermined temperature. This can be sensed by temperature sensor 1' attached to outdoor heat exchanger 1, which sensor then supplies a frost signal to microprocessor 12 (steps 502 and 503). On the other hand, the refrigerant which absorbed heat from outdoor heat exchanger 1 is introduced into R-side of a four-way reversing valve 4.
When receiving an excess frost signal from temperature sensor 1' as mentioned above (point T1 in FIG. 3), microprocessor 12 actuates timer 11 to count time (step 506). After a predetermined time elapses (point T1 in FIG. 3), microprocessor 12 operates such that invertor 8 outputs an AC voltage of low frequency to compressor 5 (steps 507 and 508). Accordingly, compressor 5 drives at low speed, so that the difference between discharge pressure and suction pressure in the compressor is reduced to Pl (refer to FIG. 3). When the time of timer 1 1 reaches T2 (steps 509 and 510) microprocessor 12 sends a signal to a four-way reversing valve 4 to connect R-side and P-side with A-side and B-side thereof, respectively as shown in FIG. 2A.
At this time, the gaseous refrigerant of high temperature and high pressure which had flowed from A-side to P-side of a four-way reversing valve 4 during the heating operation before the reversal into the defrost operation flows reversely from P-side to B-side and is sucked into compressor 5, thereby being compressed therein. Therefore, the suction pressure and the discharge pressure will correspond to those of R-side and P-side of four-way reversing valve 4 during the heating operation, respectively, while they corresponded to those of P-side and R-side during the defrost operation, respectively. In the reversal into the defrost operation, the refrigerant which has flowed from compressor 5 to P-side of four-way reversing valve 4 flows through P- and B-sides of the valve to compressor 5. This refrigerant gas of high temperature and high pressure has no overloading effect on compressor 5 even if compressed therein again. This is because the pressure of the refrigerant has already been reduced to relatively low pressure P1 during the period from the time T1 to the time T2, as shown in FIG. 3. At a predetermined time T3 in the defrost operation, microprocessor 12 sends a signal to four-way reversing valve 4 to reverse the operation of compressor 5 into its heating operation mode. Simultaneously, microprocessor 12 outputs a signal to invertor 8 so that invertor 8 applies AC voltage of low frequency to compressor 5, thereby causing compressor 5 to drive at low speed for the period from the time T3 to the time T4. For the period during which compressor 5 drives at low speed, the difference between the pressure of discharge side DS and the pressure of suction side SS in the compressor is P3, as shown in FIG. 3.
After timer 11 counts the predetermined time T4 during the low speed driving of compressor 5, microprocessor 12 outputs a signal to invertor 8 so that invertor 8 applies AC voltage of high frequency to compressor 5, thereby causing the compressor to drive at high speed. At this time, the difference between the pressure of discharge side DS and the pressure of suction side SS in the compressor is PO. Thus, the operation is reversed sequentially into heating, defrosting, and heating operation modes.
Referring to FIG. 6, there is shown the other embodiment of the present invention which is different from the above-mentioned embodiment, in that the compressor is stopped before each reversal of operation modes.
FIG. 7 which is a flow chart illustrating the process of the reversal from the heating operation mode to the cooling operation mode and vice versa shows another embodiment of the present invention.
When an operator applies electric power to the apparatus of the present invention, initializing procedure for the operation of heating mode or cooling mode is carried out in step 701. When a predetermined temperature is detected by room temperature sensor 10 provided in the room during the cooling mode operation, microprocessor 12 receives a signal corresponding to the temperature (step 702). In step 703, it is determined whether the signal is the operation mode reversal signal.
If the signal is not the operation mode reversal signal, the program proceeds to step 712 to continuously carry out cooling operation. If the signal is the operation mode reversal signal, the value TA of the timer is stored into a timer buffer T (step 704). Then, invertor 8 outputs low frequency, thereby causing compressor 5 to drive at low speed (step 705). In the next step 706, the timer counts up.
In such manner, compressor 5 drives at low speed, so that the difference between the pressure of discharge side DS and the pressure of suction side SS in the compressor is P1. In step 707, it is determined whether a predetermined time TB elapsed after the low speed driving of compressor 5. If predetermined time TB did not elapse, step 706 is repeated. If predetermined time TB elapsed, invertor 8 outputs frequency of 0 in step 708, thereby causing compressor 5 to stop. In step 709, the timer counts up. In step 709, it is determined whether a predetermined time TC elapsed. If a predetermined time TC did not elapse, step 709 is repeated. If predetermined time TC elapsed, invertor 8 applies high frequency voltage to compressor 5, thereby causing compressor 5 to operate at its heating mode (step 711).
As apparent from the above description, the invertor outputs frequency of low or 0 for a predetermined period before the reversal of operation mode, in accordance with the present invention, so that the compressor drives at low speed, thereby reducing pressure noise caused by large difference between discharge pressure and suction pressure in the compressor. As a result, it is possible to improve considerably room pleasantness obtained by the air conditioner. Furthermore, the coming of a large pressure refrigerant into the compressor can be avoided, thereby preventing the compressor from being damaged by the coming refrigerant.
|
An air conditioning system includes a compressor which is reversed in order to switch from a heating mode to a defrost mode, or in order to switch between heating and cooling modes. Prior to being reversed, the compressor is automatically reduced to a slower speed greater than zero for a predetermined time period to minimize damage and noise when reversal occurs. The compressor is reversed while at the slower speed when switching the system to a defrost mode. When switching between heating and cooling modes, the compressor speed is first reduced to the slower speed for the first predetermined time period and then to zero speed for a second predetermined time period, before the compressor is reversed.
| 8
|
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This patent application is a divisional patent application of U.S. non-provisional patent application 13/964,288 filed on Aug. 12, 2013 and entitled “Method and Apparatus for Laser Mosquito Control”, which is hereby incorporated by reference in its entirety.
TECHNICAL FIELD OF THE INVENTION
[0002] The present invention relates generally to methods and apparatuses used for pest control and more specifically, to methods and apparatuses that use a laser to injure or destroy mosquitoes or other flying pests.
STATEMENT OF FEDERALLY FUNDED RESEARCH
[0003] None.
INCORPORATION-BY-REFERENCE OF MATERIALS FILED ON COMPACT DISC
[0004] None.
BACKGROUND OF THE INVENTION
[0005] Without limiting the scope of the invention, its background is described in connection with pest control, including as insects and specifically mosquitoes, range from chemical insecticides, electric bug traps, and other devices. These devices often use an attractant like scent, ultraviolet light, or bait, to lure insects into the trap. One specific example is an electric-UV trap which includes an ultraviolet light source that attracts insects surrounded by an electrified grid which electrocutes the insects as they try to reach the ultraviolet light source. Although somewhat effective the trap produces loud sparks and spatters debris making it a less attractive device. Similarly, chemical pesticides are non-selective and can poison non-target species as well as pollute the environment.
[0006] U.S. Pat. No. 5,915,949, entitled, “Method and apparatus for laser pest control,” discloses a method for controlling pests which uses a laser beam to exterminate pests hidden behind or within a solid barrier. The laser light must have a wavelength and power to sufficiently exterminate the pests hidden behind or within the barrier without damaging the barrier, and can be used to control ant and termite infestation of common household building materials and agricultural pest control of crop fields.
SUMMARY OF THE INVENTION
[0007] The present invention provides a laser pest control device for injuring and/or killing one or more flying pests, and in particular, to injure or destroy mosquitoes.
[0008] The present invention provides an apparatus for damaging a flying pest comprising: a housing; a continuous perforated side wall extending from the housing; a laser contacting surface connected to the continuous perforated side wall and positioned opposite the housing, wherein the laser contacting surface comprises an outer perimeter in communication with the continuous perforated side wall, and extending to an inner perimeter to form a central aperture; a laser beam generator attached to the housing and positioned to transmit a laser beam generally radially downward toward the laser contacting surface; a laser rotating mechanism in communication with the laser beam generator to generate a laser beam and rotate the laser beam in a 360 degree pattern on the laser contacting surface between the outer perimeter and the inner perimeter, wherein the laser beam contacts and damages a flying pest; a control mechanism in communication with the laser beam generator to control the generation of the laser beam and in communication with the laser rotating mechanism to control one or more parameters relating to the 360 degree pattern; and a power supply in electrical communication with the control mechanism, the laser rotating mechanism, and the laser beam generator.
[0009] The present invention provides an apparatus for damaging a mosquitoes comprising: a housing; a UV light and/or bait in communication with the housing; a continuous perforated side wall extending from the housing; a laser contacting surface connected to the continuous perforated side wall and positioned opposite the housing, wherein the laser contacting surface comprises an outer perimeter in communication with the continuous perforated side wall, and extending to an inner perimeter to form a central aperture; a laser beam generator attached to the housing and positioned to transmit a laser beam generally radially downward toward the laser contacting surface; a laser rotating mechanism in communication with the laser beam generator to generate a laser beam and rotate the laser beam in a 360 degree pattern on the laser contacting surface between the outer perimeter and the inner perimeter, wherein the laser beam contacts and damages a flying pest; a control mechanism in communication with the laser beam generator to control the generation of the laser beam and in communication with the laser rotating mechanism to control one or more parameters relating to the 360 degree pattern; a power supply in electrical communication with the control mechanism, the laser rotating mechanism, and the laser beam generator; and a counting device to count the number of mosquitoes killed or damaged by the present invention.
[0010] The laser beam generator may have a power in the range of about 1 to 100 watts and produce a wavelength of between 400 and 1100 nm. The laser rotating mechanism may rotate the laser beam at between 1 and 100 Hz in a 360 degree pattern that may be in a clockwise direction, a counter-clockwise direction or both.
[0011] The laser beam generator may produce two or more laser beams. For example, the laser beam generator may produce at least a first laser beam and at least a second laser beam and the 360 degree pattern of the least a first laser beam may be in a clockwise direction and the 360 degree pattern of the least a second laser beam may be in a counter-clockwise direction.
[0012] The materials of the instant invention may be light absorbing materials and particularly laser light absorbing materials to contain or adsorb errant laser beams. The laser contacting surface, the continuous perforated side wall or both may have of a laser light absorbing material coating for absorbing and containing errant laser beams. The laser contacting surface, the continuous perforated side wall or both may be made from a laser light absorbing material for absorbing and containing errant laser beams.
[0013] The present invention also provides a method of damaging a flying pest using a rotating laser system by providing a laser apparatus including at least one laser beam being electrically powered, wherein the laser apparatus comprises a housing, a continuous perforated side wall extending from the housing to a laser contacting surface, a laser beam generator attached to the housing and positioned opposite the laser contacting surface, a laser rotating mechanism in communication with the laser beam generator and an electric power source; generating one or more laser beams with the laser beam generator to transmit the one or more laser beams generally radially downward toward the laser contacting surface; and rotating the one or more laser beams with the laser rotating mechanism in a 360 degree pattern on the laser contacting surface at a rotation speed to form one or more rotating laser beams, wherein upon entering the laser apparatus a flying pest will contact the one or more rotating laser beams and be damaged.
[0014] The present invention also provides a method of damaging mosquitoes using a rotating laser system by providing a laser apparatus including at least one laser beam being electrically powered, wherein the laser apparatus comprises a housing, a continuous perforated side wall extending from the housing to a laser contacting surface, a laser beam generator attached to the housing and positioned opposite the laser contacting surface, a laser rotating mechanism in communication with the laser beam generator and an electric power source; generating one or more laser beams with the laser beam generator to transmit the one or more laser beams generally radially downward toward the laser contacting surface; and rotating the one or more laser beams with the laser rotating mechanism in a 360 degree pattern on the laser contacting surface at a rotation speed to form one or more rotating laser beams, wherein upon entering the laser apparatus a flying pest will contact the one or more rotating laser beams and be damaged.
[0015] The present invention provides a method of reducing transmission of diseases associated with mosquitoes using a rotating laser system by providing a laser apparatus including at least one laser beam being electrically powered, wherein the laser apparatus comprises a housing, a continuous perforated side wall extending from the housing to a laser contacting surface, a laser beam generator attached to the housing and positioned opposite the laser contacting surface to generate a laser beam with a wavelength of 350-700 nm, a laser rotating mechanism in communication with the laser beam generator to rotate the laser beam in a 360 degree pattern at between 0.1-100 Hz, and an electric power source; generating one or more laser beams with the laser beam generator to transmit the one or more laser beams generally radially downward toward the laser contacting surface; rotating the one or more laser beams with the laser rotating mechanism in a 360 degree pattern on the laser contacting surface at a rotation speed to form one or more rotating laser beams; contacting a mosquito with the one or more rotating laser beams to damage the mosquito and reduce the mosquito population; and reducing a transmission of one or more diseases associated with mosquitoes. The one or more diseases associated with mosquitoes may be Arboviral Encephalitides, Malaria, Dengue Fever, Dog Heartworm, Rift Valley Fever, West Nile Virus, or Yellow Fever.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] For a more complete understanding of the features and advantages of the present invention, reference is now made to the detailed description of the invention along with the accompanying figures and in which:
[0017] FIG. 1 is an image of one embodiment of the apparatus of the present invention used to injure or destroy mosquitoes or other flying pests.
[0018] FIG. 2 is a cut away image of the apparatus in FIG. 1 along the a-aa line.
DETAILED DESCRIPTION OF THE INVENTION
[0019] While the making and using of various embodiments of the present invention are discussed in detail below, it should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention and do not delimit the scope of the invention.
[0020] To facilitate the understanding of this invention, a number of terms are defined below. Terms defined herein have meanings as commonly understood by a person of ordinary skill in the areas relevant to the present invention. Terms such as “a”, “an” and “the” are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration. The terminology herein is used to describe specific embodiments of the invention, but their usage does not delimit the invention, except as outlined in the claims.
[0021] The laser pest control device uses a laser cutting means that is adjustable to project focused laser beams outwards at a plurality of angles to contact flying pests to destroy the pest, damage the pest of both. FIG. 1 illustrates a laser pest control device 10 that includes a housing 12 having a laser contacting surface 14 with an outer perimeter 16 a and an inner perimeter 16 b being either circular or multi-sided. The laser contacting surface 14 and/or the continuous perforated side wall 18 may be made of or coated with a laser light absorbing material for absorbing and containing errant laser beams. The inner perimeter 16 b forms a central aperture 20 . The central may be of any diameter necessary for the particular application or may be not present and be a continuous surface. Attached to the outer perimeter 16 a is a generally continuous perforated side wall 18 that connects the laser contacting surface 14 to the housing 12 . The continuous perforated side wall 18 is extended generally perpendicular around the outer perimeter 16 a , and generally upward to the housing 12 .
[0022] FIG. 2 is an image of the device illustrated in FIG. 1 cut along the a-aa line. The housing 12 includes a second surface 24 opposite the laser contacting surface 14 , with an outer perimeter 16 a and an inner perimeter 16 b being either circular or multi-sided, the second surface 24 and the continuous perforated side wall 18 enclose an interior that opens at the central aperture 20 bounded by the continuous perforated side wall 18 . The laser pest control device includes a laser housing 30 connected at a central position 26 and extending downward from the second surface 24 underneath the housing 12 . The laser housing 30 includes a laser beam generator 32 oriented a sufficient distance below the second surface 24 , and a laser beam rotation mechanism (not shown) to allow the laser beam 34 when generated to rotate in a 360 degree pattern such that the laser beam 34 contacts the laser contacting surface 14 as it rotates. The laser beam generator 32 may generate one or more laser beams 34 as desired by the particular application. The laser beam 34 is transmitted generally radially outwards from the laser beam generator 32 and may include various optical enhancements known to the skilled artisan including but not limited to splitters, lenses, reflectors, detractors, and the like known to those skilled in the art. In addition, the path of the laser beam 34 may be adjusted by an adjustment means (not shown) for angular adjustments of the various paths. The laser beam 34 can be directed in a plurality of angles downward onto the laser contacting surface 14 . The laser beam 34 is generated by the laser beam generator 32 in a continuously rotating 360 degree arc that may be either clockwise or counter-clockwise, or a combination of clockwise and counter-clockwise, using a single or multiple laser beams 34 . The laser pest control device may include a multiple laser beam configuration that includes at least two opposed laser beams at different angles or two, three, four, five, six, seven, eight, nine or more laser beams at a plurality of angles and in opposed, concurrent paths, or a mixture thereof. For example, one embodiment can have up to about ten opposed laser beams with each beam being opposed to the next and generated at different angles.
[0023] The laser pest control device may operate at specific rotation speeds and intensities of the laser beams, but is not limited to a certain constant rotation speed or direction. The speed of rotation of each laser beam 34 is dictated by the laser beam rotation mechanism to control whatever angular direction transmitted from the laser beam generator 32 , and can be increased or decreased as necessary depending on the particular embodiment. The limit of the rotational speed for the rotation of each laser beam is only limited by the physical limits of rotation of the laser beam rotation mechanism, as determined by those skilled in the art. The laser beam rotation mechanism is known to the skilled artisan and may be a mechanical device to rotate the laser generator, a mirror that oscillates, an electrical device or other device known to the skilled artisan. Any scattered or reflected laser beams may absorbed by the laser beam absorbing materials such that any errant laser beams are contained within the housing 12 as a safety measure.
[0024] The laser pest control device includes a laser housing 30 including a system control mechanism connected to and controlling the laser beam generator 32 . The laser housing 30 includes electronic circuitry within, and/or connected to a system control mechanism to control the laser beam rotation mechanism and in turn the angular directions of the laser beam(s), the rotation direction, the rotation speed and other operating parameters of the laser beam generator and the parameters of the laser beam rotation mechanism.
[0025] The skilled artisan can adjust the circuitry to control the speed of rotation of the laser beam and/or the intensity of laser beam, and/or the angular direction of the laser beam as necessary. Furthermore, the system control mechanism is capable of controlling a plurality of laser beams generated simultaneously by the laser beam generator and individually control the speed of rotation of each laser beam and/or the intensity of each laser beam, and/or the angular direction of each laser beam.
[0026] The system control mechanism, the laser beam rotation mechanism and the laser beam generator are positioned within the housing 12 and electronically connected to a power source. The power source may be of any sufficient power to run the system. For example, the power source may be a direct connection to a power grid, a rechargeable battery, a plurality of rechargeable batteries, a solar cell, a solar power pack, an electrical generator or a combination thereof. For example, in one embodiment, the power source includes a solar power source connecting a solar cell, and one or more batteries to the system control mechanism, the laser beam rotation mechanism and the laser beam generator. In another embodiment, the power source includes a direct connection to a power grid, a battery backup, a solar cell, and a power control switch to direct the power to/from the direct connection to recharge the battery or to power the device; to use the solar cell to power the device; to use the solar cell to recharge the battery; or other variations thereof known to those skilled in the art.
[0027] The system control mechanism may also have an interface that includes a display and or controls to allow the control of the parameters of the system control mechanism, the laser beam rotation mechanism and the laser beam generator. The interface can provide user control of the rotation speed and angular direction, and may optionally provide control of the intensity of the laser beams and/or a visual indication of the rotational speeds of the rotating laser beams. Electrical circuitry is known to those skilled in the art. A number of associated electronic and mechanical components known to those skilled in the art are not illustrated, but can be incorporated without interfering with the objects and advantages of the present invention.
[0028] In operation, the laser pest control device may be position in the desired location. Upon applying power to the laser pest control device, the system control mechanism, the laser beam rotation mechanism and the laser beam generator positioned within the housing are electronically engaged. In one embodiment, the interface is used to control the parameters of the system control mechanism, the laser beam rotation mechanism and the laser beam generator and the angular directions of the laser beam(s), the rotation direction, the rotation speed, and other operating parameters are set. In another embodiment these parameters are present into the device and no further modification is allowed or required. The laser beam rotation mechanism and the laser beam generator produce a laser beam that contacts the laser contacting surface at a point and is rotated about the laser contacting surface. The rotating laser beam is only accessible from the central aperture and through the perforations in the continuous perforated side wall. As a pest enters the central aperture, it will at some point contact the rotating laser beam which will at that point either damage the pest, damage at least a portion of the wings of the pest, injure the pest or destroy the pest. Similarly, the pest may enter the perforations in the continuous perforated side wall, and at some point contact the rotating laser beam, which will at that point either damage the pest, damage at least a portion of the wings of the pest, injure the pest or destroy the pest. In addition, the rotation direction, the rotation speed and other operating parameters may be adjusted to optimize the contacting of the pest and the laser beam.
[0029] In another embodiment, power may be applied to the laser pest control device to engage the system control mechanism, the laser beam rotation mechanism and the laser beam generator positioned within the housing. The laser beam rotation mechanism and the laser beam generator produce a first laser beam that contacts the laser contacting surface at a first point, and is rotated in a first direction about the laser contacting surface, and the laser beam generator produce a second laser beam that contacts the laser contacting surface at a second point, and is rotated in a second direction about the laser contacting surface. This creates laser beams that are rotating in opposite directions. The rotating laser beams are only accessible from the central aperture and through the perforations in the continuous perforated side wall. As a pest enters the central aperture it will at some point contact at least one of the rotating laser beams which will at that point either damage the pest, damage at least a portion of the wings of the pest, injure the pest or destroy the pest. Similarly, the pest may enter the perforations in the continuous perforated side wall and at some point at least one of the rotating laser beams which will at that point either damage the pest, damage at least a portion of the wings of the pest, injure the pest or destroy the pest.
[0030] The laser pest control device may be of any size and scale desired by the skilled artisan. For example, the laser pest control device may be a personal use size ranging from a housing that is less than a foot in diameter and has a continuous perforated side wall of less than a foot in height. The laser pest control device may be a commercial use size ranging from a housing that is more than a foot in diameter and has a continuous perforated side wall of more than a foot in height. The laser pest control device may also be an industrial use size ranging from a housing several feet in diameter and has a continuous perforated side wall of several feet in height. The laser pest control device may be adapted for use in any environment, e.g., warehouses, pool areas, fields, gardens, greenhouses and other environments where pests reside.
[0031] The laser beam may be continuous or pulsed. The laser beam generator may be any type of commercially available laser of sufficient power, such as a CO 2 , Nd-YAG, Nd-glass, helium-neon, ruby, aluminum-gallium-arsenide, dye, helium-cadmium, argon, krypton, or KTP-YAG laser. Wavelengths for these known lasers vary from about 0.4 to 10.6 microns, but wavelengths outside this range, for example, all infrared, visible and ultraviolet light, could also be employed. The laser beam generator may be any type of commercially available laser of sufficient power, such as a 20-274 mW Green laser, 250-849 mW Green laser, 2-349 mW Violet Laser, 400 mW Blue Laser, 50-1299 mW Blue Laser, 0.6-5.0 mW Blue Laser, 0.6-59 mW Yellow Laser, 2-14 mW Yellow Laser, 200-671 nm Red Laser, 500-699 mW Infrared Laser, 1200-1300 mW Infrared Laser, 700-1399 mW Infrared Laser, 2000-2399 mW Infrared Laser. Specific examples include a 447 nm Blue laser, 473 nm Blue laser, 532 nm Green laser, 532 nm Green laser, 589 nm Yellow laser, 593.5 nm Yellow laser, 635 nm Red laser, 640 nm Red laser, 658 nm Red laser, 671 nm Red laser, 808 nm IR laser, 808 nm IR laser, 1064 nm IR laser and 1064 nm IR laser. Depending on the type of pest, the power level of the laser source should be at least about 0.1 watt for insects and other small or microscopic creatures, but may be between 0.1 watt and 1 watt, 1 watt to 2 watts, 2 watts to as high as 1000 watts. In addition, the present invention may be adjustable in the number of watts and power output produced by the invention. In embodiments where there are multiple lasers beams, each beam may have the same or a different wavelength and/or power. One specific example includes a blue violet laser beam (about 405 nm) with a power output of 1 watt, 0.75 watts or 0.5 watts.
[0032] One embodiment of the laser beam rotation mechanism includes a commercially available moving mirror imaging unit, such as those of the LK series available from General Scanning, Inc., or a unit driven by an oscillator or function generator such as the Model 3020 Sweep/Function Generator made by Dynascan Corporation, to rotate the laser beam. The laser beam rotation mechanism may also include accessories that focus the beam to a spot to maintain a desired beam diameter throughout the area. A lens or equivalent device, such as a combination of curved mirrors, may be used to cause the beam to diverge (widen) with increasing distance. The rotation speed may be varied depending on the specific pest being targeted, and may range from a rotation speed of 1 Hertz (cycles per second), which is typical, with speeds up to 100 KHz or more.
[0033] In addition, instead of relying on the pest to randomly enter the laser pest control device, one or more attractants may be used and take a variety of forms. In general, anything that is effective to lure the target pests into the scanned area can be used, such as an ultraviolet light source which attracts a variety of insects. Other possible attractants include an incandescent or fluorescent light, sound generator, pest hormone, odor generator, an object with a specific color, and bait known to the skilled artisan.
[0034] Optional accessories include a beam widening lens, a beam narrowing lens, and a cone-shaped shade for rigidly connecting lens. In addition, optional sensors may be connected to the pest control system for recording, storing and transmitting various data. For example, a camera, a microphone and a counting mechanism may be used to count the number of pests that contact the device at any unit of time. In addition, a storage device may be in communication with the counting mechanism to record various data relative to the number of pests/time, date and time, location, etc. Optionally, a transmitter may be connected to the storage device, counting mechanism, or both to allow data transfer over wired or wireless systems. In addition, the housing may include various sensors and electronic devices including a camera, processors, storage devices, communication devices, timers storage device to store data, e.g., time, date, GPS location, etc. The invention may also include a Wi-Fi, Bluetooth or cellular mechanism to send and receive data, and to allow the remote control of the mechanisms including laser wavelength, laser power, laser rotation, data acquisition, on and off of components, etc. In addition, the housing may include a mechanism to prevent tampering and removal of the device. This may include an alarm to sound and/or flash when tampered with or an alert signal sent to a remote location.
[0035] It is contemplated that any embodiment discussed in this specification can be implemented with respect to any method, kit, reagent, or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention.
[0036] It will be understood that particular embodiments described herein are shown by way of illustration and not as limitations of the invention. The principal features of this invention can be employed in various embodiments without departing from the scope of the invention. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific procedures described herein. Such equivalents are considered to be within the scope of this invention and are covered by the claims.
[0037] All publications and patent applications mentioned in the specification are indicative of the level of skill of those skilled in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.
[0038] The use of the word “a” or “an” when used in conjunction with the term “comprising” in the claims and/or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” The use of the term “or” in the claims is used to mean “and/or” unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and “and/or.” Throughout this application, the term “about” is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects.
[0039] As used in this specification and claim(s), the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
[0040] The term “or combinations thereof” as used herein refers to all permutations and combinations of the listed items preceding the term. For example, “A, B, C, or combinations thereof” is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, AB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context.
[0041] All of the compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.
|
The present invention provides an apparatus for damaging a flying pest comprising: a housing connected to a continuous perforated side wall to a laser contacting surface; a laser beam generator and a laser rotating mechanism attached to the housing and positioned to transmit a laser beam generally radially downward toward the laser contacting surface in a 360 degree pattern on the laser contacting surface, wherein the laser beam contacts and damages a flying pest; a control mechanism in communication with the laser beam generator to control the generation of the laser beam and in communication with the laser rotating mechanism to control one or more parameters relating to the pattern; and a power supply in electrical communication with the control mechanism, the laser rotating mechanism, and the laser beam generator.
| 0
|
FIELD OF THE INVENTION
[0001] This invention concerns an efficient process for peeling citrus fruits. More particularly, the process uses an enzyme to weaken and/or dissolve the albedo between the citrus peel and the citrus fruit sections which it surrounds.
BACKGROUND
[0002] The process of this invention permits the efficient peeling of citrus fruits so that individual segments of the fruit can be readily prepared. As is well known, citrus fruit has an outer peel and inner fruit segments separated from one another by membranes that also surround each individual segment. Between the outer peel and the membranes surrounding the individual segments is a white, pithy material known as the albedo.
[0003] In the past, citrus peeling has been accomplished by hand peeling the skin and removing the albedo to expose the fruit segments. Typically, the skin peeling and albedo removal has been done with a knife, which leads to removal and loss of some of the fruit. Complete removal of the albedo, and its white color, from the fruit segments requires additional processing time and care.
[0004] Peeling methods using mechanical equipment of various types is also known to those in the business. Generally, however, such mechanical peeling processes leave the peeled fruit in a condition that still requires hand removal of some portion of the albedo.
[0005] Processes have also been proposed to use an enzyme, such as pectinase, to dissolve and/or weaken the albedo so that the skin can be removed from the segments of meat inside the citrus fruit. For example, U.S. Pat. Nos. 5,170,698 and 5,196,222 to Kirk concern a process and related apparatus to peel citrus fruit where the fruit is perforated, given an equatorial cut, and deposited in a canister. The canister is filled with an albedo degrading solution, such as an aqueous solution of commercial pectinase, or a mixture of enzyme solutions. The albedo degrading solution is vacuum infused into the fruit to substantially disintegrate the albedo of the fruit.
[0006] Another peeling process simply removes a strip of citrus outer peel substantially at the equator of the fruit. The fruit is immersed in an enzyme solution. Then, a vacuum is applied to remove air from the citrus fruit and released. See, for example, U.S. Pat. No. 5,989,615.
[0007] Another possible peeling process involves submerging fruit in a fluid followed by the application of a vacuum. The vacuum may be applied in one or two steps. Thereafter, the vacuum is released and pressure is applied to the fluid. The fluid may contain pectinase. See, U.S. Patent Publication US 2004/0043126.
[0008] It has been found, however, that those prior art methods do not function well when scaled to commercial operations.
SUMMARY
[0009] The process of the present invention prepares citrus fruits by preparing the fruit for processing by the steps of grading the fruit into substantially uniform size ranges or a mix of graded fruit and washing the fruit to remove surface debris, dirt, residues and naturally occurring waxes. A surface active agent may be used in the washing step. The clean, graded fruit is then subjected to a perforating process that creates a plurality of holes through the outer peel of the fruit and extending into the albedo inside the outer peel. The perforated fruit is then rinsed to remove any particle of the outer peel and albedo that may remain on the fruit.
[0010] After rinsing, the fruit is placed in a chamber. After the chamber is closed, a vacuum is applied to the inside of the chamber and the fruit contained therein. After a predetermined period of time that allows the pressure inside the fruit to equilibrate with the vacuum, an enzyme effective to degrade the albedo is introduced into the vacuum chamber. Sufficient enzyme is introduced to cover all the fruit contained in the vacuum chamber.
[0011] After the enzyme has been introduced, the vacuum is released and the chamber pressure is vented to atmospheric pressure. The fruit may then be subjected to heat and undergoes an incubation process. Heat accelerates the enzyme activity. The enzyme then attacks and breaks-down the albedo of the fruit pieces. Following incubation, the fruit is cooled, then peeled, and the enzyme is deactivated.
[0012] Subsequently, the fruit is rinsed, the outer peel is removed, and the individual segments are prepared for further processing.
[0013] Further details of these, as well as other, steps are discussed in the detailed description which follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] Many objects and advantages of the present invention will be apparent to those skilled in the art when this description is read in conjunction with the appended drawings wherein like reference numerals are applied to like elements and wherein:
[0015] FIG. 1 is a schematic illustration of a citrus fruit;
[0016] FIG. 2 is a schematic diagram of process steps according to this disclosure;
[0017] FIG. 3 is a front view in partial cross section of a fruit perforating unit of this disclosure;
[0018] FIG. 4 is a partial cross-sectional view taken along the line 4 - 4 of FIG. 3 ;
[0019] FIG. 5 is a partial cross-sectional view taken along the line 5 - 5 of FIG. 4 ;
[0020] FIG. 6 is an enlarged, partial view of a perforation roller used in the fruit perforating unit;
[0021] FIG. 7 is an enlarged, partial view of a swing roller used in the fruit perforating unit;
[0022] FIG. 8 is a schematic diagram of the enzyme standardization process of this disclosure; and
[0023] FIG. 9 is a chart of a calibration curve.
DETAILED DESCRIPTION OF THE INVENTION
[0024] In commercial processing of citrus fruit to obtain citrus fruit segments, large quantities of freshly harvested citrus fruit are provided to the process. The process of this invention is suitable for use with citrus fruits including, for example, grapefruit, oranges, lemons, and limes. Depending upon the particular citrus fruit to be processed, certain features of the apparatus may require modification, some of which will be discussed below.
[0025] Some characteristics of citrus fruit, grapefruit in particular, are helpful background for this invention. FIG. 1 shows, for example, a grapefruit 10 which has been cut transversely to show its internal structure. The outside of the grapefruit is a tough, waxy outer peel 12 that contains cells with grapefruit essential oils. Toward the center, the grapefruit 10 includes a plurality of fruit sections 14 , each of which is surrounded by a membrane 16 . Between that membrane 16 and the outer peel 12 is a pithy white layer 18 , also known as the albedo.
[0026] The first step in the process involves an initial inspection of the exterior of freshly harvested fruit 10 . That inspection step involves determining whether the individual fruits are suitable for the process. To that end, the pieces of fruit are examined to determine such qualities as firmness, cleanliness, and rotted condition. Rotted fruit is rejected and discarded or used in byproduct process streams. Soft fruit is likewise rejected, but may be used in other byproduct process streams including, for example, juice extraction. Fruit which is excessively dirty is pre-washed to an acceptable level for handling in the process. For quality analysis purposes, a sample of fruit from each truckload is examined and a record is made of the percentage portions which are too dirty, rotten, or too mushy.
[0027] With reference to FIG. 2 , the next step involves sizing 20 the fruit so that the pieces of fruit satisfy minimum size criteria. For example, grapefruit are preferably sized so that the minimum diameter is about 3.25 inches, while oranges are preferably sized so that the minimum diameter is about 2.875 inches. These preferred sizes are selected, in part, so that the resulting fruit segments have appropriate size for commercial sale. These preferred minimum diameters may, of course, be selected to have different values depending on the processing equipment to be used; however, the preferred values expressed are believed to be workable sizes for commercial operations. Other kinds of citrus fruit that are typically smaller than oranges and grapefruit, namely lemons or limes, would be expected to have different, smaller preferred diameters. Fruit which fails to meet the minimum preferred diameter criterion is rejected for the process and passed to other by product streams, such as, for example, juice extraction. Fruit that successfully passes the sizing operation is temporarily stored in bins that may be fashioned from a suitable conventional plastic material.
[0028] Next, the bins with appropriately sized fruit are dumped into the processing line which a washing step 22 is performed. Washing is accomplished by advancing the fruit by a suitable conveyor that moves the fruit through suitable washing apparatus that includes rotating brushes that effectively scrub the outer surface of the pieces of fruit. As the fruit progresses through the washing apparatus water is sprayed on the fruit surface to aid the scrubbing operation. In addition, the fruit is sprayed with a suitable surface active agent, e.g., an alkaline detergent having a concentration of about 14,000 ppm, to further enhance the scrubbing operation. The scrubbed fruit is then immersed in a weak peracetic acid solution for sanitizing purposes. For example, the peracetic acid with a concentration of 70 ppm may be advantageously used.
[0029] After sanitization, the fruit is subjected to a skin preparation step 24 . In this skin preparation step, the outer peel of the grapefruit is treated to enhance access to the albedo by an enzyme solution to be applied later. This skin preparation step may involve, for example, abrasion of the outer peel or perforation of the outer peel. Other techniques may also be apparent to those skilled in the art. Nevertheless, the skin preparation step 24 at least partially removes some of the outer peel so that access is provided to the albedo at multiple locations on the fruit. With the abrasion technique, the outer peel is scuffed to roughen it and expose parts of the albedo randomly distributed about the surface of the fruit.
[0030] The currently preferred skin preparation technique, however involves perforation where the outer peel of each fruit is mechanically penetrated to produce a plurality of holes. For oranges and grapefruit, mechanical perforation using pins having a length of about 0.1875 inches, and a diameter of about 0.0276 inches (about 0.7 mm) has been found to be successful. The mechanical perforation step is intended to provide perforations randomly distributed over at least about 75% of the surface of each piece of fruit. Preferably, the perforations are randomly distributed over substantially the entire surface of each piece of fruit.
[0031] Mechanical perforation can be accomplished, for example, using a perforator assembly 30 (see FIG. 3 ) which includes a housing 32 having a pair of ends. One end has an inlet opening sized to simultaneously receive multiple pieces of fruit and an inlet housing 34 that includes an inlet ramp 36 for delivering fruit to the inlet opening. The second end of the perforator assembly 30 has a discharge opening that delivers perforated fruit to a discharge chute 38 .
[0032] The perforator assembly 30 also includes an internal screw conveyor 40 that is rotatable about its longitudinal axis. The conveyor 40 includes a generally helical surface extending generally radially outwardly from the axis. The helical surface makes a plurality of revolutions about its axis between the ends of the housing 32 , for example six full revolution of the helical surface may be provided. The pitch of the helical surface for each revolution is selected so that at least one piece of fruit can be received between axially adjacent parts of the helical surface, although the pitch may be sufficient to accommodate a plurality of pieces of fruit between such axially adjacent parts of the helical surface. To drive the screw conveyor 40 , a suitable conventional motor (not shown) may be provided at one end of the conveyor 40 . When the screw conveyor 40 rotates, it mechanically advances fruit from the inlet opening at the first end to the discharge opening at the second end.
[0033] A plurality of parallel, generally cylindrical, elongated rollers 42 , 42 ′ (see FIG. 4 ) support the fruit as it moves through the perforator assembly 30 . By way of example, as many as ten such rollers may be used. Preferably, the rollers 42 , 42 ′ are uniformly spaced from one another along an arc (see FIG. 5 ) that is centered on the axis of the screw conveyor 40 . In this manner the minimum spacing between the edge of the screw conveyor 40 and the roller is substantially the same for each roller 42 , 42 ′. Each roller 42 , 42 ′ is rotatably mounted in the perforator assembly 30 so as to be rotatable about its longitudinal axis. Suitable conventional motors 44 , 46 are provided to rotate the rollers 42 , 42 ′ and are drivingly connected to the rollers 42 , 42 ′ with a conventional drive mechanism. The motor 44 drives the rollers 42 , while the motor 46 drives the rollers 42 ′ on the other side of the perforator assembly 30 .
[0034] The rollers 42 , 42 ′ preferably comprise a plurality of pin rollers 50 with a swing roller 48 disposed between pairs of pin rollers 50 . As best seen in FIG. 6 , the surface of each pin roller 42 includes a multiplicity of perforator pins 44 . These pins 44 may be arranged in longitudinal rows, as shown, or in any other desired pattern. The pins 44 are sized to provide the desired perforations for the fruit being processed. The pins 44 may be cylindrical or non-cylindrical and may include a blunt wire tip. When processing grapefruit and/or oranges, pins having a diameter of about 0.0275 inches (0.7 mm) and a length of about 0.1875 inches have been found to be suitable. Moreover, the pins 44 are spaced from one another so that the weight of the fruit will cause the fruit to be impaled by the pins but the pins are not so closely spaced that the fruit is supported by so many pins 44 that the fruit is not effectively impaled.
[0035] Each swing roller 58 (see FIG. 7 ) includes a generally helical surface element 52 that extends along substantially its entire length. The helical surface element 52 may be a surface attachment as shown, or may be a groove (not shown), or a combination of both. As the swing roller 58 rotates, the helical surface element 52 tends to push the pieces of fruit laterally with respect to the axis of the screw conveyor 40 . To accomplish this action where the screw conveyor 40 rotates in a counterclockwise direction (looking downstream from the inlet 36 ), the swing rollers 48 (see FIG. 4 ) on the right side rotate clockwise and have a right-handed helical surface element 52 . Conversely, the swing rollers 48 ′ on the left side rotate counterclockwise and have a left-handed helical surface element 52 ′.
[0036] As the fruit enters the perforator assembly 30 (see FIG. 3 ) from the inlet opening, the screw conveyor 40 advances the individual pieces of fruit toward the discharge chute 38 . Although the precise interaction between the rollers 42 , 42 ′, the screw conveyor 40 , and the individual pieces of fruit is not fully understood and characterized, the swing rollers 48 ′ and associated pin rollers 50 on the left side tends to push fruit laterally to the left of the screw conveyor axis, while the swing rollers 48 and associated pin rollers 50 on the right side tends to push fruit laterally to the right of the screw conveyor axis. Interaction between the screw conveyor 40 and the fruit tends to rotate the fruit about an axis extending substantially radially from the axis of the screw conveyor 40 . The pins 44 of the rollers 50 puncture the outer peel of the fruit as the rollers themselves rotate. That rotation of the rollers 50 tends to cause the fruit to also rotate about a second axis substantially parallel to the axis of the rollers 50 and the axis of the screw conveyor 40 . Action of the helical surface elements of the swing roller 48 , 48 ′ tends to cause the fruit to rotate about a third axis substantially perpendicular to the axis of the screw conveyor 40 . Accordingly, as the fruit moves through the perforator assembly 30 , it is subjected to rotation about multiple axes so that virtually the entire surface of the fruit is exposed to the pins 44 and perforated by them.
[0037] Fruit discharged from the discharge chute 38 of the perforator assembly 30 may be collected in, for example, a container such as a large, reusable basket. Moreover, the fruit discharged from the perforator assembly 30 is periodically inspected to determine what portion of the fruit surface has been effectively perforated. If about 75% or less of the surface is effectively perforated, the volume of fruit fed to the inlet of the perforator assembly 30 is reduced. Moreover, at a predetermined time interval, for example once about every 30 minutes, a piece of fruit is subjected to vacuum, and then submerged in colored water. Based on the resulting coloring of the outer peel, the uniformity of the perforation step can be assessed and recorded for process control purposes.
[0038] After the perforation step is completed ( FIG. 2 ) the fruit is rinsed 54 to remove any particles of citrus peel that may adhere to the surface of the fruit.
[0039] Next, the containers of fruit are deposited in a vacuum chamber. The vacuum chamber used for this process is large, and may have dimensions of about ten feet in length, about four feet in width, and a depth of about four feet. The depth, if desired, may also be as great as about ten feet; however, the depth must be selected such that the bottom-most fruit in the chamber are not crushed by the weight of fruit above it in the chamber. To provide substantially continuous movement of fruit through the process, a pair of vacuum chambers may be used. In such an arrangement, fruit can be loaded into an open vacuum chamber while operations proceed in the second vacuum chamber. Then, when operations in the second vacuum chamber are finished, the first vacuum chamber can be closed and vacuum operation proceed therein while the second vacuum chamber is emptied and loaded with fruit.
[0040] With the fruit in the vacuum chamber and the chamber closed, a vacuum 56 is applied to the interior of the vacuum chamber. The vacuum in the chamber preferably likes in the range of about 1 to about 29 inches of mercury (in. Hg), and most preferably is about 27 in. Hg. This vacuum level is maintained in the vacuum chamber for an initial period of about 1 second to about 2 hours, and preferably for about 7 minutes. The precise amount of time for the vacuum step depends upon the amount of fruit which must be processed and the level of vacuum desired. For example, if fruit must be processed substantially continuously, a short time at a high vacuum may be appropriate; whereas, a small occasional operation may proceed in occasional batches so a long time at a lower vacuum may be acceptable.
[0041] Separately from the movement of fruit, an enzyme solution is prepared 58 . The enzyme solution includes pectinase and water, with the pectinase concentration preferably being in the range of about 0.01% to about 40.00%. The percentages are weight percentages. The particular percentage used will depend upon the particular enzyme being used. Among the preferred enzymes for this process are Novozyme (Novoshape KE 545005) from Novo and Crystalzyme PML-MX from Valley Research. A concentration of about 0.15% is suitable for those preferred enzymes. When prepared, the temperature of the enzyme solution is preferably maintained in the range above freezing to less than the denaturing temperature of the enzyme, preferably in the range of greater than 32° F. to about 130° F., and most preferably about 70° F. The particular temperature selected from this temperature range is also picked so as to be below the deactivation (denaturation) temperature for the enzyme.
[0042] With the enzyme solution prepared 58 and fruit in the vacuum chamber under a vacuum condition, the enzyme solution is transferred 60 into the vacuum chamber while the vacuum is maintained. For example, this transfer 60 into the vacuum chamber may be accomplished by appropriate valves which allow the enzyme solution to enter the vacuum chamber from the bottom. The enzyme solution is applied to the vacuum chamber until all the fruit in the chamber is covered by the solution. By covering the fruit with a perforated lid when the fruit is loaded into the vacuum chamber, any tendency of the fruit to float above the enzyme solution is substantially avoided. This transfer step 60 preferably takes place over a time period of about 1 to about 120 minutes preferably about 1 to about 10 minutes, and most preferably about 3 minutes.
[0043] Generally speaking, the known processes for enzymatic treatment of citrus fruit involve batch processing at least at the process point where enzymatic treatment occurs. When earlier processes for enzymatic treatment of citrus fruit have been scaled from laboratory-scale to commercial scale, the process performance has not been uniform as to the various pieces of fruit in each batch. On a commercial level, the enzymatic treatment can occur in tanks that are, for example, 10 feet long by 4 feet wide and 4 to 10 feet deep. While the exact reasons for such lack of uniform processing are not fully known, deep tanks filled with enzymatically active liquid have a hydrostatic pressure gradient that increases from the top of the tank to the bottom of the tank. That hydrostatic pressure gradient opposes any vacuum that may be applied to the head space at the top of the tank and appears to counteract the effect of the vacuum on the perforated fruit. In addition to that hydrostatic effect, surface tension resistance to formation of air bubbles escaping from perforations, as well as resistance air flow through the long channel formed by the perforation step, resist release of gas from inside the fruit when bathed in liquid.
[0044] The sequence of steps in applying the enzyme to the perforated fruit is believed to be very important. While the precise mechanisms are not yet fully understood, it appears that applying the vacuum to the perforated fruit prior to submerging fruit in the enzyme solution allows any air and/or other gas inside the fruit to be substantially uniformly and consistently vented to the vacuum chamber with minimal resistance and to facilitate enzyme penetration. Moreover, any hydrostatic effects and surface tension effects are effectively eliminated because no gas/liquid interface exists during the vacuum process. Rather, the prolonged vacuum in the chamber outside the fruit establishes a pressure differential so that air and or gas inside the fruit vents to the lower pressure of the vacuum chamber until the pressure inside the fruit essentially equilibrates with the vacuum pressure outside the fruit.
[0045] The vacuum in the chamber is then released. Upon release of the vacuum, the enzyme solution enters the perforations in the outer peel of the fruit and, thus, has access to the albedo of the fruit. About 30% of the enzyme solution in the chamber is absorbed by or infused into the perforated fruit. That portion of the enzyme solution that is not absorbed by the fruit is drained 62 from the vacuum chamber for use in a subsequent batch of fruit. Before the enzyme solution drained from the vacuum tank is used for another batch of fruit, however, several additional steps occur. Periodically, the drained enzyme is analyzed so that the enzyme concentration can be standardized 64 . That standardization process may occur as frequently as once for each batch of fruit; but, the standardization process may occur less frequently, such as once for every two to four batches. Based on the standardization process, substantially pure enzyme additions may be made to replenish the enzyme solution and return its enzyme concentration to the target concentration. The technique for this standardization process is an important part of this invention and is discussed separately below.
[0046] After each application of enzyme solution 60 to the vacuum chamber, the enzyme solution drained from a previous batch is topped-up or topped-off 66 to replace enzyme absorbed by the previous batch. To top-off 66 , fresh enzyme solution at the target enzyme concentration is used, e.g., at 0.15% concentration using the most preferred enzyme concentration discussed above.
[0047] The enzymatically treated fruit is then placed in an incubation bath 62 for an incubation period ranging from about 5 to about 120 minutes, preferably from about 15 to about 60 minutes, and most preferably about 45 minutes. The incubation bath preferably is water (but it may include enzyme) at a temperature in the range from about freezing to less than the denaturing temperature for the enzyme being used, preferably in the range of greater than about 32° F. to about 155° F., more preferably in the range of about 100° F. to about 150° F., and most preferably about 122° F. (50° C.). The temperature may preferably be selected in those ranges such that the enzyme has maximum activity per unit substrate. During the incubation period, the enzyme attacks the albedo between the fruit outer peel and the albedo from the membrane surrounding the fruit, substantially destroys the albedo thereby loosening the outer peel from the membrane surrounding the fruit, and substantially avoiding a subsequent need for further removal of the albedo.
[0048] After the incubation step 62 , the fruit is cooled 64 . Cooling can be effected by allowing the fruit to equilibrate with room temperature. Alternatively, cooling can be accomplished by immersing the fruit in cold water for a time sufficient to reduce the external temperature of the fruit to a level where it can be handled.
[0049] With the fruit cooled, it is peeled 66 . That peeling step can be done by hand or mechanically, although it is preferred that hand peeling be used. During the hand peeling step, any residual albedo can be scraped from the membrane covered segments.
[0050] After the fruit has been peeled, the enzyme is deactivated 68 . Deactivation of the enzyme is effected by placing the fruit in a water bath or otherwise heating it to a temperature at or above the denaturing temperature. Suitable deactivation temperature lies in the range of about 100° F. to about 280° F., more preferably in the range of 170° F. to about 200° F., and most preferably about 194° F. (90° C.) for a deactivation time in the range of about 1 second to about 3 hours, most preferably about 15 seconds. Deactivation techniques other than heating may also be used. For example, enzyme deactivation may be accomplished using an unfavorable environment, such as an acidic environment, a basic environment, or a pressure environment. Yet another enzyme deactivation technique may be a chemical deactivation.
[0051] After enzyme deactivation, the peeled fruit is rinsed 70 , and the fruit is then separated into segments 72 . If desired, the membrane surrounding the fruit segments may be removed so that only the meat of the citrus sections remains.
[0052] The process of this invention generates high quality, substantially uniform, and consistent enzymatically peeled citrus fruit segments and/or sections that can be further packaged for retail sale and consumption. Moreover, the process allows commercial scale use of enzyme peeling of citrus fruit.
[0053] As noted above, the foregoing process may be used for high throughputs of fruit such that the process is substantially continuous even though steps such as the vacuum chamber operation take place batchwise. Where the vacuum treatment step 56 occurs for short time intervals, e.g., under 30 minutes, the enzyme standardization step 64 must be accomplished rapidly. Past experience with techniques for determination of enzyme concentration and activity indicate that special reagents and as much as a day may be required to accurately evaluate enzyme concentration, particularly when the enzyme concentration is quite small. Such time periods are impractical if the enzyme concentration must be evaluated in a time frame measured in minutes.
[0054] A procedure that allows enzyme standardization in a time frame measured in minutes begins by preparing a standard substrate 100 (see FIG. 8 ) of the material on which the enzyme acts. For example, when using a pectinase, a standard substrate may be prepared by dispersing 2-10% pectin mixture in distilled water along with a preservative and sufficient acid to activate the preservative without having a significant affect on pH of the solution. The quantity of pectin mixture used is selected such that the amount of pectin will exceed the amount of pectin that would be destroyed by the enzyme used. The pectin mixture may preferably comprise 50% low methoxy pectin and 50% high methoxy pectin. The preservative may, for example comprise 50% sodium benzoate and 50% potassium sorbate. With that preservative, citric acid may be used. That substrate solution is boiled to completely hydrate the pectin. The thickened substrate solution is then cooled and may be stored at ambient temperature. When cooled, the substrate can be stored as long as six months.
[0055] A series of enzyme solutions each having a known enzyme concentration 102 is then prepared. The known concentrations range from 0% at the lower end to a value exceeding the nominal enzyme concentration, i.e. bracketing the nominal enzyme concentration. For the most preferred example discussed herein, the nominal or target enzyme concentration is 0.15%, so a concentration range from 0% to 0.20% in increments of 0.01% may be used.
[0056] Each of the known enzyme solutions is then mixed with a standard volume of the standard substrate. For example, 20 ml of each solution may be mixed with 330 g. of the standard substrate. Viscosity is then measured 104 for each mixture of a known enzyme solution with the standard substrate. Viscosity may be measured, for example, using a Brookfield LRV viscometer with a #2 Spindle operating at a speed of 60 rpm, and taking the measurement after 5 minutes.
[0057] Viscosities for the known enzyme concentrations may then be plotted to create a calibration curve 106 . An example of a calibration curve is shown in FIG. 9 , where the abscissa 120 is the viscosity and the ordinate 122 is the enzyme concentration. The data points of the calibration curve may be statistically analyzed to provide the best curve fit. The nominal or target enzyme concentration 124 is less than the highest standard enzyme concentration 126 so that the range of known concentrations (and the associated viscosities) will bracket the nominal enzyme concentration 124 and its nominal viscosity 128 . It will be noted from FIG. 9 that the calibration curve is linear for low concentrations. At higher concentrations, the calibration curve may be nonlinear.
[0058] To evaluate the enzyme concentration of the solution drained from the vacuum chamber 64 (see FIG. 2 ), a sample of the solution 108 (see FIG. 8 ) is taken, e.g., 20 ml. That sample is then mixed 110 with a standard amount (e.g., 330 g.) of the standard substrate. Using the same Brookfield viscometer with the same spindle and speed, viscosity of the enzyme sample is determined 112 , again after 5 minutes. To be sure that the measured viscosity of the unknown sample is accurate, a 20 ml sample of distilled water may also be mixed with the standard amount of the standard substrate and be subjected to the same viscosity determination. That viscosity sample using distilled water will determine whether any adjustment of the measured viscosity for the unknown sample needs to be made.
[0059] The measured viscosity for the unknown sample is compared 114 to the calibration curve ( FIG. 9 ) to determine its enzyme concentration. For example, knowing the viscosity 130 of the unknown sample, the calibration curve graphically provides the corresponding enzyme concentration 132 Knowing the enzyme concentration of the sample, the quantity of pure enzyme required to raise the level of enzyme concentration to the nominal level can be determined 116 . in any of several ways. For example, a table can be conveniently prepared to specify the amount of enzyme required for a convenient quantity, e.g., 1000 pounds of solution, as a function of the measured enzyme concentration in the sample. Alternatively, a graphical correlation between enzyme concentration and required pure enzyme could be used. Other techniques, including without limitation use of a programmable computer using commercially available programs, can also be used to determine the required pure enzyme. Moreover, a programmable computer using commercially available programs could also be used to house the calibration data, determine the best curve fit, evaluate the unknown enzyme concentration based on its viscosity, and determine the amount of pure enzyme required for either (i) a predetermined unit of enzyme solution (e.g., 1000 pounds) or (ii) the actual weight of enzyme solution drained from the vacuum chamber.
[0060] Regardless of the specific technique used to determine the required amount of pure enzyme, by adding the thus determined quantity of pure enzyme to the drained solution, the solution is fortified and its enzyme concentration is returned to the nominal concentration. Any additional volume required to fill the vacuum chamber can then be provided using fresh, nominal enzyme concentration solution.
[0061] This procedure allows the enzyme concentration of the drained liquid to be evaluated in minutes, rather than hours. Moreover, the procedure is well suited to rapid batch type processes such as the use of alternating vacuum chambers as described above.
[0062] This enzyme treatment process also digests the outer peel's cell walls and facilitates the release of grapefruit oil. For sufficiently large volumes of fruit throughput, the waste, i.e., outer peel and albedo, may be further processed to produce essential citrus oil.
[0063] Using the process described above, a batch of enzyme solution can be recycled, replenished with additional fresh solution, and fortified with pure enzyme to maintain its nominal standard concentration level. Moreover, the standardization process described permits the same enzyme solution to be used as many as 10 to 20 consecutive times before being discarded. Filtration of the drained enzyme solution is an enhancement that may further increase the useful life of a batch of enzyme solution.
[0064] A further enhancement of the process is the addition of a surfactant to enhance the enzyme performance. The surfactant is a surface active agent, such as a food-grade detergent, which lowers surface tension in the enzyme solution and makes the cells more recipient to the enzyme.
[0065] Throughout this specification certain numerical values have been identified and introduced by the word “about”, “essentially”, and the like. Those numerical values are not intended to be limited to the precise values stated, but are intended to include variations within 5% above and/or below the specific figure used, as the context may suggest.
[0066] It will now be apparent to those skilled in the art that a new, useful, nonobvious process for peeling citrus fruit has been disclosed. Moreover, it will be apparent to those skilled in the art that numerous modifications, variations, substitutions and equivalents exist for features of the invention that do not materially depart from the spirit and scope of the invention, as defined by the appended claims. Accordingly, it is expressly intended that all such modifications, variations, substitutions, and equivalents which fall within the spirit and scope of the appended claims be embraced thereby.
|
An efficient process for enzymatically peeling citrus fruit applies a vacuum to perforated fruit and, while maintaining that vacuum, introduces an enzyme solution to the perforated fruit. The fruit is infused with the enzyme by releasing the vacuum pressure. After incubating the enzyme, the albedo of the fruit is weakened and the citrus peel can be readily removed. The peeled fruit may be divided into sections and the encompassing membrane removed.
| 0
|
[0001] The present invention relates to polysaccharide nanofibers having antimicrobial properties and a method of making them. In particular, the invention relates to polysaccharide nanofibers having silver nanoparticles dispersed throughout the fibers. The fibers may be produced by electrospinning and may be used in wound care.
BACKGROUND OF THE INVENTION
[0002] The incorporation of silver into fibrous wound dressings is known. Generally, the silver is held on the surface of the fibers or dressing. Although this imparts antimicrobial properties to the dressing, it can lead to several disadvantages. Excess silver may need to be used because, due to its presence at the surface, the silver may be released or made inactive quickly. The excess, while providing a reservoir, can result in an unacceptable physical appearance of the dressing due to discoloration of the silver, or may result in staining of the skin of the patient. The incorporation of particles into fibrous wound dressings has been described in U.S. Pat. No. 7,229,689 but the method of incorporation involves the addition of silver from an ion exchange resin in order to avoid discoloration. It would be desirable to use silver in a fibrous dressing in such a manner that the silver is distributed evenly through the fibers so that a sustained release of silver is obtained from the dressing. It would also be desirable to use silver in the form of nanoparticles as silver nanoparticles have been shown to possess antimicrobial properties and present a larger surface area for release.
[0003] WO 2005/073289 discloses the mixing of metal particles with a polymer dope, prior to extrusion and solidification into fibers or films. One of the problems associated with the incorporation of nanoparticles into fibers is the difficulty of dispersing the particles uniformly as particles tend to agglomerate.
[0004] Electrospinning is a well known fabrication technique, which can be used to produce polymer fibers in the range 1 nm to 1 μm. The process of electrospinning polymer solutions involves the formation of an electrically charged liquid jet from the surface of a polymer solution in the presence of an electric field. The liquid jet undergoes stretching effects and drying as the solvent evaporates, and is deposited as polymer fiber on a suitably positioned, oppositely charged target. These electrospun polymer nanofibers are most commonly deposited in the form of a non-woven web.
[0005] In the past, relatively few natural polymers were successfully electrospun into nanofibers. Whereas synthetic polymers can have carefully controlled molecular weight and molecular weight distribution and are typically produced with long, flexible, linear chains, natural polymers are generally more complex and have strong hydrogen bonding, which leads to relatively low chain flexibility. This often results in natural polymers with unfavorable conformations.
SUMMARY OF THE INVENTION
[0006] We have found that it is possible to produce polysaccharide nanofibers with antimicrobial properties. In particular, we have found that it is possible to incorporate silver particles into polysaccharide nanofibers.
[0007] Accordingly, a first aspect of the present invention provides polysaccharide nanofibers having antimicrobial properties, said nanofibers comprising, for example, alginate and having silver nanoparticles dispersed throughout the fibers.
[0008] Such fibers have the advantage that they present a large surface area for delivery of silver to a wound. They may also have the advantage that the silver is released to the wound in a sustained manner. By the term dispersed throughout the fiber is meant that the nanoparticles are distributed within the fibers. The particles may be distributed through the whole thickness of the fiber and, preferably, are uniformly distributed. In this way a predictable dosage of silver may be delivered to the wound.
[0009] By the term nanoparticle is meant a particle having a diameter of from 1 nm to 100 nm, generally between 1 nm-50 nm and preferably between 1 nm-10 nm.
[0010] By the term nanofiber is meant a fiber having a diameter of less than 1 micron, generally between 1 nm-500 nm, preferably between 20 nm-500 nm.
[0011] Preferably, the silver particles are present in the fibers at a concentration of between 0.002% (w/w) and 2% (w/w), more preferably between 0.02% (w/w) and 1% (w/w).
[0012] The polysaccharide nanofibers are preferably gel forming fibers, by which is meant that the fibers are hygroscopic fibers which upon the uptake of wound exudate become moist, slippery or gelatinous and thus reduce the tendency for the surrounding fibers to adhere to the wound. The gel forming fibers can be of the type which retain their structural integrity on absorption of exudate or can be of the type which lose their fibrous form and become a structureless gel. The gel forming fibers may comprise, in addition to alginate, sodium carboxymethylcellulose, pectin, chitosan, hyaluronic acid, or other polysaccharides. The gel forming fibers preferably have an absorbency of at least 2 grams of 0.9% saline solution per gram of fiber (as measured by the free swell method). Preferably, the gel forming fibers have an absorbency of at least 10 g/g as measured in the free swell absorbency method, more preferably between 15 g/g and 25 g/g.
[0013] Alginate is a natural polysaccharide existing widely in many species of brown seaweeds. The alginate for use in the present invention can be sodium alginate of the type containing a high proportion of guluronate but can also be of the type containing a high proportion of mannuronate.
[0014] The polysaccharide nanofibers may be produced by electrospinning. We have found that polysaccharide nanofibers produced by electrospinning advantageously may have silver nanoparticles uniformly dispersed throughout the fibers. The distribution can be measured by transmission electron microscopy.
[0015] A second aspect of the invention relates to an aqueous solution for spinning polysaccharide nanofibers, said solution comprising, for example:
from 2% (w/w) to 8% (w/w) of sodium alginate; from 0.05% (w/w) to 5% (w/w) of water soluble polymer; and from 0.00015% (w/w) to 0.2% (w/w) of silver compound.
[0019] Preferably, the solution contains from 0.1% by weight to 1% by weight of a water soluble polymer such as polyethylene oxide, polyvinyl alcohol or polyvinyl pyrrolidone or a mixture thereof. More preferably, the water soluble polymer has a long-chain linear structure and high molecular weight.
[0020] The solution may also comprise from 2% by weight to 20% by weight of a polar aprotic solvent such as DMSO to break down hydrogen bonding within the polysaccharide and improve the polymer chain entanglement during electrospinning. The solution may also comprise from 0.01% w/w to 1% w/w of non-ionic surfactant such as Triton X-100 to alter the surface tension of the solution.
[0021] Preferably, the aqueous solution of sodium alginate has a weight proportion of PEO to alginate ratio between 2% and 25% and a DMSO concentration between 5% (w/w) and 10% (w/w), with small concentrations of silver nitrate. Advantageously, silver nanoparticles can be formed in-situ in such a solution by photochemical reduction of a silver compound such as silver nitrate. Silver nanoparticles are formed when silver ions dissociate from a silver compound when it is dissolved, and gain an electron in an oxidation-reduction reaction with a reducing agent such as carboxyl and/or hydroxyl groups of polymers. This results in silver atoms which act as seeds onto which other silver ions are reduced, resulting in clusters of silver atoms which grow into nanoparticles as more silver accumulates and clusters join together. These solutions can then be electrospun to form nanofibers with diameters in the range 1 nm-1 μm, which desirably contain a uniform distribution of silver nanoparticles.
[0022] Accordingly, a third aspect of the invention relates to a process for forming polysaccharide nanofibers by:
a) making a solution comprising, for example:
from 2% (w/w) to 8% (w/w) of sodium alginate; from 0.05% (w/w) to 5% (w/w) of water soluble polymer; and from 0.00015% (w/w) to 0.2% (w/w) of silver compound; and
b) electrospinning the solution to form nanofibers.
[0028] The electrospun nanofibers may then be ionically cross-linked in a bath containing excess calcium ions, in order to transform some or all of the sodium alginate to calcium alginate. The calcium alginate or sodium/calcium alginate nanofibers, containing silver nanoparticles may then be soaked in water to remove the excess calcium, before being dried. Preferably, the dried fibers comprise calcium alginate and sodium alginate in the ratio of 80% calcium alginate to 20% sodium alginate.
[0029] Preferably, the solution is prepared in ambient light and then stored in the dark prior to electrospinning within 12 hours of preparation, more preferably within 6 hours of preparation and more preferably within 4 hours of preparation.
[0030] Preferably, the solution has a viscosity prior to spinning of between 1 Pa:s and 10 Pa:s.
[0031] More preferably, the solution comprises an anti-agglomeration agent such as a non-ionic triblock copolymer or an organoalkoxysilane.
DESCRIPTION OF THE DRAWINGS
[0032] FIG. 1 a is a graph of UV-visible spectra showing the development of silver particles in alginate solution containing 5 mmol.L −1 AgNO 3 .
[0033] FIG. 1 b is a graph showing growth of the 450 nm peak for alginate solutions containing a range of AgNO 3 concentrations both in ambient light conditions.
[0034] FIG. 2 is an EDX spectrum of a silver nanoparticle within the alginate fibers.
[0035] FIG. 3 a ; is a TEM image of electrospun alginate nanofibers containing silver particles electrospun after 7 days.
[0036] FIG. 3 b is a TEM image of electrospun alginate nanofibers containing silver particles electrospun within 4 hours of preparation (micron bars: 200 μm).
[0037] FIG. 3 c is a higher magnification TEM image of an electrospun alginate nanofibers containing silver particles electrospun of FIG. 3 b (micron bar: 500 μm).
[0038] FIG. 4 a is an image of electrospun alginate discs without silver, on nutrient agar plates covered by a lawn of s. aureus.
[0039] FIG. 4 b is a close up image of an electrospun alginate disc without silver, on nutrient agar plates covered by a lawn of s. aureus.
[0040] FIG. 4 c is an image of electrospun alginate discs containing silver nanoparticles, on nutrient agar plates covered by a lawn of s. aureus.
[0041] FIG. 4 d is a close up image of an electrospun alginate disc containing silver nanoparticles, on nutrient agar plates covered by a lawn of s. aureus.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0042] The invention will now be illustrated by the following non-limiting examples.
Example 1
[0043] PEO (Mw: >5000000 g.mol −1 ) was dissolved in deionized water to a concentration of 1% -4 % (w/w). The solution was stirred until it appeared homogenous. After allowing time for degassing, a calculated mass of the PEO solution was mixed into a known mass of a solvent consisting of DMSO and deionized water, with a DMSO concentration between 2% (w/w) and 20% (w/w), preferably between 5% (w/w) and 10% (w/w). Sodium alginate was then slowly added to a vortex in the PEO/water/DMSO solution such that the total polymer concentration in the solution was between 3% (w/w) and 8% (w/w), preferably between 5% (w/w) and 6% (w/w) and the PEO to alginate ratio was between 2% and 10% by weight, preferably between 2% and 5% by weight. The solution was stirred thoroughly until it was consistently viscous and homogenous. Additions of the surfactant Triton X-100 were made, using a micropipette to a vortex in the alginate solution, such that the concentration was varied between 0.1% (w/w) and 1% (w/w).
[0044] In another solution, the deionized water was partially or entirely substituted for a dilute solution of AgNO 3 , before the alginate was added, such that the AgNO 3 concentration in the alginate solution was between 0.1 mmol.L and 10 mmol.L −1 .
[0045] In another solution, a known volume of a 0.1 mol.L −1 aqueous solution of AgNO 3 was added to the alginate using a micropipette, such that the final concentration of AgNO 3 in the alginate solution was between 0.1 mmol.L −1 and 10 mmol.L −1 .
[0046] In another solution, PEO (Mw 600,000-1,100,000 g.mol −1 ) was used instead of PEO (Mw: >5 000000 g.mol −1 ). In this solution the proportion of PEO to alginate ratio used was in the range 10% to 40% by weight, preferably 15% to 25% by weight.
[0047] These solutions were either centrifuged for 3 mins to 10 mins at 2000 rpm to 4000 rpm to remove air bubbles from the solution, or they were simply left until the solutions were clear of bubbles.
[0048] It was found that as soon as silver nitrate was mixed into the polymer solution in ambient light conditions, a reduction reaction took place. This caused a color change in the solution, from the clear yellow of an alginate solution to a dark pink or grey over time. The results of spectrophotometry confirmed these observations and can be seen in FIG. 1 . It can be seen that over the first four hours after preparation of the silver containing solutions, the absorbance increases rapidly. From then on the rate of increase is reduced. The development of multiple peaks and a broadening of the peak in FIG. 1 b indicate that as time progresses the silver particles grow and become aggregated.
[0049] The effect of solution aging time, that is to say the time between preparation and electrospinning, on the morphology and distribution of silver particles in the alginate fibers can clearly be seen in FIG. 2 . The sample produced 7 days after solution preparation has large aggregated silver particles, non-uniformly distributed, whereas the sample electrospun from fresh solution contains more evenly distributed silver particles, which are significantly smaller. With shorter solution aging times the aggregation of silver nanoparticles is reduced. It has also been found that if solutions are stored in the dark after an initial one hour aging time, particle growth and aggregation is inhibited so that alginate fibers with uniformly distributed silver nanoparticles can more easily be produced.
[0050] The alginate solutions were electrospun from a stainless steel needle of gauge size between 22 G and 31 G, which was connected to a syringe. Solution was maintained at the tip of the needle by means of a digitally controlled syringe pump, such that the flow rate was in the range 10-30 μl.min −1 . An applied voltage in the range 5 kV to 30 kV, preferably 10 kV to 20 kV was applied to the needle, which was positioned between 10 cm and 50 cm, preferably between 15 cm and 25 cm away from the collector.
[0051] After electrospinning, nanofibrous webs were removed from the collector and ionically cross-linked in a bath either containing an aqueous solution of CaCl 3 , an organic solution of CaCl 3 followed by an aqueous solution of CaCl 3 , or an aqueous organic solution of CaCl 3 . After cross-linking, the fibers were soaked in either deionized water, or a mix of water and organic solvent, in order to remove any excess CaCl 3 or resulting NaCl from the fibers. Samples were then dried before characterization.
[0052] The electrospun alginate samples were characterized using scanning electron microscopy (SEM), transition electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDX). Samples, taken for SEM before and after cross-linking, were mounted on aluminium stubs and sputter coated with 10 nm Pt/Pd before imaging. TEM samples were collected on carbon coated copper grids during electrospinning. (See FIGS. 3 a, 3 b and 3 c .)
[0053] In order to test for antimicrobial efficacy, samples of the cross-linked alginate fibers with and without silver nanoparticles were punched into 8 mm diameter disks and sterilized in 100% ethanol before use.
[0054] Staphylococcus aureus , a common wound pathogen, was grown in nutrient broth overnight and then used to inoculate nutrient agar plates, to create a lawn of bacteria. The sample discs were then placed onto the agar plates and incubated at 37° C. for approximately 15 hrs. In this time, the lawn of s. aureus grew to form visible colonies on the agar plates. Inhibition of the growth of these colonies around the sample discs is an indicator as to the antimicrobial efficacy of the material.
[0055] Results of the antimicrobial sensitivity assay can be seen in FIGS. 4 a, 4 b, 4 c and 4 d. It is clear that the electrospun alginate samples have no inhibitory effect on the growth of the s. aureus colonies, whereas the samples containing silver nanoparticles all inhibited the growth of the bacterial colonies directly under the discs as well as in zone around the discs.
[0056] The electrospun webs were also characterized for release into water and Solution A. Solution A is an aqueous solution with physiological concentrations of sodium chloride and calcium chloride. The release rate was found to reduce after three or four days of immersion in Solution A although even after two weeks, silver was being released. This demonstrates the desirable sustained release of silver from electrospun alginate webs.
Example 2
[0057] The second example describes the addition of a stabilizing agent in the process described above, which restricts the growth of the silver nanoparticles and prevents them from aggregating. This allows nanofibers to be electrospun over a range of time periods, without losing the uniform distribution of fine silver nanoparticles.
[0058] The stabilizing agent used is an aqueous amphiphilic tri-block copolymer consisting poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) blocks. This copolymer is capable of forming micelles around metallic nanoparticles, stabilizing them as a colloid in the aqueous solution.
|
Polysaccharide nanofibers having anti-microbial properties, said nanofibers comprising an alginate and having silver nanoparticles dispersed throughout the nanofibers.
| 3
|
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. Ser. No. 08/101,204 filed Aug. 3, 1993, now abandoned, which is a divisional of U.S. Ser. No. 07/766,498 filed Sep. 26, 1991 and issued as U.S. Pat. No. 5,234,578, which is a continuation-in-part of U.S. Ser. No 07/236,817, filed Aug. 26, 1988, now abandoned.
FIELD OF THE INVENTION
This invention relates generally to apparatus for the fluidized catalytic cracking of heavy hydrocarbon streams such as vacuum gas oil and reduced crudes. This invention relates more specifically to an apparatus for reacting hydrocarbons in an FCC reactor and separating reaction products from the catalyst used therein.
BACKGROUND OF THE INVENTION
The fluidized catalytic cracking of hydrocarbons is the main stay process for the production of gasoline and light hydrocarbon products from heavy hydrocarbon charge stocks such as vacuum gas oils. Large hydrocarbon molecules, associated with the heavy hydrocarbon feed, are cracked to break the large hydrocarbon chains thereby producing lighter hydrocarbons. These lighter hydrocarbons are recovered as product and can be used directly or further processed to raise the octane barrel yield relative to the heavy hydrocarbon feed.
The basic equipment or apparatus for the fluidized catalytic cracking (hereinafter FCC) of hydrocarbons has been in existence since the early 1940's. The basic components of the FCC process include a reactor, a regenerator and a catalyst stripper. The reactor includes a contact zone where the hydrocarbon feed is contacted with a particulate catalyst and a separation zone where product vapors from the cracking reaction are separated from the catalyst. Further product separation takes place in a catalyst stripper that receives catalyst from the separation zone and removes entrained hydrocarbons from the catalyst by counter-current contact with steam or another stripping medium. The FCC process is carried out by contacting the starting material whether it be vacuum gas oil, reduced crude, or another source of relatively high boiling hydrocarbons with a catalyst made up of a finely divided or particulate solid material. The catalyst is transported like a fluid by passing gas or vapor through it at sufficient velocity to produce a desired regime of fluid transport. Contact of the oil with the fluidized material catalyzes the cracking reaction. During the cracking reaction, coke will be deposited on the catalyst. Coke is comprised of hydrogen and carbon and can include other materials in trace quantities such as sulfur and metals that enter the process with the starting material. Coke interferes with the catalytic activity of the catalyst by blocking active sites on the catalyst surface where the cracking reactions take place. Catalyst is transferred from the stripper to a regenerator for purposes of removing the coke by oxidation with an oxygen-containing gas. An inventory of catalyst having a reduced coke content, relative to the catalyst in the stripper, hereinafter referred to as regenerated catalyst, is collected for return to the reaction zone. Oxidizing the coke from the catalyst surface releases a large amount of heat, a portion of which escapes the regenerator with gaseous products of coke oxidation generally referred to as flue gas. The balance of the heat leaves the regenerator with the regenerated catalyst. The fluidized catalyst is continuously circulated from the reaction zone to the regeneration zone and then again to the reaction zone. The fluidized catalyst, as well as providing a catalytic function, acts as a vehicle for the transfer of heat from zone to zone. Catalyst exiting the reaction zone is spoken of as being spent, i.e., partially deactivated by the deposition of coke upon the catalyst. Specific details of the various contact zones, regeneration zones, and stripping zones along with arrangements for conveying the catalyst between the various zones are well known to those skilled in the art.
The rate of conversion of the feedstock within the reaction zone is controlled by regulation of the temperature of the catalyst, activity of the catalyst, quantity of the catalyst (i.e., catalyst to oil ratio) and contact time between the catalyst and feedstock. The most common method of regulating the reaction temperature is by regulating the rate of circulation of catalyst from the regeneration zone to the reaction zone which simultaneously produces a variation in the catalyst to oil ratio as the reaction temperatures change. That is, if it is desired to increase the conversion rate an increase in the rate of flow of circulating fluid catalyst from the regenerator to the reactor is effected. Since the catalyst temperature in the regeneration zone is usually held at a relatively constant temperature, significantly higher than the reaction zone temperature, any increase in catalyst flux from the relatively hot regeneration zone to the reaction zone effects an increase in the reaction zone temperature.
The hydrocarbon product of the FCC reaction is recovered in vapor form and transferred to product recovery facilities. These facilities normally comprise a main column for cooling the hydrocarbon vapor from the reactor and recovering a series of heavy cracked products which usually include bottom materials, cycle oil, and heavy gasoline. Lighter materials from the main column enter a concentration section for further separation into additional product streams.
As the development of FCC units has advanced, temperatures within the reaction zone were gradually raised. It is now commonplace to employ temperatures of about 525° C. (975° F.). At higher temperatures, there is generally a loss of gasoline components as these materials crack to lighter components by both catalytic and thermal mechanisms acting independently. At 525° C., it is typical to have 1% of the potential gasoline components thermally cracked into lighter hydrocarbon gases. As temperatures increase, to say 1025° F. (550° C.), most feedstocks can lose up to 6% or more of the gasoline components to thermal cracking.
One improvement to FCC units, that has reduced the product loss by thermal cracking, is the use of riser cracking. In riser cracking, regenerated catalyst and starting materials enter a pipe reactor and are transported upward by the expansion of the gases that result from the vaporization of the hydrocarbons, and other fluidizing mediums if present upon contact with the hot catalyst. Riser cracking provides good initial catalyst and oil contact and also allows the time of contact between the catalyst and oil to be more closely controlled by eliminating turbulence and backmixing that can vary the catalyst residence time. An average riser cracking zone today will have a catalyst to oil contact time of 1 to 5 seconds. A number of riser reaction zones use a lift gas as a further means of providing a uniform catalyst flow. Lift gas is used to accelerate catalyst in a first section of the riser before introduction of the feed and thereby reduces the turbulence which can vary the contact time between the catalyst and hydrocarbons.
In most reactor arrangements, catalysts and conversion products still enter a large chamber for the purpose of initially disengaging catalyst and hydrocarbons. The large open volume of the disengaging vessel exposes the hydrocarbon vapors to turbulence and backmixing that continues catalyst contact for varied amounts of time and keeps the hydrocarbon vapors at elevated temperatures for a variable and extended amount of time. Thus, thermal cracking can again be a problem in the disengaging vessel. A final separation of the hydrocarbon vapors from the catalyst is performed by cyclone separators that use centripetal acceleration to disengage the heavier catalyst particles from the lighter vapors which are removed from the reaction zone.
In order to minimize thermal cracking in the disengaging vessel, a variety of systems for directly connecting the outlet of the riser reactor to the inlet of a cyclone are suggested in the prior art. Directly connecting the cyclone inlet to the riser outlet in what has been termed a “direct coupled cyclone system” requires a means for relieving pressure surges that can otherwise overload the cyclones and cause catalyst to be carried over into the product stream separation facilities located downstream of the reactor. The development of these systems to handle the overload problem in a variety of ways increases the practicality of directly coupling the riser outlet to the cyclone inlet. Direct coupling of cyclones can greatly reduce thermal cracking of hydrocarbons.
It is also known, for purposes of controlling thermal cracking, to lower the temperature of the reaction products upon leaving the cyclone separators by the use of a quench liquid. Quenching the product stream reduces its temperature below that at which thermal cracking can occur and reduces the loss of gasoline products by continued cracking to light ends.
DISCLOSURE STATEMENT
U.S. Pat. No. 4,624,771, issued to Lane et al. on Nov. 25, 1986, discloses a riser cracking zone that uses fluidizing gas to pre-accelerate the catalyst, a first feed introduction point for injecting the starting material into the flowing catalyst stream, and a second downstream fluid injection point to add a quench medium to the flowing stream of starting material and catalyst.
U.S. Pat. No. 4,624,772, issued to Krambeck et al. on Nov. 25, 1986, discloses a closed coupled cyclone system that has vent openings, for relieving pressure surges, that are covered with weighted flapper doors so that the openings are substantially closed during normal operation.
U.S. Pat. No. 4,234,411, issued to Thompson on Nov. 18, 1980, discloses a reactor riser disengagement vessel and stripper that receives two independent streams of catalyst from a regeneration zone.
U.S. Pat. No. 4,479,870, issued to Hammershaimb et al. on Jun. 30, 1984, and U.S. Pat. No. 4,822,761, issued to Walters et al. on Apr. 18, 1989, teach the use of lift gas having a specific composition in a riser conversion zone at a specific set of flowing conditions with the subsequent introduction of the hydrocarbon feed into the flowing catalyst and lift gas stream.
U.S. Pat. No. 3,133,014 shows the use of a spray nozzle in a reactor vapor line to cool high boiling hydrocarbons and prevent the formation of coke deposits on the vapor line wall.
U.S. Pat. Nos. 3,290,465; 4,263,128; 4,256,567, and 4,243,514 generally teach the use of quench streams for the purpose of preventing thermal cracking of hydrocarbons in transfer lines.
U.S. Pat. Nos. 3,221,076 and 3,238,271 show the direct transfer of vapors from a cyclone separator in a reaction vessel to a contacting vessel for quenching or removing fine catalyst particles that are transported with vapors.
BRIEF DESCRIPTION OF THE INVENTION
It is an object of this invention to provide an FCC apparatus that improves the control of contact time between catalyst and hydrocarbons.
It is a further object of this invention to provide an FCC apparatus that operates with high reaction temperatures and decreases thermal stresses in FCC structure due to temperature gradients.
It is a yet further object of this invention to provide an FCC apparatus having reduced times of contact between the catalyst and hydrocarbons, and reduced exposure of the hydrocarbon feeds to elevated temperature exposure.
It is another object of this invention to provide an FCC apparatus that will facilitate the separation of catalyst and hydrocarbon vapors.
It is a yet another object of this invention to improve the recovery of cracked hydrocarbon products from the disengagement zone and stripper section of the reaction process.
These and other objects are achieved by the process of this invention which is an FCC apparatus that converts FCC feed by contact with catalyst in a riser conversion zone, maintains a carefully contact time between the catalyst and hydrocarbon feed, and rapidly quenches hydrocarbon products recovered from the cyclone separators to avoid thermal cracking. This apparatus of this invention places a quench chamber above a reactor vessel and a hot stripper below a reactor vessel to provide a progressively decreasing temperature profile up the structure of the FCC arrangement and equipment for sequential reaction control. A riser contains the primary catalytic reactions of the hydrocarbon vapor and delivers the reacted vapors to the reactor structure. Starting from the bottom of the structure the hot stripper has the highest temperature and desorbs or displaces hydrocarbons from the catalyst to terminate long residence time catalytic reactions. Above the hot stripper bulk separation equipment divides the main vapor and catalyst stream to limit residence time of major catalytic reactions. At a yet higher elevation and lower internal temperature quench equipment arrests thermal reactions of the vapor stream. This structure arrangement permits reliable control of reaction time to obtain desired products and enhances mechanical reliability of the structure.
In addition the progressively decreasing temperature gradient lowers thermally induced stresses in the shells of the vessels that make up the structure. In normal operation the stripping vessel will operate at the highest temperature. A reactor vessel housing means for making an initial separation between the catalyst and the hydrocarbon vapors will operate a lower temperature than the stripping vessel. Finally, the quench vessel that cools the product vapors will operate at the lowest temperature. Connecting a reactor vessel on top of a hot stripping vessel and a quench vessel on top of a hot stripping vessel provides a uniformly decreasing temperature profile up the structure of the reactor, stripper and quench vessels. This uniformly changing temperature gradient through lowers thermally induced stresses.
Accordingly, in one embodiment this invention is an apparatus for the fluidized catalytic cracking of hydrocarbons. The apparatus includes a riser portion that comprises a substantially vertical riser, means for introducing catalyst into a lower portion of the riser, means for introducing a hydrocarbon feed into the riser and a transfer conduit in communication with the upper end of the riser. The invention also incorporates means for separating catalyst from gases. The means for separating define an inlet in closed communication with the conduit, a catalyst outlet, and a vapor outlet and are at least partially located in the reactor vessel. A stripping vessel located below the reactor vessel communicates with the catalyst outlet and defines a substantial collection volume for receiving catalyst separated by the means for separating catalyst. The stripping vessel also contains means for contacting the catalyst collected therein with a stripping medium and means for heating catalyst in said stripper vessel. A vapor line carries hydrocarbon vapors away from the vapor outlet and into means for quenching the hydrocarbon vapors. The means for quenching have a location above reactor vessel.
In an alternate and more limited embodiment of this invention the apparatus of this invention comprises a reactor vessel having a center line and a substantially vertical riser having a center line horizontally offset from the reactor vessel. A catalyst nozzle communicates with a lower part of the riser for introducing catalyst into a lower portion of the riser. A lift gas nozzle in communicates with a lower portion of the riser at a location above the catalyst nozzle for introducing a lift gas into a lower portion of the riser. A feed nozzle in communicates with the riser at a location above the lift gas nozzle for introducing a hydrocarbon feed into the riser. A transfer conduit defines a conduit outlet and a conduit inlet in communication with the upper end of the riser. Means for separating catalyst from gases are located in the reactor vessel. The means for separating define a separation inlet in closed communication with the conduit outlet, and a catalyst outlet and a vapor outlet. A stripping vessel, located below the reactor vessel and in communication with the catalyst outlet, has a substantial collection volume for receiving catalyst separated by the means for separating catalyst, and includes means for contacting the catalyst collected therein with a stripping medium and heating catalyst in the stripper vessel. A gas tube has one end in communication with the stripping vessel and a second end in communication with the transfer conduit. A vapor line is in communication with the vapor outlet for carrying hydrocarbon vapors away from the vapor outlet. A quench vessel is located on top of the reactor vessel for quenching hydrocarbon vapors from the vapor line.
In another limited embodiment this invention is an apparatus for the fluidized catalytic cracking of hydrocarbons. The apparatus comprises: a reactor vessel; a substantially vertical riser extending coaxially into the reactor vessel; a catalyst nozzle in communication with the riser for introducing catalyst into a lower portion of the riser; a lift gas nozzle in communication with the riser for introducing a lift gas into a lower portion of the riser; a feed nozzle in communication with the riser and located above the lift gas nozzle for introducing a hydrocarbon feed into an upper portion of the riser; a disengaging vessel surrounding the upper end of the riser for separating catalyst from hydrocarbon vapors; a collector located at the upper end of the riser in the disengaging vessel; a transfer conduit in communication with the collector; a cyclone separator defining an inlet in closed communication with the conduit, a catalyst outlet, and a vapor outlet; a stripping vessel located below the reactor vessel and in communication with the catalyst outlet the stripping vessel having a substantial collection volume for receiving catalyst from the catalyst outlet and means for contacting the catalyst collected therein with a stripping medium and heating catalyst in the stripping vessel; a vapor line in communication with the vapor outlet; and, means for quenching vapors withdrawing from the reactor vessel by the vapor line.
Other aspects and embodiments and advantages of this invention are disclosed in the following detailed description of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic elevation showing a cross-section an FCC reactor suitable for the practice of this invention along with an FCC regenerator.
FIG. 2 is a cross section of an alternate reactor vessel arrangement suitable for use in this invention.
DETAILED DESCRIPTION OF THE INVENTION
The apparatus of this invention will be described with references to the drawings. These references are not meant to limit the process or the apparatus to the particular details of the drawing disclosed in conjunction therewith. Looking first at the operation of the riser conversion zone, a lift gas stream 10 enters an inlet conduit 12 that passes the lift gas into the lower portion of a riser 14 . Hot catalyst from a regenerated standpipe 16 passes through a control valve 18 and is mixed with the lift gas in a junction between the standpipe and lower riser generally referred to as a Y-section and denoted as conduit 20 in FIG. 1 and including a catalyst nozzle. Lift gas carries the catalyst up the riser from lower section 14 to upper riser section 22 and conditions the catalyst by contact therewith. Between the upper and lower riser section, feed nozzles 24 inject hydrocarbon feed into the flowing stream of catalyst and lift gas. Hydrocarbon feed is converted as it travels to the end 26 of the riser. At the top 26 , the riser ends with an abrupt change of direction that directs the mixture of converted feed components and catalyst into transfer conduit 28 . FIG. 1 depicts the use of an external riser where the entire length of the riser is located outside of the reactor vessel.
The catalysts which enter the riser and can be used in the process of this invention include those known to the art as fluidizing catalytic cracking catalysts. These compositions include amorphous clay type catalysts which have for the most part been replaced by high activity crystalline alumina silicate or zeolite containing catalysts. Zeolite catalysts are preferred over amorphous type catalysts because of their higher intrinsic activity and their higher resistance to the deactivating effects of high temperature exposure to steam and exposure to the metals contained in most feedstocks. Zeolites are the most commonly used crystalline alumina silicates and are usually dispersed in a porous inorganic carrier material such as silica, aluminum, or zirconium. These catalyst compositions may have a zeolite content of 30% or more.
Feeds suitable for processing by this invention, include conventional FCC feedstocks or higher boiling hydrocarbon feeds. The most common of the conventional feedstocks is a vacuum gas oil which is typically a hydrocarbon material having a boiling range of from 343-552° C. and is prepared by vacuum fractionation of atmospheric residue. Such fractions are generally low in coke precursors and heavy metals which can serve to deactivate the catalyst.
This invention is also useful for processing heavy or residual charge stocks, i.e., those boiling above 500° C. (930° F.) which frequently have a high metals content and which usually cause a high degree of coke deposition on the catalyst when cracked. Both the metals and coke serve to deactivate the catalyst by blocking active sites on the catalyst. Coke can be removed, to a desired degree, by regeneration and its deactivating effects overcome. Metals, however, accumulate on the catalyst and poison the catalyst by fusing within the catalyst and permanently blocking reaction sites. In addition, the metals promote undesirable cracking thereby interfering with the reaction process. Thus, the presence of metals usually influences the regenerator operation, catalyst selectivity, catalyst activity, and the fresh catalyst make-up required to maintain constant activity. The contaminant metals include nickel, iron and vanadium. In general, these metals affect selectivity in the direction of less gasoline and more coke. Due to these deleterious effects, the use of metal management procedures within or before the reaction zone are anticipated when processing heavy feeds by this invention. Metals passivation can also be achieved to some extent by the use of appropriate lift gas in the upstream portion of the riser.
The finely divided regenerated catalyst entering the bottom of a reactor riser leaves the regeneration zone at a high temperature. Where the riser is arranged vertically, the bottom section will be the most upstream portion of the riser. In most cases, the riser will have a vertical arrangement, wherein lift gas and catalyst enter the bottom of the riser and converted feed and catalyst leave the top of the riser. Nevertheless, this invention can be applied to any configuration of riser including curved and inclined risers. The only limitation in the riser design is that it provide a substantially smooth flow path over its length.
Where employed, contact of the hot catalyst entering the riser with a lift gas accelerates the catalyst up the riser in a uniform flow regime that will reduce backmixing at the point of feed addition. Reducing backmixing is important because it varies the residence time of hydrocarbons in the riser. Addition of the lift gas at a velocity of at least 1.8 meters per second is necessary to achieve a satisfactory acceleration of the catalyst. The lift gas used in this invention is more effective when it includes not more than 10 mol % of C 3 and heavier olefinic hydrocarbons and is believed to selectively passivate active metal contamination sites on the catalyst to reduce the hydrogen and coke production effects of these sites. Selectively passivating the sites associated with the metals on the catalyst leads to greater selectivity and lower coke and gas yield from a heavy hydrocarbon charge. Some steam may be included with the lift gas and, in addition to hydrocarbons, other reaction species may be present in the lift gas such as H 2 , H 2 S, N 2 , CO, and/or CO 2 . However, to achieve maximum effect from the lift gas, it is important that appropriate contact conditions are maintained in the lower portion of the riser. A residence time of 0.5 seconds or more is preferred in the lift gas section of the riser, however, where such residence time would unduly lengthen the riser, shorter residence times for the lift gas and catalyst may be used. A weight ratio of catalyst to hydrocarbon in the lift gas of more than 80 is also preferred.
After the catalyst is accelerated by the lift gas, it enters a downstream portion of the riser which is generally referred to as the upper section. Feed may be injected into the start of the section by nozzles as shown in the FIGS. 1 and 2 or any device that will provide a good distribution of feed over the entire cross-section of the riser. Atomization of the feed, as it enters the riser, promotes good distribution of the feed. A variety of distributor nozzles and devices are known for atomizing feed as it is introduced into the riser. Such nozzles or injectors may use homogenizing liquids or gas which are combined with the feed to facilitate atomization and dispersion. Steam or other non-reactive gases may also be added with the feed, for purposes of establishing a desired superficial velocity up the riser. The superficial velocity must be relatively high in order to produce an average residence time for the hydrocarbons in the riser of less than 5 seconds. Shorter residence times permit the use of higher reaction temperatures and provide additional benefits as discussed below; thus where possible the feed has a residence time of 2 seconds or less. In more limited embodiments of this invention, the residence time may be as low as 0.1 second and in some cases as low as 0.05 seconds.
The catalyst and feed mixture has an average temperature of at least 520° C. (970° F.). Higher temperatures for the catalyst and feed mixture are preferred with temperatures of 540° C. (1000° F.) and 550° C. (1025° F.) being particularly preferred. The combination of a short residence time and higher temperatures in the riser shifts the process towards primary reactions. These reactions favor the production of gasoline and tend to reduce the production of coke. Furthermore, the higher temperatures raise gasoline octane. The short catalyst residence time within the riser is also important for maintaining the shift towards primary reactions and removing the hydrocarbons from the presence of the catalyst before secondary reactions that favor coke production have time to occur. The ability to carefully limit residence time also permits the cessation of cracking reactions to produce higher boiling range products where desired.
The high velocity stream of catalyst and hydrocarbons is then rapidly separated at the end of the riser. This can be accomplished in a number of ways. FIG. 1 shows one arrangement where the catalyst and hydrocarbons pass directly into a cyclonic separation system or the riser can be configured so as to abruptly change direction before this initial separation. Following separation, the separated vapors begin their path toward the product recovery zone while the separated catalyst is directed toward the stripping zone.
The catalyst and hydrocarbon stream carried from the riser by transfer conduit 28 can be diluted by the injection of a suitable diluent through a diluent conduit 30 . The diluent is mixed with the hydrocarbons and catalyst as they progress through conduit 28 . Horizontally arranged transfer conduit 28 carries the hydrocarbons and vapor into a reactor vessel 29 . Slightly farther downstream in conduit 28 , a stream of separated hydrocarbons, as hereinafter described, enters the top of conduit 28 through a tube 32 which is connected to conduit 28 just ahead of the inlet of a first cyclone separator 34 . Hydrocarbon vapor, catalyst, and diluent, when present, pass directly into cyclone separator 34 where separation of catalyst and product vapors occurs. Separator 34 discharges catalyst downwardly through a dip leg 36 and into a hereinafter described stripping zone, while hydrocarbon vapors and small amounts of entrained catalyst are carried from the top of separator 34 through a cross-over conduit 38 and into a second cyclone separator 40 . Cross-over conduit 38 contains an optional weighted flapper door 41 for relieving pressure surges. Cyclone separator 40 performs a more complete separation to recover additional catalyst still entrained in the product vapor. Additional amounts of recovered catalyst are downwardly discharged through a dip leg 42 while hydrocarbon vapors having a very low loading of catalyst particles exit the top of the cyclone through an outlet conduit 44 .
The diluent that enters transfer conduit 28 will usually comprise steam. Adding diluent ahead of the separation devices lowers the partial pressure of the hydrocarbons as they enter the cyclones. As the catalyst and hydrocarbons pass into the transfer conduits and through the separation devices, turbulence will vary the residence time of the hydrocarbons in these various devices. Therefore, the addition of diluent at this point, to lower the partial pressure of the hydrocarbons, attenuates the effects of catalytic and thermal cracking. Thus, initial contact with a diluent ahead of the cyclones prevents the loss of product by overcracking. Suppressing cracking reactions by the addition of diluent also allows the reaction time to be controlled. As a result, hydrocarbon reactions occur mainly in the riser and, as previously mentioned, can be limited to a short time. Short reaction times again favor the preferred primary reaction mechanism. Reactions that yield the desired distillate and gasoline products are primary reactions that occur quickly. Coke producing secondary reactions, primarily the polymerization and condensation of polycyclic compounds, over the acid catalyst, are secondary reactions that take longer to occur. The polycyclic compounds that combine in these secondary reactions are first generated by primary reactions such as naphthene cracking and the dealkylation of side chains. It is believed that by careful control, a short reaction time allows the primary reactions to occur while preventing most of the secondary reactions. Therefore, the addition of a diluent can increase the production of distillate and raise the quantity and octane of the gasoline product.
However, the addition of diluent through conduit 30 must be limited to avoid condensation of heavier hydrocarbon components in the cyclone separators or transfer conduits and excessive cooling of the catalyst. For this purpose, the temperature of the combined catalyst and hydrocarbon stream should not be reduced below the dew point of the heavier species.
Hydrocarbons separated from the catalyst in a manner hereinafter described are returned to the cyclones to remove any entrained catalyst that may accompany it back into the transfer conduit. For this purpose, the lower end of tube 32 is shown in open communication with the interior of reactor vessel 29 . In order to pass hydrocarbons from vessel 29 back into the transfer conduit, a positive pressure must be maintained that will provide the necessary driving force. In order to regulate the pressure drop, these hydrocarbons are transferred back into the transfer conduit through an extended length of gas tube 32 . High gas velocities should be avoided since they can impart momentum to the catalyst that will erode the transfer conduit. Gas tube 32 is arranged to direct catalyst into the top of the transfer conduit. The top has the advantage of placing any gas jet developed by the entry of gas into the transfer conduit across the vertical dimension of the transfer conduit which is usually larger than the width of the conduit.
Both tube 32 and diluent conduit 30 also inject gas into the upper surface of the transfer conduit in order to keep catalyst, that tends to flow along the bottom of the conduit, away from the outlets of tubes 32 and conduit 30 .
In FIG. 1, transfer conduit 28 communicates the catalyst and hydrocarbons with the cyclones that are located within reactor vessel 29 . The careful control of reaction times requires that catalyst be communicated in as direct a fashion as possible to the separation device. The transfer conduit and cyclone arrangement of the FIG. 1 differs from a number of those commonly used in the prior art by the direct connection of the transfer conduit to the inlet of cyclone 34 . For this reason, transfer conduit 28 can be described as a closed conduit notwithstanding the presence of tube 32 and diluent conduit 30 . It is possible to alter the arrangement of Figure to minimize the volume of the reactor vessel by using cyclone separators that are designed to withstand the internal pressure of the product stream and locating any additional stages of cyclone separators outside of the reactor vessel and discharging separated catalyst from external cyclones back into the stripper vessel.
For the most part, cyclones 34 and 40 are of a conventional design but will generally have a larger capacity, at least in separator 34 , for accommodating the larger volume of solids and gases that will enter the cyclones because of the direct coupling of the separator inlet to the transfer conduit. For those units where instabilities in operation, caused by such things as interruption in the flow of catalyst into the riser or the occasional injection of large amounts of water, will cause pressure surges in the riser, provision should be made to prevent these surges from overloading the cyclones. When the cyclone is overloaded, the spiralling effect of the flow through the cyclone that separates particles from fluid, is interrupted and the cyclone begins to act as a simple conduit transferring large amounts of catalyst out of the top of the cyclone with the converted products. Pressure surges, at least in part, can be relieved by venting the cross-over conduit 38 between the two cyclones.
A preferred method of venting uses a flapper door 42 . Flapper door 42 covers an opening on the cross-over conduit that is used for venting excessive pressure from the cyclone and preventing overloading of cyclone 40 when cyclone 34 becomes overloaded with catalyst. Door 42 is weighted to minimize leakage during periods of normal operation when it is not opened by internal pressure in the cross-over conduit. The higher operating pressure inside the reactor vessel also tends to keep door 42 closed. Door 42 can be weighted or alternately counter-balanced such that it will open at a predetermined pressure difference between the internal pressure of cross-over conduit 38 and the reactor pressure outside the conduit. In this case, the venting of cross-over conduit 38 will only protect cyclone separator 40 , generally referred to as a secondary cyclone, from overloading. It is expected that during the venting operation the amount of catalyst particles leaving the secondary cyclone through conduit 44 will increase, however, this increase for a short period of time will not impair operation of the downstream separation facilities. A similar type vent can be provided on the portion of the transfer conduit located within vessel 29 to also protect cyclone separator 34 from catalyst overload. Additional details on the direct coupling of a riser to cyclones and for protecting the cyclones against overload can be obtained from the previously mentioned prior art.
Dip legs 36 and 42 discharge recovered catalyst into a catalyst stripping section. In the embodiment of the Drawing, dip legs 36 and 42 discharge the catalyst into a relatively dense bed 46 of catalyst particles having an upper bed level 48 .
An important element of this invention is the use of a hot catalyst stripping zone. The term “hot catalyst stripping zone” refers to a stripper having a temperature above at least 970° F. Greater advantages are obtained when the stripper is maintained above 1000° F. The high temperature riser operation provides high temperature catalyst that in turn keeps the stripper hot. In many instances, hot catalyst from the separator will have sufficient heat to maintain the necessary stripper temperature.
Where a higher stripper temperature than can be obtained from the riser catalyst is desired, any suitable method may be used to heat the catalyst within the stripping zone. Acceptable methods include the use of heat transfer tubes, controlled oxidation of hydrocarbons in the stripper as well as direct and indirect transfer of heat from regenerated catalyst. One form of indirect heat transfer, to raise the temperature of the spent catalyst, can use a catalyst to catalyst heat exchanger within the stripper that circulates hot catalyst from the regenerator through heat exchange tubes and back to the regenerator in a closed system.
FIG. 1 shows another approach for heating the catalyst wherein a continuous stream of hot catalyst particles taken from a regenerator 72 by a reheat conduit 50 in an amount regulated by a control valve 52 enters a stripper riser 54 . A lift medium, such as steam, from a conduit 56 lifts hot catalyst from the bottom of riser 54 . Hot regenerated catalyst particles flow out of the upper end of riser 54 and contact a baffle 58 that redirects the catalyst downward into bed 46 . The hot regenerated catalyst heats the spent catalyst particles in bed 46 which are then transferred downward into a stripping vessel 60 having a series of baffles 62 for counter-currently contacting the downward flowing catalyst particles with a stripping medium, such as steam, that enters the stripping zone through a conduit 64 . A distributor 66 distributes the stripping medium over the cross-section of the stripping vessel 60 . Stripped hydrocarbon vapors, as well as stripping medium, rise upwardly through bed 46 and enter the bottom of tube 32 for return to the cyclone separators in the manner previously described. Stripped and fresh catalyst particles are taken from the stripper 60 by a spent catalyst standpipe 68 , in an amount regulated by a control valve 70 , and transferred to regenerator 72 for the oxidative removal of coke from its surface.
Catalyst entering the stripper is kept hot to remove additional hydrocarbons from the spent catalyst by vaporizing the higher boiling hydrocarbons from the surface of the catalyst. Since the commonly employed zeolite catalysts can act as an effective adsorbent, a large quantity of hydrocarbons can be absorbed on the surface of the catalyst. Although heating the catalyst will also tend to raise temperatures and again may promote some thermal cracking, any hydrocarbons that remain absorbed on the catalyst are lost by combustion in the regeneration zone. Thus, some small loss to thermal cracking in the stripping zone is preferable to the larger loss of adsorbed product which may be burned in the regenerator.
Any catalyst introduced into the stripper for the purpose of heating should be taken from the hottest section of the regenerator in order to minimize the amount of hot catalyst introduced therein. Although the hot clean catalyst is favored as a heating medium due to its high heat capacity and ready availability, the regenerated catalyst can also act as a clean adsorbent which, if introduced in large quantities, can absorb more additional hydrocarbons than the heat released thereby will desorb from the spent catalyst. Therefore, it is preferable to take relatively small amounts of hot regenerated catalyst from the regenerator for the purpose of heating catalyst in the stripper.
Spent catalyst taken from stripper 60 through spent catalyst standpipe 68 enters regenerator 72 for the oxidative removal of coke from the surface thereof. A conduit 76 conveys compressed air into a distributor grid 78 that distributes the air over the cross-section of a lower regenerator vessel 80 . Regenerated catalyst is carried by a recirculation conduit 82 into lower regenerator vessel 80 and mixed with air from distributor 78 and spent catalyst from conduit 68 . Combustion of coke deposits begins as oxygen reacts with coke at the elevated temperature of the catalyst and air mixture. Air and combustion gas carry the catalyst and gas mixture upward into regenerator riser 84 . A riser arm 86 having an opening 88 directs the catalyst and gas mixture downward to at least partially disengage gases from the catalyst. The gas mixture plus any entrained catalyst flow upwardly and are collected by cyclone separators 90 . A plenum 92 collects combustion gas from the cyclone separators for removal from the regenerator through a nozzle 94 . Catalyst recovered from the cyclone separators is discharged through conduits 96 where it is collected by a cone 98 along with catalyst that was initially disengaged by discharge through opening 88 . The regenerated catalyst conduit 16 returns regenerated catalyst from cone 98 to riser 14 , as previously described. Hot catalyst for reheat conduit 50 is also withdrawn from standpipe 50 . Other details and variations on the operation of an FCC regenerator are well known by those skilled in the art.
Looking again at the reactor, converted hydrocarbons that leave separator 40 through conduit 44 undergo quick quenching to avoid thermal cracking. In order to prevent thermal cracking, these vapors will preferably be quenched to a temperature below about 500° C. Quenching may be accomplished by the injection or contact of the vapor stream with a suitable quench fluid. Quench mediums that can be used include light oil, steam, water or heavy oil. When using light oil, steam or water, care must be taken to avoid condensation of higher boiling compounds on the walls of the piping leading to the product separation facilities. These lighter compounds are either used in or easily converted to the gas phase as these light quench materials rapidly cool the higher boiling components of the product stream. The resulting large concentration of gas in the quench stream may not adequately flush coke condensible compounds from the transfer piping. Heavy quench liquids are preferred since they prevent coke accumulation by providing a large volume of liquid wash.
Quench liquid may be injected into the converted hydrocarbons using spray nozzles, showered head injection or staged injection of two or more quench mediums. The quench may be added directly to the cyclone outlets or to a manifold or plenum chamber that collects the hydrocarbon vapors from several cyclone outlets. Thus, the quench vessel can comprise a section of piping or a conduit through which the quench and product vapors pass.
FIG. 1 shows an alternate form of incorporating the quench medium that uses a liquid contacting zone. Substantial advantages are achieved in the quench operation when it employs a liquid contacting zone as shown in FIG. 1 . In this type of quench apparatus the quench conduit 44 carries product vapor from each cyclone separator 40 directly into a quench chamber 100 . Quench chamber 100 is separated from the reactor by a partition 111 . Product vapors entering quench chamber 100 will normally have a temperature in the range of from 480-565° C. (900-1050° F.). These vapors leave the end of conduit 44 and travel around an end cover 102 . The purpose of end cover 102 is to prevent the quench liquid, as hereinafter described, from spilling back into the conduit 44 . In a first series of contacting trays comprising heat removal trays 104 , the rising hydrocarbon vapors are contacted by the quench liquid. Heat removal trays 104 are preferably disc and donut trays. At the top of the heat removal trays, a quench liquid is introduced by an extended distributor 106 . The quench is preferably a heavy hydrocarbon having a boiling point range of 290-600° C. (550-1100° F.). A portion of the liquid quench may also be introduced through nozzle 108 below a liquid level 110 at the bottom of the quench chamber to independently control the temperature of the collected liquid. By the addition of quench liquid, the temperature of the collected liquid may be kept below 400° C. (750° F.) or preferably below 370° C. (700° F.). Maintaining the quench liquid below 400° C. prevents the small degree of hydrocarbon cracking which might otherwise occur at higher temperatures and adversely affect the flash point of the bottoms product. This quench material is generally described as a main column bottoms stream which is obtained from the separation facilities for the product stream and will normally include a slurry of catalyst particles. In new FCC units that use high efficiency cyclones, the main column bottoms typically carries about 0.01 to 0.05 wt. % catalyst and other insolubles, but can have solids concentrations as high as 0.15 to 0.2. Older FCC units using a slurry settler will have a much higher wt. % of particulates averaging about 1 to 2%. This quench will usually enter the quench chamber at a temperature in the range of 230-345° C. (450-650° F.). A nozzle 112 withdraws liquid quench from the bottom of chamber 100 . The nozzle 112 has a location well below the top discharge conduits 44 and should be located as low as possible in the quench chamber in order to keep the full volume of quench liquid in circulation. For this reason, it is also preferable to have several withdrawal nozzles spaced about the circumference of the quench chamber. Temperature of the liquid quench as it is withdrawn through nozzle 112 will be between 315-400° C. (600-750° F.). After removal, the quench is normally passed through heat exchange equipment to lower its temperature and pumped back to distributor 106 for return to the top of heat removal trays and to the bottoms quench nozzle 108 . The product vapors will also contain a certain amount of heavy material having a boiling point above the entering temperature of the quench medium which will collect and increase the total volume of the quench liquid. Therefore, a portion of the circulating quench medium is withdrawn continuously as heavy oil product to keep the liquid level 110 below the top of conduit 44 .
The quench chamber may contain additional contacting trays which receive the lighter product vapors that have risen above trays 104 and are contacted by a hydrocarbon reflux stream that is relatively lighter than the quench medium passed over trays 104 . In its preferred form, a second series of contacting trays comprising fractionation trays 116 receive the ascending product vapors while an extended distributor 118 delivers a hydrocarbon reflux stream to the top of the fractionation trays that flows counter-currently to the rising vapors. It is preferred that the reflux stream be a heavy cycle oil having a boiling range of 230-400° C. (450-750° F.). As the product vapor enters the fractionation trays, it will usually have a temperature between 275-400° C. (525-750° F.). In the case of heavy cycle oil addition, this will usually enter the fractionation trays at a temperature in the range of 260-320° C. (500-600° F.). The relatively cool vapors are collected at the top of quench chamber 100 and withdrawn through a nozzle 120 . The vapors are carried overhead via line 122 to additional separation facilities for further separation into the various components of the product slate.
Quench chamber 100 and the cyclones are supported from the top of the reactor vessel. In this type of arrangement proper design of partition 111 and discharge conduit 44 is important to the operation of the apparatus of this invention. Partition 111 is designed to withstand a liquid loading on its upper side and a pressure loading on its lower side. The pressure loading results from the higher pressure employed in the reactor vessel relative to the quench chamber provides a driving force for transferring vapors to the quench chamber. The hemispherical shape of partition 111 , as shown in the drawing, serves two objectives, one is to withstand the pressure loading on its bottom side when it is greater than the liquid loading on the top side of the partition and to facilitate removal of the bottoms liquid by forming a channel towards the outer periphery of the dome shaped partition. although any shape of partition can be used, it is preferable to avoid a partition that is concave to the quench chamber since this will form a stagnant area of hydrocarbon vapors in upper reactor portion.
Contact of partition 111 with the relatively cool quench liquid on its upper side cools the partition. If the product vapors are allowed to come in contact with the cooled surface, this will promote condensation of the relatively heavy hydrocarbons and the accumulation of coke on the lower surface of the partition. For this reason, a layer of an insulating ceramic material is usually used to cover the entire lower surface of partition 111 . This insulating material is composed of an insulating refractory lining having a thickness ranging from 2 to 5 inches depending on the insulating properties of the material. The design and use of such materials is well known to those skilled in the art. Condensation of high boiling product vapors into coke deposits is a similar concern for the discharge conduits 44 . The outer surface of conduit 44 is in contact with liquid from the quench and is cooled thereby. An insulating type refractory lining usually covers the inside of discharge conduit 44 . In the case of conduit 44 , this lining will have a thickness that can vary between 1 to 5 inches depending on the insulating properties of the material. The lining should have a thickness which will keep the surface of the lining that is in contact with the hydrocarbon vapors at a temperature within 9° C. of the vapor temperature in contact therewith.
When the quench chamber is incorporated into the top of the reactor, it can replace a portion of the main column that is generally used separating the recovered vapor products from the reactor. A main column will ordinarily contain a quench section. The incorporation of this invention will allow at least the quench system to be removed from the main column. The embodiment of this invention shown in the Drawing also includes the addition of fractionation trays for the rectification of the vapor leaving the heat removal section. Additional fractionation trays, pump around circuits, and withdrawal points may be added to obtain additional product cuts from the quench chamber.
Again FIG. 1 demonstrates the use of cyclones for the initial separation of catalyst from hydrocarbon products. Other arrangements for the initial separation of catalyst from hydrocarbons can be used in this invention. One such arrangement is shown in U.S. Pat. No. 5,182,085, the contents of which are hereby incorporated by reference. FIG. 2 demonstrates another embodiment of this invention that does not use cyclones for the initial separation of the catalyst from the product vapors and a reactor riser having an upper end extending inside the reactor vessel.
Referring to FIG. 2, regenerated catalyst from a regenerator (not shown) is transferred by a conduit 214 , at a rate regulated by a control valve 216 , to a Y-section 218 . Lift gas injected into the bottom of Y-section 218 , by a conduit 220 , carries the catalyst upward through a lower riser section 222 . Feed is injected into the riser above lower riser section 222 by feed injection nozzles 224 .
The mixture of feed, catalyst and lift gas travels up an intermediate section of the riser 226 and into an upper internal riser section 228 that terminates in an upwardly directed outlet end 230 that is located in a dilute phase region 232 of a reactor vessel 234 . The gas and catalyst are separated in dilute phase section 232 . Vapor lines 236 collect gas from the dilute phase section through transfer conduits 237 and transfer it to a collection chamber 238 . From collection chamber 238 , a T-type piping arrangement 240 distributes the gas which still contains a small amount of catalyst particles to a pair of cyclone separators 242 . The T-type piping arrangement includes a single conduit 241 that serves as quench chamber and into which one or more quench lines 243 inject a quench fluid. Cooled and relatively clean product vapors are recovered from the outlets of cyclones 242 by a manifold 244 and withdrawn from the process through an outlet 246 .
Catalyst separated by cyclone separators 242 is carried back to reactor vessel 234 by dip pipe conduits 248 . Spent catalyst from dilute phase section 232 and the dip pipe conduits form a dense catalyst bed 250 in a lower portion of the reactor vessel 234 . The dense catalyst bed extends downward into a stripping vessel 252 that operates as a stripping zone. Stripping fluid enters a lower portion of the stripping vessel 252 through a distributor 254 and travels upward through the stripping vessel and reactor vessel in countercurrent flow to the downward moving catalyst. As the catalyst moves downward, it passes over reactor stripping baffles 256 and 258 and stripper baffles 260 and 262 and is transferred into the regenerator by a conduit 264 .
The reactor riser of this embodiment of the invention is laid out to perform an initial separation between the catalyst and gaseous components in the riser. In this type of arrangement the end of the riser 230 must terminate with one or more upwardly directed openings that discharge the catalyst and gaseous mixture in an upward direction into a dilute phase section of the reactor vessel. The open end of the riser can be of an ordinary vented riser design as described in the prior art patents of this application or of any other configuration that provides a substantial separation of catalyst from gaseous material in the dilute phase section of the reactor vessel. It is believed to be important that the catalyst is discharged in an upward direction in order to minimize the distance between the outlet end of the riser and the top of the dense phase catalyst bed in the reactor vessel. The flow regime within the riser will influence the separation at the end of the riser. Typically, the catalyst circulation rate through the riser and the input of feed and any lift gas that enters the riser will produce a flowing density of between 3 lbs/ft 3 to 30 lbs/ft 3 , more typically 3 lbs/ft 3 to 20 lbs/ft 3 , and an average vel about 10-100 ft/sec. for the catalyst and gaseous mixture.
The manner in which the gaseous vapors are withdrawn from the dilute phase volume of the reactor vessel will influence the initial separation and the degree of re-entrainment that is obtained in the reactor vessel. In order to improve this disengagement and avoid re-entrainment, FIG. 2 shows the use of an annular collector 292 that surrounds the end 230 of the riser. Collector 292 is supported from the top of the reactor vessel 234 by withdrawal conduits 236 . Withdrawal conduits 236 are symmetrically spaced around the annular collector and communicate with the annular collector through a number of symmetrically spaced openings to obtain a balanced withdrawal of gaseous components around the entire circumference of the reactor riser. All of the stripping gas and gaseous components from the reactor riser are withdrawn by annular collector 292 .
FIG. 2 shows an arrangement for transferring gases from the conduits 236 to the cyclones that avoids a mal-distribution of the catalyst and gas mixture to the different cyclones. The simplest way to connect the gas conduits with the cyclones is to directly couple one conduit to a corresponding cyclone. This arrangement would also have the advantage of minimizing the flow path between the annular collector of the riser and the cyclones where the final separation of catalyst and gas is performed. However, for reasons related to the complex hydrodynamics in the dilute phase region 232 , it has been found that mixtures of catalyst and gas that are taken from the reactor through a series of conduits may preferentially flow to one conduit. The resulting heavier loading of catalyst and gas can overload the cyclone to which it is directed. For this reason, the Figure shows the use of a chamber 238 that commonly collects the gas from all cyclone conduits 36 and redistributes the gas to the individual cyclones. Although providing chamber 238 and T-section 240 increases the residence time for the catalyst and gas mixture as it flows from the reactor vessel to the cyclone inlets, this minor increase in residence time will not have a substantial impact on the quality of the product recovered from the cyclones. The avoidance of mal-distribution may also be accomplished by the use of a catalyst and gas separation device other than cyclones.
A quench fluid contacts vapor products passing from withdrawal conduits 236 to cyclones 242 . Any lowering of the reactor vapor stream temperature will decrease product losses. Accordingly contacting the reactor vapors with the quench at any point downstream of the riser will produce some benefit. Contacting reactor vapors after substantial removal of the catalyst particles minimizes the volume of quench needed to achieve a desired degree of cooling and the amount of quench lost by adsorption on the catalyst. The quick separation arrangement of this invention provides a particularly advantageous arrangement for use of a quench. The ballistic separation of the riser effluent provides faster separation of the catalyst from the vapor than normally attained by the use of cyclones. The rapidly separated vapors from the ballistic separation section exit with only minor catalyst particle loading, typically on the order of 0.1-1.0 lb/ft 3 . Rapid separation and efficient separation minimizes thermal cracking as well as volumetric requirements of quench fluid.
The quench fluid can contact the product vapors at any point between the inlets for withdrawal vapor lines 236 and the cyclones 242 . Mixing of the quench fluid with the product vapors downstream of cyclones 242 can add from 0.5 to 5 seconds of high temperature exposure to the product vapors. Secondary cyclones, such as cyclones 242 typically have a high volume which exacerbates the problem of extended residence time. The most rapid quenching is obtained by contacting the quench stream immediately downstream of the ballistic separation. In the preferred form of this invention the quench enters single conduit 241 . Addition of quench to single conduit 241 has the advantage of providing a location external to the reactor vessel for the addition of quench as well as offering a relatively small cross-sectional area for immediate and complete mixing of the quench fluid with the vapors.
Catalyst that is initially separated from the gaseous components as it enters the reactor vessel, passes downward through the vessels as previously described. As this catalyst progresses through the vessel, it preferably contacts a series of baffles that improve the contact of the catalyst with a stripping gas that passes upwardly through the vessel. In the embodiment of the invention shown in the FIG. 2, the catalyst passes through a stripping section in the upper portion of the vessel referred to as a disengaging vessel and a separate stripping vessel located therebelow. The Figure shows the baffles 256 and 262 located on the exterior of the vessel walls and baffles 258 and 260 located down the length of the riser through the lower portion of the reactor vessel and the stripping vessel. These stripping baffles function in the usual manner to cascade catalyst from side to side as it passes through the vessel and increase the contact of the catalyst particles with the stripping steam as it passes upward in countercurrent contact with the catalyst.
The stripping vessel of FIG. 2 also provides hot stripping using catalyst from the regeneration zone to supply heat to the stripping section. A suitable lift system can be used to transport the catalyst upward from the regeneration zone into a stripping zone at a desired elevation.
With the cyclones removed from the reactor vessel, the diameter of the reactor vessel can be kept low enough such that the average residence time in the dilute phase of the reactor vessel is less than three seconds. Nevertheless, this embodiment of the invention also applies to an arrangement where the secondary separation device, such as cyclones 242 , are located within the reactor vessel and the only locations for quench contacting are inside the reactor vessel. In such an arrangement the a separate disengaging vessel is at least partially contained with the reactor vessel to minimize the volume into which the catalyst and hydrocarbons are initially discharged. In the embodiment shown in FIG. 2 the reactor vessel also provides the disengaging vessel.
In another alternate arrangement of this invention it is possible to use the vented riser in a manner to eliminate the disengaging vessel altogether. Such an arrangement withdraws catalyst and vapors from an extended riser through ports on the sides of the riser. The ports have a location below an open top of the riser and transfer the catalyst and hydrocarbon vapors to cyclones or other separation devices. The end of the riser extends upwardly by a distance sufficient to form a suspended layer of catalyst that seals the end of the riser. Under normal circumstances this type of riser arrangement operates in much the same manner as the riser and cyclone arrangement shown in FIG. 1 and does not permit catalyst or vapor to exit the top of the riser. However, the open end of the riser relieves pressure surges during upset conditions by venting vapors and catalyst into the open volume of the reactor vessel. Additional details of this arrangement are shown in pending application U.S. Ser. No. 790,924.
The unexpected advantages of the FCC arrangement of this invention are demonstrated by the following examples of FCC operations. These examples compare the operation of a conventional FCC operation with the operation of an FCC unit that operates in accordance with this invention. The data for both of these operations are presented in the following case studies which are calculated yield estimates based on simulations that have been developed from pilot plant data and operating data from commercial FCC units.
EXAMPLE 1
In a base case, a feed having a composition as set forth in the Table 1 was charged to a riser and contacted with a low rare earth catalyst having less than 1 wt. % rare earth exchange, a dealuminated zeolite content of about 30 wt. % in an active matrix component and a MAT activity of 68 . The catalyst was passed from the regenerator to the riser at a temperature of about 1321° F. The feed and catalyst mixture passed through the riser at an average temperature of 970° F. for an average time of three seconds and was discharged directly into a reactor vessel. Separated catalyst from the cyclone was discharged into a subadjacent stripping zone and contacted with a stripping steam at conditions that maintained an average stripping zone temperature of 970° F. Vapors removed from the catalyst in the stripping zone were vented into the reactor vessel and withdrawn through a first cyclone that operates in closed communication with the second cyclone to recover product vapors from the reactor vessel. Additional amounts of catalyst particles separated from the product vapors by the cyclones were discharged into the stripping zone. A vapor line carried all of the product vapors from the second stage cyclone to a main column fractionator. The cooled vapors had the composition set forth in Table 2.
EXAMPLE 2
In a first light olefin case, a feed again having the composition as set forth in the Table 1 was charged to a riser and contacted with a low rare earth catalyst having less than 1 wt. % rare earth exchange, a dealuminated zeolite content of about 30 wt. % in an active matrix component and a MAT activity of 68 . The catalyst was passed from the regenerator at a temperature of 1350° F. The feed and catalyst mixture passed through the riser for an average riser residence time of three seconds and was discharged from the riser outlet at an average temperature of 1025° F. directly into the first stage of a cyclone separator. Separated catalyst from the first stage cyclone dropped into a subadjacent stripping zone and into contact with a stripping steam at conditions that maintained an average stripping zone temperature of 1100° F. Vapors removed from the catalyst in the stripping zone were vented into a second stage of the cyclone separator that also received, in closed communication, vapors recovered from the first cyclone. Additional amounts of catalyst particles were separated from the product and stripping gases by the second cyclone stage and discharged into the stripping zone. All of the vapor from the second stage cyclone was discharged directly into a quench zone. The quench zone contacted the vapors from the second stage cyclone with cycle oil from the main column fractionator that cooled the product vapors to a temperature of 800° F. The cooled vapors had the composition set forth in Table 2.
EXAMPLE 3
In a second light olefin case, a feed again having the composition as set forth in the Table 1 was charged to a riser and contacted with a low rare earth catalyst having less than 1 wt. % rare earth exchange, a dealuminated zeolite content of about 40 wt. % in an active matrix component and a MAT activity of 72 . The catalyst was passed from the regenerator at a temperature of 1351° F. The feed and catalyst mixture passed through the riser for an average riser residence time of three seconds and was discharged from the riser outlet at an average temperature of 1025° F. directly into the first stage of a cyclone separator. Separated catalyst from the first stage cyclone dropped into a subadjacent stripping zone and into contact with a stripping steam at conditions that maintained an average stripping zone temperature of 1100° F. Vapors removed from the catalyst in the stripping zone were vented into a second stage of the cyclone separator that also received, in closed communication, vapors recovered from the first cyclone. Additional amounts of catalyst particles were separated from the product and stripping gases by the second cyclone stage and discharged into the stripping zone. All of the vapor from the second stage cyclone was discharged directly into a quench zone. The quench zone contacted the vapors from the second stage cyclone with cycle oil from the main column fractionator that cooled the product vapors to a temperature of 800° F. The cooled. vapors had the composition set forth in Table 2.
As compared to the base case, the data demonstrates that the high temperature operation, direct discharge of the riser effluent into the cyclone system, the hot stripping operation, and the immediate quenching of the reactor products after discharge from the cyclones provide significant yield advantages for the first light olefin case both in terms of conversion, olefin production and gasoline octane. The conversion, olefin and gasoline octane advantages more than offset the slightly higher coke and light gas production obtained by the process of this invention as compared to the prior art process.
Further improvements in conversion, olefin product and gasoline octane were obtained by the use of a slightly more active catalyst. The rapid quenching and quick quench of this invention permits the beneficial use of a more active catalyst.
TABLE 1
API
23.41
UOP MOLECULAR K
11.73
WT.
361.5
NICKEL, PPM
0.55
VANADIUM, PPM
0.60
SULFUR, WT. %
2.38
RAMMSBOTTOM CARBON, WT. %
0.70
PERCENT BOILING AT 650 ° F.
0.0
TABLE 2
Example 2
Example 3
Example 1
Light
Light
Base
Olefin
Olefin
Case
Case #1
Case #2
Conversion, LV %
75.9
80.4
83.0
YIELDS, LV % on FEED
C 3 =
7.8
10.5
12.5
C 3
2.8
3.1
3.5
C 3 =/C 3
0.74
.77
0.78
C 4 =
8.5
12.2
13.9
C 4
6.0
7.1
6.5
C 4 =/C 4
0.58
0.63
0.68
C 5 =
6.6
7.1
7.8
C 5
5.0
4.3
4.3
C 5 =/C 5
0.57
.62
0.64
C 5 + Gasoline
58.1
55.6
54.9
LCO + MCB
24.5
19.6
17.0
Coke, wt. %
5.1
6.02
6.4
C 2 minus, wt. %
3.6
4.43
4.65
C 5 + Gasoline
RON
92.6
94.0
94.8
MON
80.0
81.8
82.1
|
An FCC apparatus places a quench chamber above a reactor vessel and a hot stripper below a reactor vessel to provide a progressively decreasing temperature profile up the structure of the FCC arrangement and equipment for sequential reaction control. A riser contains the primary catalytic reactions of the hydrocarbon vapor and delivers the reacted vapors to the reactor structure. Starting from the bottom of the structure the hot stripper has the highest temperature and desorbs or displaces hydrocarbons from the catalyst to terminate long residence time catalytic reactions. Above the hot stripper bulk separation equipment divides the main vapor and catalyst stream to limit residence time of major catalytic reactions. At a yet higher elevation and lower internal temperature quench equipment arrests thermal reactions of the vapor stream. This structure arrangement permits reliable control of reaction time to obtain desired products and enhances mechanical reliability of the structure.
| 2
|
FIELD OF THE INVENTION
[0001] The wind-energy power machine and storage energy power generating system and wind-driven power generating system belong to a field of wind-energy power machine and power generating technology.
BACKGROUND OF THE INVENTION
[0002] The expected consumption and the shortage of the resources such as petroleum and coal etc., environment contaminant problem, cost and economic value as well as the society sustainable development all promote people to pay great attention to the new type energy and clean energy technology, and research them in great enthusiasm. The technology of wind-driven power generating system and its equipment manufacture have developed as a new industry branch, and the application is being increasing, however, regarding to the demand to energy and electric power and the percentage, the wind-driven power generating technology and its product and the total power generating quantity are still in the junior and passive situation, a great deal of installation of such wind-driven generator still rely on the government encouragement and preferential investment, the primary reason is that at present wind-driven generators and installations have many problems which restrict development, wind-driven generators and installations and natural requirements are to overcome many technical bottlenecks and make improvements.
[0003] At present the known wind-driven generators are most three-blade rotator direct reduction gear box and generator type, the utilization efficiency of the wind energy is low and the generating power is also low due to its structure and technology, again, it is installed on the high tower subjected to sunshine and rain, as a result the equipment trends to be damaged, and the maintenance difficult and cost high, its guide mechanism and brake device consume energy as well; in addition the wind-driven generator must be activated at the rotation beginning, therefore it can be envisaged that the activate moment must be large enough and the wind-driven generator can only rotate under sufficient wind speed, but it must rotate within a defined narrow wind speed range, otherwise wind-driven generator would damage, hence such type wind-driven generator has small effective power generating hours all the year round and is difficult to be large scaled, because the construction site must be selected at the region where the year wind energy resources are abundant, therefore the geographical and natural condition is substantial high, the site construction cost is high, these disadvantage factors make the investment reward rate very low and the investment callback period long, all these factors restrict and impede the development of wind-driven power generating system.
SUMMARY OF THE INVENTION
[0004] An object of the present invention is to provide a wind-driven generator, which is capable of solving the above mentioned problems with respect to the wind-driven generator and installations of the construction site, which seeks to generate more power and more electric energy within fewer footprint, while it reduces the investment for the construction site and the operation cost, and improves to utilize wind energy and popularize the power generating in order to gain excellent economic effects.
[0005] To achieve the object, the present invention is through the following technical solution realized.
[0006] A wind-energy power machine includes a vertically installed rotational center rotating body 1 around which there are several equally distributed frame portions 2 , each frame portion has a wind pressure push mechanism 3 ; the wind pressure push mechanism 3 has symmetric and horizontal support shafts 3 b on two vertical outer side surfaces at the location which is slightly above the midpoint measured from the bottom in the height of the side surfaces, or at any locations away from the above mentioned location within a certain distance, and the wind pressure push mechanism is installed on the frame portions 2 at the same vertical height by means of bearings 3 d , due to the support position of the support shafts 3 b the support shaft serves as the horizontal centerline of the wind pressure push mechanism, the weight of the lower portion volume is slightly heavier than the upper portion volume, which makes the wind pressure push mechanism easily overturn towards upper to raise and open when it is against the wind, so that a whole wind-bearing surface is parallel to the wind direction or keeps an almost parallel state without wind resistance, while in the process of a free wind the wind pressure push mechanism returns to close against the frame portions 2 under the action of the slightly heavier weight of the lower portion and the air stream, so that the whole wind-bearing surface is perpendicular to the wind direction or keeps an almost perpendicular state receiving the wind force, thus, the wind-energy power machine A is formed, which can directionally rotate to output power in the way that it receives wind from any direction to form the driving force.
[0007] The upper and lower end shaft portion 1 b , 1 a of the above described center rotating body 1 are provided with bearings 6 a , 6 , hence the wind-energy power machine is vertically installed on a high frame or an independent frame E or a high frame structure B, which provides stable rotation for the wind-energy power machine, the both shaft portions 1 c , 1 d of the center rotating body are also provided with a clutch 7 or a coupling 7 a according to the different demand of the constitution of the power transmission, the shaft portion 1 C which serves as the terminal power output of the wind-energy power machine is provided with a transmission member 10 or 15 as well.
[0008] The above described frame portion 2 comprises a column 2 a , a lower cross beam 2 b , an upper cross beam 2 c and an outer side column 2 d . At the location which is measured from the bottom in the height of the outer side column and the column of frame portion in the vertical direction slightly above the midpoint, or at any location away from the above mentioned location within certain a distance, symmetric threaded holes or through-holes having one level centerline and being symmetrical are provided on the outer side column and the column. The wind pressure push mechanism 3 is installed by the seat bearing 3 d by means of bolts; the column has through-holes 2 e at many locations so as to install the frame portions 2 onto the center rotating body 1 with fasteners; the outer side column is provided with an adjustment device 2 f which adjusts the opening degree of the wind pressure push mechanism.
[0009] The wind pressure push mechanism 3 has a concave body 3 a , which has a front surface receiving the wind and having a concave shape so that it can accumulate the wind energy to strengthen push force, the bottom of its frame has a positioning plate 3 c.
[0010] The above described wind pressure push mechanism can also be mounted on the outer side column 2 d and an inner side column 2 f which is installed on the upper and lower cross beams of the frame portions 2 away from the center rotating body with a certain distance to form a larger leverage.
[0011] A wind-energy power machine includes a vertically installed rotational center rotating body 1 around which there are several equally distributed frame portions 4 , each frame portion has a wind pressure push mechanism 5 which can change with the wind direction and follow the bias vertical shaft center of the centerline of a support shaft 5 b and a support shaft cam set 5 c to make settings for the function demands when it is against the wind to automatically open, so the whole wind-bearing surface is parallel to the wind direction or keeps an almost parallel state without wind resistance, while in the process of a free wind the wind pressure push mechanism self closes, so the whole wind-bearing surface receives the wind push action, the centrifugal force generated by the wind pressure push mechanism when the wind-energy power machine A is rotating can be balanced by balance servo devices 5 c , 5 g , and it returns to close in cooperation with the free wind, that is, it rotates when its rotation direction conforms with the wind direction, such that the wind-energy power machine A is formed which can directionally rotate to output power in the way that it receives any wind from any direction to form the driving action.
[0012] The upper and lower end shaft portions of the above described center rotating body 1 are provided with bearings 6 a , 6 , hence the wind-energy power machine is vertically installed on the independent frame or high frame structure which builds a wind-energy power machine A that independently provides power, or the wind-energy power machine is installed in a large scale high frame structure B which is designed and planned to install more wind-energy power machines; the both shaft portions 1 c , 1 d of the center rotating body are also provided with a clutch 7 or couplings 7 a , the lower shaft portion is provided with a brake 8 , the shaft portion 1 C of the wind-energy power machine A which serves as the terminal power output is provided with a transmission member 10 or 15 as well.
[0013] The frame portion 4 comprises an upper cross beam 4 b and a lower cross beam 4 a , the upper and lower cross beams 4 b , 4 a near the center rotating body have through-holes 4 C so that the upper and lower cross beams can be assembled with the fix plate 1 e of the center rotating body with bolts; each of outer ends of the upper and lower cross beams of each frame portion far away from the center rotating body with a certain distance has threaded holes or through-holes 4 d being symmetric with each other for installing the support shaft cam set 5 C and/or support shaft 5 b of the wind pressure push mechanism 5 with the seat bearings, the upper cross beam is provided with a centrifugal force balance device 5 g , and the contact location with the fix plate 5 f of the upper and lower cross beams has a damper cushion 4 e ; the centrifugal force balance device 5 g has a hollow cylinder 5 g 1 , a compression spring 5 g 2 is provided inside, an inner end thereof is tied with tie cord 5 g 3 , a front end thereof is provided with a small roller 5 g 4 , the tie cord is connected thereon and one end of the tension spring is connected to a lug 5 e ; the half of the tie cord is a flexible steel cable and the other half of the cord is a tension spring.
[0014] The wind pressure push mechanism 5 is a concave body 5 a : 5 a 1 , 5 a 2 , which has a front surface receiving the wind and having a concave shape so that it can accumulate the wind energy to strengthen the push force, at any position of the body within a certain range which is apart from the ⅔ width of the horizontal width of the upper and lower frame measured outside from the side near the center rotating body or at least above ½ width a definite distance, a support shaft 5 b is provided on the upper frame, the bottom plane of the lower frame is provided with a centrifugal force balance servo device; a female cam in a pair of mate male and female support shaft cam set 5 C: 5 C 1 , 5 C 2 is installed on the corresponding lower cross beam 4 a of the frame portion, the female cam 5 C 1 also has male and female adjustable positioning rack 5 C 3 which may adjust the open degree of the wind pressure push mechanism 5 and restrict the centrifugal force, the male and female cams match with each other in the inclination between 25 and 55 degree; the support shaft 5 b is installed on the upper cross beam with a seat slide bearing 5 d , it can be controlled to rotate with the vertical centerline of the support shaft and the support shaft cam as the center of rotation according to the defined rotation degree and the automatic open and close function demand; a fix plate 5 f is provided at the upper and lower locations at the outer side of the wide side of the centerline.
[0015] An energy storage power generating system includes two motor units and their equipments which use the energy, one of the motor units is a main power source which constantly rotates when there is wind, it includes at least one to a multiple of wind-energy power machines A:A 1 ,A 2 . . . An which drive generator G in operation to generate electricity, or it transmits the power through a power output shaft 17 , the clutch 7 , a gear that connect the power output end gear of the corresponding wind-energy power machine to a first common transmission shaft 18 provided with a constant speed controller 9 , the power is then through transmission member 10 , 11 transmitted to the second common transmission shaft 19 which is shared by the standby power source, and the common transmission member 10 , 11 drive the generator G to generate electricity, or through the integration of vertical series connection and parallel connection combined system AB the generator is driven to generate electricity.
[0016] The other motor unit is a standby power source, it includes at least one to a multiple of wind-energy power machines A:A 1 . . . An, at least one to a multiple of air compressors W:W 1 . . . Wn, which generate high pressurized air, and sufficient containers T:T 1 . . . Tn which accumulate the pressurized air and at least a turbine S which uses the pressurized air to generate rotation power or a pneumatic motor R or a fluid pump 100 , and a high pressure air piping U and a solenoid valve V as well as sub-container 21 provided on each floor; the at least one to a multiple of wind-energy power machines drive the air compressors to do work, or through the power output shaft 17 , the clutch 7 , the bevel gear 15 which connects with the respective wind-energy power machine the power is transmitted to a common transmission shaft 20 , the transmission member 10 , 11 or the reduction gearbox Q drive the air compressor to do work, or through the integration of vertical series connection and parallel connection combined system AB the power is transmitted to drive the air compressor in operation, the generated pressurized air is accumulated in the containers; the connection piping U between the container of the air compressor and the next container is provided with a check valve Y, the solenoid valve v and the throttle valve V 1 are provided in the piping U between the container and the turbine or the pneumatic motor or the fluid pump; the turbine and the pneumatic motor are driven in operation by the pressurized air supplied by the container, and through the second common transmission shaft, the clutch and the common transmission member the generator is driven to generate electricity.
[0017] The above described containers are provided with the piping connected with the sub-containers 21 provided on each floor, the sub-containers supply the pressurized air through a solenoid valve 24 , a piping 23 to the cylinder 22 or the pneumatic motor or pneumatic clutch of the rolling door; the necessary location of the above described power output shaft, the common transmission shaft 17 , 18 , 19 , 20 are provided with the support bearing 6 and the clutch 7 , in addition the necessary location of the common transmission shaft is provided with the coupling 7 a.
[0018] The described motor units as the main power source and as the standby power source are selected by means of an automatic controller system which controls the time to alternately operate the motor unit, the controlling mode or program is as follows: if there is natural wind, both the wind-energy power machine units and the air compressor set or the fluid pump operate simultaneously to do work, but the turbine S or the pneumatic motor R or the water-wheel machine 100 is in the shutdown state, the clutch on the second common transmission shaft 19 is disconnected, the motor unit as the main power source drives the generator G in operation to generate electricity.
[0019] When the natural wind blows so weakly that the speed of the motor unit as main power source or the power output or the generator power is lower than a predetermined value, the automatic controller system sends a command to disconnect the clutch of the first common transmission shaft 18 , at the same time the solenoid valve automatically opens, the throttle valve V 1 controls the flow rate of the pressurized air in the container, the pressurized air is inputted into the turbine or the pneumatic motor and the rotation power is generated, the clutch of the second common transmission is automatically closed, the output power drives the generator to generate electricity, or it controls and drives the water-wheel machine and power generating unit to generate electricity.
[0020] Another constitution of the motor unit as standby power source for the A energy storage power generating system includes at least one to a multiple of wind-energy power machines A:A 1 . . . An, at least one fluid pump 100 . . . 100 n , one upper reservoir 200 and one lower reservoir and water-wheel machine 300 ; the wind-energy power machine drives the fluid pump in operation to do work, or through the power transmission shaft 17 , the clutch 7 , the bevel gear 15 which connect the respective wind-energy power machine the power is transmitted to the common transmission shaft 20 with the coupling 7 a supported by a bracket and the seat bearing 6 , the transmission member 10 , 11 drives the fluid pump in operation, or through the integration of vertical series connection and parallel connection combined system AB the fluid pump is driven in operation, the water is drawn to the upper reservoir through the input piping 102 and output piping 101 connected with the lower reservoir, and then through the piping 201 , a connected solenoid valve 202 and the throttle valve the water controls and drives the water-wheel machine in operation to output the power in order to drive the generator in operation to generate electricity.
[0021] The integration of vertical series connection and parallel connection combined system AB constitutes as follows. A multiple of wind-energy power machines A of the motor unit as the main power source are installed on each floor of the high frame structure B respectively in aligned with each other in the same common vertical axis and vertically installed on the installation frame N 1 , N 2 with the bearings 6 , 6 a , the air compressor W, the container T, the turbine S or the pneumatic motor and the generator G are installed on one of the floors, hence there are both upper and lower motor units, or the wind-energy power machines in series connection on several upper or lower floors constitutes one motor unit, each wind-energy power machines A of each unit is connected with the clutch 7 or coupling 7 a , while the wind-energy power machines A of the power output end of the motor unit need in connection with the clutch 7 and the first transmission shaft 12 ; the motor unit as the standby power source may constitute in the same way.
[0022] The motor unit as the main power source transmits the power through the first transmission shaft 12 , the bevel gear 15 or gear and the connected reduction gearbox Q, the clutch 7 and the common transmission member 10 , 11 to drive the generator in operation to generate electricity. The motor unit as the standby power source transmits the power through the bevel gear or gear of the first transmission shaft 12 , the transmission shaft 25 , the reduction gearbox Q and the common transmission member 10 , 11 to drive the air compressor to do work, the pressurized air is accumulated in the containers T; when the speed or the output power of the motor unit as the main power source or generator is lower than the predetermined value or the generator doesn't do work, the automatic controller system controls the clutch on the unit end to be disconnected, the solenoid valve V and the throttle valve V 1 in the piping connected with container and turbine S automatically open, the pressurized air enters through piping U into the turbine S or the pneumatic motor R, they output the rotation power through the transmission shaft 26 , common transmission member 10 , 11 to drive the generator in operation to generate electricity.
[0023] An energy storage power generating system includes an automatic control system, at least one to a multiple of wind-energy power machines A:A 1 . . . An, at least one to a multiple of air compressors W:W 1 . . . Wn, a multiple of pressurized air containers T:T 1 . . . Tn, at least one turbine S or pneumatic motor R or fluid pump 100 and water-wheel machine, a pressurized air piping U, a solenoid valve V and a throttle valve V 1 and a generator G; the at least one or a multiple of wind-energy power machines drive the air compressor 15 to do work, or through the power output shaft 17 which connects the wind-energy power machine, the clutch 7 , the bevel gear 15 the power is transmitted to the common transmission shaft 20 , the transmission member 10 , 11 or the reduction gearbox to drive the air compressor in operation, or through the integration of vertical series connection and parallel connection combined system AB the power is transmitted to drive the air compressor in operation, the generated pressurized air is accumulated in the containers; the connection piping U between the container and the next container of the air compressor is provided with the check valve Y, the solenoid valve and the throttle valve are provided in the piping between the container and the turbine or the pneumatic motor or the fluid pump; the turbine or the pneumatic motor are driven in operation by the pressurized air supplied by the containers and directly drives the generator in operation, or through the second common transmission shaft, the clutch and the common transmission member the generator is driven to generate electricity.
[0024] According to the output strength of the wind-energy power machine or the speed change which is set by the system the standard value is compared, the automatic control system estimates, controls and selects the required rotation of the matched air compressor, and optimizes the operation efficiency; the automatic control system also controls the opening and closing of the solenoid valve and operates the throttle valve so that it controls the output power of the turbine or the pneumatic motor or the fluid pump and the operation of the clutch.
[0025] The above described container is provided with the piping connected with subsidiary container 21 on each floors, the pressurized air is supplied through the solenoid valve 24 , the piping 23 to the cylinder 22 and pneumatic motor or the pneumatic clutch for the rolling door L; the power output shaft, the common transmission shaft 19 , 20 have support component with the seat bearing 6 and the clutch 7 on the necessary locations, the common transmission shaft is also provided with the coupling 7 a on the necessary location.
[0026] A wind-driven power generating system includes a multiple of wind-energy power machines A and generators G which constitute a multiple of generator units, or certain quantity of wind-energy power machines A are provided on the large special open high level frame structure B through the vertical integration system C or horizontal integration system D or the combination of systems C, D, so that it is possible to construct a motor unit with larger power, and furthermore connected with a generator to become a large scale power generating unit, it is also possible to arrange many large scale power generating units and output electricity respectively, or the combination of respective large scale power generating unit and substation can constitute larger scale power generating system.
[0027] The floor height, total height and the area of the above described high frame structure B can be designed and planned according to the demand of power and scale, there is partitioned floor F between two stories, but there is no fixed wall body in the surroundings, however, there is a shield such as a movable rolling door L which is activated pneumatically or electrically, the shield is used to block off the wind from all directions when there is storm or when the equipment needs to be maintained.
[0028] There is an impermeable wind collection wall M which integrally extends in a certain length in the southeast, northeast, northwest and southwest direction of the frame structure B, the wall body only on the side near the column B 1 of the frame structure has a movable window M 1 from which the wind cab escape and which can be opened and closed by a pneumatic cylinder 22 or an electrical windlass and which is same level as each floor; on the wind collection wall M 2 and the top platform of the frame structure B are provided with power generating device M 3 with a plurality of photoelectric tubes which can generate electricity, the generated electricity can be transmitted to the power supply network of the present system. The frame structure has a lift inside.
[0029] The frame structure B has installation frame N 1 , N 2 for mounting the wind-energy power machines in the location where the wind-energy power machine A is installed in the inside space of each floor, each center rotating body 1 of the wind-energy power machine in this location on each floor lies in the same vertical centerline, there is an installation window O in the respective floor so that each wind-energy power machine which aligns with each other on each floor can be connected with the clutch 7 or the coupling 7 a.
[0030] According to the rotation speed range of the wind-energy power machine, the automatic control system or the anemometer P provided outside the frame structure B detects the wind strength and outputs signals to the control system to automatically control the pneumatically or electrically activated rolling door and the open degree of the wind collection window, so as to control and adjust the override wind which surpasses the predetermined value within the defined range, so that the wind-energy power machine can steadily and credibly rotate to provide power; fully closing the rolling door enables all the wind-energy power machines to stop operation, and locally closing the respective rolling door or the brake 8 enables the single wind-energy power machine to stop operation; it is also possible to select the opening and closing by manually controlling or manually operation through the control panel K of the control system.
[0031] The vertical integration system C can connect the wind-energy power machines on several floors with clutch 7 or coupling 7 a so as to constitute a large scale motor unit with large power, the wind-energy power machine with terminal power output connects the first transmission shaft 12 with the clutch 7 , the bevel gear 15 on the shaft is engaged with the input shaft gear of the reduction gearbox Q, the power output shaft of the reduction gearbox Q is connected with generator G through the coupling, the generator is driven to generate electricity.
[0032] Each wind-energy power machine is vertically installed on the installation frame N 1 , N 2 with the bearings 6 , 6 a mounted on the shaft portions 1 a , 1 b of the center rotating body; the installation frame N 1 is provided on the floor cross beam B 2 with a certain height, the lower portion forms a space which receives the clutch 7 ; the lower shaft portion 1 C of the center rotating body penetrates the through-hole O of the middle installation frame, and the upper shaft portion 1d of the center rotating body of the lower wind-energy power machine penetrates the installation window O of the floor, they are connected by means of the clutch 7 in this space, the installation frame N 2 is provided on the bottom or upper portion of the upper floor.
[0033] The horizontal integration system D and the generator G are provided between two wind-energy power machines A, the two wind-energy power machines transmit the power to the respective horizontal transmission shaft 13 through the bevel gear 15 of the respective center rotating body 1 , again through the clutch 7 connected with the horizontal common transmission shaft 14 provided with constant speed controller 9 , transmission member 10 , 11 to transmit power in order to drive the generator in operation to generate electricity; the horizontal transmission shaft and the horizontal common transmission shaft are installed on the cross beam B 2 of the floor with bracket and bearing 16 ; the above described transmission member 10 may be a sprocket or gear belt wheel or belt wheel or general gear, the transmission member 11 may be a chain or gear belt or belt.
[0034] Furthermore, all the wind-energy power machines can also transmit power through a front transmission shaft having the clutch 7 , one end of the shaft is engaged with the gear on the lower shaft portion of the center rotating body of the wind-energy power machine, the gear on the other end is engaged with the gear on the horizontal transmission shaft 13 , each wind-energy power machine may output power or disconnect power through the clutch provided on the transmission shaft; each wind-energy power machine is vertically installed on the installation frame N 1 ,N 2 with the bearings 6 a , 6 provided on the upper and lower portions of the center rotating body.
[0035] The benefit effect of the wind-energy power machine and its energy storage power generating system and the wind-driven power generating system according to the present invention mainly consists in that it utilizes the natural wind energy as the power source, the wind-energy power machine doesn't directly drive the generator when the wind-energy power machine starts, it starts under light loading, thereafter it connects the generator through the clutch or the vertical integration system or the horizontal integration system or the combined system of the vertical series connection and parallel connection to make the generator rotation to generate electricity, therefore it is possible to drive the wind-energy power machine under light wind, whereas it is possible to gain stronger wind power even if the wind speed is lower through the wind accumulation action of the wind collection wall, thereby the wind-energy power machine can operate more effectively; in addition the site selection of the construction for the wind-energy power machine and its power generating system is easier to popularize than the general wind-driven generator which is restricted by the natural condition of the geographical environment, its prospect of developing and utilizing the wind energy resources is very good;
[0036] in that, the wind-energy power machine has maximal expandability of the power capability of single motor, and the larger power scale and the power generating capability of the large scale power generating system are formed by means of the vertical series connection and the parallel connection or the vertical and the horizontal integration system, the popularization of the wind-energy power machine can reduce the reliance on the fossil power plant and eliminate the negative influence to the environment, it is helpful to the flourish of the economic development and the optimization of the natural environment.
[0037] in that, the present wind-energy power machine is not restricted by any wind direction, the wind from any direction can drive the wind-energy power machine to rotate in the same direction without guide mechanism which consumes energy as the general wind-driven generator, and increase the wind efficiency; regarding to the structure it can safely operate under strong wind circumstance, its wind area is large and the surface receiving wind is perpendicular to the wind direction, hence the wind efficiency is very high.
[0038] in that, the energy storage power system accumulates the wind energy when the wind blows, when there is no wind, the accumulated energy is gradually released to drive the turbine or the pneumatic motor or the fluid pump and the water-wheel machine and drive the generator in operation to generate electricity, this increases the effective power generating hours and power generating quantity with the wind-driven power generating.
[0039] in that, the construction of the power plant may develop towards to the high space utilizing the high frame structure which sufficiently uses the integration towards the high space, the construction footprint may reduce several times, tens times or more in comparison with conventional construction way of the wind-driven power generating site under the same capacity of power generating, it can save a large quantity of construction field; it has been proved that the strength of air stream in the high space is several times as that in the lower space, therefore it can be understood that the power generating efficiency and the effect of the wind-driven power plant according to the present invention which uses the high space are several times as that of the conventional wind-driven power plant which uses the windmill; integrating the function and the benefit effect, the present invention will create better life for the human.
BRIEF DESCRIPTION OF THE DRAWINGS
[0040] FIG. 1 is a schematic plane view of the storage energy power generating system according to the present invention.
[0041] FIG. 2 is a front view of the wind-energy power machine according to the present invention showing the center rotating body 1 , frame 2 and wind pressure push mechanism 3 .
[0042] FIG. 3 is a front view of the wind pressure push mechanism 3 for the wind-energy power machine according to the present invention.
[0043] FIG. 4 is a front view of the wind-energy power machine according to the present invention showing the opening state when one side of the wind pressure push mechanism 3 is against the wind.
[0044] FIG. 5 is a top view of the wind-energy power machine according to the present invention showing the opening state when one side of the wind pressure push mechanism 3 is against the wind.
[0045] FIG. 6 is a front view of the wind-energy power machine according to the present invention showing another structure of frame 4 and center rotating body 1 .
[0046] FIG. 7 is a front view of the wind pressure push mechanism 5 for the wind-energy power machine according to the present invention; FIG. 7-1 is a A-A section view; FIG. 7-2 is a right side view.
[0047] FIG. 8 is a perspective view of the frame 4 for wind-energy power machine according to the present invention, which has 4 set of frame portions and 8 set of wind pressure push mechanisms.
[0048] FIG. 9 is a front exploded view of the female cam of the wind pressure push mechanism for the wind-energy power machine according to the present invention; FIG. 9-1 is a top view; FIG. 9-2 is a positioning male rack.
[0049] FIG. 10 is a front view of the male cam for the wind-energy power machine according to the present invention.
[0050] FIG. 11 is a front view of the centrifugal force balance homing device.
[0051] FIG. 12 is a schematic view of the wind-energy power machine according to the present invention mounted on an independent machine frame.
[0052] FIG. 13 is a perspective view showing the installation of shaft of the center rotating body and seat bearing mounted on the installation frame N 1 and clutch.
[0053] FIG. 14 is a schematic view of another embodiment of the storage energy power system according to the present invention.
[0054] FIG. 15 is a front view of the storage energy power system according to the present invention, which integrates a combination system of vertical connection in series and parallel connection.
[0055] FIG. 16 is a perspective view showing the wind-driven power generating system according to the present invention.
[0056] FIG. 17 is a front view of the vertical integration system for the wind-driven power generating system according to the present invention.
[0057] FIG. 18 is a front view of the horizontal integration system for the wind-driven power generating system according to the present invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0058] The embodiments of the invention will now be described in detail with reference to the accompanying drawings.
[0059] Firstly referring to FIG. 1 , a storage energy power generating system comprises two series of motor units and a power generating mechanism, in which one motor unit mainly provides power to drive generator as the main power source for electricity generation when there is natural wind energy; it includes at least one to a multiple of wind-energy power machines A:A 1 , A 2 . . . An, each wind-energy power machine transmits power through power output shaft 17 to the first common transmission shaft 18 , power output shaft is supported by the support component with the bearing 6 , in which there is provided with a clutch which controls power transmission or disconnection individually, this makes individual wind-energy power machine not affect any one wind-energy power machine in totality when it stops operation for maintenance; the front end gear of the power output shaft is each engaged with the gear on the lower end portion 1 c of the center rotating body for the respective wind-energy power machine or connected in transmission, the bevel gear 15 of the distal end of the power output shaft 17 is engaged with the bevel gear 15 of the first common transmission shaft, the first common transmission shaft transmits the power through the clutch 7 , transmission members 10 , 11 to the second common transmission shaft 19 , and again through the sprocket of the common transmission member and chain or through gear and belt or through suitable form of other power transmission drive the generator G to generate electricity; the first common transmission shaft comprises several shafts which are connected with coupling 7 a , between the shafts there is provided with constant speed controller 9 , the shaft end is provided with clutch 7 in order to control the power output or disconnection, the first and second common transmission shaft are provided with coupling 7 a at suitable shaft section, and secured by the seat bearing 6 and support member on the cross beam B 2 or B 3 .
[0060] When the motor unit as the main power source rotates to drive the generator G for electricity generation, the turbine S or the pneumatic motor R or the water-wheel machine 300 of the motor unit as standby power source stays at shutdown state not to operate to transmit power, at the same time the clutch at the power output end of the second common transmission shaft is opened, but the wind-energy power machine unit as the standby power source and the air compressor W unit or the fluid pump 100 are working for energy storage.
[0061] The other series of the motor unit as the standby power source includes at least one to a multiple of wind-energy power machines A:A 1 . . . An) at least one to a multiple of air compressors W:W 1 . . . Wn, and enough number of high pressure energy storage containers T:T 1 . . . Tn and at least one turbine S or the pneumatic motor R or the fluid pump 100 and the water-wheel machine 300 , and pressurized gas transmission piping U and solenoid valve V, throttle valve V 1 and generator G; by means of the power output shaft 17 which links the power output end gear of the wind-energy power machine, the power is transmitted to the common transmission shaft 20 , and through the transmission member 10 , 11 the air compressors W is driven in operation; the front end gear of each power output shaft is respectively engaged with the gear on the lower end portion 1 c of the center rotating body 1 , or connected with transmission member in suitable way; each power output shaft is supported and secured by the support component with bearing 6 , in which there is provided with a clutch 7 which controls power transmission or disconnection individually, this makes any individual wind-energy power machine not affect other wind-energy power machine in totality due to its shutdown; the other end bevel gear of each power output shaft is respectively engaged with the bevel gear 15 provided on the common transmission shaft 20 , the coupling 7 a connects two or several common transmission shaft 20 , and is supported by the support component with bearing 6 .
[0062] The check valve is provided in the piping U between the energy storage container T and the next energy storage container T of the compressor; throttle valve V 1 and solenoid valve V is provided in the piping U connecting the energy storage container with turbine and pneumatic motor or fluid pump, between two piping there is further provided parallel connection bypass gate valve X; in addition, energy storage container transmits the pressurized gas through a piping and the valve X to the subsidiary energy storage container 21 provided on each floor, the link line of the energy storage container connects to the pneumatic motor of the pneumatically rolling door L and the cylinder 22 or the pneumatic clutch which opens and closes the door and window of the wind collection wall, and when the cylinder and pneumatic motor or the pneumatic clutch are to operate, the solenoid valve 24 receives command to open and output pressurized gas.
[0063] The motor unit as main power source and as standby power source may use integration of combination system of vertical series connection and parallel connection or other suitable way to transmit power so that it drives generator to generate electricity; utilizing wind-energy power machine A which is prone to integrate the expandable function and the large special open high level frame structure B, through the integration of combination system of vertical series connection and parallel connection, the construction of energy storage power generating system towards the high space may constitute the large-scale and high effective all-weather power plant.
[0064] FIG. 2 shows the static and basic constitution having a center rotating body 1 , a frame 2 and a wind pressure push mechanism 3 for the wind-energy power machine A, the column 2 a , lower cross beam 2 b , upper cross beam 2 c and outer side column 2 d of the frame are constituted by welding or with fasteners, there are a multiple of through-holes 2 e at many locations of the column, the frame is secured onto the center rotating body by means of fasteners; the center rotating body is tubular, the both ends are welded with solid shafts, the lower end shaft portion 1 a is provided with the ball bearing 6 to be assembled on the installation frame N 1 , the shaft portion 1 a can also have a brake 8 , shaft portion 1 c is provided with a clutch or coupling or gear; the upper end shaft portion 1 b is provided with rolling bearing or ball bearing 6 a to be assembled on the installation frame N 2 , the shaft portion 1 d is connected with shaft portion 1 c by means of clutch 7 or coupling.
[0065] At the location which is measured from the bottom in the height of the column 2 a of frame portion and outer side column 2 d in the vertical direction slightly above the midpoint or at any location away from the above mentioned location within certain distance, there are symmetric through-holes at the same level line. The wind pressure push mechanism 3 has support shaft 3 b at same vertical height which has same level centerline and is provided with seat bearing 3 d to be assembled in the above mentioned through-hole with bolts; each of one side of all outer side column 2 d is provided with an adjustment device 2 f for adjusting the opening degree of the wind pressure push mechanism, it may adjust the height by means of threads.
[0066] The constitution of the wind pressure push mechanism 3 is shown in the front view of FIG. 3 , right side view of FIG. 3-1 and A-A section view of FIG. 3-2 . The wind pressure push mechanism 3 has a frame, its side which receives the wind is a concave body 3 a so that it can accumulate the wind energy to strengthen the push force, it may be made of metal or non-metal plate and is bent along the four sides with certain height and width to form a component with four sides which have definite height. The wind pressure push mechanism has a horizontal support shafts 3 b being symmetric and at the same level centerline on two vertical outer side surfaces of the frame at the location which lies in the height of the outer side frame of the wind pressure push mechanism in the vertical direction slightly above the midpoint, or at any location away from the above mentioned location within a certain distance. The weight which forms the lower volume of the wind pressure push mechanism is slightly heavier than the upper portion, so that the wind pressure push mechanism can be raised to open when it is against the wind, even if under the action of gentle breeze and centrifugal force; its bottom has a positioning plate 3 C, when it conforms to the wind direction, the wind pressure push mechanism homes to close under the action of lower weight and air stream, and the positioning plate presses against the lower cross beam 2 b.
[0067] The front view of FIG. 4 and the top view of FIG. 5 schematically show the main constitution of the wind-energy power machines A, which has 4 set of frame 4 and 4 set of wind pressure push mechanism 3 and center rotating body 1 , in which the wind pressure push mechanism on the right side against the wind has been opened, the adjustment device 2 f restricts the open degree, and the arrow direction represents the air stream direction; the left side is in the wind received process in the wind direction, the wind pressure push mechanism presses against the lower cross beam to form a wind-driven state in the direction perpendicular to the wind direction. The frame portion and wind pressure push mechanism may have different quantity.
[0068] FIG. 6 shows another combination of different frame 4 and center rotating body 1 for the wind-energy power machines A according to the present invention, the lower cross beam 4 a and the upper cross beam 4 b of the frame portion are mounted on the fix plate 1 C of the center rotating body 1 with bolts 4 C; at the outer side end location which is away from the center rotating body a certain distance in the horizontal width direction, there is through-hole 4 d with each symmetric mount seat bearing 5 d and/or cam set 5 c of the support shaft which has same vertical centerline; the frame portion and the wind pressure push mechanism may have many sets.
[0069] The front view of FIG. 7 , the right side view of FIG. 7-1 and the A-A section view of FIG. 7-2 show the main structure of the wind pressure push mechanism 5 which fits to the frame 4 , and the concave body 5 a consists of frame 5 a 1 and concave plate 5 a 2 , the concave plate may be a main plate with surroundings which are bent along the circumference of the plate in integrity to a definite height; within a certain range which is apart from the ⅔ width of the horizontal width of the upper and lower frame or at least ½ width a definite distance, there are support shaft 5 b and support shaft cam set 5 c ( 5 c 1 , 5 c 2 ) with same vertical centerline, outside its wide side there is provided with the fix plate of wind pressure push mechanism which presses against the cross beam, between the upper frame positioning plate and the support shaft there is provided with a lug 5 e which connects the link cord 5 g 3 .
[0070] FIG. 8 shows the main constitution of a wind-energy power machines A, which has 4 set of frame portion 4 and 8 set of wind pressure push mechanism 5 , the right part of the drawing shows the state of a set of wind pressure push mechanism, in which it has been opened so that the whole plane is parallel to the wind direction when it is against the wind, this forms a status without resistance against the wind, while the other 3 set of wind pressure push mechanism are all in the home and close position, one set of wind pressure push mechanism on the left side is in the process, in which it is against the wind facing the wind pressure to be driven, such that a wind-energy power machines A is formed that can receive wind energy in any direction to rotate. The straight arrow represents the wind direction, and the arc arrow represents the rotation direction of the wind-energy power machine.
[0071] The upper cross beam is provided with centrifugal force balance homing device 5 g , and the lug 5 e for connecting the link cord 5 g 3 ; the upper support shaft 5 b of the wind pressure push mechanism is mounted on the lower portion of the upper cross beam with the seat bearing 5 d , and the support shaft cam set 5 C may be referred to FIG. 9 and 10 , FIG. 9 , FIG. 9-1 is female cam 5 c 1 , it has a inner sleeve 5 C 3 with male and female racks shown as the front view of FIG. 9-2 and the top view of FIG. 9-3 , adjusting the angle of the male and female racks, the open degree of the wind pressure push mechanism can be adjusted; FIG. 10 shows the male cam 5 c 2 , the match inclination therebetween is within 25 to 55 degree; the male cam is mounted on the base of the wind pressure push mechanism 5 , and the female cam is mounted on the corresponding position of the lower cross beam installation through-hole 4 d.
[0072] FIG. 11 briefly shows the constitution of the centrifugal force balance homing device 5 g , a hollow cylinder 5 g 1 , an inside compression spring 5 g 2 , the flexible steel cable of link cord 5 g 3 , which connects to the inside end of the compression spring on one end, the outside end of the cord hangs to the small ball 5 g 4 and connects to the tension spring and again connects to the lug.
[0073] FIG. 12 shows a wind-energy power machines A mounted on the independent machine frame E, the upper portion of the center rotating body 1 is mounted on the upper beam with ball bearing 6 a , the lower end shaft portion 1 a is mounted on the lower beam with roller bearing 6 , and the shaft portion is also provided with brake 8 and gear 10 . The perspective view of FIG. 13 shows that the lower end shaft portion 1 a of the center rotating body 1 is provided with brake and bearing 6 , and the shaft portion 1 c is provided with clutch 7 , when shaft portion 1 c and shaft portion 1 d abut together, the shaft portion 1 c is then provided with clutch 7 , the bearing 6 is mounted on the installation frame N 1 , and the installation frame is secured to the cross beam B 3 .
[0074] FIG. 14 is the schematic plane view of one embodiment of the energy storage power generating system, the upper part of the drawing is the motor unit series as main power source which constantly rotates when there is wind, they include at least one to a multiple of wind-energy power machines A:A 1 ,A 2 . . . An, each transmits the power through power output shaft 17 , clutch 7 , bevel gear 15 to the first common transmission shaft 18 , the first common transmission shaft consists of several shafts which are connected with coupling 7 a , and is mounted on the cross beam B 2 or B 3 with seat bearing 6 and support member, this transmission shaft is also provided with constant speed controller 9 , and the power output end is provided with clutch 7 , sprocket 10 of the transmission member, chain 11 , the power is then transmitted to the second common transmission shaft 19 , the common transmission member drives the generator G to generate electricity, or through the integration of vertical connection and parallel connection combined system the generator is driven to generate electricity.
[0075] Regarding to the series of the motor unit as the standby power source, at least one to a multiple of wind-energy power machines A:A 1 ,A 2 . . . An transmit the power through the power output shaft 17 which connects the respective wind-energy power machine to the common transmission shaft 20 , then the transmission members 10 , 11 drive the fluid pump 100 to rotate and do work; power output shaft 17 is mounted on the floor beam through the support member with the seat bearing 6 , this power output shaft is provided with a clutch 7 so that it can be disconnected or transmit the power; the fluid pump draws water through an inlet pipe 102 from the lower reservoir to the upper reservoir 200 , the outlet pipe 101 is connected with a solenoid valve 202 ; when the natural wind blows weakly and the speed of the motor unit as main power source or the power output or the generator power is lower than a predetermined value, the automatic controller system sends a command to disconnect the clutch of the first common transmission shaft, at the same time the solenoid valve 202 automatically opens, the water from the upper reservoir drives the water-wheel machine 300 and outputs the power through the transmission members 10 , 11 and the second common transmission shaft 19 and the closed clutch 7 and the common transmission member 10 , 11 , so as to drive the generator in operation and generate electricity.
[0076] In the practical application, the fluid pump is provided on the upper reservoir, in this case the flexible connection for the high pressure driven fluid pump is preferable, in this way the problem of long distance power transmission for the wind-energy power machine is well solved. The present application is well suitable for the geographical environment where there is no much water resources but there is water potential difference between upper and lower reservoir, this can be combined with wind energy and fluid energy to build all-weather power plant.
[0077] FIG. 15 is a front view of a combined system AB which integrates the vertical series connection and parallel connection, this is another embodiment of the energy storage power generating system. The integration number and constitution of the wind-energy power machine A of the motor unit as main power source are same as those of the motor unit as standby power source, the number of wind-energy power machine mainly depends on the power demand scale. The present embodiment only shows a type example of 7-storied construction which utilizes a high frame, the same module can be arranged on the floors of the high frame structure B, this can easily and flexibly expand the scale of the power and generator set; the wind-energy power machine A of the present invention is characterized in that it can be developed towards the high space.
[0078] The center rotating bodies 1 of wind-energy power machines arranged on the upper and lower three floors and the installation windows O are aligned in the same vertical centerline, the shaft portion of the center rotating body of each wind-energy power machine is fitted with a bearing 6 , 6 a and vertically mounted on the installation frames N 2 , N 1 ; shaft portions 1 c , 1 d are connected each other with a coupling 7 a or clutch 7 , and a generator G, an air compressor W, a cylinder T and a turbine S etc. are installed on the middle floor, the wind-energy power machines on the both of upper and lower floors adjacent to the middle floor serve as the terminal power output, their center rotating bodies are fitted with clutches and connected separately with first transmission shaft 12 , the motor unit as main power source drives the generator to generate electricity through the first transmission shaft and the gear and the reduction gearbox Q and then through the connected power output shaft 26 , the clutch 7 and the common transmission member.
[0079] The constitution of the motor unit as standby power source is same as that of the motor unit as main power source, the power drives the air compressor W through the first transmission shaft 12 and the transmission shaft 25 and the reduction gearbox Q and the transmission member 10 , 11 , the pressurized air accumulates in the storage container T, and the container T and turbine S are connected with solenoid valve through pipe U; the power from turbine or pneumatic motor drives the generator in operation to generate electricity through transmission shaft 26 , clutch 7 , common transmission member 10 , 11 .
[0080] The both motor units as main power source and as standby power source can control and select the time of alternately in operation or stopping power output by means of an automatic controller system, the motor unit as main power source operates to provide power to drive the generator in operation for generating electricity when there is wind energy, but the motor unit as standby power source and the air compressor are also in operation to do work and accumulate high pressure air in the storage container, however, the turbine or the pneumatic motor is in the shutdown state; it is only when the wind is so weak that the speed or power of the motor unit as main power source or the electricity output of the generator is lower than a predetermined value that the motor unit as standby power source then outputs the power; when the automatic control circuit detects that the generator or the motor unit as main power source operates in disorder until under the predetermined value, then the solenoid valve is to open, at the same time the clutch on the first common transmission shaft end disconnects, and the turbine or the pneumatic motor begins to operate, while the clutch on the transmission shaft 26 automatically closes, the output power drives the generator to continue in normal operation generating electricity. The power transmission form here described is only a preferable example, obviously, it is possible that there is other suitable transmission form.
[0081] FIG. 16 shows the constitution of the wind energy power generating system according to the present invention, and shows the high frame structure B with wind-energy power machines A locally arranged on the two-storied frame; a certain quantity of wind-energy power machines are installed in the specially opened large scale high frame structure B which is constructed to sufficiently utilize the high space, in the way that utilizes the vertical integration system C or the horizontal integration system or the both, such that one or several large scale power generating units are formed and output electric power, again individual large scale power generating unit is combined with transformer station to constitute a larger scale power generating system with capacity of hundreds or thousands MW.
[0082] The described large scale high frame structure B is a specially designed frame, it may be steel structure or steel reinforced concrete structure; the described high structure may be tens meters or more to hundreds or thousands meters high. There is an impermeable wind collection wall which integrally extends in a certain length in the southeast, northeast, northwest and southwest direction of the frame structure, the wall body only on the side near a column B 1 of the frame structure has a window M 1 which can be opened and closed by a pneumatic cylinder or a electrical controller and which is at same level as each floor, the wind collection wall M 2 with large area and the top platform of the frame structure are provided with a power generating device M 3 with a large quantity of photoelectric tubes which transform light to electricity, the generated electricity can be incorporated to the power supply network of the present system. Each floor of the frame structure has not fixed shield wall body in the four sides, but there is a pneumatic or electric rolling door L to prevent from the storm invading or when shutdown due to some factors; every several floors is provided with a wind anemometer P in the southeast and northwest direction, there is also provided with control-box K of the automatic controller system on every floor, all the windows and rolling doors can be controlled to certain degree through automatic control system to control the wind-energy power machine kept operating within the permissible changeable range of the predetermined value.
[0083] The straight arrow in the Figure represents the wind direction, and the arc arrow represents the rotation direction of the wind-energy power machine A; the drawing shows the state in which the right wind pressure push mechanisms 5 of all wind-energy power machines automatically open and are parallel to the wind direction, while the other 3 sets of the wind pressure push mechanisms are in the close state. In the Fig., the wind collection wall M is only the exemplary, all the wall bodies M 2 can be arranged with photoelectric power generating device M 3 from top to bottom; the movable window M 1 is between the wall body and the column B 1 , the cylinder 22 of the close and open device is provided in the middle location.
[0084] FIG. 17 shows the vertical integration system C, the generator G is installed on the middle floor, a multiple of wind-energy power machines A which are in the same vertical centerline are provided on the upper and lower several floors, respectively, the respective center rotating bodies 1 are serially connected with the couplings or the clutchs, the shaft portion of the wind-energy power machine as the terminal power output is connected with the first transmission shaft 12 by the clutch 7 , the coupling 7 a transmits the power through the gear 15 and the reduction gearbox Q to the generator to drive it in operation for generating electricity. The upper shaft portion 1 b of the center rotating body 1 for the wind-energy power machine is provided with the ball bearing 6 a , the lower shaft portion is provided with the roller bearing 6 in order to install the wind-energy power machine vertically on the installation frame N 2 and N 1 .
[0085] Only one representative vertical integration system is shown in the Figure, with respect to the special large scale high frame structure B, a multiple of vertical integration systems C or integrated combination systems of series connection and parallel connection can be arranged in the vertical direction and/or horizontal direction.
[0086] FIG. 18 schematically shows the constitution of the horizontal integration system D arranged on certain floor of the high frame structure B, its upper or lower floor may have a pluarality of horizontal integration systems to form a grouped large scale power generating system. As shown in the Fig., In the left and right space there are provided with several wind-energy power machines A, the generator G is installed in the middle region; wind-energy power machines are vertically installed on each respective installation frame N 1 , N 2 with the bearings 6 , 6 a mounted on the shaft portions of the center rotating body; the installation frame N 1 is provided on the floor cross beam B 2 with a certain height, the lower portion forms a space which receives gear 15 ; in the left and right region there is provided with a horizontal transmission shaft 13 connected with clutch 7 or coupling 6 a , the bevel gear thereon is engaged with the bevel gear 15 on the lower end shaft portion of the respective wind-energy power machine; the power output ends of the both horizontal transmission shaft are provided with the clutch 7 connected with the horizontal common transmission shaft 14 , and can connect the generator through the chain and sprocket, and the shaft 14 may also have constant speed controller 9 .
[0087] In addition, all wind-energy power machine A can also transmit power through a front transmission shaft provided with the clutch, the gear on the shaft end is engaged with the gear on the center rotating body shaft portion 1 c of the wind-energy power machine, the gear on the other shaft end is engaged with the gear on the horizontal transmission shaft 13 , each wind-energy power machine can output or disconnect the power through the clutch provided on this transmission shaft.
[0088] The constitution of the frame portion and the installation way of the wind pressure push mechanism may be variably changed, FIG. 19 shows another constitution of the frame portion 2 , the wind pressure push mechanism 3 is mounted on the outer side column 2 d and inner side column 2 f which is away from the center rotating body 1 a certain distance to form a larger leverage so that the wind pressure push mechanism can receive increased driving force generated by the wind. The right part of the Figure shows the process of the wind pressure push mechanism against the wind which is opened to form the whole surface almost in the state parallel to the wind direction, while the left part of the Figure shows the process of a free wind in which the wind pressure push mechanism closes and presses against the upper and lower cross beams and forms the whole surface almost in the state perpendicular to the wind direction.
[0089] FIG. 20 schematically shows the wind pressure push mechanism 5 which is vertically installed on the same vertical centerline between the upper cross beam 4 b and the lower cross beam 4 a away from the center rotating body 1 with a certain distance; the right part of the Figure shows the state of the wind pressure push mechanism against the wind which is opened to form the whole surface in the state parallel to the wind direction, while the left part of the Figure shows the state of a free wind in which the wind pressure push mechanism closes and receives the wind force to be driven.
|
A wind-energy power machine and it's energy-storage generation system and wind-energy power generation system relate to a field of wind-energy power, generating technology and generating device. The wind-energy power machine is composed of a central rotor, a plurality sets of frames and at least a set of wind-pressure pushing mechanism provided within each set of frame. The central rotor vertically rotatablely mounted within a mounting frame in a special high-story frame structure with wind collecting wall is formed to a large scale power and generating system by means of combining with vertical or horizontal integrated system, or both systems in series and in parallel.
| 8
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to velocity-measuring devices and, more particularly, to velocity-measuring devices which have an audible output and may be removably attached to skis and the like.
2. Description of the Prior Art
A velocity-measuring device which can be removably fixed to the rear end of a snow or water ski is disclosed in U.S. Pat. No. 4,546,650. The device employs a microcomputer which calculates speeds and/or distance traveled by a skier and displays the selected parameter on a readout device carried by the trailing end of a ski. A toothed wheel is constrained to rotate about an axis lateral to the rear end of the ski and is positioned to contact the snow or water and rotate when it is moved in direction to the axis of the ski. The water-snow-contacting wheel carries two permanent magnets which cooperate with a sensor mounted on the housing of the device to sense the passing of the magnets. In order to determine his or her maximum speed, average speed, or the distance traveled, a skier would have to remove his or her skis to see the visual display, a distinct disadvantage. Moreover, while in motion, no information is made available to the skier about his or her current speed, a shortcoming especially in situations in which the skier is trying to ski to his or her maximum advantage along a portion of a down-hill run, or the like.
A speed indicating device or gauge which may be mounted on the forward flat upper surface of the water ski is known from U.S. Pat. No. 3,978,725. This indicator is so mounted that the user of the ski during water skiing may view this speed indicating device. The velocity sensing is achieved by a pilot tube-like device in which one end of the tube is connected to the meter and the other end is disposed on the ski underside and at the rear thereof. The tube is filled with liquid to a point near the rear of the tube where a flexible diaphragm seals the tube. The diaphragm is actuated by the pressure of the fluid flow created by the rate of travel of the ski in the water, No. provision is seen for storing the output nor of any electronic circuitry. Clearly, the device cannot be used on a snow ski or the like, nor does it provide an audible output.
Other devices, which may be attached to skis and the like for measuring velocity, are revealed in U.S. Pat. Nos. 3,505,878 and 4,262,537. These devices are fastened to a ski by screws and must be mechanically powered, thereby interfering with the natural operation of the ski, distinct shortcomings.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a velocity-measuring device which may be removably fixed to a snow ski, water ski, ice-boat, skateboard, bicycle, arm band or the like and provide current audio information to the user while he or she is in motion.
Another object of the present invention is to provide a velocity-measuring device which may be removably fixed to a snow ski, water ski, ice-boat, skateboard, bicycle, arm band or the like and provide an audio summary of velocity and velocity-related data concerning a completed run.
A further object of the present invention is to provide a velocity-measuring device which may be removably fixed to a snow ski, water ski, ice-boat, skateboard, bicycle, arm band or the like and provide an audible audio output of current performance to the user, while he or she is in motion.
An additional object of the present invention is to provide a velocity-measuring device which may be removably fixed to a snow ski, ice-boat, water ski, skateboard, bicycle, arm band or the like and provide an audible output constituting a summary of velocity and velocity-related data concerning a competed run.
The velocity-measuring device of the present invention s a small, battery operated, microprocessor-based electronic device which provides an audible output of user performance. It may be mounted to the front half of a snow ski, just in front of the binding toe piece, where it is clearly in the air stream generated by the moving ski. In other variants, the device may be mounted on a skateboard, a water ski, a surfboard, a wind-surfer, a bicycle, an ice-boat, an arm-band or the like. Velocity through the air is measured by microprocessor-based circuitry, which reads the speed of a small, integral wind turbine wheel, performs all conversions and calculations, and controls a voice synthesis circuit.
The device of the present invention requires minimum operator interaction. The only operator controls are two push buttons and a volume control with integral battery power off/on switch. A loudspeaker and/or an earphone jack is provided for audible outputs.
Clearly audible synthesized speech output of information allows the user to hear his or her current speed with minimum diversion of his attention from the main goal of safe skiing or operating other person-supporting moving structures. Also, upon completion of a run, the device of the present invention may provide, on demand, a comprehensive summary of average speed, maximum speed, elapsed time and distance covered for the run, as well as a recapitulation of the speed during the run if desired.
The device of the present invention has three operating modes. The first, its reset mode, occurs when the device is first activated and each time the user initiates current operating mode. It initializes all hardware, software, and output parameters. In the current operating mode, the device performs real time velocity measurements and effects audible outputs of velocity at predetermined intervals, for example at five second intervals. In the third mode, a summary mode, the device provides an audible summary of the latest operating mode interval. No measurements are performed during summary mode. The four output parameters, namely average speed, maximum speed, time and distance, continuously sequence until the device is either deactivated or reset by the operator.
The device of the present invention measures air speed, so its operation is completely independent of contact with either the ground surface, the snow surface, the water surface, the ice surface or the like, as the cases may be. It is also mounted, in the snow ski embodiment and similar realizations, in front of the boot attachment where it is relatively protected from physical abuse. A fabric hooks-to-hooks or loops-to-hooks mounting system (of the type sold under the trademark VELCRO®) provides secure attachment to the ski surface or the like, which is also readily removable for security purposes. The volume of the audible output is adjustable to suit the user's requirements. Also, the circuitry may provide audible indication of low battery voltage.
All operational functions, as well as internal calculations and conversions, are completely under software control and may be modified by program changes.
From one vantage point, the invention can be viewed as being in combination with a movable structure adapted to ride on or over a surface while supporting or carrying at least one person. A velocity-measuring device, which includes means responsive to air flow, develops an electrical signal representative of current velocity of the movable structure. Voice synthesizing means, responding to the electrical signal representation of velocity, provides periodic voice synthesized audible outputs indicative of current velocity of the movable structure.
The invention can also be seen as being a combination of a movable structure adapted to ride on or over a surface while supporting or carrying at least one person and a velocity-measuring device for developing an electrical signal representative of current velocity of the movable structure. Voice synthesizing means respond to the electrical signal representation of current velocity and provide periodic voice synthesized audible output indicative of current velocity of the movable structure.
From a slightly different point of view, the invention can be seen as being in combination with a structure adapted to be carried by a person, for example supported on the arm of the person. A velocity-measuring device having means responsive to air flow develops an electrical signal representative of velocity of the structure (and thus the person). Voice synthesizing means responsive to the electrical signal representative of velocity provides periodic voice synthesized audible output indicative of velocity of the structure (and thus the person).
The invention can also be viewed as a combination of a structure adapted to be removably fixed to a person and a velocity-measuring device fixed to the structure for developing an electrical signal representative of current velocity of the structure and thus the person. Voice synthesizing means respond to the electrical signal representation of current velocity and provide periodic voice synthesized audible outputs indicative of current velocity of the structure of thus the person.
The device and the synthesizer are preferably removably fixed to the structure. The means responsive to the electrical signal provides periodic voice synthesized audible output indicative of current velocity of the structure at substantially five second intervals.
The means responsive to the electrical signal may include a loudspeaker for providing the voice synthesized audible output.
The means responsive to the electrical signal may include earphone means for providing the voice synthesized audible output.
The device may include responsive to the electrical signal for providing representations of the velocities of the structure for playback after a run.
The device may include means responsive to the electrical signal for producing voice synthesized representations of average speed, maximum speed, elapsed time and distance in its summary mode upon request.
The structure may be any snow- or ice-engaging structure, a snow ski, a skateboard, a water ski, a surfboard, a wind-surfer, a bicycle, an ice-boat, a band (such as an arm-band which is adapted to be attached to a person and carry the device) or the like.
The invention can also be viewed as a circuit for measuring velocity which includes means for producing an electrical signal representative of velocity. Microprocessor means, including, programming means, respond to the electrical signal for generating output signals representative of current velocity. Speech synthesizer means coupled to the microprocessor means respond to the output signals for developing synthesized audio signals representing velocity. Sound producing means coupled to said speech synthesizer respond to the synthesized audio signals for producing an audible output reporting velocity and/or velocity-related data.
The invention can also be viewed as a combination of a support, a velocity measuring device and a fabric mounting system. The velocity-measuring device includes means responsive to air flow for developing an electrical signal representative of current velocity of the support. Voice synthesizing means respond to the electrical signal representative of current velocity for providing voice synthesized audible outputs indicative of current velocity of the support. The fabric mounting system removably fixes the velocity-measuring device to the support.
The fabric mounting system preferably comprises a first elongated fabric member fixed to a surface of the support and a second fabric member fixed to a surface of the device and which can be brought into contact with the first elongated fabric member.
The invention achieves other objects and is characterized by other features and advantages which, with the foregoing objects, are to become apparent from the following description when considered in conjunction with the accompanying drawings. It is to be understood, however, that the invention is not limited to the embodiments illustrated and described, since it may be embodied in various forms within the scope of the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a pictorial illustration of a velocity-measuring device of the present invention as applied to one ski of a pair of snow skis, in accordance with an exemplary embodiment of the present invention.
FIG. 2 is a pictorial view of portions of the pair of snow skis of FIG. 1, the velocity-measuring device being shown removably fixed to the upper forward surface of the left ski, in accordance with the above-noted exemplary embodiment of the present invention.
FIG. 3 is an enlarged, partially exploded view of the device and a portion of the left ski of FIG. 2, showing the velocity-measuring device as viewed from the tips of the skis.
FIGS. 4A-4C are respectively top, front and side views of the velocity-measuring device of FIGS. 1-3, the side view being shown in cross-section to illustrate the placement of some of the internal components, the section being taken along section lines 4C-4C of FIGS. 4A and 4B.
FIG. 5 is a simplified, block diagram of the circuitry of the velocity-measuring device constructed in accordance with the present invention.
FIGS. 6A and 6B are, when taken together, a detailed schematic circuit diagram of the velocity-measuring device which may be used to carry out the present invention.
FIGS. 7-13 are respective pictorial illustrations of adaptations of the velocity-measuring device of the present invention as applied respectively to a skateboard, a water ski, a bicycle, the arm of a person, a surfboard, a wind-surfer and an ice-boat.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 1, a person 10, illustrated as a skier, is shown in a snow skiing attitude aboard a pair of snow skis 11 and 12, with a pair of ski poles 13 and 14 in hand. A velocity-sensing device 15, constructed in accordance with the present invention and shown in more detail in FIGS. 2, 3 and 4A-4C, is attached to the upper surface of the left ski 12 forward of the person 10. The person 10 has conventional earphones 16 over his ears, the earphones 16 being attached to the velocity-sensing device 15 via a conventional cord 17 and a plug-and-jack arrangement for the purpose of supplying audible signals indicative of the velocity of the skis from the device to the person. A loudspeaker (not shown) could be used as an alternative to the earphones.
As illustrated in FIGS. 2 and 3, the velocity-sensing device 15 includes a "Thorgren" fan positioned in a hollow cylindrical open ended housing 18 supported above a principal housing 20 by an upstanding flange. The housing 18 constitutes a stationary portion of a wind turbine which includes conventional turbine blades 30 mounted for rotation, by wind forces, about an axle coincident with the axis of the cylindrical housing 18. Rotor and stator members of conventional construction are provided within the housing 18, the stator includes a pick up coil or the like which develops an electrical pulse train output, the frequency of which depends linearly and directly on the angular velocity of the rotor as driven by the turbine blades 30. The rotor includes a disk and carries a pair of "Bunting" centerless ground magnets (FIG. 4C).
An earphone jack 24 is provided in the rear wall of the principal housing 20. A volume control knob 21 is provided adjacent to and above the upper wall of the housing 20 for the purpose of setting the level of the audio available via the earphone jack 24. Two push buttons 22 and 23 (also shown schematically in FIG. 5) are conveniently provided for respectfully initiating a resetting of the device 15 and for initiating a summary mode of operation, subsequent to a ski run or the like.
As best shown, as an exploded view, in FIG. 3, the velocity-measuring device 15 is removably fixed to the ski 12 by a fastener arrangement of loops-to-hooks fabric or a hooks-to-hooks fabric connection (such as the fabric fastener commercially sold under the trademark VELCRO®). As shown, a first elongated fabric member 26 is fixed to the upper surface of the ski 12 by a mastic, double-sided tape 26 or the like. The entire bottom surface of the principal housing 20 is fixed to a second fabric member 27 by a second mastic, double-sided tape 28 or the like. When the opposing surfaces of the two fabric members 25 and 27 are brought together, the device 15 is firmly, yet removably, fixed to the ski 12. The position of the device along the member 26 can be conveniently selected by the user and, because the width of the fabric member 27 is greater than the width of the fabric member 26, the device 15 may be rocked from side-to-side and, thus, can be removed from the ski rather easily.
Turning briefly to FIGS. 7-13, it can be seen that the velocity measuring device 15 may be carried by structures other than a snow ski (FIGS. 1-3). In FIGS. 7 and 8, the device of the present invention is shown attached respectively to a skateboard 41 and to the right ski 42 of a pair of water skis 42, 43, a person 10 being shown in each case as being carried by the skateboard and water skis. As shown in FIG. 9, the person 10 is illustrated as being a bicycle rider, the device 15 being removably mounted on a central portion of the handlebar of a bicycle 44. In FIG. 10, the person 10 has a flexible, removable armband 45, of the fabric fastening type, on which the device 15 is mounted. On other variants, the person 10 could be riding a surfboard 46 or a wind surfer 47, shown respectively in FIGS. 11 and 12 with the velocity measuring device 15 being removably fixed to an upper surface thereof. In FIG. 13, an ice-board 48 is shown generally the device 15 being removably fixed to an upper surface of the forward leg of the convention T-structure of the ice-boat. A seat 50 is provided to enable a user to operate the ice-boat. In each of the cases shown in FIGS. 7-13, the device 15 may include an earphone jack (see FIGS. 1-3) so that the person 10 using the structures for sport may receive the audio output from a voice synthesizer within the housing 20 (FIGS. 1-3). It is to be understood, as noted above, that a loudspeaker could be provided within the housing 20 (see FIG. 4A) so that the audio output can be heard without the earphone or as an alternative to the earphones.
An exemplary embodiment of the velocity-measuring device 15 is illustrated in FIGS. 4A-4C, FIGS. 4A and 4B are respectively top and front elevational views of the device, while FIG. 4C is a side cross-sectional view, the section having been taken along section lines 4C-4C in FIGS. 4A and 4B. As shown in FIGS. 4A-4C the device 15 includes the main housing 20 which supports, by an integral web or the like, the open-ended cylindrical housing 18 within which wind turbine is housed and positioned for rotation effected by air (wind) flow, a plurality of turbine blades 30 being provided for this purpose. An earphone jack 24 is visible in FIGS. 4A-4C as are the volume control knob 21 and the summary mode initiating button 23. The reset button 22 is visible in FIG. 4B. In FIG. 4C, a volume control rheostat 39 mechanically coupled to the volume-control knob 21 is visible, the rheostat 39 being mounted on a printed circuit board 31 which is fixed to the upper, inner surface of the housing 20 by four screws, two of which (designated by numerals 32 and 34) are visible, conventional hollow cylindrical spacers 35 and 36 being provided to space the printed circuit board 31 from the top interior surface of the housing 20. It is to be appreciated that other circuit components, including generally shown components 37, 38 and 40, visible in FIG. 4C, are also mounted on the circuit board 31. A loudspeaker 33 is mounted on the circuit board 31 for the purpose of providing an audible output which may be heard by the user, such as the skier 10 (FIG. 1), were he to elect not to use the earphones 16 (FIG. 1). The device 15 is powered from a nine (9) volt battery 29 which is removably positioned within the housing 20.
The details of construction of the wind turbine positioned within the cylindrical housing 18 is best seen in FIG. 4C. The turbine blades 30 (two being visible in FIG. 4C) are mounted for rotation, by wind forces, about an axle 41 coincident with the central axis of the cylindrical housing 18. The axle 41 is carried by a pair of bearings positioned centrally in respective spaced apart blade guards 42 and 43. The integral central or hub portion of the blades 30 is fixed to the axle 41 for rotation therewith and include hollow portions within which are carried two "Bunting", centerless magnets 44 and 45. The magnets 44 and 45 rotated with the axle 41, as a result of wind (air) flow through the housing 18, past a fixed conventional magnetic pickup 46. It is to be understood that the magnetic pickup arrangement described above may be replaced by other sensing arrangements. For example, the velocity (speed) signal could be produced optically, the spinning turbine blades 30 (or other moving part of the turbine) could repeatedly break a low power IR-LED light beam. The resulting pulsed light beam would be translated into an electric signal by a phototransistor. Other possible arrangements, include a plurality of magnets associated with reed switches or Hall-effect transistors could be used to produce a suitable signal. A contact wheel or an ultrasonic doppler echo-radar may be used instead.
Briefly stated, the circuitry of the velocity-measuring device includes two main electronic subsystems, a microprocessor subsystem and the voice synthesis/output subsystem. Several other auxiliary subsystems serve to enhance the operation of the main subsystems and provide operator interface. The entire circuit may be mounted on a single printed circuit board (PCB). Two momentary contact push buttons, a volume control rheostat with an integral battery power switch, a miniature speaker, and a phone jack are mounted within the housing and are attached to the PCB by wires.
Turning to FIG. 5, the circuitry of the velocity-measuring device of the present includes a power supply and low battery detector section, a speed encoder section, a microprocessor section, including an EPROM and address latch, and a speech synthesizer section, including an address latch, audio amplifier and sound producer (earphones or loudspeaker).
As shown in FIG. 5, the low battery detector section is illustrated as a voltage comparator 51 which receives its input voltage from the voltage regulator 52 operatively arranged to supply to other circuit components a regulated d.c. operating voltage V cc . A power switch 50, which is mechanically ganged to the volume control rheostat 39 (also visible in FIG. 4C), is provided for connecting the nine (9) volt battery 29 (also shown in FIG. 4C) to the voltage regulator 52 as its input.
The voltage regulator 52 functions to keep V cc at a given regulated level over a range of input voltage, thus assuring that the voltage level of the battery 29 need not be exact and that the velocity-measuring device will operate properly, event when the terminal voltage of the battery 29 falls as its charge is reduced or it ages. Whenever the terminal voltage of the battery 29 falls to a level insufficient to supply the voltage regulator 52 or lower, as reflected in the voltage supplied to the voltage comparator 51, the voltage comparator produces a low voltage signal which is supplied to a microprocessor 53, which may be as shown in FIGS. 6A, 6B a 80C40 CMOS microprocessor running at 9.36 MHz. It is to be understood that other microprocessors could be used, as well. The microprocessor 53 monitors the two operator actuated push buttons 22 and 23, and performs all timing, counting and calculating functions in real-time.
The voltage regulator 52 supplied operating voltage V cc to all the active circuit components, as is conventional. One of these components includes an integrated circuit speech synthesizer 54, which is an allophone synthesizer and receives its power input via a battery saver circuit 55 and lead 56, only when the microprocessor 53 calls upon the synthesizer to produce an output. The battery saver circuit 55 acts as a controlled switch supplying V cc to the speech synthesizer 54 whenever an enabling signal is received from the microprocessor 53 on its idle data output lead. The software used contains all allophones and builds phrases under control of he microprocessor 53.
The microprocessor 53 provides one output in the form of control signal to a transistor-switch comprising the battery saver circuit 55 controlling battery power to the voice synthesis circuit 54. The power to this circuit is turned off during idle voice synthesis periods of greatly extend battery life. Because the remaining components have minimal power requirements automatic power control for them is not necessary.
The CMOS microprocessor 53 is provided with velocity input data from the speed encoding section which includes a wind (air flow) turbine pickup 46 (also shown in FIG. 4C). The pickup 46 may be a winding responsive to the charging magnetic field associated with the traveling magnets 44 and 45 (FIG. 4C). The output from the wind turbine pickup 46 is approximately a pulse train having a frequency which varies substantially linearly and directly with respect to the angular velocity of the turbine blades 30 (FIG. 4C) and thus represents the current velocity of air flow through the turbine. The pulse train output from the pickup 46 is fed to a Schmitt trigger circuit 57 having its output coupled to a flip-flop circuit 58. A train of pulses having a repetition rate substantially directly proportional to velocity is produced by the flip-flop circuit 58 and supplied, as velocity (speed) data, to the CMOS microprocessor 53. The microprocessor 53 is provided with a program on one of its data lines from a programmed EPROM 60 which is controlled by the microprocessor 53 via an address latch 61. The program supplied from the EPROM 60 may take many forms and be conveniently written in a selected one of a number of languages. In a realized embodiment of the invention, a wiring diagram of which is illustrated in FIGS. 6A-6B, the EPROM 60 was programmed, using assembly language, for 8048 and relatives. A computer-based print out of an exemplary program and source code is incorporated hereinbelow as Appendix A. The wiring diagram in FIGS. 6A-6B includes part designations and component values, allowing those skilled in the art to construct the exemplary circuit of the present invention, without difficulty. As an aid to those skilled in the art who may wish to use the source code set out in Appendix A, a symbol table is set out hereinbelow as Appendix B.
A second output from the microprocessor 53 is fed as a controlling input to the speech synthesizer data input terminal of the speech synthesizer 54. An address input is supplied to the synthesizer 54 via an address latch 62 under control of the microprocessor 53. The speech synthesizer 54 produces an output in the form of synthesized voice sounds which are fed to a low voltage amplifier 63 which amplifies the speech output and supplies it to the earphone jack 24 and/or loudspeaker 33 (FIGS. 4A-4C).
The microprocessor 53 executes one another of two program segments depending on whether the reset push button 22 or the summary push button 23 has been pushed and, in the even a low battery voltage signal is received from the voltage comparator 51, a special program segment calling for the synthesizer 54 to produce an audio output which indicates in verbal terms that the battery 29 is too low to assure that the velocity measuring device can operate accurately.
The major output function of the microprocessor 53 is to control the speech synthesis process. All of the input signal monitoring, timing, conversion, and calculation functions of the microprocessor 53 eventually result in internal numeric variables to be outputted to the user. The microprocessor 53 converts these numeric variables into signals that are compatible with the speech synthesizer 54 by utilizing vocabulary and speech sound lookup tables and related information included in program memory of the EMPROM 60. The microprocessor 53 interacts with the speech synthesizer 54 via a latched output bus and interrupt lines required by the speed synthesizer, the microprocessor 53 outputs each in proper sequence and timing to the speech synthesizer 54, which actually generates the electronic speech signal.
In ski mode, the program provides for audible numbers (0-99) representing current speed at intervals of five seconds. In summary mode, audible numbers indicating average speed (0-99), maximum speed (0-99), elapsed time (minutes:seconds), and distance covered (tenths of a mile) for the previous run are provided along with audible descriptive labels.
In addition, "ready" and "set-go" outputs are provided at power-up and reset respectively to cue the user. The "battery low" output is provided when the battery voltage drops below about five bolts. All calculations and audible outputs are under software control, and can therefore be modified through programming changes. Inasmuch as an allophone speech synthesizer is employed and it can synthesize any words and phrases, the device can easily be reconfigured to speak different units (such as, kilometers per hour) or even to calculate and/or announce different parameters; e.g. "safe speed exceeded". The device could produce its audio output in languages other than English, for example, German, French and the like, by reprogramming.
The output from the speech synthesizer 54 is fed to the miniature speaker 33 (FIG. 4C) and earphone jack (FIGS. 4A-4C) via a low voltage audio amplifier 63. The volume of the output is controlled by the operator via the volume control rheostat 39.
It is to be understood that the foregoing description of the preferred embodiments of invention and the accompanying illustrations thereof have been set out by way of example, not by way of limitation. Numerous other embodiments and variants of of the invention are possible without departing from the spirit and scope of the invention, its scope being defined in the appended claims. ##SPC1##
|
A combination of a movable structure (adapted to ride on or over a surface while supporting or carrying at least one person) and a velocity-measuring device which includes means responsive to air flow develop an electrical signal representative of current velocity of the movable structure. A voice synthesizing means, responsive to the electrical signal representation of current velocity, provides periodic voice synthesized audible outputs indicative of current velocity of the movable structure. The movable structure may be a snow ski, a water ski or a skateboard, as well as a number of other sport participating implements, such as a bicycle, an ice boat and the like.
| 6
|
This application is a continuation of U.S. patent application Ser. No. 12/081,168, filed Apr. 11, 2008, now U.S. Pat. No. 8,259,287, which is a continuation of U.S. patent application Ser. No. 11/098,615, filed Apr. 5, 2005, now U.S. Pat. No. 7,411,654, each of the foregoing applications is incorporated herein its entirety by reference.
FIELD
The present invention relates to a lithographic apparatus and a method for manufacturing a device.
BACKGROUND
A lithographic apparatus is a machine that applies a desired pattern onto a substrate, usually onto a target portion of the substrate. A lithographic apparatus can be used, for example, in the manufacture of integrated circuits (ICs). In that instance, a patterning device, which is alternatively referred to as a mask or a reticle, may be used to generate a circuit pattern to be formed on an individual layer of the IC. This pattern can be transferred onto a target portion (e.g. including part of one, or several dies) on a substrate (e.g. a silicon wafer). Transfer of the pattern is typically via imaging onto a layer of radiation-sensitive material (resist) provided on the substrate. In general, a single substrate will contain a network of adjacent target portions that are successively patterned. Known lithographic apparatus include so-called steppers, in which each target portion is irradiated by exposing an entire pattern onto the target portion at one time, and so-called scanners, in which each target portion is irradiated by scanning the pattern through a radiation beam in a given direction (the “scanning”-direction) while synchronously scanning the substrate parallel or anti-parallel to this direction. It is also possible to transfer the pattern from the patterning device to the substrate by imprinting the pattern onto the substrate.
It has been proposed to immerse the substrate in the lithographic projection apparatus in a liquid having a relatively high refractive index, e.g. water, so as to fill a space between the final element of the projection system and the substrate. The point of this is to enable imaging of smaller features since the exposure radiation will have a shorter wavelength in the liquid. (The effect of the liquid may also be regarded as increasing the effective NA of the system and also increasing the depth of focus.) Other immersion liquids have been proposed, including water with solid particles (e.g. quartz) suspended therein.
However, submersing the substrate or substrate and substrate table in a bath of liquid (see for example U.S. Pat. No. 4,509,852, hereby incorporated in its entirety by reference) means that there is a large body of liquid that must be accelerated during a scanning exposure. This requires additional or more powerful motors and turbulence in the liquid may lead to undesirable and unpredictable effects.
One of the solutions proposed is for a liquid supply system to provide liquid on only a localized area of the substrate and in between the final element of the projection system and the substrate using a liquid confinement system (the substrate generally has a larger surface area than the final element of the projection system). One way which has been proposed to arrange for this is disclosed in WO 99/49504, hereby incorporated in its entirety by reference. As illustrated in FIGS. 2 and 3 , liquid is supplied by at least one inlet IN onto the substrate, desirably along the direction of movement of the substrate relative to the final element, and is removed by at least one outlet OUT after having passed under the projection system. That is, as the substrate is scanned beneath the element in a −X direction, liquid is supplied at the +X side of the element and taken up at the −X side. FIG. 2 shows the arrangement schematically in which liquid is supplied via inlet IN and is taken up on the other side of the element by outlet OUT which is connected to a low pressure source. In the illustration of FIG. 2 the liquid is supplied along the direction of movement of the substrate relative to the final element, though this does not need to be the case. Various orientations and numbers of in- and out-lets positioned around the final element are possible, one example is illustrated in FIG. 3 in which four sets of an inlet with an outlet on either side are provided in a regular pattern around the final element.
Another solution which has been proposed is to provide the liquid supply system with a seal member which extends along at least a part of a boundary of the space between the final element of the projection system and the substrate table. Such a solution is illustrated in FIG. 4 . The seal member is substantially stationary relative to the projection system in the XY plane though there may be some relative movement in the Z direction (in the direction of the optical axis). A seal is formed between the seal member and the surface of the substrate. Desirably the seal is a contactless seal such as a gas seal. Such a system with a gas seal is illustrated in FIG. 5 and disclosed in EP-A-1 420 298 hereby incorporated in its entirety by reference.
In EP-A-1 420 300 the idea of a twin or dual stage immersion lithography apparatus is disclosed. Such an apparatus is provided with two stages for supporting the substrate. Leveling measurements are carried out with a stage at a first position, without immersion liquid, and exposure is carried out with a stage at a second position, where immersion liquid is present. Alternatively, the apparatus has only one stage.
The seal member disclosed in EP-A-1 420 298 has several problems. Although the system can provide immersion liquid between the final element of the projection system and the substrate, the immersion liquid can sometimes overflow and sometimes recirculation of immersion liquid in the space between the final element of the projection system and the substrate occurs which can result in imaging errors when the radiation beam is projected through the recirculation areas thereby heating immersion liquid up and changing its refractive index. Furthermore, overflow of the seal member is hard to avoid in certain circumstances.
SUMMARY OF THE INVENTION
It is desirable to provide a seal member or barrier member which overcomes some of the above mentioned problems. It is an aspect of the present invention to provide a seal member or barrier member in which turbulent flow is reduced and in which overflowing of the immersion liquid is reduced.
According to an aspect of the present invention, there is provided a lithographic apparatus including a substrate table constructed to hold a substrate; a projection system configured to project a patterned radiation beam onto a target portion of the substrate, and a barrier member having a surface surrounding a space between a final element of the projection system and the substrate table configured to contain a liquid in the space between the final element and the substrate; the barrier member including a liquid inlet configured to provide liquid to the space and a liquid outlet configured to remove liquid from the space; wherein the liquid inlet and/or liquid outlet extend(s) around a fraction of the inner circumference of the surface.
According to another aspect of the present invention, there is provided a lithographic apparatus including a substrate table constructed to hold a substrate; a projection system configured to project a patterned radiation beam onto a target portion of the substrate, and a barrier member having a surface surrounding a space between a final element of the projection system and the substrate table configured to contain a liquid in the space between the final element and the substrate; the barrier member including a liquid inlet configured to provide liquid to the space, the inlet including a chamber in the barrier member separated from the space by a plate member, the plate member forming at least part of the surface and having a plurality of through holes extending between the chamber and the space for the flow of liquid therethrough.
According to another aspect of the present invention, there is provided a lithographic apparatus including a substrate table constructed to hold a substrate; a projection system configured to project a patterned radiation beam onto a target portion of the substrate; a liquid supply system configured to supply liquid to a space between a final element of the projection system and a substrate; and a control system configured to dynamically vary the rate of extraction of liquid by the liquid supply system from the space and/or dynamically vary the rate of supply of liquid by the liquid supply system such that a level of liquid in the space is maintained between a predetermined minimum and a predetermined maximum.
According to another aspect of the present invention, there is provided a lithographic apparatus including a substrate table constructed to hold a substrate; a projection system configured to project a patterned radiation beam onto a target portion of the substrate; and a liquid supply system configured to provide liquid to a space between a final element of the projection system and a substrate; wherein the liquid supply system includes an extractor configured to remove liquid from the space, the extractor including a two dimensional array of orifices through which the liquid can be extracted from the space.
According to another aspect of the present invention, there is provided a device manufacturing method including projecting a patterned beam of radiation onto a substrate using a projection system, wherein a barrier member has a surface which surrounds the space between a final element of the projection system which projects the patterned beam and the substrate thereby containing a liquid in a space between the final element and the substrate; providing liquid to the space through a liquid inlet; and removing liquid from the space via a liquid outlet, wherein the liquid inlet and/or liquid outlet extend(s) around a fraction of the inner circumference of the surface.
According to another aspect of the present invention, there is provided a device manufacturing method including projecting a patterned beam of radiation onto a substrate using a projection system, wherein a liquid is provided between a final element of the projection system and the substrate, the liquid being contained by a barrier member having a surface, the liquid being provided to the space through an inlet which includes a chamber in the barrier member separated from the space by a plate member and the plate member having a plurality of through holes extending between the chamber and the space through which the liquid flows.
According to another aspect of the present invention, there is provided a device manufacturing method including projecting a patterned beam of radiation onto a substrate using a projection system, wherein liquid is provided to a space between the final element of a projection system and the substrate and the rate of extraction of liquid from the space is dynamically varied and/or the rate of supply of liquid to the space is dynamically varied to maintain the level of liquid in the space between a predetermined minimum and a predetermined maximum.
According to another aspect of the present invention, there is provided a device manufacturing method including projecting a patterned beam of radiation onto a substrate using a projection system, wherein liquid is provided to a space between a final element of a projection system and a substrate; liquid being extracted from the space through an extractor which includes a two dimensional array of orifices.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the present invention will now be described, by way of example only, with reference to the accompanying schematic drawings in which corresponding reference symbols indicate corresponding parts, and in which:
FIG. 1 depicts a lithographic apparatus according to an embodiment of the present invention;
FIGS. 2 and 3 depict a liquid supply system used in a prior art lithographic projection apparatus;
FIG. 4 depicts a liquid supply system according to another prior art lithographic projection apparatus;
FIG. 5 depicts a seal member as disclosed in European Application No. 03252955.4;
FIG. 6 depicts schematically, in cross-section, a seal member of the present invention;
FIGS. 7 a and b depict, in plan, a seal member of the present invention;
FIGS. 8 a - c depict variations in flow direction through the seal member with hole diameter to plate thickness ratio of immersion liquid;
FIGS. 9 a - e illustrate different embodiments of overflows according to the present invention;
FIGS. 10 a - e depict different embodiments for liquid extraction according to the present invention; and
FIG. 11 depicts the control system for the management of immersion liquid in the seal member according to the present invention.
DETAILED DESCRIPTION
FIG. 1 schematically depicts a lithographic apparatus according to an embodiment of the present invention. The apparatus includes an illumination system (illuminator) IL configured to condition a radiation beam B (e.g. UV radiation or DUV radiation). A support (e.g. a mask table) MT is constructed to support a patterning device (e.g. a mask) MA and is connected to a first positioning device PM configured to accurately position the patterning device in accordance with certain parameters. A substrate table (e.g. a wafer table) WT is constructed to hold a substrate (e.g. a resist-coated wafer) W and is connected to a second positioning device PW configured to accurately position the substrate in accordance with certain parameters. A projection system (e.g. a refractive projection lens system) PS is configured to project a pattern imparted to the radiation beam B by patterning device MA onto a target portion C (e.g. including one or more dies) of the substrate W. A reference frame RF is configured to support the projection system PS.
The illumination system may include various types of optical components, such as refractive, reflective, magnetic, electromagnetic, electrostatic or other types of optical components, or any combination thereof, for directing, shaping, or controlling radiation.
The support supports, e.g. bears the weight of, the patterning device. It holds the patterning device in a manner that depends on the orientation of the patterning device, the design of the lithographic apparatus, and other conditions, such as for example whether or not the patterning device is held in a vacuum environment. The support can use mechanical, vacuum, electrostatic or other clamping techniques to hold the patterning device. The support may be a frame or a table, for example, which may be fixed or movable as required. The support may ensure that the patterning device is at a desired position, for example with respect to the projection system. Any use of the terms “reticle” or “mask” herein may be considered synonymous with the more general term “patterning device.”
The term “patterning device” used herein should be broadly interpreted as referring to any device that can be used to impart a radiation beam with a pattern in its cross-section such as to create a pattern in a target portion of the substrate. It should be noted that the pattern imparted to the radiation beam may not exactly correspond to the desired pattern in the target portion of the substrate, for example if the pattern includes phase-shifting features or so called assist features. Generally, the pattern imparted to the radiation beam will correspond to a particular functional layer in a device being created in the target portion, such as an integrated circuit.
The patterning device may be transmissive or reflective. Examples of patterning devices include masks, programmable mirror arrays, and programmable LCD panels. Masks are well known in lithography, and include mask types such as binary, alternating phase-shift, and attenuated phase-shift, as well as various hybrid mask types. An example of a programmable mirror array employs a matrix arrangement of small mirrors, each of which can be individually tilted so as to reflect an incoming radiation beam in different directions. The tilted mirrors impart a pattern in a radiation beam which is reflected by the mirror matrix.
The term “projection system” used herein should be broadly interpreted as encompassing any type of projection system, including refractive, reflective, catadioptric, magnetic, electromagnetic and electrostatic optical systems, or any combination thereof, as appropriate for the exposure radiation being used, or for other factors such as the use of an immersion liquid or the use of a vacuum. Any use of the term “projection lens” herein may be considered as synonymous with the more general term “projection system”.
As here depicted, the apparatus is of a transmissive type (e.g. employing a transmissive mask). Alternatively, the apparatus may be of a reflective type (e.g. employing a programmable mirror array of a type as referred to above, or employing a reflective mask).
The lithographic apparatus may be of a type having two (dual stage) or more substrate tables (and/or two or more mask tables). In such “multiple stage” machines the additional tables may be used in parallel, or preparatory steps may be carried out on one or more tables while one or more other tables are being used for exposure.
Referring to FIG. 1 , the illuminator IL receives radiation from a radiation source SO. The source and the lithographic apparatus may be separate entities, for example when the source is an excimer laser. In such cases, the source is not considered to form part of the lithographic apparatus and the radiation is passed from the source SO to the illuminator IL with the aid of a beam delivery system BD including, for example, suitable directing mirrors and/or a beam expander. In other cases the source may be an integral part of the lithographic apparatus, for example when the source is a mercury lamp. The source SO and the illuminator IL, together with the beam delivery system BD if required, may be referred to as a radiation system.
The illuminator IL may include an adjusting device AD to adjust the angular intensity distribution of the radiation beam. Generally, at least the outer and/or inner radial extent (commonly referred to as σ-outer and σ-inner, respectively) of the intensity distribution in a pupil plane of the illuminator can be adjusted. In addition, the illuminator IL may include various other components, such as an integrator IN and a condenser CO. The illuminator may be used to condition the radiation beam, to have a desired uniformity and intensity distribution in its cross-section.
The radiation beam B is incident on the patterning device (e.g., mask MA), which is held on the support (e.g., mask table MT), and is patterned by the patterning device. Having traversed the mask MA, the radiation beam B passes through the projection system PS, which projects the beam onto a target portion C of the substrate W. With the aid of the second positioning device PW and a position sensor IF (e.g. an interferometric device, linear encoder or capacitive sensor), the substrate table WT can be moved accurately, e.g. so as to position different target portions C in the path of the radiation beam B. Similarly, the first positioning device PM and another position sensor (which is not explicitly depicted in FIG. 1 but which may be an interferometric device, linear encoder or capacitive sensor) can be used to accurately position the mask MA with respect to the path of the radiation beam B, e.g. after mechanical retrieval from a mask library, or during a scan. In general, movement of the mask table MT may be realized with the aid of a long-stroke module (coarse positioning) and a short-stroke module (fine positioning), which form part of the first positioning device PM. Similarly, movement of the substrate table WT may be realized using a long-stroke module and a short-stroke module, which form part of the second positioning device PW. In the case of a stepper, as opposed to a scanner, the mask table MT may be connected to a short-stroke actuator only, or may be fixed. Mask MA and substrate W may be aligned using mask alignment marks M 1 , M 2 and substrate alignment marks P 1 , P 2 . Although the substrate alignment marks as illustrated occupy dedicated target portions, they may be located in spaces between target portions (these are known as scribe-lane alignment marks). Similarly, in situations in which more than one die is provided on the mask MA, the mask alignment marks may be located between the dies.
The depicted apparatus could be used in at least one of the following modes:
1. In step mode, the mask table MT and the substrate table WT are kept essentially stationary, while an entire pattern imparted to the radiation beam is projected onto a target portion C at one time (i.e. a single static exposure). The substrate table WT is then shifted in the X and/or Y direction so that a different target portion C can be exposed. In step mode, the maximum size of the exposure field limits the size of the target portion C imaged in a single static exposure.
2. In scan mode, the mask table MT and the substrate table WT are scanned synchronously while a pattern imparted to the radiation beam is projected onto a target portion C (i.e. a single dynamic exposure). The velocity and direction of the substrate table WT relative to the mask table MT may be determined by the (de-)magnification and image reversal characteristics of the projection system PS. In scan mode, the maximum size of the exposure field limits the width (in the non-scanning direction) of the target portion in a single dynamic exposure, whereas the length of the scanning motion determines the height (in the scanning direction) of the target portion.
3. In another mode, the mask table MT is kept essentially stationary holding a programmable patterning device, and the substrate table WT is moved or scanned while a pattern imparted to the radiation beam is projected onto a target portion C. In this mode, generally a pulsed radiation source is employed and the programmable patterning device is updated as required after each movement of the substrate table WT or in between successive radiation pulses during a scan. This mode of operation can be readily applied to maskless lithography that utilizes programmable patterning device, such as a programmable mirror array of a type as referred to above.
Combinations and/or variations on the above described modes of use or entirely different modes of use may also be employed.
FIG. 6 illustrates the seal member or barrier member 12 of the present invention. Working radially outwardly from the optical axis of the projection system, there is provided a plurality of inlets 124 through which immersion liquid 500 is provided to the space 11 between the projection system PS and the substrate W. On the bottom surface 80 of the seal member 12 there is then provided a liquid removal device 180 such as the one disclosed in U.S. application Ser. No. 10/921,348 filed Aug. 19, 2004, hereby incorporated in its entirety by reference. Radially outwardly of the liquid removal device 180 is provided a recess 320 which is connected through inlet 322 to the atmosphere and via outlet 324 to a low pressure source. Radially outwardly of recess 320 is a gas knife 420 . The arrangement of these three items on the bottom surface 80 of the seal member 12 is described in detail in U.S. Application 60/643,626 filed Jan. 14, 2005 hereby incorporated in its entirety by reference. At the top inner surface of the seal member 12 is a vertically extending protrusion or dike 220 over which immersion liquid 500 can flow into overflow area 222 and which can then be extracted through hole array 224 via a low pressure source attached to port 228 .
FIG. 6 is a schematic cross-section of the seal member 12 . Each of the five elements described above are not necessarily present around the entire circumference of the seal member. This is particularly the case with the immersion liquid inlets 124 and the liquid outlet or extractor (i.e. the dike 220 /hole array 224 ). As can be seen in FIG. 7 a , these can be advantageously provided only around a localized inner circumference of the seal member 12 and desirably opposite each other. As can be seen from figures, the liquid inlets 124 and liquid outlet are at different distances from the substrate W. Suitable fractions of length of liquid inlets 124 and/or liquid outlet is less than ½, desirably less than ⅓ of the inner circumference of the seal member 12 . Desirably the length of the liquid inlets 124 and/or liquid outlet is more than 1/20, more desirably more than 1/15 or 1/10 of the inner circumference of the seal member 12 . This helps in creating a laminar non-turbulent flow of immersion liquid from the outlets 124 , across the space 11 (i.e. a cross-flow) between the projection system PS and the substrate through the target portion TP through which the radiation beam images the substrate, and out of the space through hole array 224 . It is also possible to encourage flow of the immersion liquid across the space 11 by providing the liquid extraction unit 180 on the opposite side of the seal member 12 to the inlet ports 124 but this is not necessarily the case. Alternatively, the extraction unit 180 can be positioned around the entire circumference, perhaps with a larger extraction pressure applied to it opposite the inlets 124 . FIG. 7 b illustrates another embodiment in which three liquid outlets or extractors 224 are provided around the inner circumference of the barrier member 12 . The three outlets are positioned at roughly 120° apart, with the biggest outlet being opposite to the liquid inlets 124 and the other two outlets being smaller and positioned on either side of the inlets 124 .
The way in which the liquid is provided to the liquid inlets 124 and the design of the liquid inlets 124 themselves will now be described in detail with reference to FIGS. 6 and 8 . As can be seen in FIG. 6 , immersion liquid is provided through inlet 128 into the seal member 12 . A first pressure drop is created in the immersion liquid by forcing it through an orifice 121 which puts a first chamber 120 into liquid communication with a second chamber 122 . In reality orifice 121 is a plurality of individual holes created in plate 123 , separating the chambers 120 and 122 . The plurality of holes 121 are arranged in a regular one-dimensional array in the illustrated embodiment, but other arrangements such as two or more parallel rows of holes 121 one above another can also be used. The holes 121 distribute the flow over plate 126 , which separates chamber 122 from the space 11 , in the tangential direction and ensure a homogeneous flow over the whole width of the array of orifices 124 irrespective of the configuration of the supply 128 . Once the immersion liquid has entered the second chamber 122 , it enters through orifices 124 into the space 11 between the projection system PS and the substrate W. The orifices 124 are provided in a (regular) two-dimensional array in the plate 126 of the seal member 12 . This creates a parallel, homogeneous flow inside the space 11 . The array of orifices 124 is positioned towards the lower surface 80 of the plate 126 , desirably below the level of the projection system PS when the seal member 12 is in use.
The present inventors have found that the ratio of orifice 124 diameter d to outer plate 126 thickness t may be considered in controlling the direction in which the immersion liquid leaves the chamber 122 . This is even the case if all of the orifices 124 are drilled through the plate 126 in a plane which will be parallel to the substrate Win use.
As can be seen from FIG. 8 a , if the diameter d of the orifice 124 is greater than the thickness t of the outer plate 126 , the flow of immersion liquid can exit at an angle illustrated by arrow 127 i.e. non parallel to the substrate W surface. In FIG. 8 b , the wall thickness t is equal to the diameter d of the orifice 124 and in FIG. 8 c , the diameter d of the orifice 124 is less than the thickness t of the outer wall 126 . It has been found that the orifice diameter should be less than the thickness of the plate 126 . Typically the plate thickness will be of the region of 0.4 mm and the diameter of the orifice 124 is in the region of 0.15 min for flow to exit parallel to the substrate surface and parallel to the direction in which the orifice is machined in the plate 126 (the plate 126 is not necessarily vertically orientated and can be inclined as illustrated). The dimensions are a trade off between having small enough orifices 124 to create a large enough pressure drop and having a plate thickness thick enough to give the desired stiffness. As a result, a much more laminar flow with a lower velocity and less mixing is produced than with prior art designs. The parallel flow is encouraged by making the small orifice in a relatively thick plate. The desired ratio of plate thickness t to orifice diameter d is at least 1:2.5 so that the flow can be directed in the same direction as the axis of the orifice. The orifices are machined (drilled) substantially parallel to each other and substantially parallel to the plane of the substrate W and substantially perpendicular to the surface of the plate 126 through which they extend. The orifices can be cut by laser as small as 20 μm and as large as desired. Another way of manufacturing small holes in a plate is by electroforming (electrolytical deposition) of, for example, nickel. Holes with a diameter of 5 to 500 μm in a sheet of thickness between 10 μm and 1 mm are possible using this technique. This technique can be used to produce both inlets and outlets as described elsewhere in this description. However, unlike with the other manufacturing methods, it is difficult to align accurately the axis of the through hole using this method.
It has been found that the number of orifices and the angle their axis makes with the outer plate 126 as well as their diameter has an effect on the direction in which the liquid flows. Generally, with a single hole, flow is directed slightly away from the axis of the hole towards the side of the plate with which the axis of the hole makes an acute angle, i.e. in FIG. 8 , if the axis of the hole is parallel to the substrate W, slightly downwards from horizontal towards the substrate. The more holes that are present, the more pronounced the effect. This effect can be used to redirect flows of any fluid types in many applications (e.g. airshowers, purge hoods) and thereby eliminate or reduce the need for vanes or deflection plates or use of the Coanda effect. The effect is so strong that it can act against the force of gravity. It is thought that the origin of the effect is the interaction of a large number of asymmetrical fluid jets. The flow deflection also occurs when the fluid flows into a large volume of the same fluid, so the flow deflection is not related to the teapot leakage problem where tea leaks along the spout of the teapot. If the outer wall 126 is vertical, the axis of the orifices 124 should be parallel to the substrate W upper surface. If the outer wall 126 is included, as illustrated, in order to achieve flow parallel to the substrate surface, it has been found that the axis of the orifices 124 should be inclined away from the top surface of the substrate by about 20 degrees, desirably in the range of from 5 to 40 degrees.
The two-step pressure drop (there is a pressure drop as described, when the liquid goes through orifices 121 and clearly there will also be a pressure drop when the liquid passes through orifices 124 ) is arranged to be over the whole of the width of the supply and height of the supply. In this way the first pressure drop ensures that the flow is provided evenly over the orifices 124 irrespective of the supply channel configuration (i.e. the channel between input 128 and chamber 120 ), as described.
The laminar flow is desirable because it prevents recirculation of immersion liquid which can result in those recirculated areas of liquid becoming hotter or colder than the remaining liquid and therefore having a different refractive index or resulting in certain areas of the resist being more dissolved by the immersion liquid than others (i.e. a non-uniform concentration of resist in the immersion liquid which can change the refractive index of the immersion liquid) and also preventing transport of the resist to the projection lens.
Desirably the density of holes in the plate 126 is of the order of 15 holes per square mm. A range of from 1 to 30 holes per square mm is desirable.
In prior art seal members, liquid has been extracted either from the bottom surface 80 of the seal member 12 or from a single outlet positioned in the inner wall of the seal member 12 defining the space 11 . The outlet has either been a one dimensional array of holes around the entire circumference of the inner surface of the seal member 12 or has been an annular groove around the circumference. A problem with this type of liquid extraction is that the holes in the inner wall of the seal member are either extracting or are not extracting and the transition between extraction and non extraction can result in undesirable vibrations of the seal member 12 . One solution which has been proposed is disclosed in European Patent Application No. 04256585.3, hereby incorporated in its entirety by reference. In that document, a dike 220 is provided similar to the one illustrated in FIG. 6 . Here, if the level of immersion liquid 500 in the space rises above the level of the dike, it overflows the dike into a pool or overflow 220 behind the dike and with a lower level than the dike. The immersion liquid may then be removed from the overflow 222 . Again a difficulty with this system is that extraction either tends to happen or does not happen and there is a difficulty with the control of the amount of extraction resulting in occasional overflow.
In the present invention, a two dimensional array of holes or mesh 224 is provided in a wall of the seal member 12 through which liquid is extracted Immersion liquid which either overflows a dike 220 or flows above the level of the lower most hole of the 2d array 224 is extracted by extractor 228 . Desirably a non-homogenous array of holes in the wall of the seal member is used in which the number of holes per unit area and/or size of holes increases from a minimum furthest away from the substrate to a maximum nearest the substrate or at lowest position. Thus there is a smaller resistance for the immersion liquid to pass through the array at the lowest level and a higher resistance for air at the upper level of the plate. Thus by using a vertical gradient in the hole distribution (either in size or density or both) the resistance of the plate to flow is increased with increasing vertical height. Thus the problem of the flow of air out through the holes pushing away water and thereby making level control difficult is addressed. Such embodiments are illustrated in FIGS. 9 a - e . In an alternative embodiment illustrated in FIGS. 10 a - e no dike is present and the immersion liquid is removed as soon as its level reaches above the lower most hole of array 224 . As is illustrated in FIGS. 7 a and b , the extraction arrangements illustrated in FIGS. 9 a - e and 10 a - e may be provided only around a fraction of the inner circumference of the seal member 12 , desirably opposite the inlets 124 . However, clearly the outlets illustrated in FIGS. 9 a - e and 10 a - e can be provided the whole way around the inner circumference of the seal member 12 . It is possible to provide a different level of under pressure to the outlet 228 around the circumference of the seal member in the latter embodiment thereby arranging for different extraction rates around the inner circumference of the seal member 12 . Arranging for different extractions rates either by varying the pressure of an extractor extending around the entire circumference of the seal member 12 or by arranging for only a localized extractor can help in promoting laminar flow of immersion liquid from the inlets 124 across the target portion TP and out through the extractor.
The array of holes 224 may include holes of the order of between 0.1 and 0.5 mm in diameter. A density of 0.25 to 5 holes per square mm is desirable. The use of the two dimensional array of holes has the benefit that the immersion liquid 11 is more easily controlled because a higher immersion liquid level wets more holes of the array 224 resulting in a higher extraction rate. Conversely, a lower level of immersion liquid will wet fewer holes and thereby result in a lower extraction rate. In this way the extraction of immersion liquid is automatically regulated without the need for adjusting the extraction rate at outlet 228 . This is particularly the case when the hole array 224 is vertically or at least partly vertically orientated. The use of a dike 220 allows the array of holes 224 to extend to a lower level than the dike increasing the extraction capacity. If the barrier member 12 is made liquid philic (hydrophilic in the case that the immersion liquid is water) build up of liquid level due to surface tension effects can be minimized.
The overflow 220 allows sudden and short build-up of immersion liquid without the risk of over spilling. For example, during moving of the substrate W or a closing disc up closer to the surface of the seal member 12 there will be a sudden decrease in the volume of the space 11 and therefore a rise in immersion liquid level. The ditch 222 can accommodate some of this excess liquid while it is extracted.
It should be appreciated that the array of holes 310 could be provided as a mesh or equivalent.
FIGS. 9 a - e illustrate different configurations for the dike embodiment of the extractor. In FIG. 9 a , the immersion liquid enters a volume 330 before being extracted by extractor 228 . By contrast, in the design of FIG. 9 b , it is arranged that the immersion liquid enters a narrow gap 340 before being extracted at outlet 228 . Due to capillary forces, the gap 340 is completely filled with immersion liquid (if it is designed narrow enough) and if the under-pressure is matched with the size of the holes 224 the formation of bubbles in the extracted immersion liquid or the inclusion of bubbles in the extracted immersion liquid can be prevented thereby making the extraction flow a single phase flow and thereby preventing deleterious vibrations. In FIGS. 9 c and 9 d , different angles of the wall in which the array of holes 224 are formed are illustrated. In FIG. 9 e a top plate 223 is added above the overflow area which enhances the extraction capacity due to the fact that the suction of the liquid is brought closer to the projection system PS, where the liquid meniscus tries to follow the projection system contour. The purpose of these diagrams is to illustrate that many configurations are possible which still have the aspects of the present invention.
FIGS. 10 a - e illustrate various embodiments without the dike 220 . Any angle of inclination of the wall in which the array of holes 224 are formed is possible and different configurations of paths for the immersion liquid to follow to the outlet 228 are illustrated. For example, in FIG. 10 b , the gap 340 is similar to the gap in FIG. 9 b such that single phase flow extraction is possible, in FIG. 10 e , the top plate 223 is similar to that in FIG. 9 e.
Another way to help minimize the risk of overflow of immersion liquid is illustrated in FIG. 11 . The system illustrated in FIG. 11 matches the amount of incoming immersion liquid with the amount of removed immersion liquid by dynamically varying the rates of extraction and input. As can be seen, immersion liquid is supplied to the seal member 12 through inlet 128 and is removed through outlets 184 , 228 and 328 as is described above in reference to FIG. 6 . Having a controllable supply allows more flexibility in operating circumstances. For example, more variations in the leak flow rate through outlet 328 are allowable and even if the extraction system 224 does not have sufficient capacity to cope with the maximum flow, that does not necessarily lead to overflow because the supply of immersion liquid can be reduced to compensate. Even with a constant supply flow, a controllable extraction is desirable because different operating conditions, for example scanning in a different direction, can result in variable leak or extraction parameters which can be coped with by varying the extraction. Each extraction port includes a controllable valve 1228 , 1184 , 1328 . The outlet ports 228 , 128 , 328 are all connected to a low pressure sources 2228 , 2148 , 2328 via a valve as illustrated. Extracted immersion liquid is lead to a reservoir 1500 which, if the immersion liquid is to be recycled, can be the source for the inlet 1248 . The supply is controlled by a valve 1128 and an overflow path to the reservoir 1500 is provided with a valve 1148 controlling that.
The water level control mechanism allows the supply rate of immersion liquid to be varied as well as the extraction through the overflow 224 , through the liquid extractor 180 and through the recess extractor 320 . Each of the valves 1228 , 1148 , 1128 , 1184 , 1328 are variable valves though they may be valves which are either on or off. The amount of extraction can be varied either by varying the under pressure applied, using the valves controlling the under pressure or by varying the valves 1128 , 1184 , 1328 or by varying the bypass to ambient (also illustrated in FIG. 11 ).
There are three options to determine when a dynamic control action is needed. These are direct feedback in which the level of the immersion liquid is measured, indirect feedback in which the extraction flows from each of the extractors is measured or feed-forward in which a knowledge of the extraction flow and the operating circumstances is used to adjust the supply and/or extraction flows when circumstances change.
The water level may be measured in several ways, for example by a float in the reservoir 1500 or in the space 11 , or by measuring the pressure of water at the bottom of the seal member 12 . By determining the position of the water surface by reflection and detection of acoustical or optical signals on the upper surface of the immersion liquid. Further possibilities are by measuring the absorption or transmission of an acoustical, optical or electrical signal as a function of the amount of water or by measuring heat loss of a submerged wire in a known position in the space 11 , the further the wire is submerged, the higher the heat loss.
In an embodiment, there is provided a lithographic apparatus, comprising: a substrate table constructed to hold a substrate; a projection system configured to project a patterned radiation beam onto a target portion of the substrate; a liquid supply system configured to supply liquid to a space between the projection system and the substrate table; and a control system configured to dynamically vary a rate of extraction of liquid by the liquid supply system from the space and/or dynamically vary a rate of supply of liquid by the liquid supply system such that a level of liquid in the space is maintained between a certain minimum and a certain maximum.
In an embodiment, the control system is configured to dynamically vary the rate or rates in response to a determination of a level of liquid in the space. In an embodiment, the lithographic apparatus further comprises a pressure sensor configured to measure a pressure of the liquid at a certain position in the space to determine the level of liquid in the space. In an embodiment, the lithographic apparatus further comprises an optical and/or acoustic source and a corresponding optical and/or acoustic detector configured to determine the level of liquid in the space by reflection and subsequent detection of an optical and/or acoustic signal off the top surface of the liquid. In an embodiment, the lithographic apparatus further comprises an acoustical/optical/electrical signal generator configured to generate an acoustical/optical/electrical signal in liquid in the space and a detector configured to detect the acoustical/optical/electrical signal to determine the level of liquid in the space. In an embodiment, the lithographic apparatus further comprises a wire configured to be submerged in the liquid at a certain location in the space and a detector configured to measure a temperature of the wire to determine the level of liquid in the space. In an embodiment, the lithographic apparatus further comprises a float configured to float on the top surface of the liquid in the space and a sensor configured to measure a position of the float to determine the level of liquid in the space. In an embodiment, the control system is configured to actively vary the rate or rates based on a measurement of an amount of liquid extracted from the space by the liquid supply system. In an embodiment, the control system is configured to dynamically vary the rate or rates in a feed forward manner based on operating circumstances of the apparatus. In an embodiment, the lithographic apparatus further comprises valves configured to control the rate of extraction and/or supply. In an embodiment, the lithographic apparatus further comprises valves configured to control an under pressure applied to a liquid extractor of the liquid supply system.
In an embodiment, there is provided a device manufacturing method, comprising: projecting a patterned beam of radiation onto a substrate using a projection system of a lithographic apparatus, wherein liquid is provided to a space between the projection system and the substrate and a rate of extraction of liquid from the space is dynamically varied and/or the rate of supply of liquid to the space is dynamically varied to maintain a level of liquid in the space between a certain minimum and a certain maximum.
In an embodiment, there is provided a lithographic apparatus, comprising: a substrate table constructed to hold a substrate; a projection system configured to project a patterned radiation beam onto a target portion of the substrate; and a barrier member having a surface surrounding a space between the projection system and the substrate table, the barrier member being configured to at least partly confine a liquid in the space, the barrier member comprising a liquid inlet configured to provide liquid to the space and a liquid outlet configured to remove liquid from the space, wherein the liquid inlet and/or the liquid outlet extends around a fraction of the inner periphery of the surface.
In an embodiment, the fraction is less than about ½. In an embodiment, the fraction is less than about ⅓. In an embodiment, the fraction is more than about 1/20. In an embodiment, the fraction is more than about 1/15. In an embodiment, the liquid inlet and the liquid outlet are positioned on the surface such that they face one another across the space. In an embodiment, the liquid inlet and liquid outlet are positioned along different parts of the surface around the inner periphery. In an embodiment, the liquid outlet is arranged to provide a variable liquid extraction rate along its length in the direction following the inner periphery. In an embodiment, a maximum extraction rate is provided substantially opposite the liquid inlet. In an embodiment, the liquid outlet extends substantially around the inner periphery. In an embodiment, the liquid inlet and the liquid outlet extend around a fraction of the inner periphery of the surface, the fraction of the inner periphery for the liquid inlet being smaller than the fraction of the inner periphery for the liquid outlet. In an embodiment, the liquid outlet is positioned radially outwardly, relative to the optical axis of the projection system, of the liquid inlet. In an embodiment, the lithographic apparatus comprises at least three liquid outlets, one liquid outlet facing the liquid inlet across the space and one liquid outlet on each side of the liquid inlet.
In an embodiment, there is provided a device manufacturing method, comprising: projecting a patterned beam of radiation onto a substrate using a projection system, wherein a barrier member has a surface which surrounds a space between the projection system and the substrate, the barrier member configured to at least partly contain a liquid in the space; providing liquid to the space through a liquid inlet; and removing liquid from the space via a liquid outlet, wherein the liquid inlet and/or the liquid outlet extends around a fraction of the inner periphery of the surface.
Although specific reference may be made in this text to the use of lithographic apparatus in the manufacture of ICs, it should be understood that the lithographic apparatus described herein may have other applications, such as the manufacture of integrated optical systems, guidance and detection patterns for magnetic domain memories, flat-panel displays, liquid-crystal displays (LCDs), thin-film magnetic heads, etc. It should be appreciated that, in the context of such alternative applications, any use of the terms “wafer” or “die” herein may be considered as synonymous with the more general terms “substrate” or “target portion”, respectively. The substrate referred to herein may be processed, before or after exposure, in for example a track (a tool that typically applies a layer of resist to a substrate and develops the exposed resist), a metrology tool and/or an inspection tool. Where applicable, the disclosure herein may be applied to such and other substrate processing tools. Further, the substrate may be processed more than once, for example in order to create a multi-layer IC, so that the term substrate used herein may also refer to a substrate that already contains multiple processed layers.
Although specific reference may have been made above to the use of embodiments of the invention in the context of optical lithography, it should be appreciated that the present invention may be used in other applications, for example imprint lithography, and where the context allows, is not limited to optical lithography. In imprint lithography a topography in a patterning device defines the pattern created on a substrate. The topography of the patterning device may be pressed into a layer of resist supplied to the substrate whereupon the resist is cured by applying electromagnetic radiation, heat, pressure or a combination thereof. The patterning device is moved out of the resist leaving a pattern in it after the resist is cured.
The terms “radiation” and “beam” used herein encompass all types of electromagnetic radiation, including ultraviolet (UV) radiation (e.g. having a wavelength of or about 365, 248, 193, 157 or 126 nm) and extreme ultra-violet (EUV) radiation (e.g. having a wavelength in the range of 5-20 nm), as well as particle beams, such as ion beams or electron beams.
The term “lens”, where the context allows, may refer to any one or combination of various types of optical components, including refractive, reflective, magnetic, electromagnetic and electrostatic optical components.
While specific embodiments of the present invention have been described above, it will be appreciated that the present invention may be practiced otherwise than as described. For example, the present invention may take the form of a computer program containing one or more sequences of machine-readable instructions describing a method as disclosed above, or a data storage medium (e.g. semiconductor memory, magnetic or optical disk) having such a computer program stored therein.
The present invention can be applied to any immersion lithography apparatus, in particular, but not exclusively, those types mentioned above.
The descriptions above are intended to be illustrative, not limiting. Thus, it will be apparent to one skilled in the art that modifications may be made to the invention as described without departing from the scope of the claims set out below.
|
A liquid supply system for an immersion lithographic apparatus provides a laminar flow of immersion liquid between a final element of the projection system and a substrate. A control system minimizes the chances of overflowing and an extractor includes an array of outlets configured to minimize vibrations.
| 6
|
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a division of U.S. National application Ser. No. 12/004,437 filed Dec. 19, 2007, now pending, which claims the benefit of U.S. Provisional Application No. 60/876,890, filed Dec. 22, 2006; the entire disclosures of the prior applications are herein incorporated by reference.
FIELD OF THE INVENTION
[0002] Porous infusible polymer parts which contain small controlled amounts of porosity, preferably where the pores are elongated, for example cylindrical, are better able to stand rapid heating without damage after imbibing moisture.
BACKGROUND OF THE INVENTION
[0003] Polymers are ubiquitous in current society, the most common types of polymers being used being thermosetting and thermoplastic polymers. However a third type of polymer is also used, the so-called infusible polymer (IP). These are polymers that are not crosslinked and so should theoretically be thermoplastic, but their melting and/or softening points are at a higher temperature than their decomposition temperature, so before liquefying as they are being heated, they decompose. Typically these types of polymers in commercial use have high decomposition temperatures, so their maximum use temperatures are usually quite high. Polymers of these types include, but are not limited to, polyimides, poly(p-phenylenes), and polymers composed mostly or all of repeat groups of the formula
[0000]
[0000] wherein X is NH, N-Phenyl, O (oxygen) or S (sulfur), and Ar is p-phenylene, 4,4′-biphenylene or 1,4-naphthylylene.
[0004] Since these IPs cannot be formed as typical thermoplastics, the polymers are often chemically formed, and the resulting polymer, if not already a powder, is ground to a powder. This powder is then subjected to pressure and optionally heat in a mold to consolidate the powder into a shaped part. Also, optionally, the shaped part can be then sintered to further consolidate the polymer. In many ways this type of shaping process is similar to that employed in the more familiar powdered metallurgy.
[0005] Most polymers, when exposed to moisture, either as liquid water or water vapor (in the air for instance), absorb some amount of water. If the polymer is then heated rapidly to well above the boiling point of water, the absorbed water will have a considerable vapor pressure and try to escape from the polymer. If the diffusion of the water from the polymer is slow, the internal pressure of the water may cause the formation of voids within the polymer (blistering), thereby reducing or destroying the usefulness of the polymer part. For instance, if the polymer is a part of a jet engine that stands at ambient temperature in a humid climate and/or in the rain, the part may absorb a considerable amount of water. When the engine is started, sections of the engine, including where such IP parts are located, may be heated rapidly, and as a result these parts may blister. Some method of avoiding such blistering while not substantially reducing the utility of the part would be desirable.
[0006] Porous and foamed polyimides are known; see for instance U.S. Pat. Nos. 5,444,097 and 4,780,097, U.S. Published Patent Application No. 2006/0039984, and D. W. Kim et al., J. Appl. Polym. Sci. 94:1711-18 (2004). In all these references, the pores are more or less spherical (either by measurement or photograph and/or by method of preparation), and in many cases the pores are a substantial volume of the total volume of the polymer plus pores.
[0007] Japanese Patent Application 04-077533A describes a porous material characterized by being made by consolidating a matrix which may be a “resin” which includes “polyimide resin” and “unidirectional” (parallel) carbon fibers which are removed from the composite electrolytic oxidation.
SUMMARY OF THE INVENTION
[0008] In one aspect, the present invention is a part comprising an infusible polymer, wherein said polymer comprises voids present in a range of from about 0.2 to about 10 volume percent, said voids being elongated, wherein a ratio of a longest dimension of said voids to a smallest dimension of said voids is at least 10:1.
[0009] In another aspect, the present invention is a process for the production of a part comprising an infusible polymer having elongated voids, the process comprising the steps:
[0010] (a) forming a mixture by mixing particles of an infusible polymer with 0.2 to 10 volume percent of a second polymer, wherein said volume percentage is based on the total volume of said infusible polymer and said second polymer, and said second polymer is in the form of elongated pieces wherein a ratio of a longest dimension of said pieces to a smallest dimension of said pieces is at least 10:1;
[0011] (b) subjecting said mixture to pressure to form a part; and
[0012] (c) heating said part to a temperature to burn off said second polymer;
[0000] provided that said infusible polymer has a decomposition point above the temperature at which the second polymer is burned off.
BRIEF DESCRIPTION OF THE FIGURE
[0013] FIG. 1 shows a part made by the presently described process, more specifically an X-Ray tomograph showing the voids in the part (see Example 12).
DETAILED DESCRIPTION OF THE INVENTION
[0014] Herein certain terms are used, and they are defined below:
[0015] The term “infusible polymer” or “IP” as used herein is a polymer that is essentially uncrosslinked but does not melt or soften enough to be melt processed—that is, processed in a molten or softened state—below its decomposition temperature. Useful types of IPs include polyimides, poly(p-phenylenes), and polymers composed mostly or all of repeat groups of the formula
[0000]
[0000] wherein X is NH, N-Phenyl, O (oxygen) or S (sulfur), and Ar is p-phenylene, 4,4′-biphenylene or 1,4-naphthylylene. Polyimides are preferred. Since it is often difficult or impossible to prove by test that IPs are not crosslinked, they will be considered for the purposes herein uncrosslinked if their indicated chemistry of formation is such that one would reasonably believe them, based on such chemistry, to be uncrosslinked.
[0016] By “burn off” is meant to remove all or substantially all polymer by heating, either in a chemically inert or chemically reactive atmosphere below the decomposition temperature of the IP. For example, when heated to a particular temperature, the second polymer (SP) may depolymerize or otherwise pyrolyze to its constituent monomers or other decomposition products. In a chemically reactive atmosphere such as air, the SP may be oxidized by the oxygen in the air to form volatile products such as water and/or carbon dioxide. In this context, “substantially all” means that not all of the second polymer is removed from the fusible polymer, but enough is removed that voids having the proper shape and “dimensions” are formed.
[0017] By “elongated” is meant that the ratio of the longest dimension of the item should be at least 10 times the shortest dimension, preferably the ratio should be at least 25, and more preferably at least 100. This holds for both voids and pieces of the SP. As referenced herein, the ratio is the average for such elongated voids, and does not include voids caused by incomplete consolidation of the IP. Since this ratio is determined by the fiber length and diameter, it is taken as that ratio for the fibers used in making the composition. If fibers are not used in making the composition, the void's average long and short dimensions shall be determined by X-Ray Tomography (see below).
[0018] By “volume percent voids” (porosity) is meant the volume occupied by the SP in the mixture of the IP and SP when forming the porous part, assuming both of these polymers are fully consolidated. This is a calculated number using the following calculation:
[0000]
%
Voids
=
(
Wt
·
SP
/
DenSP
)
×
100
[
(
Wt
·
SP
/
DenSP
)
+
(
Wt
·
IP
/
DenIP
)
]
[0000] wherein Wt. is “weight of”, and Den is “density of”. If the IP powder already has other items incorporated into the powder particles themselves such as one or more fillers, the density of the IP shall be taken as the density of the particle composition. Similarly if the SP has other items in the composition, the density of the SP will be taken as the density of that composition.
[0019] By a “part” is meant any shaped object. It may be a final shape that is useful directly, or a “preform”, “blank” or “standard shape” that will be cut and/or machined into its final shape.
[0020] The ratio of the longest dimension to the shortest dimension of the SP pieces or the voids is measured on a number of either of these items, and the results averaged to get the ratio. For example, if the SP pieces are fibers the lengths and diameters of each of the fibers are measured. The length of each fiber is then divided by the fiber's diameter (assuming a circular cross section), and the results of a number of these ratios is averaged.
[0021] The porous IP part is made by mixing particles of the IP, typically a fine powder, with elongated particles of the SP. The mixing should preferably be done so as to obtain a uniform dispersion of the SP in the IP. This mixture is then subjected to pressure in a mold to shape it. At this point, pressure may be the only “force” for consolidation to a solid part, but some heat may also be used. At least at the beginning of the consolidation, the temperature should not exceed the decomposition point of the SP, in order to “imprint” the volume taken up by the SP in the internal part of the IP part. However, once the IP part shape has been set, if desired the decomposition temperature of the SP can be exceeded. One probably would often not want to exceed the decomposition temperature of the SP while the part was in mold because excessive pressure could be generated and/or the mold may be fouled by the SP decomposition product(s). After the part is formed it may be removed from the mold and heated (sintered). The sintering can not only remove the SP by pyrolysis and/or chemical reaction (oxidation in air for instance), but may also assist in densifying the final part. Subject to the point made in this paragraph, conditions for forming the part from the IP particulate can be the same as is normally used and/or recommended for the IP.
[0022] The SP pieces are essentially the “templates” for the size and shape of the voids to be formed in the IP. They may be of any elongated shape meeting the requirements of the SP size and shape. However a preferred form for the SP is a fiber, especially a fiber with a circular cross section, in other words the latter will form a void in the shape of a tube with a (more or less) circular cross section. In this instance, as mentioned above, the ratio of the longest dimension to the shortest dimension for both the SP and the void will be the length of the fiber divided by its diameter. One reason fibers are preferred is that they may be readily formed from many thermoplastics, and in many instances the fibers are relatively inexpensive.
[0023] The SP is a minimum of about 0.2 volume percent, preferably 0.5 volume percent and more preferably about 1.0 volume percent of the total volume of the SP and IP. The maximum amount of SP is about 10 volume percent, preferably about 7 volume percent, preferably about 5 volume percent, and very preferably about 3 volume percent of the total volume of the SP and IP present. Any maximum and minimum volume percents may be combined to form a preferred volume percent range.
[0024] In the present porous IPs, the fibers, and hence the pores, are preferably not parallel, more preferably not substantially parallel, to one another because the fibers are typically mixed with the particulate IP in a random fashion before consolidation. By “substantially parallel” is meant that the long axis of any given random pore is at least a 10° angle to any other randomly chosen pore. Put another way, the average angle between the longitudinal axes of any two pores is at least 10°. Note however this does not mean that there is no general alignment of the fibers (and hence pores), even though not even substantially parallel, the fibers and pores may have a preferred orientation.
[0025] Preferably the present parts are at least about 1 mm thick in their smallest cross sectional dimension, more preferably at least about 2 mm thick.
[0026] Second polymers suitable use in the present invention include: polypropylene, polyethylene, acrylic polymer, cellulose acetate, and cellulosic polymers, for example. Other suitable polymers may be known to one of ordinary skill in the polymer arts, and such polymers would not be outside of the scope of the present invention. There is a class of polymer made to readily depolymerize or pyrolyze cleanly at a given temperature, for instance some polymers made for masking applications in electronics. These polymers are also useful herein. These polymers made to decompose are often (meth)acrylates or copolymers of (meth)acrylates with other monomers. Of course the particular SPs useful with any particular IP will depend on the decomposition temperature of the particular IP used. The pyrolysis or reaction temperature of the SP should of course be just below or preferably significantly below the IP decomposition temperature. Whatever SP is used and whether it is a simple thermal degradation or a reaction (for example oxidation), the less residue from the removal of the SP that remains in the IP part, the better.
[0027] A preferred type of IP is a polyimide. Polyimides typically are derived from tetracarboxylic acids (or their derivatives such as dianhydrides) and diamines such as pyromellitic dianhydride (PMDA) and diaminodiphenyl ether (ODA) and 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and ODA. A typical example of a polyimide prepared by a solution imidization process is a rigid, aromatic polyimide composition having the recurring unit:
[0000]
[0000] wherein R 5 is greater than about 60 to about 85 mole percent p-phenylene diamine (PPD) units and about 15 to less than about 40 mole percent m-phenylene diamine (MPD) units.
[0028] The tetracarboxylic acids preferably employed in the practice of the invention, or those from which derivatives useful in the practice of this invention can be prepared, are those having the general formula:
[0000]
[0000] wherein A is a tetravalent organic group and R 6 to R 9 , inclusive, comprise hydrogen or a lower alkyl, and preferably methyl, ethyl, or propyl. The tetravalent organic group A preferably has one of the following structures:
[0000]
[0000]
[0000] wherein X comprises at least one of —O—, —S—, —SO 2 —, —CH 2 —, —CH 2 CH 2 —, and
[0000]
[0029] As the aromatic tetracarboxylic acid component, there can be mentioned aromatic tetracarboxylic acids, acid anhydrides thereof, salts thereof and esters thereof. Examples of the aromatic tetracarboxylic acids include 3,3′,4,4′-biphenyltetracarboxylic acid, 2,3,3′,4′-biphenyltetracarboxylic acid, pyromellitic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, bis(3,4-dicarboxyphenyl)thioether, bis(3,4-dicarboxyphenyl)phosphine, 2,2-bis(3′,4′-dicarboxyphenyl)hexafluoropropane, and bis(3,4-dicarboxyphenyl)sulfone.
[0030] These aromatic tetracarboxylic acids can be employed singly or in combination. Preferred is an aromatic tetracarboxylic dianhydride, and particularly preferred are 3,3′,4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, and mixtures thereof.
[0031] As an organic aromatic diamine, use is preferably made of one or more aromatic and/or heterocyclic diamines, which are themselves known to the art. Such aromatic diamines can be represented by the structure: H 2 N—R 10 —NH 2 , wherein R 10 is an aromatic group containing up to 16 carbon atoms and, optionally, containing up to one heteroatom in the ring, the heteroatom comprising —N—, —O—, or —S—. Also included herein are those R 10 groups wherein R 10 is a diphenylene group or a diphenylmethane group. Representative of such diamines are 2,6-diaminopyridine, 3,5-diaminopyridine, m-phenylenediamine, p-phenylene diamine, p,p′-methylene dianiline, 2,6-diaminotoluene, and 2,4-diaminotoluene.
[0032] Other examples of the aromatic diamine components, which are merely illustrative, include benzene diamines such as 1,4-diaminobenzene, 1,3-diaminobenzene, and 1,2-diaminobenzene; diphenyl(thio)ether diamines such as 4,4′-diaminodiphenylether, 3,4′-diaminodiphenylether, 3,3′-diaminodiphenylether, and 4,4′-diaminodiphenylthioether; benzophenone diamines such as 3,3′-diaminobenzophenone and 4,4′-diaminobenzophenone; diphenylphosphine diamines such as 3,3′-diaminodiphenylphosphine and 4,4′-diaminodiphenylphosphine; diphenylalkylene diamines such as 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylpropane, and 4,4′-diaminodiphenylpropane; diphenylsulfide diamines such as 3,3′-diaminodiphenylsulfide and 4,4′-diaminodiphenylsulfide; diphenylsulfone diamines such as 3,3′-diaminodiphenylsulfone and 4,4′-diaminodiphenylsulfone; and benzidines such as benzidine and 3,3′-dimethylbenzidine.
[0033] Other useful diamines have at least one non-heteroatom containing aromatic rings or at least two aromatic rings bridged by a functional group. These aromatic diamines can be employed singly or in combination. Preferably employed as the aromatic diamine component are 1,4-diaminobenzene, 1,3-diaminobenzene, 4,4′-diaminodiphenylether, and mixtures thereof.
[0034] The porous IP may contain materials other than the IP itself. It may contain materials that IP compositions normally contain such as filler(s), reinforcing agent(s), pigment(s), and lubricant(s), etc. These may be present when the IP is formed, so that a particulate containing the one or more of these materials is produced. This particulate containing the other material(s) in addition to the IP is used in the present process. Alternatively the other materials to be added to the IP may be mixed in with the IP and SP in the present process and the whole consolidated together. A combination of these two methods may be used to add different materials to the composition. Of course any other materials meant to be in the final composition should be thermally stable up to the temperature at which the SP is removed from the part.
[0035] The void containing (porous) parts described are particularly useful wherein they are heated rapidly (often much) above the boiling point of water after having been exposed to water at lower (ambient) temperature which allowed them to imbibe water. Their tendency to blister (form uncontrolled voids) under these conditions is greatly reduced. It is believed that the elongated pores of the present parts form pathways which allows the escape of water (vapor) which may form when “wet” parts are heated rapidly.
[0036] This makes them useful, for instance, in parts used in (including parts adjacent to) jet engines, internal combustion engines, turbochargers, electrical and electronic parts subject to high temperatures (either internally or externally generated). Even though these parts contain porosity, the controlled nature of the porosity and its relatively low level gives parts whose physical properties such as strength and toughness which usually are not greatly affected by the porosity. Of course jet engines, internal combustion engines, turbochargers, and electrical and electronic parts subject to high temperatures (either internally or externally generated) may comprise a part comprising the porous IP described herein.
[0037] The shape of the voids, and their dimensions, may be measured and “visualized” by using X-ray microtomography, as generally described in A. Susov and D. van Dyck, Desktop X - Ray Microscopy and Microtomography , Journal of Microscopy, vol. 191, p. 151-158 (1998), which is hereby incorporated by reference. FIG. 1 , which is a cross section of a part made as described in Example 12, shows the voids made after the polypropylene fibers were “burned off”.
[0038] All patents and other references described in the examples are hereby incorporated by reference, as if fully set forth herein.
[0039] In the Examples, certain abbreviations are used. They are:
BPDA—3,3′,4,4′-biphenyltetracarboxylic dianhydride MPD—-phenylenediamine PPD—p-phenylenediamine
Example 1
[0043] Particles of a polyimide resin comprising 50 wt % of a polyimide based on BPDA, PPD, and MPD (with a 70/30 weight ratio of PPD/MPD) and 50 wt % of synthetic graphite were prepared according to the method described in U.S. Pat. No. 5,886,129 (e.g., Example 7) and milled through a 20 mesh screen.
Example 2
[0044] Polypropylene fibers (˜3-4 denier) were cut to lengths from about 0.5 mm to about 3 mm. These cut fibers, at 1 wt % loading, were dispersed into resin from Example 1 by combining fiber and resin in a Waring-type blender and blended at high speed for 15 sec. Test samples in the form of micro-tensile bars were molded according to the method described in U.S. Pat. No. 4,360,626 (esp. column 2, lines 54-60). Specific gravity was determined. Tensile strength and elongation were determined according to ASTM D 638-03, using an 1122 model Instron®. The crosshead speed was 0.2 in/sec (5.1 mm/sec) and an extensometer was attached to the bar during testing to measure elongation. The results are reported in Table 1.
Examples 3 and 4
[0045] Test samples were prepared containing 2 and 4 wt % polypropylene fiber according to the method of Example 2. Physical testing results are reported in Table 1.
Comparative Example A
[0046] Test samples were prepared from resin described in Example 1 with 2 wt % of polypropylene fiber. Fiber and resin mixing were accomplished by roll mixing overnight, not in a blender. Physical testing results are reported in Table 1.
Comparative Examples B and C
[0047] Test samples were prepared from resin described in Example 1, according to the method in Example 2 but without the polypropylene fiber, either with or without treatment in the blender. Physical testing results are reported in Table 1.
[0048] In Table 1 Specific Gravity is gm/mL, Tensile Strength to break is MPa, and Elongation is percent.
[0000]
TABLE 1
Fiber
Spec
Example
wt %
Blended
Grav
Tens Str
Elongation
2
1
Yes
1.6559
91.0
5.5
3
2
Yes
1.6264
76.5
3.1
4
4
Yes
1.5600
71.7
2.3
A
2
No
1.6220
56.5
1.1
B
0
No
1.6925
97.9
6.5
C
0
Yes
1.6852
97.9
5.4
[0049] Although there is some decrease in physical properties when porosity is present, especially when the fiber is not well dispersed, the porosity does not lead to very large decreases in these properties, especially at the 1% level.
Example 5
[0050] Samples from the preceding examples were conditioned for a thermal shock test by soaking in 95° C. liquid water for 14 days. The samples were then thermally shocked by placing them in an oven preheated to 325° C., 350° C., 375° C., or 400° C. for 1 h. After the 1 h heat soak, the samples were removed from the oven, allowed to cool and then examined for the presence of blisters. The presence of blisters as noted under “Observations” in Table 2, below, indicate which samples failed the test, and the temperature at which the blisters first appear. The test results are reported in Table 2.
[0000]
TABLE 2
325° C.
350° C.
375° C.
400° C.
Example
Observations
Observations
Observations
Observations
2
None
None
None
None
3
None
None
None
None
4
None
None
None
None
A
Small blisters
Small blisters
Small
Small
blisters
blisters
B
None
Small blisters
Blistered
Blistered
C
Blistered
Blistered
Blistered
Blistered
Examples 6-11
[0051] Other samples were prepared using the method described in Example 2 using different fibers at 4 wt % fiber loading. These fibers, which were nominally 3 mm long, were obtained from Engineered Fibers Technology, LLC (Shelton, Conn. 06484, U.S.A.). In order to be considered suitable for producing controlled porosity in polyimide parts, it must be possible to mold the parts without blistering during the sintering step. The results for molding of samples with these fibers are reported in Table 3. These results possibly could be changed (improved) by altering the heating cycle when the fibers are “burned off”, especially by heating more slowly. These Examples illustrate that a variety of fibers, and of different diameters, may be used to form the pores.
[0000]
TABLE 3
Example
Fiber Material
Denier*
Result
6
Polyethylene
4
No
Blisters
7
Cellulose Acetate
1.5
No
Blisters
8
Polyvinylalcohol
0.3
Blistered
9
Lyocell ® Tencel
1.5
No
(cellulosic)
Blisters
10
Acrylic
0.3
No
Blisters
11
Acrylic
1.5
Blistered
*Denier is the number of grams per 9000 meters of a single filament of fiber.
Example 12
[0052] By a method similar to that in Example 2, 1.2 weight percent of polypropylene fiber was blended with the polyimide. The mixture was placed in a mold which was placed in a hydraulic press and compressed at 276 MPa. These parts were sintered under nitrogen using a heating cycle of ambient temperature to 400° C. over a period of 59 hours, and then held at 400° C. for 3 hours, and then cooled. The parts were then machined into final parts. One of these parts was then subjected to X-Ray Tomography, the result of which is shown in FIG. 1 , which is from a video of that tomography. The “lines” visible in the Figure are the pores formed by pyrolysis of the polypropylene fiber and are voids in the polyimide (which was “subtracted out” from the tomograph). A scale marker is shown in the Figure. This is only a portion of the part, the polyimide (“solid”) portion of which is not shown, but in FIG. 1 extends as in the form of a rectangle to the overall periphery of the voids shown. Note that the fibers appear to have a preferred orientation, but are not substantially parallel.
|
Porous infusible polymer (IP) parts are made by incorporating 0.2 to 10 volume percent organic fibers, preferably with short lengths, into the particulate IP, consolidating the mixture under pressure and optionally heating, and then “burning off” the fibers. After the fibers are burned off the resulting part has porosity in which the pores are elongated, usually retaining the shape of the organic fibers. When these parts are exposed to moisture (which they usually absorb) and then suddenly heated they tend not to blister from vaporization of the water. This makes them useful as parts for aircraft (jet) and other engines and other applications where sudden temperature increase may occur.
| 8
|
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] Embodiments of the present invention relate generally to a method and an apparatus for a drilling operation. More particularly, the invention relates to a rotating control head. Still more particularly, the invention relates to the actuation and cooling of a rotating control head.
[0003] 2. Description of the Related Art
[0004] Drilling a wellbore for hydrocarbons requires significant expenditures of manpower and equipment. Thus, constant advances are being sought to reduce any downtime of equipment and expedite any repairs that become necessary. Rotating equipment is particularly prone to maintenance as the drilling environment produces abrasive cuttings detrimental to the longevity of rotating seals, bearings, and packing elements.
[0005] In a typical drilling operation, a drill bit is attached to a drill pipe. Thereafter, a drive unit rotates the drill pipe through a drive member, referred to as a kelly as the drill pipe and drill bit are urged downward to form the wellbore. In some arrangements, a kelly is not used, thereby allowing the drive unit to attach directly to the drill pipe. The length of the wellbore is determined by the location of the hydrocarbon formations. In many instances, the formations produce gas or fluid pressure that may be a hazard to the drilling crew and equipment unless properly controlled.
[0006] Several components are used to control the gas or fluid pressure. Typically, one or more blow out preventers (BOP) are mounted to the well forming a BOP stack to seal the mouth of the well. Additionally, an annular BOP is used to selectively seal the lower portions of the well from a tubular body that allows the discharge of mud through the outflow line. In many instances, a conventional rotating control head, also referred to as a rotating blow out preventor, is mounted above the BOP stack. An internal portion of the conventional rotating control head is designed to seal and rotate with the drill pipe. The internal portion typically includes an internal sealing element mounted on a plurality of bearings.
[0007] The internal sealing element may consist of both a passive seal arrangement and an active seal arrangement. The active seal arrangement is hydraulically activated. Generally, a hydraulic circuit provides hydraulic fluid to the active seal rotating control head. The hydraulic circuit typically includes a reservoir containing a supply of hydraulic fluid and a pump to communicate the hydraulic fluid from the reservoir to the rotating control head. As the hydraulic fluid enters the rotating control head, a pressure is created to energize the active seal arrangement. Preferably, the pressure in the active seal arrangement is maintained at a greater pressure than the wellbore pressure. Typically, the hydraulic circuit receives input from the wellbore and supplies hydraulic fluid to the active seal arrangement to maintain the pressure differential. However, the hydraulic circuit in the conventional active seal rotating control head has a less than desirable response time to rapidly changing wellbore pressure.
[0008] During the drilling operation, the drill pipe is axially and slidably forced through the rotating control head. The axial movement of the drill pipe causes wear and tear on the bearing and seal assembly and subsequently requires repair. Typically, the drill pipe or a portion thereof is pulled from the well and a crew goes below the drilling platform to manually release the bearing and seal assembly in the rotating control head. Thereafter, an air tugger in combination with a tool joint on the drill string are typically used to lift the bearing and seal assembly from the rotating control head. The bearing and seal assembly is replaced or reworked and thereafter the crew goes below the drilling platform to reattach the bearing and seal assembly into the rotating control head and operation is resumed. The process is time consuming and can be dangerous.
[0009] Additionally, the thrust generated by the wellbore fluid pressure and the radial forces on the bearing assembly causes a substantial amount of heat to build in the conventional rotating control head. The heat causes the seals and bearings to wear and subsequently require repair. The conventional rotating control head typically includes a cooling system that circulates oil through the seals and bearings to remove the heat. However, the oil based cooling system may be very expensive to implement and maintain.
[0010] There is a need therefore, for a cost-effective cooling system for a rotating control head. There is a further need therefore for a cooling system in a rotating control head that can be easily implemented and maintained. There is a further need for an effective hydraulic circuit to actuate the active sealing arrangement in a rotating control head and to maintain the proper pressure differential between the fluid pressure in the rotating control head and the wellbore pressure. There is yet a further need for an improved rotating control head.
SUMMARY OF THE INVENTION
[0011] The present invention generally relates to an apparatus and method for sealing a tubular string. In one aspect, a drilling system is provided. The drilling system includes a rotating control head for sealing the tubular string while permitting axial movement of the string relative to the rotating control head. The drilling system also includes an actuating fluid for actuating the rotating control head and maintaining a pressure differential between a fluid pressure in the rotating control head and a wellbore pressure. Additionally, the drilling system includes a cooling medium for passing through the rotating control head.
[0012] In another aspect, a rotating control head is provided. The rotating control head includes a sealing member for sealing a tubular string while permitting axial movement of the string relative to the rotating control head. The rotating control head further includes an actuating fluid for actuating the rotating control head and maintaining a pressure differential between a fluid pressure in the rotating control head and a wellbore pressure.
[0013] In another aspect, a method for sealing a tubular in a rotating control head is provided. The method includes supplying fluid to the rotating control head and activating a seal arrangement to seal around the tubular. The method further includes passing a cooling medium through the rotating control head and maintaining a pressure differential between a fluid pressure in the rotating control head and a wellbore pressure.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
[0015] [0015]FIG. 1 is a cross-sectional view illustrating a rotating control head in accord with the present invention.
[0016] [0016]FIG. 2A illustrates a rotating control head cooled by a heat exchanger.
[0017] [0017]FIG. 2B illustrates a schematic view of the heat exchanger.
[0018] [0018]FIG. 3A illustrates a rotating control head cooled by flow a gas.
[0019] [0019]FIG. 3B illustrates a schematic view of the gas in a substantially circular passageway.
[0020] [0020]FIG. 4A illustrates a rotating control head cooled by a fluid mixture.
[0021] [0021]FIG. 4B illustrates a schematic view of the fluid mixture circulating in a substantially circular passageway.
[0022] [0022]FIG. 5A illustrates the rotating control head cooled by a refrigerant.
[0023] [0023]FIG. 5B illustrates a schematic view of the refrigerant circulating in a substantially circular passageway.
[0024] [0024]FIG. 6 illustrates a rotating control head actuated by a piston intensifier in communication with the wellbore pressure.
[0025] [0025]FIG. 7A illustrates an alternative embodiment of a rotating control head in an unlocked position.
[0026] [0026]FIG. 7B illustrates the rotating control head in a locked position.
[0027] [0027]FIG. 8 illustrates an alternative embodiment of a rotating control head in accord with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0028] Generally, the present invention relates to a rotating control head for use with a drilling rig. Typically, an internal portion of the rotating control head is designed to seal around a rotating tubular string and rotate with the tubular string by use of an internal sealing element, and rotating bearings. Additionally, the internal portion of the rotating control head permits the tubular string to move axially and slidably through the rotating control head on the drilling rig. FIG. 1 generally describes the rotating control head and FIGS. 2 - 6 illustrate various methods of cooling and actuating the rotating control head. Additionally, FIGS. 7 and 8 illustrate alternate embodiments of the rotating control head.
[0029] [0029]FIG. 1 is a cross-sectional view illustrating the rotating control head 100 in accord with the present invention. The rotating control head 100 preferably includes an active seal assembly 105 and a passive seal assembly 110 . Each seal assembly 105 , 110 includes components that rotate with respect to a housing 115 . The components that rotate in the rotating control head are mounted for rotation on a plurality of bearings 125 .
[0030] As depicted, the active seal assembly 105 includes a bladder support housing 135 mounted on the plurality of bearings 125 . The bladder support housing 135 is used to mount bladder 130 . Under hydraulic pressure, as discussed below, bladder 130 moves radially inward to seal around a tubular such as a drilling pipe (not shown). In this manner, bladder 130 can expand to seal off borehole 185 through the rotating control head 100 .
[0031] As illustrated in FIG. 1, upper and lower caps 140 , 145 , respectfully, fit over the upper and lower end of the bladder 130 to secure the bladder 130 within the bladder support housing 135 . Typically, the upper and lower caps 140 , 145 are secured in position by a setscrew (not shown). Upper and lower seals 155 , 160 , respectfully, seal off chamber 150 that is preferably defined radially outwardly of bladder 130 and radially inwardly of bladder support housing 135 .
[0032] Generally, fluid is supplied to the chamber 150 under a controlled pressure to energize the bladder 130 . The hydraulic control (not shown) will be illustrated and discussed in FIGS. 2 - 6 . Essentially, the hydraulic control maintains and monitors hydraulic pressure within pressure chamber 150 . Hydraulic pressure P1 is preferably maintained by the hydraulic control between 0 to 200 psi above a wellbore pressure P2. The bladder 130 is constructed from flexible material allowing bladder surface 175 to press against the tubular at approximately the same pressure as the hydraulic pressure P1. Due to the flexibility of the bladder, it also may conveniently seal around irregular shaped tubular string such as a hexagonal kelly. In this respect, the hydraulic control maintains the differential pressure between the pressure chamber 150 at pressure P1 and wellbore pressure P2. Additionally, the active seal assembly 105 includes support fingers 180 to provide support to the bladder 130 at the most stressful area of the seal between the fluid pressure P1 and the ambient pressure.
[0033] The hydraulic control may be used to de-energize the bladder 130 and allow the active seal assembly 105 to release the seal around the tubular. Generally, fluid in the chamber 150 is drained into a hydraulic reservoir (not shown), thereby reducing the pressure P1. Subsequently, the bladder surface 175 loses contact with the tubular as the bladder 130 becomes de-energized and moves radially outward. In this manner, the seal around the tubular is released allowing the tubular to be removed from the rotating control head 100 .
[0034] In the embodiment shown in FIG. 1, the passive seal assembly 110 is disposed below the active seal assembly 105 . The passive seal assembly 110 is operatively attached to the bladder support housing 135 , thereby allowing the passive seal assembly 110 to rotate with the active seal assembly 105 . Fluid is not required to operate the passive seal assembly 110 but rather it utilizes pressure P2 to create a seal around the tubular. The passive seal assembly 110 is constructed and arranged in an axially downward conical shape, thereby allowing the pressure P2 to act against a tapered surface 195 to close the passive seal assembly 110 around the tubular. Additionally, the passive seal assembly 110 includes an inner diameter 190 smaller than the outer diameter of the tubular to allow an interference fit between the tubular and the passive seal assembly 110 .
[0035] [0035]FIG. 2A illustrates a rotating control head 200 cooled by heat exchanger 205 . As shown, the rotating control head 200 is depicted generally to illustrate this embodiment of the invention, thereby applying this embodiment to a variety of different types of rotating control heads. A hydraulic control 210 provides fluid to the rotating control head 200 . The hydraulic control 210 typically includes a reservoir 215 to contain a supply of fluid, a pump 220 to communicate the fluid from the reservoir 215 to the rotating control head 200 and a valve 225 to remove excess pressure in the rotating control head 200 .
[0036] Generally, the hydraulic control 210 provides fluid to energize a bladder 230 and lubricate a plurality of bearings 255 . As the fluid enters a port 235 , the fluid is communicated to the plurality of bearings 255 and a chamber 240 . As the chamber 240 fills with a fluid, pressure P1 is created. The pressure P1 acts against the bladder 230 causing the bladder 230 to expand radially inward to seal around a tubular string (not shown). Typically, the pressure P1 is maintained between 0-200 psi above a wellbore pressure P2.
[0037] The rotating control head 200 is cooled by the heat exchanger 205 . The heat exchanger 205 is constructed and arranged to remove heat from the rotating control head 200 by introducing a gas, such as air, at a low temperature into an inlet 265 and thereafter transferring heat energy from a plurality of seals 275 and the plurality of bearings 255 to the gas as the gas passes through the heat exchanger 205 . Subsequently, the gas at a higher temperature exits the heat exchanger 205 through an outlet 270 . Typically, gas is pumped into the inlet 265 by a blowing apparatus (not shown). However, other means of communicating gas to the inlet 265 may be employed, so long as they are capable of supplying a sufficient amount of gas to the heat exchanger 205 .
[0038] [0038]FIG. 2B illustrates a schematic view of the heat exchanger 205 . As illustrated, the heat exchanger 205 comprises a passageway 280 with a plurality of substantially square curves. The passageway 280 is arranged to maximize the surface area covered by the heat exchanger 205 . The low temperature gas entering the inlet 265 flows through the passageway 280 in the direction illustrated by arrow 285 . As the gas circulates through the passageway 280 , the gas increases in temperature as the heat from the rotating control head 200 is transferred to the gas. The high temperature gas exits the outlet 270 as indicated by the direction of arrow 285 . In this manner, the heat generated by the rotating control head 200 is transferred to the gas passing through the heat exchanger 205 .
[0039] [0039]FIG. 3A illustrates a rotating control head 300 cooled by a gas. As shown, the rotating control head 300 is depicted generally to illustrate this embodiment of the invention, thereby applying this embodiment to a variety of different types of rotating control heads. A hydraulic control 310 supplies fluid to the rotating control head 300 . The hydraulic control 310 typically includes a reservoir 315 to contain a supply of fluid and a pump 320 to communicate the fluid from the reservoir 315 to the rotating control head 300 . Additionally, the hydraulic control 310 includes a valve 345 to relieve excess pressure in the rotating control head 300 .
[0040] Generally, the hydraulic control 310 supplies fluid to energize a bladder 330 and lubricate a plurality of bearings 355 . As the fluid enters a port 335 , a portion is communicated to the plurality of bearings 355 and another portion is used to fill a chamber 340 . As the chamber 340 fills with a fluid, a pressure P1 is created. Pressure P1 acts against the bladder 330 causing the bladder 330 to move radially inward to seal around a tubular string (not shown). Typically, the pressure P1 is maintained between 0 to 200 psi above a wellbore pressure P2. If the wellbore pressure P2 drops, the pressure P1 may be relieved through valve 345 by removing a portion of the fluid from the chamber 340 .
[0041] The rotating control head 300 is cooled by a flow of gas through a substantially circular passageway 380 through an upper portion of the rotating control head 300 . The circular passageway 380 is constructed and arranged to remove heat from the rotating control head 300 by introducing a gas, such as air, at a low temperature into an inlet 365 , transferring heat energy to the gas and subsequently allowing the gas at a high temperature to exit through an outlet 370 . The heat energy is transferred from a plurality of seals 375 and the plurality of bearings 355 as the gas passes through the circular passageway 380 . Typically, gas is pumped into the inlet 365 by a blowing apparatus (not shown). However, other means of communicating gas to the inlet 365 may be employed, so long as they are capable of supplying a sufficient amount of gas to the substantially circular passageway 380 .
[0042] [0042]FIG. 3B illustrates a schematic view of the gas passing through the substantially circular passageway 380 . The circular passageway 380 is arranged to maximize the surface area covered by the circular passageway 380 . The low temperature gas entering the inlet 365 flows through the circular passageway 380 in the direction illustrated by arrow 385 . As the gas circulates through the circular passageway 380 , the gas increases in temperature as the heat from the rotating control head 300 is transferred to the gas. The high temperature gas exits the outlet 370 as indicated by the direction of arrow 385 . In this manner, the heat generated by the rotating control head 300 is removed allowing the rotating control head 300 to function properly.
[0043] In an alternative embodiment, the rotating control head 300 may operate without the use of the circular passageway 380 . In other words, the rotating control head 300 would function properly without removing heat from the plurality of seals 375 and the plurality of bearings 355 . This embodiment typically applies when the wellbore pressure P2 is relatively low.
[0044] [0044]FIGS. 4A and 4B illustrate a rotating control head 400 cooled by a fluid mixture. As shown, the rotating control head 400 is depicted generally to illustrate this embodiment of the invention, thereby applying this embodiment to a variety of different types of rotating control heads. A hydraulic control 410 supplies fluid to the rotating control head 400 . The hydraulic control 410 typically includes a reservoir 415 to contain a supply of fluid and a pump 420 to communicate the fluid from the reservoir 415 to the rotating control head 400 . Additionally, the hydraulic control 410 includes a valve 445 to relieve excess pressure in the rotating control head 400 . In the same manner as the hydraulic control 310 , the hydraulic control 410 supplies fluid to energize a bladder 430 and lubricate a plurality of bearings 455 .
[0045] The rotating control head 400 is cooled by a fluid mixture circulated through a substantially circular passageway 480 on an upper portion of the rotating control head 400 . In the embodiment shown, the fluid mixture preferably consists of water or a water-glycol mixture. However, other mixtures of fluid may be employed, so long as, the fluid mixture has the capability to circulate through the circular passageway 480 and reduce the heat in the rotating control head 400 .
[0046] The circular passageway 480 is constructed and arranged to remove heat from the rotating control head 400 by introducing the fluid mixture at a low temperature into an inlet 465 , transferring heat energy to the fluid mixture and subsequently allowing the fluid mixture at a high temperature to exit through an outlet 470 . The heat energy is transferred from a plurality of seals 475 and the plurality of bearings 455 as the fluid mixture circulates through the circular passageway 480 . The fluid mixture is preferably pumped into the inlet 465 through a fluid circuit 425 . The fluid circuit 425 is comprised of a reservoir 490 to contain a supply of the fluid mixture and a pump 495 to circulate the fluid mixture through the rotating control head 400 .
[0047] [0047]FIG. 4B illustrates a schematic view of the fluid mixture circulating in the substantially circular passageway 480 . The circular passageway 480 is arranged to maximize the surface area covered by the circular passageway 480 . The low temperature fluid entering the inlet 465 flows through the circular passageway 480 in the direction illustrated by arrow 485 . As the fluid circulates through the circular passageway 480 , the fluid increases in temperature as the heat from the rotating control head 400 is transferred to the fluid. The high temperature fluid exits out the outlet 470 as indicated by the direction of arrow 485 . In this manner, the heat generated by the rotating control head 400 is removed allowing the rotating control head 400 to function properly.
[0048] [0048]FIGS. 5A and 5B illustrate a rotating control head 500 cooled by a refrigerant. As shown, the rotating control head 500 is depicted generally to illustrate this embodiment of the invention, thereby applying this embodiment to a variety of different types of rotating control heads. A hydraulic control 510 supplies fluid to the rotating control head 500 . The hydraulic control 510 typically includes a reservoir 515 to contain a supply of fluid and a pump 520 to communicate the fluid from the reservoir 515 to the rotating control head 500 . Additionally, the hydraulic control 510 includes a valve 545 to relieve excess pressure in the rotating control head 500 . In the same manner as the hydraulic control 310 , the hydraulic control 510 supplies fluid to energize a bladder 530 and lubricate a plurality of bearings 555 .
[0049] The rotating control head 500 is cooled by a refrigerant circulated through a substantially circular passageway 580 in an upper portion of the rotating control head 500 . The circular passageway 580 is constructed and arranged to remove heat from the rotating control head 500 by introducing the refrigerant at a low temperature into an inlet 565 , transferring heat energy to the refrigerant and subsequently allowing the refrigerant at a high temperature to exit through an outlet 570 . The heat energy is transferred from a plurality of seals 575 and the plurality of bearings 555 as the refrigerant circulates through the circular passageway 580 . The refrigerant is preferably communicated into the inlet 565 through a refrigerant circuit 525 . The refrigerant circuit 525 includes a reservoir 590 containing a supply of vapor refrigerant. A compressor 595 draws the vapor refrigerant from the reservoir 590 and compresses the vapor refrigerant into a liquid refrigerant. Thereafter, the liquid refrigerant is communicated to an expansion valve 560 . At this point, the expansion valve 560 changes the low temperature liquid refrigerant into a low temperature vapor refrigerant as the refrigerant enters inlet 565 .
[0050] [0050]FIG. 5B illustrates a schematic view of the vapor refrigerant circulating in the substantially circular passageway 580 . The circular passageway 580 is arranged in an approximately 320-degree arc to maximize the surface area covered by the circular passageway 580 . The low temperature vapor refrigerant entering the inlet 565 flows through the circular passageway 580 in the direction illustrated by arrow 585 . As the vapor refrigerant circulates through the circular passageway 580 , the vapor refrigerant increases in temperature as the heat from the rotating control head 500 is transferred to the vapor refrigerant. The high temperature vapor refrigerant exits out the outlet 570 as indicated by the direction of arrow 585 . Thereafter, the high temperature vapor refrigerant rejects the heat to the environment through a heat exchanger (not shown) and returns to the reservoir 590 . In this manner, the heat generated by the rotating control head 500 is removed allowing the rotating control head 500 to function properly.
[0051] [0051]FIG. 6 illustrates a rotating control head 600 actuated by a piston intensifier circuit 610 in communication with a wellbore 680 . As shown, the rotating control head 600 is depicted generally to illustrate this embodiment of the invention, thereby applying this embodiment to a variety of different types of rotating control heads. The piston intensifier circuit 610 supplies fluid to the rotating control head 600 . The piston intensifier circuit 610 typically includes a housing 645 and a piston arrangement 630 . The piston arrangement 630 is formed from a larger piston 620 and a smaller piston 615 . The pistons 615 , 620 are constructed and arranged to maintain a pressure differential between a hydraulic pressure P1 and a wellbore pressure P2. In other words, the pistons 615 , 620 are designed with a specific surface area ratio to maintain about a 200 psi pressure differential between the hydraulic pressure P1 and the wellbore pressure P2, thereby allowing the P1 to be 200 psi higher than P2. The piston arrangement 630 is disposed in the housing 645 to form an upper chamber 660 and lower chamber 685 . Additionally, a plurality of seal members 605 are disposed around the pistons 615 , 620 to form a fluid tight seal between the chambers 660 , 685 .
[0052] The piston intensifier circuit 610 mechanically provides hydraulic pressure P1 to energize a bladder 650 . Initially, fluid is filled into upper chamber 660 and is thereafter sealed. The wellbore fluid from the wellbore 680 is in fluid communication with lower chamber 685 . Therefore, as the wellbore pressure P2 increases more wellbore fluid is communicated to the lower chamber 685 creating a pressure in the lower chamber 685 . The pressure in the lower chamber 685 causes the piston arrangement 630 to move axially upward forcing fluid in the upper chamber 660 to enter port 635 and pressurize a chamber 640 . As the chamber 640 fills with a fluid, the pressure P1 increases causing the bladder 650 to move radially inward to seal around a tubular string (not shown). In this manner, the bladder 650 is energized allowing the rotating control head 600 to seal around a tubular.
[0053] A fluid, such as water-glycol, is circulated through the rotating control head 600 by a fluid circuit 625 . Typically, heat on the rotating control head 600 is removed by introducing the fluid at a low temperature into an inlet 665 , transferring heat energy to the fluid and subsequently allowing the fluid at a high temperature to exit through an outlet 670 . The heat energy is transferred from a plurality of seals 675 and the plurality of bearings 655 as the fluid circulates through the rotating control head 600 . The fluid is preferably pumped into the inlet 665 through the fluid circuit 625 . Generally, the circuit 625 comprises a reservoir 690 to contain a supply of the fluid and a pump 695 to circulate the fluid through the rotating control head 600 .
[0054] In another embodiment, the piston intensifier circuit 610 is in fluid communication with a nitrogen gas source (not shown). In this embodiment, a pressure transducer (not shown) measures the wellbore pressure P2 and subsequently injects nitrogen into the lower chamber 685 at the same pressure as pressure P2. The nitrogen pressure in the lower chamber 685 may be adjusted as the wellbore pressure P2 changes, thereby maintaining the desired pressure differential between hydraulic pressure P1 and wellbore pressure P2.
[0055] [0055]FIG. 7A illustrates an alternative embodiment of a rotating control head 700 in an unlocked position. The rotating control head 700 is arranged and constructed in a similar manner as the rotating control head 100 shown on FIG. 1. Therefore, for convenience, similar components that function in the same manner will be labeled with the same numbers as the rotating control head 100 . The primary difference between the rotating control head 700 and rotating control head 100 is the active seal assembly.
[0056] As shown in FIG. 7A, the rotating control head 700 includes an active seal assembly 705 . The active seal assembly 705 includes a primary seal 735 that moves radially inward as a piston 715 wedges against a tapered surface of the seal 735 . The primary seal 735 is constructed from flexible material to permit sealing around irregularly shaped tubular string such as a hexagonal kelly. The upper end of the seal 735 is connected to a top ring 710 .
[0057] The active sealing assembly 705 includes an upper chamber 720 and a lower chamber 725 . The upper chamber 720 is formed between the piston 715 and a piston housing 740 . To move the rotating control head 700 from an unlocked position to a locked position, fluid is pumped through port 745 into an upper chamber 720 . As fluid fills the upper chamber 720 , the pressure created acts against the lower end of the piston 715 and urges the piston 715 axially upward until it reaches the top ring 710 . At the same time, the piston 715 wedges against the tapered portion of the primary seal 735 causing the seal 735 to move radially inward to seal against the tubular string. In this manner, the active seal assembly 705 is in the locked position as illustrated in FIG. 7B.
[0058] As shown on FIG. 7B, the piston 715 has moved axially upward contacting the top ring 710 and the primary seal 735 has moved radially inward. To move the active seal assembly 705 from the locked position to the unlocked position, fluid is pumped through port 755 into the lower chamber 725 . As the chamber fills up, the fluid creates a pressure that acts against surface 760 to urge the piston 715 axially downward, thereby allowing the primary seal 735 to move radially outward as shown on FIG. 7A.
[0059] [0059]FIG. 8 illustrates an alternative embodiment of a rotating control head 800 in accord with the present invention. The rotating control head 800 is constructed from similar components as the rotating control head 100 shown on FIG. 1. Therefore, for convenience, similar components that function in the same manner will be labeled with the same numbers as the rotating control head 100 . The primary difference between the rotating control head 800 and rotating control head 100 is the location of the active seal assembly 105 and the passive seal assembly 110 .
[0060] As shown on FIG. 8, the passive seal assembly 110 is disposed above the active seal assembly 105 . The passive seal assembly 110 is operatively attached to the bladder support housing 135 , thereby allowing the passive seal assembly 110 to rotate with the active seal assembly 105 . The passive seal assembly 110 is constructed and arranged in an axially downward conical shape, thereby allowing the pressure in the rotating control head 800 to act against the tapered surface 195 and close the passive seal assembly 110 around the tubular. Additionally, the passive seal assembly 110 includes the inner diameter 190 , which is smaller than the outer diameter of the tubular to allow an interference fit between the tubular and the passive seal assembly 110 .
[0061] As depicted, the active seal assembly 105 includes the bladder support housing 135 mounted on the plurality of bearings 125 . The bladder support housing 135 is used to mount bladder 130 . Under hydraulic pressure, bladder 130 moves radially inward to seal around a tubular such as a drilling tubular. Generally, fluid is supplied to the chamber 150 under a controlled pressure to energize the bladder 130 . Essentially, a hydraulic control (not shown) maintains and monitors hydraulic pressure within pressure chamber 150 . Hydraulic pressure P1 is preferably maintained by the hydraulic control between 0 to 200 psi above a wellbore pressure P2. The bladder 130 is constructed from flexible material allowing bladder surface 175 to press against the tubular at approximately the same pressure as the hydraulic pressure P1.
[0062] The hydraulic control may be used to de-energize the bladder 130 and allow the active seal assembly 105 to release the seal around the tubular. Generally, the fluid in the chamber 150 is drained into a hydraulic reservoir (not shown), thereby reducing the pressure P1. Subsequently, the bladder surface 175 loses contact with the tubular as the bladder 130 becomes de-energized and moves radially outward. In this manner, the seal around the tubular is released allowing the tubular to be from the rotating control head 800 .
[0063] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
|
The present invention generally relates to an apparatus and method for sealing a tubular string. In one aspect, a drilling system is provided. The drilling system includes a rotating control head for sealing the tubular string while permitting axial movement of the string relative to the rotating control head. The drilling system also includes an actuating fluid for actuating the rotating control head and maintaining a pressure differential between a fluid pressure in the rotating control head and a wellbore pressure. Additionally, the drilling system includes a cooling medium for passing through the rotating control head. In another aspect, a rotating control head is provided. In yet another aspect, a method for sealing a tubular in a rotating control head is provided.
| 4
|
BACKGROUND OF THE INVENTION
[0001] This invention presents the rapid testing for nutrients in products including, but not limited, medicines, food supplements or additives, cosmetics, drinks, fruits, vegetables, and etc. Rapid testing for nutrients is very useful in maintenance and improvement of health of living organisms, including human, on the earth. Adequate nutrition is closely related to the human health in both developed countries and developing countries. Validation of nutrients in terms of amount and composition is a keystone to reach adequate nutrition. There are existing methods to validate nutrients by utilizing expensive instruments and complicated chemicals. These methods can only be operated in laboratories by professionals. Therefore, consumers can only rely on the published testing data or read the labels to learn the nutrition facts. A simple and rapid testing for nutrients will allow consumers to validate the nutrient by themselves and help them to reach adequate nutrition.
[0002] The rapid testing in this invention can be very easily performed by individuals at most places, such as home, office, market, school, hospital, laboratories and etc. The rapid testing does not require expensive instruments, chemicals, or professional trainings.
SUMMARY OF THE INVENTION
[0003] This invention presents the rapid testing for nutrients in products including, but not limited, medicines, food supplements or additives, cosmetics, drinks, fruits, vegetables, and etc. The rapid testing is performed on strips coated with indicators. Nutrients such as Vitamin C can be detected in very small volume. The detection is semi-quantitative by naked eye or becomes quantitative with help of a hand-held device. The rapid testing in this invention can be very easily performed by individuals at most places, such as home, office, market, school, hospital, laboratories and etc. The rapid testing does not require expensive instruments, chemicals, or professional trainings.
BRIEF DESCRIPTION OF DRAWINGS AND FIGURES
[0004] FIG. 1 . The Rapid Testing for Nutrient in Medicine, Cosmetics, Drinks, Fruits, and Vegetables
[0005] 2 micro liters of samples from corresponding products was applied on the rapid testing strips. Results were read after 2 min. Amount of vitamin C in medicine, cosmetic product, juice, Lime and tomato can be estimated by naked eye. Orange contains much less amount of vitamin C than lime.
[0006] FIG. 2 . Testing rang and sensitivity
[0007] Rapid testing of vitamin C from a serial diluted vitamin C standard solution. The minimum testing concentration is 0.01%. The minimum detectable amount of vitamin C in 2 micro liters is 0.2 micro grams.
[0008] FIG. 3 . Rapid Testing for Vitamin C in Different Brand of Products for Vitamin Supplement
[0009] 2 ul of samples from corresponding products was applied on the rapid testing strips. Results were read after 5 to 10 min. Amount of vitamin C in different brand of nutrient supplements can be estimated by naked eye. Some brand of nutrient supplements may not contain the correct amount of vitamin C as label claimed. Optimization of materials in the rapid testing will achieve better results.
[0010] FIG. 4 . Supporting Materials for Rapid Testing
[0011] Filter paper (Lane A) and poster (Lane B) as supporting material for rapid testing shown different shapes of spots whereas the testing range and sensitivity are similar.
[0012] FIG. 5 . Concentration of Indicator for Rapid Testing
[0013] Different concentrations of indicator were coated on supporting materials of rapid testing. 2× of indicator shown better result than 1× and 4× of indicator coated. Optimization of indicator concentration and processes applied in the rapid testing will achieve better results.
[0014] FIG. 6 . Volume of Samples for Rapid Testing
[0015] Testing samples applied on rapid testing shown a little difference in testing results when different concentration of indicator were coated on testing strips (Panel A, 2×; and Panel B, 4×). Large volume of sample shown stronger signals. Rapid testing strips also can dip into samples to perform the testing if enough samples available (Panel C).
[0016] FIG. 7 . Specificity of Rapid Testing for Nutrient
[0017] Common influencing substances such as acid, base and oxide substances were tested on rapid testing. As shown in Panel A, 100 mM Hydrochloride Acid (HCl) and Citric Acid (CA) shown a very little signal comparing with the vitamin C at the similar concentration in Panel C. 100 mM Sodium Hydroxide (NaOH) and 30% Hydroperoxide (H2O2) did not see any signal on rapid testing strips.
DETAILED DESCRIPTION OF THE INVENTION
[0018] Testing or detection of nutrients in products is mostly conducted in laboratories well equipped with expensive instrument and chemicals. The people operated the testing or detection requires professional training. It is impossible for general population to access these testing and detections. However, it will greatly benefit consumers if they are provided with simple and rapid testing for nutrients, which will guide them to make correct choice in case they do not know the nutrient fact of the products, or the label of products did not match the real content of products.
[0019] There are many nutrients in the products consumed by human. There also have different method to detect each of nutrients. There even are many different methods to detect the same nutrient. Usually the samples containing nutrients are not ready to be tested or detected. Therefore, many different procedures and process for sample preparation make the nutrient testing even more complicated.
[0020] Nutrients consumed by human include protein, fat, carbohydrates, vitamins, minerals, and etc. Each nutrient is detected by different methods and procedure. The methods to detect these nutrients include chemical reactions, physical procedures, biological process, High Performance Liquid Chromatography (HPLC), Gas Chromatography (GC), Mass Spectrometry (MS), gel electrophoresis. Some of these methods need to be performed in well equipped laboratories, some of the methods demand expensive equipments, and some of the methods require well trained professionals to perform the detection.
[0021] The same nutrient can be detected by different methods depended on formulation of nutrient and application of the nutrient. For examples, the method to detection of pure vitamin C is different from the methods to detect formulated vitamin C as medicine. The pure vitamin C can be detected with either by infrared absorption with an expensive instrument or by chemical reaction with alkaline cupric tartrate in laboratories. Quantitation of pure vitamin C involves more complicated chemical reaction, such as mixing vitamin C with sulfuric acid and starch, then titrating with iodine.
[0022] There are three formulations of vitamin C as medicine and each formulation are tested with different methods also. Three formulations of vitamin C as medicine are injection solution formulation, oral solution formulation and tablets formulation. To detect vitamin C in injection formulation or oral solution, add trichloroacetic acid and activated charcoal into injection solution, filter through a fluted filter a few times until clear. Add pyrrole in to filtrate and heat at 50° C. Vitamin C is present if solution developed blue color. Vitamin C in injection solution or oral solution can also be detected by Gas Chromatography and it respond to the flame test for sodium. To detect vitamin C in tablets, the tables need to be processed and prepared for the testing. The finely powdered tables are triturated with sufficient diluted alcohol. The solution is filtered and filtrate is used for detection as injection solution.
[0023] Quantitation of vitamin C in about medicines is conducted by different methods also. One method involves mixing vitamin C solution with metaphosphoric-acetic acids and titrating with standard dichlorophenol-indophenol solution until a rose-pink color persists for at least 5 seconds. The other method recommended for vitamin injection solution is more complicated and instrument demanding. There are five steps in the method, mobile phase, standard preparation, assay preparation, high performance liquid chromatography, and procedure. The mobile phase consists of dibasic sodium phosphate and monobasic potassium phosphate, adjusting pH to 2.5 with phosphoric acid. Dissolve an accurately weighed quantity of USP vitamin C RS in mobile phase to obtain a Standard Solution with a known concentration of vitamin C about 0.5 mg/ml. For assay preparation, dilute vitamin C containing solution quantitatively with Mobile phase to obtain a Vitamin C Solution having a concentration of vitamin C about 0.5 mg/ml. The high performance liquid chromatography is equipped with a 245-nm detector and a 6 mm×150 mm column that contains packing L39. The flow rate is about 0.6 ml per minute. Chromatograph the Standard Solution first and record the peak responses as directed under procedure. The column efficiency is not less than 3500 theoretical plates, the tailing factor is nor more than 1.6 and the relative standard deviation for replicated Vitamin Solution is not more than 1.5%.
[0024] The procedure for the high performance liquid chromatography includes separately injection of equal volume (about 4 ul) of the Standard Solution and Vitamin C Solution in to chromatograph, record the chromatograms, and measure the responses for the major peak. Calculate the quantity, in mg, of vitamin C in each ml of the Vitamin C Solution taken by the formula: CD(r u /r s ). in which C is the concentration, in mg per ml of vitamin C in Standard Solution, D is the dilution factor, and r u and r s are the peak response obtained from the Vitamin C Solution and the Standard Solution respectively.
[0025] It is beyond the scope here to list and detail all the different methods to test or detect all different nutrients. The aforementioned methods for vitamin C testing and detection just serve as an example to illustrate how complicated and difficult for a general population to perform the testing by themselves. These testing needs non-house held chemicals, needs expensive instruments such as Infrared Spectrometers, Gas Chromatography and high performance liquid chromatography, needs well-equipped laboratories and requires well-trained professional skills. Therefore, a simple and easy-to-use testing for nutrients will greatly appreciated by those consumers who would like to validate the nutrients in their consumable products.
[0026] Present invention provides a rapid testing for nutrients by using strips that indicate the parameter of nutrients when contact with nutrients containing products. In one embodiment, the rapid testing strips can test nutrients in different products with broad testing range and high sensitivity. As shown in FIG. 1 , vitamin C in medicine, cosmetic products, drinks, fruit and vegetable can be tested. It only needs 2 ul of liquid sample to perform the testing. The testing range of Vitamin C is from 20% to 0.02% as indicated in FIGS. 1 and 2 . The sensitivity is about 0.4 ug. The testing range can go further lower and sensitivity can go even higher if use larger volume of liquid samples during the test.
[0027] In a preferred embodiment, using small volume of samples on strip testing will keep original color in the non-reacted area, which will increase the contrast between reacted area and non-reacted area. Therefore, the sensitivity of the testing is increased, and reading results by naked eye is more distinguishable and reliable. Using small volume of samples on strip testing also decreases the demanding for samples volume and avoids using sample holder. The large volume of samples can also be applied on the rapid testing strips. The testing strips can dip into samples containing nutrition, or samples can be poured onto the testing strips.
[0028] One additional embodiment of present invention is to apply electronic devices on the strip testing. The devices scan reacted area and non-reacted area to calculate accurately the amount of nutrients in the testing samples. The computer program in the devices performs background subtraction, relative signal differences between reacted area and non-reacted area, quantitation and analysis. The electronic devices are either on desk top or hand-held. The electronic devices can also be integrated into current existing testing instruments.
[0029] To develop simple and easy-to-use rapid testing for nutrients, strip as testing vehicle is invented as one of embodiment of this invention. Supporting materials of the strips for rapid testing can be plastic, paper, cotton, synthetic, natural or recycled fabric. Coating or pre-treatment of supporting materials may increase performance of the testing. Supporting materials can have color or colorless. The shape of rapid testing can be disc, ball, cube, strips, strap, stick, square, sheet, round, or patch. Indicators used on strips can have different color including, but not limited, red, blue, green, black, orange, yellow, purple. The indicators include, but not limited, synthetic dye, natural dye, food color, organic chemicals or non-organic chemicals. The rapid testing strips may contain single indicator or multiple indicators. The amount of indicators on the rapid testing strips is ranged broadly and is optimized according to testing performance.
EXAMPLE 1
Rapid Testing for Nutrients
[0030] Nutrients such as vitamin C in medicine, cosmetic products, juices, fruits and vegetable are tested with Rapid Testing invented herein. The medicine is vitamin C tablet containing 500 mg of vitamin C from Nature Made (Purchased from Costco); The cosmetic product containing 20% of vitamin C from SkinCeuticals Serum 20; The Juice 1 containing 0.06% of vitamin C from Tropicana Essentials (Purchased from Safeway); The Juice 2 containing 0.025% of vitamin C from Hawaiian Punch (Purchased from Safeway); The orange, lime and tomato were purchased from Safeway also. The vitamin C tablet was dissolved in 5 ml H20. The clear supernatant extract was used as testing samples; the original liquid from cosmetic product and juices was used as testing samples; squished juices from orange, lime and tomato were directly tested by rapid testing. The vitamin C in standard curve was diluted from pure vitamin C from Sigma. 2 micro liters of samples were applied on rapid testing strips. The result was read two minutes later.
[0031] As estimated data of rapid testing in FIG. 1 , the vitamin C tablet and cosmetic product do contain correct amount of vitamin C; Tropicana Essentials contains more vitamin C than Hawaiian Punch; Lime contains large amount of vitamin C; to our surprise, even tomato contains more vitamin C than orange. We tasted the orange and it is a kind of sweetish, which may explain it because grade of maturity and storage condition of fruits will affect the amount of vitamin C contained in the fruits. These testing data were corresponding to the actual amount of vitamin C contained in the products respectively. In 100 g of products, orange contains 50 mg vitamin C, lime contains 40 mg vitamin C and tomato contains 10 mg vitamin C (http://en.wikipedia.org/wiki/Vitamin_C#Plant_sources Tomato contains 0.01% of vitamin C and Tropicana Essentials juice contains 0.06% of vitamin C. The testing data of tomato and Tropicana Essentials juice in rapid testing is very close to the vitamin C standard cure at 0.02%, 0.04% and 0.08% respectively as shown in FIG. 1 . Therefore, rapid testing for nutrients in this invention is applicable for nutrient testing in most products.
EXAMPLE 2
Range and Sensitivity of Rapid Testing
[0032] The pure vitamin C from Sigma was serial diluted. Concentration from 20% to 0.01%. 2 micro liters of sample containing different concentration of vitamin C was applied on rapid testing. Result was read 2 minutes afterward as shown in FIG. 2 . Sample containing 0.01% of vitamin C can be detected with rapid testing by naked eye. With electronic devices, the sensitivity can increased at least to 0.01% of vitamin C. The minimum detectable amounts of vitamin C in 2 micro liters are 0.2 micro grams by naked eye or less than 0.2 micro grams by electronic devices.
EXAMPLE 3
Validation of Nutrients in Commercial Products
[0033] Amount of vitamin C in five commercial available products for vitamin C supplement were validated by rapid testing. 1) The vitamin C tablet made by Nature Made contains 500 mg vitamin C (Nature Made); 2) Multi-vitamin tablet for Children made by Kirkland contains 250 mg vitamin C (Children); 3) Multi-vitamin tablet for adult made by Kirkland contains 120 mg vitamin C (Adult); 4) the One Day Women's multi-vitamin contains 60 mg vitamin C (Women); and 5) The Tropicana Essentials Juice contains 60 mg vitamin C per 100 ml juice (Juice).
[0034] The above four tablets containing vitamin C were dissolved in 5 ml water to make final vitamin C concentration at 10% (Nature Made); 5% (Children); 2.4% (Adult) and 1.2% (Women). The filtrates from each tablet were performed on rapid testing strip. The original Tropicana Essentials Juice containing 0.06% of vitamin C was directly applied on the same rapid testing strip. A serial diluted Standard Solution containing vitamin C at 5%, 2.5%, 1.25%, 0.63%, 0.32% and 0.16% were applied on the same testing strip to serve as standard curve for quantitation purpose.
[0035] Validating results by rapid testing indicated that the vitamin C tablet made by Nature Made contains correct amount of vitamin C, whereas all three multi-vitamin tables did not contain correct amount of vitamin C as shown in FIG. 3 . The Tropicana Essentials Juice contains correct amount of vitamin C.
EXAMPLE 4
Optimizing Rapid Testing for Nutrient
[0036] Supporting materials, indicator coated on supporting materials and volume of samples used on rapid strips can be optimized to achieve the best testing conditions. As show in FIG. 4 , filter paper generates round and even spot than poster. The plastic sheet or synthetic fabrics can also be applied in this invention.
[0037] As an embodiment, the indicator coated on strips in this invention is methylthionine chloride, 3,7-bis(dimethylamino)phenothiazin-5-ium chloride or Methylene Blue. The molecular formula is C 16 H 18 ClN 3 S. Its CAS number is 61-73-4: its EC number is 200-515-2. The methylthionine chloride was dissolved in ethanol at 0.001% to 5% (W/V) to make stock indicator solution. The stock indicator solution was diluted from 0 times to 100 times to make coating solution. The preferred concentration for stock indicator solution is depended on the supporting materials used. 0.05% of methylthionine chloride in stock solution was used in this invention when using filter paper as supporting material.
[0038] Dilution of stock indicator solution was also depended on the supporting marterials used and readout methods or devices. As indicated in FIG. 5 , high concentration of indicator may not have the best readout at 1.25% of vitamin C, but may have highest sensitivity. As an embodiment in this invention, 4 times dilution from stock indicator solution was used to prepare the rapid testing for nutrient.
[0039] There are different ways to use the rapid testing for nutrient. The sample to be tested can be spotted on the testing strips, testing strips can be dipped in samples, or testing strips can be immersed in to samples. As an embodiment, spotting samples on testing strips or dipping testing strips into samples are preferred in this application because these two methods create a boundary between reacted area and unreacted area. As shown in FIG. 6 , unreacted area will serve as background to increase the contrast of testing and therefore, increase the sensitivity and reliability of rapid testing. The boundary between reacted area and unreacted area can be recognized very well by electronic devices to make the rapid testing quantitative. Application of electronic devices makes the quantitation of the rapid testing more objective and accurate. These advantages are hardly be taken if the testing strips were immersed into samples.
EXAMPLE 5
Specificity of Rapid Testing for Nutrient
[0040] Common influencing substances such as acid, base and oxidizing substances were tested on rapid testing. Hydrochloride Acid (HCl) from Sigma is a strong acid and Citric Acid (CA) from Sigma is a weak acid existing in some fruits or vegetables. Sodium Hydroxide (NaOH) from Sigma is a strong base and Hydroperoxide (H2O2) from Fisher is most representative oxidizer. The acid and base were prepared at 100 mM to mimic the conditions naturally existed acidic or basic influencing substances. 30% Hydroperoxide was prepared to exaggerate conditions the potential oxidizing substances may create.
[0041] As shown in Panel A of FIG. 7 , acidic substances such as HCl and Citri Acid only generate a very little signal in rapid testing comparing with the vitamin C at the similar concentration in Panel C. Basic substance such as NaOH and oxidizing substance such as and Hydroperoxide did not see any signal on rapid testing strips as shown in Panel B of FIG. 7 . The above testing result indicated that the rapid testing for nutrient in this invention is predominantly specific to vitamin C. Acidic substance may cause a little noise and basic substances and oxidizing substances will not affect the specificity of the rapid testing for vitamin C in this invention.
[0042] The invention has been described using exemplary preferred embodiments. However, for those skilled in this field, the preferred embodiments can be easily adapted and modified to suit additional applications without departing from the spirit and scope of this invention. Thus, it is to be understood that the scope of the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and similar arrangements based upon the same operating principle. The scope of the claims, therefore, should be accorded the broadest interpretations so as to encompass all such modifications and similar arrangements.
|
This invention presents the rapid testing for nutrients in products including, but not limited, medicines, food supplements or additives, cosmetics, drinks, fruits, vegetables, and etc. The rapid testing is performed on strips coated with indicators. Nutrients such as Vitamin C can be detected in very small volume. The detection is semi-quantitative by naked eye or becomes quantitative with help of a hand-held device. The rapid testing in this invention can be very easily performed by individuals at most places, such as home, office, market, school, hospital, laboratories and etc. The rapid testing does not require expensive instruments, chemicals, or professional trainings.
| 6
|
CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority to Chinese application number 201410096164.9, filed on Mar. 14, 2014, the contents of which are incorporated herein in their entireties.
FIELD OF THE INVENTION
The present invention relates to optical films, particularly to a quantum dot film applied to the backlight module.
BACKGROUND OF THE INVENTION
The backlight module is provider of light source for the liquid crystal display (LCD). All the colors showed by the liquid crystal display are derived from the light emitted by the backlight module. Currently commercially available light sources in the backlight module are mainly divided into two types, i.e., cold cathode fluorescent lamp (CCFL) and light emitting diode (LED). Compared the two light sources, LEDs have obvious advantages in the aspects of energy saving, environmental protection, small size, long life, and so on. As the cold cathode fluorescent lamp contains mercury, it not only results in high cost but also harms the environment greatly. To protect the environment, gradually replacing cold cathode fluorescent lamp with LEF will be an inevitable result. But, for the color saturation showed by the liquid crystal display, the light emitted from the cold cathode fluorescent lamp has good color saturation, and the color saturation of ordinary white LEDs is relatively poor. Therefore, it is very important to improve the color saturation of the liquid crystal display with LED light source.
The color saturation of LCD is usually shown with the NTSC color gamut which is the sum of color shown by the display under the NTSC standard. The color gamut of ordinary white light LED is 68-70% NTSC, it is very negative for the color performance of display. Currently there are two main ways to improve the color gamut of LED. The first method requires use of many LED light sources which are able to emit different colors to make color saturation exceeding 90% NTSC color gamut. Due to the higher costs of the LED light sources with different colors, the working life of the LED light sources are uneven. As a result, this method cannot be universally used. The second method requires use of ordinary white LED which emits mainly blue light. By using quantum dots, a portion of the blue light is converted into red light and green light. Compared with the white light emitted by the traditional LED, more red, green, and blue light goes through the filter and therefore displaying brighter, richer colors. But as the cost of quantum dot is higher, this method requires consideration of the light conversion efficiency of the quantum dots, stability, and other factors.
BRIEF SUMMARY OF THE INVENTION
In order to solve the problem of poor color saturation of the liquid crystal display, the present invention provides a novel quantum dot film which can be applied to the backlight module. The quantum dot film of this invention has the advantages of improving the color gamut and increasing brightness.
The quantum dot film comprises a quantum dot layer having an upper surface and a lower surface, an upper waterproof layer and a lower waterproof layer which are on the upper surface and the lower surface of the quantum dot layer respectively. The quantum dot layer comprises, by weight, 100 parts of an adhesive, 5-20 parts of silica gel particles, 1-20 parts of diffusion particles, and 0.1-20 parts of quantum dots. The surfaces of the silica gel particles have micropore structures; the quantum dots are adsorbed in micropores of the silica gel particles or dispersed in the adhesive; the silica gel particles and the diffusion particles are dispersed in the adhesives.
Preferably, the quantum dot layer comprises, by weight, 100 parts of an adhesive, 5-20 parts of silica gel particles, 5-15 parts of diffusion particles and 9-11 parts of quantum dots.
Preferably, in the quantum dot layer, the weight of the quantum dot adsorbed in the micropore of the silica gel particles is 60-100% of the weight of all the quantum dots in the quantum dot layer.
Preferably, in the quantum dot layer, the weight of the quantum dot adsorbed in the micropore of the silica gel particles is 80-100% of the weight of all the quantum dots in the quantum dot layer.
Depending on the kind and luminous efficiency of quantum dots, an appropriate amount of quantum dots can be added into the above-mentioned quantum dot layer.
Further, the quantum dot material is selected from one kind of semiconductor material, or a mixture of two or more kinds of semiconductor materials.
The semiconductor material comprises a Group IIB-VIB element, or a Group IIIB-VIB element. The Group IIB-VIB element comprises CdS, CdSe, CdTe and ZnSe. The group IIIB-VB element comprises InP and InAs.
Further, the particle size of the silica gel particles is 2-30 μm, the pore size of the micropore structure on the surface of the silica gel particle is 10-30 nm, the particle size of the quantum dots is 1-20 nm. Preferably, the particle size of the silica gel particles is 18-20 μm, the pore size of the micropore structure on the surface of the silica gel particle is 12-20 nm. Preferably, the particle size of the quantum dots is 2-9 nm.
The silica gel particles may adsorb quantum dots in the micropores. When the light is refracted repeatedly in the micropores, the quantum dots may convert the light to the light with required wavelength. Micropores structure can significantly improve the luminous efficiency of quantum dots.
Further, the quantum dots comprise the red light quantum dots and green light quantum dots, the weight ratio of the red light quantum dots and the green light quantum dots is 1:1-1:15.
Preferably, the weight ratio of the red light quantum dots and the green light quantum dots is 1:2-1:10, or 1:3-1:6. More preferably, the weight ratio of the red light quantum dots and the green light quantum dots is 2:7-2:9.
The particle size range of the red light quantum dots is 6-9 nm, the particle size range of the green light quantum dots is 2-5 nm.
The red light quantum dot material is selected from CdS, CdSe, CdTe, ZnSe, InP, InAs, or a mixture of two or more these materials. The green light quantum dot material is selected from CdS, CdSe, CdTe, ZnSe, InP, InAs, or a mixture of two or more these materials.
Depending on the different light emitted from different backlight source, to adjust the weight ratio of the quantum dot of different types, such as, for the most common white LED which emits blue light mainly, one can adjust the red and green light quantum dots to obtain the desired mixed light.
The emission spectrum of the quantum dot is determined by the size of quantum dots (main factor) and its chemical composition, so the quantum dot of different components can emit light with different wavelengths by controlling the size of the quantum dot.
The wavelength of the light emitted by the quantum dots which are illuminated by the light source, is mainly determined by the particle size of the quantum dots. Based on the need, one can adjust the size of quantum dots to obtain red light quantum dots or green light quantum dots. Adjusting the weight ratio of the red light quantum dots and green light quantum dots can result in light with different wavelengths (different colors), thereby the desired mixed light desired.
Further, the diffusion particles are spherical or ellipsoid shape, the particle size range of the diffusion particles is 3-35 μm; the particle size of the diffusion particles is the same, or the variation coefficient of the particle size of the diffusion particles is less than or equal to 15%.
The diffusion particles are made of one or more materials selected from the group of polymethyl methacrylate (PMMA), polybutyl methacrylate, polystyrene, silicone resin, titanium dioxide, calcium carbonate, and barium sulfate.
Further, the diffusion particles are made of PMMA or titanium dioxide, with the particle size of 5-20 μm.
The adhesive is made of one or more materials selected from polystyrene resin, polymethyl methacrylate (PMMA), acrylic resin, urethane resin, and epoxy resin.
Further, the thickness of the quantum dot layer is 10-200 μm. Further, the thickness of the quantum dot layer is 150-200 μm.
Further, the present invention provides a quantum dot film for application to the backlight module, which comprises, by weight, 2 parts of red light quantum dots, 7-9 parts of green light quantum dots, 5-20 parts of silica gel particles, 5-15 parts of diffusion particles, 100 parts of polystyrene resin or polymethyl methacrylate. The particle size of the red light quantum dots is 6-9 nm. The particle size of the green light quantum dots is 2-5 nm. The particle size of said silica gel particles is 18-20 μm, the pore size of the micropore structure on the surface of the silica gel particle is 12-20 nm. The diffusion particles are made of PMMA or titanium dioxide with the particle size of 5-20 μm. The thickness of the prepared quantum dot layer is 150-200 μm. The waterproof layers are arranged on the upper surface and lower surface of the quantum dot layer, the waterproof layer is coating with a protective coating layer.
The present invention also provides a backlight module which comprises an above-described quantum dot film.
Further, the upper surface of the upper waterproof layer is equipped with protective coating layer, anti-dazzle structure, prism structure or diffusion layer; the lower surface of the lower waterproof layer is also equipped with protective coating layer, the lower surface of this protective coating layer has irregular protrusions of 1-10 μm.
The waterproof layer comprises one or more layers of thin film which can prevent a gas (vapor) to pass through. The thin film can comprise, e.g., PVA coated high barrier film, polyvinylidene chloride film (PVDC), ethylene/vinyl alcohol copolymer film (EOVH), nylon material, an inorganic oxide coated film. In general, the thickness of the waterproof layer is 10-100 μm.
The thickness of the protective coating layer is 4-12 μm, the material is selected from acrylic resin, urethane resin, or epoxy resin, or mixture of two above materials. The protective coating layer contains 0.1%-10% by weight of the diffusion particles with particle size of 1-10 μm. The material of the diffusion particles in the protective coating layer is the same as or different from the material of diffusion particles in quantum dot layer.
Further, the material of waterproof layer is PVA coated high barrier film or polyvinylidene chloride film (PVDC), the thickness of the waterproof layer is 20-40 μm. Further, the material of the protective coating layer is acrylic resin, the thickness of the protective coating layer is 10-12 μm, the protective coating layer contains 5%-10% by weight of the diffusion particles with particle size of 5-10 μm.
The anti-dazzle structure, prism structure and diffusion layer may be prepared by the method in prior art, or may be the product purchased on the market.
The present invention also provides a method for preparing the above-described quantum dot film, and the method comprises the following steps:
(1) mixing the silica gel particles and quantum dots;
(2) adding the mixture of silica gel particles and quantum dots obtained in step (1) into the adhesive to obtain an adhesive mixture, then adding diffusion particles into the adhesive mixture and further mixing to give an adhesive coating liquid;
(3) applying the adhesive coating liquid obtained in step (2) onto the upper surface of the lower waterproof layer, which is cured to form a quantum dot layer;
(4) bonding the upper waterproof layer onto the upper surface of the quantum dot layer.
In the quantum dot film of the present invention, the surface of the silica gel particles dispersed in the film has micropores structure, the quantum dots can be adsorbed in the micropores, when the light pass through the film, the light in the micropores of the silica gel particles are refracted constantly, to improve the utilization of quantum dots. In practical applications, equivalent to just adding a small amount of quantum dots, we can achieve excellent luminous efficiency and greatly improves the luminous efficiency of quantum dots.
Since the diffusion particles and silica gel particles both have the advantages of atomizing the light source, and improving the brightness of front face, the quantum dot film of the present invention improve the color gamut, and improve the brightness at the same time, the quantum dot film can substitute the diffusion film in the backlight module, saving cost.
BRIEF DESCRIPTIONS OF THE DRAWINGS
FIG. 1 is a structural schematic view of the quantum dot layer in the quantum dot film provided by the present invention;
FIG. 2 is a schematic view of the structure of quantum dot film with protective coating layer provided by the present invention, wherein, 102 is the silica gel particles, 101 is quantum dots adsorbed on the silica gel particles, 103 is diffusion particles, 104 is the adhesive; 201 is the quantum dot layer; 202 , 203 are upper and lower waterproof layer respectively, 204 is the protective coating layer.
DETAILED DESCRIPTION OF THE INVENTION
As shown in FIG. 1 , the quantum dot layer in the quantum dot film provided by the present invention comprise silica gel particles 102 , quantum dots 101 , some quantum dots 101 are adsorbed in the micropores of silica gel particles 102 , diffusion particles 103 and the adhesive 104 .
As shown in FIG. 2 , the quantum dot film with protective coating layer provided by the present invention comprises quantum dot layer 201 , an upper waterproof layer 202 and a lower waterproof layer 203 are arranged on the upper surface and the lower surface of the quantum dot layer 201 respectively; the upper surface of the upper waterproof layer is also provided with a protective coating layer, the lower surface of the lower waterproof layer is also provided with a protective coating layer 204 .
The present invention provides the following method to test the performance of the quantum dot film:
Brightness test: Take a quantum dot film of 32-inch, the quantum dot film is placed in a backlight module of 32-inch, lights at the rated voltage of 24V, measure the brightness and viewing angle with a luminance meter (produced by Suzhou Fushida Scientific Instrument Co., LTD. Model: BH-7).
Color gamut test: Take a quantum dot film of 32-inch, the quantum dot film is placed in a backlight module of 32-inch, the display is adjusted to the working state required, then, all of the red, green and blue signals are input to the display, test the chromaticity coordinates of the center point with a brightness meter (Model: BH-7) respectively, the NTSC value is calculated by the fixed formula.
Example 1
The present invention provides a quantum dot film applied to the backlight module, comprises, by weight, 2 parts of red light quantum dots, 8 parts of green light quantum dots, 15 parts of silica gel particles, 10 parts of diffusion particles, 100 parts of polystyrene resin. The particle size of the red light quantum dots is 6 nm. The particle size of the green light quantum dots is 2 nm. The particle size of said silica gel particles is 18 μm, the pore size of the micropore structure on the surface of the silica gel particle is 15 nm. The diffusion particles are PMMA with the particle size of 20 μm. The thickness of the prepared quantum dot layer is 150 μm. The waterproof layers are arranged on the upper and lower surface of the quantum dot layer, the waterproof layer is coating with protective coating layer. The waterproof layer is polyvinylidene chloride film (PVDC), the thickness of the waterproof layer is 20 μm. The material of the protective coating layer is acrylic resin, the thickness of the protective coating layer is 10-12 μm, the protective coating layer contains 5% by weight of the diffusion particles with particle size of 5-8 μm.
Example 2
The present invention provides a quantum dot film applied to the backlight module, comprises, by weight, 2 parts of red light quantum dots, 8 parts of green light quantum dots, 5 parts of silica gel particles, 15 parts of diffusion particles, 100 parts of polystyrene resin. The particle size of the red light quantum dots is 8 nm. The particle size of the green light quantum dots is 3 nm. The particle size of said silica gel particles is 20 μm, the pore size of the micropore structure on the surface of the silica gel particle is 12 nm. The diffusion particles are PMMA with the particle size of 20 μm. The thickness of the prepared quantum dot layer is 150 μm. The waterproof layers are arranged on the upper and lower surface of the quantum dot layer, the waterproof layer is coating with protective coating layer. The waterproof layer is polyvinylidene chloride film (PVDC), the thickness of the waterproof layer is 40 μm. The material of the protective coating layer is acrylic resin, the thickness of the protective coating layer is 10-12 μm, the protective coating layer contains 10% by weight of the diffusion particles with particle size of 8-10 μm.
Example 3
The present invention provides a quantum dot film applied to the backlight module, comprises, by weight, 2 parts of red light quantum dots, 8 parts of green light quantum dots, 20 parts of silica gel particles, 5 parts of diffusion particles, 100 parts of polymethyl methacrylate. The particle size of the red light quantum dots is 9 nm. The particle size of the green light quantum dots is 5 nm. The particle size of said silica gel particles is 20 μm, the pore size of the micropore structure on the surface of the silica gel particle is 20 nm. The diffusion particles are titanium dioxide with the particle size of 5 μm. The thickness of the prepared quantum dot layer is 150 μm. The waterproof layers are arranged on the upper and lower surface of the quantum dot layer, the waterproof layer is coating with protective coating layer. The waterproof layer is polyvinylidene chloride film (PVDC), the thickness of the waterproof layer is 30 μm. The material of the protective coating layer is acrylic resin, the thickness of the protective coating layer is 10-12 μm, the protective coating layer contains 8% by weight of the diffusion particles with particle size of 6-9 μm.
Example 4
The present invention provides a quantum dot film applied to the backlight module, comprises, by weight, 0.02 parts of red light quantum dots, 0.08 parts of green light quantum dots, 5 parts of silica gel particles, 1 parts of diffusion particles, 100 parts of acrylic resin. The particle size of the red light quantum dots is 6 nm. The particle size of the green light quantum dots is 2 nm. The particle size of said silica gel particles is 2 μm, the pore size of the micropore structure on the surface of the silica gel particle is 10 nm. The diffusion particles are polybutyl methacrylate with the particle size of 3 μm. Almost all the quantum dots are absorded in the micropore structure of the silica gel particle. The thickness of the prepared quantum dot layer is 10 μm. The waterproof layers are arranged on the upper and lower surface of the quantum dot layer, the waterproof layer is coating with protective coating layer. The waterproof layer is ethylene/vinyl alcohol copolymer film (EOVH), the thickness of the waterproof layer is 10 μm. The material of the protective coating layer is acrylic resin, the thickness of the protective coating layer is 4-12 μm, the protective coating layer contains 1% by weight of the diffusion particles with particle size of 1-5 μm.
Example 5
The present invention provides a quantum dot film applied to the backlight module, comprises, by weight, 3 parts of red light quantum dots, 8 parts of green light quantum dots, 12 parts of silica gel particles, 10 parts of diffusion particles, 100 parts of polystyrene resin. The particle size of the red light quantum dots is 8 nm. The particle size of the green light quantum dots is 3 nm. The particle size of said silica gel particles is 15 μm, the pore size of the micropore structure on the surface of the silica gel particle is 20 nm. The diffusion particles are polystyrene with the particle size of 20 μm. The weight of the quantum dot adsorbed in the micropore of the silica gel particles is about 60% of the weight of all the quantum dot in the quantum dot layer. The thickness of the prepared quantum dot layer is 120 μm. The waterproof layer are arranged on the upper and lower surface of the quantum dot layer, the waterproof layer is coating with protective coating layer. The waterproof layer is nylon material, the thickness of the waterproof layer is 50 μm. The material of the protective coating layer is urethane resin, the thickness of the protective coating layer is 4-12 μm, the protective coating layer contains 2% by weight of the diffusion particles with particle size of 5-8 μm.
Example 6
The present invention provides a quantum dot film applied to the backlight module, comprises, by weight, 4 parts of red light quantum dots, 16 parts of green light quantum dots, 20 parts of silica gel particles, 20 parts of diffusion particles, 100 parts of polymethyl methacrylate. The particle size of the red light quantum dots is 9 nm. The particle size of the green light quantum dots is 5 nm. The particle size of said silica gel particles is 30 μm, the pore size of the micropore structure on the surface of the silica gel particle is 30 nm. The diffusion particles are silicone resin with the particle size of 20-35 μm, the variation coefficient of the particle size of the diffusion particles is 15%. The weight of the quantum dot adsorbed in the micropore of the silica gel particles is 90% of the weight of all the quantum dot in the quantum dot layer. The thickness of the prepared quantum dot layer is 200 μm. The waterproof layer are arranged on the upper and lower surface of the quantum dot layer, the waterproof layer is coating with protective coating layer. The waterproof layer is ethylene/vinyl alcohol copolymer film, the thickness of the waterproof layer is 100 μm. The material of the protective coating layer is epoxy resin, the thickness of the protective coating layer is 4-12 μm, the protective coating layer contains 10% by weight of the diffusion particles with particle size of 5-10 μm.
Example 7
The present invention provides a quantum dot film applied to the backlight module, comprises, by weight, 2 parts of red light quantum dots, 7 parts of green light quantum dots, 10 parts of silica gel particles, 6 parts of diffusion particles, 100 parts of polystyrene resin. The particle size of the red light quantum dots is 8 nm. The particle size of the green light quantum dots is 3 nm. The particle size of said silica gel particles is 18 μm, the pore size of the micropore structure on the surface of the silica gel particle is 20 nm. The diffusion particles are PMMA with the particle size of 20 μm. The weight of the quantum dot adsorbed in the micropore of the silica gel particles is about 80% of the weight of all the quantum dot in the quantum dot layer. The thickness of the prepared quantum dot layer is 150 μm. The waterproof layer are arranged on the upper and lower surface of the quantum dot layer, the waterproof layer is coating with protective coating layer. The waterproof layer is PVA coated high barrier film, the thickness of the waterproof layer is 20 μm. The material of the protective coating layer is acrylic resin, the thickness of the protective coating layer is 10-12 μm, the protective coating layer contains 6% by weight of the diffusion particles with particle size of 5-10 μm.
Example 8
The present invention provides a quantum dot film applied to the backlight module, comprises, by weight, 2 parts of red light quantum dots, 9 parts of green light quantum dots, 14 parts of silica gel particles, 8 parts of diffusion particles, 100 parts of polymethyl methacrylate. The particle size of the red light quantum dots is 6-9 nm. The particle size of the green light quantum dots is 2-5 nm. The particle size of said silica gel particles is 20 μm, the pore size of the micropore structure on the surface of the silica gel particle is 15 nm. The diffusion particles are polymethyl methacrylate with the particle size of 15 μm. The thickness of the prepared quantum dot layer is 200 μm. The waterproof layers are arranged on the upper and lower surface of the quantum dot layer, the waterproof layer is coating with protective coating layer. The waterproof layer is polyvinylidene chloride film, the thickness of the waterproof layer is 40 μm. The material of the protective coating layer is acrylic resin, the thickness of the protective coating layer is 10-12 μm, the protective coating layer contains 10% by weight of the diffusion particles with particle size of 5-10 μm.
Example 9
The present invention provides a quantum dot film applied to the backlight module, comprises, by weight, 2 parts of red light quantum dots, 8 parts of green light quantum dots, 16 parts of silica gel particles, 6 parts of diffusion particles, 100 parts of polystyrene resin. The particle size of the red light quantum dots is 6-9 nm. The particle size of the green light quantum dots is 2-5 nm. The particle size of said silica gel particles is 20 μm, the pore size of the micropore structure on the surface of the silica gel particle is 30 nm. The diffusion particles are PMMA with the particle size of 20 μm. The thickness of the prepared quantum dot layer is 150 μm. The waterproof layers are arranged on the upper and lower surface of the quantum dot layer, the waterproof layer is coating with protective coating layer. The waterproof layer is PVA coated high barrier film, the thickness of the waterproof layer is 100 μm. The material of the protective coating layer is acrylic resin, the thickness of the protective coating layer is 10-12 μm, the protective coating layer contains 5%-10% by weight of the diffusion particles with particle size of 5-10 μm.
Comparative Example 1
Provides a film applied to the backlight module, comprises, by weight, 15 parts of silica gel particles, 10 parts of diffusion particles, 100 parts of polystyrene resin. The particle size of said silica gel particles is 18 μm, the surface of the silica gel particle has micropore structure with the pore size of 15 nm. The diffusion particles are PMMA with the particle size of 20 μm. The thickness of the prepared film is 150 μm.
The resulting film does not contain quantum dots, and have poor color saturation.
Comparative Example 2
Provides a film applied to the backlight module, comprises, by weight, 2 parts of red light quantum dots, 8 parts of green light quantum dots, 10 parts of diffusion particles, 100 parts of polystyrene resin. The diffusion particles are PMMA with the particle size of 20 μm. The thickness of the prepared quantum dot layer is 150 μm. The waterproof layer are arranged on the upper and lower surface of the quantum dot layer, the waterproof layer is coating with protective coating layer. The waterproof layer is polyvinylidene chloride film, the thickness of the waterproof layer is 50 μm. The material of the protective coating layer is acrylic resin, the thickness of the protective coating layer is 10-12 μm, the protective coating layer contains 5% by weight of the diffusion particles with particle size of 5-10 μm, the diffusion particles are PMMA.
The resulting film does not contain silica gel particles, the luminous efficiency of the quantum dots is poor, and the color saturation is also low.
TABLE 1
The test result of the optical performance of the
quantum dot film provided by the Examples and of
the flim provided by the Comparative Examples
Item
Brightness
NTSC
Example 1
1834
96%
Example 2
1765
94%
Example 3
1854
97%
Example 4
1652
89%
Example 5
1625
91%
Example 6
1654
92%
Example 7
1804
95%
Example 8
1823
97%
Example 9
1650
90%
Comparative Example 1
1821
68%
Comparative Example 2
1831
81%
The test datas in table 1 show that, the quantum dot films applied to backlight module of the present invention have high NTSC value, good color saturation, and higher brightness. In particular, the quantum dot film applied to the backlight module provided in the Examples 1 to 3, Example 7 and 8, have higher NTSC value, better color saturation, and higher brightness.
The above are only preferred embodiments of the present invention, not intended to limit the scope of the present invention. All equalization changes and modifications according to the contents of the present invention, are encompassed within the patent scope of the present invention.
|
The invention relates to the optical films, in particular to a quantum dot film applied to a backlight module. The quantum dot film aims to solve the problem that the color saturation of a liquid crystal displayer is poor. The novel quantum dot film comprises a quantum dot layer, and an upper waterproof layer and a lower waterproof layer are arranged on the upper surface of the quantum dot layer and the lower surface of the quantum dot layer respectively. The quantum dot layer comprises, by weight, 100 parts of adhesives, 5-20 parts of silica gel particles, 1-20 parts of diffusion particles and 0.1-20 parts of quantum dots. The surface of the silica gel particles is provided with a micropore structure. The quantum dots are adsorbed in micropores of the silica gel particles or dispersed in the adhesives. The silica gel particles and the diffusion particles are dispersed in the adhesives. The quantum dot film is applied to the backlight module and has the advantages of improving the color gamut and illuminance.
| 2
|
This application is a continuation of my copending application Ser. No. 99,922, filed Dec. 3, 1979, abandoned.
SUMMARY OF THE INVENTION
This invention relates to a process for decorating articles, particularly articles of adornment, such as jewelry, by applying multiple coatings and forming a pattern. A wide range of effects can be obtained by selection of visibly different coatings and varying the pattern.
Essentially, the process involves the application of at least two coating layers of solvent soluble coatings containing a binder to the article in which the solvent is a common solvent for the binder and redistributing the layers while the final layer is wet with solvent to expose one or more of the underlying layers. Redistribution can be accomplished by a variety of methods such as the selective application of pressure to certain portions of the final layer or by partial removal of one or more layers. After the pattern is formed the article is allowed to dry and can be protected with an additional layer of transparent or translucent coating.
FIGURE DESCRIPTION
FIG. 1 is a perspective view of an earring being decorated in a concentric wood ring effect by the process of this invention using manual pressure.
FIG. 2 is a perspective view of a ring being decorated by a different embodiment of the process of this invention in which a jet of air is used to redistribute the layers of coloring matter.
FIG. 3 is a perspective view of another embodiment of this invention in which a star die is used to redistribute the colored layers in a belt buckle by selective application of pressure.
FIG. 4 is a perspective view of scraping with a knife being used for removing and redistributing portions of the coatings on a pendant to obtain a pattern.
DETAILED DESCRIPTION
The method of decorating articles according to the invention relates primarily, but not exclusively, to articles of adornment, such as jewelry. As used herein, the term "articles" is intended to embrace portions of the body, specifically fingernails and toenails as well as articles which are not commonly considered as jewelry, for example, belt buckles, small boxes, paper weights and the like.
A wide variety of coating compositions are suitable for use in this invention the only essential requirement being that the several coatings required, i.e. two or more visually different coatings, contain binders having a common solvent and that the common solvent be used for applying the final decorative layer. The final decorative layer is the last layer applied before the step of redistribution of the coatings to form a pattern is conducted. While an additional layer can be applied, for example for protection of the decorated article, such an additional layer is not considered a final decorative layer unless it is redistributed to form a pattern in accordance with this invention and it is dissolved in a solvent which is common for the layer or layers beneath. Thus, a protective layer can be, but is not necessarily, soluble in the same solvents as the decorative layers which are essential to this invention and the application of a final protective layer is not essential to the method of this invention. However, it is often desirable and advantageous to utilize a clear or colored transparent protective layer for the articles decorated in accordance with this invention.
The coating compositions used in this invention comprise three essential ingredients, namely a solvent, a binder and a coloring agent which can be a transparent soluble dye or a pigment. The solvent required in the process of this invention is a common solvent for the binder in the various layers, it being recognized in the art that pigments are insoluble coloring agents.
The essential constituents of the coating compositions useful in the method of this invention can vary widely as long as the requirement for a common solvent for the binder in the several layers is satisfied and the coatings are visually different. Typically, the solvent is an organic solvent such as ketone or an ester, but water can serve as the solvent as well as mixtures of water and organic solvent.
The binder can be an organic polymer such as a cellulose ester, for example cellulose acetate, or an acrylate polymer such as poly(methyl acrylate) or it can be a naturally derived binder, such as shellac. Suitable binders include, but are not limited to, those present in compositions known as lacquers. Typical lacquers eminently suitable for use in the invention are those marketed as fingernail polish.
The coloring agent in the coating compositions used in this invention can be in the form of a pigment which is insoluble in the composition and which results in an opaque or partially opaque coating, or in the form of a dye which is soluble in the composition and gives a colored transparent or translucent coating. Pigments are either organic or inorganic. Dyes are normally organic in nature.
A wide variety of pigments or dyes can be used. For example the coloring agents whether they be pigments, dyes or mixtures thereof can be selected to give coatings which are of any hue and character including black and white, irridescent, metallic, phosphorescent or fluorescent.
By appropriate selection of the coatings in the various layers and distribution of the coatings an almost limitless variety of pattern effects can be obtained including textured, speckled, marbled, frosted, flaked or lined. It is also possible to obtain predetermined patterns such as specific designs, numbers, letters and the like.
In its simplest form the method of this invention involves the application of two coatings which are visually different and which have a common solvent, one on top of the other and redistribution of the coatings while the top layer is solvent wet. It should be recognized that redistribution while the topmost layer is solvent wet can be accomplished by drying the topmost layer and rewetting it with a common solvent for it and the first layer. The same principles and procedures apply whether two or more coatings are utilized.
Redistribution of the coatings is accomplished by any suitable means such as by the application of pressure selectively to the coating or by scraping. Pressure can be applied manually, with an instrument such as a knife, or brush, or with a patterned die or with a fluid such as liquid, gas or air.
The selection of coatings and patterns insofar as the aesthetic effect obtained is not critical to this invention. It should be apparent that complimentary or clashing color combinations can be selected and that practically any kind of variegated or even psychedelic pattern is possible.
It is essential to this invention that the solvent in the final decorative layer be of a type and a concentration which at least softens the layer immediately beneath it. Thus, the method of this invention does not embrace multiple coatings in which the layer beneath the final decorative layer is cured in such a way that it is not soluble in solvent used for the final decorative layer. Illustrative of underlay coatings which are not part of this invention are those which are cured by the cross-linking or oxidation with air so that they are no longer substantially soluble in or softened by the common solvent.
It is also essential to this invention that the final decorative layer be uniformly applied and then redistributed in such a way that at least certain portions, one or more of the underlying layers, become visible to form the desired pattern. Thus, the process of this invention should be distinguished from painting a house, for example, where a topcoat different in color from the primer layer is used, because the object there is to obtain a uniform top layer and not to redistribute the top layer after it is uniformly applied so that the underlayer shows through in a pattern. The process of this invention is also to be distinguished from the method commonly referred to as "antiquing" because in antiquing a final uniform layer is not applied and then selectively removed while wet and because the solvent for the final layer is not typically a solvent for the base layer. Rather, the top layer is normally applied in a streaked or speckled pattern from a solvent which does not disturb the base layer.
Finally the process of this invention is distinguished from artistic techniques used in oil or acrylic painting, for instance, where paint applied with a brush or spatula is redistributed on the surface with a spatula or other implement. In such techniques the final layer is not normally applied uniformly as in this invention but in a desired pattern which is subsequently altered.
The invention is illustrated by the following non-limiting examples.
EXAMPLE 1
As shown in FIG. 1 an earring 10 is coated with five layers by alternating layers of two different colored fingernail polishes 11 and 12. Each layer is dried briefly before the next layer is applied except that while the last layer is still wet pressure is applied to the center of the coated earring with the finger 14 covered with a tissue 13 moistened with fingernail polish remover to redistribute the coatings. A clear concentric ring effect as shown in FIG. 1 is obtained. After drying a protective coating of clear or translucent fingernail polish is applied.
EXAMPLE 2
In FIG. 2 a ring 20 coated outside the fingerhole area 21 with several layers 22 of differently colored fingernail polishes is shown. Each layer is briefly dried prior to application of the next layer. A jet of air 23 is directed against the coated area while it is still wet with the final coating. A concentric ring effect is obtained. Optionally, a protective coating of clear or transluscent fingernail polish is applied after the final decorative layers have dried.
EXAMPLE 3
In FIG. 3 a belt buckle 30 coated on its face 31 with several layers 32 of differently colored acrylic lacquers is shown. Each layer is briefly dried prior to the application of the next layer. While the final layer is still wet a die 33 with a star relief design 34 is pressed against the coated belt buckle. A star shaped design is obtained on the face of the belt buckle. After drying of the coatings the belt buckle is optionally overcoated with a clear or translucent protective lacquer layer.
EXAMPLE 4
In FIG. 4 a pendant 40 is coated on one face 41 with several layers of acrylic lacquer 42. Each coating is dried before the application of the next layer. While the final layer is still wet the coatings are redistributed with a knife 43 in the desired pattern. Some of the coating is removed and the remainder allowed to flow out and dry. After drying the pendant is optionally overcoated with a clear or translucent protective lacquer layer.
|
A process for decorating articles, such as jewelry, is disclosed in which the article is coated with two or more visibly different layers having binders soluble in a common solvent, each layer is dried before the next layer is applied and the final layer is applied wet with the solvent in sufficient concentration to at least soften the binder of any underlying layer. A pattern is made by applying pressure selectively to or otherwise redistributing the final and any at least softened underlying layer to expose one or more of the underlying layers. For example, a concentric wood ring effect is obtained by applying a greater pressure to the central portion of an article such as a ring coated with multiple layers of lacquer.
| 0
|
RELATED APPLICATIONS
The present application claims the benefit of U.S. Provisional Applications 61/262,628 and 61/319,114, the disclosures of which are hereby incorporated by reference.
TECHNICAL FIELD
The present invention relates generally to tiles for covering surfaces, and more specifically to composite tiles with the composite elements mechanically connected together, and improved methods for manufacturing said tiles.
BACKGROUND
Tiles have been used to cover different surfaces for a long time. They are used in different environments to provide different functions, for example as a hard wearing surface, decoration or water proofing. The size, shape, material and surface finishing of each tile installed in a tiling array can all be varied according to the use requirements. A tiling array as defined herein is an array of tiles in various shapes, sizes and materials that fit together to continuously cover a surface.
One type of installation is where a surface is covered in a tiling array composed of the same general type of tile, although certain characteristics such as the colour and size may be varied to produce visually appealing decorative patterns. Precise alignment of the tiles is required to achieve the visual effect.
Another type of installation is where a tile is installed as a decorative insert in another floor covering array, such as hardwood flooring or parquets where adjacent flooring planks are connected together with an interlocking tongue and groove system. Currently it is difficult to install certain types of tile, such as stone or metal tiles, as decorative inserts because such types of tiles lack coupling regions.
Traditional tiles are typically affixed to surfaces by a labour-intensive method in which each tile is individually placed on the surface and affixed thereto using adhesive between an underside of the tile and the surface. This process is repeated until the surface is covered in an array of tiles. As these traditional tiles do not have an integral positioning mechanism, the alignment process depends on the skill of the installer, who can optionally use spacing inserts or other tools. Significant time, usually at least one day, is required to allow the adhesive to harden before any grout application process can start, such that the total time is at least 2 days. This has made the installation cost high for small jobs.
A further complication arises during installation because traditional tiles have significant dimensional variance: 2 mm is not unusual, and in some cases up to 5 mm. To accommodate the variance, installers have to leave space between the tiles. The gap between the tiles is filled in a manual labour-intensive process with a material known as grout, which hardens after application. The final appearance depends on the skill of the installer applying the grout, and installation by a non professional is tedious and prone to producing an unappealing finish. The composition of the grout is varied according to the use requirement, for example in wet environments the grout provides water proofing to prevent permeation of water to the underside of the tile. The grout is usually flexible enough to accommodate any thermal expansion.
If additional layers, such as cushioning or underlay layers, need to be installed then each tile will have to be connected to the layer, which further lengthens the installation process.
There is therefore a need to manufacture a tile which can be easily and quickly installed by a non-professional and which overcomes the above drawbacks.
Various attempts have been made to produce a tile which can be readily installed in a reduced amount of time, with minimal need for manual alignment of each tile.
One example is the Snapstone® tiling system (disclosed at www.snapstone.com) produced by the Snapstone Co. LLC. This utilizes a porcelain tile which is glued to a substrate having a push fit interlocking mechanism arranged along its edges which locks adjacent tiles together. After installing the Snapstone® tiles on a floor in a floating tile installation, the gaps between the interlocking tiles are filled with grout manually.
Although an improvement on traditional tiles, the Snapstone® tiling system is a partial solution because the installation process still requires the grouting step. Additionally, the Snapstone® tile also requires the use of adhesive to fasten the tile to the substrate. This is a significant drawback because the adhesive compound can fail in use, especially through moisture damage.
Another partial solution is disclosed in U.S. patent application Ser. No. 11/701,777, the contents of which are hereby incorporated by reference. A substrate which is formed in an injection moulding process, preferably Reaction Injection Moulding (“RIM”), is attached to a pre-formed tile to form a laminated groutless tile. The means of attachment is by bonding between the substrate and tile, such as by use of an adhesive. The edges of the substrate of the resulting laminate tile are then linear milled parallel to the edges of the tile to produce coupling members.
Manufacturing a tile using reaction injection moulding is relatively slow, taking between 10 and 20 minutes to make a single tile. Additionally, use of RIM results in the dimensions of the end product varying from the designed dimensions due to dimensional changes during curing. This and the material used result in any sealing effect with adjacent substrates being sub-optimal.
The process of milling after moulding disclosed in U.S. patent application Ser. No. 11/701,777 increases the manufacturing cost and time, wastes material and space, and places restrictions on the precision and types of coupling members that can be made.
In use, the tile of U.S. patent application Ser. No. 11/701,777 suffers from substrate-to-tile debonding due to failure of the adhesive.
The invention as claimed herein overcomes some or all of the above mentioned drawbacks and provides an improved method of manufacture with lower production cost.
SUMMARY
It is an objective of the presently claimed invention to provide an improved method of manufacturing a mechanically-held tile wherein the process of directly mechanically connecting a substrate to a tile occurs during an injection process. Preferably the process of forming an interlocking system for engagement with other tiles also occurs during the injection process. The tiles thus manufactured can be placed on a subfloor in a floating tile array which can be readily removed and reused, such as an interconnecting tile array.
Herein is disclosed a method of manufacturing a mechanically-held tile, comprising providing a tile having a durable surface, an underside and an anchoring region, locating the tile in a mould, providing a substrate in the mould, and injecting a first flowable material into said mould which flows into contact and mechanically engages with the anchoring region, the said first flowable material solidifying into a retaining member which exerts a holding force on the tile and the substrate.
Tile is defined herein as a piece of material with a definite size that is usable to cover surfaces for aesthetic and/or functional purposes. It can be made from any material, for example ceramic, porcelain, natural stones of all kinds, marble, granite, limestone, sandstone, slates, artificial stone of all kinds, made with cement base or resin base, wood, plastic of all kinds, fiber board, cement, laminates, metal, glass, resin, leather, etc.
The claimed tile of the invention can have any size or shape provided it can form continuous covering of a surface when arranged together with others in a tiling array, including for example tiles in the same geometric shapes, squares, rectangles, hexagons, or any other shapes that complement each other.
A wide variety of coupling regions on the substrate may be used that facilitate connection with the coupling regions of other tiles or surface-covering materials. The coupling region is preferably provided on at least one lateral side of the substrate. The coupling region can also be partially enclosed within an underside of the substrate, facilitating easy insertion of separate coupling members. The coupling region should preferably vertically and horizontally connect a tile to an adjacent tile.
In exemplary embodiments, the coupling regions comprises cooperating male and female members, such as hook and lock, tongue and groove, interlock and snap buttons. Either or each type of members can be located along all, some or just one of the edges of the substrate in a distribution determined by the tiling system. In other embodiments such as temporary tiling arrays which are frequently re-used, only female members are provided, with removable double ended male members being inserted into some of the female members after manufacture according to the claimed invention. The above examples are just exemplary embodiments and it will be understood that a wide variety of alternative embodiments can be used. In other embodiments, the coupling members may not be formed: the composite or self-grouting tile produced will be readily layable with other similar tiles. In all cases, the tiles of the claimed invention can be laid in a floating array or affixed to the subfloor.
In exemplary embodiments, the injection system used is the insert moulding system wherein one or more components of the tile are located within the mould prior to injection in the positions relative to each other that these components will adopt in the mechanically-held tile.
In certain embodiments, providing the substrate is achieved by injecting a first flowable material, which solidifies to form said substrate integrally with said retaining member, said substrate further comprising an integral coupling region for connecting the mechanically-held tile with an adjacent coupling region.
In other embodiments, the substrate having a coupling region is provided in the mould, and the injecting comprises injecting a first flowable material into the mould which both engages an engagement region provided on the substrate and the anchoring region, and solidifies to form the retaining member. The substrate may be made of any suitable material including for example plastic, resin, metal, wood and laminates.
In yet other embodiments, the substrate is provided by injection of a second flowable material into the mould which flows into the mould forming the substrate and integral coupling region, and further comprising substantially concurrent or consecutive injection of a first flowable material to engage the anchoring region, thus mechanically anchoring the substrate to the tile by the retaining member.
The first flowable material is preferably a single common thermoplastic that is molten when heated. Preferably it sets quickly, during which it substantially maintains its volume so that shrinkage is minimized. Other materials such as resin that solidifies in by a chemical reaction in a process called Reaction Injection Molding may be alternatively used as the first flowable material. The material will flow into and fill space left in the mould.
Preferably the first flowable material is a relatively soft material capable of tightly mechanically holding the tile and substrate together. Even more preferably, when the first flowable material forms a retaining member that also functions as a grout gasket, it is waterproof and compressible but resilient when hardened, thus forming a waterproof seal between adjacent tiles when in a tiling array. The surface of the grout gasket may be patterned in the mould.
The first flowable material in certain embodiments involving concurrent injection is more than one material, so that the different desired components can have different properties and behaviors. The second flowable material where used may also have different material properties when hardened, so that different components have different properties and behaviours. For example, the first flowable material may be relatively compressible after it is set to form a grout gasket; the second flowable material may be relatively less compressible when used to form the supporting substrate. The supporting substrate provides strength and in certain embodiments connects other components such as the underlay. Preferably where a separate material is used to make the supporting substrate it is made of a low cost material. Other substantially concurrent or consecutive injections can be performed using other flowable materials to form functional layers or regions with different properties.
The material of the substrate may be one of the following thermoplastics: acrylonitrile butadiene styrene (ABS), polyethylene (PE), polypropylene (PP). Other plastics that on hardening are relatively rigid and can support the tile may be equally alternatively selected and employed by one skilled in the art without exercising any inventive activity.
The material of the grout gasket may be thermoplastic rubber (TPR). Other plastics that on hardening are relatively soft may be equally alternatively selected and employed by one skilled in the art without exercising any inventive activity.
Disclosed herein is providing the anchoring region of the tile by a surface or a step that extends from and is located generally inwardly from an outer edge of the tile. Many tiles have a suitable surface to act as the anchoring region from the original manufacturing process.
Most natural or artificial stone tiles come with a “chamfer” on all edges when they are manufactured; the original purpose is to smooth the “jagged” edges formed when stone is cut. If the tile comes with this “chamfer”, then that chamfer will constitute the anchoring region as material will flow onto the chamfer, overlapping all or a portion of the periphery of the durable surface and mechanically anchoring the substrate to the tile.
Most ceramic or porcelain tiles are made by firing pressed clay; when such clay is pressed in a pressing mold, the top of the tile is usually smaller than the base of the tile; such difference in dimension is called “rebate” which allows the pressed clay to be released from the press mold. If the tiles comes with such “rebate”, nothing need to be done as material will flow onto the rebate.
In the event that the tile does not have the chamfer or rebate when it is originally manufactured, artificial surfaces can be made on the upper surface of the tile to form the anchoring region in lieu of the chamfer or rebate. Where there is a chamfer or rebate but it is insufficient, it can be modified to provide a suitable anchoring region.
Also disclosed herein is an anchoring region of the tile provided by machining the outer edge of said tile or machining a recess in the underside of the tile.
In certain embodiments the anchoring region is formed by cutting a step or an angle on at least two or all sides of the tile by cutting tools. This method is also used if the tile is cut from a bigger tile or slab as the cut tile will naturally lack a chamfer or rebate on some or all sides. Various types of angles and steps can be employed that extend inwardly from the edge of the tile and provide a sufficient surface for the flowable material to mechanically grip. The anchoring region may have a horizontal component of about 1 mm measured from the tile edge, and the total width of the grout gasket may be about 2 mm, such that about 1 mm of the grout gasket overlays the 1 mm extent of the anchoring region. The extent of the anchoring region is selected based on the materials used to provide sufficient fixing, balanced against aesthetic considerations of the visible extent of the grout gasket in plan view. Preferably the anchoring region extends continuously around the whole periphery of the tile.
When the periphery of the durable surface is not accessible, for example when a grout gasket is not required, the anchoring region is machined or molded during tile formation in an accessible area such as the underside of the tile. Various types of recess can be employed that extend generally away from the plane of the underside and provide a sufficient surface for the flowable material to mechanically grip. This has the advantage that the tile can be securely attached mechanically, and may be optionally employed where additional mechanical anchoring is required. The size of each anchoring region on the underside is minimized in order to minimize any effect on the tile's strength. More anchoring regions on the underside may be provided when greater mechanical anchoring is needed.
In certain embodiments where the tile is disposed directly on the substrate, the substrate is provided with engagement regions that the flowable material flows into and engages with such that on solidifying to form the retaining member it mechanically holds the substrate and tile together. The engagement regions can take several forms. At the simplest, an underside of the substrate may constitute the engagement region. In other embodiments, spaced protrusions extending towards the underside of the tile and generally perpendicular to a plane of the substrate may constitute the engagement region. In other embodiments, one or more through-channels in the substrate provide access to engagement regions on an underside of the substrate. Surface gripping features may be provided on the engagement region to enhance the mechanical engagement. Preferably a plurality of through-channels are provided on the substrate so that the flowable material can flow into the channels and join up to form an interconnected structure disposed on and preferably flush with the underside of the substrate. The areas where the interconnected structure contacts the underside may comprise the engagement regions. The interconnected structure in some embodiments is an underlayment layer, which may be resilient to provide cushioning. The interconnected structure may have a grid arrangement. Preferably the channels are provided in a peripheral zone of the substrate and the first flowable material flows around a peripheral region of the tile to form a grout gasket. Preferably the interconnected structure when formed grips the substrate across a substantial portion of the underside of the substrate.
In some embodiments the substrate may be provided with a lip around its periphery extending substantially perpendicularly away from the plane of the substrate in one or both substantially perpendicular directions. The through-channels may be formed in said lip. The tile may be directly arranged on the substrate so that the flowable material flows around a vertical portion of the edge of the tile to form a rim and onto an anchoring region of the tile, but ingress between the tile and substrate is restricted. Preferably where protrusions or a lip is provided the protrusions or lip mechanically hold the tile at a minimum number of fixing points to restrict lateral movement, such as at each corner of the tile. All of the arrangements of the aforesaid engagement regions may be combined in compatible forms.
It is a further objective to provide an easy to install tile that eliminates the need for grout during installation.
It is a further objective to manufacture a tile with a very high dimensional reproducibility and reduces the need for subsequent calibration or machining.
By locating the tile in the mould and injecting a material which surrounds the periphery of the tile the dimensional variance is substantially reduced. The dimensional variance of a tile may exist in one, two or three dimensions corresponding to the width, length and thickness, and may vary across the tile as well as from tile to tile. Each can be compensated separately, depending on the position of the tile and design of the mould. For example, the thickness variation can be compensated without compensating the width and length by arranging for no flowable material to flow around the periphery of the tile. A tile with thickness compensated will have a substrate of variable thickness but the resulting composite tile will have a uniform height and can be laid flat with other tiles presenting a substantially co-planar surface. By compensating the variation to produce uniform tiles, the tiles may be aligned and spaced quickly on a surface, and form an array of level tiles.
Herein is disclosed a grout gasket formed from the first or second flowable material extending outwardly from one or more sides of the durable surface. The retaining member may function as the grout gasket.
Herein is further disclosed a grout gasket formed from the first or second flowable material which at least partially encapsulates the lateral sides and the anchoring region of the tile.
Use of a grout gasket also eliminates the need for precise positioning of the tile within the mould, provided that the flowable material can mechanically engage with the anchoring region.
In certain embodiments, one or more additional components selected from the group of strengthening ribs, a cushioning layer, a ventilation layer, a conduit layer, an underlayer and an acoustic layer are provided and fixed to the tile whilst the tile is in the mould. These functional layers may be located where required, such as on the underside of the durable surface or substrate. To prevent the tile from sounding hollow when used in a floating installation, it is preferred to provide an acoustic layer such as a layer of silicone gel on the underside of the durable surface. The functional layers may be attached by any means, but are preferably mechanically held in place by a force exerted between the durable surface and substrate by the retaining member.
Herein is further disclosed a mechanically-held composite tile comprising a tile having a durable surface, an underside and an anchoring region, a substrate disposed proximal to or in close contact with the underside, and a looping member as a grout gasket extending around a periphery of the tile and mechanically engaging the anchoring region, with at least a portion of the looping member extending into contact with an engagement portion of the substrate to exert a holding force on the substrate and tile.
The substrate may have an integral coupling region for connecting the tile with an adjacent coupling region. Tiles having such a coupling region are also referred to herein as interconnectable tiles. Tiles without an integral coupling region will also have high dimensional precision and have a grout gasket, and as such may be placed directly together or attached to a surface by known methods such as with adhesive or mounting adhesive pads.
An acoustic layer may be disposed directly on the underside of the tile. Other layers may be also provided between tile and substrate.
Preferably the looping member is formed in an injection process, and is made of a compressible but resilient material, capable of mechanically gripping and holding the tile and substrate together by itself.
The anchoring region of the tile may be provided as discussed above.
The engagement region may be provided by an underside of the substrate accessed by through-channels in the substrate.
The looping member may have portions which comprise an interconnected underlayment structure in engagement with the engagement region, which mechanically grips the substrate.
Herein is also disclosed a self-grouting tile for a self-grouting tile system, each self-grouting tile comprising a tile portion having design dimensions of a width x, a length y, and a thickness z, and actual dimensions of a width x+δ x , a length y+δ y , and a thickness z+δ z , where δ x , δ y , and δ z each represent a manufacturing deviance from x, y, and z, respectively, and δ x ranges from −0.01x to 0.01x, δ y ranges from −0.01y to 0.01y and δ z ranges from −0.05z to 0.05z, the self-grouting tile further including a mechanical anchoring region formed therein; a tile support structure surrounding all edges of the tile portion to create a tile self-grouting portion, the tile self-grouting portion integrally formed with a tile base support portion, the tile self-grouting portion having a design width and length of t x and t y respectively such that, in the x-y horizontal plane of the tile portion the design self-grouting tile dimension is x+t x and y+t y , and due to the manufacturing deviance of the tile, the actual self-grouting portion width in the x direction is t x −δ x and the actual length in the y direction is t y −δ y , the tile base support portion of the tile support structure having a vertical design thickness of t z , and an actual thickness of t z −δ z such that the self-grouting tile design dimensions in the x, y, and z directions are substantially achieved regardless of any manufacturing deviance of the tile portion; and the tile support structure self-grouting portion or the tile base support portion mechanically engaging with the tile through the mechanical anchoring region in the tile.
The tile support structure of the self-grouting tile may further include coupling regions as discussed above for facilitating interconnection with adjacent self-grouting tiles.
Other aspects of the invention are also disclosed.
The claimed method of the invention thus produces a tile as claimed faster than a tile produced by existing methods. It does not require adhesive to affix the composite parts of the tile together, nor does it need to be milled, reducing the number of post-processing steps.
The claimed tile also has greater dimensional uniformity due to the compensation of the tile's intrinsic variation in one or more dimensions, and can thus be laid fast and accurately.
BRIEF DESCRIPTION OF DRAWINGS
Embodiments of the invention are described in more detail hereinafter with reference to the drawings, in which:
FIG. 1 shows the manufacturing steps of the prior art in U.S. patent application Ser. No. 11/701,777;
FIG. 2 shows the manufacturing steps according to an embodiment of the claimed invention;
FIG. 3 shows the manufacturing steps according to another embodiment of the claimed invention;
FIG. 4 a - 4 d show different views of an embodiment of an interconnectable tile made according to the claimed invention;
FIGS. 5 a and 5 b illustrate an alternative embodiment of a tile according to the claimed invention.
FIG. 6 shows different exemplary embodiments of forming the anchoring region on a tile according to the claimed invention;
FIG. 7 a - 7 e show different exemplary embodiments of coupling regions that can be employed with the claimed invention;
FIGS. 8 a and 8 b illustrate a method used to manufacture an interconnectable tile; FIG. 8 c illustrates an example of a finished tile according to the claimed invention; FIGS. 8 d and 8 e illustrate a method used to manufacture an interconnectable tile according to a further embodiment; FIG. 8 f illustrates a tile made by the method of FIGS. 8 d and 8 e.
FIGS. 9 a and 9 b illustrate a tile according to the claimed invention installed as a decorative insert and as a parquet respectively
FIGS. 10 a and b illustrate the plan and cross-sectional views respectively of a tile dimensionally compensated according to the claimed invention.
DETAILED DESCRIPTION
Improved methods of making a mechanically-held tile in an injection process using a pre-formed component are disclosed herein.
In the following description, the methods of manufacture of the mechanically-held tile and the like are set forth as preferred examples. It will be apparent to those skilled in the art that modifications, including additions and/or substitutions may be made without departing from the scope and spirit of the invention. Specific details may be broadly described so as not to obscure the features of the invention; however, the disclosure is written to enable one skilled in the art to practice the teachings herein without undue experimentation.
FIG. 1 shows four steps of a prior art method of manufacturing a tile with an interconnecting mechanism. Firstly, a standard tile is located 100 in a mould with its durable surface flush against one of the surfaces of the mould. Then, a flowable material is injected 105 into the mould, flowing around the tile and into spaces left in the mould between tile and mould walls to form the substrate and an oversized surrounding lip. The tile and substrate are joined by non-mechanical methods. Thirdly the tile with substrate is removed from 110 the mould and finally a flange is milled 115 in the substrate where it protrudes from the sides of the tile to form an interconnecting mechanism.
FIG. 2 shows an improved method according to the current invention, which has a reduced number of steps. A tile with anchoring region is located 200 first in a mould, with the durable surface flush against a surface of the mould. This is followed by injection 205 of a flowable material into the mould, flowing around the tile and into spaces between the tile and mould to form the substrate. The mould walls have a shaped surface corresponding to a negative profile of a desired coupling region, such that the flowable material flows into and abuts against the shaped surface to form the coupling region during injection. The flowable material during injection 205 flows around gaps between the mould wall and tile, into engaging contact with an anchoring region of the tile to mechanically engage it and self-anchor the substrate and tile together. The gap is about 1 mm around the periphery of the durable tile. The tile can be removed 210 from the mould when the flowable material has sufficiently hardened to form a retaining member.
Referring to FIG. 3 , an alternative embodiment of the method in which both a tile is located 300 in a mould and a substrate with a coupling region is also located 305 in the same mould. The locating 300 , 305 steps are shown at an equivalent position in time because depending on the configuration of the mould the order of placing in the mould can be varied, or carried out simultaneously. Once arranged in the mould such that the anchoring regions are fluidly accessible, a flowable material is injected 310 into the mould, flowing into the fluidly accessible regions and into engaging contact with the anchoring region on the tile and the engagement region on the substrate. The tile can then be removed 315 from the mould when the flowable material has sufficiently hardened.
FIG. 4 a shows a plan view of a square tile with a durable surface 400 , having a grout gasket 405 formed by injection of a fluid material. The grout gasket 405 surrounds all of the edges of the durable surface of the tile. A pair of protruding male members 410 is disposed at a spaced interval on the substrate 415 ( FIG. 4 b ) on two adjacent sides of each tile. The male members 410 are for cooperation with female members 420 ( FIG. 4 b ) in the substrate.
FIG. 4 b shows an underside of the tile of FIG. 4 a but omits the tile.
In section views FIGS. 4 c and 4 d it can be seen that the grout gasket 405 extends upwardly from the substrate to cover all of each lateral edge of the tile. FIG. 4 d is an enlarged view of an edge of 4 c , in which an inwardly sloping surface on the upper edge of the tile forms the anchoring region 425 .
FIG. 5 a shows an exploded layered view of an alternative embodiment of the tile according to the claimed invention. Tile 500 is disposed for fluid-tight contact on a substrate 505 , which has a lip 510 around its periphery. Through-channels 515 are provided in the periphery of the substrate and extend through the lip. In the embodiment shown the through-channels 515 are open on one side. A grout gasket 520 forms a looping member around a peripheral region of the tile 500 . Spaced protrusions 525 extend downwardly from all sides of the grout gasket 520 , into and through the through-channels 515 . Extending in a plane across an underside of the substrate 505 from each of the protrusions 525 is an interconnected grid structure 530 , formed during the injection process.
FIG. 5 b shows a view of the underside of the finished tile of FIG. 5 a . The interconnected structure 530 is disposed tightly on the underside 535 of the substrate. The interconnected structure generally comprises a grid, having evenly spaced intersecting lines arranged at approximately 45 and 90 degrees to each other. Reinforcement is provided where the lines intersect. A peripheral line closest to and parallel with the edges of the substrate has discontinuities where the underside 535 of the substrate has a recess, such as coupling regions 540 in the form of arrow-headed female members. A replaceable double-headed male member (not shown) can be inserted into two opposing female members on two adjacent interconnectable tiles to connect the tiles. The intersecting lines may be wholly or partially received in guideways (not shown) in the underside of the substrate. Areas of the underside of the substrate away from the guideways may be relatively recessed to minimize material usage.
The embodiment of FIGS. 5 a, b is made by placing the substrate 505 , which has the through-channels, and coupling regions 540 in the mould in sequence with the tile 500 , the tile's durable surface being flush against a surface of the mould, but with its edges being spaced from the mould walls. A first flowable material plastic is then injected into the closed mould. The flow of the plastic material will vary depending on the mould design, but it will flow on a portion of the underside 535 of the substrate, and via guideways (not shown) will join up to form the interconnected grid structure 530 . The regions where the interconnected structure 530 contacts the underside 535 comprise all or part of the engagement regions. The guideways may be provided in the mould wall or in the underside of the substrate. The plastic also flows through the through-channels towards the tile, and towards the sides of the tile to form the grout gasket 520 . The plastic will also flow to the anchoring regions on the durable surface of the tile, and will mechanically anchor everything together after solidifying into a single piece.
Referring now to the top three illustrations of FIG. 6 , various examples of anchoring regions 600 on an upper edge of the tile are shown. A sloping surface extending over a partial (such as a natural chamfer) or a full height (such as made by a cutting saw) of the edge or an inward step can be used, and other non-shown variants will be realizable by the skilled user. The 4 th illustration of FIG. 6 shows a tile where the anchoring region is a rebate 605 drilled or molded during tile formation into an underside of the tile. The lateral extent on the underside, distribution and depth can be varied, as can the shape and size of the rebate 605 . The rebate 605 has a pinch point located towards the underside of the substrate such that once fluid material has flowed into the rebate and solidified, the solidified material cannot be removed.
FIGS. 7 a , 7 b and 7 d are side views illustrating different exemplary male 700 and female 705 coupling members for functioning as cooperating coupling regions. In FIG. 7 d internal detail of a coupling region is also shown in dotted lines. They show hook and lock, tongue and groove, and interlock respectively. FIGS. 7 c and 7 e are bottom views. FIG. 7 c shows snap buttons, whereas FIG. 7 e shows coupling members comprising two female members and a double headed male insert as connector.
FIG. 8 a shows the first step of a method according to the invention: locating the tile in a shaped mould. Tile 800 has a chamfer 805 around its periphery. Anchoring regions in the underside (not shown) may also or alternatively be used. The tile is located in the lower half of a mould 810 with the durable surface flush against a floor of the mould 810 . Space is provided around the sides of the tile 800 . The upper half of the mould has the female profile 815 of the desired substrate and integral coupling region.
In FIG. 8 b the two halves of the mould are fluid tightly joined, and flowable material is injected to form a one-piece substrate 820 and grout gasket 825 around the tile. FIG. 8 c shows an interconnectable tile after the injection process of FIG. 8 b has terminated. In the exemplary embodiment of FIGS. 8 a - 8 c , a tongue-and-groove coupling region is formed; however, it is understood that other coupling geometries, including, but not limited to, the coupling configurations of FIGS. 7 a - 7 e can be formed by the process of FIGS. 8 a - 8 b by selection of a corresponding mould configuration.
FIGS. 8 d and 8 e depict a molding method for forming a tile with a substrate portion and a further molded portion such as the tile of FIG. 5 . The tile 800 with the chamfered portion 805 is placed in the first half of the mould. Substrate 840 , substantially corresponding to substrate 505 of FIG. 5 , is placed behind tile 800 or alternatively is molded to tile 800 in a separate molding step. Substrate 840 includes through-channels 845 through which a polymeric material can flow. Flowable polymeric material 820 is injected into the mold to create gasket/grout portion 825 and the interconnected regions depicted in FIG. 5 (not visible in the cross-sectional views of FIGS. 8 d and 8 e ). The finished tile of FIG. 8 f is substantially similar to that of FIG. 5 b . While the tile of FIG. 5 b is configured to receive a double-headed male interconnecting element, it is understood that the process of FIGS. 8 d and 8 e can be used to form other interconnection structures, either male or female, through selection of the appropriate mould shape.
For different applications, the interconnectable tile can be installed in combination with other covering materials that already have a connecting system, for example solid and engineered wood planks, parquet systems and so on. In such cases, the coupling regions of the interconnectable tile should be capable of cooperating with those of the other covering materials to form a mating couple. Examples of other covering materials include wood planks and parquet, laminate, bamboo, etc. that come with interconnecting systems such as tongue and groove. FIG. 9 a shows an interconnectable tile 900 in a floor covering of tongue and groove wooden planks 905 . FIG. 9 b shows an interconnectable tile 900 in a parquet array 910 . Although the same reference numeral is used to refer to the tile, the tile may have various configurations and coupling regions.
FIG. 10 a shows a plan view of a self-grouting tile 1000 which has nominal dimensions of x and y in the length and width dimensions and manufacturing deviations δ x , δ y , in the x and y dimensions respectively. Typically, δ x ranges from −0.01x to 0.01x and δ y ranges from −0.01y to 0.01y The nominal design thickness of the grout is t x and t y respectively, such that, in the x-y horizontal plane of the tile portion, the nominal design self-grouting tile dimension is x+t x and y+t y . However, due to the manufacturing deviance of the tile, the actual self-grouting portion width in the x direction is t x δ x and the actual length in the y direction is t y −δ y . Thus the actual tile dimensions are compensated by the surrounding tile self-grouting portion 1005 such that the width is x+(t x −δ x ) and the length is y+(t y −δ y ) resulting in a length and width of the tile plus self-grouting portion substantially equal to the design dimensions regardless of the actual dimensions of each individual starting tile.
Similarly, the tile base support portion of the tile support structure has a vertical design thickness of t z , and an actual thickness of t z −δ z such that the thickness is z+(t z −δ z ).
The tile self-grouting portion 1005 formed integrally with the tile base support portion 1010 ( FIG. 10 b ) constitutes the tile support structure. The dimensions shown in FIG. 10 are representative only and not to scale. In a typical tile, the variation in the x and y directions is about 3 mm (1%). In the z direction it may be up to +/−0.4 mm (5%). Although not shown, the deviation may vary across the tile and therefore so will the compensation.
Thus in a particular example, if a tile of 305 mm×305 mm×8 mm, being the length, width and height respectively, the tile will come with manufacturing deviances as shown in Table 1 below.
After compensation by the tile support structure the self-grouting tile will have substantially reduced dimensional variance as shown in Table 1, with figures rounded to nearest significant place.
TABLE 1
Tile actual
%
Compensated
%
Dimension
dimensions/mm
variation
dimensions/mm
variation
X
305 +/− 3
1
307 +/− 0.1
0.04
Y
305 +/− 3
1
307 +/− 0.1
0.04
Z
8 +/− 0.4
5
11 +/− 0.1
0.01
The injection process substantially compensates whatever dimensional variation of the decorative body, resulting in this example in a substantially reduced dimensional variance of 0.1 mm in all three dimensions.
FIG. 10 b illustrates how a manufacturing deviations δ z of the tile in the z dimension can be compensated by the tile base support portion of design thickness t z.
The anchoring region of the tile and coupling regions are not shown but are as discussed above with reference to other embodiments.
The foregoing description of embodiments of the present invention is not exhaustive and any update or modifications to them are obvious to those skilled in the art. Reference is made to the claims for determining the scope of the presently claimed invention.
INDUSTRIAL APPLICABILITY
The claimed invention is suitable for use in the tile manufacture and installation industry, particularly in the manufacture of interconnecting tiles in a one-step thermoplastic injection process. It is also suitable for use in providing tiles that can be used with a wide variety of interlocking materials that provide coverage of surfaces, such as wooden flooring systems and as a decorative insert.
|
A method of making a mechanically-held tile is disclosed by providing a tile having a durable surface, an underside and an anchoring region, locating the tile in a mold, and injecting a polymer into the mold to form a substrate with an integral coupling region. Alternatively, a substrate can be provided in addition to the tile; the injected material mechanically anchors the substrate to the tile. A surrounding grout gasket can also be formed during injection. Injections can be consecutive or concurrent to tailor the properties of the substrate, grout gasket and other layers or regions. Also disclosed is a multi-part tile made by such a process, and a tile with intrinsic manufacturing deviations compensated by a grout gasket. The tile can be interconnected via the coupling regions with other surface-covering materials.
| 4
|
REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation-in-part of PCT/US2011/023717, filed Feb. 4, 2011, published on Aug. 11, 2011, as WO 2011/097458, which claims the benefit of U.S. Provisional Patent Application No. 61/301,389, filed Feb. 4, 2010. The disclosures of the above applications are hereby incorporated by reference in its entirety into the present disclosure.
STATEMENT OF GOVERNMENT INTEREST
[0002] This invention was made with government support under Grant Nos. CA68409, CA122093 and CA55791 awarded by National Institutes of Health. The government has certain rights in the invention.
FIELD OF THE INVENTION
[0003] The present invention is directed to devices for photodynamic therapy (PDT) and more particularly to such devices for irradiating complex surfaces of the oral cavity and possibly other anatomic sites. The present invention is further directed to the corresponding methods for making and using such devices.
DESCRIPTION OF RELATED ART
[0004] Currently, PDT of cancer and precancer and other lesions within the oral cavity is performed using lens-terminated optical fibers that deliver a cone of light in the forward direction. Such fibers are often handheld and pointed by the physician to the target area. Surfaces near the back of the tongue are very difficult to irradiate in that way. Irregular surfaces along gum lines and under the tongue typically receive non-uniform irradiation that is extremely difficult or impossible to characterize and leads to imprecise and irreproducible dosimetry. Further, light reflected from the irradiated surface exposes normal tissue in the mouth to light, which leads to normal tissue damage unless those areas are carefully shielded prior to irradiation. That is very time consuming and adds significantly to the cost and complexity of the procedure.
SUMMARY OF THE INVENTION
[0005] A need thus exists in the art to solve both of the above problems.
[0006] It is therefore an object of the invention to provide such a solution.
[0007] It is another object of the invention to provide optimal administration of photodynamic therapy irradiation to complex surfaces of the oral cavity.
[0008] It is still another object of the invention to provide an approach that may be suitable to other anatomic sites where conforming the treatment field and shielding nearby normal tissues are important.
[0009] To achieve the above and other objects, the present invention is directed to various embodiments of PDT in which the irradiation is conformed to the target tissue surface. A device for conforming photodynamic therapy to a specific anatomic location (e.g., in the oral cavity) conforms the radiation to the target tissue surface and avoids delivering light to the rest of the oral cavity. A first embodiment has a body of oral impression material molded to conform to the anatomic surface, a light source at least partially embedded in body of oral impression material and a reflective surface formed on the body of oral impression material. A second embodiment has a light pipe comprising a straight section, a reflective coating on the straight section and an output window on the straight section, the light pipe having an input end, and a light source connected to the input end. A third embodiment has a light source, an optical body having an output window and a hole for insertion of the source, and a freeform reflector formed on a surface of the optical body. In fourth and fifth preferred embodiments, one surface of the light guide is textured to direct light to an output window on the opposing side. In those embodiments, the light guide can be flexible to conform the output window to a lesion to be treated.
[0010] By conforming the irradiation to the target tissue surface, the PDT light dose becomes more uniform and more reproducible and is much easier to characterize. The device makes direct contact with the target tissue surface, and the sides and back of the device are coated with reflecting material. Therefore, there is minimal or no light delivered to the healthy surrounding tissue. That will minimize or eliminate the need for shielding normal tissue during treatment.
[0011] The invention enables more uniform and reproducible irradiation of specific tissue surfaces and eliminates or greatly reduces the need for shielding of normal tissue in the oral cavity and other anatomic sites, including those where irregular or difficult to reach surfaces create significant challenges to clinicians.
[0012] Any of the preferred embodiments, or any other embodiment, can be implemented as a “use once” disposable device. Also, the present invention can be used in dermal applications to treat stubborn spots or in cases in which only a determined region needs to be treated.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Preferred embodiments of the invention will now be set forth in detail with reference to the drawings, in which:
[0014] FIG. 1 shows a device according to a first preferred embodiment;
[0015] FIG. 2 shows a device according to a second preferred embodiment;
[0016] FIG. 3 shows a device according to a third preferred embodiment;
[0017] FIG. 4 shows a device according to a fourth preferred embodiment; and
[0018] FIG. 5 shows a device according to a fifth preferred embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] Preferred embodiments of the present invention will now be set forth in detail with reference to the drawings, in which like reference numerals refer to like elements or steps throughout. Five preferred embodiments will be disclosed, although those skilled in the art who have reviewed the present disclosure will readily appreciate that other embodiments can be realized.
[0020] The first preferred embodiment, shown in FIG. 1 as 100 , exploits a combination of oral impression materials and cylindrical diffusing tip optical fibers. Oral impression materials are available commercially and are used routinely to create molds of surfaces in the oral cavity. For example, those materials may be used to create a mold for an oral prosthesis.
[0021] In the first preferred embodiment, the material 102 is introduced into the oral cavity at the site to receive photodynamic therapy. The material hardens and assumes the shape of the tissue surface T intended to receive the PDT. It is then removed, and surfaces 104 of the impression material 102 not contacting the tissue T to be treated are coated with highly reflecting material 106 to eliminate irradiation of normal tissue and direct the light back to the treated tissue surface T.
[0022] To enable light delivery, a cylindrical diffusing tip optical fiber 108 , a linear array of light emitting diodes, or another suitable source is introduced into the oral impression material 102 at the time it is introduced into the oral cavity—that is, prior to hardening. Thus, the light delivery source 108 is embedded into the form-fitting oral impression material, and a connection 110 to a laser or an LED power supply (not shown) is also provided. The light delivery source 108 embedded into the oral impression material 102 is envisioned as a “use once” disposable. Other geometries are straightforward extensions of that idea.
[0023] The second preferred embodiment uses lightpipes to achieve both high illumination uniformity and efficiency. Lightpipes are routinely used in non-imaging optics, but they require significant expertise and design effort to achieve the required illumination quality given specific application constraints.
[0024] FIG. 2 shows a device 200 according to the second preferred embodiment. The device 200 comprises a straight lightpipe section 202 and an optional tapered lightpipe section 204 . This configuration is illustrative rather than limiting; other configurations may include a straight section, a tapered section, a freeform section, or any combination of these. A light source 206 such as a light-emitting diode or an optical fiber illuminator is connected to the input end of the device. The shape of the opposite end 208 of the lightpipe is tailored to extract light outside the device and deliver uniform illumination into the oral cavity. Another possibility is that light exits directly from that side without being reflected to the side window. In the example shown, the lightpipe end 208 is cut at an angle so that light exits the device through a side window 210 . The lightpipe length and shape are optimized to homogenize light and provide high illumination uniformity at the device output. The tapered lightpipe section 204 , which is optional, provides improved compactness.
[0025] The device 200 can be either hollow or solid and, as noted above, can be composed of a straight section, a tapered section, a freeform section, or any combination of these. Hollow lightpipes use reflective material 212 on the lightpipe walls to guide light within the lightpipe. Solid lightpipes can be made of glass or plastic and use either reflective coatings or total internal reflection to contain light within the lightpipe. If a reflective coating is used, a window such as the window 210 depicted in FIG. 2 must be left uncoated so that light can exit the device.
[0026] The device 200 simply needs to be connected to a fixed light source 206 and is envisioned as a “use once” disposable. Alternatively, a removable and disposable jacket covering the device can be used if multiple uses are desired.
[0027] The third preferred embodiment, shown in FIG. 3 as 300 , uses a tailored freeform reflector shape 302 to provide uniform illumination in the oral cavity. Light delivery is achieved with an array of light-emitting diodes or a cylindrical fiber diffuser 108 similar to the one used in the first preferred embodiment. The source 108 is inserted through a hole 306 in the sidewalls 308 of the device 300 to allow precise positioning of the source 108 relative to the reflector 302 . The device 300 is hollow, but a material 310 with scattering properties may be used to fill the device 300 and improve illumination uniformity. All surfaces 314 are reflective except a transparent window 312 that allows light to be extracted outside the device 300 . In the example shown, the window 312 is placed at the extremity of the front end 316 of the device 300 , but its position and size may vary.
[0028] The back end of the device 300 is made of the freeform reflector shape 302 optimized to obtain high light extraction efficiency and high spatial illumination uniformity. The shape is optimized from a first-order shape sometimes used for solar concentrators with cylindrical absorbers. That first-order shape is derived using the general edge-ray principle of non-imaging optics. Provided an optimal placement of the source with respect to the reflector, cylindrical reflectors may also be optimized.
[0029] The device 300 is envisioned as a “use once” disposable. Alternatively, a removable and disposable jacket covering the device can be used if multiple uses are desired.
[0030] The fourth preferred embodiment, shown in FIG. 4 as 400 , is based on an approach similar to those used in the design of backlight displays to provide a targeted illumination with known dosimetry. Light from an array 402 of optical fibers connected to a light source (such as a laser, not shown) or an array of light emitting diodes is coupled to a light guide 404 made of plastic or another suitable material. One side 406 of the light guide 400 is textured in an appropriate way to cause light extraction from the light guide 400 towards the side 408 opposite to the textured side, referred to as the output window.
[0031] A fifth preferred embodiment, similar to the fourth preferred embodiment, is shown in FIG. 5 as 500 . An optical fiber 502 connected to a light source (such as a laser, not shown) or a light emitting diode is coupled to a light guide 504 made of plastic or another suitable material. An initial portion 506 of the light guide 504 may optionally be tapered to increase the size of the light guide. One side 508 of the light guide is textured (partially or entirely) in an appropriate way to cause light extraction from the light guide towards the side 510 opposite to the textured side, referred to as the output window.
[0032] One major advantage of the fourth and fifth preferred embodiments is that if the plastic material selected is flexible, the shape of the output window 408 or 510 can conform to non-flat lesions for an optimal treatment. Additionally, used in near-contact in the oral cavity, the device of the fourth or fifth preferred embodiment avoids having to shield the healthy tissue prior to treatment. Simulations show that the fourth and fifth preferred embodiments can achieve desired performance.
[0033] While five preferred embodiments and variations thereon have been disclosed above, those skilled in the art who have reviewed the present disclosure will readily appreciate that other embodiments can be realized within the scope of the invention. For example, disclosures of specific light sources are illustrative rather than limiting, as other light sources can be used, such as a fiber, an optics-terminated fiber such as a lens-terminated fiber or a fiber terminated with a diffractive optical element, an array of light-emitting diodes, or a combination of these. Also, one or more such light sources can be used. Moreover, some or all of the features of multiple embodiments can be combined. Therefore, the present invention should be construed as limited only by the appended claims.
|
A device for conforming photodynamic therapy to a specific anatomic location (e.g., in the oral cavity) conforms the radiation to the target tissue surface and avoids delivering light to the rest of the oral cavity. Embodiments can include a body of oral impression material molded to conform to the anatomic surface, a light pipe, a freeform reflector formed on a surface of the optical body, or a light guide having a textured surface to direct light to an opposing output window. The light guide can be made of flexible plastic to conform the output window to the lesion.
| 0
|
CROSS REFERENCE TO RELATED APPLICATIONS
The present application is a continuation application of U.S. patent application Ser. No. 09/939,655, filed on Aug. 28, 2001, now U.S. Pat. No. 6,577,525 issued on Jun. 10, 2003, the disclosure of which is herewith incorporated by reference in its entirety.
FIELD OF THE INVENTION
The present invention relates to the field of resistor-based memory circuits. More particularly, it relates to a method for precisely sensing the resistance value of a resistor-based memory cell, for example, a Magnetic Random Access Memory (MRAM) magnetic memory cell.
BACKGROUND OF THE INVENTION
A resistor-based memory such as a magnetic random access memory (MRAM) typically includes an array of resistor-based magnetic memory cells. The logic state of such a magnetic memory cell is indicated by its resistance. One resistance value, e.g., the higher value, may be used to signify a logic high while another resistance value, e.g., the lower value, may be used to signify a logic low. The value stored in each memory cell can be determined by measuring the resistance value of the cell to determine whether the cell corresponds to a logic high or low. Such direct measurements are often difficult to simply and easily implement and require a number of comparators which increases the cost and size of the memory circuit. A simplified, more reliable method of sensing the resistance value of a resistor-based memory cell is desired.
SUMMARY OF THE INVENTION
The present invention provides a simple and reliable method and apparatus for sensing the logic state of a resistor-based memory cell. Resistance is measured by first charging a first capacitor to a predetermined voltage, discharging the first capacitor through a resistance to be measured while discharging a second capacitor through an associated reference resistance of known value and comparing the discharge characteristics e.g. the discharge voltage of two capacitors to determine a value of resistance to be measured relative to the reference resistance.
In one exemplary embodiment, a pair of second capacitors are used, each discharging through an associated reference resistance, one having a value corresponding to one possible resistance value of the resistance to be measured and the other having a value corresponding to another possible resistance value of the resistance to be measured. The combined discharge characteristics of the pair of second capacitors, e.g. an average of the discharge capacitor voltage, is compared with the discharge characteristics e.g. the discharge voltage of the first capacitor to determine a value of the resistance to be measured relative to an average value of the two reference resistances.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other features and advantages of the invention will become more apparent from the detailed description of the exemplary embodiments of the invention given below with reference to the accompanying drawings in which:
FIG. 1 shows the invention employed in an exemplary MRAM device;
FIG. 2 shows a schematic diagram of one aspect of the invention;
FIG. 3 shows a schematic diagram of an additional aspect of the invention;
FIG. 4 shows the discharge rate characteristics of capacitors employed in the invention;
FIG. 5 shows a schematic diagram of an additional aspect of the invention;
FIG. 6 shows a schematic diagram of an additional aspect of the invention; and
FIG. 7 shows the invention utilized in a computer system.
DETAILED DESCRIPTION OF THE INVENTION
A portion of a MRAM array 100 with which the present invention may be used is shown in FIG. 1 . The logical state of an MRAM memory element e.g. 204 is represented by the resistance of that element. In the present invention, resistance is determined by holding a voltage constant across a cell's resistive element and comparing a voltage produced by the current that flows through that resistive element with a voltage produced by the current flow through a known reference resistance. To read the binary state of a memory cell element, the absolute magnitude of resistance need not be known; only whether the resistance is above or below a value that is intermediate to the logic high and logic low values. Accordingly, to provide a reference current flow for comparison purposes the resistive elements within rightmost column 108 of array 100 are preprogrammed to hold all ‘0’ values, while those within column 110 immediately to its left are preprogrammed to hold all ‘1’ values. The current flowing through these two columns when a particular row line of the array 100 is selected by grounding a rowline, e.g. rowline 120 , will heretofore be designated as I 0 and I 1 as shown in FIG. 1 .
During the reading process, all column and row lines are driven with the same array voltage V A , except for the one row line, e.g. 120 that is desired to be read. That row line 120 is driven to ground. When row 120 is grounded, a resistive element of a selected column, e.g. column 109 , can be read by a sensing circuit 300 described below As shown in FIG. 1, both ends of all resistive elements not being measured are maintained at the same potential, V A . Thus, unwanted current flow through these resistive elements due to “sneak” resistance is negligible. A current I sense flows through the grounded resistive element of a selected column within the row 120 for allowing measurement of the resistance by the sensing circuit 300 (not shown in FIG. 1 ).
FIG. 2 shows a circuit 200 for regulating current through and voltage across a resistive element 204 being measured. An operational amplifier 220 has one terminal 222 connected to V A , while the other terminal 224 is connected to the column line 109 for the resistance element 204 which is being sensed. The gate 242 of NMOS transistor 240 is connected to the output of operational amplifier 220 . The source 246 of transistor 240 is connected to one terminal of the resistive element 204 being read, while the other terminal of resistive element 204 is driven to ground by the grounding of wordline 120 described earlier. Operational amplifier 220 and transistor 240 act in concert to keep one terminal of resistive element 204 stably at V A despite the fact that the other terminal is grounded. In this way, I sense can flow through transistor 240 and resistive element 204 , while current lost through sneak resistor 225 is minimized.
To sense the amount of resistance of resistance element 204 , the current flow through resistance element 204 must be determined, since the voltage across resistance element 204 is held constant at V A . FIG. 3 shows how the current regulating circuit 200 combined with a voltage comparator 304 , and a reference voltage generating circuit 115 to provide a method and apparatus for determining current flow through sensed resistance element 204 . As shown in FIG. 3, the active wordline 120 is also connected to reference resistance elements R0 and R1 associated with column lines 108 and 110 , which are pre-set to ‘0’ and ‘1’ resistance values respectively. Each column line of array 110 which has resistance elements which may be written to or read has its own sensing circuit and comparator which are active when the column is addressed to select with the grounded rowline, which resistive memory element within a given row is being read. Thus, connection line 320 shows how the reference voltage generating circuit 115 is connected to other columns of array 100 . As noted, each column line (e.g. 109 shown in FIG. 3.) has a voltage having a reference input 113 and sensed voltage input 116 .
The reference voltage generating circuit 115 includes a first 202 and second 244 regulating circuit each associated with a respective reference resistance element 108 , 110 . These regulating circuits respectively hold the voltage across reference resistors elements 108 and 110 at V A in the manner described above with reference to FIG. 2 . The resistance elements R 0 , R 1 have respective known resistance values corresponding to one of the logic states of a memory element and the other corresponding to the other possible logic state. The reference voltage generating circuit 115 also includes capacitors C 1 and C 0 respectively associated with the reference resistance elements R 0 and R 1 . Each of the capacitors C 1 and C 0 has one lower terminal grounded and the other upper terminal connectable to a common voltage line 132 through a respective switch element 134 , 136 . The switch elements 134 , 136 are configured to connect the upper terminals of the capacitors C 1 , C 0 to either a source of voltage V A or to the common voltage line 132 . The common voltage line 132 is connected to the reference voltage input 113 of comparator 304 .
As noted, the comparator 304 also has a voltage input 116 . This is connected through another switch element 206 to an upper terminal of a sensing capacitor C sense , the lower terminal of which is grounded. Switch element 206 is adapted to connect the upper terminal of comparator C sense to either a source of voltage V A or to the input 116 of comparator 304 . The input 116 is also connected to the upper (drain) terminal of transistor 240 which has it's source terminal connected to the resistance element 204 , the resistance of which is to be measured.
All of the switch elements 134 , 136 and 206 switch together to either connect the upper terminals of capacitors C sense , C 1 , an C 0 to the voltage V A , or to connect the upper terminal of capacitor C sense to input 116 and the upper terminals of capacitors C 1 and C 0 to common voltage line 132 . When the switch elements are in the latter condition the capacitors C sense , C 1 , and C 0 are connected in a way which provides the current flows I0, I1 and Isense through respective resistance elements R0, R1 and 204 .
The circuit of FIG. 3 operates as follows. Capacitors C sense , C 1 , and C 0 are first fully charged to V A by switch elements 134 , 136 206 simultaneously connecting their upper terminals to a V A voltage source. After the capacitors C sense , C 1 , and C 0 are charged the switch elements 134 , 136 , and 206 are simultaneously operated to connect the upper terminal of capacitor C sense to input 116 and the upper terminal of capacitors C 0 and C 1 to the common voltage line 132 . As a result all three capacitors begin discharging in unison in the direction symbolized by current flow arrows I sense , I 1 and I 0 . The rate at which the capacitors C 1 and C 0 discharge is determined by the resistance of the path through which they discharge.
The capacitor C sense will also discharge through resistance element 204 and the decaying voltage on capacitor 204 is applied to sense voltage input 116 of comparator 304 . The discharge of both capacitors simultaneously will provide a reference voltage on voltage line 132 which is the average voltage instantaneously on capacitors C 1 , C 0 . Thus, as capacitors C 1 and C 0 discharge, this average voltage will decay. This average voltage is applied to the reference voltage input of comparator 304 . The capacitor C sense will discharge significantly faster if resistance element 204 has a resistance representing a ‘0’ value (e.g. 950 KΩ) than a resistance representing a ‘1’ value (e.g. 1 MΩ). Consequently, the voltage on C sense will discharge either more slowly or more quickly than the average voltage discharge of C 1 and C 0 , hereafter noted as V av . The combined average voltage across capacitors C 1 and C 0 as seen by comparator 304 decays with time as shown by V av in FIG. 4. V av falls between the decaying voltage on capacitor Csense when a logical ‘1’ and a ‘0’ resistance is set in resistance element 204 . Because the resistive memory element 204 being sensed will either store a 1 or a 0, its discharge voltage V sense will (intentionally) never be equal to V av , instead V sense will always be measurably higher or lower than V av . Accordingly, the difference between the sensed and reference discharge voltages (V sense and V av ) will be compared by the comparator 304 at sense time t sense , which will provide an electrical ‘1’ or ‘0’ output representing the stored logic value of resistance element 204 .
Thus, determining whether a resistive memory element holds a ‘1’ or a ‘0’ does not require quantitatively measuring V sense , instead, it is only necessary to compare V sense with V av using a comparator 304 . A circuit for comparing V sense to V av can be achieved with less components than a circuit for quantitatively measuring V sense . The frequency with which the voltages V sense and V av can be compared is limited only by the capacitance values of C 0 , C 1 , and C sense which must also produce an integrating effect across their respective resistance elements.
FIG. 5 shows an alternative embodiment in which only a single capacitor C av is used in the reference voltage across 115 a . In such an embodiment, the desired V av could be obtained by discharging capacitor C av across a single resistor R median of known value which lies between resistance values corresponding to a logical ‘0’ and ‘1’ value. For example, if 950 KΩ corresponds to a typical MRAM resistance for a binary ‘0’, and 1 MΩ corresponds to the typical MRAM resistance for a binary ‘1’, then a median resistance value is set for example at 975 KΩ. By discharging capacitor C av across such a median resistance, a value for V av for comparison with V sense can be provided. In this embodiment, the R median resistance can be provided by using a single column, e.g. 108 , of reference resistance elements in array 100 having this value, or dispensing with reference resistance element in the array in favor of an out-of array reference resistance element which has the R median value.
FIG. 6 illustrates how the current regulating circuit 200 and sensing circuit 300 of the invention are arranged with a memory array 100 . In FIG. 6, the columns which connect with storage resistive elements are labeled 107 , 109 , while the reference columns remain shown in 108 , 110 .
The sensing circuit 300 of the present invention compares two discharge voltages V sense and V av and immediately makes a determination which logical value to output on bit-out line 330 . Thus, a method and apparatus for quickly measuring MRAM values while minimizing the number of necessary components is achieved.
FIG. 7 is a block diagram of a processor-based system 350 utilizing a MRAM array 100 constructed in accordance with one of the embodiments of the present invention. The processor-based system 350 may be a computer system, a process control system or any other system employing a processor and associated memory. The system 350 includes a central processing unit (CPU) 352 , e.g., a microprocessor, that communicates with the MRAM array 100 and an I/O device 354 over a bus 356 . It must be noted that the bus 356 may be a series of buses and bridges commonly used in a processor-based system, but for convenience purposes only, the bus 356 has been illustrated as a single bus. A second I/O device 306 is illustrated, but is not necessary to practice the invention. The processor-based system 350 also includes read-only memory (ROM) 360 and may include peripheral devices such as a floppy disk drive 362 and a compact disk (CD) ROM drive 364 that also communicates with the CPU 352 over the bus 356 as is well known in the art.
While the invention has been described and illustrated with reference to specific exemplary embodiments, it should be understood that many modifications and substitutions can be made without departing from the spirit and scope of the invention. Accordingly, the invention is not to be considered as limited by the foregoing description but is only limited by the scope of the appended claims.
|
An MRAM memory integrated circuit is disclosed. Resistance, and hence logic state, is determined by discharging a first charged capacitor through an unknown cell resistive element to be sensed at a fixed voltage, and a pair of reference capacitors. The rate at which the parallel combination of capacitors discharge is between the discharge rate associated with a binary ‘1’ and ‘0’ value, and thus offers a reference for comparison.
| 6
|
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a divisional application of Ser. No. 08/815,551, filed Mar. 12, 1997, U.S. Pat. Ser. No. 6,207,602, which is a continuation application of Ser. No. 08/648,201, filed May 14,1996, now abandoned, which is a continuation application of Ser. No. 08/344,419, filed Nov. 23, 1994, now abandoned.
This invention relates to nonwoven fabrics and to fabric laminates which comprise multiconstituent fibers formed from a select combination of polyolefin polymers. The invention more particularly relates to nonwoven fabrics and laminates of the type described having improved fabric properties and processing characteristics.
Nonwoven fabrics produced from spun polymer materials are used in a variety of different applications. Among other uses, such nonwoven fabrics are employed as the cover sheet for disposable diapers or sanitary products. There is considerable interest in making disposable diapers more comfortable and better fitting to the baby. An important part of the diaper comfort is the softness or hardness of the nonwovens used to make the diaper, including the diaper topsheet, barrier leg cuffs, and in some advanced designs, the fabric laminated to the backsheet film. In some diaper designs, a high degree of fabric elongation is needed to cooperate with elastic components for achieving a soft comfortable fit.
One approach to improved diaper topsheet softness is to use linear low density polyethylene (LLDPE) as the resin instead of polypropylene for producing spunbonded diaper nonwoven fabrics. For example, Fowells U.S. Pat. No. 4,644,045 describes spunbonded nonwoven fabrics having excellent softness properties produced from linear low density polyethylene. However, the above-described softness of LLDPE spunbonded fabric has never been widely utilized because of the difficulty in achieving acceptable abrasion resistance in such products. The bonding of LLDPE filaments into a spunbonded web with acceptable abrasion resistance has proven to be very difficult. Acceptable fiber tie down is observed at a temperature just below the point that the filaments begin to melt and stick to the calender. This very narrow bonding window has made the production of LLDPE spunbond fabrics with acceptable abrasion resistance very difficult. Thus, the softness advantage offered by LLDPE spunbonded fabrics has not been successfully captured in the marketplace.
The present invention is based upon the discovery that blending a relatively small proportion of polypropylene of a select class with the polyethylene imparts greatly increased abrasion resistance to a nonwoven fabric formed from the polymer blend, without significant adverse effect on the fabric softness properties. It is believed that the polyethylene and the polypropylene form distinct phases in the filaments. The lower-melting polyethylene is present as a dominant continuous phase and the higher-melting polypropylene is dispersed in the dominant polyethylene phase.
A number of prior publications describe fibers formed of blends of linear low density polyethylene and polypropylene. For example, U.S. Pat. No. 4,839,228 and EP 394,954 teach that useful fibers are formed from blends which are predominantly polypropylene. WO 90/10672 describes that useful fibers are prepared from blends of polypropylene and polyethylene, especially LLDPE, where the ratio of polypropylene to polyethylene is from 0.6 to 1.5. U.S. Pat. No. 4,874,666 describes fibers formed from a blend of LLDPE and high molecular weight crystalline polypropylene of melt flow rate below 20 g/10 minutes. U.S. Pat. Nos. 4,632,861 and 4,634,739 describe fibers formed from a blend of a branched low density polyethylene blended with from 5 to 35 percent polypropylene.
SUMMARY OF THE INVENTION
In accordance with the present invention, nonwoven fabrics and nonwoven fabric laminates are formed from fibers of a select blend of specific grades of polyethylene and polypropylene which give improved fabric performance not heretofore recognized or described, such as high abrasion resistance, good tensile properties, excellent softness and the like. Furthermore, these blends have excellent melt spinning and processing properties which permit efficiently producing nonwoven fabrics at high productivity levels.
The nonwoven fabrics of the present invention are comprised of fibrous material in the form of continuous filaments or staple fibers of a size less than 15 dtex/filament formed of a dispersed blend of at least two different polyolefin polymers. The polymers are present as a lower-melting dominant continuous phase and at least one higher-melting noncontinuous phase dispersed therein. The lower-melting continuous phase forms at least 70 percent by weight of the fiber. The physical and rheological behavior of these blends is part of a phenomenon observed by applicants wherein a small amount of a higher modulus polymer reinforces a softer, lower-modulus polymer and gives the blend better spinning, bonding and strength characteristics than the individual constituents. The lower melting, relatively low molulus polyethylene provides desirable properties such as softness, elongation and drape; while the higher-melting, higher modulus polypropylene phase imparts one or more of the following properties to the dominant phase: improved ability to bond the web; improved filament tie-down (reduces fuzz); improved web properties—tensiles, and/or elongation and/or toughness; rheological characteristics which improve spinning performance and/or web formation (filament distribution).
According to one advantageous and important aspect of the present invention, the lower-melting continuous phase comprises a linear low density polyethylene polymer of a melt index of greater than 10 (ASTM D1238-89, 190° C.) and a density of less than 0.945 g/cc (ASTMD-792). At least one higher-melting noncontinuous phase comprises a polypropylene polymer with melt flow rate of greater than 20 g/10 min (ASTM D1238-89, 230° C.).
In one of the preferred embodiments of the invention, the lower-melting continuous phase forms at least 80 percent by weight of the fiber and comprises a linear low density polyethylene having a density of 0.90-0.945 g/cc and a melt index of greater than 25 g/10 minutes.
In another preferred embodiment, said lower-melting polymer phase comprises linear low density polyethylene as described above and said higher-melting polymer phase comprises an isotactic polypropylene with a melt flow rate greater than 30 g/10 minutes.
In still another preferred embodiment said lower-melting polymer phase comprises at least 80 percent by weight low pressure, solution process, linear short chain branched polyethylene with a melt index of greater than 30 and a density of 0.945 g/cc and said higher-melting polymer phase comprises 1 to 20 percent by weight of isotactic polypropylene.
In another embodiment of the invention, said lower-melting polymer phase comprises linear low density polyethylene with a melt index of 27 and said higher-melting polymer phase comprises an isotactic polypropylene with a melt flow rate of 35 g/10 minutes.
According to another aspect of the present invention, the lower-melting dominant continuous phase is blended with a higher-melting noncontinuous phase of propylene co- and/or ter- polymers. When propylene co- and/or ter-polymers are used as the higher-melting noncontinuous phase, the lower melting continuous phase may be comprised of one or more polyethylenes selected from the group consisting of low density polyethylene, high pressure long chain branched polyethylene, linear low density polyethylene, high density polyethylene and copolymers thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings which form a portion of the original disclosure of the invention:
FIG. 1 diagrammatically illustrates one method and apparatus for manufacturing the nonwoven webs according to the invention;
FIG. 2 is a fragmentary plan view of a nonwoven web of the invention;
FIG. 3 is a diagrammatical cross-sectional view of a nonwoven fabric laminate in accordance with the invention; and
FIG. 4 is a diagrammatical cross-sectional view of a laminate of the nonwoven fabric of FIG. 2 with a film.
DETAILED DESCRIPTION
Linear low density polyethylene (LLDPE) is produced in either a solution or a fluid bed process. The polymerization is catalytic. Ziegler Natti and single-site metallocene catalyst systems have been used to produce LLDPE. The resulting polymers are characterized by an essentially linear backbone. Density is controlled by the level of comonomer incorporation into the otherwise linear polymer backbone. Various alpha-olefins are typically copolymerized with ethylene in producing LLDPE. The alpha-olefins which preferably have four to eight carbon atoms, are present in the polymer in an amount up to about 10 percent by weight. The most typical comonomers are butene, hexene, 4-methyl-1-pentene, and octene. The comonomer influences the density of the polymer. Density ranges for LLDPE are relatively broad, typically from 0.87-0.95 g/cc (ASTM D-792).
Linear low density polyethylene melt index is also controlled by the introduction of a chain terminator, such as hydrogen or a hydrogen donator. The melt index for a linear low density polyethylene can range broadly from about 0.1 to about 150 g/10 min. For purposes of the present invention, the LLDPE should have a melt index of greater than 10, and preferably 15 or greater for spunbonded filaments. Particularly preferred are LLDPE polymers having a density of 0.90 to 0.945 g/cc and a melt index of greater than 25.
Examples of suitable commercially available linear low density polyethylene polymers include the linear low density polyethylene polymers available from Dow Chemical Company, such as the ASPUN series of Fibergrade resins, Dow LLDPE 2500 (55 MI, 0.923 density), Dow LLDPE Type 6808A (36 MI, 0.940 density), and the Exact series of linear low density polyethylene polymers from Exxon Chemical Company, such as Exact 2003 (31 MI, density 0.921).
The higher-melting polypropylene component can be an isotactic or syndiotactic polypropylene homopolymer, or can be a copolymer or terpolymer of propylene. The melt flow rate of the polypropylene should be greater than 20 g/10 min., and preferably 25 or greater. Particularly suitable are polypropylene polymers having an MFR of 35 to 65. Examples of commercially available polypropylene polymers which can be used in the present invention include SOLTEX Type 3907 (35 MFR, CR grade), HIMONT Grade X10054-12-1 (65 MFR), Exxon Type 3445 (35 MFR), Exxon Type 3635 (35 MFR) AMOCO Type 10-7956F (35 MFR), and Aristech CP 350 J (melt flow rate approximately 35). Examples of commercially available copolymers of propylene include Exxon 9355 which is a random propylene copolymer with 3% ethylene, 35 melt flow rate; and co- and ter-polymers of propylene from the Catalloy™ series from Himont.
The lower-melting polyethylene component and the higher-melting polypropylene component can be present in proportions ranging from 70 percent by weight polyethylene and 30 percent polypropylene to 99 percent by weight polyethylene and 1 percent polypropylene. In these proportions, the lower-melting polyethylene component is present as a substantially continuous phase and the higher-melting polypropylene is present as a discontinuous phase dispersed in the polyethylene phase.
Appropriate combinations of polymers are combined and blended before being melt-spun into fibers or fibrous webs. A high degree of mixing is used in order to prepare blends in which the polypropylene component is highly dispersed in the polyethylene component. In some cases such mixing may be achieved in the extruder as the polymers are converted to the molten state. However, in other cases it may be preferred to use an extra mixing step. Among the commercially available mixers that can be used are the Barmag 3DD three-dimensional dynamic mixer supplied by Barmag AG of West Germany and the RAPRA CTM cavity-transfer mixer supplied by the Rubber and Plastics Research Association of Great Britain.
The blended polymer dispersion is then either melt-spun into fibers, which may be formed into a web for instance by carding, airlaying, or wetlaying, or melt-spun directly into fibrous webs by a spunbonding or meltblowing process. The web can then be bonded to form a strong, soft biconstituent-fiber nonwoven fabric. Webs of the blended polymer dispersion can be made according to any of the known commercial processes for making nonwoven fabrics, including processes that use mechanical, electrical, pneumatic, or hydrodynamic means for assembling fibers into a web, for example carding, wetlaying, carding/ hydroentangling, wetlaying/hydroentangling, and spunbonding. The webs of the blended polymer dispersion can then be bonded by a multiplicity of thermal bonds to give the webs sufficient strength and abrasion resistance to be useful in, for example, diaper applications. Preferably the bonds are thermal bonds formed by heating the fibers so that via a combination of heat and pressure they become tacky and fuse together at point of contact between the fibers. The thermal bonds may be formed using any of the techniques known in the art for forming discrete thermal bonds, such as calendering. Other thermal bonding techniques, such as through-air bonding and the like, may also be used.
FIG. 1 is a diagrammatical view of an apparatus, indicated generally by the reference number 10 , for producing a spunbonded nonwoven web in accordance with the present invention. Various spunbonding techniques exist, but all typically include the basic steps of extruding continuous filaments, quenching the filaments, drawing or attenuating the filaments by a high velocity fluid, and collecting the filaments on a surface to form a web. The spunbonding apparatus 10 is illustrated as a slotdraw type spunbonding apparatus, although, as will be appreciated by the skilled artisan, other spunbonding apparatus may be used. Spunbonding apparatus 10 includes a melt spinning section including a feed hopper 12 and an extruder 14 for the polymer. The extruder 14 is provided with a generally linear die head or spinneret 16 for melt spinning streams of substantially continuous filaments 18 . The substantially continuous filaments 18 are extruded from the spinneret 16 and typically are quenched by a supply of cooling air 20 . The filaments are directed to an attenuation device 22 , preferably in the form of an elongate slot which includes downwardly moving attenuation air which can be supplied from forced air above the slot, vacuum below the slot, or eductively within the slot, as is known in the art. In the attenuation device 22 , the filaments become entrained in a high velocity stream of attenuation air and are thereby attenuated or drawn. The air and filaments are discharged from the lower end of the attenuation device 22 and the filaments are collected on a forming wire 24 as a nonwoven spunbond web W .
The web W is conveyed to a bonding station 26 to form a coherent bonded nonwoven fabric. In the embodiment shown, the web is thermally bonded using a pair of heated calender rolls 27 and 28 . Thermal bonds are formed by heating the filaments so that they soften and become tacky, and fuse together contacting portions of the filaments. The operating temperature and the compression force of the heated rolls 27 and 28 should be adjusted to a surface temperature and pressure such that the filaments present in nonwoven web soften and bind the fibrous nonwoven web to thereby form a coherent nonwoven fabric. The pattern of the calender rolls may be any of those known in the art, including point bonding patterns, helical bonding patterns, and the like. The term point bonding is used herein to be inclusive of continuous or discontinuous pattern bonding, uniform or random point bonding, or a combination thereof, all as are well known in the art.
Although bonding station 26 has been illustrated in FIG. 1 as heated calender rolls, the rolls can, in other embodiments of the invention, be replaced by other thermal activation zones. For example, the bonding station may be in the form of a through-air bonding oven, a microwave or other RF treatment zone. Other bonding stations, such as ultrasonic welding stations, can also be used in the invention. In addition other bonding techniques known in the art can be used, such as adhesive bonding.
The thermally bonded nonwoven fabric is then wound by conventional means onto roll 29 . The nonwoven fabric can be stored on roll 29 or passed to end use manufacturing processes, for example for use as a component in a disposable personal care article such as diapers and the like, medical fabrics, wipes, and the like.
FIG. 2 illustrates a thermally bonded spunbonded nonwoven fabric W produced in accordance with the present invention. The nonwoven fabric W may be laminated into structures having a variety of desirable end-use characteristics. FIG. 3 is a diagrammatical cross-sectional view of a nonwoven fabric laminate in accordance with one embodiment of the invention. In this embodiment, the laminate, generally indicated at 40 , is a two-ply laminate. Ply 41 comprises a web which may be a meltblown nonwoven web, a spunbonded web, or a web of staple fibers. Ply 42 comprises a nonwoven web formed of a highly dispersed blend of polyolefin polymers, such as the nonwoven fabric W produced as described above.
The plies may be bonded and/or laminated in any of the ways known in the art. Lamination and/or bonding may be achieved, for example, by hydroentanglement of the fibers, spot bonding, through-air bonding and the like. For example, when ply 41 is a fibrous web, lamination and/or bonding may be achieved by hydroentangling, spot bonding, through-air bonding and the like. In the embodiment shown in FIG. 3, plies 41 and 42 are laminated together by passing through a heated patterned calender to form discrete thermal point bonds indicated at 43 . It is also possible to achieve bonding through the use of an appropriate bonding agent, i.e., an adhesive. The term spot bonding is inclusive of continuous or discontinuous pattern bonding, uniform or random point bonding or a combination thereof, all as are well known in the art.
The bonding may be made after assembly of the laminate so as to join all of the plies or it may be used to join only selected of the fabric plies prior to the final assembly of the laminate. Various plies can be bonded by different bonding agents in different bonding patterns. Overall, laminate bonding can also be used in conjunction with individual layer bonding.
Laminates of a spunbond web from the highly blended polymer dispersion as described above with a web of meltblown microfibers have utility as barrier fabrics in medical applications, protective clothing applications, and for hygiene applications such as barrier leg cuffs. Of particular utility for hygiene applications are spunbond/meltblown laminates of reduced basis weight, such as made with a 17 grams per square meter (gsm) spunbonded web of this invention and 2-3 gsm meltblown web. Such barrier laminates could be used, for example, as barrier leg cuffs in diapers.
Another type of nonwoven fabric laminate may be made by combining nonwoven web of this invention with a film, for example a film of a thermoplastic polymer, such as a polyolefin, to make barrier fabrics useful for hygiene applications such as barrier leg cuffs and diaper backsheets. FIG. 4 illustrates one such laminate, which includes a ply or layer 42 ′ comprising a nonwoven web formed of a highly dispersed blend of polyolefin polymers, such as the nonwoven fabric W of FIG. 2, laminated to a polyolefin film layer 44 , such as for example a polyethylene film of a thickness of 0.8 to 1 mil. Lamination and/or bonding of the nonwoven layer 42 ′ to the film layer 44 can be achieved by adhesive lamination using a continuous or discontinuous layer of adhesive. This adhesive approach may yield a diaper backsheet with superior softness and hand. The nonwoven fabric laminate could also be produced by thermal lamination of the nonwoven fabric of this invention and film webs together. This approach has the advantage of eliminating the cost of the adhesive. It may also be desirable to utilize coextruded film webs that include a sealing/bonding layer in combination with a polyolefin layer in the film web that, when combined with the nonwoven fabrics of the invention, maximize softness and good thermal bonding characteristics. The nonwoven fabric laminate could also be produced by direct extrusion of the film layer 44 on ply 42 ′.
EXAMPLE 1
Ninety percent by weight of a linear low density polyethylene (LLDPE) with a melt flow of 27 (Dow 6811 LLDPE) and ten percent by weight of a polypropylene (PP) polymer with a melt flow approximately 35 (Aristech CP 350 J) were dry blended in a rotary mixer. The dry-blended mixture was then introduced to the feed hopper of an extruder of a spunbond nonwoven spinning system. Continuous filaments were meltspun by a slot draw process at a filament speed of approximately 600 m/min and deposited upon a collection surface to form a spunbond nonwoven web, and the web was thermally bonded using a patterned roll with 12% bond area. For comparison purposes, nonwoven spunbond fabrics were produced under similar conditions with the same polymers, using 100% PP and 100% LLDPE.
As shown in table 1, the 100% LLDPE spunbond samples exhibited superior softness (75 and 77.5) compared to the 100% polypropylene spunbond sample ( 30 ). However, the abrasion resistance of the 100% LLDPE sample, as seen from the fuzz measurement, was relatively high (12.5 and 2.4) compared to the 100% PP sample (0.3). The nonwoven fabric formed from the 90% LLDPE/10% PP blend had a high softness (67.5) only slightly less than the 100% LLDPE fabric, and had abrasion resistance (fuzz value) of 1.0 mg., which is significantly better than the values seen for 100% LLDPE. The blend sample also showed improved CD tensile compared to products made with 100% LLDPE.
TABLE 1
Sample
A
B
C
D
C = comparison I = invention
C
C
C
I
Composition:
% polypropylene
100
0
0
10
% polyethylene
0
100
100
90
filament dia. (microns)
17.5
20.9
20.9
22.5
Basis weight (gsm) 1
23.1
25.2
24.6
24.8
Loft @ 95 g/in 2 (mils) 2
9.8
9.0
7.8
9.3
Fuzz (mg) 3
0.3
12.5
2.4
1.0
Softness 4
30
75
77.5
67.5
Strip Tensile (g/cm) 5
CD
557
139
157
164
MD
1626
757
639
467
Peak Elongation (%)
CD
90
116
129
108
MD
93
142
106
119
TEA (in. g./in
CD
852
297
346
354
MD
2772
2222
1555
1389
1 gsm = grams per square meter
2 Loft was determined by measuring the distance between the top and the bottom surface of the fabric sheet while the sheet was under compression loading of 95 grams per square inch. The measurement is generally the average of 10 measurements.
3 Fuzz is determined by repeatedly rubbing a soft elastomeric surface across the face of the fabric a constant number of times. The fiber abraded from the fabric surface is then weighed. Fuzz is reported as mg weight observed.
4 Softness was evaluated by an organoleptic method wherein an expert panel compared the surface feel of Example Fabrics with that of controls. Results are reported as a softness score with higher values denoting a more pleasing hand. Each reported value is from a single fabric test sample, but reflects the input of several panel members.
5 Tensile, Peak Elongation and TEA were evaluated by breaking a one inch by seven inch long sample generally following ASTM D1682-64, the one-inch cut strip test. The instrument cross-head speed was set at 5 inches per minute and the gauge length was set at 5 inches per minute. The Strip Tensile Strength, reported as grams per centimeter, is generally the average of at least 8 measurements. Peak Elongation is the percent increase in length noted at maximum tensile strength.
#TEA, Total Tensile Energy Absorption, is calculated from the area under the stress-strain curve generated during the Strip Tensile test.
EXAMPLE 2
(Control)
A control fiber was made by introducing 100% Dow LLDPE 2500 (55 MI, 0.923 density) to a feed hopper of a spinning system equipped with an extruder, a gear pump to control polymer flow at 0.75 gram per minute per hole, and a spinneret with 34 holes of L/D=4:1 and a diameter of 0.2 mm. Spinning was carried out using a melt temperature in the extruder of 215° C. and a pack melt temperature of 232° C. After air quench, the resulting filaments were drawn down at a filament speed of approximately 1985 m/min using an air aspiration gun operating at 100 psig to yield a denier of 3.01 and denier standard deviation of 0.41.
EXAMPLE 3
Ninety parts by weight of Dow LLDPE Type 2500 (55 MI, 0.923 density) and ten parts of Himont X10054-12-1 polypropylene (65 MFR) were dry blended in a rotary mixer and then introduced to the feed hopper of the spinning system described in Example 2. Spinning was carried out using a pack melt temperature of 211° C. After air quench, the resulting filaments were drawn down at a filament speed of approximately 2280 M/Min using an air aspiration gun operating at 100 psig to yield a denier of 2.96 and a denier standard deviation of 1.37.
EXAMPLE 4
Ninety parts by weight of Dow LLDPE Type 2500 (55 MI, 0.923 density) and ten parts of Soltex 3907 polypropylene (35 MFR, 1.74 die swell, CR grade) were dry blended in a rotary mixer and then introduced to the feed hopper of the spinning system described in Example 2. Spinning was carried out using a pack melt temperature of 231° C. and an extruder melt temperature of 216° C. After air quench, the resulting filaments were drawn down at a filament speed of approximately 2557 M/Min using an air aspiration gun operating at 100 psig to yield a denier of 2.64 and a denier standard deviation of 0.38.
EXAMPLE 5
Ninety parts by weight of Dow LLDPE Type 6808A (36 MI, 0.940 density) and ten parts of Soltex 3907 polypropylene (35 MFR, 1.74 die swell, CR grade) were dry blended in a rotary mixer and then introduced to the feed hopper of the spinning system described in Example 2. Spinning was carried out using a pack melt temperature of 231° C. and an extruder melt temperature of 216° C. After air quench, the resulting filaments were drawn down at a filament speed of approximately 2129 M/Min using an air aspiration gun operating at 100 psig to yield a denier of 3.17 and a denier standard deviation of 2.22.
The quality of spinning for a given formulation has been found to roughly correlate with the denier standard deviation. A reduced standard deviation suggests more stable or higher quality spinning. Thus it is unexpected and contrary to the teaching of the prior art that the blend using a 35 MFR polypropylene in Example 4 yielded a more stable spinning than seen with the corresponding LLDPE control in Example 2.
EXAMPLE 6
Eighty parts by weight of a linear low density polyethylene pellets of 55 melt index and 0.925 g/cc density and twenty parts by weight polypropylene pellets of 35 melt flow rate were dry blended in a rotary mixer. The dry-blended mixture was then introduced to the feed hopper of a spinning system equipped with an extruder with a 30:1 l/d ratio, a static mixer, and a gear pump for feeding the molten polymer to a heated melt block fitted with a spinneret. Filaments were extruded from the spinneret and drawn using air aspiration.
EXAMPLE 7
Samples of continuous filament spunbonded nonwoven webs were produced from blends of a linear low density polyethylene with a melt flow rate of 27 (Dow 6811A LLDPE) and a polypropylene homopolymer (Appryl 3250YR1, 27 MFR) in various blend proportions. Control fabrics of 100 percent polypropylene and 100 percent polyethylene were also produced under similar conditions. The fabrics were produced by melt spinning continuous filaments of the various polymers or polymer blends, attenuating the filaments pneumatically by a slot draw process, depositing the filaments on a collection surface to form webs, and thermally bonding the webs using a patterned calender roll with a 12 percent bond area. The fabrics had a basis weight of approximately 25 gsm and the filaments had an average mass/length of 3 dtex. The tensile strength and elongation properties of these fabrics and their abrasion resistance were measured, and these properties are listed in Table 2. As shown, the 100 percent polypropylene control fabric had excellent abrasion resistance, as indicated by no measurable fuzz generation; however the fabrics had relatively low elongation. The 100 percent polyethylene control fabric exhibited good elongation properties, but very poor abrasion resistance (high fuzz values and low Taber abrasion resistance) and relatively low tensile strength. Surprisingly, the fabrics of the invention made of blends of polypropylene and polyethylene exhibited an excellent combination of abrasion resistance, high elongation, and good tensile strength. It is noted that the CD elongation values of the blends actually exceeded that of the 100% polyethylene control. This surprising increase in elongation is believed to be attributable to the better bonding of the filaments of the blend as compared to the bonding achieved in the 100% polyethylene control, which resulted in the fabrics of the invention making good use of the highly elongatable filaments without bond failure.
TABLE 2
MECHANICAL PROPERTIES OF
POLYPROPYLENE (PP)/POLYETHYLENE (PE) BLEND FABRICS
25/75
15/85
Fabric
100% PP
PP/PE
PP/PE
100% PE
MD Tensile (g/cm) 6
925
764
676
296
CD Tensile (g/cm) 6
405
273
277
63
MD Elongation (%) 6
62
170
199
168
CD Elongation (%) 6
70
190
224
131
Fuzz (mg) 7
0.0
0.3
0.5
19.0
Taber Abrasion 8
40
32
22
10
(cycles - rubber wheel)
Taber Abrasion 8
733
200
500
15
(cycles - felt wheel)
6 Tensile and Peak Elongation were evaluated by breaking a one inch by seven inch long sample generally following ASTM D1682-64, the one-inch cut strip test. The instrument cross-head speed was set at 5 inches per minute and the gauge length was set at 5 inches per minute. The Strip Tensile Strength, reported as grams per inch, is generally the average of at least 8 measurements. Peak Elongation is the percent increase in length noted at maximum tensile strength.
7 Fuzz is determined by repeatedly rubbing a soft elastomeric surface across the face of the fabric a constant number of times. The fiber abraded from the surface is then weighed. Fuzz is reported as mg weight observed.
8 Conducted according to ASTM D3884-80 where the number of cycles was counted until failure. Failure was defined as the appearance of a hole of one square millimeter or greater in the surface of the fabric.
|
Nonwoven fabrics and fabric laminates are formed from continuous filaments or staple fibers of a select blend of specific grades of polyethylene and polypropylene which give improved fabric performance not heretofore recognized or described, such as high abrasion resistance, good tensile properties, excellent softness and the like. Furthermore, these blends have excellent melt spinning and processing properties which permit efficiently producing nonwoven fabrics at high productivity levels. The polymers are present as a lower-melting dominant continuous phase and at least one higher-melting noncontinuous phase dispersed therein. The lower-melting continuous phase forms at least 70 percent by weight of the fiber and comprises a linear low density polyethylene polymer of a melt index of greater than 10 and a density of less than 0.945 g/cc. At least one higher-melting noncontinuous phase comprises a polypropylene polymer with melt flow rate of greater than 20 g/10 min.
| 3
|
This is a continuation of my copending application Ser. No. 478,367, filed on Mar. 24, 1983. A verified statement claiming small entity status has been filed and remains proper for purposes of the present continuation application.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to women's wearing apparel, and, more particularly to clothing that enables mothers to unobtrusively breast feed their babies.
2. Description of the Prior Art
The need for clothing to make breast feeding possible without having to undress has been recognized for centuries by societies clothed for warmth and modesty. The need has been addressed by more than twenty prior U.S. patents which have issued over the last century. Some of those patents have been directed toward underwear and sleepwear, while others have been directed towards dresses and blouses for mothers nursing babies. The present invention can function for sleepwear, lingerie and other underwear; however, the major application is for apparel worn in public.
The majority of prior art nursing apparel includes a vertical slit, which is unobtrusive when not in use for feeding but which spreads open to expose the breast when the child is nursing. Duenckel U.S. Pat. No. 232,246 which issued on Sept. 14, 1880; Coyle U.S. Pat. No. 660,843, which issued on Oct. 30, 1900; Jacoby U.S. Pat. No. 1,013,778, which issued on Jan. 2, 1912; and Gerich U.S. Pat. No. 2,911,650, which issued on Nov. 10, 1959 are illustrative.
References to "vertical" as used herein shall mean vertical relative to the waist of the wearer of the garment and to the floor when such wearer stands erect. "Horizontal" as used herein shall mean horizontal relative to the waist of a wearer of the garment and to the floor when such wearer stands erect.
Garments have been devised which minimized, and in some cases attempted to avoid, exposure of the nipple, areola and adjacent flesh. Coyle U.S. Pat. No. 778,014 which issued on Dec. 20, 1904, discloses a foldable side flap. Culver U.S. Pat. No. 890,614, which issued on June 16, 1908, discloses a pullout flexible curtain for shielding the breast during feeding. Rouff U.S. Pat. No. 907,290, which issued on Dec. 22, 1908, discloses a swinging placket. A garment showing a button-down flap which folds up to expose the breast during feeding is disclosed by Elowsky U.S. Pat. No. 1,290,142 which issued on Jan. 7, 1919. Dodd U.S. Pat. No. 4,106,122, which issued on Aug. 15, 1978, discloses a halter with pleated flaps which extends down over the breasts.
Timmons U.S. Pat. No. 4,144,593, which issued on Mar. 20, 1979, discloses a nursing garment which features a large front panel hinged at the top to cover an open, shaped area surrounding both breasts. When the fasteners are released along the bottom and sides of this open area the baby may be inserted under the panel to nurse. The baby is therefore, concealed from the mother's view and more importantly, the baby cannot see the mother.
Stagg U.S. Pat. No. 1,206,480, which issued on Nov. 28, 1916, discloses a double front nursing waist which features a completely detachable outer portion which is fastened at the shoulders and waist and which conceals the breast and face of the child during nursing. Nursing garments such as that disclosed by the Stagg Patent do not permit the child to view the mother. However, many mothers and specialists now recognize the importance of eye contact between the mother and the nursing child for promoting calm, steady nursing and for forming and maintaining the mother-child bond.
Pinch U.S. Pat. No. 4,004,294, which issued on Jan. 25, 1977, and Johnson U.S. Pat. No. 4,031,566, which issued on June 28, 1977, disclose shaped apertures which retain their shape when opened, thus permitting some flesh of the breast to be visible. Both utilize fastening systems, such as a Velcro loop or pile, which are necessary to insure modest coverage during nonfeeding times, but which tend to cause fuss and noise at the start and conclusion of feeding.
The nursing garments of the prior art discussed above permit at least a portion of the breast or the flesh adjacent to the nipple to be exposed during feeding. Some of them conceal the baby from the mother or conceal the mother from the baby. Many also are operative for feeding only after releasing and adjusting various fastening devices, which can be bothersome, abrasive and noisy, and may direct attention to the nursing pair. There is a need therefore, for a nursing garment which permits the mother and the baby to see each other's face without exposing the mother's breast, or any portion thereof, to onlookers. There is a further need for such a garment which permits covenient breast feeding without the fuss, bother, irritation, hazard and noise associated with fastening devices.
SUMMARY OF THE INVENTION
The present invention provides an improved front for clothing to be worn by a mother for breast feeding a child in a convenient, quiet and unobtrusive manner. "Front" as used herein shall mean that portion of the clothing intended in normal use to be positioned on the front of the woman.
The improved front of the clothing of the present invention includes an upper member having a lower edge, and a lower member having an upper edge. At least the upper edge of the lower member is made of such a resilient material that the upper edge tends to assume a nonaccess position and can be moved downwardly to an access position. The upper and lower members are so positioned relative to each other when worn by the woman that at least a portion of the upper member overlaps at least a portion of the lower member, and the nonaccess position is one in which the upper edge of the lower member is above the breast and the lower edge of the upper member is suspended to an area below the breast and below the upper edge of the lower member. The access position is one in which the upper edge of the lower member is pulled downwardly under the breast to make the breast accessible to the baby while the lower edge of the upper member remains suspended to the area below the breast to permit the upper member to shield the breast from view to all except the baby. Thus, in both the access and the nonaccess positions the lower edge of the upper member remains suspended to the area below the breast.
The upper and lower members of the clothing of the present invention may be independent members, unattached to each other. Alternatively, the upper and lower members may form a portion of a single garment.
The upper edge of the lower member may be so positioned on the lower member that the upper edge assumes a horizontal orientation in the nonaccess position relative to the woman when the clothing is worn. The upper edge of the lower member may alternatively be so positioned on the lower member that the upper edge assumes a diagonal orientation in the nonaccess position relative to the woman when the clothing is worn. "Diagonal" as used herein shall mean diagonal with respect to the horizontal and vertical as defined herein.
There may be a first and second upper edge of the lower member, the first upper edge being associated with one breast and the second upper edge being associated with the other breast. There may also be a first and second upper member, each having one lower edge. The lower edge of the first upper member overlaps the first upper edge and the lower edge of the second upper member overlaps the second upper edge. Each of the first and second upper members may include a means of attaching the lower edges of the first and second upper members to the lower member for use when the first and second upper edges of the lower member are in the nonaccess position.
Preferably, the clothing is so constructed that the upper member overlaps the lower member while the upper edge of the lower member is in the access position to an extent sufficient to shield the breast from view while permitting the baby to view the woman's face while the baby is feeding.
The lower edge of the upper member is preferably freely suspended, being unattached to the lower member. The upper member may be attached to the garment at some point other than along the lower edge.
In contrast to the aforementioned prior art garments, the clothing of the present invention has horizontal or diagonal edges, which can form accessways across the chest area. When the upper edge of the lower member is moved into the access position, an accessway is defined by the upper edge of the lower member and the lower edge of the upper member. The horizontal and diagonal designs cause the upper member, which overlaps the lower member, to fall over the breast obscuring it from view. The fabric forming the upper and lower members may be cut, folded and sewn to form curved, scalloped, variegated or straight horizontal or diagonal edges. The uppermost member continues to cover the breast entirely even when the lower member is stretched (not folded) down to slightly below the nipple. The baby's mouth tucks just under the upper member, enabling the child to nurse without exposing the mother's breast to the sight of any onlookers.
The stretchy upper edge of the lower member of the present invention, by virtue of its resiliency, tends to conform to the shape of the wearer. When in the nonaccess position, the lower member provides the mother double coverage over all or part of the breast area, letting her move and raise her arms without having the clothing gap apart even though the members are not fastened together. During feeding, when the upper edge of the lower member is pulled down to just below the nipple, it conforms to body contours rather than folding at a right angle or in some other manner to expose the breast. The upper member only shifts out slightly if at all. It need never be dropped down or lifted up and away from the breast, so that a bra or the breast is always covered entirely, at least by the upper member. Because no fastening system, such as Velcro, snaps, zippers or buttons, is required, unusual movements or sounds which would draw attention to the nursing couple are avoided.
The clothing may serve as the bodice of any type of women's apparel, such as a blouse, shirt, top of a dress, jumpsuit, or sportswear, loungewear, or sleepwear.
Furthermore, the clothing of the present invention can be adapted to conform to stylistic trends and the preferences of the wearer.
When not in use for feeding, the clothing of the present invention looks normal. The clothing can be worn with a variety of bras such as nursing bras, low cut bras or, if preferred, with no bra.
BRIEF DESCRIPTION OF THE DRAWINGS
The following detailed description of the preferred embodiment can be better understood if reference is made to the attached drawings in which:
FIG. 1 is a perspective, cutaway view of one embodiment of the nursing clothing of the present invention;
FIG. 2 is a view of the woman wearing the clothing of FIG. 1 while feeding the baby;
FIG. 3 is a view of the clothing shown in FIG. 1;
FIG. 4 is a view of the lower member of the clothing with the upper edge in the nonaccess position and,
FIG. 5 is a view of the lower member of the clothing with the upper edge in the access position.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1 through 5 show one embodiment of the clothing, a nursing garment 10, of the present invention. The garment 10 accomplishes the purposes stated above by using overlapping fabric members having horizontal or diagonal orientation across the chest. Referring to FIG. 1, the garment 10 includes an upper member 20, and a lower member 30. Upper and lower members 20 and 30, respectively, may be attached in some suitable manner to each other. Alternatively, they may be unattached to each other, forming separate pieces. The separate pieces may be styled to permit a lower member 30 to be worn with a variety of interchangeable upper members 20 of different styles. Similarly, the separate pieces may permit an upper member 20 to be worn with a variety of interchangeable lower members 30.
Upper member 20 may be attached to a shoulder portion 36 or may itself form part of the shoulder portion 36. Shoulder portion 36 may take any form, such as straps across the shoulders in a sundress or to the back of the neck in a halter, or any conventional means for draping the garment over the shoulder of the wearer. Although the preferred embodiment includes a shoulder portion 36, such as that shown in FIG. 3, it should be understood that strapless garments may also be designed to incorporate the principal features of the present invention.
The upper member 20 includes lower edge 22 and upper edge 24. The upper member 20 continually covers the breast and is always visible to the wearer and others. At all times it remains generally undisturbed, falling over the breast due to gravity. It is attractively styled in keeping with the complete garment and ensemble.
The lower member 30 includes an upper edge 32 which is made of a resilient material. The resilient material of the upper edge 32 of the lower member 30 may be attached to nonresilient fabric of the lower member 30. Alternatively, the entire lower member 30 including the upper edge 32, may be made of such resilient material. However, any suitable material, such as a stretchy lycra fabric or knit, or elasticized thread or band may be used, provided the upper edge 32 of lower member 30 is sufficiently resilient (a) to permit upper edge 32 to be pulled down to permit the baby to have access to the breast and (b) to allow upper edge 32 to return to the nonaccess position above the breast when released. The resiliency required is such that, when worn, upper edge 32 will naturally tend toward the nonaccess position, where both breasts are covered by lower member 30. When pulled downwardly, however, upper edge 32 will readily yield to permit ease of access for the child and minimum effort for the mother. When upper edge 32 is moved to the access position for feeding, an accessway is defined between the lower edge 22 of the upper member 20 and the upper edge 32 of the lower member 30.
In the nonaccess position, the lower member 30 is at least partially covered by the upper member 20, both of which cover all or most of the breast. Thus, even when the wearer raises her arms, the upper and lower members 20 and 30, do not fall apart to expose the breast.
Lower member 30 in the access position is stretched by hand to the base of the breast and is there held by the natural configuration and weight of the breast itself. In the feeding or access position, the lower member 30 no longer covers the breast being given to the baby and may itself be covered less by the upper member 20. For the design having the horizontal upper edge, FIGS. 3, 4, and 5 illustrate a basic approach that can be incorporated into any bodice whether sleeved, or sleeveless, with straps or strapless. The upper member 20 includes one or more panels or ruffles across the chest that is an integral decorative part of the clothing or garment design. The upper member 20 is unattached at its lower edge 22 which, in the embodiment shown, extends along the base of the breast. Upper member 20 may however, be provided with a means for releasably attaching upper member 20 to lower member 30 for use when the woman is not nursing the child.
The upper member 20 may be attached by any suitable means along its upper edge 24 or its side edges to any suitable portion of the garment. For example, the side edges of the upper member 20 may be sewn to the side seams of the garment 10. As stated above, it may even be an integral part thereof. The lower edge 22 is suspended by gravity from the upper edge 24. When the mother leans forward slightly, the lower edge 22, again due to gravity, will fall away slightly from her body. With a small, silent movement of the mother's hand the upper edge 32 of the lower member 30 is tucked under her breast and the baby takes the nipple, unseen by others.
In the preferred embodiment, the upper member 20 should extend down over the breast far enough to conceal the breast from onlookers yet should not extend so far that the baby's head is entirely covered. Mothers have observed that feeding proceeds most smoothly when eye contact is maintained while feeding. In addition, psychologists have suggested that the bonding between mother and child is strengthened and the welfare of the child is enhanced if the mother and child can look into each other's faces while feeding. Therefore, upper member 20 should cover only the baby's mouth and should not obstruct the baby's view of the mother's face. The mother wearing garment 10 naturally holds the child in such a position that one or both of the baby's eyes can focus on the mother.
Following the feeding, the mother can unobtrusively release the lower member 30 from under her breast. The lower member 30 will naturally and silently ease back up over the breast to the nonaccess position to once again provide increased privacy and security.
The upper edge 32 of lower member 30 may have a conventional elastic band sewn therein or may be made of a stretch-knit fabric which is resilient enough to resume a nonaccess position when the feeding session is over. Elasticized thread or various stitch patterns which promote elasticity may also be employed. The lower member 30 may be attached to the garment 10 at side seams of the garment 10, generally corresponding to the sides of the wearer. The lower member 30 covers that portion of the wearer's body extending upwardly from generally the waist or above to the breast. The lower member 30 must extend from at least the base of the breast to a level which is higher in the nonaccess position than the lower edge 22 of upper member 20. Lower member 30 can also extend below the waist when garment 10 is a dress, jumpsuit or lingerie. The length and position of the upper edge 32 of lower member 30 determine the elasticity appropriate to a particular garment 10 to permit easy, comfortable access for nursing or breast pumping. Following feeding, the upper edge 32 must conveniently contract back to its nonaccess, nonnursing position.
The bodice of any type of women's garment, including a blouse, shirt, sweater, dress, sportshirt, loungewear or sleepwear may be adapted to incorporate the features of the present invention. In another embodiment of garment 10, (not shown) a diagonal design for upper edge 32 of lower member 30 may be used. This design may be incorporated into all sorts of garments to provide discreet access to the individual breast. The diagonal may include any stylistic modification of a diagonal, such as a V-shaped edge, without exceeding the scope of the present invention.
The upper member 20 of the garment 10 may assume a variety of shapes. Upper member 20 may be a plurality of pieces. Cowls, bibs, neck scarves, bands, ruffles, flounces, bows, dickeys, shawls, extended collars, a plurality of petal-shaped extensions, or any other suitable modification which would serve the purposes of the present garment 10 can be used. Those skilled in the art of fashion design will recognize that numerous stylistic modifications can be made to both the upper member 20 and lower member 30 without exceeding the scope of the present invention.
Similarly, numerous stylistic modifications can be made to the generally horizontally or diagonally oriented upper edges 32 of lower member 30 without exceeding the scope of the present invention. The edges may be straight or curved, regular or irregular, scalloped or variagated. The diagonal upper edge 32 can assume a V or W-shape.
The lower member 30 may be a garment having a V-shaped, oval or round neckline. The shaped neckline may function as upper edge 32. Any suitable modification of upper member 20, such as those described above, may be positioned over this embodiment of lower member 30.
There may be a first and a second upper edge 32 of lower member 30, the first upper edge being associated with one breast and the second upper edge being associated with the other breast. In the embodiment of the present invention having two upper edges 32, the upper member 20 may take the form of first and second individual members, one over each breast. They may be pockets, which can be functional or nonfunctional. The upper members 20 may alternatively be ensignia or any other useful or decorative attachments. In this embodiment, first and second pockets forming first and second upper members 20, may conceal the first and second upper edges 32 of lower member 30 under each pocket. The bottom edge of the first and second upper members 20, corresponding to lower edge 22 of upper member 20, are not sewn to the garment. However, some other means of releasable attachment, such as temporary closures may be used.
One embodiment of garment 10 provides shoulder straps for shoulder portion 36. The straps can be made of any suitable, desirable widths and they serve to provide bra coverage. In particular, a finished band folded in half over the top of the shoulder but unfolded adjacent to the connections at the front and back of garment 10 conceals any type of bra, including nursing bras which are often not as streamlined as nonnursing bras. The upper member 20 and the back of the garment 10 are suspended from the strap.
|
Improved clothing to be worn by a woman for breast feeding a baby which includes an upper member having a lower edge and a lower member having an upper edge. The upper edge of the lower member is made of such a resilient material that the upper edge tends to assume a nonaccess position, covering the breasts, but which can be pulled down to an access position under the breast to make it accessible to the baby. The upper and lower members are so positioned relative to each other when worn by a woman that at least a portion of the upper member overlaps the lower member. The lower edge of the upper member is suspended to an area below the breast to permit the upper member to shield the breast when the upper edge of the lower member is in either the access or nonaccess positions.
| 0
|
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention relates to shaving compositions delivered as aerosols exhibiting enhanced foaming qualities.
[0003] 2. The Related Art
[0004] Shaving is an inherently abrasive treatment of the skin. Cosmetic foams have been created to lubricate the cutting process. Lubrication markedly reduces the trauma induced by a razor.
[0005] Emollient ingredients of shaving creams are substantial contributors to reduction of irritation caused by the razor action.
[0006] Emollients have long been incorporated into cleansing compositions. For instance, U.S. Pat. No. 5,002,680 (Schmidt et al.) discloses a mild skin-cleansing aerosol mousse. Nice skinfeel after washing is imparted to the skin through a combination of mild surfactants, skinfeel polymers and high levels of moisturizing emollients. Similar skin cleansing compositions have been reported in U.S. Pat. No. 6,407,044 B2 (Dixon) wherein a hydrocarbon propellant system was used to generate a cleansing foam.
[0007] A problem with use of high levels of emollients is that they depress foam formation often even collapsing the bubbles. Systems are needed which foam well despite the presence of high levels of emollient oils.
SUMMARY OF THE INVENTION
[0008] A shaving cream composition is provided which includes:
[0009] (i) from about 1 to about 20% of a propellant comprising dimethyl ether and hydrocarbons in a relative weight ratio of about 5:1 to about 1:5;
[0010] (ii) from about 0.5 to about 25% of an anionic surfactant;
[0011] (iii) from about 0.05 to about 20% of a C 12 -C 24 fatty alcohol;
[0012] (iv) from about 5 to about 40% of a hydrophobic emollient;
[0013] wherein a total weight ratio of all hydrophobic emollients to all anionic surfactants present in the composition ranges from about 50:1 to greater than about 1:1.
DETAILED DESCRIPTION OF THE INVENTION
[0014] Now it has been found that a combination of factors can influence generation of a rich, long lasting shaving foam despite the presence of very high emollient levels. One factor is utilization of fatty alcohols which were found to interact with the surfactants to create small sustainable bubbles. Another factor is the use of dimethyl ether as at least one component of the propellant system. Fatty alcohol, dimethyl ether and the emollient all combine to provide a rich lasting foam that also delivers substantial emollient to the interface between skin and razor.
[0015] Accordingly, a first aspect of the present invention is that of a propellant. The propellant is present in amounts from about 1 to about 20%, preferably from about 3 to about 15%, optimally from about 5 to about 10% by weight of the composition. The propellant is a mixture of dimethyl ether and a C 3 -C 6 hydrocarbon. Suitable hydrocarbons include n-butane, isobutane, n-propane, isopropane, n-pentane, isopentane and mixtures thereof. Amounts of the dimethyl ether and total hydrocarbon are present in a relative weight ratio ranging from about 5:1 to about 1:5, preferably from about 4:1 to about 1:4, optimally from about 2:1 to about 1:2, and most optimally from about 1:1 to about 1:1.5.
[0016] Another component of the present invention is that of one or more anionic surfactants. These will be present in amounts from about 0.5 to about 25%, preferably from about 1 to about 15%, more preferably from about 3 to about 10%, optimally from about 4 to about 8% by weight of the composition.
[0017] Anionic surfactants useful herein include: acyl isethionates, acyl sarcosinates, alkylglycerylether sulfonates, alkyl sulfates, acyl lactylate, methylacyl taurates, paraffin sulfonates, linear alkyl benzene sulfonates, N-acyl glutamates, alkyl sulfosuccinates, alpha sulfo fatty acid esters, alkyl ether carboxylates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, alpha olefin sulphates, the alkyl ether sulfates (with 1 to 12 ethoxy groups) and mixtures thereof, wherein said surfactants contain C8 to C22 alkyl chains and wherein the counterion is preferably selected from the group consisting of Na, K, NH 4 , N(CH 2 CH 2 OH) 3 . Most preferred are lauryl ether sulfates.
[0018] Although soaps (i.e. salts of C 10 -C 22 fatty acids) are often used in shaving formulations, these materials are relatively irritating to the skin. For purposes of this invention, amounts of the soap advantageously is limited to no more than about 10%, ordinarily no more than about 2%, and preferably less than 10% or especially less than 0.1% by weight of the composition. Similarly, unsaponified soaps which are known as C 10 -C 24 fatty acids advantageously can also be avoided because of their acidity and foam inhibiting properties, particularly stearic acid. Levels of fatty acid, particularly stearic acid, is best held to less than 1%, preferably less than 0.8%, optimally less than 0.1% by weight of the composition. Under some circumstances, an amine neutralized fatty acid such as triethanolammonium stearate can be employed, particularly at levels from about 0.2 to about 1% by weight.
[0019] Amphoteric surfactants may be included in compositions of this invention. Amounts may range from about 0.5 to about 15%, preferably from about 1 to about 10%, optimally from about 3 to about 6% by weight. Illustrative of the amphoteric surfactant are cocoamidopropyl betaine, lauroamphoacetates and diacetates, alkyl dimethylamine oxides and combinations thereof. Particularly preferred are combinations of anionic and amphoteric surfactants, especially present in relative weight ratios of total anionic to total amphoteric surfactant ranging from about 10:1 to about 1:1, preferably about 3:1 to about 1.5:1.
[0020] The pH of the composition may range from about 4.5 to about 12.5. However, the pH is preferably near neutral and may range from about 6.5 to about 9.5, preferably from about 6.7 to about 8.5, optimally from about 7 to about 7.5.
[0021] Another component of compositions according to this present invention is a C 12 -C 24 fatty alcohol. This material may be present in an amount from about 0.05 to about 20%, preferably from about 0.2 to about 8%, more preferably from about 0.5% to about 5%, optimally from about 1 to about 3% by weight of the composition.
[0022] Illustrative fatty alcohols include stearyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, behenyl alcohol and combinations thereof.
[0023] Hydrophobic emollients are an important component of the present invention. These materials may be present from about 5 to about 40%, preferably from about 8 to about 30%, more preferably from about 10 to about 25%, optimally from about 15 to about 20% total hydrophobic emollient by weight of the composition.
[0024] Hydrophobic emollients may be in the form of natural oils (particularly vegetable oils), synthetic esters, hydrocarbons and silicone oils.
[0025] Natural oils include triglycerides such as sunflower seed oil, cottonseed oil, safflower oil, olive oil, rapeseed oil, canola oil, linseed oil, shea nut oil, palm oil, corn oil, babassu oil, peanut oil, sesame oil and combinations thereof. Chemically modified versions of vegetable oils may also be utilized. For instance, suitable may be brominated soybean oil and maleated soybean oil. Lanolin oils are another category of natural oils suitable for the present invention. Particularly useful is lanolin alcohol.
[0026] Synthetic esters may include:
[0027] (1) Alkenyl or alkyl esters of fatty acids having 10 to 20 carbon atoms. Examples thereof include isopropyl palmitate, isopropyl oleate, methyl palmitate, isoarachidyl neopentanoate, isononyl isonanonoate, oleyl myristate, oleyl stearate, and oleyl oleate.
[0028] (2) Wax esters such as beeswax, spermaceti wax and tribehenin wax.
[0029] (3) Sterols esters, of which cholesterol fatty acid esters are examples thereof.
[0030] (4) Sugar ester of fatty acids such as sucrose polybehenate and sucrose polycottonseedate.
[0031] Silicone oils may be divided into the volatile and nonvolatile variety. The term “volatile” as used herein refers to those materials which have a measurable vapor pressure at ambient temperature. Volatile silicone oils are preferably chosen from cyclic (cyclomethicone) or linear polydimethylsiloxanes containing from 3 to 9, preferably from 4 to 5, silicon atoms.
[0032] Nonvolatile silicone oils useful as an emollient material include polyalkyl siloxanes, polyalkylaryl siloxanes and polyether siloxane copolymers. The essentially nonvolatile polyalkyl siloxanes useful herein include, for example, polydimethyl siloxanes with viscosities of from about 5×10 −6 to 0.1 m 2 /s at 25 C. Among the preferred nonvolatile emollients useful in the present compositions are the polydimethyl siloxanes having viscosities from about 1×10 −5 to about 4×10 −4 m 2 /s at 25 C.
[0033] Another class of nonvolatile silicones are emulsifying and non-emulsifying silicone elastomers. Representative of this category is Dimethicone/Vinyl Dimethicone Crosspolymer available as Dow Corning 9040, General Electric SFE 839, and Shin-Etsu KSG-18. Silicone waxes such as Silwax WS-L (Dimethicone Copolyol Laurate) may also be useful.
[0034] Hydrocarbons which are suitable as hydrophobic emollients include petrolatum, mineral oil, C 11 -C 13 isoparaffins, polyalphaolefins, and especially isohexadecane, available commercially as Permethyl 101A from Presperse Inc.
[0035] Advantageously the total weight ratio of all hydrophobic emollients to all anionic surfactants may range from about 50:1 to greater than about 1:1, preferably from about 30:1 to about 2:1, optimally from about 5:1 to about 1.5:1.
[0036] Hydrophilic emollients may also be included in compositions of this invention. These type are usually polyhydric alcohols which include glycerol, polyalkylene glycols and more preferably alkylene polyols and their derivatives, including propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol and derivatives thereof, sorbitol, hydroxypropyl sorbitol, hexylene glycol, 1,3-butylene glycol, isoprene glycol, 1,2,6-hexanetriol, ethoxylated glycerol, propoxylated glycerol and mixtures thereof. The amount of hydrophilic emollient may range anywhere from about 0.5 to about 30%, preferably between about 1 and about 10% by weight of the composition. When both hydrophobic and hydrophilic emollients are present they may range from about 20:1 to greater than about 1:1 in weight ratio.
[0037] Preservatives may also desirably be incorporated into the compositions of this invention to protect against the growth of potentially harmful microorganisms. Preservatives which have more recently come into use include hydantoin derivatives, propionate salts, and a variety of quaternary ammonium compounds. Cosmetic chemists are familiar with appropriate preservatives and routinely choose them to satisfy the preservative challenge test and to provide product stability. Particularly preferred preservatives are phenoxyethanol, methyl paraben, propyl paraben, imidazolidinyl urea, sodium dehydroacetate and benzyl alcohol. The preservatives should be selected having regard for the use of the composition and possible incompatibilities between the preservatives and other ingredients in the emulsion. Preservatives are preferably employed in amounts ranging from 0.01% to 2% by weight of the composition.
[0038] Skin conditioners may be incorporated into compositions of this invention. For instance, these materials can be cationic polysaccharides and particularly cationic guar gums with number average molecular weights ranging from 1000 to 3 million; polymers formed from acrylic and/or methacrylic acid; cationic polymers of dimethyl dialkyl ammonium salts and acrylic acids; cationic homopolymers of dimethyl dialkylammonium salts; cationic polyalkylene and ethoxy polyalkylene imines; polyethylene glycol of molecular weight from 100,000 to 4 million; and combinations thereof. Particularly suitable are sodium polyacrylate, hydroxyethyl cellulose and combinations thereof. Most particularly useful are quaternary materials identified by the CTFA names of polyquaternium-3, polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-11 and polyquaternium-24. Most preferred is guar hydroxypropyl trimonium chloride sold as Jaguar C13S by Rhone Poulenc. Amounts of the conditioners may range from about 0.01 to about 2%, preferably from about 0.1 to about 1%, optimally from about 0.2 to about 0.8% by weight of the composition.
[0039] Sunscreen actives may be included in the compositions. Particularly preferred are Parsol MCX®, Parsol 1789® and benzophenone-3. Inorganic sunscreen actives may be employed such as microfine titanium dioxide, zinc oxide, polyethylene and various other polymers. Amounts of the sunscreen agents when present may generally range from 0.1 to 15%, preferably from 2 to 8%, optimally from 3 to 6% by weight.
[0040] Anti-microbial agents which are intended for deposition onto body surfaces may also be formulated into the compositions. Illustrative are the aluminum salts including aluminum chlorohydrate, aluminum zicronium tetrachlorohydrex glycinate, zinc phenosulfonate, chlorhexidine, hexetidine, zinc citrate, 2,4,4′-trichloro-2′-hydroxydiphenyl ether (triclosan) and 3,4,4′-trichlorocarbanilide (triclocarbon). Amounts of the anti-microbials may be utilized at levels from about 0.0001 to about 15%, preferably from about 0.1 to about 5% by weight.
[0041] Compositions of the present invention may include vitamins. Illustrative vitamins are Vitamin A (retinol), Vitamin B 2 , Vitamin B 6 , Vitamin C, Vitamin E and Biotin. Derivatives of the vitamins may also be employed. For instance, Vitamin C derivatives include ascorbyl tetraisopalmitate, magnesium ascorbyl phosphate and ascorbyl glycoside. Derivatives of Vitamin E include tocopheryl acetate, tocopheryl palmitate and tocopheryl linoleate. DL-panthenol and derivatives may also be employed. Total amount of vitamins when present in compositions according to the present invention may range from 0.001 to 10%, preferably from 0.01% to 1%, optimally from 0.1 to 0.5% by weight.
[0042] A variety of herbal extracts may optionally be included in compositions of this invention. Illustrative are green tea, chamomile, licorice and extract combinations thereof. The extracts may either be water soluble or water-insoluble carried in a solvent which respectively is hydrophilic or hydrophobic. Water and ethanol are the preferred extract solvents.
[0043] Colorants, fragrances, opacifiers and abrasives may also be included in compositions of the present invention. Each of these substances may range from about 0.05 to about 5%, preferably between 0.1 and 3% by weight.
[0044] Compositions of the present invention will contain water in amounts ranging from about 10% to about 92%, preferably from about 30 to about 70%, optimally from about 40 to about 60% by weight.
[0045] Hydrophobic emollients are delivered to the shaving surface by the composition in average droplet size ranging from about 0.00001 to about 350, more preferably from about 0.0001 to about 5, optimally from about 0.001 to about 1 micron in diameter.
[0046] The term “comprising” is meant not to be limiting to any subsequently stated elements but rather to encompass non-specified elements of major or minor functional importance. In other words the listed steps, elements or options need not be exhaustive. Whenever the words “including” or “having” are used, these terms are meant to be equivalent to “comprising” as defined above.
[0047] Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material ought to be understood as modified by the word “about”.
[0048] All documents referred to herein, including patents, patent applications and printed publications, are hereby incorporated by reference in their entirety in this disclosure.
[0049] The following examples will more fully illustrate the embodiments of this invention. All parts, percentages and proportions referred to herein and in the appended claims are by weight unless otherwise illustrated.
EXAMPLES 1-8
[0050] Shaving creams according to the present invention are detailed in the Table below.
Example (Weight %) Ingredient 1 2 3 4 5 6 7 8 Sunflower Seed 24.0 24.0 16.0 16.0 12.0 12.0 19.5 19.5 Oil Lanolin 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Alcohol/ Cholesterol Cocoamide 1.8 1.8 1.8 2.5 2.5 2.5 2.5 2.5 Monoethanol- amide Myristyl 1.9 1.9 1.9 2.8 1.9 2.8 2.0 3.0 Alcohol Lauryl Alcohol — — — — 0.9 — 1.0 — Petrolatum 3.5 3.5 3.5 3.5 4.5 4.5 1.5 7.5 Glycerol 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 Cocoamido- 3.2 6.3 3.2 6.3 3.2 3.2 3.2 3.2 propyl Betaine Sodium 6.3 3.2 6.3 3.2 6.3 6.3 6.3 6.3 Laureth Sulphate Guar 0.1 0.1 0.3 0.3 0.3 0.3 0.4 0.5 Hydroxy- propyl Trimonium Chloride Isopropyl 1.4 1.4 1.4 1.4 2.7 2.7 2.7 2.7 Palmitate Tetrasodium 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 EDTA DMDM 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Hydantoin Etidronic Acid 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Fragrance 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Dimethyl 3.0 2.0 2.0 3.0 2.0 1.0 2.0 2.0 Ether Propane 0.5 0.5 0.5 0.5 1.5 0.5 0.5 2.5 Isobutane 2.5 0.5 2.5 0.5 2.5 3.5 2.0 0.5 Water to to to to to to to to 100 100 100 100 100 100 100 100
[0051] The shaving creams outlined in the Table are packaged in an aerosol metal can fitted with a conventional aerosol spray head with nozzle. Prior to use, instructions on the can request a user to thoroughly shake the combination before expressing the foam by pressing downward on the spray head. After the cream has been placed on a human face, underarm or legs, a razor is applied over the skin area to remove hair by cutting. These formulations are particularly suitable for legs and underarm.
EXAMPLE 9
[0052] This Example evaluates the effect of different propellant mixtures on the quality of the foam. The formula detailed in the Table below was utilized for evaluations under this Example.
INGREDIENT WEIGHT % Sunflower Seed Oil 21.3 Petrolatum 5.7 Glycerin 3.7 Sodium Lauryl Ether Sulphate (3 EO) 6.6 Cocoamidopropyl Betaine 3.3 Water Balance
[0053] The formula of shaving cream outlined above was packaged in aerosol metal canisters fitted with a conventional aerosol spray head with nozzle. Each canister was also filled with a propellant in equal weight throughout. Identity of the propellant is found in the Table below. Samples were evaluated in a Compression (Squeeze) Test and measured for the Liquid Fraction of the foam.
[0054] Measurement of Liquid Fraction of Foam
[0055] Liquid volume fractions of foams were obtained by weighing a known volume of foam. The weight of the foam essentially can all be attributed to its liquid fraction as the remaining volume of foam consists of air. To measure the liquid fraction, foam was expelled from a sample canister into a plastic Petri dish having a volume of 5.2 ml. The level of the foam was carefully adjusted to the height of the dish with a metal spatula so that the foam was contained within the volume of the dish. The weight of the dish with the foam was recorded. After subtracting the weight of the dish, the weight of the foam was used to calculate the liquid phase volume. The weight of the foam is divided by the density of the formulation to obtain the volume of the liquid portion of the formula. The liquid fraction is then the volume of the liquid divided by the total volume of foam (in these tests, 5.2 ml). Samples were measured in triplicate.
[0056] Rheology of Foams—Compression (Squeeze) Test
[0057] The Compression Test measures the force required to compress the foam generated from a formulation expelled from a canister. Measurements were performed using a Rheometric Scientific ARES controlled strain rheometer (SR-5, Rheometric Scientific, Piscataway, N.J.). The rheometer was set up with parallel plates 50 mm in diameter with a gap of 2.0 mm between the plates. Foams were loaded between the parallel plates and then tests were formed using programmed extension mode which subjects the foams to an axial deformation applied at a programmed rate. The foam samples were compressed at controlled rate of 0.25 mm/second, brought back to initial state at a rate of 0.33 mm/sec and then extended at a rate of 0.25 mm/sec. Tests were performed at 25° C. The output is the normal force (grams) associated with the compression and extension of the foams.
[0058] Higher force values reflect a more rigid, better foam quality. When product is expelled from a canister, some is in gaseous form and some extrudes as a liquid. The greater the amount of liqued, the lower the foam quality.
Liquid Fraction Compression Test Aver- Std Normal Sam- Propellant % age dev Force Aver- Std ple Can DME A70* w/w % % (g) age dev A 1 100 0 25.93 26.39 1.94 111 210.3 117.5 2 24.72 180 3 28.51 340 B 1 80 20 16.97 16.96 0.38 502 431.0 67.0 2 17.33 369 3 16.57 422 C 1 66 33 18.05 17.14 0.85 419 435.7 36.9 2 17.00 478 3 16.37 410 D 1 33 66 5.53 10.64 4.60 500 517.3 28.3 2 11.94 550 3 14.45 502 E 1 20 80 4.24 7.36 3.91 505 514.0 50.1 2 11.75 568 3 6.08 469 F 1 0 100 5.24 5.65 0.74 539 499.0 45.2 2 6.51 450 3 5.20 508
[0059] Sample A was found to deliver a dead non-springy foam. This is evidenced by the relatively low compression test average of 210.3 g force. Samples B through E were able to be worked during hand washing and did not break into undesirable smaller segments of foam. The working ability is attributed to the relatively high level of liquid fraction. By contrast, Sample F was extremely fluffy, containing too much air and did not wash-off well from the skin. It is evident that such as in Samples B through E combinations of dimethyl ether and hydrocarbon are necessary to obtain a satisfactory shaving cream product.
|
A shaving cream composition and method is provided wherein the cream composition is packaged in an aerosol dispenser and includes a propellant system of dimethyl ether and hydrocarbon, an anionic surfactant, a fatty alcohol and a hydrophobic emollient. Total weight ratio of all hydrophobic emollients to all anionic surfactants ranges from about 50:1 to greater than about 1:1. An improved shaving experience is achieved through use of the dimethyl ether/hydrocarbon propellant, fatty alcohol and high level of hydrophobic emollient.
| 0
|
CLAIM OF PRIORITY
[0001] The present application claims priority from Japanese patent application JP 2011-249789 filed on Nov. 15, 2011, the content of which is hereby incorporated by reference into this application.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a wireless communication system, a wireless communication method, and a gateway, and more particularly to a wireless communication system such as a mobile communication system, a wireless communication method such as a mobile communication system, and a distributed gateway used in the wireless communication system such as the mobile communication system, which enhance a load distribution effect of a communication network.
[0004] 2. Background Art
[0005] In general, a mobile communication system has a hierarchical structure. A WiMAX system will be described as an example of the mobile communication system having the hierarchical structure.
[0006] FIG. 23 is a diagram illustrating an outline of the WiMAX system.
[0007] The WiMAX system includes a mobile station (MS) 700 , a base station (BS) 600 , a BS 601 , a BS 602 , an access service network gateway (ASN-GW) 100 that manages the BSs, and a connectivity service network (CSN) 400 . The CSN 400 has authentication, authorization, and accounting (AAA) related to accounting and authentication. Also, the CSN 400 has a home agent (HA) in a system that supports an IP. When the CSN 400 provides an internet service, the CSN 400 is connected to an internet 500 .
[0008] The WiMAX system has a hierarchical structure in which the plurality of BS 600 , BS 601 , and BS 602 are connected to the ASN-GW 100 through a network 5002 , a network 5003 , and a network 5001 . One of reasons that the mobile communication system has the hierarchical structure resides in the mobility realization of the MS 700 . For example, let us consider a case in which the MS 700 travels from the BS 600 to the BS 601 . The BS 600 of a travel source and the BS 601 of a travel destination are consolidated in the identical ASN-GW 100 , to thereby realize handover in which the ASN-GW 100 detects the travel of the MS 700 , and continues service.
[0009] FIG. 25 is a diagram illustrating a connection sequence of the WiMAX specified by WiMAX Forum of a standards body.
[0010] The MS 700 , the BS 600 , the ASN-GW 100 , and the CSN 400 exchange messages with each other in conformity with the provision ( 800 to 821 ), and establish a radio path 822 between the MS 700 and the BS 600 , and a generic routing encapsulation (GRE) capsuling path 823 between the BS 600 and the ASN-GW 100 . When the MS 700 accesses to the internet, the MS 700 transmits user data to the BS 600 as radio data 7100 . The BS 600 transfers the received user data to the ASN-GW 100 as GRE capsuling data 7101 . Further, the ASN-GW 100 transfers the user data to the CSN 400 , and the CSN 400 transfers the user data to the internet 500 .
[0011] FIG. 26 is a diagram illustrating a GRE packet format of the GRE capsuling data between the BS and the ASN-GW. A GRE packet includes an IP header 7050 , a GRE header 7051 , and user data 7052 . The user data 7052 is an IP packet transmitted by the MS 700 . IP addresses of the BS 600 and the ASN-GW 100 are stored in the IP header 7050 , and used as communication addresses of the BS 600 and the ASN-GW 100 which terminate a GRE tunnel. A GRE KEY specified in, for example, an RFC 2784 GRE and an RFC 1701 GRE is included in the GRE header 7051 , and used to identify the MS 700 .
[0012] In the mobile system thus stratified, the user data communicated by the MS 700 passes through the BS 600 via a radio zone as the radio data 7100 , passes through the network 5002 and the network 5001 between the BS 600 and the ASN-GW 100 , and arrives at the CSN 400 through the ASN-GW 100 . The CSN 400 transfers the user data to the internet 500 according to routing.
[0013] FIG. 24 is a functional schematic diagram of the ASN-GW in the WiMAX system.
[0014] Also, the WiMAX Forum specifies that a function of the ASN-GW is divided into a function of processing signaling and a function of processing bearer data in a form illustrated in FIG. 24 . A function unit for processing signaling is called “ASN-GW decision point 200 ”, and a function unit for processing the bearer data is called “ASN-GW enforcement point 300 ”.
[0015] As a related art, JP-A-2009-253678 proposes a method in which a load of a device is checked and allocated as an allocation method to the bearer data processing function.
SUMMARY OF THE INVENTION
[0016] In the above-mentioned related art mobile communication system, because a hierarchical network is applied, a plurality of base stations are intensively connected to the ASN-GW 100 . For that reason, data communicated by a large number of MSs behind the plurality of BSs is multiplexed every time the data passes through the networks 5002 and 5003 , further multiplexed by the network 5001 that bundles the networks together to arrive at the ASN-GW 100 , and is converged. That is, a data traffic volume is increased more as the data comes closer to the ASN-GW 100 . It is assumed that the increase in the data traffic presses a network capacity with the development of the mobile communication and an increase in the capacity of the content in recent years, and needs for decreasing a network load are demanded. Also, JP-A-2009-253678 has proposed that the signaling function unit and the bearer data function unit are separated from each other, and the bearer data function unit checks the amount of load of the bearer data function unit, and allocates the load to users. However, although the load of the bearer data function unit within the device can be distributed, a data traffic load of the overall network cannot be distributed. When the ASN-GWs are simply distributed as a solution, it is assumed that handover across the ASN-GWs frequently occurs, and the amount of signaling for handover is increased. As a result, service may be discontinued in a system applying no mobile IP.
[0017] The present invention has been made in view of the above, and one object of the present invention is to distribute a network load by terminating bearer data by a bearer data processing device arranged in a network close to a base station, and transferring the bearer data to an internet connected to the same network. Another object of the present invention is to process handover as handover within a gateway for the base station by converging signaling processing devices.
[0018] In order to achieve the above object, according to the present invention, there is provided a mobile communication system having a hierarchical structure such that a plurality of base stations are connected to a gateway through networks, and each of the plurality of base stations communicates with a plurality of mobile stations, in which the gateway includes a signaling processing device and bearer data processing devices, the signaling processing device is concentrated, and the bearer data processing devices are distributed to the networks close to the base stations. The signaling processing device of the gateway determines, in response to a connection request from each mobile station, the bearer data processing device connected to the network close to the base station covering the mobile station according to a position of the base station, and connects the base station to the determined bearer data processing device. Also, with the provision of a plurality of the bearer data processing devices within an area of each network, when a certain bearer data processing device is in failure, another bearer data processing device which is not in failure is specified, and notified the base station of.
[0019] According to the first solving means of the present invention, there is provided a wireless communication system comprising a hierarchical structure such that a plurality of base stations are connected to a gateway through a network, and each of the plurality of base stations communicates with a plurality of wireless terminals, wherein
[0020] the gateway includes a signaling processing device for processing signaling, and one or a plurality of bearer data processing devices for processing bearer data,
[0021] the plurality of base stations, the network, and one or a plurality of the bearer data processing devices are defined as one area,
[0022] one signaling processing device is concentrated for a plurality of the areas,
[0023] the signaling processing device includes a position management table indicating which area each of the base stations is located in, and which area the bearer data processing devices are set with respect to the areas in which
[0024] the respective base stations are located, the signaling processing device allocates the bearer data processing device to the area in which the base station is located in response to a connection request from any one of the wireless terminal,
[0025] each of the bearer data processing devices has an information table that stores wireless terminal addresses, base station addresses, and capsulation key information necessary for encapsulating and decapsulating in association with each other,
[0026] each of the bearer data processing devices is located on the basis of the area in which the base stations are located, and communicates the bearer data with one or the plurality of base stations within the area,
[0027] each of the base stations transmits the connection request including base station identification information to the signaling processing device according to a request from the wireless terminal,
[0028] upon receiving the connection request, the signaling processing device refers to the position management table, and executes bearer data processing device search processing for specifying a bearer data processing device address of the bearer data processing device connected to the base station on the basis of the base station identification information included in the connection request,
[0029] the signaling processing device transmits an address to be allocated to the wireless terminal to the base station,
[0030] the signaling processing device transmits the bearer data processing device address of the bearer data processing device specified by the bearer data processing device search to the base station,
[0031] the signaling processing device and the bearer data processing device exchange the capsulation key information necessary for encapsulating and decapsulating between the base station and the bearer data processing device,
[0032] the signaling processing device transmits a setup request including the wireless terminal address, the base station address, and the capsulation key address to the bearer data processing device in which the capsulation key information is specified by the bearer data processing device search, and
[0033] the bearer data processing device sets the wireless terminal address, the base station address, and the capsulation key information to the information table according to the setup request received from the signaling processing device, and completes a connection of a capsulation path between the base station and the bearer data processing device.
[0034] According to the second solving means of the present invention, there is provided a wireless communication method in a wireless communication system comprising a hierarchical structure such that a plurality of base stations are connected to a gateway through a network, and each of the plurality of base stations communicates with a plurality of wireless terminals, wherein
[0035] the gateway includes a signaling processing device for processing signaling, and one or a plurality of bearer data processing devices for processing bearer data,
[0036] the plurality of base stations, the network, and one or a plurality of the bearer data processing devices are defined as one area,
[0037] one signaling processing device is concentrated for a plurality of the areas,
[0038] the signaling processing device includes a position management table indicating which area each of the base stations is located in, and which area the bearer data processing devices are set with respect to the areas in which the respective base stations are located,
[0039] the signaling processing device allocates the bearer data processing device to the area in which the base station is located in response to a connection request from any one of the wireless terminal,
[0040] each of the bearer data processing devices has an information table that stores wireless terminal addresses, base station addresses, and capsulation key information necessary for encapsulating and decapsulating in association with each other,
[0041] each of the bearer data processing devices is located on the basis of the area in which the base stations are located, and communicates the bearer data with one or the plurality of base stations within the area,
[0042] each of the base stations transmits the connection request including base station identification information to the signaling processing device according to a request from the wireless terminal,
[0043] upon receiving the connection request, the signaling processing device refers to the position management table, and executes bearer data processing device search processing for specifying a bearer data processing device address of the bearer data processing device connected to the base station on the basis of the base station identification information included in the connection request,
[0044] the signaling processing device transmits an address to be allocated to the wireless terminal to the base station,
[0045] the signaling processing device transmits the bearer data processing device address of the bearer data processing device specified by the bearer data processing device search to the base station,
[0046] the signaling processing device and the bearer data processing device exchange the capsulation key information necessary for encapsulating and decapsulating between the base station and the bearer data processing device,
[0047] the signaling processing device transmits a setup request including the wireless terminal address, the base station address, and the capsulation key address to the bearer data processing device in which the capsulation key information is specified by the bearer data processing device search, and
[0048] the bearer data processing device sets the wireless terminal address, the base station address, and the capsulation key information to the information table according to the setup request received from the signaling processing device, and completes a connection of a capsulation path between the base station and the bearer data processing device.
[0049] According to the third solving method of the present invention, there is provided a gateway in a wireless communication system comprising a hierarchical structure such that a plurality of base stations are connected to the gateway through a network, and each of the plurality of base stations communicates with a plurality of wireless terminals, wherein
[0050] the gateway includes a signaling processing device for processing signaling, and one or a plurality of bearer data processing devices for processing bearer data,
[0051] the plurality of base stations, the network, and one or a plurality of the bearer data processing devices are defined as one area,
[0052] one signaling processing device is concentrated for a plurality of the areas,
[0053] the signaling processing device includes a position management table indicating which area each of the base stations is located in, and which area the bearer data processing devices are set with respect to the areas in which the respective base stations are located,
[0054] the signaling processing device allocates the bearer data processing device to the area in which the base station is located in response to a connection request from any one of the wireless terminal,
[0055] each of the bearer data processing devices has an information table that stores wireless terminal addresses, base station addresses, and capsulation key information necessary for encapsulating and decapsulating in association with each other,
[0056] each of the bearer data processing devices is located on the basis of the area in which the base stations are located, and communicates the bearer data with one or the plurality of base stations within the area,
[0057] from each of the base stations, the connection request including base station identification information is transmitted to the signaling processing device according to a request from the wireless terminal,
[0058] upon receiving the connection request, the signaling processing device refers to the position management table, and executes bearer data processing device search processing for specifying a bearer data processing device address of the bearer data processing device connected to the base station on the basis of the base station identification information included in the connection request,
[0059] the signaling processing device transmits an address to be allocated to the wireless terminal to the base station,
[0060] the signaling processing device transmits the bearer data processing device address of the bearer data processing device specified by the bearer data processing device search to the base station,
[0061] the signaling processing device and the bearer data processing device exchange the capsulation key information necessary for encapsulating and decapsulating between the base station and the bearer data processing device,
[0062] the signaling processing device transmits a setup request including the wireless terminal address, the base station address, and the capsulation key address to the bearer data processing device in which the capsulation key information is specified by the bearer data processing device search, and
[0063] the bearer data processing device sets the wireless terminal address, the base station address, and the capsulation key information to the information table according to the setup request received from the signaling processing device, and completes a connection of a capsulation path between the base station and the bearer data processing device.
[0064] It is possible, according to the present invention, to distribute a network load by terminating bearer data by a bearer data processing device arranged in a network close to a base station, and transferring the bearer data to an internet connected to the same network. Also, it is possible, according to the present invention, to process handover as handover within a gateway for the base station by converging signaling processing devices.
BRIEF DESCRIPTION OF THE DRAWINGS
[0065] FIG. 1 is a diagram illustrating a mobile communication system according to an embodiment of the present invention;
[0066] FIG. 2 is a configuration diagram of a signaling processing device according to an embodiment of the present invention;
[0067] FIG. 3 is a configuration diagram of a bearer data processing device according to an embodiment of the present invention;
[0068] FIG. 4 is a diagram illustrating an example of a BS position management table according to an embodiment of the present invention;
[0069] FIG. 5 is a diagram illustrating an example of a position management table in the bearer data processing device;
[0070] FIG. 6 is a diagram illustrating an example of an information table necessary for bearer data assembly and disassembly in the bearer data processing device;
[0071] FIGS. 7A and 7B are diagrams illustrating an IPinIP encapsulation processing and decapsulation processing;
[0072] FIG. 8 is a diagram illustrating an example of a table storing statistical information necessary for accounting in the bearer data processing device;
[0073] FIG. 9 is a sequence diagram illustrating connection processing according to an embodiment of the present invention;
[0074] FIG. 10 is a flowchart illustrating allocation processing in the bearer data processing device according to an embodiment of the present invention;
[0075] FIG. 11 is a flowchart illustrating bearer data transfer in the bearer data processing device according to an embodiment of the present invention;
[0076] FIG. 12 is a diagram illustrating a format example of a setup request to the bearer data processing device;
[0077] FIG. 13 is a diagram illustrating decapsulation processing;
[0078] FIG. 14 is a diagram illustrating encapsulation processing;
[0079] FIG. 15 is a sequence diagram illustrating disconnection processing according to an embodiment of the present invention;
[0080] FIG. 16 is a diagram illustrating an example of the BS position management table according to an embodiment of the present invention;
[0081] FIG. 17 is a diagram illustrating a format of a BSID according to an embodiment of the present invention;
[0082] FIG. 18 is a flowchart illustrating the allocation processing in the bearer data processing device according to an embodiment of the present invention;
[0083] FIG. 19 is a diagram illustrating an example of the BS position management table according to an embodiment of the present invention;
[0084] FIG. 20 is a flowchart illustrating the allocation processing in the bearer data processing device according to an embodiment of the present invention;
[0085] FIG. 21 is a diagram illustrating an example of the BS position management table according to an embodiment of the present invention;
[0086] FIG. 22 is a flowchart illustrating the allocation processing in the bearer data processing device according to an embodiment of the present invention;
[0087] FIG. 23 is a schematic diagram of a WiMAX system which is one of the mobile communication systems;
[0088] FIG. 24 is a schematic diagram of a function of an ASN-GW in the WiMAX system;
[0089] FIG. 25 is a diagram illustrating a connection sequence of the WiMAX; and
[0090] FIG. 26 is a diagram illustrating a packet format of GRE capsuling data.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A. First Embodiment
[0091] Hereinafter, a description will be given of a WiMAX system according to an embodiment of the present invention.
1. System
[0092] FIG. 1 is a diagram illustrating a configuration of a WiMAX system according to this embodiment.
[0093] The WiMAX system according to this embodiment includes an MS 700 , a BS 600 , a BS 601 , a BS 602 , a GW-EP 301 , a GW-EP 302 , and a GW-EP 303 which are bearer data processing units of an ASN-GW, a GW-DP 201 which is a signaling function unit of the ASN-GW, a CSN 400 , an internet 500 , an internet 501 , an internet 502 , and a network 5001 , a network 5002 , and a network 5003 which are connected with devices. The GW-DP 201 , the GW-EP 301 , the GW-EP 302 , and the GW-EP 303 are characteristic configurations of this embodiment. Also, as characteristic definitions of this embodiment, it is assumed that the GW-EP 301 , the BS 600 , the BS 601 , and the network 5002 are in an area 1, and the GW-EP 302 , the GW-EP 303 , the BS 602 , and the network 5003 are in an area 2.
[0094] FIG. 2 is a diagram illustrating a configuration of the GW-DP 201 according to the embodiment of the present invention.
[0095] The GW-DP 201 includes an I/O port 2005 having a physical interface connected to the BSs and the CSN, a packet buffer 2006 that stores data received from the I/O port 2005 therein, a control unit 2002 that decrypts the received data to create an appropriate response message, a program memory 2003 in which software is stored, a GW-EP position management unit 2004 that manages position information on the BS and the GW-EP, and an EP-IF 2007 that communicates with the EP-GW.
[0096] FIGS. 4 and 5 illustrate an example of a table stored in the EP-GW position management unit 2004 . The table of FIG. 4 includes an index, a BS IP address, and an area, and the area in which the BSs are located is specified and set in advance. A table of FIG. 5 includes an area, a GW-EP IP address, and a state. The state is information such as a flag showing an IP address of the GW-EP set within the area and a state of the GW-EP are normal, or failure.
[0097] FIG. 3 is a diagram illustrating configurations of the GW-EP 301 , the GW-EP 302 , and the GW-EP 303 according to the embodiment of the present invention. Each of the GW-EP 301 , the GW-EP 302 , and the GW-EP 303 includes an I/O port 3014 having a physical interface that connects the BS and the CSN to each other, an encapsulation/decapsulation processing unit 3015 that dissembles and assembles data received from the I/O port 3014 , a control unit 3011 that instructs and sets information necessary for the disassembly and assembly of the data, a program memory 3012 in which software is stored, an accounting statistics collection unit 3013 that stores statistics data that are an accounting base, a DP-IF 3016 that provides a notice to the GW-DP, and a bus 3010 that connects the respective function units to each other.
[0098] FIG. 6 illustrates an example of a table stored in the encapsulation/decapsulation processing unit 3015 . The table of FIG. 6 includes an index, an MS IP address, a BS IP address, a down link GRE KEY, an up link GRE Key, and a connection type. Further, the table can include an index, an HA IP address, an SPI, and an MIP KEY necessary for a mobile IP connection.
[0099] FIG. 8 illustrates an example of a table stored in the accounting statistics collection unit 3013 . The table includes an index, the number of down link bytes, the number of up link bytes, the number of down link packets, and the number of up link packets.
2. Connection Sequence
[0100] Subsequently, a connection sequence according to this embodiment will be described.
[0101] FIG. 9 is a diagram illustrating an example of a procedure for determining the allocation of the GW-EPs in the connection sequence.
[0102] The MS 700 transmits an SBC-REQ 800 that is a connection request to the BS 600 when making a request for connection. The BS 600 that has received the SBC-REQ 800 transmits MS_PreAttachment_Req. 801 corresponding to the connection request to the GW-DP 201 . Upon receiving the MS_PreAttachment_Req. 801 , the GW-DP 201 specifies the GW-EP suitable for connection to the BS 600 that has transmitted the MS_PreAttachment_Req. 801 with the use of the tables of FIGS. 4 and 5 in the EP-GW position management unit 2004 of FIG. 2 .
[0103] FIG. 10 is a flowchart illustrating processing for specifying the GW-EP suitable for the BS 600 that has transmitted the request for connection.
[0104] Upon receiving the MS_PreAttachment_Req. 801 , the control unit 2002 starts steps in FIG. 10 , and allows the operation to proceed to Step S 2002 . In Step 2002 , the control unit 2002 specifies an IP address of the BS. A source IP address included in an IP header of the MS_PreAttachment_Req. 801 is the IP address of the BS. Upon specifying the BS IP address, the control unit 2002 allows the operation to proceed to Step 2003 . In Step 2003 , an area in which the BS is located is specified with the use of the table of FIG. 4 . First, the control unit 2002 searches the BS IP address extracted in Step 2002 from a BS IP address column of the table. An area column on the same row as that of the matched index is the area in which the BS is located. For example, if the BS IP address of the extracted BS 600 is 192.168.10.2, it is found that the index matches an index 1, and an area thereof is 1. After specifying the area, the control unit 2002 allows the operation to proceed to Step 2004 . In Step 2004 , the control unit 2002 specifies the IP address of the suitable GW-EP with the use of the table in FIG. 5 . The control unit 2002 searches the area specified in Step 2003 from an area row, and acquires the GW-EP IP address on the matched row. In the case of the area 1 in the above-mentioned example, 192.168.100.1 becomes the GW-EP IP address. After acquiring the GW-EP IP address, the control unit 2002 allows the operation to proceed to Step 2005 . In this Step 2005 , the control unit 2002 determines whether a state of the GW-EP IP address acquired in Step 2004 is normal, or failure. If failure, the operation is returned to Step 2004 , and the control unit 2002 searches another GW-EP IP address. If the state is normal, the control unit 2002 returns the operation to Step 2006 , and completes the operation.
[0105] Returning to FIG. 9 , when GW-EP search processing 830 is completed, the GW-DP 201 transmits a response message MS_PreAttachment_Rsp 802 responsive to the MS_PreAttachment_Req. 801 to the BS 600 . The BS 600 transmits a MS_PreAttachment_Ack 804 to the GW-DP 201 as a response to reception of the response message MS_PreAttachment_Rsp 802 . Upon receiving the MS_PreAttachment_Ack 804 , the GW-DP 201 transmits an EAP-Request 805 to the BS 600 for conducting authentication. Upon receiving the EAP-Request 805 , the BS 600 transfers the EAP-Request 805 to the MS 700 as an EAP-REQ 806 , and thereafter transmits an EAP-RSP 807 response from the MS 700 to the GW-DP 201 as an EAP-Response 808 .
[0106] An network access identifier (NAI) called “identity” is included in the EAP-Response 808 . Upon receiving the EAP-Response 808 , the GW-DP 201 extracts the NAI. The NAI has a format of user@Domain, and a domain to which the MS 700 joins can be known by viewing the domain. The GW-DP 201 determines a connection type (simple IP or mobile IP) for each of the domains in advance, and further extracts the domain from the extracted NAI. The GW-DP 201 knows the domain from the extracted domain, and determines whether the connection type of the MS 700 that has made the request for connection is the simple IP, or the mobile IP. After determination of the connection type, the GW-DP 201 transmits an Access-Request 809 to an authentication server set within the CSN 400 . Thereafter, an EAP authentication 810 is conducted between the authentication server and the MS 700 , and if authentication results are successful, an Access-Accept 811 is transmitted to the GW-DP 201 from the authentication server. The Access-Accept 811 includes an IP address to be allocated to the MS 700 . After receiving the Access-Accept 811 , the GW-DP 201 extracts the IP address to be allocated to the MS 700 , stores the IP address in the GW-DP 201 , and thereafter transmits the IP address to the BS 600 as an EAP-Success 812 . Further, the BS 600 transmits an EAP-SUC 813 .
[0107] After that, signals necessary for connection are exchanged between the BS 600 and the GW-DP 201 in conformity with the connection sequence specified by the WiMAX Forum (information exchange 814 , radio encryption key/MS information exchange 815 ). With advancing of the processing, the GW-DP 201 transmits a Path_Reg_Req. 816 to the BS. The Path_Reg_Req. 816 specifies that the IP address of the GW-EP specified by GW-EP search processing 830 can be allocated. In the above-mentioned example, the GW-DP 201 notifies the BS 600 of 192.168.100.1. Upon receiving the Path_Reg_Req. 816 , the BS 600 transmits a Path_Reg_Rsp. 819 which is a response message to the GW-DP 201 . The GW-DP 201 transmits a Path_Reg_Ack 820 as a response to reception of the Path_Reg_Rsp. 819 . In the Path_Reg_Req. 816 and the Path_Reg_Rsp. 819 , GRE KEY information necessary for encapsulating and decapsulating is exchanged between the BS 600 and the GW-EP 301 .
[0108] FIG. 13 is a diagram illustrating decapsulation processing. The GRE KEY is a KEY stored in a GRE header of a packet format illustrated in FIG. 13 , which is an identifier that specifies the MS.
[0109] The GW-DP 201 transmits a setup request 831 to the GW-EP 301 in which the GRE KEY information is specified by the GW-EP search processing 830 .
[0110] FIG. 12 illustrates an example of a format of the setup request.
[0111] The setup request includes an IP header 8311 , an UDP header 8312 , a type 8313 , and one or a plurality of information elements 8310 . The type 8313 is used for distinguishing the setup request 831 and a setup response 832 . The information elements 8310 include information set from the GW-DP to the GW-EP. In the first embodiment, elements of the MS IP address, the BS IP address, the down link GRE KEY, and the up link GRE KEY are included as the information elements of the setup request 831 . Also, if the information terminal is a system that supports the mobile IP, an HA IP address and the connection type (simple IP or mobile IP) necessary for the mobile IP can be also included.
[0112] The GW-EP 301 receives the setup request 831 transmitted from the GW-DP 201 from the DP-IF 3016 of FIG. 3 . The received message is decrypted by the control unit 3011 , and the MS IP address, the BS IP address, the down link GRE KEY, the up link GRE KEY, and the connection type are set to blank indexes of the table in FIG. 6 , of the encapsulation/decapsulation processing unit 3015 . If the HA IP address, the SPI, and the MIP KEY are included in the information element for the mobile IP, the control unit 3011 sets the mobile IP for the connection type, and also sets values thereof. If no information related to the mobile IP is included in the information element for the simple IP, the control unit 3011 sets the simple IP for the connection element. Upon finishing setting for the respective tables, the GW-EP 301 creates the setup response 832 , and transmits the setup response 832 to the GW-DP 201 .
[0113] Returning to FIG. 9 , upon completing the setting for the GW-EP 301 , a GRE capsuling path 823 is completed between the BS 600 and the GW-EP 301 . Thereafter, a DHCP exchange 824 is conducted, and the GW-DP 201 notifies the MS 700 of the IP address to be allocated to the MS 700 , which is extracted and stored when receiving the Access-Accept 811 , and completes the connection. When supporting the mobile IP, the GW-DP 201 establishes the HA and a mobile IP 825 set in the CSN 400 .
[0114] Subsequently, the routing operation of the user data will be exemplified by a case in which the MS 700 accesses to the internet. The MS 700 transmits the user data from the MS 700 toward a destination of the internet for connection to the internet. The user data arrives at the BS 600 through a radio zone. The BS 600 conducts GRE encapsulating on the user data with the use of the GRE KEY of the GRE capsuling path established by the above-mentioned connection sequence, and transmits the user data to the GW-EP 301 as GRE capsuling data 7101 . Upon receiving the GRE capsuling data from the I/O port 3014 , the GW-EP 301 transfers the GRE capsuling data to the encapsulation/decapsulation processing unit 3015 .
[0115] The data reception leads the encapsulation/decapsulation processing unit 3015 to conduct routing processing according to a flowchart of FIG. 11 .
[0116] FIG. 11 is a flowchart illustrating the bearer data transfer in the bearer data processing device according to the embodiment of the present invention. In Step 3002 , the encapsulation/decapsulation processing unit 3015 determines whether a protocol type present in the IP header of the received data is GRE, or not. If yes, the operation proceeds to Step 3003 whereas if no, the operation proceeds to Step 3011 . In Step 3003 , the encapsulation/decapsulation processing unit 3015 extracts the GRE KEY included in the GRE header of the received data. After extraction of the GRE KEY, the operation proceeds to Step 3004 . In Step 3004 , the MS is specified with the use of the table in FIG. 6 . For example, if the extracted GRE KEY is 0xFFFF0001, the encapsulation/decapsulation processing unit 3015 searches a row of the up link GRE KEY in FIG. 6 for searching the matched index, and acquires the matched index. Information related to the MS such as the MS IP address and the connection type are present on the row of the same index. After specifying the MS, the encapsulation/decapsulation processing unit 3015 allows the operation to proceed to Step 3005 , and conducts GRE decapsulation processing to eliminate the GRE capsuling.
[0117] FIG. 13 is a diagram illustrating the GRE decapsulation processing.
[0118] In the GRE decapsulation processing, the encapsulation/decapsulation processing unit 3015 removes an IP header 7066 and a GRE header 7067 from the CRE capsuling data which is received data indicated on an upper stage of FIG. 13 , extracts user data 7068 , and allows the operation to proceed to Step 3006 . In Step 3006 , the encapsulation/decapsulation processing unit 3015 measures the number of bytes of the user data 7068 , and notifies the accounting statistics collection unit 3013 of the index and the number of bytes acquired in Step 3004 .
[0119] FIG. 8 is a diagram illustrating an example of a table that stores statistics information necessary for accounting in the bearer data processing device. The accounting statistics collection unit 3013 adds the notified number of bytes to the number of up link bytes in the statistics information table in FIG. 8 corresponding to the notified index, and adds +1 to the number of up link packets.
[0120] After addition, the operation proceeds to Step 3007 . In Step 3007 , the encapsulation/decapsulation processing unit 3015 determines whether the connection type is the simple IP or the mobile IP. If the connection type is the simple IP, the encapsulation/decapsulation processing unit 3015 transfers the user data to the I/O port 3014 , and allows the operation to proceed to Step 3009 . If the connection type is the mobile IP, the encapsulation/decapsulation processing unit 3015 allows the operation to proceed to IPinIP encapsulating processing 53008 of Step 3008 .
[0121] FIG. 7A is a diagram illustrating the IPinIP encapsulation processing.
[0122] In the IPinIP encapsulation processing, an IP header 7100 is allocated to the user data 7068 extracted in the GRE decapsulating processing capsulation processing 3005 indicated on an upper stage of FIG. 7A . The HA IP address is set to the destination IP address 7101 of the allocated IP header, and the IP address of the GW-EP 301 is set to a source IP address 7102 . After conducting the IPinIP encapsulating processing, the encapsulation/decapsulation processing unit 3015 transfers the user data to the I/O port 3014 , and allows the operation to proceed to Step 3009 . In Step 3009 , the encapsulation/decapsulation processing unit 3015 conducts appropriate routing processing, and transmits the data to the network 5002 . If the network 5002 is connected to the internet 501 , the data is transferred to the internet 501 in conformity with a normal IP routing.
[0123] On the other hand, when the user data of down link which is transmitted from the internet 501 to the MS 700 arrives at the GW-EP 301 , the user data is transferred to the encapsulation/decapsulation processing unit 3015 through the I/O port 3014 , and the routing processing of FIG. 11 is executed. In Step 3002 , the encapsulation/decapsulation processing unit 3015 checks whether the protocol type of the IP header is the GRE, or not. Because the data received from the internet 501 is not the GRE capsuling data, the determination is no, and the operation proceeds to Step 3011 . In Step 3011 , the encapsulation/decapsulation processing unit 3015 checks whether the protocol type of the IP header is IPinIP, or not. This is different depending on whether the connection type is the mobile IP or the simple IP, and if the connection type is the mobile IP, the check determination is yes, and the operation proceeds to IPinIP decapsulation processing in Step 3012 .
[0124] FIG. 7B is a diagram illustrating the IPinIP decapsulation processing.
[0125] In the IPinIP decapsulation processing, the encapsulation/decapsulation processing unit 3015 removes an IP header 7110 from an IPinIP packet indicated on an upper stage of FIG. 7B , and extracts user data 7078 . After extraction of the user data, the operation proceeds to Step 3013 . In the encapsulation/decapsulation processing unit 3015 , if the connection type is the simple IP, the determination in Step 3011 is no, and the operation proceeds to Step 3013 . In Step 3013 , the encapsulation/decapsulation processing unit 3015 searches the IP address that matches the destination address of the IP header from the table of FIG. 6 . If there is the matched IP address, the encapsulation/decapsulation processing unit 3015 acquires the index corresponding to the matched MS IP address, and allows the operation to proceed to Step 3014 . In Step 3014 , the encapsulation/decapsulation processing unit 3015 measures the number of bytes of the received data for statistics collection that is a base of accounting, and notifies the accounting statistics collection unit 3013 of the number of bytes and the index acquired in Step 3013 . The accounting statistics collection unit 3013 adds the notified number of bytes to the number of down link bytes in the table of FIG. 8 , which corresponds to the index number, and increments the counter of the number of down link packets by +1. Upon completion of down link data amount collection 3014 , the operation proceeds to Step 3015 .
[0126] FIG. 14 is a diagram illustrating GRE encapsulation processing.
[0127] In the GRE encapsulation processing of Step 3015 , the encapsulation/decapsulation processing unit 3015 allocates a GRE header 7077 and an IP header 7076 to the received user data 7078 as illustrated in FIG. 14 . The GRE KEY of the GRE header 7077 allocates the down link GRE KEY corresponding to the index acquired in Step 3013 . Upon completion of the GRE encapsulation processing, the encapsulation/decapsulation processing unit 3015 transfers the GRE capsuling data to the I/O port 3014 , and allows the operation to proceed to Step S 3009 . In Step 3009 , the encapsulation/decapsulation processing unit 3015 transfers the data to the BS 600 according to the routing information.
[0128] The BS 600 transfers the data received from the GW-EP 301 to the MS 700 as the radio data 7100 .
[0129] Subsequently, a disconnection sequence will be described.
[0130] FIG. 15 is a diagram illustrating an example of the disconnection sequence.
[0131] When the connection is to be disconnected, the MS 700 transmits a DRG-REQ 840 that is a request for disconnection to the BS 600 . The reception of the DRG-REQ 840 leads the BS 600 to execute a disconnection sequence (Path_Dereg_Req. 842 , Path_Dereg_Rsp. 843 , Path_Dereg_Ack 844 ) between the BS 600 and the GW-DP 201 . The GW-DP 201 conducts the disconnection sequence from the BS 600 , and at the same time, if the connection type is the mobile IP, disconnects a mobile IP path 846 from the CSN 400 . The GW-DP 201 transmits a setup cancel request 847 to the GW-EP 301 . A format of the setup cancel request 847 is identical with the format of the setup request illustrated in FIG. 12 , and whether the format is of the setup request or the setup cancel request is distinguished by the contents of the type 8313 . The information elements 8310 of the setup cancel request include the MS IP addresses, and the control unit 3011 of the GW-EP 301 that receives the setup cancel request 847 searches the table in FIG. 6 , and clears information on the matched index. After clearing, the control unit 3011 acquires the number of down link bytes, the number of up link bytes, the number of down link packets, and the number of up link packets in FIG. 8 corresponding to the index, from the accounting statistics collection unit 3013 of the GW-EP 301 , sets those acquired numbers for the information elements 8310 of a setup cancel response 848 , and transmits the information elements 8310 to the GW-DP 201 .
[0132] The GW-DP 201 that has received the setup cancel response 848 extracts the number of down link bytes, the number of up link bytes, the number of down link packets, and the number of up link packets, which are stored in the setup cancel response 848 , and stores those extracted numbers in a given attribute of an Accounting-Request (stop) 849 , and transmits the stored numbers to the CSN 400 . Upon receiving the accounting-Request (stop) 849 , the CSN 400 transmits an Accounting-Response 850 to the GW-DP 201 .
[0133] Because the MS 700 can access to the GW-EP 301 connected to the network 5002 close to the BS 600 through the internet 501 , traffic can be prevented from being converted on the network 5001 . Also, during disconnection, the statistics information is transmitted from the GW-EP to the GW-DP 200 , to thereby enable information necessary for accounting to be notified the CSN 400 of.
B. Second Embodiment
[0134] In a second embodiment, a description will be given of another method of the BS management table in the GW-EP search flowchart of FIG. 10 . FIG. 16 illustrates a table held by the EP-GW position management unit 2004 in the GW-DP 201 of FIG. 2 . This table includes items of the index, the BS network address, and the area, and specifies the area for each of the BS network addresses. The connection sequence of the MS is the sequence of FIG. 9 which is identical with that of the first embodiment. The GW-DP 201 receives the MS_PreAttachment_Req. 801 transmitted from the BS 600 to implement the GW-EP search processing 830 .
[0135] FIG. 10 is a flowchart illustrating allocation processing of the bearer data processing device according to the embodiment of the present invention. In the GW-EP search processing 830 , the flowchart of FIG. 10 is implemented, and in Step 2002 , the GW-DP 201 extracts the BS IP address of the MS_PreAttachment_Req. 801 in the same method as that of the first embodiment. For example, it is assumed that the BS IP address extracted in Step 2002 is 192.168.20.25. Upon completion of the extraction, the GW-DP 201 allows the operation to proceed to Step 2003 , and specifies the area. The table of FIG. 16 is used for specifying the area.
[0136] FIG. 16 is a diagram illustrating an example of the BS position management table according to the embodiment of the present invention. Areas corresponding to the BS network addresses are set in the table of FIG. 16 . When the BS IP address is 192.168.20.25, it is found by searching a BS network address column that the BS IP address is included in a network address of 192.168.20.0/24 in index 2. The area on the same row as that of the matched index is an obtained area. In the case of the index 2, an area 2 is obtained. After the area could be specified, the GW-DP 201 allows the operation to proceed to Step 2004 , and the subsequent steps are identical with those in the first embodiment.
[0137] The advantage of the second embodiment resides in that the BS IP network address can be used as the BS management table to reduce the number of table setting.
C. Third Embodiment
[0138] In a third embodiment, a description will be given of another method in the GW-EP search processing of FIG. 9 .
[0139] FIG. 17 illustrates a format of a BSID. The BSID is an identifier specified for identifying the BS, and in this example, has a length of 48 bits. High-order 24 bits 6001 are specified by an operator ID or an NAP ID and the standards of WiMAX forum. Low-order 24 bits can be used for identifying the BS. A first bit 6002 is specified as a determination flag to determine whether low-order 23 bits are intended for an NSP or for identifying the BS. In the third embodiment, 7 bits of 23 bits 6003 used for the BS identification are used as an area ID 6004. The 7 bits used as the area ID are made to match the area number. For example, when the area ID is 0000001, the area ID indicates an area 1.
[0140] The MS connection sequence in the third embodiment will be described with reference to FIG. 9 . As in the first embodiment, the GW-DP 201 receives the MS_PreAttachment_Req. 801 transmitted from the BS 600 to implement the GW-EP search processing 830 . The MS_PreAttachment_Req. 801 includes the BSID.
[0141] FIG. 18 is a flowchart illustrating the allocation processing in the bearer data processing device according to the embodiment of the present invention. In the GW-EP search processing 830 , the flowchart of FIG. 18 is implemented. In Step 2012 , the GW-DP 201 extracts the BSID. In the MS_PreAttachment_Req. 801 , the BSID is included in the message, and the GW-DP 201 extracts the BSID of 48 bits. As an example, it is assumed that the extracted BSID is 000100 010345(HEX). After extraction of the BSID, the operation proceeds to Step 2013 . It is found that the bit corresponding to the area ID of the above-mentioned extracted BSID is 01, and it is found that the BS is located in the area 1. After specifying the area, the GW-DP 201 specifies the GW-EP IP address with the use of the table 5 in FIG. 5 as in the first embodiment. Thereafter, the same processing as that in the first embodiment is conducted.
[0142] The advantage of the third embodiment resides in that the BS management information can be reduced by setting the area information for the BSID.
D. Fourth Embodiment
[0143] In a fourth embodiment, a description will be given of another method in the GW-EP search processing of FIG. 9 .
[0144] FIG. 19 illustrates a table held by the EP-GW position management unit 2004 in the GW-DP 201 of FIG. 2 . The table includes items of the index, the BS IP address, and the GW-EP IP address.
[0145] The connection sequence of the MS is the sequence of FIG. 9 which is identical with that of the first embodiment. The GW-DP 201 receives the MS_PreAttachment_Req. 801 transmitted from the BS 600 to implement the GW-EP search processing 830 .
[0146] FIG. 20 is a flowchart illustrating the allocation processing in the bearer data processing device according to the embodiment of the present invention. In the GW-EP search processing 830 , the flowchart of FIG. 20 is implemented. In Step 2022 , the GW-DP 201 extracts the BSIP in the same method as that of the first embodiment. After extraction of the BSIP address, the operation proceeds to Step 2023 . In Step 2023 , the GW-DP 201 searches the extracted BSIP address on a column of the BSIP address of the table in FIG. 19 , and acquires the GW-EP IP address on the same row as that of the matched index. For example, when the BS IP address is 192.168.10.2, the BS IP address matches an index 1, and acquires a corresponding GW-EP IP address 192.168.200.10. After acquiring the GW-EP IP address, the GW-DP 201 allows the operation to proceed to Step 2034 , and executes the sequence of FIG. 9 as in the same manner as that of the first embodiment.
[0147] Also, as the same BS management method, the management can be achieved by the BSID instead of the BS IP address. FIG. 21 illustrates a management table that associates the BSID with the GW-EP IP address. Also, FIG. 22 illustrates a GW-EP search flowchart. A difference from FIG. 20 resides in that the GW-EP address is searched on the basis of the BSID.
[0148] The GW-EP and/or the GW-DP can be configured by using an appropriate router or computer.
[0149] Also, the present invention has been described by exemplifying the GW-EPs and the GW-DP, but can be applied to an appropriate bearer data processing device or signaling processing device. The present invention is not limited to the GRE and the GRE KEY, but can be applied to appropriate encapsulation/decapsulation and a key (capsuling key) necessary for the encapsulation/decapsulation.
|
User traffic transmitted and received by a mobile station is distributed so as not to be converged on a gateway. The gateway includes a signaling processing device and bearer data processing devices, the signaling processing device is concentrated, and the bearer data processing devices are distributed to networks close to base stations. The signaling processing device recognizes, in response to a connection request from each mobile station, a position of the base station covering the mobile station, allocates the bearer data processing device connected to the network close to the base station, and connects the base station to the allocated bearer data processing devices.
| 7
|
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation application of U.S. application Ser. No. 11/758,242, filed Jun. 5, 2007, which is a continuation application of U.S. Pat. No. 7,231,351, issued Jun. 12, 2007, which claims the benefit of U.S. Provisional Application Ser. No. 60/379,291, filed May 10, 2002. This application is related to U.S. application Ser. No. 09/799,385, filed on Mar. 5, 2001. The prior applications are incorporated herein by their reference.
BACKGROUND
[0002] The invention relates to alignment of audio recordings with transcripts of the recordings.
[0003] Many current speech recognition systems include tools to form “forced alignment” of transcripts to audio recordings, typically for the purposes of training (estimating parameters for) a speech recognizer. One such tool was a part of the HTK (Hidden Markov Model Toolkit), called the Aligner, which was distributed by Entropic Research Laboratories. The Carnegie-Mellon Sphinx-II speech recognition system is also capable of running in forced alignment mode, as is the freely available Mississippi State speech recognizer.
[0004] The systems identified above force-fit the audio data to the transcript. Typically, some amount of manual alignment of the audio to the transcript is required before the automatic alignment process begins. The forced-alignment procedure assumes that the transcript is a perfect and complete transcript of all of the words spoken in the audio recording, and that there are no significant segments of the audio that contain noise instead of speech.
SUMMARY
[0005] In a general aspect, the invention features a method of alignment of transcripts in which there may be moderate transcript inaccuracies, untranscribed speech, and significant non-speech noise. No manual alignment is required as part of the method.
[0006] In one aspect, in general, the invention features a method for aligning an audio recording and a transcript comprising. A number of search terms are formed from the transcript. Each search term is associated with a location within the transcript. Possible locations of the search terms are determined in the audio recording. The audio recording and the transcript are then aligned using the possible locations of the search terms.
[0007] In another aspect, in general, the invention features a method for searching an audio recording. A search expression is accepted, and then a search is performed for spoken occurrences of the search expression in the audio recording. This search includes (a) searching for text occurrences of the search expression in a text transcript of the audio recording, and (b) searching for spoken occurrences of the search expression in the audio recording. Representations of the results of the searching for the spoken occurrences of the search expression are presented enabling access to portions of the audio recording corresponding to each of the results of the searching.
[0008] Aspects of the invention can include one or more of the following features:
[0009] Forming the search terms includes forming one or more search terms for each of a number of segments of the transcript.
[0010] Forming the search terms for each of the segments includes forming one or more search terms for each of a number of text lines of the transcript.
[0011] Determining possible locations of the search terms includes applying a word spotting approach to determine one or more possible locations for each of the search terms.
[0012] Determining the possible locations of the search terms includes associating each of the possible locations with a score characterizing a quality of match of the search term and the corresponding possible location.
[0013] The time-aligned transcript is provided as an output of the method.
[0014] A user interface is provided for browsing or searching the audio recording or the time-aligned transcript.
[0015] The audio recording and time-aligned transcript are packaged together in digital form, for example, on a CD, DVD, or in a single binary file.
[0016] The package also includes software for browsing or searching the audio recording or time-aligned transcript.
[0017] Aspects of the invention can include one or more of the following advantages:
[0018] The approach is robust to transcription gaps and errors, and to periods of non-speech signals in the audio recording.
DESCRIPTION OF DRAWINGS
[0019] FIG. 1 is a diagram of a transcript alignment system.
[0020] FIGS. 2A-B are pseudocode for the main algorithm.
[0021] FIG. 3 is pseudocode for a gap alignment procedure.
[0022] FIGS. 4A-B are pseudocode for an optimized alignment procedure.
[0023] FIG. 5 is pseudocode for a blind alignment procedure.
[0024] FIG. 6 is a diagram that illustrates a user interface for the transcript alignment system.
DESCRIPTION
1 Overview
[0025] Referring to FIG. 1 , a transcript alignment system 100 is used to process an audio recording 120 of the speech of one or more speakers 112 that have been recorded through a microphone 110 or some other recording system. A transcript 130 of the audio recording is also processed by the system. As illustrated in FIG. 1 , a transcriptionist 132 has listened to some or all of audio recording 120 and entered a text transcription on a keyboard. Alternatively, transcriptionist 132 has listened to speakers 112 live and entered the text transcription at the time speakers 112 spoke. Transcript 130 is not necessarily complete. That is, there may be portions of the speech that are not transcribed. The transcript may also have substantial portions that include only background noise when the speakers were not speaking. Transcript 130 is not necessarily accurate. For example, words may be mis-represented in the transcript. Furthermore, the transcript may have text that does not reflect specific words spoken, such as annotations or headings.
[0026] Generally, alignment of audio recording 120 and transcript 130 is performed in a number of phases. First, the text of transcript 130 is processed to form a number of queries 140 , each query being formed from a segment of the transcript, such as from a single line of the transcript. The location in transcript 130 of the source segment for each query is stored with the queries. A wordspotting-based query search 150 is used to identify putative query location 160 in the audio recording. For each query, a number of time locations in audio recording 120 are identified as possible locations where that query term was spoken. Each of the putative query locations is associated with a score that characterizes the quality of the match between the query and the audio recording at that location. An alignment procedure 170 is used to match the queries with particular of the putative locations. This matching procedure is used to form a time-aligned transcript 180 . Time-aligned transcript includes an annotation of the start time for each line of the original transcript that is located in the audio recording. A user 192 then browses the combined audio recording 120 and time-aligned transcript 180 using a user interface 190 . One feature of this interface is that the user can use a wordspotting-based search engine 195 to locate search terms. The search engine uses both the text of time-aligned transcript 180 and audio recording 120 . For example, if the search term was spoken but not transcribed, or transcribed incorrectly, the search of the audio recording may still locate the desired portion of the recording. User interface 190 provides a time-synchronized display so that the audio recording for a portion of the text transcription can be played to the user.
[0027] Transcript alignment system 100 makes use of wordspotting technology in the wordspotting query search procedure 150 and in search engine 195 . One implementation of a suitable wordspotting based search engine is described in co-pending U.S. patent application Ser. No. 09/799,385, filed on Mar. 5, 2001. The wordspotting based search approach of this system has the capability to:
accepts a search term as input and provides a collection of results back with a confidence score and time offset for each allows the caller to specify the number of search results to be returned, which may be unrelated to the number of actual occurrences of the search term in the audio.
[0030] Transcript alignment system 100 attempts to align lines of transcript 150 with a time index into audio recording 120 . The overall alignment procedure carried out by transcript alignment system 100 consists of three main, largely independent phases, executed one after the other: gap alignment, optimized alignment, and blind alignment. The first two phases each align as many of the lines of the transcript to a time index into the media, and the last then uses best-guess, blind estimation to align any lines that could not otherwise be aligned.
2 Phase 0: Searching
[0031] The first two phases of alignment (“gap alignment” and “optimized alignment”) depend on the results from searches executed for every line in the transcript. Therefore the first phase, which is carried out in wordspotting query search 150 (see FIG. 1 ), includes executing all of the searches and gathering the results.
[0032] Three search terms (queries) are constructed from each line of the transcript:
Full Line: The entire line as written in the transcript (less punctuation) (e.g., “This is the spoken line”). Full Line With Pauses: The entire line with pauses inserted between each word (e.g., “This [PAU] is [PAU] the [PAU] spoken [PAU] text”). Two Words: The first two words in the line, with no pause inserted between them (e.g., “This is”).
[0036] Often, non-professional speakers will pause between words, interject “um”s, or “ah”s, or otherwise say something other than all of the words in a line of the transcript in a single smooth, continuous stream of speech. When spoken smoothly, the first search term will match well; if disfluencies are interjected, the second search term will match better. In the case of mumbling or very large pauses between words, the third search term will match best. As we continue to develop this algorithm, we may find other search terms that would work well in certain cases. For example, it would be reasonable to insert pauses in place of punctuation characters only rather than between each word.
[0037] Acronyms and numbers are handled specially: because it is impossible to tell whether the text “SCSI” is pronounced “S C S I” or “scuzzy”, or if “123” is “one hundred twenty three” or “one two three”. So rather than include acronyms and numbers in the search, these are replaced with the ampersand operator, except at the beginning and end of the line, where they are simply dropped. The ampersand operator tells the search engine to search for the text before the operator to appear in close proximity (in time) with the text after the operator. Multiple acronyms or numbers may be dropped and replaced with a single ampersand operator. The ampersand operator is not counted as a word in the two-word search term, and no pauses are added before or after the ampersand operator in the search term with pauses added.
[0038] Next, all of the search terms are run through the word spotting based search engine, and all of the results collected. The number of search results requested for each search is a function of the length of the media—we request 6 search results per minute of media in the current implementation. That number is doubled for every ampersand operator in the search term, as those operators tend to dramatically reduce the number of search results returned.
[0039] Each search result consists of a confidence score and a time offset, and indicates the confidence (score) with which the search engine believes that the search term occurs at that time offset in the media. Because there are three search terms for each line in the transcript, there are three distinct sets of search results for each line.
3 Phase 1: Gap Alignment
[0040] The gap alignment process goes through all of the lines, looking for a search result for a line that looks like it is most probably correct. That search result is then (tentatively) selected as correct and a time index for that line is set at the time offset of the chosen search result. The file is then divided into two segments, and the process is repeated on each segment separately. This approach handles incomplete or moderately inaccurate transcriptions.
[0041] The search result that is “most probably correct” is a heuristic determination. The specific heuristic used here is:
the search result must be the highest-ranked result for that search term for that line that the search result must have a score above a certain score threshold the gap between the score of highest-ranked result and the score of next-highest ranked result must be greater than a certain gap threshold if there is more than one line that has a search result that meets the above criteria, the line with the greatest gap is selected as “most probably correct”.
[0046] Finding the result with the greatest gap between the highest and next-highest scoring results is actually more important than finding the result with the highest absolute confidence score, because it is important that the result be unique. If there are several high-scoring results for a line, it is impossible to tell which one actually corresponds to that specific line in the transcript. However, if there is one reasonably high-scoring result and all of the rest of the results score much lower, there can be some confidence that the one high-scoring result corresponds to that particular line in the transcript.
[0047] This process of selecting the most probable search result is carried out recursively, dividing the media into smaller and smaller segments. At each level, only those search hits that occur within the current segment of the media file are considered when selecting the highest-scoring and next-highest-scoring results—all results outside that segment are ignored. So there could be many search results that score higher than the highest search result for this segment of the media, and many more that score higher than the next-highest scoring result that is within that segment. However, all of those extraneous results will be ignored when computing the gap between the highest two search results that are within the current segment of the media file.
[0048] Selecting a search result that meets the heuristic of “most probably correct” that is not actually correct can have catastrophic effects on the accuracy of the resulting alignment, particularly early in the overall alignment process. So at every level of this recursive gap alignment process, the next-most-probably correct line (the line that also meets the criteria in terms of score and gap thresholds, but has the next-largest gap between the highest and second-highest result score) is also evaluated in the same way as the most probably correct line: that result is tentatively selected for that line, the segment of media is divided and the process is called recursively over the two sub-segments. If the next-most-probably-correct result produces a better alignment than the most probably correct one, than it is used instead, and all result selections from the most-probably-correct result are thrown out.
[0049] The basis for determining which of these two most probably correct search results produces the best alignment is the score returned from the subordinate recursive calls to the gap alignment procedure. Each level of this recursive process returns a score that is the sum of the score of the result selected at that level and the scores returned by its two subordinate recursive calls. Since these scores indicate the confidence that the search engine has for the search result, and since that the aggregate score returned is made up entirely of these confidence scores, the aggregate score returned from any given level of the recursive process is also a measure of the total confidence for the results selected by that level and all of its subordinate levels.
[0050] Also returned from each level of this recursive process is a set of tentative result selections. At each level, either the line with the “most probably correct” result or the line with the “next most probably correct” result will be tentatively selected, and that line will be tentatively marked as aligned. This tentative selection will then be returned along with all of the tentative selections from the subordinate recursive calls made for that result.
[0051] When the topmost level of this recursive process completes, the tentative selections that it returns are fixed as definite selections. Again, these selections consist of one of the returned audio search results for one of the search terms for a specific line. When these results are made definite, that line goes from being “unaligned” to being “aligned” to the media at the time offset given by the selected search result.
[0052] The first time this whole process is carried out, it is done using a very high gap threshold and only the search results from the “full line” search term. When it completes and the returned tentative result selections are made definite, the entire process is carried out again using the same high gap threshold and only the results from the “full line with pauses” search term. However, some (hopefully many) of the lines of the transcript have now already been aligned to specific time offsets in the media—and those alignments are considered fixed and unchangeable. So for the second (and all subsequent) times this process is carried out, each group of unaligned lines is considered independently, and only in relation to the segment of the media that falls between the time offsets of the enclosing aligned lines.
[0053] When the second pass is completed for all of the groups of unaligned lines and the tentative result selections are fixed as definite, a third pass is executed using the same high gap threshold and only the search results from the “two word” search term.
[0054] We know from experience with the audio search engine that some media produces excellent, high-scoring search results, while other media produces somewhat lower scores. For a human user, this is not a problem, as the results with the highest confidence will show up at the top of the list, regardless of the absolute score. In fact, the “gap” concept comes from experience with the audio search engine in which it became clear that the only way to tell which search results were correct and which were incorrect without listening to each one was to look for large gaps between a small number of high-scoring results and all of the lower-scoring incorrect results. However, since a significant gap in a high-scoring file will be larger than that in a low-scoring file, there is no single gap size to detect in the result list to determine correct results from incorrect ones.
[0055] When that completes, the gap threshold is lowered, and all three passes (one for each search term) are executed again. Finally, the gap threshold is lowered one more time, and all three passes are done again. All told, this results in nine passes:
full line search term, very high gap threshold full line with pauses search term, very high gap threshold two word search term, very high gap threshold full line search term, high gap threshold full line with pauses search term, high gap threshold two word search term, high gap threshold full line search term, medium gap threshold full line with pauses search term, medium gap threshold two word search term, medium gap threshold
4 Phase 2: Optimization Alignment
[0065] Optimization alignment uses a brute force approach: it tries all possible combinations of search results for each line above a minimum score to find the sequence of results with the highest total score.
[0066] This is again a recursive process. At every level of the optimization process, all of the search results above a minimum score threshold for the first line in the group of unaligned lines are tentatively selected in turn, and for each one the process recursively calls itself on all of the remaining lines. The aggregate score for each tentatively-selected search result is the sum of the score for that result and the result returned from the recursive call of the optimization process over the remaining lines. The process returns the highest aggregate score and the sequence of tentative result selections for that line and all subsequent lines that produced the highest aggregate score. If there is no result for the first unaligned line that is above the minimum score threshold, then the result is simply the result returned from the recursive call to the process on all of the subsequent unaligned lines.
[0067] In order to keep this process from taking too long to run, there is a maximum threshold on the number of lines that can be optimize aligned at once. That is, if there are more contiguous unaligned lines in a group than is allowed by the threshold for optimized alignment, then the group is divided first by making a tentative selection of a search result above the minimum score threshold for one line and then using that to divide the original group of unaligned lines into two smaller groups. The optimized alignment process is then called on each of the two smaller groups. Because the first step in the process is to check the number of lines to be optimized, the smaller groups may themselves be similarly split before the optimization process described above actually begins. When dividing a group of unaligned lines, the line used to make the division is the line with the greatest gap between the highest-scoring search result and the next highest scoring search result, where the highest scoring search result is above the minimum score threshold.
[0068] Like the gap alignment, when the topmost level of this recursive process completes, the tentatively-selected lines are fixed as definite selections and the lines go from being marked “unaligned” to being marked “aligned”. Also like the gap alignment process, this process is performed over each group of unaligned lines separately.
[0069] The first time this whole optimized alignment process runs, the minimum score threshold is set high and the only search results that are considered are those for the “full line” search term. After the process completes and any tentative selections returned are fixed as definite selections, the process is repeated for the “full line with pauses” search term, with the same high score threshold. The process is then executed again with the same score threshold and the search results from the “two word” search term. The score threshold is then lowered and all of these three steps are repeated. Finally, the score threshold is lowered again and all of these steps are repeated on last time. This give nine total executions of the optimized alignment process, much like the gap alignment process.
5 Phase 3: Blind Alignment
[0070] The final phase of alignment is not based on search results at all—instead a simple, blind mathematical approach is used. The simple formula is based on the (invalid, but workable) assumption that every alphanumeric letter takes the same amount of time to speak. So first, the time window in which these lines must have been said is given by the time offset of the last aligned line immediately before this group of unaligned lines and that of the first aligned line after the unaligned group. The total number of letters spoken in that time window is the total number of letters in the unaligned lines plus the number of letters on the last aligned line immediately before the first unaligned line. The letters from the last aligned line are included because the time offset for that line reflects the time the speaker began speaking the text on that line—so the time required to finish speaking the text on that line must be taken into account. The time window is then divided by the total number of letters to produce an average time per letter. This statistic is then used to “align” each line by multiplying the number of letters on all of the unaligned lines before it plus the number of letters on the last unaligned line by the average time per letter.
[0071] When this step is complete, all lines in the transcript that have spoken text will have been aligned to the media.
6 Scoring
[0072] It is valuable to have some simple metric by which to judge how well the transcript was aligned to the media. This can provide feedback to the recording technician regarding the quality of the recording or can be taken to reflect the quality of the transcript. Also, this score can be used to estimate the number of alignment errors that are likely to have been made during the alignment process.
[0073] Through the gap alignment and optimized alignment phases, specific search results were first tentatively selected and then fixed or definitely selected for many of the lines in the transcript—at which point the time offset of the definitely selected search result was taken to be the time offset at which that line occurred in the media, and the line was marked as “aligned”. The overall alignment score metric is the average score for the definitely selected search results for each spoken line of the transcript. If there is no spoken text on the line to align, it is ignored in the score calculation. Those lines that could not be aligned by selecting a search result, and which were therefore “aligned” through the blind alignment process, are included in the average but contribute a score of zero.
7 Pseudocode
[0074] FIGS. 2-5 include pseudocode for procedures introduced above.
8 User Interface
[0075] FIG. 6 illustrates user interface 190 for displaying an aligned transcript to the user and allowing them to use it to provide enhanced access to the media.
[0076] The interface includes the Media Player and Transcript windows. So long as the Track button in the Transcript window is selected, these windows will be tied together: the Transcript will always have the line currently being played in media player centered and highlighted in its window. If the user uses the slider in the Media Player window to adjust the current playback position of the media, the Transcript window will immediately jump to the appropriate line in the transcript for the new media position. Conversely, if the user clicks on a line in the Transcript window other than the one currently highlighted, that line will become highlighted and the Media Player window will adjust the current playback position of the media to correspond to the time offset of the newly-selected line. The highlighted line in the Transcript window will change from one line to the next as the Media Player window plays the media. When the Track button on the Transcript window is not selected, the Transcript window continues to highlight the line that corresponds to the current position in the media Player window, but does not keep that line centered. This allows the user to quickly skim through the transcript without thrashing the Media Player window.
[0077] Next, the search window allows the user to simultaneously search the audio portion of the media and the transcript simultaneously. When the user enters a search term and presses the go button, an audio search engine is used to search the media file for the search term, and a text search engine is used to search the transcript. The results from both search engines are then compiled into a single list, using the time offsets given in the aligned transcript to eliminate duplicates—instances where both search engines found the same occurrence of the search term. The results from the text search engine are presented to the user first in the result list with the maximum confidence score, followed by the results from the audio search engine in confidence-score order. When the user clicks on a result in the result list, the Media Player window will queue the media to that location, and the Transcript will scroll to bring the corresponding line of the transcript to the center of the window and highlight it.
[0078] Lastly, the Bookmarks window will allow a user to mark a specific location in the media and, by extension, the transcript and provide a comment on the reason that the bookmark was placed. Clicking on a bookmark behave exactly the same way as clicking on a search result.
9 Packaging
[0079] The result of time aligning and audio recording to the transcript is optionally packaged together in digital form, for example, on a Compact Disk (CD), Digital Versatile Disk (DVD), in a single computer archive, or some other form of digital container. For instance, in the case of a CD, the audio recording, the time-aligned transcript, and software to implement the user interface and the search engine are all stored on the CD. A user can then use the CD to browse and search the audio recording.
10 Applications
[0080] The approach described above is applicable to a variety of situations including the following:
alignment of court transcripts to audio recordings of those transcripts alignment of journalistic or insurance interviews with recordings of those interviews alignment of television closed captioning to a television program alignment of monitored data to transcripts, for example, to align transcripts of air-traffic communication to recordings in a crash investigation alignment of movie or theatrical scripts to audio recordings of actors performing the scripts (note that in this case, the “transcript” comes before the production of the original audio, as opposed to the audio be produced and then the transcript being made during or after the production of the audio).
11 Alternatives
[0086] In alternative versions of the system, other audio search techniques can be used. These can be based on word and phrase spotting techniques, or other speech recognition approaches.
[0087] In alternative versions of the system, rather than working at a granularity of lines of the text transcript, the system could work with smaller or larger segments such as words, phrases, sentences, paragraphs pages.
[0088] Other speech processing techniques can be used to locate events indicated in transcript 130 . For example, speaker changes may be indicated in transcript 130 and these changes are then located in audio recording 120 and used in the alignment of the transcript and the audio recording.
[0089] The approach can use other or multiple search engines to detect events in the recording. For example, both a word spotter and a speaker change detector can be used individually or in combination in the same system.
[0090] The approach is not limited to detecting events in an audio recording. In the case of aligning a transcript or script with a audio-video recording, video events may be indicated in the transcript and located in the video portion of the recording. For example, a script may indicate where scene changes occur and a detector of video scene changes detects the time locations of the scene changes in the video.
[0091] The approach described above is not limited to audio recordings. For example, multimedia recordings that include an audio track can be processed in the same manner, and the multimedia recording presented to the user. For example, the transcript may include closed captioning for television programming and the audio recording may be part of a recorded television program. The user interface would then present the television program with the closed captioning.
[0092] Transcript 130 is not necessarily produced by a human transcriptionist. For example, a speech recognition system may be used to create an transcript, which will in general have errors. The system can also receive a combination of a recording and transcript, for example, in the form of a television program this includes closed captioning text.
[0093] The transcript is not necessarily formed of full words. For example, certain words may be typed phonetically, or typed “as they sound.” The transcript can include a stenographic transcription. The alignment procedure can optionally work directly on the stenographic transcript and does not necessarily involve first converting the stenographic transcription to a text transcript.
[0094] Alternative alignment procedures can be used instead of or in addition to the recursive approach described above. For example, a dynamic programming approach could be used to select from the possible locations of the search terms. Also, an in which search terms and a filler model are combined in a grammar can be used to identify possible locations of the search terms using either a word spotting or a forced recognition approach.
[0095] The system can be implemented in software that is executed on a computer system. Different of the phases may be performed on different computers or at different times. The software can be stored on a computer-readable medium, such as a CD, or transmitted over a computer network, such as over a local area network.
[0096] It is to be understood that the foregoing description is intended to illustrate and not to limit the scope of the invention.
|
An approach to alignment of transcripts with recorded audio is tolerant of moderate transcript inaccuracies, untranscribed speech, and significant non-speech noise. In one aspect, a number of search terms are formed from the transcript such that each search term is associated with a location within the transcript. Possible locations of the search terms are then determined in the audio recording. The audio recording and the transcript are then aligned using the possible locations of the search terms. In another aspect a search expression is accepted, and then a search is performed for spoken occurrences of the search expression in an audio recording. This search includes searching for text occurrences of the search expression in a text transcript of the audio recording, and searching for spoken occurrences of the search expression in the audio recording.
| 8
|
RELATED APPLICATION
[0001] This is a §371 of International Application No. PCT/FR2006/000254, with an international filing date of Feb. 3, 2006 (WO 2006/082327 A1, published Aug. 10, 2006), which is based on French Patent Application No. 05/01082, filed Feb. 3, 2005.
TECHNICAL FIELD
[0002] This disclosure relates to the field of image processing, more specifically, to the process of obtaining an image of phase from an image of intensity.
BACKGROUND
[0003] The problem of obtaining an image of phase from an image of intensity has been considered during the last twenty years. In <<Relationship between two-dimensional intensity and phase in Fresnel Diffraction zone>>, Abramoshkin et al. (1989) provide the value of the phase gradient from intensity, the intensity gradient and Green's functions in an infinite space.
[0004] More precisely, Fornaro et al. discloses in <(<Interferometric SAR phase unwrapping Using Green's Formulation>> using the Fast Fourier Transforms for computing the phase from phase gradient by using Green's functions.
[0005] The formulation using the Fourier Transform is used in WO 00/26622, which describes the process of obtaining such a phase image. That process concerns the retrieval of phase of a radiation wave field by solving the equation of the energy transfer. The rate of variation of the intensity of the image is determined first, orthogonally with respect to the surface that spans the wave field (i.e., when measuring the intensity in the two separate surfaces). This rate is then subject to the following computation process: defining an integral transform, multiplication by a filter corresponding to the inversion of the differential operator, and defining the inverse integral transform. The result is multiplied by the function of intensity with respect to the surface. The filters have the form based on the characteristics of the optical system used for acquiring the intensity data, such as the numerical aperture and spatial frequencies.
[0006] More specifically, the Fourier transform is the Fourier transform in two dimensions.
[0007] However, one of the major problems in the field of image processing is the computation time for applications involving solution of the equations characteristic to the image.
[0008] Thus, the computation times are not sufficient to perform the computations for a large number of images.
[0009] Further, it should be noted that WO '622 does not mention the boundary conditions, by supposing that the phase is zero at infinity.
SUMMARY
[0010] I provide a process of retrieval of phase of the radiation wave field comprising the following steps:
compute a representative measure of the intensity variation of the radiation wave field on a selected surface extending globally from one end to another of the radiation wave field; compute a representative measure of the intensity of the radiation wave field on the selected surface; transform the representative measure of the intensity variation to produce a first representation of integral transform and to apply to the first representation of integral transform a first filter to produce a first representation of modified integral transform; apply a first function of the first representation of integral transform to the first representation of modified integral transform to produce an untransformed representation; apply a correction based on the measure of intensity on the selected surface to the untransformed representation; transform the untransformed corrected representation to produce a second representation of integral transform and to apply to the second representation of integral transform a second filter; apply a second function of the second integral transform to the second modified representation of integral transform to produce a measure of phase of the radiation wave field on the selected surface extending globally from one end to another of the radiation wave field, wherein the first and second filters are measures of a representation of a Green's function in a space of eigenfunctions of the Helmholtz equation with separable coordinates such that the first and second integral transforms are one-dimensional integral transforms in the space of the radiation wave field.
[0019] The first function may use a trigonometric function of the cosine type, and the second function uses a trigonometric function of the sine type.
[0020] By the same token, it is possible that the first function uses a trigonometric function of the sine type, and the second function uses a trigonometric function of the cosine type.
[0021] As an advantage, the first and second integral transforms are produced by using a Fourier transform, for example, a fast transform. According to one alternative, the first and second filters are sensibly the same. The surfaces may be sensibly planar.
[0022] I also provide a computer program, possibly saved on a support, to execute the different steps of the process.
[0023] I further provide an apparatus of reconstruction of phase of a radiation wave field comprising:
a means for acquisition of a representative measure of the intensity variation of the radiation wave field on a selected surface extending globally from one end to another of the radiation wave field; a means for acquisition of a representative measure of the intensity of the radiation wave field on the said selected surface; a processing means to sequentially perform the following steps:
(i) transform the representative measure of the intensity variation to produce a first representation of integral transform and to apply to the first representation of integral transform a first filter to produce a first representation of modified integral transform; (ii) apply a first function of the first representation of integral transform to the first representation of modified integral transform to produce an untransformed representation; (iii) apply a correction based on the measure of intensity on the selected surface to the untransformed representation; (iv) transform the untransformed corrected representation to produce a second representation of integral transform and to apply to the second representation of integral transform a second filter; (v) apply a second function of the second integral transform to the second modified representation of integral transform to produce a measure of phase of the radiation wave field on the selected surface extending globally from one end to another of the radiation wave field, wherein the first and second filters are measures of a representation of a Green's function in a space of eigenfunctions of the Helmholtz equation with separable coordinates such that the first and second integral transforms are one-dimensional integral transforms in the space of the radiation wave field.
[0033] The means of acquisition of a representative measure of the intensity variation of the radiation wave field may comprise at least one mobile platform. The means of acquisition of a representative measure of the intensity variation of the radiation wave field may also comprise at least a lens with a variable length of focus.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] My disclosure is better understood due to the description made hereafter for purely explanatory purposes of a representative example, with reference to the annexed figures where:
[0035] FIG. 1 represents image data;
[0036] FIG. 2 shows a comparison between the number of complex multiplications in my methods and in WO 00/26622 for a processed image with dimensions from 64×64 pixels to 128×128 pixels;
[0037] FIG. 3 shows a comparison between the number of complex multiplications in my methods and in WO 00/26622 for a processed image with dimensions from 1024×1024 pixels to 2047×2047 pixels;
[0038] FIG. 4 shows the data from initial images at the start of the algorithm;
[0039] FIGS. 5A , 5 B and 5 C, which should be read in a successive manner, represent one exemplary implementation mode; and
[0040] FIGS. 6-9 represent devices for implementation of my methods.
[0041] My disclosure is described in detail below in the Cartesian coordinate system and with a rectangular image. It is understood that one skilled in the art is capable, in reading this description, to adapt the information contained herein for the other types of images and/or the other types of coordinates.
DETAILED DESCRIPTION
[0042] I provide a method of reconstruction of the function φ({right arrow over (r)}) of phase in a point {right arrow over (r)}=(x, y) of a 2D plane from samples of the first-order differences in points (x, y)=(nΔx, mΔy). We compute the phase only in the points for which x=nΔx and y=mΔy, where the lines of the two-dimensional (2D) grid intersect, i.e., in the centers of points where elements (pixels) of a two-dimensional sensor of the luminous energy are situated, for example, of a CCD camera. The phase differences of the first order in the points (x, y)=(nΔx, mΔy) are obtained by computation of the gradient of the phase from the derivative of the intensity ∂I/∂z along the optical axis z. This computation is detailed later. To facilitate the transition from the discrete notation to the continuous notation, the description of terms used in the description of the process is presented in the Table I.
[0043] Fornaro et al. used the first Green's identity for evaluation of the phase from the differences of the first order presented in the continuous form as a gradient vector {right arrow over (F)}({right arrow over (r)}). The phase is computed as a sum of the integral over the support region S of the image of phase and over the boundary C of this region:
[0000] φ( {right arrow over (r)} ′)=∫ S {right arrow over (F)} ( {right arrow over (r)} )·∇ g ( {right arrow over (r)}, {right arrow over (r)} ′) d{right arrow over (r)}− φ( {right arrow over (r)} )[ {circumflex over (n)} S ·∇g ( {right arrow over (r)}, {right arrow over (r)}′ )] d{right arrow over (c)} Equation 1
[0000] where {circumflex over (n)} S is a unity vector perpendicular to C and oriented exterior to S as shown in FIG. 1 , and where g({right arrow over (r)}, {right arrow over (r)}′) is a Green's function. In Equation 1, the phase φ enters both in the left-hand side and in the integral on the contour C. This double introduction of the same value in the two parts of Equation 1 does not obtain the phase if it is not zero or known a priori on the contour C.
[0044] Therefore, the integration of the phase on the contour C means that the phase should either be known, be equal to zero, or be pre-calculated by another optical device, for example, the Shack-Hartmann arrangement of lenses, prior to reconstructing the phase inside the surface S. The integration on the contour in Equation 1 can also be eliminated if the chosen Green's function satisfies the Neumann boundary conditions on the contour C of the surface S:
[0000] {circumflex over (n)} S ·∇g ( {right arrow over (r)}, {right arrow over (r)}′ )=0 Equation 2
[0045] Equation 2 is valid for the Green's function, and therefore the phase reconstructed according to the Equation 1 satisfies Neumann boundary conditions. The integration on the contour C can also be eliminated if the chosen Green's function satisfies, on the contour C, Dirichlet boundary conditions and if it is known that the phase is zero on C, that is written as:
[0000] g ( {right arrow over (r)}, {right arrow over (r)}′ )=0 , {right arrow over (r)}εC, {right arrow over (r)}′εS
[0000] φ( {right arrow over (r)} )=0, {right arrow over (r)}εC Equation 3
[0046] As previously, Equation 3 is valid for the Green's function and for the phase on the contour C, therefore the phase computed according to (1) using the Green's function from Equation 3satisfies Dirichlet boundary conditions.
[0047] Further, it is known that the Green's function satisfies the equation:
[0000] ∇ 2 g ( {right arrow over (r)},{right arrow over (r)} ′)=−δ( {right arrow over (r)},{right arrow over (r)} ′) Equation 4
[0000] where δ({right arrow over (r)},{right arrow over (r)}′) is the Dirac function.
[0048] To satisfy preceding equations, a Green's function may be chosen to be expressed in the form of a series in eigenfunctions of the Helmholtz equation as follows. One skilled in the art will note that it automatically satisfies the boundary conditions (2) or (3) according to the chosen form, and also the identity (4).
[0049] For a rectangular support region S, these special functions are:
[0000] U m,n ( {right arrow over (r)} )= A m,n cos(ξ n x )cos(η m y ), m,n= 0, . . . , ∞ Equation b 5
[0000] for the Neumann boundary conditions, and
[0000] U m,n ( {right arrow over (r)} )= A m,n sin(ξ n x )sin(η m y ), m,n= 0, . . . , ∞ Equation 6
[0000] for the Dirichlet boundary conditions.
[0050] For a support S of dimensions a×b, the constant A m,n in 5and 6 is equal to √{square root over (2)}a −1/2 b −1/2 if m or n are zero and 2a −1/2 b −1/2 otherwise, where a is the length, b is the height of the rectangular region of support S as in FIG. 1 .
[0051] The eigenvalues associated with the functions (5) and (6) are also used, which are:
[0000]
σ
m
,
n
2
=
ξ
n
2
+
η
m
2
,
ξ
n
=
n
π
a
,
η
m
=
m
π
b
,
m
,
n
=
0
,
…
,
∞
.
Equation
7
[0052] The Green's function for the domain S is written as an infinite series in eigenfunctions of the Helmholtz equation:
[0000]
g
(
r
→
,
r
→
′
)
=
∑
m
,
n
=
0
,
σ
m
,
n
2
≠
0
∞
σ
m
,
n
-
2
U
m
,
n
(
r
→
)
U
m
,
n
(
r
→
′
)
.
Equation
8
[0053] The derivation of the general expression (8) and the verification of the boundary conditions (2) and (3) are readily realizable by one skilled in the art for such a function.
[0054] Thus, if the Green's function (8) is used as g({right arrow over (r)},{right arrow over (r)}′) in the Equation 1, the integration on the contour in the Equation 1 can be suppressed and the phase can be expressed in the compact form:
[0000] φ( {right arrow over (r)} ′)=∫ S {right arrow over (F)} ( {right arrow over (r)} )·∇ g ( {right arrow over (r)}, {right arrow over (r)}′ ) dS Equation 9
[0000] in which it is noted that the gradient is computed with respect to the variable {right arrow over (r)}, that is ∇=∇ {right arrow over (r)} .
[0055] One aspect is to compute numerically the Equation 9 using the defined Green's functions to obtain the required phase, in preserving the acceptable computation time. The solution is obtained by the possibility to use a one-dimensional Fast Fourier Transform (1DFFT).
[0056] The use of this transform in one dimension is not straightforward for one skilled in the art taking into consideration general equations above. I provide below the various steps for comprehension of the fact that it is possible to use such a transform in one dimension.
[0057] Several preliminary transformations are necessary. To facilitate calculations, I point out various intermediate stages of calculation which should not be regarded as essential components, but simply the means of obtaining a form of equation with which it is possible to implement the transforms in an adequate dimension.
[0058] For more clarity, the Neumann boundary conditions are considered first, with γ=a/b and the Green's function in the expression of the Equation 8 with special functions (5):
[0000]
g
(
r
→
,
r
→
′
)
=
∑
m
=
0
,
m
2
+
n
2
≠
0
∞
A
m
,
n
2
cos
(
η
m
y
)
cos
(
η
m
y
′
)
×
∑
n
=
0
∞
cos
(
ξ
n
x
)
cos
(
ξ
n
x
′
)
(
π
/
a
)
n
2
+
(
π
/
b
)
m
2
Equation
10
[0059] The cases n=0, m≠0 and n≠0, m=0 are separated to obtain:
[0000]
g
(
r
→
,
r
→
′
)
=
2
π
-
2
γ
∑
n
=
1
∞
n
-
2
cos
(
ξ
n
x
)
cos
(
ξ
n
x
′
)
+
2
π
-
2
γ
-
1
∑
m
=
1
∞
m
-
2
cos
(
η
m
y
)
cos
(
η
m
y
′
)
+
4
a
-
1
b
-
1
∑
m
=
1
∞
cos
(
η
m
y
)
cos
(
η
m
y
′
)
∑
n
=
1
∞
cos
(
ξ
n
x
)
cos
(
ξ
n
x
′
)
(
n
/
a
)
2
+
(
m
/
b
)
2
.
Equation
11
[0060] However, it is known that:
[0000]
∑
n
=
1
∞
cos
(
nu
)
n
2
+
α
2
=
π
2
α
cosh
[
α
(
π
-
u
)
]
sinh
(
απ
)
-
1
2
α
2
,
0
≤
u
≤
2
π
,
Equation
12
[0061] Therefore,
[0000]
a
-
1
b
-
1
∑
n
=
1
∞
cos
(
ξ
n
x
)
cos
(
ξ
n
x
′
)
(
n
/
a
)
2
+
(
m
/
b
)
2
=
π
2
m
f
m
γ
(
x
,
x
′
)
-
1
2
γ
m
2
,
m
≠
0
,
with
Equation
13
f
m
γ
(
x
,
x
′
)
=
1
sinh
(
γ
m
π
)
{
cosh
[
η
m
(
a
-
x
)
]
cosh
(
η
m
x
′
)
,
if
x
>
x
′
cosh
[
η
m
(
a
-
x
′
)
]
cosh
(
η
m
x
′
)
,
if
x
<
x
′
.
Equation
14
[0062] However,
[0000]
∑
n
=
1
∞
n
-
2
cos
(
nu
)
cos
(
nv
)
=
1
12
{
3
u
2
+
3
(
v
-
π
)
2
-
π
2
,
if
0
≤
u
≤
v
3
v
2
+
3
(
u
-
π
)
2
-
π
2
,
if
0
≤
u
≤
v
.
Equation
15
[0063] Therefore, the Green's function is given according to this aspect by:
[0000]
g
(
r
→
,
r
→
′
)
=
2
π
-
1
∑
m
=
1
∞
m
-
1
cos
(
η
m
y
)
cos
(
η
m
y
′
)
f
m
γ
(
x
,
x
′
)
+
γ
6
a
2
{
3
x
2
+
3
(
x
′
-
a
)
2
-
a
2
,
if
x
≤
x
′
3
(
x
′
)
2
+
3
(
x
-
a
)
2
-
a
2
,
if
x
′
<
x
.
Equation
16
[0064] However, it is also known that:
[0000]
g
(
r
→
,
r
→
′
)
=
2
π
-
1
∑
m
=
1
∞
n
-
1
cos
(
ξ
n
x
)
cos
(
ξ
n
x
′
)
f
m
γ
_
(
y
,
y
′
)
+
γ
_
6
b
2
{
3
y
2
+
3
(
y
′
-
b
)
2
-
b
2
,
if
y
≤
y
′
3
(
y
′
)
2
+
3
(
y
-
b
)
2
-
b
2
,
if
y
′
<
y
,
Equation
17
[0000] where γ =γ −1 with:
[0000]
f
n
γ
_
(
y
,
y
′
)
=
1
sinh
(
γ
_
n
π
)
{
cosh
[
ξ
n
(
b
-
y
)
]
cosh
(
ξ
n
y
′
)
,
if
y
>
y
′
cosh
[
ξ
n
(
b
-
y
′
)
]
cosh
(
ξ
n
y
′
)
,
if
y
<
y
′
.
Equation
18
[0065] By taking the derivatives of these expressions of the Green's function with respect to x and y, it follows that:
[0000]
g
y
(
r
→
,
r
→
′
)
=
-
2
b
-
1
∑
m
=
1
∞
sin
(
η
m
y
)
cos
(
η
m
y
′
)
f
m
γ
(
x
,
x
′
)
and
Equation
19
g
x
(
r
→
,
r
→
′
)
=
-
2
a
-
1
∑
n
=
1
∞
sin
(
ξ
n
x
)
cos
(
ξ
n
x
′
)
f
n
γ
_
(
y
,
y
′
)
Equation
20
[0000] and in inserting equation (9) it follows that:
[0000]
φ
(
x
′
,
y
′
)
=
2
b
-
1
∑
m
=
1
M
′
-
1
cos
(
η
m
y
′
)
∫
0
a
f
m
γ
(
x
,
x
′
)
D
x
(
η
m
)
x
+
2
a
-
1
∑
n
=
1
N
′
-
1
cos
(
ξ
x
x
′
)
∫
0
b
f
n
γ
_
(
y
,
y
′
)
D
y
(
ξ
n
)
y
Equation
21
[0000] where M′ and N′ are integers. They can be chosen to attain the required numerical precision. In particular, I choose these two numbers as powers of two, greater than M+1 and N+1, respectively, where M and N represent the dimensions of the image to process.
[0066] Due to the presence of the factors sin(η m y) and sin(ξ n x) in equations (19) and (20), the integration [with respect to y in the first sum of the right-hand side of Equation 21 to obtain D x (η m ) and with respect to x in the second sum of the right-hand side to obtain D y (ξ n )] allows one to compute the sequences D x (η m ) and D y (ξ n ) as the imaginary parts (taken with the negative sign) of the Fourier Transform (FT) of the derivatives (with respect to y and with respect to x, respectively) of the phase.
[0067] These two sequences can be computed numerically by using the algorithm of the Discrete Fourier Transform, by algorithm of the Fast Fourier Transform (1DFFT or FFT 1D), as applied to the phase differences of the first order F y and F x respectively:
[0000] D x (η m )=− {FFT└ F y ( n, m ), n =const┘} η m Equation 22
[0000] D y (ξ n )=− {FFT[ F x ( n, m ), m =const]} ξ n Equation 23
[0068] It is noted that n=const means that the first index (i.e., n) is fixed in F y (n, m) whereas the FFT 1D of the resultant sequence, in which the second index (i.e., m ) varies, is computed. Inversely, m=const means that the second index (i.e., m) is fixed in F x (n, m) whereas the FFT 1D of the resultant sequence, in which the first index (i.e., n) varies, is computed. The indices η m and ξ n indicate the discrete frequencies for which the 1D FFT should be evaluated.
[0069] In addition, taking into consideration calculation above, in case of Dirichlet boundary conditions, the phase is given in the same way by:
[0000]
φ
(
x
′
,
y
′
)
=
2
b
-
1
∑
m
=
1
M
′
-
1
sin
(
η
m
y
′
)
∫
0
a
f
m
γ
(
x
,
x
′
)
D
x
(
η
m
)
x
+
2
a
-
1
∑
n
=
1
N
′
-
1
sin
(
ξ
n
x
′
)
∫
0
b
f
m
γ
_
(
y
,
y
′
)
D
y
(
ξ
n
)
y
Equation
24
[0000] with the real parts of the Fourier transforms in one dimension:
[0000] D x (η m )= {FFT└ F y ( n, m ), n =const┘} η m
[0000] D y (ξ n )= {FFT[ F x ( n, m ), m =const]} ξ n Equation 25
Computation From The Intensity
[0070] Again with reference to Abramoshkin et al., the gradient of the phase from the Green's function is known:
[0000]
∇
φ
(
r
→
′
)
=
∫
S
∂
I
(
r
→
)
∂
z
∇
g
(
r
→
,
r
→
′
)
r
→
,
Equation
26
[0000] where the Green's function used is the Green's function for the infinite space:
[0000]
g
(
r
→
,
r
→
′
)
=
-
1
2
π
ln
r
→
-
r
→
′
.
Equation
27
[0071] Therefore, by re-using Equation 1,
[0000]
φ
(
r
→
′
)
=
-
k
∫
S
[
I
(
r
→
;
z
)
]
-
1
{
∫
S
∂
I
(
r
→
″
)
∂
z
∇
g
(
r
→
″
,
r
→
)
r
→
″
}
·
∇
g
(
r
→
,
r
→
′
)
r
→
+
∮
C
φ
(
r
→
)
[
n
^
S
·
∇
g
(
r
→
,
r
→
′
)
]
c
→
.
Equation
28
[0072] By using the Green's function (that cancel the second integral on the contour), it follows that:
[0000]
φ
(
r
→
′
)
=
-
k
∫
S
[
I
(
r
→
;
z
)
]
-
1
{
∫
S
∂
I
(
r
→
″
)
∂
z
∇
g
(
r
→
″
,
r
→
)
r
→
″
}
·
∇
g
(
r
→
,
r
→
′
)
r
→
Equation
29
[0000] with, for Neumann conditions:
[0000]
φ
y
′
(
x
′
,
y
′
)
=
2
b
-
1
∑
m
=
1
M
′
-
1
cos
(
η
m
y
′
)
∫
0
a
f
m
γ
(
x
,
x
′
)
P
x
(
η
m
)
x
,
φ
x
′
(
x
′
,
y
′
)
=
2
a
-
1
∑
n
=
1
N
′
-
1
cos
(
ξ
n
x
′
)
∫
0
b
f
m
γ
_
(
y
,
y
′
)
P
y
(
ξ
n
)
y
,
with
Equation
30
P
x
(
η
m
)
=
-
{
FFT
[
∂
I
∂
z
(
n
,
m
)
,
n
=
const
]
}
η
m
P
y
(
ξ
n
)
=
-
{
FFT
[
∂
I
∂
z
(
n
,
m
)
,
m
=
const
]
}
ξ
n
.
Equation
31
[0073] One also obtains the equivalent functions for the Dirichlet boundary conditions.
[0074] Equation 28 is substantially that used in WO '622. In WO '662, the second term is cancelled by supposing that the phase is zero on the contour, whereas my phase can be nonzero. The calculation is nevertheless realizable by Neummann and Dirichlet boundary conditions cancelling this term. In addition, in WO '622, Equation 28 is expressed in the Fourier domain and calculated by Fourier transforms of Fourier in two dimensions. On the contrary, I carry out this calculation of phase by using the Fourier transforms in one dimension thanks to the use of specific Green's functions which substantially decreases the number of complex operations, and thus the computing time of the algorithms associated with my method.
[0075] As illustrated in FIGS. 2 and 3 , the number of complex multiplications is calculated between my solution by the 1D Fourier transform, and the solution of WO '622 depending on the size of the processed image. It is clear that my solution saves considerably the image processing time for the phase reconstruction.
Processing Algorithm for Phase Reconstruction
[0076] I now provide an example. For this, the following notations are used:
Abbreviations:
[0000]
BC—Boundary Conditions;
1D FFT—One-dimensional direct Fourier Transform;
1D IFFT—One-dimensional inverse Fourier Transform;
[. . . ]—Real part of the complex number in brackets;
[. . . ]—Imaginary part of the complex number in brackets.
The following parameters of the initial images:
M×N, where M is the number of rows in the image, indexed by i=1, . . . , M; and N is the number of columns, indexed by j=1, . . ., N.
Constants:
[0000]
a=N′=2 i ≧N+1;
b=M′=2 j ≧M+1;
H max =225 (for the 32-bit computer);
γ=a/b, Δν y =π/b, M max =min{M′, H max / 65 };
β=b/a, Δν x =π/a, N max =min{N′, H max /β}.
[0088] FIG. 4 shows the first step of the algorithm in which, from an image, one computes ∂I/∂z by difference between intensity images in the planes z 1 and z 2 . This difference is of course computed pixel by pixel in the images I 2 (m, n) and I 1 (m, n). It will be understood that, in case of arbitrary coordinates, this measure of ∂I/∂z corresponds in fact to any measure of the intensity variation over a surface.
[0089] In a general way, the algorithm gives the possibility, each time when this is necessary, of choosing between Neumann and Dirichlet boundary conditions.
[0090] FIGS. 5 a , 5 b and 5 c show an implementation of the equations described above. It is also noted that the discrete nature of the real data in the images (values in x and y being obtained from pixel data), allows a discrete calculation of the integrals given in the equations and an formulation of calculations in the form of finite discrete sums. The modes of calculations of these discrete sums are given in the algorithm as an example and can of course vary according to choices without limiting the scope of the appended claims.
[0091] Illustrated in FIG. 5 a , the oblique hatchings of the initial image denote the FFT window used for calculations. This window exceeds the useful image and can be filled by 0, according to the known method of the “zero padding”, or “zero-filling”, or by any other well known method in the field of the image processing.
[0092] The vertical lines of FIG. 1 indicate the direction of the 1D FFT in this illustrated part of the algorithm. In this mode of implementation, the FFT is calculated by fixing a column while varying the row index.
[0093] In addition, it can be noted from FIG. 5 a the introduction of the parameter M max used preferably according to this implementation mode to avoid divergence of the terms in hyperbolic sine and a specific calculation of the coefficient c y (m,n) if the index representing the coordinates exceeds this threshold value.
[0094] One will recognize, by Operation A, obtaining the phase derivative with respect to y as described in the first part of Equation 30. It is noted that Operation A requires the operation of division by a measure of intensity which can make the solution diverge if this intensity is zero. In this case, it is possible to carry out a determination of the zeros of the intensity beforehand to correct the divergence and/or to assign a minimum value to the intensity in the event of zero intensity in a considered point of space.
[0095] According to Equation 22, the method of calculation applies a 1D Fourier transform to the phase gradient with respect to y to obtain the first part of the phase as in Equation 21. This first term φ 2 (m, n) is obtained as a result of the Operation B of FIG. 5 c.
[0096] In the same manner (not shown), the phase derivative with respect to x is obtained as described in the first part of Equation 30, and according to Equation 23, one applies then the method of calculation using the 1D Fourier transform applied to the phase gradient with respect to x to obtain the second part of the phase φ 1 (m, n), as in Equation 21.
[0097] The reconstructed phase is computed by φ(m, n)=φ 1 (m, n)+φ 2 (m, n).
[0098] In a general way, illustrated in FIGS. 5A , 5 B and 5 C, the algorithm thus comprises, after the calculation of a measure of intensity variation on a surface (∂I/∂z in the illustrated realization mode), the application of a first integral transformation, preferably in the form of a Fast Fourier Transform, to obtain the variable named r x (m, n) depending on the used boundary conditions. This variable is then multiplied (in the Fourier space or, more generally, in the projection space) by a filter corresponding to the functions ƒ n γ and ƒ m γ , possibly modified by the calculation constraints of the type M max .
[0099] In accordance with Equations 19 and 20, these filters ƒ n γ and ƒ m γ are representations of a Green's function in a space of eigenfunctions of the Helmholtz equation, for example the functions associated with Equations 5 and 6.
[0100] Inverse integral transforms are then applied, for example, Inverse Fourier Transforms, by taking the real or imaginary parts according to boundary conditions.
[0101] For example, as Equation 26 indicates, the division by a measure of intensity, for example, that taken on a computation plane of the intensity variation, makes it possible to obtain the gradient of the phase with respect to one of the coordinates.
[0102] In conformity with Equations 21, 22, and 23, a one-dimensional integral transform, for example, of Fourier type, is then applied, a second filter to the obtained variable [D x (m, n) in the proposed realization mode] is applied, and an inverse integral transform is applied, to obtain substantially one of the terms of the expression defining the required phase.
[0103] It is understood that using the example of implementation of the algorithm given in the figures and described above, it is to make modifications of implementation, for example, according to computation power of the used computers or according to specific characteristics of the image.
[0104] Regarding the description made above of the equations necessary for the implementation of the algorithm and of the processing algorithm itself, it will be understood that the described realization mode is only a non-restrictive example.
[0105] In particular, in the case of a nonrectangular support, it is possible to determine the eigenfunctions of the Helmholtz equation for a special form of support. As an indication only, the form of these functions in case of a circular support is given by:
[0000] U m,n (ρ, φ)=[cos( m φ)+sin( m φ)] J m (πα mn ρ/ a ), m, n= 0, . . . , ∞ Equation 5
[0000] where J m is the Bessel function or order m with J′ m (πα mn )=0, m, n=0, . . . , ∞, i.e. πα mn is the n-th zero of the derivative of Bessel function of order m. Equation 8 allows then to obtain the associated Green's function.
[0106] The use of the Green's function associated with this eigenfunction is particularly useful if the phase reconstruction in a circular area gives the sufficient information about the topography of the object of circular geometry, such as for example in case of visualization and measurement of the front face of an optical fiber.
[0107] One skilled in the art will be able to determine these eigenfunctions in the case of triangular or semi-infinite supports.
[0108] In addition, I describe an implementation mode utilizing one-dimensional discrete Fourier transforms, but one skilled in the art will be able to implement one-dimensional discrete Bessel transforms, as a curvilinear analogue of the Fourier transforms. It is also possible to use any type of integral transformation as a projection of a function on a function space, for example, determined by the type of function used in equations 5 or 5′.
[0109] In any case, if the eigenfunctions of Helmholtz equation are expressed in separable coordinates, in particular if the support of the image is not distorted too much, my methods can be used and integral transformations can be carried out in only one dimension.
[0110] For very distorted supports, conformal mapping transforms can be used to reduce these supports to simpler supports, or to define this support as a composition of simpler supports.
[0111] Moreover, it is understood that the implementation mode described for an image is also applicable for any type of radiation wave field in the whole luminous spectrum. To apply my methods at the various spectra, it is possible to modify the acquisition setups as described in the following section devoted to the setups associated with the invention.
Measurement Setups
[0112] In accordance with the example in FIG. 4 , it is advisable to use devices of measurement of the intensity in distinct planes. These measurements are carried out in planes perpendicular to the optical axis.
[0113] To do this, as illustrated in FIG. 6 , the acquisition of an image of a transparent sample is carried out. Measurements can be taken on the two perpendicular planes, the position of the sample can be modified compared to a fixed optical device or to move the optical device.
[0114] In FIG. 6 , for a transparent sample, the device comprises an image sensor 61 , for example, in form of a CCD sensor, an optical projection system 62 to project the light coming from sample 63 towards the sensor. The light is emitted by an optical illuminating system 64 . The sample is mobile along the Z axis due to a displacement device (not shown).
[0115] As shown in FIG. 7 , the sample is fixed at a motionless platform 75 . The optical device still includes a sensor 71 , a projection system 72 and an illumination system 73 , and it includes also a movable platform 76 to which elements 71 , 72 and 73 are attached. This platform is set in motion by a displacement system 77 in form of, for example, a motor or a piezoelectric element.
[0116] As shown in FIG. 8 , I include a measurement device using one or more lenses with variable focal distances. In this case, a lens with a variable focal distance 88 is placed for example at the position of the projection system and, according to an alternative, a lens with variable focal distance 89 is placed at the position of the illumination system for measurements of a fixed transparent sample. In this case, the displacement in intensity measurements corresponds to the difference in focal distances, Δz=F 2 −F 1 . In case of two lenses, the modifications of the focal distances will be done simultaneously for the two lenses. This system is also realizable with only one lens with a variable focal distance.
[0117] As shown in FIG. 9 , for the diffusing and non-transparent sample, one can use a beam splitter 90 intended to direct a luminous beam coming from the illuminating system 94 . One can then use the set of the elements previously described such as the sensor, the projection system, the whole unit being either fixed or mobile, as well as one or more lenses with variable focal distances, as previously described.
[0118] The image sensor is connected to an image processing device including a software for the implementation of the algorithm.
[0119] The images of phase obtained by this software can then be visualized on a computer screen.
[0000]
TABLE I
Term in the
continuous
Description of the term
notation
in the continuous notation
Relation to the discrete notation
Relation to the geometry of a CCD type sensor
r = (x, y) and
Vectors from the origin to the points
Grid of points with coordinates (m, n) for each
Coordinates of the centre of an element on the
r ′ = (x′, y′)
in the two-dimensional space
integer number m and n.
CCD sensor
S
Support region for the phase
Grid of points with coordinates (m, n) where
All the active elements of the sensor
m = 1, . . ., M and n = 1, . . ., N.
x = a
Boundary line to the phase support
The column of the grid with the column index
The column of the passive elements of the
region S, in the y direction
n = N + 1
sensor situated to the right of all the active
elements of the sensor.
y = b
Boundary line to the phase support
The row of the grid with the row index
The row of the passive elements of the sensor
region S, in the x direction
m = M + 1
situated beneath all the active elements of the
sensor
C
Boundary to the phase support
Two rows of the grid of points with coordinates
All the passive elements of the sensor (or its
region S
(0, n) and (M + 1, n) where n = 1, . . ., N,
boundary) that enclose the rectangular area of
as well as two columns with coordinates (m, 0)
active pixels
and (m, N + 1) where m = 1, . . ., M
|
A method of reconstructing a phase of a radiation wave field including determining a representative measure of an intensity variation of the radiation wave field on a selected surface extending globally from one end to another of the radiation wave field, determining a representative measure of the intensity of the radiation wave field on the selected surface, transforming the representative measure of the intensity variation to produce a first representation of integral transform and to apply to the first representation of integral transform a first filter and producing a first representation of modified integral transform, applying a first function of the first representation of integral transform to the first representation of modified integral transform and producing an untransformed representation, applying a correction based on the measure of intensity on the selected surface to the untransformed representation, transforming the untransformed corrected representation to produce a second representation of integral transform and applying a second filter to the second representation of integral transform, and applying a second function of the second integral transform to the second modified representation of integral transform to produce a measure of phase of the radiation wave field on the selected surface extending globally from one end to another of the radiation wave field, wherein the first and second filters are measures of a representation of a Green's function in a space of eigenfunctions of the Helmholtz equation with separable coordinates such that the first and second integral transforms are one-dimensional integral transforms in the space of the radiation wave field.
| 6
|
This application claims the benefit of Provisional application Ser. No. 60/128,745 filed Apr. 12, 1999.
FIELD OF THE INVENTION
This invention relates broadly to developments concerning equipment for electrical measurements on conductors. The invention will be described herein with reference to fault indicators for power distribution cables, it will be appreciated, however, that the invention does have broader applications, including for example in stand alone current measurements on electrical conductors.
BACKGROUND OF THE INVENTION
Equipment for detection and location of faults on power lines involve typically the measurement of the magnetic fields produced by the alternating current in power lines, using a single magnetic field sensing coil.
In substations, this involves expensive current transformers, which must also provide insulation between the power line conductor and earth potential.
There is also equipment which can be located throughout a network which does not provide its own insulation between the phase and earth potential because it is mounted either at phase potential or at earth potential.
Such equipment normally derives a signal proportional to the average or peak magnetic field by rectifying the waveform to produce a DC voltage and this is used for the detection and location of faults. By deriving a signal proportional to the average or peak magnetic field, other waveform parameters, phase, and harmonic content information is removed from the signal. DC voltages are suitable for analogue amplification, for operating analogue control devices and for interpretation by analogue comparators.
When the power lines experience a fault, high currents flow in the conductors of the lines, producing a rapid increase in the magnetic fields around the conductors. Therefore, if an increase is detected by the equipment, this is indicative of a fault current having passed the magnetic field sensing coil. Typically, within the equipment a derivative of the output signal of the magnetic field sensing coil is produced in an analogue electronic circuit, to detect increases in the amplitude of current flow. The currents flowing in the conductors of the power lines, particularly during a fault situation, may typically vary between 5 to 25,000 Amperes. The average magnetic field around the power line conductors therefore has a high dynamic range, which is typically between 1 to 10,000.
The types of coil which may be used to measure magnetic fields in such equipment are i) air-cored coils which are typically cylindrical, ii) air-cored toroids, iii) coils, cylindrical or toroidal, which are cored with a ferromagnetic or paramagnetic medium other than air. Each type of coil has specific advantages and disadvantages. Air-cored coils do not saturate in the presence of high magnetic fields and can therefore be used to detect magnetic fields with a high dynamic range. However, with air-cored coils, particularly cylindrical coils mounted at earth potential some distance from the power line conductor, low magnetic fields generate only low induced signals in the coil and may therefore be difficult to detect accurately, in particularly when background signals may contribute to the measurements.,
On the other hand, coils cored with a para- or ferromagnetic medium, increase the induced signal in the coil due to the high permeability which results in an increase of the magnetic field inside the coil due to magnetic polarisation of the medium. However, such coils have the disadvantage of saturating once the “true” magnetic field to be measured exceeds a particular value, and therefore the characteristics of fields in excess of that particular value cannot be measured with such coils.
In the equipment for detection and location of faults on power lines, the average magnetic field signal derived from the coils is processed using an analogue circuit. Some fault detectors may employ an analogue variable gain control utilising for example a variable resistor such as a Junction Field Effect Transistor (JFET) to increase the dynamic range for the measurement, however, due to the analog nature of such circuits the output signal is then not directly representative of measured magnetic field strength. In some fault detectors, such as those described in U.S. Pat. No. 4,947,126 and U.S. Pat. No. 5,270,898, a gain may be employed which is switched between a high and low value by analogue circuitry utilizing for example, switches or relays. However, due to the analogue nature of such circuits, a dynamic range of greater than 16:1 is difficult to attain and scaling of the amplitude is normally lost. The amplitude of the signal in the sensing coil and that of the output signal lose their one-to-one relationship and this cannot be restored using analogue circuitry alone.
The equipment described above has the limitation of providing little information on the magnetic field, waveform, phase or harmonic content and electric field waveform, phase or harmonic content preceding, during and after the fault, since the information utilised is substantially limited to the identification of sudden changes in the amplitude of the magnetic field detected by the magnetic field sensing coil. The further information about the magnetic field and electric field preceding, during and after the fault can be useful in determining the characteristics of the fault. These characteristics include the severity of the fault (ratio of fault current to pre-fault current), the time and duration of the fault current and the time for the protection equipment to operate, whether the fault was phase to phase or phase to earth, and whether the fault current was accompanied by a fuse or circuit breaker operation (loss of voltage) or a substantial variation in the voltage.
Furthermore, the equipment described above is not able to discriminate between a fault current and what is referred to as magnetising inrush currents, which are typically observed when voltage is applied to a non-faulted power system following an extended outage period. Therefore, when the equipment detects loss of system voltage, it usually inhibits its detection of faults until a predetermined period after voltage is reapplied, resulting in a period during which fault detection for the power line concerned is impossible.
SUMMARY OF THE INVENTION
In accordance with a first aspect of the present invention there is provided a method for measuring at least one characteristic parameter of an alternating current in a conductor, the method comprising the steps of:
measuring the magnetic field around the conductor at a point along the conductor;
deriving an analogue voltage signal representative of the measured magnetic field;
adding a direct current (DC) offset signal to an alternating current (AC) component of the measured magnetic field;
amplifying the analogue voltage signal;
converting the amplified voltage signal into a digital voltage signal;
measuring the digital voltage signal and, when the amplitude of digital voltage signal reaches a predetermined value, adjusting a gain setting of the amplification; and
generating an output signal representative of the parameter of the alternating current based on the amplified voltage signal and the gain setting.
The step of adding a DC offset signal allows for making the measured magnetic field suitable for amplification while substantially maintaining waveform information.
Accordingly, in at least preferred embodiments of the present invention, a large dynamic range can be realised for the magnetic field/alternating current measurements. Preferably, the method can be used in conjunction with an air-cored coil not to be limited by a saturation effect.
The characteristic parameter of the alternating current may be one of the group of waveform characteristics of the alternating current such as amplitude of the alternating current; frequency of the alternating current; phase of the alternating current; harmonic content of the alternating current; and a derivative of the alternating current. More than one parameters may be measured simultaneously.
The method may preferably further comprise the step of integrating the analogue voltage signal for obtaining the waveform of the alternating current in the conductor.
Thereby, in at least preferred embodiments of the present invention, even low magnetic field strengths may be measured at high main settings.
In one embodiment, the step of adding a DC offset signal comprises the step of varying the DC offset signal in response to a DC component in the digital voltage signal.
In a preferred embodiment, the method further comprises the step of digitally filtering the digital voltage signal to determine the ratio of a mains voltage signal at a mains frequency of the conductor and an harmonic voltage signal at an harmonic of the mains frequency. In one embodiment, a second harmonic is utilised for determining whether a magnetic field signal around the conductor is caused by magnetising inrush current.
Preferably, the method further comprises the step of measuring an electric field in the vicinity of the conductor; and deriving a second analogue voltage signal representative of the measured electric field in the vicinity of the conductor.
In one embodiment, the step of measuring the electric field comprises the step of placing a capacitor arrangement in the vicinity of the conductor; and the method further comprises the steps of amplifying the second analog voltage signal; converting the amplified second voltage signal into a second digital voltage signal; measuring the second digital voltage signal and, if the amplitude of the second digital voltage signal reaches a second predetermined value, adjusting a second gain setting of the second amplification; and generating a second output signal representative of at least one parameter of a voltage signal in the conductor derived from the second amplified voltage signal and the second gain setting.
The characteristic parameter of the voltage signal may be one of the group of waveform characteristics of the voltage signal such as amplitude of the voltage signal; frequency of the voltage signal; phase of the voltage signal; and harmonic content of the voltage signal. More than one parameters may be measured simultaneously.
In accordance with a second aspect of the present invention there is provided an apparatus for measuring at least one characteristic parameter of an alternating current in a conductor, the apparatus comprising:
measuring means for measuring the magnetic field around the conductor at a point along the conductor;
means for deriving an analogue voltage signal representative of the measured magnetic field;
trimming means for providing a DC offset signal to an AC component of the measured magnetic field;
amplification means for amplifying the analogue voltage signal;
converting means for converting the amplified voltage signal into a digital voltage signal;
gain control means for adjusting a gain setting of the amplification depending on the amplitude of the digital voltage signal; and
means for generating an output signal representative of the parameter of the alternating current based on the amplified voltage signal and the gain setting.
The trimming means allows for making the measured magnetic field suitable for amplification while substantially maintaining waveform information.
The characteristic parameter of the alternating current may be one of the group of waveform characteristic of the alternating current such as amplitude of the alternating current; frequency of the alternating current; phase of the alternating current; and harmonic content of the alternating current. More than one parameters may be measured simultaneously.
The apparatus may preferably further comprise means for integrating the analogue voltage signal to obtain the waveform of the alternating current in the conductor.
In one embodiment, the apparatus further comprises filtering means for filtering the digital signal and means for determining the ratio of a mains voltage signal at a mains frequency of the conductor and an harmonic voltage signal at an harmonic of the mains frequency.
Preferably, the apparatus further comprises a second measuring means for measuring an electric field in the vicinity of the conductor; and means for deriving a second analogue voltage signal corresponding to the measured electric field in the vicinity of the conductor.
In one embodiment, the apparatus further comprises second amplification means for amplifying the second analog voltage signal; second converting means for converting the second amplified voltage signal into a second digital voltage signal; second gain control means for adjusting a second gain setting of the second amplification means depending on the second digital voltage signal; and a second means for generating a second output signal representative of at least one parameter of a voltage signal in the conductor derived from the second amplified voltage signal and the second gain setting.
The characteristic parameter of the voltage signal may be one of the group of waveform characteristics of the voltage signal such as amplitude of the voltage signal; frequency of the voltage signal; phase content of the voltage signal; and harmonic content of the voltage signal. More than one parameters may be measured simultaneously.
The amplification, conversion, gain control and output may be performed by the same respective components for both the electric and magnetic field measurements in the apparatus.
In one embodiment, the amplification means comprises first and second operational amplifiers in series, wherein the analogue voltage signal is applied to the non-inverting input of the first operational amplifier, and the output of the first operational amplifier is connected to the non-inverting input of the second operational amplifier.
In one embodiment, the gain control means comprises a digitally controlled analogue switch having a low “off” resistance and a high “on” resistance.
Preferably, the trimming means comprises a serial to parallel shift register, wherein the outputs of the shift register are connected to a resister network to form a digital to analogue converter.
The present invention may be more readily understood from the description of preferred forms of an apparatus for electrical measurements on conductors given below with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram illustrating a device in accordance with one embodiment of the present invention.
FIGS. 2 a, b and c are graphs illustrating some characteristics of the device of FIG. 1 .
FIG. 3 is a circuit diagram showing a detail of a device in accordance with another embodiment of the present invention.
FIG. 4 is a circuit diagram showing another detail of the embodiment of FIG. 3 .
FIG. 5 is a schematic diagram illustrating a device in accordance with another embodiment of the present invention.
FIG. 6 is a schematic diagram illustrating a “distance to fault calculation” method.
FIG. 7 is a schematic, perspective view of a device in accordance with another embodiment of the present invention.
FIG. 8 is a schematic diagram of a coil for use in a method and/or a device in accordance with embodiments of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In FIG. 1, an AC signal in a power line 10 generates a magnetic field 12 around the power line 10 . A conductive coil 14 of the device 16 is placed in the vicinity of the power line 10 in a manner such that at least a portion of the magnetic field lines of the magnetic field 12 passes through the loops of the coil 14 , thereby inducing an AC signal in the coil 14 , which is connected to an internal ground 18 of the device 16 through an analogue amplification stage 20 . An integrator 21 is provided before the amplification stage 20 . In the analogue amplification stage 20 , the AC voltage across the coil 14 is amplified and the amplified AC voltage signal is inputted into an analogue to digital converter 22 of a microcontroller 24 .
The microcontroller 24 controls a gain control unit 26 which in turn controls the gain of the analogue amplification stage 20 . When the microcontroller 24 detects that the amplitude of the converted AC voltage signal has reached a predetermined value, it generates a control signal to the gain control unit 26 , in response to which the gain control unit 26 reduces the gain of the amplification stage 20 . Thereby, saturation of the amplification stage 20 can be avoided and measurements can continue for higher AC voltage signals from the coil 14 .
In the microcontroller 24 , the converted AC voltage signal is correlated with the control signals sent to the gain control unit 26 , and the control unit 24 generates an output signal 28 which is representative of waveform, which includes the amplitude, phase and harmonic content of the AC voltage signal in the coil 14 , which is a measure for the alternating current signal in the power line 10 .
In FIGS. 2 a to c , the output signal 28 , the amplified voltage signal 30 and the amplitude of an AC signal 32 in the power line 10 are illustrated.
Referring again to FIG. 1, the device 16 further comprises an offset compensation unit 34 . The offset compensation unit 34 receives a digital signal from the micro controller 24 representative of a DC component in the amplified AC voltage signal. The offset compensation unit 34 outputs a DC trimming signal which is added through a resistor 36 to the integrated AC voltage signal across the coil 14 at the input of the amplification stage 20 .
Within the offset compensation unit 34 , the amplitude of the generated DC trimming signal is varied to maintain the digital DC component signal received from the microcontroller 24 at a minimum. This corresponds to a fixed offset of the analogue signal entering the A/D converter 22 . This can allow the amplification stage 20 to be operated at high gains without loss of performance caused by amplification of DC offset voltages.
Turning now to FIG. 3, the input signal 100 and an offset correction signal 110 are added through resistor 120 . This signal is applied to the non-inverting input of operational amplifier 130 . The DC gain of amplifier 130 is equal to G 1 R2 R in ,
where R in is the input resistance between the inverting input of the amplifier and the reference voltage for the amplifier (VCC/2). Device 140 is a digitally controlled analog switch that is chosen to have an “off” resistance much higher than the resistor labelled R 2 / 63 . Similarly, the “on” resistance of the analog switch is chosen to be much less than the resistor labelled R 2 / 63 . Thus, when a control signal from the microcontroller 150 is activated, 140 is switched “ON”, its resistance is low, so the DC gain of the amplifier 130 is given by G 1 R2 R2 / 63 1 63 64 .
When device 140 is switched “OFF”, its resistance is high, so the DC gain of the amplifier is given by G 1 R2 φ 1 0 1 .
Thus, the activation signal from the microcontroller 150 is used to set the DC gain of the amplifier 130 to either 64 or 1. Capacitors C 1 and C 2 are small value devices and are used to filter out ringing in the output signal following a gain change. the microcontroller 150 is used to set the DC gain of the amplifier 130 to either 64 or 1. Capacitor C 1 is a small value device and is used to filter out ringing in the output signal following a gain change.
Amplifier 160 amplifies the signal from amplifier 130 and has gains set by R 3 , R 3 / 3 , R 3 / 15 , switch 170 , and switch 180 . The gains of this stage are shown below:
Signal
Signal
labelled
labelled
Gain of
B1G16
B1G4
Amplifier 160
0
0
1
0
1
4
1
0
16
By combining the gains of amplifiers 130 and 160 , the following gain settings are possible:
Signal
Signal
Signal
labelled
labelled
labelled
B1G64
B1G16
B1G4
Gain (total)
0
0
0
1
0
0
1
4
0
1
0
16
1
0
0
64
1
0
1
256
1
1
0
1024
The resistor R 4 and capacitor C 3 are used to lowpass filter the signal prior to the analog to digital converter in the microcontroller.
Turning now to FIG. 4, the circuitry described below provides a technique to digitally correct for offset voltage in low cost, low power operational amplifiers. This allows the amplifiers to be operated at high gains without loss of performance caused by amplification of offset voltages.
Circuit Operation:
Devices 200 and 210 are serial to parallel shift registers. The most significant bit of shift register 200 is named D 7 and is connected to the input of shift register 210 . This gives a twelve digital output D 0 -D 11 . The inputs to the shift register ( 200 + 210 ) are generated by the microcontroller and are labelled DACDATA and DACCLK. These outputs are connected to the R- 2 R resistor network 220 to form a digital to analog converter. The output range of this digital to analog converter is from zero to (4095/4096) (SHIFTVCC), when SHIFTVCC is a predetermined DC signal. The output of the digital to analog converter is attenuated by resistor R 1 and R 2 and added to voltage VCC/2 to give a small voltage that varies around VCC/2. This voltage is filtered by C 1 and buffered by buffer 230 to give signal B 1 TRIM.
The trimming software functions by setting the amplifier circuit shown in FIG. 3 to maximum gain. In the presence of a low input signal, the value of B 1 TRIM that minimises the DC offset voltage seen by the microcontroller 150 is obtained using a binary search technique.
Returning now to FIG. 1, the microcontroller 24 also performs an analysis of the frequency components of the amplified AC voltage signal, and thus of the frequency components of the magnetic field 12 .
A lowpass filter is used to provide a signal proportional to the amplitude of the mains frequency component of the magnetic field (M 1 ). A bandpass filter is used to provide a signal proportional to the second harmonic component of the magnetic field (M 2 ). If the ratio of M 2 /M 1 exceeds a predetermined ratio, then the magnetic field signal is determined to be caused by magnetising inrush current.
In FIG. 5, in another embodiment a device 300 further comprises a capacitor arrangement 310 for measuring the electric field generated by the AC voltage signal on the power line 10 . Both the signal from the capacitor arrangement 310 and the coil arrangement 330 are processed substantially as described before for the embodiment incorporating only a coil for the measurement of magnetic fields. As such, signal processing means 315 , 335 generate respective output signals 318 , 338 from the respective capacitor arrangement 310 or coil arrangement 330 . Similarly as for the magnetic field measurements, this results in an electric field measurement in which a value representing a parameter of the electric field can be determined on a “continuous” scale.
The device 300 allows the detection of a common but elusive type of fault, commonly called self-clearing fault. These faults are characterised by high levels of current but do not cause a trip. By measuring an increase or decrease in the magnitude of the electric field, accompanied by changes in the current, self-clearing faults may be detected and stored.
The device 300 incorporating the capacitor arrangement 310 for measuring the electric field can also be used to perform what is commonly referred to as a “distance to fault calculation”.
Referring now to FIG. 6, the impedance of the line between the supply and the fault indicator is dominated by inductance L S and resistance R S .
The impedance of the line between the fault indicator and the fault is dominated by inductance L F and resistance R F .
The impedance of the line and load beyond the fault location is dominated by inductance L L and resistance R L .
During the fault, it is assumed that the voltage at the fault is small compared to the supply voltage.
The voltage seen at the fault indicator is: V F = i F R F + L F iF t , 1.1
where iF is the fault current and iF t
is the time derivative of the fault current.
If the voltage at the fault indicator is measured when i F is zero, then we have: V F = L F i F t iF = 0
Rearrangement gives L F = V F t iF iF = 0 1.2
Thus, we may calculate the inductance of the line between the fault indicator and the fault.
Now, the per/metre inductance of the line is a constant that varies little with the configuration or voltage of the line. Thus it is considered to be approximately constant for all lines. We may write:
L
F
=k×d,
where k is the inductance per metre and d is the length of the line in metres.
Similarly, we have: d = L F k . 1.3
Combining (1.2) and (1.3) gives d = V F t i F iF = 0 k 1.4
Equation (1.4) is the basis for the distance to fault measurement technique. Note that this technique is used in other products.
If several devices incorporating electrical field measurements components are used, the distance to fault reported by each indicator may be used to refine the search for the location of the fault.
It will therefore be apparent from the above description that the preferred embodiments of the present invention provide a method or means to obtain within the memory of a microprocessor, fully scaled current and voltage wave forms which have not been rectified. This may be achieved without saturation or phase shift over a much greater dynamic range than was previously available. Also, preferred embodiments of the invention allow a user to establish multiple parameters of these waveforms which can then be used to base decisions on the presence of fault current. Each additional waveform parameter aids in the process deciding what is a fault current.
Currently available devices on the band are not able to cover the same dynamic range, maintain scaling, maintain the same level of waveform information, or combine the same range of waveform parameters in decision making. This is in par due to the available devices requiring rectification of the measured waveform.
It will be appreciated by a person skilled in the art that numerous variations and/or modifications may be made to the present invention as shown in the specific embodiments without departing from the spirit or scope of the invention as broadly described. The present embodiments are, therefore, to be considered in all respects to be illustrative and not restrictive.
For example, it will be appreciated that the present invention is not limited to measurements performed on a single conductor, but rather the measurements could be conducted on a plurality of adjacent power lines. In such circumstances, one or more sensors (such as coil 14 of FIG. 1) could be used.
For example, it will be appreciated that the measurement may also be performed utilising two or more coils with an angular offset between them to establish the characteristics of the magnetic field.
|
A method for measuring at least one characteristic parameter of an alternating current in a conductor, the method including the steps of measuring the magnetic field around the conductor at a point along the conductor; deriving an analogue voltage signal representative of the measured magnetic field; amplifying the analogue voltage signal; converting the amplified voltage signal into a digital voltage signal; measuring the digital voltage signal and, when the amplitude of digital voltage signal reaches a predetermined value, adjusting a gain setting of the amplification; and generating an output signal representative of the parameter of the alternating current based on the amplified voltage signal and the gain setting.
| 6
|
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an apparatus, method, and system for display supports. Specifically, the present invention relates to compact, positional, magnetic display supports for displaying an object against a surface with magnetically adherent material.
[0003] 2. Description of the Related Art
[0004] When creating a wall display, retailers have used various and substantially permanent systems for displaying items. Retail display racks are used to display a wide variety of different products that are offered for sale. The systems have included large display cases, shelves, hooks, racks, and notched display rods affixed to the wall into which levered struts can be inserted to support shelves. In many cases, the shelves are permanently bolted, nailed, or glued to the wall. In other cases, large pegboards are attached to the wall to be used with movable posts and hooks, particularly for home use.
[0005] In the past, these display racks have suffered from a number of disadvantages. For example, past displays are not designed to have a background art attached, and for those displays that do have background art attached, it is disrupted or destroyed with holes, grooves, slots, etc. As a result, the type of background art is limited. Additionally, past displays have often been manufactured having a fixed size and arrangement for displaying the products. These past displays have also been limited in the location, arrangement, and ease of re-arrangement of the advertising and signs that accompany the display, which help sell the products displayed thereon. The individual shelves on past display racks have also often been difficult to adjust without removing the surrounding shelves. As inventory is reduced, or exhausted, and products are individually sold and removed from the display systems, the display begins to appear incomplete and unattended.
[0006] Some display racks are expensive to manufacture, time consuming to set up, and take up large amounts of storage space when they are not in use. Particularly concerning is the damage caused to the underlying structure, such as a wall, when a display rack is installed or removed. The underlying structure is often left with large screw holes, scratched or damaged paint, and occasional structural damage. Additionally, current systems are too permanent, and they generally prevent flexibility in the positioning of the display systems. Finally, current display systems often require installers with special experience and equipment to construct and place the display system.
[0007] Accordingly, several objects and advantages of the present invention are:
to provide a display system that may position many types of products, of various sizes, in any orientation and at any angle; to provide a quick and convenient method of attaching a display system to a display surface; to provide a display system that is readily movable at will, that does not alter or deface the supporting surface; to provide a display system that may be used in the retail environment, trade shows, kitchen, closet, garage, anywhere; to provide a display system that may use a magnetically adherent material, which may be reversed for use with seasonal sales or promotions; to provide a display system that can be set up, moved, and removed quickly without technical expertise; to provide a display system that may display products from any location, including walls and ceilings; and to provide a display system utilizing a magnetically adherent material decorated with graphics, including vinyl, paint, stickers, etching, etc.
SUMMARY OF THE INVENTION
[0015] The present invention has been developed in response to the present state of the art, and in particular, in response to the problems and needs in the art that have not yet been fully solved by currently available display racks. Accordingly, the present invention has been developed to provide a process, apparatus, and system for a positionable magnetic display support that overcomes many or all of the above-discussed shortcomings in the art.
[0016] Specifically, the present invention provides a positionable magnetic display support. The magnetic display support includes at least one magnetic base and a display mount protruding from the magnetic base. The magnetic base is configured to removably attach to a magnetically adherent surface. The display mount is configured to support a variety of items, such as tools, clothing, toys, etc.
[0017] In one embodiment, the positionable magnetic display support includes two magnetic bases connected via a display rod. The magnetic base positions the display rod perpendicular to a ferrous wall to support a shoe.
[0018] In one embodiment, the positionable magnetic display support includes stabilizing members for holding an object into a position in conjunction with the display mount.
[0019] Reference throughout this specification to features, advantages, or similar language does not imply that all of the features and advantages that may be realized with the present invention should be or are in any single embodiment of the invention. Rather, language referring to the features and advantages is understood to mean that a specific feature, advantage, or characteristic described in connection with an embodiment is included in at least one embodiment of the present invention. Thus, discussion of the features and advantages, and similar language, throughout this specification may, but do not necessarily, refer to the same embodiment.
[0020] Furthermore, the described features, advantages, and characteristics of the invention may be combined in any suitable manner in one or more embodiments. One skilled in the relevant art will recognize that the invention can be practiced without one or more of the specific features or advantages of a particular embodiment. In other instances, additional features and advantages may be recognized in certain embodiments that may not be present in all embodiments of the invention.
[0021] These features and advantages of the present invention, as well as other features and advantages not listed, will become more fully apparent from the following description and appended claims, or may be learned by the practice of the invention as set forth hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] In order that the advantages of the invention will be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments that are illustrated in the appended drawings. Understanding that these drawings depict only typical embodiments of the invention and are not therefore to be considered to be limiting of its scope, the invention will be described and explained with additional specificity and detail through the use of the accompanying drawings, in which:
[0023] FIG. 1 illustrates a display support according to one embodiment of the present invention;
[0024] FIG. 2 illustrates a close-up view of a display support supporting a shoe according to one embodiment of the present invention;
[0025] FIG. 3 illustrates a side view of a display support attached to a wall according to one embodiment of the present invention;
[0026] FIG. 4 illustrates various display supports attached to a wall and supporting articles of clothing according to one embodiment of the present invention;
[0027] FIG. 5 illustrates a display support attached to a wall and having a plurality of display mounts according to one embodiment of the present invention; and
[0028] FIG. 6 illustrates a goggle display support according to one embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0029] For the purposes of promoting an understanding of the principles of the invention, reference will now be made to the exemplary embodiments illustrated in the drawings, and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended. Any alterations and further modifications of the inventive features illustrated herein, and any additional applications of the principles of the invention as illustrated herein, which would occur to one skilled in the relevant art and having possession of this disclosure, are to be considered within the scope of the invention.
[0030] Reference throughout this specification to “one embodiment,” “an embodiment,” or similar language means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment,” “in an embodiment,” and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment.
[0031] FIG. 1 illustrates a display support 10 according to one embodiment of the present invention. The display support 10 comprises a magnetic base 12 , to which a display mount, or display module, 14 is attached. In this embodiment, the magnetic base 12 comprises two magnets and the display mount 14 is a rod. The magnetic base 12 is configured to attach to a surface 16 with magnetically adherent properties to position the display mount 14 perpendicular to the surface 16 .
[0032] The surface 16 may comprise any type of magnetically adherent material. Additionally, the surface 16 may be covered with any type of decorative liner. For example, the surface 16 may be covered with a vinyl liner having a preferred drawing, picture, design, advertisement, etc. In other embodiments, the surface 16 may be covered with paint, stickers, etched with particular designs, etc.
[0033] The display mount 14 may be comprised of any material. In one embodiment, the display mount 14 comprises a pliable material so that the display mount 14 may be bent and manipulated into any configuration. The bendable feature of the display mount 14 provides adaptability in the display support 10 for displaying a variety of products. Specifically, the display mount 14 may be manipulated to display a much greater variety of products ranging in different sizes, shapes, and materials, such as, but not limited to clothes, tools, toys, books, or any type of product meant to be displayed or stored.
[0034] FIG. 2 illustrates a display support 10 attached to a surface 16 and supporting a shoe 26 according to one embodiment of the present invention. In this embodiment, the display support 10 comprises the magnetic base 12 attached to the surface 16 , the display mount 14 , and stabilizing members 18 . The stabilizing members 18 each comprise a magnetic base 20 attached to a stabilizing display rod, or stabilizing display member 22 . The stabilizing members 18 may be positioned at any location on the surface 16 to provide support to the display support 10 or to stabilize the display item 24 positioned on the display support 10 . The shoe 26 rests on the display mount 14 and the stabilizing members 18 removably hold the shoe 26 in any position against the display mount 14 . The stabilizing display rod 22 may be curved, straight, or bendable like the display mount 14 described in FIG. 1 . The stabilizing display rod 22 may be made of any type of material.
[0035] FIG. 3 illustrates a side view of a display support 10 attached to a surface 16 according to one embodiment of the present invention. In this embodiment, the display support system 10 comprises a single display rod 32 extending from the magnetic base 12 . The magnetic base 12 attaches to the surface 16 , which is attached to a supporting surface 30 . The surface 16 may be glued, screwed, clamped, or secured by any means to the supporting surface 30 .
[0036] The surface 16 may be any type of magnetically adherent material and the supporting surface 30 may be drywall, or another type of material. In one embodiment, the surface 16 may be integrated into the supporting surface 30 . For example, the supporting surface 30 may comprise a multiplicity of magnetically adherent materials, such as small metal pellets (not shown). The magnetically adherent materials may be pressed, glued, sprayed, etc. onto the surface 16 or supporting surface 30 .
[0037] Additionally, in one embodiment, display mount supports 31 may be used to provide additional support to the magnetic base 12 or to prevent the display item 24 (See FIG. 2 ) from sagging or falling. In one embodiment, the display mount support 31 comprises a slide 33 moveably connected to the display rod 32 and a support rod 35 attached to the slide 33 . A stopper 37 may be attached to the support rod 35 to prevent slippage. The stopper 37 may be any material such as rubber or an additional magnet.
[0038] In another embodiment, the slide 33 is open on a top edge so that the display mount support 31 may be easily placed below the display rod 32 at any time without removing a product.
[0039] FIG. 4 illustrates various display supports 10 attached to the surface 16 and supporting articles of clothing 34 according to one embodiment of the present invention. In this embodiment, the display support 10 comprises the magnetic base 12 and display mounts 14 . The display mount 14 may be configured to hold different articles of clothing 34 , such as a T-shirt or pants.
[0040] The display support 10 may further comprise magnetic couplers 36 for positioning the article of clothing 34 in different positions, rather than a hanging configuration. The magnetic couplers 36 are configured to hold, position, or attach the articles of clothing 34 against the surface 16 .
[0041] FIG. 5 illustrates a display support attached to a surface 16 and having a plurality of display mounts 14 according to one embodiment of the present invention. The magnetic base 12 supports a connecting display member 38 , which is configured to support a plurality of display mounts 14 . The connecting display member 38 may be constructed similar to the surface 16 , that is, the connecting display member 38 may be a magnetically adherent material. The connecting display member 38 may also be configured to connect a plurality of magnetic bases 12 for supporting a large or long display item 24 .
[0042] In one embodiment, magnetic bases 12 of the display mounts 14 couple to the connecting display member 38 . In another embodiment, the display mounts 14 connect directly to the connecting display member 38 with glue, screws, friction, etc.
[0043] Referring still to FIG. 5 , the display mounts 14 may be configured to hold any kind of accessory, such as jewelry, watches, rings, glasses, tools, kitchen utensils, etc. For illustration purposes, the display mounts 14 in this embodiment are configured to hold watches 36 and glasses 40 . For display mounts 14 configured to hold watches 41 , the display mount 14 comprises a watch band member 42 . A watch band of the watch 41 simply wraps around the watch band member 42 to secure the watch 41 to the display mount 14 . The watch band member 42 may be configured to hold a plurality of watches 41 . For display mounts 14 configured to hold glasses 40 , the display mount 14 comprises a nose piece rest 44 and a crossbar 46 . The glasses 40 rest over the nose piece rest 44 and the crossbar 46 of the display mount 14 .
[0044] FIG. 6 illustrates one embodiment of a goggles display support 10 for holding soft-sided goggles 48 according to one embodiment of the present invention. In this embodiment, the display support 10 utilizes the magnetic couplers 36 to hold the straps 52 of the goggles 48 against the surface 16 . The goggles 48 may be placed over an illustration, such as a skier's face, and held in place with the magnetic couplers 36 .
[0045] In another embodiment, the display support 10 utilizes the stabilizing member 18 (See FIG. 2 ) to hold the goggles 48 at a nose rest portion 50 . The stabilizing display rod 22 (See FIG. 2 ) of the stabilizing member 18 may be straight, bendable, curved, or tilted from the magnetic base 20 (See FIG. 2 ).
[0046] It is understood that the above-described arrangements are only illustrative of the application of the principles of the presently illustrated invention. The present invention may, however, be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
[0047] For example, although the illustrative embodiment(s) have/has described the use of a display mount 14 attached to the magnetic base 12 , it is envisioned that the display mount 14 may be detachable from the magnetic base 12 so that the display mount 14 may be configured with a plurality of connecting ends (not shown) to connect to a plurality of magnetic base 12 . Additionally, it is envisioned that the display mounts 14 and the stabilizing display rods 22 may be configured into any shape. Specifically, there may be display mounts 14 and 22 for positioning shirts, pants, shoes, glasses, socks, jewelry, tools, etc.
[0048] In addition, although many illustrated embodiments show the use of one, two, or more magnetic base 12 for holding and positioning the display items 24 against a surface 16 , it is envisioned that any number of magnetic base 12 may be used for any one of the embodiments. For large objects, larger magnetic base 12 may be used.
[0049] Finally, although the illustrative embodiments show the use of a rod for a display mount 14 , it is envisioned that the display mount 14 may be any shape, such as round, square, rectangular, etc.
[0050] Thus, while the present invention has been fully described above with particularity and detail in connection with what is presently deemed to be the most practical and preferred embodiment(s) of the invention, it will be apparent to those of ordinary skill in the art that numerous modifications, including, but not limited to, variations in size, materials, shape, form, function and manner of operation, assembly and use may be made, without departing from the principles and concepts of the invention as set forth in the claims.
|
A display support for displaying an object having a magnetic base attached to a display module and removably attached to a surface with a magnetically adherent material. The display system may include more than one magnetic bases and the display module may connect each of the magnetic bases. The support module may be separable from the magnetic bases to allow for differently shaped display modules, different lengths of display modules, or for display modules with different display characteristics, such as hooks. Stabilizing members may be used to help stabilize the object on the display module enabling a person to display/hold items at any angle. The stabilizing members may also be used to support objects such as jewelry, glasses, watches, tools, kitchen utensils, etc. Magnetic couplers may be used to position the objects in particular positions against the surface.
| 0
|
FIELD OF THE INVENTION
This invention relates to craps game tables and more particularly to such craps game tables which have electronic and electrical event summary displays as well as individual bet placement layouts.
BACKGROUND OF THE INVENTION
The gaming industry, sanctioned by increasing numbers of states, has experienced dynamic growth. Casinos, spurred by growing competition, are investing heavily in theme buildings and more elaborate equipment to compete for game players.
In the industry there is a desire to enhance the attractiveness of the game tables to the game players. What is appreciated by the more experienced game player is more information upon which to base their betting decisions and hunches. Such information, comparable to a race horse's track history, makes the game more interesting to intelligent better informed patrons. From the casino's viewpoint, such historical event information allows for the possibility of heretobefore unavailable bet combinations; bet combinations which will challenge and entice game players with enormous long shot and pool payoffs which will be exceptionally profitable to the casino.
OBJECTS AND STATEMENT OF THE INVENTION
It is an object of this invention to disclose innovations to the craps game table which will stimulate the interest of veteran game players. It is an object of this invention to summarize historical event information. It is an object of this invention to disclose a new dimension to a craps game table by presenting the possibility of new bet combinations for the game player to consider. It is a further object of this invention to disclose an innovation to the craps game table which promotes interest among game players, offers exciting payoffs, and concurrently is exceptionally lucrative for casinos. It is an object of this invention to allow game players to wager on events sequentially occurring in two and more moves. It is yet a further object of this invention to disclose a format for a craps game table which provides individual bet placement areas for each game player to facilitate identification of their bets.
One aspect of this invention provides for a craps game table comprising: a dice rolling area; event registration means for registering a combination rolled; an electronic recent event display; and, a computer programmed to display and summarize the most recent events.
A preferred aspect of this invention provides for a craps game table as above wherein the table is configured with individual bet placement layouts each adapted to allow the placement of bets on two or more sequential bets.
Various other objects, advantages and features of novelty which characterize this invention, are pointed out with particularity in the claims annexed to, and form part of this disclosure. For a better understanding of the invention, its operating advantages, and the specific objects attained by its users, reference should be made to the accompanying drawings and description, in which preferred embodiments of the invention are illustrated.
FIGURES OF THE INVENTION
The invention will be better understood and objects other than those set forth will become apparent to those skilled in the art when consideration is given to the following detailed description thereof. Such description make reference to the annexed drawings wherein:
FIG. 1 is a plan view of a craps game table, having individual bet placement areas and an electronic event summary display.
FIG. 2 is across sectional view of the craps table shown in FIG. 1 taken along line 2--2.
FIG. 3 is an enlarged broken away view of the croupier display and event entry portion of the craps table shown in FIG. 1.
FIG. 4 is an enlarged view of a top portion of the croupier display shown in FIG. 3.
FIG. 5 is an enlarged view of a bottom portion of the croupier display shown in FIG. 3.
FIG. 6 is an enlarged view of an individual bet placement layout as shown on FIG. 1.
FIG. 7 is an enlarged view of an electronic event display as shown on FIG. 6.
FIG. 8 is an enlarged view of a come/don't come bet placement area shown in the bet placement layout in FIG. 6.
FIG. 9 is an enlarged view of a don't pass bet placement area shown in the bet placement layout in FIG. 6.
FIG. 10 is an enlarged view of a pass bet placement area shown in the bet placement layout in FIG. 6.
FIG. 11 is an enlarged view of an odd bet placement area shown in the bet placement layout in FIG. 6.
FIG. 12 is an enlarged view of an even bet placement area shown in the bet placement layout in FIG. 6.
FIG. 13 is an enlarged view of the combination rolled - event summary display shown on the interior sidewall of the craps table in FIGS. 1 and 2.
FIG. 14 is an enlarged view of the outcome total - event summary display shown on the interior sidewall of the craps table in FIGS. 1 and 2.
The following is a discussion and description of the preferred specific embodiments of this invention, such being made with reference to the drawings, wherein the same reference numerals are used to indicate the same or similar parts and/or structure. It should be noted that such discussion and description is not meant to unduly limit the scope of the invention.
DESCRIPTION OF THE INVENTION
Turning now to the drawings and more particularly to FIG. 1 we have a plan view of a craps game table 10, the subject of this invention. The craps game table 10 comprises a dice rolling area 11; event registration means (preferably a keyboard 19) for registering a combination rolled; an electronic recent event display 15,16,17,18; and, a computer(not shown) programmed to summarize and display the most recent events. A dice rolling area 10 forms the central part of the table 11. An upright wall 14, surrounding the dice rolling area 11, separates a peripheral portion of the table 10 therefrom. The peripheral portion of the table has individual bet placement layouts 8 on three sides therearound and a croupier's event summary 17, 18 and an event registration means therefor; preferably a condition event entry keyboard 19. A peripheral rail 13 extends around the most preferably oval shaped table 10.
FIG. 2 is a cross sectional view of the craps table 10 shown in FIG. 1 taken along line 2--2. FIG. 2 best shows how the dice rolling area 11 and the upright sidewalls 14 together form a pit for throwing dice (not shown). Four electronic recent event displays 15,16,17,18 are positioned on the upright wall 14 at four locations around the table so that they may be viewed from the individual bet placement areas 8.
FIG. 3 is an enlarged broken away view of the croupier display 17,18 and event entry portion 19 of the craps table 10. The event entry portion 19 comprises a keyboard 19 having a separate key for each possible dice combination which may be rolled. The keyboard 10 also includes a delete key to delete a combination entered in error. The keyboard 10 may be replaced by a computer aided scanning device for reading the top face of the dice after each roll and thereby, automatically identify and enter each dice combination defining an event.
FIG. 4 is an enlarged view of a top portion 17 of the croupier display shown in FIG. 3. A similar type of display 17 is used on the interior sidewall 14 of the craps table 10 as shown in FIGS. 1 and 2. Top portion 17 comprises a row of nine--two digit displays, 17a through 17i each two digit display shows the total numerical value of a recent event. The 2 digit displays are chronologically arranged so that the last event is always displayed on the left display 17a and the ninth last event is displayed on the right display 17i. Intervening events are chronologically ordered therebetween. A lower portion of the display 17 comprises a digital display 17x recording the roll time of the last event.
FIG. 5 is an enlarged view of a bottom portion 18 of the croupier display shown in FIG. 3. The top portion thereof comprises a row of nine--two digit event combination displays 18a through 18i, each two digit display shows the combination, e.g. 4+6 rolled on a recent event. These events are chronologically ordered so that the last combination appears on the left display 18a and the earliest appears on the most right display 18a. The lower section portion of the display 18 comprises a row of nine indicators. Each indicator 18j through 18r shows whether the come-out point (first roll of a turn) or craps was the outcome on one of the last nine events. As above these indicators 18j through 18r are chronologically ordered so that the last event appears on the left display 18a and the earliest appears on the most right indicator 18i. Between the top row of nine two displays 18a through 18i and the bottom row of nine indicators 18j through 18r there are eighteen identical digital time displays such as 18x. Each of these time displays indicates the time at which the adjacent event combination displays 18a through 18i or indicators 18j through 18r occurred.
FIG. 6 is an enlarged view of an individual bet placement layout 8 shown on FIG. 1. The individual bet placement layout 8 comprises an electronic event display 22 (best seen enlarged on therefor FIG. 7 and a plurality of pressure sensitive bet placement areas 23, 24, 25, 26, and 27. Areas 23 through 27 include a come/don't come bet placement area 23 (best seen enlarged on FIG. 8); a don't pass bet placement area 24 (best seen enlarged on FIG. 9); a pass bet placement area 25 (best seen enlarged on FIG. 10); an odd bet placement area 26 (best seen enlarged on FIG. 11); and, an even bet placement area 27 (best seen enlarged on FIG. 12). A flag lamp 20 is positioned beside each individual bet placement area to alert the croupier when a bet is placed on one of the pressure sensitive bet placement areas 23, 24, 25, 26, or 27. Each of the bet placement areas 24, 25, 26, or 27 are electrically connected to a digital clock 28 (See FIG. 7) which will indicate the time at which the bet is placed on the bet placement area. A digital payout ratio display 21 is programmed to display the payoff, of an outcome based on events sequentially occurring over two or more moves, of the last touched bet placement area 23, 24, 25, 26, or 27.
FIG. 7 is an enlarged view of the electronic event display 22 shown on FIG. 6. This display 22 summaries the total number of times each two dice combination has been rolled after a time which appears on digital display 30.
FIG. 8 is an enlarged view of the come/don't come bet placement area 23 shown in the bet placement layout in FIG. 6. Flag lamp 20 shown thereon alerts the croupier when a bet is placed on the pressure sensitive bet placement layout 23. The bet placement layout 23 is marked to allow game players to wager on events sequentially occurring in two or more moves.
FIG. 9 is an enlarged view of the don't pass bet placement area 24 shown in the bet placement layout in FIG. 6. When a bet is placed on the pressure sensitive bet placement area 24 flag lamp 20 is turned on and clock 35 records the time at which the bet is placed. In the configuration shown the game player may bet on the outcome of up to nine sequential moves.
FIG. 10 is an enlarged view of the pass bet placement area 25 shown in the bet placement layout in FIG. 6. When a bet is placed on the pressure sensitive bet placement area 25 flag lamp 20 is turned on and clock 35 records the time at which the bet is placed. In the configuration shown the game player may bet on the outcome of up to nine sequential moves.
FIG. 11 is an enlarged view of the odd bet placement area 26 shown in the bet placement layout in FIG. 6.
FIG. 12 is an enlarged view of the even bet placement area 27 shown in the bet placement layout in FIG. 6.
FIG. 13 is an enlarged view of the combination rolled - event summary display shown on the interior sidewall 14 of the craps table 10 in FIGS. 1 and 2. Twenty-one three digit displays, one of which is designated 15a, record the number of times each dice combination has been rolled after a recorded time shown on clock 15b. Number of rolls indicator 15c records the number of rolls which have occurred after the recorded time on clock 15b. The number of odd rolls after the recorded time on the clock 15b is shown on display 15x. The number of even rolls after the recorded time on the clock 15b is shown on display 15y.
FIG. 14 is an enlarged view of the outcome total - event summary display 16 shown on the interior sidewall 14 of the craps table 10 in FIGS. 1 and 2. Eleven three digit displays, one of which is designated 16a record the number of times each two dice total has been rolled after a recorded time shown on clock 15b. Number of rolls indicator 16b records the number of rolls which have occurred after the recorded time on clock 15b. The number of field rolls after the recorded time on the clock 15b is shown on display 16c. The number of non-field rolls after the recorded time on the clock 15b is shown on display 16d. A field roll is generally one of the statistically less frequently rolled two dice totals such as 2, 3, 11, or 12. Some casinos define a field roll to include other less frequently occurring totals, in addition to the totals mentioned above.
In the course of play, the craps-type gaming device is used as follows. Referring first to the shared information on displays 15 and 16, as shown in FIGS. 13 and 14, the host of the gaming device sets the clock 15b. This is entirely an arbitrary time which may coincide with any event such as a croupier start of shift. That clock is suitable for recording time for a period of several or more hours. Commencing with the first roll of dice after the clock is initiated, the croupier then enters the dice-roll related information through the keyboard 19 or from similar manual or automatic means for sensing the numeric value of each die on each roll of the dice. That information is immediately recorded in the computer and is then displayed on displays 15 and 16. For example, if the first roll of the dice showed the numerical values 6 and 4, the croupier would press the 6+4 key on the keyboard and this information would be immediately displayed in the third display window (6+4) of the top row of display 15 in a color, highlighted by the croupier to differentiate it as the point and remaining highlighted until the point is made or craps is thrown, and different from the color used by displaying past recorded rolls. Since 6+4 is an even number, a one (1), indicating a single occurrence, would be displayed on the three digit Even display 15y. Of course, if the value were odd, the numerical value of Odd display 15x would be incremented. Simultaneously, the Number of Rolls display 15c would also be incremented and being correlated with the clock, would show the numerical value one (1) indicating that since play began, as recorded in clock 15b, there has been a single roll.
Simultaneously, since 6+4 equal 10, one of the three digit displays 16a would be incremented, namely, the display that indicates the number of occurrences of the numeral "10". The Number of Rolls display 16b would also be incremented. Assuming that the host has decided to offer betting on "field", the host would establish the values for Field such as the statistically less frequently rolled two dice total, 2, 3, 11 or 12. Of course, the casino may define a field roll to include other less frequently occurring totals including, for example, 4 and 10. Depending on how the host defines "field", and assuming that Field rolls comprise the above mentioned 2, 3, 11 or 12 values, then the roll in the example given above, namely 10, would be a "non-field" roll and would be recorded and displayed in Non-Field display 16d. Otherwise, it would be recorded and displayed in Field display 16c.
It will be understood that as the game continues, with each succeeding roll of the dice, and regardless of whether a player's turn has ended, that is, in a cumulative manner commencing at the time at which the clock was started, each roll of the dice will be recorded by the croupier and will increment the appropriate digital display 15a, 15c, 15x, 15y, 16a, 16b, 16c, and/or 16d.
Assume now that the game has been in progress so that the various displays indicate the cumulative occurrences of various dice-related information, and a player commences play at one of the stations 8. Referring now to FIGS. 6 through 12, play, as it relates to a single player, will be described. A player may place a bet by placing a chip on one of the pressure sensitive areas 23, 24, 25, 26 and/or 27. This placement records the time and type of the bet. Of course, area 23 is a common craps bet, namely, "Come"; a bet placed on Come wins if the first roll of a player's turn is 7 or 11 or if the player rolling the dice has made the Come Out point.
Referring to areas 24 and 25 of Station 8, it will be seen that a player may also make a "Don't Pass" or a "Pass" bet as in a standard craps game. But to create further complexity and therefore generate interest in players, areas 24 and 25 at each station also have in the right hand portion of the area (shown as an ellipse) pressure sensitive spots at that station for numerals 2 through 9. Rather than simply making a Don't Pass or Pass bet, the player may place a chip on, for example, the pressure sensitive spot with the numeral 3 on area 25. That represents a wager by the player that the player rolling the dice will pass three consecutive times. If that occurs, the player wins at appropriate odds; if not, the player loses. When the bet is placed on spot 3 of area 25, it trips an electronic switch that records the time and begins the running of a clock to indicate the time at which the bet was commenced which must precede any player's roll of the dice which is recorded by the croupier.
Continuing the description of the play, and using the same example as indicated above, and with attention drawn to FIGS. 4 and 5, dice-roll related information will be recorded and displayed on displays 17 and 18. Display 17 generally provides information regarding the last number rolled for each of the last 9 rolls. The most recent roll is shown in the left hand display 17a and the ninth last roll is displayed in display 17b. At the select ion of the host, this display may be reset at the beginning of each player's turn or may be cumulative since the initiation of clock 15b.
In display 18, as in display 15, the information generally provides dice-roll related information regarding the "Point" and whether or not that point has been "made" or craps has occurred prior to making the point. This is in accordance with standard craps rules.
By way of example, assuming the role of 6+4 has been completed and the croupier has electronically recorded that information through the keyboard 19. In display 17 the number then appearing in display 17a will immediately be transferred to the next right-adjacent display, and so on, until the number of the tenth previous roll is removed from display 17. Simultaneously, since this was the first roll of a player's turn, the value 10 constitutes the player's "Come Out Point" or simply, "Point" and this will be displayed in display 18a which is the left most display on display board 18. In the bottom row of displays on display board 18, display 18c will be blank until, on successive rolls of the player, the point 10 is either made or craps is thrown. Upon that occurrence, and of course the recording of that event by the croupier, display 18c will either display "Made" or "Craps". The timer in display board 17 indicates how current the displayed numbers have occurred. In other words, how long it has been since the last roll has occurred. In display board 18, one of the 18x time displays in the row closer to the top row of the displayed numbers will display the time at which the point was established. The time in the lower row corresponding to that same vertical column will show the time at which either that point was made or craps occurred.
As will now be understood, one of the important features of the craps-type gaming device of the present invention is the correlation between the occurrence of some dice-roll related information to a particular time. Thus, not only will a gambler have access to a history of various events, i.e., dice-roll related information, over some finite but extended period of time, information as to the occurrence of that particular event may also be obtainable, depending upon the particular event.
While the invention has been described with preferred specific embodiments thereof, it will be understood that this description is intended to illustrate and not to limit the scope of the invention. The optimal dimensional relationships for all parts of the invention are to include all variations in size, materials, shape, form, function, assembly, and operation, which are deemed readily apparent and obvious to one skilled in the art. All equivalent relationships to those illustrated in the drawings, and described in the specification, are intended to be encompassed in this invention. What is desired to be protected is defined by the following claims.
|
An electronically and physically improved craps game table designed to provoke and stimulate the interest of novice, occasional, and veteran craps game player is disclosed. The craps game table comprises: a dice rolling area; event registration means for registering a combination rolled; an electronic recent event display; and, a computer programmed to display historical and recent events. A preferred aspect of this invention provides for a craps game table as above wherein the computer is additionally programmed to summarize the most recent events, and wherein the computer is programmed to display the last nine events. The craps game table may additionally be marked to allow game players to wager on events sequentially occurring in two and more moves; and the computer may be programmed to display payoffs for those sequentially occurring events. The most preferred embodiment additionally provides for multiple individual bet placement layouts around the periphery of the table. The electronically improved craps game table provides for the possibility of heretobefore unavailable bet combinations; sequential bet possibilities which will attract game players with astronomical, ever changing and electronically posted payoffs; payoffs which will be exceptionally lucrative to the casinos.
| 0
|
This is a division of application Ser. No. 08/699,129, filed Aug. 16, 1996, now U.S. Pat. No. 5,743,070.
This invention relates to packaging machinery and more particularly to a packaging machine and method of packaging which are especially well suited for loading relatively bulky and liquid products sequentially into bags of a novel, side interconnected, chain of bags.
BACKGROUND OF THE INVENTION
U.S. Pat. No. 4,969,310 issued Nov. 13, 1990 to Hershey Lerner et al. under the title Packaging Machine and Method and assigned to the assignee of this patent (the SP Patent) discloses and claims a packaging machine which has enjoyed commercial success. One of the major advantages of the machine of the SP Patent resides in a novel conveyor belt mechanism for gripping upstanding lips of bags of a chain as they are transported along a path of travel and registered at a load station. The firmness with which the lips are gripped makes the machine highly suitable for packaging bulky products which are stuffed into the bags. While the machine of the SP Patent was an advance over the prior art, especially in terms of its lip gripping capability, even greater lip gripping capabilities, if achieved, would be useful in enabling packaging of additional products. Expressed another way, the bag gripping forces of the machine of the SP Patent were dependent on clamping pressure applied between pairs of belts. Thus, while the machine was a definite advance over the art, as to any given bag size, it has a finite maximum stuffing pressure it can withstand without slippage.
Since the bag gripping is dependent on the force with which belt pairs are clamped, the length of the path of travel through the load station is limited. Thus the length of a bag along the path of travel is limited, loading of a bag while it moves along the path of travel is not possible and the concurrent loading of two or more bags is not available.
With the machine of the SP Patent there is an intermittent section which includes the loading station and a continuous section which includes a sealing station. Since the section including the loading station is intermittent, obviously the through-put of the machine is inherently less than could be achieved with a continuously operating loading section.
The machine of the SP Patent had further advantages over the prior art, including an adjustable bag opening mechanism which was adapted to accept a wide range of bag sizes and adjustable to provide a range of bag openings. While an advance over the prior art, the bag openings were six sided so that, like most of the prior art, a rectangular bag opening was not achievable.
Although one prior machine provides rectangular openings, the dimensions of the rectangular openings, both longitudinally and transversely, are limited both by the construction of the chain of bags being filled and by guide rods used to transport the bags. Thus, if an operator wished to change from one opening size to another, another and different web of bags was required. Moreover, to the extent, that the packaging machine could be adjusted to vary the configuration of the rectangular opening, such available adjustment was extremely limited because it required substitution of a different set of guide rods. Further, there was excessive packaging material waste in the form of elongate tubes which slid along the guide rails.
While the machine of the SP Patent has been sold under the designation SP-100V for vertical orientation in which products can be gravity loaded into bags and the designation SP-100H for horizontal loading of stuffable products, neither machine was suitable for adjustment from horizontal to vertical and return, nor for orientation at selected angles of product insertion between the horizontal and the vertical.
A problem has been experienced with prior art sealers having pairs of opposed belts to transport bags through a seal station. The problem is that too frequently due to weight of the products there is slippage of bags relative to the belts and sometimes of the bag fronts relative to the backs resulting in poor seal quality. Alternatively or additionally it is too often necessary to provide a conveyor or other support for bags as they are transported through the sealer station.
SUMMARY OF THE INVENTION
With the machine of the present invention, the described problems of the prior art and others are overcome and an enhanced range of available packaging sizes is achieved. In its preferred form the machine has two, independently moveable carriages which are selectively rigidly interconnected. One of these carriages supports a novel and improved bagging section, while the other supports a closure mechanism. The disclosed closure mechanism is a novel and improved sealing section. Because the machine has two separable carriages other closure carriages supporting other closure mechanisms such as bag ties and staples can readily be used.
Each of the sections is rotatably mounted on its carriage, such that once coupled the two sections may be rotated together about a horizontal axis for product loading, by gravity and/or stuffing when in the vertical and by stuffing when in the horizontal. Advantageously the two sections may also be oriented in any one of a set of angular orientations between the horizontal and the vertical.
A major feature of the present machine is that the loading section opens the bags into rectangular configurations. Not only are the bag load openings rectangular configurations, but the transverse and longitudinal dimensions of such openings for any given bag size are relatively and readily adjustable over a wide range.
The machine may be operated in either a continuous or an intermittent mode at the operator's selection. Both sections are operated in the same mode. That is if the loading section is continuous, so too is the sealing section, while both operate in the intermittent mode at the same times.
One of the outstanding advantages of the invention resides in the utilization of a novel and improved mechanism for gripping upstanding lips of bags as they are transported through the load section. This mechanism utilizes conveyor belts of a type more fully described in a concurrently filed application of Hershey Lerner entitled Plastic Transport System, attorney docket 14-160 (the Belt Patent). The Belt Patent is incorporated in its entirety by reference. Gripping is achieved by coaction of the bags upstanding lips and unique belts such that belt clamping mechanisms are neither required or relied on. To this end a pair of main transport belts are provided and positioned on opposite sides of a path of web travel. In the preferred and disclosed embodiment, each main belt has an upstanding lip contacting surface with a centrally located, transversely speaking, lip receiving recess preferably of arcuate cross-sectional configuration. A pair of lip transport belts of circular cross-section are respectively cammed into the main transport belt recesses to force bag lips into the recesses and fix the lips with a holding power far in excess of that achieved with the prior art.
Since the gripping of bag lips for support is accomplished through coaction of the bag lips and the conveyor belts, there is essentially no limit to the length of the loading station. Rather multiple numbers of open bags can be concurrently conveyed through the loading station. With a machine operating on a continuous basis and a synchronized product supply conveyor adjacent the load station, one is able to concurrently transfer a set of products into a like numbered set of bags with the transfer progressing concurrently as the bags and the conveyed products advance through the load station.
Another advantage of an elongated load station is that one may position a series of vibrator feeders along the station. As an example, a first vibratory feeder could deposit a desired number of bolts in a bag at a first location, a second feeder a like number of washers at a second location downstream from the first, and a third feeder a like number of nuts at a third location still further downstream; thus, eliminating the need for a feed conveyor.
With this arrangement extremely high rates of packaging can be achieved. For example, it is possible to load and seal 130 ten inch bags per minute. Rates achieved with the present machine are rates in excess of those that can be achieved with virtually all, if not all, prior art machines including so called "form and fill" machines.
Another feature of the invention resides in a novel and improved mechanism for breaking frangible interconnections between adjacent sides of successive bags. Assuming the machine to be in its gravity fed horizontal mode, this mechanism comprises a belt which is trained about spaced pulleys which are rotatable about respective horizontal axes. The belt has projecting pins. The belt pulleys are rotated to move the belt in synchronism with positioning of a chain of bags being fed through the load section to cause one of the pins to break the frangible bag interconnections each time a set of such interconnections is longitudinally aligned with the belt.
Moving in the downstream direction of the machine to consider other advances, another feature of the invention is in a novel and improved mechanism for adjusting the width of the load station by varying the spacing between the pairs of main and lip transport belts. This adjustment, which is infinite between maximum and minimum limits, coupled with the novel and improved bag web, provides a wide range of available transverse and longitudinal dimensions of rectangular bag openings for any given chain of like sized interconnected bags.
As loaded bags exit the load station it is desirable to advance the lead side edge and retard the trailing side edge of each bag of a chain to bring inside surfaces of the top portions of each bag back into surface to surface touching orientation for sealing. To this end a novel planetary mechanism is provided. This mechanism is driven by the moving bags themselves to effect the stretching action and reestablish inside surface to surface relationship. For larger bags oppositely directed jets of air are employed which are effective to reestablish the surface to surface orientation.
At an exit from the bagging section of the machine, the main transport belts overlie exit belts which in turn overlie the closure section transport belts, such that the closure section picks up the now longitudinally stretched top surfaces of each loaded bag. As the bags are transferred to the closure section belts, a rotary knife cuts the bags near their tops such that the lip portions that have been carried by the main transport belts are cut off and become recyclable scrap. The elevation of the cutter relative to the heat sealer is adjustable so that the extent to which upper portions of the bags are cut away provides loaded bags sized to be neat, and if desired tight, finished packages.
In order to prevent excessive heating of bags passing through the sealing section and the sealing section belts, the heat source for effecting the seals is shifted away from loaded bags and the belts when the machine is stopped and moved to a location adjacent the bags when the bags are moving. Thus, a mechanism is provided for shifting the heat sealer from a seal forming position to a storage position and return in synchronism with cycling of the machine when in the intermittent mode.
As the loaded bags pass through the seal section, a series of longitudinally aligned, juxtaposed and individually biased, pressure members act against one of the seal section conveyor belts. These pressure members bias the one belt against the bags and thence against the other belt to in turn bias the other belt against a backup element to maintain pressure on the bag tops as they are transported through the seal section. Advantageously, unlike a prior machine of similar construction, individual coil springs are used to bias the pressure members.
The belts used in the seal section are novel and improved special belts which are effective substantially to prevent any product weight induced slippage of the bags relative to the belts. The novel belts are also effective to resist longitudinal movement of the face and back of each bag relative to one another and to the belts. One provision to prevent this relative slippage is providing belts which have corrugated belt engaging surfaces with the corrugations of one belt interlocking with the corrugation of the other to produce a serpentine grip of the face and back of each bag. Further, the preferred belts are metal reinforced polyurethane to provide enhanced resistance to belt stretching. A glue and grit mixture may be applied to the surfaces of the sealer belts, further to inhibit bag slippage. A urethane coating is applied over the glue and grit to complete the improvements provided for the prevention of bag slippage.
The belts of the sealer section are driven by a stepper motor through a positive drive, so that the sealer stepper motor in synchronism with bagger stepper motor maintain belt and bag feed rates of travel that are consistent throughout the length of path of bag travel from supply through to finished package.
Lips of the bags which project from the seal section conveyor belts are heated by a contiguous heat tube sealer having an elongate opening adjacent the path of bag lip travel. Heated air and radiation emanating from this sealer effect heat seals of the upstanding lips to complete a series of packages.
Because the machine sections, unlike the machine of the SP Patent, are either both continuous or both intermittent during machine operation, successive bags passing through the closure section are juxtaposed rather than spaced. This juxtaposition provides improved sealing efficiency and sealer belt life.
A web embodying the present invention is an elongate, flattened, thermoplastic tube having face and back sides which delineate the faces and backs of a set of side by side frangibly interconnected bags. The tube includes an elongate top section which is slit to form lips to be laid over and then fixed in the main transport belts. The top section is interconnected to the bags by face and back, longitudinally endless, lines of weakness which are separated from each side edge toward the center of each bag to the extent necessary to achieve the desired rectangular openings. Thus, the present web is far simpler and less costly than the web of the prior system that provided rectangular bag openings.
The invention also encompasses a process of packaging which includes gripping the upstanding front and back lip portions between main and lip transport belts. The belts are then spread as they pass through a load station pulling bag openings into rectangular configurations as portions of bag tops are separated from the upper lip section. After bag loading, top portions of the bag inner surfaces are returned to abutting engagement, a portion of the lip section is trimmed from the bags, and the bags are sealed or otherwise closed to complete packages.
Accordingly, the objects of this invention are to provide novel and improved packaging machine, packaging materials and methods of forming packages.
IN THE DRAWINGS
FIG. 1 is a top plan view of the machine of the present invention;
FIG. 2 is a fragmentary top plan view of the bagger section of the machine of FIG. 1 and on an enlarged scale with respect to FIG. 1;
FIG. 3 is a foreshortened elevational view of the bagger section as seen from the plane indicated by the line 3--3 of FIG. 1;
FIG. 4 is a perspective view of the novel and improved bag web of the present invention showing sections of the transport belts transporting the web through the load station and a novel mechanism for providing spacing of the sides of loaded bags particularly of a small size;
FIG. 5 is a perspective view of a portion of the bag flattening mechanism shown in FIG. 4 and on an enlarged scale;
FIG. 6 is a fragmentary perspective view on the scale of FIG. 5 showing an alternate arrangement to the mechanism of FIG. 5 for flattening bags;
FIGS. 7 and 8 are enlarged sectional views from the planes respectively indicated by the lines 7--7 and 8--8 of FIG. 4 show the main and lip transport belts together with a fragmentary top portion of the bag as bag lips are folded over the main transport belts and then trapped in the grooves of the main belts;
FIG. 9 is a sectional view of the bag flattening or stretching mechanism of FIGS. 4 and 5 as seen from the plane indicated by the line 9--9 of FIG. 2;
FIG. 10 is an enlarged sectional view of the mechanism of FIG. 9 as seen from the plane indicated by the line 10--10 of FIG. 2;
FIG. 11 is an enlarged, fragmentary, sectional view of the transport belt spacing adjustment mechanism as seen from the plane indicated by the lines 11--11 of FIG. 2;
FIG. 12 is an elevational view of a portion of the machine as seen from the plane indicated by the line 12--12 of FIG. 1 showing a bag support conveyor underneath the loading and seal sections;
FIG. 13 is an elevational view of the seal section on an enlarged scale with respect to FIG. 12;
FIG. 14 is an elevational view of the angular orientation maintenance mechanism on an enlarged scale with respect to other of the drawings and as seen from the plane indicated by the line 14--14 of FIG. 12;
FIG. 15 is an enlarged sectional view of the sealer positioning mechanism and a bag support conveyor as seen from the plane indicated by the lines 15--15 of FIG. 13;
FIG. 16 is a sectional view of a web guide as seen from the plane indicated by the line 16--16 of FIG. 3;
FIG. 17 is a sectional view of the lip plow as seen from the plane indicated by the line 17--17 of FIG. 3;
FIG. 18 is an enlarged plan view of a force application element and a fragmentary plan view of the sealer belts;
FIG. 19 is an enlarged fragmentary plan view of a transfer location between the bagger and the closure sections, including a knife for trimming the tops of loaded bags prior to closure;
FIG. 20 is a further enlarged sectional view of the structure of FIG. 19 as seen from the plane indicated by the line 20--20 of FIG. 19;
FIG. 21 is a still further enlarged view of the knife and its height adjustment mechanism as seen from the plane indicated by the line 21--21 of FIG. 20;
FIG. 22 is a plan view of an alternate and preferred sealer for the closure section; and,
FIG. 23 is an elevational view of the sealer of FIG. 22.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
I. The Overall Machine
Referring to FIGS. 1 and 4 a web 15 of side connected bags is provided. The web 15 is fed from a supply shown schematically at 16 to a bagger section 17. The bagger section 17 is separably connected to a sealer section 19. The bagger and sealer sections respectively include wheeled support carriages 20, 21. The support carriages 20, 21 respectively include support frames for supporting bagging and sealing mechanisms.
In the drawings the bagging and sealing mechanisms are shown in their vertical orientations for gravity loading. The machine will be described in such orientation it being recognized that, as described more fully in section IV, the mechanisms may be positioned in a horizontal orientation and at other angular orientations.
II. The Web 15
The web 15 is an elongated flattened plastic tube, typically formed of polyethylene. The tube includes a top section 23 for feeding along a mandrel 24, FIGS. 4 and 16. The top section 23 is connected to the tops of a chain of side connected bags 25 by front and back lines of weakness in the form of perforations 27, 28. Frangible connections 30 connect, adjacent bag side edges, FIGS. 3 and 4. Each bag 25 includes a face 31 and a back 32 interconnected at a bottom 33 by a selected one of a fold or a seal. Side seals adjacent the interconnections 30 delineate the sides of the bags 25. The bag faces and backs 31, 32 are respectively connected to the top section 23 by the lines of weakness 27, 28, such that the top section 23 when the web is flattened itself is essentially a tube.
III. The Bagger Section 17
A. A Bag Feed and Preparation Portion 35
The web 15 is fed from the supply 16 into a bag feed and preparation portion 35 of the bagger section 17. The feed is over the mandrel 24 and past a slitter 36, FIG. 4. The slitter 36 separates the top section 23 into opposed face and back lips 38, 39. The feed through the bag feed and preparation portion 35 is caused by a pair of endless, oppositely rotating, main transport belts 40, 41 supported by oppositely rotating pulley sets 42, 43. The main belts 40, 41 are driven by a stepper motor 44, FIG. 3 through toothed pulleys 42T, 43T of the sets 42, 43. Other of the pulleys 42S, 43S are spring biased by springs S, FIG. 2, to tension the belts.
A plow 45 is provided and shown in FIGS. 3, 4 and 17. For clarity of illustration the slitter and the plow have been omitted from FIG. 1. The plow is positioned a short distance upstream from a roller cam 46. As the lips are drawn along by the main transport belts 41, 42, the lips 38, 39 are respectively folded over the top bag engaging surfaces 41S, 42S, of the main transport belts under the action of the plow 45 as depicted in FIG. 7.
Once the lips are folded over the tops of the main transport belts 41, 42, the roller cam 46 presses endless, lip transport and clamp belts 48, 49 into complemental grooves 51, 52 in the main transport belts 41, 42 respectively. Thus, the grooves 51, 52 function as bag clamping surfaces that are complemental with the clamping belts 48, 49. More specifically, the clamp belts are circular in cross section, while the grooves 51, 52 are segments of circles, slightly more than 180° in extent. The camming of the clamp belts into the grooves traps the lips 38, 39 between the clamp belts and the grooves. The lip clamping firmly secures the lips between the coacting belt pairs such that the lips, due to their coaction with the belts, are capable of resisting substantial stuffing forces as products are forced into the bags at a load station 60. Sections of the clamp belts which are not in the grooves 51, 52 are trained around a set of lip transport belt pulleys 50.
A bag side separator mechanism 53 is provided at a bag connection breaking station. The separator mechanism 53 includes an endless belt 54 which is trained around a pair of spaced pulleys 55 to provide spans which, as shown in FIGS. 3 and 4, are vertical. The pulleys 55 are driven by a motor 57, FIG. 2. As the belt is driven breaking pins 58 projecting from the belt 54 pass between adjacent sides of bags to break the frangible interconnections 30. Thus, as the bags depart the bag feed and preparation portion 35, they are separated from one another but remain connected to the lips 38, 39.
B. The Load Station 60
The load station 60 includes a pair of parallel belt spreaders 61, 62. The belt spreaders are mirror images of one another. As is best seen in FIG. 11, the belt spreaders respectively include channels 63, 64. The channels 63, 64 respectively guide the main transport belts 40,41, on either side of the load station 60. When the transport belts 40,41, are in the channels 63, 64, as is clearly seen in FIGS. 4 and 11, the bags 25 are stretched between the belts in a rectangular top opening configuration.
A schematic showing of a supply funnel 66 is included in FIG. 4. As suggested by that figure, the products to be packaged are deposited through the rectangular bag openings each time a bag is registered with the supply funnel at the load station.
A space adjusting mechanism is provided. This mechanism includes a spaced pair of adjustment screws 68, 69, FIG. 2. The adjustment screw 68, 69 are respectively centrally journaled by bearings 70, 71. The screws have oppositely threaded sections on either side of their bearings 70, 71 which threadably engage the belt spreaders 61, 62. Rotation of a crank 72 causes rotation of the adjustment screw 69. The screw 69 is connected to the screw 70 via belts or chains 73, which function to transmit rotation forces so that when the crank 72 is operated the screws 68, 69 are moved equally to drive the spreaders equally into an adjusted spacial, but still parallel, relationship.
As the spreaders are movably adjusted toward and away from one another, the spring biased pulleys 42S, 43S maintain tension on the main transport belts 40, 41 while permitting relative movement of spans of the belts passing through the spreader channels 63, 64. Similarly, spring biased lip transport belt pulleys 50S maintain tension on the clamp belts 48, 49. The spring biased pulleys of both sets are the pulleys to the right as seen in FIG. 2, i.e. the entrance end pulleys in the bag feed and preparation portion 35.
The main transport pulley sets 42, 43 include two idler pulleys 75, 76 downstream from the load station 60. The idler pulleys 75, 76 are relatively closely spaced to return the main transport belts 40, 41 into substantially juxtaposed relationship following exit from the load station 60.
C. Bag Stretching
As loaded bags exit the load station, it is desirable to return upper portions of the bag faces and backs into juxtaposition. To facilitate this return with smaller bags a novel and improved planetary stretcher 90 is provided. This planetary bag stretcher is best understood by reference to FIGS. 5, 9 and 10. The stretcher 90 includes a support shaft 92 mounted on frame members 94 of the bagger section, FIG. 10.
The planetary stretcher includes a bag trailing edge engaging element 95. The element 95 includes six bag engaging fingers 96. As is best seen in FIGS. 4 and 5, one of those fingers 96 is shown in a lead one of the bags 25 while the next finger is being moved into the next bag in line as the next bag departs the load station 60. As the bags move from right to left as viewed in FIG. 5, an internal ring gear portion 100 drives a planet gear 102. The planet gear orbits a fixed sun pinion 104. The planet gear is journaled on and carried by a lead edge engaging element 105 journaled on the shaft 92. The lead edge engaging element 105 has four fingers 106 which orbit at one and a half times the rate of the fingers 96. Rotation of the lead edge engaging element causes one of the fingers 106 to enter the next bag as it exits the load station and to engage a leading edge 108 of the bag, thereby stretching the bag until top portions of the bag face and back are brought into juxtaposition.
For larger bags this stretching of the now loaded bags as they exit the load station is accomplished with jets of air from nozzles 110, 112 which respectively blow against the lead and trailing edges of the bag, thus stretching the bags from their rectangular orientation into a face to back juxtaposed relationship as the transport belts are returned to juxtaposition.
D. A Transfer Location
After loaded bags have exited the load station 60 and the face and back of each bag have been brought into juxtaposition, the loaded bags are transferred to the closure section 19 at a transfer location 114. Exit conveyors 115, 116 underlie the main transport belts 40, 41 at an exit end of the bagger section 17. Loaded bags are transferred from the main transport belts to the exit conveyors. The exit conveyors in turn transfer the loaded bags to closure section conveyor belts 118, 119.
Referring to FIGS. 19-21, a rotary knife 120 is positioned a short distance downstream from the exit conveyors. The knife is rotatively mounted in an externally threaded support tube 121. The tube in turn is threadedly connected to a knife support frame section K. An adjustment lock 123 is slidably carried by the frame section K. When the lock 123 is in the position shown in solid lines in FIG. 21, it engages a selected one of a plurality of recesses R in the perimeter of the support tube 121 to fix the knife in an adjusted height position. When the lock 123 is slid to the phantom line position of FIG. 21, the tube 121 may be rotated to adjust the vertical location of the knife 120.
The knife 120 is driven by a motor 122 to sever the bag lip portions 38, 39, leaving only closure parts of the lip portions for closure, in the disclosed arrangement, by heat sealing. The trimmed plastic scrap 124, FIG. 12, from the severed lip portions is drawn from the machine with a conventional mechanism, not shown, and thereafter recycled.
IV. The Closure Section 19
As is best seen in FIG. 1, the novel and improved sealer includes a plurality of independently movable force application elements 125. One of the force elements is shown on an enlarged scale in FIG. 18. The force elements 125 slidably engage the outer surface of a bag engaging run 126 of the belt of the conveyor 119. Springs 128 bias the elements 125 to clamp the bag faces and backs together against a coacting run 130 of the conveyor belt 118. A backup 132 slidably engages the coacting run 130 to resist the spring biased force of the application elements 125.
A stepper motor 134, FIG. 1, is drivingly connected to the closure section conveyor belts 118, 119 to operate in synchronism with the stepper motor 44 of the bagger section, either intermittently or continuously.
As is best seen in FIGS. 13 and 15, a heater tube 135 is provided. A heat element 136, FIG. 15, is positioned within the tube to provide heat to fuse upstanding bag lips when the heater tube 135 is in the position shown in solid lines in FIG. 13. The heat transfer to the lips is effected by both radiation and convection through an elongate slot 135S in the bottom of the tube.
The heater tube 135 is connected to a pair of supports 137, 138. When the bags 25 are vertical the heater tube 135 is suspended by the supports 137, 138. The supports in turn are pivotally connected to and supported by a pair of cranks 140, 142. The cranks 140, 142 are pivotally supported by a section of the frame of the sealer carriage 21. The cranks 140, 142 are interconnected by a rod 144 which in turn is driven by an air cylinder 145. The air cylinder 145 is interposed between the carriage frame and the rod 144. Reciprocation of the air cylinder is effective to move the heat tube between its seal position shown in solid lines and a storage position shown in phantom, FIG. 13. When the conveyor belts 118, 119 are operating to transport bags through the closure section the sealer is down, while whenever the machine is stopped the sealer is shifted to its storage or phantom position of FIG. 13.
As is best seen in FIG. 18, the adjacent runs 126, 130 of the sealer conveyor belts 118, 119 have surfaces that are corrugated and interfitting. These interfittings corrugations provide both enhanced bag gripping and holding power and resistance to relative longitudinal movement of the runs as well as the faces and backs of the bag. The gripping and holding power of the belts is further enhanced by coating the belts with a glue and sand slurry and applying a polyurethane coating over the slurry to further enhance the frictional grip of the belts on bags being transported. The combined effects of the belt corrugations and coating substantially prevent slippage of the bags due to weight in the bags.
V. Section Interconnection and Adjustments
A. Section Interconnection
The bagger and closure sections 17,19 are physically interconnected when in use. In the disclosed arrangement this interconnection includes a pair of lock bars 150. The lock bars which are removably positioned in apertures 151,152 formed in bosses 154,155 respectively projecting from frames of the bagger and closure stations 17,19.
B. Angular Positioning
As has been indicated, the bagger and closure sections are adjustable to horizontal or vertical orientations as well as angular orientations between the horizontal and the vertical.
The bagger section 17 is rotatably supported on a pair of trunions one of which is shown at 157 in FIG. 3. As can best be seen in FIGS. 12 and 13, the sealer section 19 is rotatably supported on the carriage 21 by spaced trunions 170, 172. The trunions 157,170 & 172 are axially aligned. The end trunion 170, to the left as viewed in FIGS. 12 and 13, is associated with an angular position holder. The holder includes an apertured plate 174 secured to and forming part of the frame of the carriage 21, FIG. 14. The plate 174 includes a set of apertures 175 spaced at 15° intervals to provide incremental angular adjustments of 15° each between the horizontal and vertical orientations of the machine. Each of the apertures 175 may be selectively aligned with an aperture in a sealing section plate 176. A pin in the form of a bolt 178 projects through aligned apertures to fix the sealer section and the interconnected bagger section in a selected angular orientation.
VI. A Support Conveyor
While there normally is no need for bottom support of the bags 25 as they pass through the bagger section 17, nonetheless a conventional support conveyor 160 may be provided, see FIG. 3. More frequently a conveyor 162 will be provided under the closure section 19. In either event, suitable height adjustment and locking mechanisms 164 are provided to locate the conveyors 160,162 in appropriate position to support the weight of loaded bags being processed into packages.
VII. The Preferred Sealer
Referring to FIGS. 22 and 23, the preferred sealer for the closure mechanism is disclosed. The sealer includes an air manifold 180 for receiving air from a blower 182. In an experimental prototype a 300 cubic foot per minute variable pressure blower was used to determine optimized air flows and pressures.
The manifold 180 has three pairs of oppositely disposed outlets 184,185,186. Each outlet is connected to an associated one of six flexible tubes 188. The tubes in turn are connected to pairs of oppositely disposed, T-shaped sealer units 190,191,192 to respectively connect them to the outlets 184,185,186. The T-shaped sealer units respectively include tubular legs 190L,191L,192L extending vertically downward from their respective connections to the flexible tubes 188 to horizontal air outlet sections 190H,191H,192H. The outlet sections are closely spaced, axially aligned, cylindrical tubes which collectively define a pair of elongate heater mechanisms disposed on opposite sides of an imaginary vertical plane through the loaded bag path of travel.
Each horizontal outlet section includes an elongate slot for directing air flow originating with the blower 182 onto upstanding bag lips being sealed. Each of the sealer unit legs 191,192 houses an associated heater element of a type normally used in a toaster. Thus air flowing through the T-shaped units 191,192 is heated and the escaping hot air effects seals of the upstanding bag lips. Air flowing through the units 190 is not heated, but rather provides cooling air to accelerate solidification of the seals being formed.
The T-shaped sealer units 190,191,192 are respectively connected to the rod 144 for raising and lowering upon actuation of the air cylinder 145 in the same manner and for the same purpose as described in connection with the embodiment of FIGS. 12 and 13.
A further unique feature of the embodiment of FIGS. 22 and 23 is a vertical adjustment mechanism indicated generally at 194. The vertical adjustment 194 permits adjustment of the slope of the horizontal sections of the t-shaped units 190-192 such that the outlet from 191H is lower than that of 192H. This downward sloping of the heater mechanism in the direction of bag travel assures optimized location of the hot air being blown on the plastic. The location is optimized because as the plastic melts it sags lowering the optimum location for the direction of the hot air. Further the cooling air from the unit 190 is directed onto a now formed bead.
VIII. Operation
The carriages 20, 21 are independently wheeled to a desired location. The two are then physically interconnected by inserting the lock bars 150 into the apertures 151,152.
Assuming the bagger and sealer are in a vertical orientation, the relative heights of the bagger and closure section conveyors are adjusted as is the height of the knife 120. If the angular orientation of the machines is to be adjusted, the bolt(s) 178 is(are) removed and the bagger and sealer section are rotated about the axis of the trunions 157,170, 172 to a desired orientation. Following this rotation the bolt(s) is(are) reinserted to fix the mechanism in its desired angular orientation.
Next a web 15 of bags 25 is fed through the bagger and sealer by jogging the two. The transverse spacing of the main conveyor belts 40, 41 is adjusted by rotating the crank 72 until the load station 60 has the desired transverse dimension. A control, not shown, is set to provide a desired feed rate and a selected one of continuous or intermittent operation. Assuming continuous operation, the feed rate may be as high as 130 ten inch bags per minute.
Once the machine is in operation, the top section 21 of the web 15 is fed along the mandrel 24 and slit by the slitter 36. This forms the lips 38, 39 which are folded over the main transport belts 41, 42 by the action of the plow 45. The lip clamp belts 48, 49 descend from the elevated and spring biased pulleys 50S, as shown in FIG. 3. The roller cam 46 cams the clamp belts 48, 49 respectively into the transport belt recesses 51, 52 to provide very positive and firm support for the bags as they are further processed. As successive side connections 30 of the bags are registered with the bag side separator 53, the motor 55 is operated to drive the belt 54 and cause the breaker pins 58 to rupture the side connections 30.
As adjacent runs of the transport belts 41, 42 progress downstream from the bag feed and preparation portion 35, the belts are spread under the action of the belt spreaders 61, 62. As the belts are spread, the lips 38, 39 cause the front and back faces 31, 32 adjacent the lead edge of each bag to separate from the lips 38, 39 by tearing a sufficient length of the perforations between them to allow the lead edge to become the mid point in a bag span between the belts as the bag passes longitudinally through the load station 60. Similarly, the perforations adjacent the trailing edge are torn as the trailing part of the bag is spread until the bag achieves a full rectangular opening as shown in FIG. 4 in particular.
Next a product is inserted into the rectangular bag as indicated schematically in FIGS. 3 and 4. While the schematic showing is of discrete fasteners, it should be recognized that this machine and system are well suited to packaging liquids and bulky products which must be stuffed into a bag, such as pantyhose and rectangular items, such as household sponges.
After the product has been inserted, the adjacent runs of the main transport belts are brought back together and the loaded bag tops are spread longitudinally of the path of travel either by the planetary stretcher 90 or opposed air streams from nozzles 110, 112.
As is best seen in FIG. 3, exit ones 50E of the lip belt pulley set are spaced from the main transport belt and rotatable about angular axes. Expressed more accurately, when the machine is in a vertical loading orientation, the pulleys 50E are above the main transport belt such that the lip transport belts are pulled from the grooves 51, 52.
The now loaded bags pass through the transfer location onto the exit conveyors 115, 116 and thence to the seal station conveyors 118, 119. At this juncture the scrap 124 is severed from the loaded bags by the action of the knife 120. As the bags are advanced through the sealer section, the heater tube 135 is maintained in its lowered and solid line position of FIGS. 12, 13 and 15. If the machine is operated in its intermittent mode, the cylinder 145 is cycled in coordination with the starts and stops of the intermittently operated machine to shift the heater tube 135 between its solid line seal position and its storage position shown in phantom in the FIG. 13.
Although the invention has been described in its preferred form with a certain degree of particularity, it is understood that the present disclosure of the preferred form has been made only by way of example and that numerous changes in the details of construction, operation and the combination and arrangement of parts may be resorted to without departing from the spirit and the scope of the invention as hereinafter claimed.
|
A packaging machine and process for loading bags of a novel web of side connected bags are disclosed. The web is fed through a bagger section by a pair of grooved main transport belts and a pair of lip transport belts each disposed in the groove of the associated main belt to trap bag lips in the grooves. Adjustable belt spreaders space reaches of the transport belts as they move through a load station whereby to sequentially open the bags into rectangular configurations. A closure section in the form of a novel and improved heat sealer is releasably connectable to the bagger section. The sections are adjustable together between horizontal and vertical orientations. Processes of opening, closing and sealing side connected bags are also disclosed.
| 1
|
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application Ser. No. 61/366,340 filed Jul. 21, 2010, entitled WATERLESS DEGUMMING SYSTEM, which is herein incorporated by reference in its entirety.
FIELD OF INVENTION
[0002] The present invention relates to a method of degumming bast fibers for textile applications and to a method of pretreating lignocellulosic fiber for the production of biofuels or chemical feedstock, by the following means: rapid depressurization to vacuum and repressurization atmospheric or greater pressure; rapid temperature fluctuation; and ionic cleaning. The method described in this invention minimizes fiber damage, increases throughput potential, and reduces processing times.
BACKGROUND
[0003] In the past, U.S. Pat. No. 2,099,944 described a process of treating bast fiber plants to obtain clean cellulose fiber, lignin, and other gums, comprised of the following steps: 1) warm air drying; 2) rapid temperature reduction; and, 3) prolonged exposure to chilled ionized air. Ozone naturally attacks the carbon bonds of the lignin and nitrous oxide helps remove the pectins and other gums.
[0004] The process described is similar to modern ozonolysis systems, which are designed for pretreatment of lignocellulosic materials in order to remove lignin and facilitate enzymatic digestion of the carbohydrates into biofuels. Modern ozonolysis systems expose lignocellulosic materials within a reaction chamber at room temperature and atmospheric pressure to gaseous ozone for a prolonged period of time.
[0005] Rapid depressurization to vacuum and repressurization to atmospheric pressure or greater within a vacuum chamber or any suitable pressure vessel has never been contemplated for the purpose of degumming bast fiber. Vacuum rapidly dries and opens the fibrous material. Vacuum also aids in the penetration and diffusion of ionized air within the fibrous material upon repressurization.
[0006] U.S. Pat. No. 5,207,870 contemplates the use of vacuum to pretreat wood chips, however the process does not employ rapid pressure swings and the wood chips are in chemical liquid solution not ionized air.
[0007] U.S. Pat. No. 5,344,462 discusses the treatment of cellulose, textile fibers, and polymer films by exposure to low pressure plasma discharge. This process does not contemplate rapid pressure swings and it is designed for surface modification of the treated materials, not degumming for textile applications or pretreatment for biofuels production.
SUMMARY OF THE INVENTION
[0008] A first objective of this invention is to provide an improved waterless means of rapidly removing lignin and other gums from cellulosic fiber for the purpose of producing a variety of grades of textile fiber and for the pretreatment of ligrocellulosic fiber for biofuels or chemical feedstock production.
[0009] A second objective of this invention is to reduce the amount of energy and time required to remove the lignin and other gums from cellulosic fiber.
[0010] A third objective of this invention is to improve the quality control of the processed materials and to increase the throughput potential.
[0011] A fourth objective of this invention is to provide a means of immediately processing freshly harvested and decorticated bast fibers.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a schematic view of a waterless degumming system.
DETAILED DESCRIPTION
[0013] The following example describes a processing system capable of achieving the following actions: rapid depressurization to vacuum and repressurization to atmospheric or greater pressure; rapid temperature fluctuation: and ionic cleaning. The result of these actions separates lignocellulosic fiber into its various molecular components: cellulose, hemicelluloses, and lignin.
[0014] The system is consists of an ionic generator with fan 1 attached to ion reservoir 2 . The ionic generator 1 blows charged or ionized air into the reservoir 2 , which is attached to temperature manipulation vessel 4 by pipe 3 . Temperature manipulation vessel 4 is capable of heating of chilling the ionized air by means of coils within the vessel. Pipe 5 runs between temperature manipulation vessel 4 and vacuum reaction chamber 6 , which is supported by structural stand 7 . Pipe 5 is equipped with a valve. Reaction chamber 6 is attached to vacuum draw down tank 9 by pipe 8 with valve. Vacuum in vacuum draw down chamber 9 is pulled by vacuum pump 10 .
[0015] The system is operated in the following manner. First, ionic generator 1 is started building concentrated reserved in ion reservoir 2 and temperature manipulation vessel 4 . At the same time vacuum pump 10 is switched on to draw down vacuum tank 9 . The valves on pipes 5 and 8 are closed in order to concentrate the ions in ion reservoir 2 and create the vacuum within the vacuum draw down tank 9 .
[0016] Next, lignocelfulosic fiber is placed in reaction chamber 6 . The material is exposed to heat and mechanical rotation by common art. When vacuum is achieved in draw down tank 9 the valve on pipe 8 is opened rapidly creating a vacuum in reaction chamber 6 . Once vacuum is achieved in reaction chamber 6 the valve on pipe 8 is closed. The vacuum is maintained in reaction chamber 6 .
[0017] The rapid depressurization shocks the lignocellulosic fiber causing it to swell. The vacuum accelerates the drying process.
[0018] Next, the valve on pipe 5 is opened allowing the ionized air from ionic reservoir 2 and temperature manipulation vessel 4 to rapidly repressurize reaction chamber 6 . A secondary valve or pipe 8 may be opened allowing the ionized air to gradually flow through the reaction chamber for a period of time.
[0019] The vacuum and repressurization process facilitates the diffusion and penetration of the ionized air into the lignocellulosic fiber.
[0020] The ionized air may either be chilled or heated depending on the processing parameters. Heating and chilling is controlled in temperature manipulation vessel 4 .
[0021] Heated air helps the transfer of ions arid facilitates the cleaning of the cellulose fiber. A rapid temperature drop through exposure to chilled air cracks the gums that surround the cellulose fiber making it more accessible to the cleaning action of the ionized air.
[0022] The general process described in this invention may be repeated as many times as is necessary to achieve the desired degree of processing.
[0023] When the process is completed cellulose fiber, lignin, and the various gums may be collected through a variety of methods that are commonly known. Recovered cellulose fiber may be utilized for textile applications. Or, the carbohydrate portion, the cellulose and hennicelluloses, may be subjected to further treatment for biofuels production.
[0024] It will be understood that the previous example serves to illustrate one possible means of achieving the actions and objectives of this invention.
[0025] Although a few exemplary embodiments of the present invention have been shown and described, the present invention is not limited to the described exemplary embodiments. Instead, it would be appreciated by those skilled in the art that changes may be made to these exemplary embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
[0026] The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the description of the embodiments of the invention and the appended claims, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety.
[0028] It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation depicted in the Figures.
[0029] Moreover, it will be understood that although the terms first and second are used herein to describe various features, elements, regions, layers and/or sections, these features, elements, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one feature, element, region, layer or section from another feature, element, region, layer or section. Thus, a first feature, element, region, layer or section discussed below could be termed a second feature, element, region, layer or section, and similarly, a second without departing from the teachings of the present invention.
[0030] It will also be understood that when an element is referred to as being “connected” or “coupled” to another element, it can be directly connected or coupled to the other element or intervening elements may be present. In contrast, when an element is referred to as being “directly connected” or “directly coupled” to another element, there are no intervening elements present. Further, as used herein the term “plurality” refers to at least two elements. Additionally, like numbers refer to like elements throughout.
[0031] Thus, there has been shown and described several embodiments of a novel invention. As is evident from the foregoing description, certain aspects of the present invention are not limited by the particular details of the examples illustrated herein, and it is therefore contemplated that other modifications and applications, or equivalents thereof, will occur to those skilled in the art. The terms “having” and “including” and similar terms as used in the foregoing specification are used in the sense of “optional” or “may include” and not as “required”. Many changes, modifications, variations and other uses and applications of the present construction will, however, become apparent to those skilled in the art after considering the specification and the accompanying drawings. All such changes, modifications, variations and other uses and applications which do not depart from the spirit and scope of the invention are deemed to be covered by the invention which is limited only by the claims which follow. The scope of the disclosure is not intended to be limited to the embodiments shown herein, but is to be accorded the full scope consistent with the claims, wherein reference to an element in the singular is not intended to mean “one and only one” unless specifically so stated, but rather “one or more.” All structural and functional equivalents to the elements of the various embodiments described throughout this disclosure that are known or later come to be known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the claims.
|
A method and system for cleaning lignin and other gums from lignocellulosic fiber is disclosed. Lignocellulosic fiber is rapidly depressurized to a pressure lower than atmospheric pressure. The fiber is exposed to ionized air during the rapid depressurization. The fiber is then repressurized to a pressure equal to or greater than atmospheric pressure.
| 3
|
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application is a divisional application of U.S. patent application Ser. No. 14/257,558 filed Apr. 21, 2014, which claims priority to and the benefit of German Pat. App. No. 10 2013 207 497.2 filed Apr. 25, 2013, the disclosures of each of which are incorporated herein by reference in their entireties.
FIELD OF THE INVENTION
[0002] The present invention relates to a component having at micromechanical microphone pattern, which is implemented in a layer construction on a semiconductor substrate. The microphone pattern includes an acoustically active diaphragm, which spans a sound hole on the backside of the substrate, and a stationary acoustically penetrable counterelement, having through hole openings, which is situated in the layer construction above or below the diaphragm.
BACKGROUND
[0003] The diaphragm's being acted upon by sound takes place via the sound hole in the substrate and/or via the through holes in the counterelement. The diaphragm deflections resulting from this, perpendicular to the layer planes, are able to be detected capacitively, for example. For this, the microphone pattern is equipped with a capacitor device which includes at least one deflectable electrode on the diaphragm and at least one stationary electrode on the counterelement. The volume directly in front of and behind the acoustically active diaphragm of the component under discussion should be as airtight as possible, in order to avoid an acoustical short circuit and to achieve a good microphone sensitivity.
[0004] The higher the pressure difference between the two sides of the diaphragm, the greater is the diaphragm deflection and, with that, also the mechanical stress of the diaphragm. The microphone diaphragm of the component being discussed is not normally designed for highly dynamic pressure fluctuations and high pressure differences. Such overload situations, which may even lead to damage in the microphone pattern, may not, however, be totally excluded either during the production process nor at the point of use of the component. Thus, during the production process, in “pick′n place” assembly, very high suction pressures are used, and also at the place of use of the component, strong air blasts may occur, such as are caused by an air pistol, for example.
SUMMARY
[0005] The present invention provides measures for increasing the resistance to compression of a component named at the outset. In particular, the robustness of the microphone pattern to highly dynamic pressure fluctuations is to be increased, without the microphone sensitivity, i.e. the microphone performance, being impaired.
[0006] For this purpose, according to the present invention, at least one outflow channel is developed in the layer construction, which makes possible a rapid pressure equalization between the two sides of the diaphragm. Furthermore, according to the present invention, at least one controllable encrypting element is provided, with which the at least one outflow channel may optionally be opened or closed.
[0007] In normal operation, the active mode of the component, the outflow channel is to be held closed, in order not to impair the microphone sensitivity. Only when highly dynamic pressure fluctuations as of a specified magnitude occur, should the outflow channel be opened, so that the force of the corresponding pressure wave is conducted past the diaphragm or is weakened to such an extent that it does not lead to damage of the diaphragm. The closing element may simply be actuated as a function of the different operating modes of the component. In this case, the actuation of the closing element for closing the outflow channel may be connected to the actuation of the diaphragm. In the overload case, the outflow channel is opened automatically in the simplest case, i.e. by the acting pressure force or suction force. However, in the overload case, the closing element may also be actively actuated, for example, if the pressure conditions in the surroundings are monitored with the aid of a threshold value switch especially provided for this.
[0008] Basically there are different possibilities for implementing an outflow channel according to the present invention, having a controllable closing element. The construction of the microphone pattern has to be taken into account in this context. But the type of the overload situation that is to be avoided is also important, that is, whether an impact force or a suction force is to be reduced. As an impact force or an impact pressure, a force is designated in the following which presses the diaphragm away from the counterelement, while as a suction force a force is designated which presses or draws the diaphragm against the counterelement. The direction of the acting force must particularly be taken into account in the design of the closing element, since, in the case of an overload situation, the closing element should preferably be moved with, and not against the acting force, in order to open the outflow channel.
[0009] To compensate for impact pressure overload situations, the outflow channel may advantageously be implemented in the diaphragm range of the microphone pattern. In one preferred specific embodiment of the component according to the present invention, the outflow channel is developed at the edge of the diaphragm area, namely, in the form of a first pressure equalization opening in the edge region of the counterelement and of a second pressure equalizationopening in the edge region of the diaphragm. The two pressure equalization openings communicate with each other by forming a flow connection between the two sides of the diaphragm, depending on the diaphragm position. Since the two pressure equalization openings are situated offset to each other, the diaphragm itself may be used as a controllable closing element. For this purpose, the diaphragm, in the active mode of the component, is drawn against the counterelement, the edge region of the counterelement functioning as a seat for the diaphragm edge. In this diaphragm position, both pressure equalization openings are closed. In response to the occurrence of an impact pressure, which presses the diaphragm away from the counterelement, the pressure equalization openings are automatically opened by the diaphragm motion, and thus make possible a rapid pressure equalization between the two sides of the diaphragm. In the layer construction at least one stop is advantageously developed for the diaphragm, which limits the diaphragm deflection during the opening of the outflow channel, and thus protects against damage from an overload.
[0010] In one particularly versatile usable refinement of this specific embodiment of the present invention, the diaphragm is not only able to be moved actively in the direction of the counterelement, in order to close the outflow channel, but also to be moved actively away from the the counterelement, in orderly actively to open the outflow channel. This may be meaningful if the microphone function is not needed and/or highly dynamic pressure fluctuations are to be expected at clearly defined time periods. The actuation of the diaphragm preferably takes place electrostatically. In this case, the diaphragm is respectively pulled against a corresponding stop in the layer construction, which defines the closed position and the open position.
[0011] In one particularly advantageous specific embodiment of the component according to the present invention, which is able to be designed both for the case of an impact pressure-overload situation and also for the case of a suction pressure-overload situation, at least one outflow channel is developed laterally next to the diaphragm area and is connected to the backside of the diaphragm via a lateral access opening. The associated closing element is developed in at least one layer of the layer construction, in this case, so that it is movable perpendicular to the layer planes within the outflow channel. In this specific embodiment, the closing element is structurally independent of the diaphragm, and is also moved independently of it, in order to open or close the outflow channel.
[0012] The closed position of the closing element is preferably defined by a bottleneck in the outflow channel, which functions as an encircling stop or seat for the closing element, so that the outflow channel is closed as pressure-tightly as possible. It is important that the closing element be situated above this bottleneck, in the direction of the force occurring in the overload case, so that it is pressed out of its closed position by this force or together with this force, and the outflow channel is opened. Depending on the situation of the closing element with respect to the bottleneck in the outflow channel, the latter may thus be designed to dissipate a suction force or even an impact force. In each case it proves to be advantageous, even in this specific embodiment of the present invention, if, in the layer construction, at least one stop is developed which limits the deflection of the closing element in response to the opening of the outflow channel.
[0013] At this point, we should explicitly point out that a component, of the type under discussion, with the aid of the measures according to the present invention, is able to be designed both for impact force overload situations and for suction force overload situations. The component is advantageously equipped for this purpose with separate outflow channels and corresponding closing elements.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIGS. 1 a -1 c show schematic sectional representations through the edge region of the microphone pattern of a first component 10 according to the present invention, in the passive operating mode ( FIG. 1 a ) and the active operating mode ( FIG. 1 b ) as well as in the case of an impact pressure overload situation ( FIG. 1 c ).
[0015] FIGS. 2 a , 2 b show schematic sectional representations through the edge region of the microphone pattern of a second component 20 according to the present invention, in the active operating mode ( FIG. 2 a ) and in the case of an impact pressure overload situation ( FIG. 2 b ).
[0016] FIGS. 3 a -3 c show schematic sectional representations through the edge region of the microphone pattern of a third component 30 according to the present invention, in the passive operating mode ( FIG. 3 a ) and the active operating mode ( FIG. 3 b ) as well as in the case of an impact pressure overload situation ( FIG. 3 c ).
[0017] FIGS. 4 a , 4 b show schematic sectional representations through the edge region of the microphone pattern of a fourth component 40 according to the present invention, in the active operating mode ( FIG. 4 a ) and in the case of a suction pressure overload situation ( FIG. 4 b ).
[0018] FIGS. 5 a , 5 b show schematic sectional representations through the edge region of the microphone pattern of a fifth component 50 according to the present invention, in the active operating mode ( FIG. 5 a ) and in the case of a suction pressure overload situation ( FIG. 5 b ).
[0019] FIGS. 6 a -6 c show schematic sectional representations through the edge region of the microphone pattern of a sixth component 60 according to the present invention, in the active operating mode ( FIG. 6 a ) in the case of an impact pressure overload situation ( FIG. 6 b ) and in the case of a suction force overload situation ( FIG. 6 c ).
DETAILED DESCRIPTION
[0020] The microphone patterns of components 10 , 20 and 30 are each implemented in a layer construction on a semiconductor substrate 1 . They include an acoustically active diaphragm 11 which spans a sound hole 14 on the backside of the substrate. Moreover, the microphone patterns include a stationary acoustically penetrable counterelement 15 which, in the case of components 10 and 20 , is situated in the layer construction above diaphragm 11 , and in the case of component 30 , in the layer construction below diaphragm 11 . In particular, the sectional representations of FIGS. 1 a and 3 a , the microphone patterns of components 10 and 30 in the passive operating mode show, illustrate that diaphragm 11 is in each case made up of an edge region 111 , a parallel-sided middle region 113 and a transitional region 112 between edge region 111 and middle region 113 , and that, between edge region 111 of diaphragm 11 and counterelement 15 there is a shorter distance than between parallel-sided middle region 113 of diaphragm 11 and counterelement 15 . In counterelement 15 , through hole openings are developed which are not shown here, however, since they are located over middle region 113 of diaphragm 11 . The signal detection takes place capacitively in each case with the aid of a capacitor device which includes at least one deflectable electrode on diaphragm 11 and at least one stationary electrode on counterelement 15 .
[0021] According to the present invention, in the layer construction of microphone components 10 , 20 and 30 , in each case at least one outflow channel 17 is developed, which enables a rapid pressure equalization between the two sides of diaphragm 11 . For each outflow channel 17 , at least one controllable closing element 18 is provided, with which outflow channel 17 may optionally be opened or closed.
[0022] In the case of all three microphone components 10 , 20 and 30 , outflow channel 17 is designed with closing element 18 to reduce an overload situation, in which diaphragm 11 is pushed away by counterelement 15 , which is designated as impact force overload situations.
[0023] Outflow channel 17 is in this instance, in each case, implemented in the form of a first pressure equalization opening 171 in the edge region of counterelement 15 , and a second pressure equalization opening 172 in the edge region of diaphragm 11 . These two pressure equalization openings 171 and 172 are situated in an offset manner to each other, so that, depending on the position of diaphragm 11 , they are closed or communicate with each other, that is, they make possible an air flow between the front side of the component and sound hole 14 and thus they make possible a pressure equalization between the two sides of diaphragm 11 .
[0024] Thus, accordingly, in all three cases diaphragm 11 itself, or rather edge region 111 of diaphragm 11 , functions as controllable closing element 18 , in that the two pressure equalization openings 171 and 172 are closed when edge region 111 of diaphragm 11 is draw against counterelement 15 .
[0025] FIGS. 1 a through 1 c , 2 a , 2 b and 3 a through 3 c illustrate the method of functioning of outflow channel 17 as a function of the operating mode of the respective microphone component 10 , 20 and 30 and the diaphragm position corresponding to the operating mode.
[0026] FIG. 1 a and FIG. 3 a show component 10 and component 30 in the so-called passive operating mode. The microphone function is not activated here. Accordingly, diaphragm 11 is in its at rest position, which comes about only based on the diaphragm pattern, the mechanical properties of the diaphragm and its integration into the layer construction. In this at rest position, edge region 111 of diaphragm 11 is at a distance from counterelement 15 , so that a flow connection exists between the two pressure equalization openings 171 and 172 . Outflow channel 17 is opened in this instance, so that the forces occurring in an impact pressure overload situation are reduced.
[0027] FIG. 1 b , FIG. 2 a and FIG. 3 b show components 10 , 20 and 30 in the active operating mode, i.e. having the actuated diaphragm 11 . The actuation of diaphragm 11 for activating the microphone function may take place electrostatically, for example. In this context, diaphragm 11 is acted upon with a mechanical stress, in order to raise the microphone sensitivity. To do this, diaphragm 11 is drawn so far against counterelement 15 that edge region 111 of diaphragm 11 lies against counterelement 15 . In this diaphragm position, both pressure equalization openings 171 and 172 are closed, whereby an acoustical short circuit via outflow channel 17 is avoided and maximum microphone sensitivity is achieved.
[0028] FIG. 1 c , FIG. 2 b and FIG. 3 c show components 10 , 20 and 30 in an impact pressure overload situations. In the case of components 10 and 20 , the forces occurring in this case act upon the components' front side, while in component 30 they act upon the component's backside. In all three cases, diaphragm 11 is thereby pressed away from counterelement 15 . In the process, pressure equalization openings 171 and 172 are also opened in edge region 111 of diaphragm 11 and of counterelement 15 , so that a flow connection is created between the component front side and backside sound hole 14 . This outflow channel 17 enables a rapid pressure equalization between the two sides of diaphragm 11 , whereby the mechanical stress of the diaphragm is clearly weakened.
[0029] In the exemplary embodiment shown in FIGS. 1 a through 1 c , microphone component 10 , substrate 1 in the edge region of sound hole 14 forms an encircling mechanical stop 19 , which limits the diaphragm motion during the opening of outflow channel 17 , and in this respect functions as overload protection for diaphragm 11 on the substrate side.
[0030] In the case of microphone component 20 shown in FIGS. 2 a and 2 b , the edge region of sound hole 14 is also used as a stop for the diaphragm motion. However, in this case, in the region of outflow channel 17 a recess 141 has been developed, through which the opening cross section of outflow channel 17 to sound hole 14 is enlarged.
[0031] In microphone component 30 shown in FIGS. 3 a through 3 c , in which diaphragm 11 is situated in the layer construction above counterelement 15 , a mechanical stop 39 is developed in the layer construction above diaphragm 11 , which limits the diaphragm motion during the opening of outflow channel 17 , and thus forms an overload protection against impact pressure overload situations.
[0032] At this place, let us point out again that all the abovementioned components 10 , 20 , 30 may also be equipped with means for actuating diaphragm 11 , which enable an active opening of outflow channel 17 . Because of that, the actuating of diaphragm 11 and the microphone function are able to be decoupled. This is particularly of advantage if the occurrence of impact pressure overload situations is detected even independently of the microphone pattern, such as with the aid of a dedicated sensor component.
[0033] The microphone pattern of capacitive microphone components 40 and 50 shown in FIGS. 4 a , 4 b and 5 a , 5 b is also implemented in a layer construction on a semiconductor substrate 1 , and spans a sound hole 14 in the backside of the substrate. The microphone pattern includes an acoustically active diaphragm 11 having an edge region 111 , a middle region 113 offset in a manner that is parallel-sided to it and a transitional region 112 between edge region 111 and middle region 113 . In the layer construction above diaphragm 11 , a stationary acoustically penetrable counterelement 15 is situated.
[0034] According to the present invention, in these components 40 and 50 , there is also developed at least one outflow channel 47 in the layer construction, which enables a rapid pressure equalization between the two sides of diaphragm 11 . For each outflow channel 47 , at least one controllable closing element 48 is provided, with which outflow channel 47 may optionally be opened or closed.
[0035] In the case of microphone components 40 and 50 shown here, outflow channel 47 is designed with closing element 48 to reduce an overload situation, in which diaphragm 11 and particularly its middle region 113 is pulled against counterelement 15 , which is designated as suction force overload situations.
[0036] In this case, outflow channel 47 is situated laterally beside the diaphragm area and extends through the layer construction up to substrate 1 , where it is connected to the backside of diaphragm 11 via a lateral access opening 471 . In one layer of the layer construction, a bottleneck 472 is developed in outflow channel 47 . It functions as an encircling stop or seat for closing element 48 , which in this instance is also patterned out from the layer construction, namely, from a layer above bottleneck 472 . It is movable within outflow channel 47 perpendicular to the layer planes, in order to open or close outflow channel 47 in an optional manner.
[0037] FIGS. 4 a , 4 b and 5 a , 5 b illustrate the method of functioning outflow channel 47 as a function of the operating mode of the respective microphone component 40 or 50 .
[0038] FIG. 4 a and FIG. 5 a show components 40 and 50 in the active operating mode, in which diaphragm 11 has been drawn against counterelement 15 , in order to act upon it with a mechanical stress. Outflow channel 47 is closed in order to avoid an acoustical short circuit and to achieve a maximum microphone sensitivity. For this purpose, closing element 48 was drawn against its seat 472 in outflow channel 47 . The actuation of closing element 48 required for this may take place electrostatically, for example.
[0039] FIG. 4 b and FIG. 5 b show components 40 and 50 in a suction force overload situation. The forces occurring in this context, act upon the component front side, so that particularly middle region 113 of diaphragm 11 is drawn against counterelement 15 . In this context, however, closing element 48 is also drawn upwards, i.e. in the direction towards the front side of the component, whereby outflow channel 47 is opened. By this flow connection between the front side of the component and the sound hole 14 on the backside, the mechanical stress of diaphragm 11 is clearly weakened.
[0040] In both exemplary embodiments, in the layer construction above outflow channel 47 , a mechanical stop 49 is developed, which limits the motion of closing element 48 during the opening of outflow channel 47 , and thus forms an overload protection in suction force overload situations.
[0041] Both microphone components 40 and 50 described above may also be equipped with means for actuating closing element 48 , which enable an active opening of outflow channel 47 .
[0042] Closing elements 48 of the components under discussion, in this case, may also be used for the design of the microphone damping behavior, by providing them with suitable ventilating openings 56 , as in the case of microphone component 50 .
[0043] The microphone pattern of component 60 shown in FIGS. 6 a through 6 c includes both an outflow channel 17 in the diaphragm area, which is designed for impact pressure overload situations, and an outflow channel 47 , having a closing element 48 , which is designed for suction force overload situations. These components of the microphone pattern were described thoroughly in connection with FIGS. 1 a through 1 c and 4 a , 4 b . Therefore, we shall subsequently only explain the manner of functioning of outflow channels 17 and 47 , with the aid of FIGS. 6 a through 6 c , as a function of the operating mode of microphone component 60 .
[0044] FIG. 6 a shows component 60 in the active operating mode, i.e. with an actuated diaphragm 11 . Diaphragm 11 was drawn so far against counterelement 15 that edge region 111 of diaphragm 11 lies against counterelement 15 . In this diaphragm position, both pressure equalization openings 171 and 172 are closed, whereby an acoustical short circuit via outflow channel 17 is avoided and maximum microphone sensitivity is achieved. Outflow channel 47 is also closed, so as to achieve maximum microphone sensitivity. For this purpose, closing element 48 was drawn against its seat 472 in outflow channel 47 .
[0045] FIG. 6 b shows component 60 in an impact pressure overload situation, that is, in which diaphragm 11 is pressed away from counterelement 15 . In the process, pressure equalization openings 171 and 172 are also opened in edge region 111 of diaphragm 11 and of counterelement 15 , so that a flow connection is created between the component front side and backside sound hole 14 . This outflow channel 17 enables a rapid pressure equalization between the two sides of diaphragm 11 , whereby the mechanical stress of the diaphragm is clearly weakened. The position of closing element 48 on bottleneck 472 in outflow channel 47 does not change, since closing element 48 is additionally pressed against seat 472 by the impact pressure stress.
[0046] FIG. 6 c shows component 60 in a suction force overload situation, in which, in particular, middle region 113 of diaphragm 11 is drawn against counterelement 15 . In this context, however, closing element 48 is also drawn upwards, i.e. in the direction towards the front side of the component, whereby outflow channel 47 is opened. By this flow connection between the front side of the component and the sound hole 14 on the backside, the mechanical stress of diaphragm 11 is clearly weakened. Pressure equalization openings 171 and 172 that are situated offset to each other remain closed, since diaphragm edge 111 is drawn against counterelement 15 in the case of a suction force acting upon the microphone pattern.
[0047] Microphone component 60 is proving itself both in impact pressure overload situations and in impact force overload situations as particularly stable to pressure, since the force of the respective pressure waves is guided past diaphragm 11 , via outflow channels 17 and 47 . The microphone sensitivity is not impaired thereby, since these outflow channels 17 and 47 are closed in the active operating mode of component 60 .
|
Measures are provided for increasing the resistance to compression of a component having a micromechanical microphone pattern. In particular, the robustness of the microphone pattern to highly dynamic pressure fluctuations is to be increased, without the microphone sensitivity, i.e. the microphone performance, being impaired. The microphone pattern of such a component is implemented in a layer construction on a semiconductor substrate and includes at least one acoustically active diaphragm, which spans a sound hole on the substrate backside, and a stationary acoustically penetrable counterelement having through hole openings, which is situated above/below the diaphragm in the layer construction. At least one outflow channel is developed which makes possible a rapid pressure equalization between the two sides of the diaphragm. In addition, at least one controllable closing element is provided, with which the at least one outflow channel is optionally able to be opened or closed.
| 1
|
BACKGROUND OF THE INVENTION
The present invention relates generally to an improved floating suction head assembly of the type employed by firemen in the absence of a convenient fire hydrant and Where the suction head may be disposed on the surface of a pond, lake, stream, swimming pool etc. from which Water can be pumped. U.S. Pat. No. 4,647,374 to Michael P Ziaylek et al discloses a suction head of the type mentioned.
It is the general object of the present invention to provide an improved floating suction head assembly which is highly efficient in operation and yet extremely low in weight and which avoids the creation of turbulence and whirl pooling in use.
SUMMARY OF THE INVENTION
In fulfillment of the foregoing general object, an improved floating suction head assembly is provided for connection with fire hoses and the like and comprises a float which is generally U-shaped viewed from above in an operational or floating attitude on the surface of a pond, stream, swimming pool etc. The body and each arm of the "U" shaped float are of sealed holloW construction and are preferably generally cylindrical and fabricated of aluminum alloy or a similar durable light Weight material. An elongated holloW generally cylindrical strainer is open at one end and adapted for connection with the suction end of a firehose or the like and is closed at an opposite end. The strainer is disposed generally in a horizontal attitude and at least partially betWeen the arms of the U-shaped float with its closed end adjacent the body portion of the float. A means for detachably pivotally interconnecting the strainer and the float is provided adjacent the closed end of the former and the strainer is thus pivotally moveable with the open end thereof swingable downwardly relative to the float. Thus, a connected firehose or the like will describe a shallow arc beneath the surface of the water due to its own weight and the weight of water therewithin and will pivot the strainer downwardly with the float remaining in a horizontal position on the surface of the water.
The strainer is also preferably fabricated of aluminum alloy or the like and is of a hollow tubular construction with a plurality of small openings along and throughout its lower surface and extending upwardly along each side thereof throughout an angle of at least 60° from a vertical plane at the longitudinal centerline of the strainer. In preferred form, the small openings extend through an angle of approximately 90° from the vertical plane through the longitudinal centerline of the strainer and thus provide a perforate area with an included angle of approximately 180°. The strainer is arranged With its lower portion disposed beneath the lower surface of the float so that substantially all of its openings are exposed at all times below the float portion of the suction head. Thus, water may be drawn downwardly about the arcuate outer surfaces of the float and will flow smoothly into the side openings in the strainer as Well as the lowermost openings therein. Turbulence and whirl pooling and the attendant entrapment of air with detrimental effect on pumps etc. is thus positively avoided.
Preferably, a stop means is provided for limiting the downward pivotal movement of the strainer and a specific arrangement and dimensional relationship of strainer openings is provided for. That is the openings are approximately one half inch in diameter and the spacing therebetween is no more than one half inch. More specifically, the spacing is less than one quarter inch between the openings with the openings arranged alternately in radially extending rows of 9 and 8 each. There are preferably between 20 and 40 radial rows of openings in the strainer and in the preferred embodiment approximately 32 radial rows of openings are provided.
DESCRIPTION OF THE DRAWINGS
FIG. 1 of the drawings is a side elevational view of the Improved Floating Suction Head Assembly of the present invention floating in a body of water and with the strainer shown in both horizontal and downwardly pivoted attitudes.
FIG. 2 is a bottom view of the FLOATING SUCTION HEAD ASSEMBLY of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring particularly to FIG. 1, a body of water is partially illustrated at 10 with an improved floating suction head assembly constructed with accordance with the present invention indicated generally at 12. The suction head assembly is shown in a floating attitude partially exposed above the surface of the water 10 with its strainer in full line horizontal position and in broken line in a downwardly pivoted position. As best illustrated in FIG. 2, the suction head assembly comprises a float 14 Which is generally U-Shaped with similar spaced apart arms 16, 16 and a body or body portion 18 interconnecting the former. As shown and as presently preferred, the body and each arm in the U-shaped float are of a sealed hollow construction of aluminum alloy or other light Weight material.
An elongated hollow generally cylindrical strainer 20 is open at one end and adapted for connection With the suction end of a firehose or the like. More particularly, the strainer 20 is shown With a "quick-connect" collar 22 at an open right hand end portion thereof for connection with a firehose or the like at 24. That is, the collar 22 may be internally threaded for connection with a complimentary externally threaded portion of the firehose 24.
At a left hand and closed end portion of the strainer 20, a means is provided for pivotally interconnecting the strainer and the float and such means may comprise a pair of brackets 26, 26 best illustrated in FIG. 2 and cooperating with a pivot pin 28. The pivot pin 28 takes an L-shape as shoWn With a small pin 30 securing the same in position through appropriate openings in the brackets 26, 26. The brackets 26, 26 reside adjacent a bracket 30 which is also suitably bored to receive the pivot pin 28 and which is held on a cross bar 32 secured at its ends to the arm 16, 16 of the float 14. As will be apparent, the strainer 20 may be readily swung between the positions shown in FIG. 1 about the pivot pin 28. Alternatively, the pivot pin 28 may be removed accommodating removal of the strainer 20 for use at the end of the hose 24 independently of the float 14. For example, the strainer may then be dropped to the bottom of a pond, stream, swimming pool etc. for the suction of water therethrough.
As will also be apparent in FIG. 1, a cross bar 34 shown in broken line cooperates with a projecting end portion 36 of a handle 38 also shown in broken line. The bar 34 and portion 36 limit the downward pivoting movement of the strainer 20 relative to the float 14. If the strainer is allowed to assume an extreme downward position, particularly in a shallow pond, there may be a greater likelihood of suction of muck etc. For the bottom of the pond. The handle 38 may of course also be employed in moving the suction head assembly from a firetruck to a pond, stream etc. The stop bar 34 may be secured between the arm 16, 16 by welding or other suitable means.
In accordance with the present invention, the strainer 20 is provided with a plurality of small openings along and throughout its lower surface and extending upwardly along each side thereof throughout an angle of at least 60° from a vertical plane through a longitudinal centerline of the strainer. As best seen in FIG. 1, the openings 40, 40 extend upwardly about the sides of the strainer 20 through at least 80° from a vertical plane through the longitudinal centerline of the strainer and, more specifically, the said openings extend through an angle of approximately 90°. That is, the upwardmost row of openings 40, 40 resides approximately at the mid point of the strainer on both sides thereof so as to define an included angle of perforate area of approximately 180°. It will also be apparent in FIG. 1 that the uppermost row of openings 40, 40 is freely exposed beneath the float 14 as are all openings therebelow. That is, the strainer 20 is disposed so that approximately its lower half is exposed beneath the float 14 even when the strainer is in the upper or horizontal position shown in full line in FIG. 1. When the strainer is in its downwardly pivoted position all openings are of course also exposed beneath the float 14. This arrangement of the strainer and the openings therein relative to the float 14 contributes, together with the particular configuration and dimensions of the openings, to the highly efficient operation of the improved floating suction head Assembly of the present invention. The water Which is drawn downwardly about the float 14 and/or inwardly toward the side openings 40, 40 in the strainer passes over the gradual arcuate lower surfaces of the cylindrical arms and body of the float into the openings and Water drawn from beneath the strainer of course also passes freely through the loWermost openings therein. Thus, turbulence and whirl pooling of the water about the suction head is minimized and air entrapment is avoided as might otherwise result in detrimental effect on the pump and/or the efficiency of discharge from the firehose downstream of the pump.
As mentioned, the size and arrangement of the openings 40, 40 also contributes to the efficient turbulence free operation of the strainer. Preferably and as shown, the openings 40, 40 are approximately one half inch in diameter and the spacing therebetween is substantially less than one half inch and, preferably, less than one quarter inch. The openings 40, 40 are arranged alternately in radially extending rows of 9 and 8 each although only 8 and 7 openings are shown in each radial extending row in FIG. 2. Preferably, there are between 20 and 40 radial rows of openings in the strainer and in the presently preferred form there are approximately 32 radial rows of such openings.
From the foregoing, it will apparent that the arrangement of the strainer relative to the float together with the arrangement and dimensions of the openings in the strainer results in improved and highly efficient operation of the Floating Suction Head Assembly of the present invention. Turbulence and whirl pooling is avoided as mentioned. Moreover, the hollow, lightweight construction of the suction head throughout results in a weight reduction of as much as 100% over prior suction heads, as for example in the case of the device of the aforementioned patent.
|
A floating suction head assembly for connection with firehoses and the like comprising a U-shaped float of hollow tubular construction. A hollow tubular strainer is disposed between the arms of the float and extends therebeneath with small openings fully exposed at its bottom and along side portions thereof. The openings are one half inch in diameter with spacing therebetween of approximately one fourth inch and with alternate radial rows of 9 and 8 openings each. Thirty-two rows of openings are provided along the length of the strainer and a highly efficient turbulence free operation results with a lightweight construction.
| 1
|
TECHNICAL FIELD
The field of this invention relates to a support bracket for a pipe and more particularly to a two piece pipe clamp for automotive vehicle applications.
BACKGROUND OF THE DISCLOSURE
In automotive vehicles, there are a great number of clamps securing tubes, pipes and wires in position. Some clamps only need to secure against lateral motion such as clamps that hold rubber hoses in place. Other clamps need to secure pipes to limit the axial motion and rotational motion. Metal pipes attached to the automotive vehicle and used for transporting coolant and hydraulic brake fluid throughout the automotive vehicle need to be securely fastened to prevent as much movement and vibration as possible.
The clamps for these applications are made of metal and are welded directly to the pipe. The clamp is then bolted or screwed in place to the engine, engine compartment wall or other fixed structure in the engine compartment.
The widespread use of corrosion resistant coatings on metal pipes and conduits is intended to greatly increase the useful life of the pipe or conduit against both the degrading effects of the fluid within the pipe and also the harsh external environment encountered by the engine compartment or under the vehicular body that include road salt and water.
However, the welding of conventional clamps on these coated pipes destroys the corrosion resistant coating on the metal pipes at the welding spot. As a result, corrosion and holes eventually occur at the very spot where the clamp is secured onto the pipe at a speed or rate no slower than for untreated pipes. The intended advantage of the corrosion resistant coating is completely undermined by the welding process of the clamp onto the treated pipes.
What is needed is a clamp that affixes a corrosion resistant coated pipe securely against slippage and rotation while maintaining the integrity of the corrosion resistant coating on the pipe.
SUMMARY OF THE DISCLOSURE
In accordance with one aspect of the invention, a bracket for supporting and affixing automotive containing pipe elements in lateral, axial and rotational directions to an automotive vehicle includes a base member having a first end section constructed for securement to the vehicle. The base member has a pipe engaging section, preferably an arcuate section sized to receive a pipe element. The base member also has opposing flanges extending radially outward from opposite ends of the arcuate section.
A closure member has a substantially planar surface dimensioned to engage an indented section in the pipe element. The indented section is preferably a flat in the wall of the pipe. The closure member and opposing flanges having complementary fastener elements for affixing said closure member to the flanges whereby the substantially planar surface limits axial slippage of said pipe and prevents rotation of said pipe within the clamp.
Preferably, the base member and the closure member are made from a structural resin material such as a glass filled nylon or a polyphthalamide. The complementary fastener means desirably include apertures in either the flanges or the closure member and resilient prongs extending from the other of the flanges or the closure member. The apertures and prongs are appropriately sized such that the prongs snap fit into the apertures thereby snap fitting the closure member onto the base member.
The base member has a first end section which may take the form of a leg. The leg preferably has a n aperture therethrough with a metal ring insert molded within the aperture for engagement with a fastener that affixes the clamp assembly to the automotive vehicle.
It is also recognized that in accordance with the invention, the arcuate recess section may be on the cover member and the flat pipe engaging section may be on the base member.
In accordance with another aspect of the invention, a pipe and clamp assembly includes a pipe element having a corrosion resistant coating and an indented recess section. The clamp includes a base member and a cover member. The base member has a first end section constructed for securement to a fixed support. The base member and the cover are constructed to be fastened together about said pipe axially positioned with the indented recessed section on the pipe and forming a complementary shaped section keyed into the recessed section for preventing axial slippage of pipe and for preventing rotation of the pipe within the clamp.
In accordance with another embodiment of the invention, a method of rotationally and axially affixing a fluid flow pipe to an automotive vehicle includes the steps of providing a cylindrical pipe; applying a corrosion resistant coating on said pipe; stamping an indented flat onto a portion of said pipe. After the stamping of the flat and the application of the corrosion resistant coating, the coated and stamped pipe is assembled into a clamp that is securable to a fixed support such that a portion of the clamp abuts against the indented flat and axially extends along the entire length of the flat such that said pipe is rotationally and axially affixed to the clamp. Desirably, the method also includes the clamp comprising a base member and separate cover member being snap fitted together during the assembly step with the pipe affixed through an opening formed in the assembled clamp.
In this fashion, a corrosion resistant pipe is secured against rotational and axial motion with respect to a clamp while maintaining the intended advantages of the corrosion resistant coating of the pipe that is applied before assembly in an economical manner.
BRIEF DESCRIPTION OF THE DRAWINGS
Reference now is made to the accompanying drawings in which:
FIG. 1 is a perspective view of a pipe and clamp assembly illustrating one embodiment in accordance with the invention mounted in an automotive vehicle engine compartment;
FIG. 2 is a perspective view of the pipe element shown in FIG. 1;
FIG. 3 is a cross-sectional view of the pipe and clamp assembly taken along lines 3--3 shown in FIG. 1;
FIG. 4 is a side elevational and partially segmented view of the base member shown in FIG. 2;
FIG. 5 is an elevational view taken along lines 5--5 shown in FIG. 4;
FIG. 6 is an elevational view taken along lines 6--6 shown in FIG. 4;
FIG. 7 is an elevational view of the cover plate shown in FIG. 1;
FIG. 8 is an elevational view of the cover plate taken along lines 8--8 as shown in FIG. 7;
FIG. 9 is a cross-sectional view of the pipe and clamp assembly taken along lines 9--9 as shown in FIG. 3; and
FIG. 10 is a fragmentary view similar to FIG. 4 illustrating an alternate embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1, a pipe and clamp assembly 10 includes a pipe element 12 secured with a two piece clamp 14. The clamp 14 includes a base member 16 secured to a wall 18 of an automotive engine compartment via a threaded fastener 19. The clamp 14 also includes a cover member 20 snap fitted onto the base member 16 to surround the pipe element 12.
The pipe element 12, as shown in FIG. 2, is formed from a metal material such as steel and is coated with a state of the art commercially available corrosion resistant coating such as a galvanized coating or protective polymer coating. The corrosion resistant coated pipe is then stamped with an indented flat 22. The flat area 22 can be formed by a conventional stamping process which does not break the integrity of the corrosion resistant coating.
The clamp 14 is made from a structural thermoplastic resin material such as a glass filled nylon. For higher temperature requirements, a polyphthalanide would be suitable. As shown in FIGS. 3 and 5, the base member 16 has a leg section 24 with a hole 26 therethrough. A metal reinforcing ring 28 is anchored into the hole 26 to prevent wear and tear when it engages the threaded fastener 19 that fastens the clamp 14 onto wall 18. The anchoring may be accomplished by an insert molding the ring 28 to the base member. The leg, as shown, is bent at approximately a 90° angle to a pipe engaging section 32. However, any other angle for the leg can be chosen depending on the mounting requirements and position and clearance requirements for the particular application. The pipe engaging section 32 includes an arcuate recess 34 terminating at two opposing flanges 36, as shown in FIG. 4. The radius of the arcuate section corresponds to the outer radius of the pipe element 12. Each flange 36 has two rectangular apertures 38 therethrough as shown in FIG. 6. As each aperture 38 has in cross-section an outwardly facing tapered shoulder 40. As shown in FIGS. 3 and 5, the pipe engaging section 32 has reinforcing ribs 42 molded therein extending longitudinally from the leg section 24 to the pipe engaging section 32 opposite the arcuate recess to add structural rigidity to the clamp base member 16.
The cover member 20, as shown in FIGS. 3, 7 and 8, is a generally planar element with fastening prongs 44 integrally molded and extending upwardly from a generally planar flat surface 46 of the cover member 20. The prongs 44 are used to snap fit the cover member 20 and base member 14 together. More specifically, each prong 44 has a inclined top wall 48 and undercut shoulder 50. The inclined top wall 48 provides ease of entry into the apertures 38 with angled taper 40 and allows the prongs to flex to pass completely through the apertures and have its undercut shoulder 50 engage the surface 52 of flanges 36. A longitudinally extending rib 49 along each edge of member 20 adds to the structural rigidity of the cover member 20. A center groove 51 runs across the flat section 46 and can engage a longitudinal rib 55 in indented flat 22.
As clearly shown in FIG. 9, the flat 22 has an axial distance that is substantially the same as the width of cover member 20 such that the cover member 20 can be fitted across the flat 22 as shown in FIG. 1 with its respective edges 53 abutting against respective rises 54 at opposite ends of the flat 22.
The prongs 44 provide a self tightening feature. If the cover 20 is pulled from its center which would happen if an attempt is made to pry it open with a screw drive or similar tool, the prongs 44 bend inwardly to tighten the hold within the apertures 38.
The method for providing the clamp assembly commences with manufacturing a cylindrical pipe. The cylindrical pipe is then coated with a corrosion resistant coating. The pipe is also stamped to provide flat 22 therein. It is appreciated that the stamping of the pipe does not affect the integrity of a previously applied corrosion resistant coating. It is also appreciated that the corrosion resistant coating can be applied after the stamping of the flat 22.
After the pipe is provided with both the corrosion resistant coating and the flat 22, the pipe is then positioned in the clamp base member 10 such that its flat 22 is substantially planar with the flanges 36 and its opposite radius section abuts the pipe engaging section along the arcuate recess. The cover is snap fitted onto the base member capturing the flat such the pipe is axially and rotationally fixed to the clamp 14.
The leg section 24 can be affixed to the wall 18 or other equivalent support before or after the pipe and cover are affixed to the base member.
A second embodiment of a clamp base 116 is shown in FIG. 10. The clamp base 116 has a pipe engaging section 132 capable of receiving and retaining two parallel extending pipes (not shown). Section 132 has two parallel arcuate recesses 134 interposed between opposing flanges 136. The cover 20 is snap fitted in the same fashion as described above to retain the pipes.
Other variations and modifications are possible without departing from the scope and spirit of the present invention as defined by the appended claims.
|
A clamp assembly (10) includes a corrosion resistant coated pipe (12) secured to a plastic two piece clamp (14). The clamp has a arcuate pipe receiving base member (16) and a flat cover member (20) that is snap fitted to the base member to clamp about the pipe. The pipe has a flat (22) that abuts the cover member such that the pipe is secured against axial slippage and rotational movement with respect to the clamp (14).
| 5
|
REFERENCE TO RELATED APPLICATIONS
[0001] This is a continuation of pending International Patent Application PCT/KR2011/010201 filed on Dec. 28, 2011, which designates the United States and claims priority of Korean Patent Application No. 10-2011-0004159 filed on Jan. 14, 2011 and Korean Patent Application No. 10-2011-0124238 filed on Nov. 25, 2011, the entire contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a method for biologically treating sewage, wastewater, tannery wastewater and livestock manure, and more particularly to a method for biologically treating refractory wastewater, which can biologically treat refractory wastewater without performing physical or chemical pretreatment and can also reduce the generation of various offensive odors and sludge in a wastewater treatment process, and to an agent for treating wastewater.
BACKGROUND OF THE INVENTION
[0003] Generally, high-concentration refractory wastewater which is discharged from industries is responsible for the contamination of water in various aquatic ecological environments. Among industrial sources that discharge high-concentration refractory wastewater, livestock farms are mostly petty and stand close together in water supply source areas adjacent to large aquatic ecological environments, and thus water contamination caused thereby is significantly serious. In addition, in livestock farms, a large amount of sludge (which is formed by precipitation of impurities contained in water or oil) is generated during the treatment of livestock manure, and the generated sludge is treated at high costs and becomes a serious problem in the management of livestock farms.
[0004] Moreover, tannery wastewater which is generated in leather manufacturing companies is typical high-concentration refractory wastewater containing various organic materials, chemicals, heavy metals and the like and is treated by physical and chemical methods worldwide, and biological methods for treating tannery wastewater are used as auxiliary methods.
[0005] In Korea, in the case of tannery wastewater, the T-N discharge limit was 60 mg/l and the COD discharge limit was 90 mg/l. It was considered that these discharge limits were very strict limits which could not be substantially satisfied with current technologies. For this reason, in the year 2004, the Korean Ministry of Environment relaxed the T-N discharge limit to 200 mg/l for some raw hide processing facilities only. Even at present (August, 2010), leather manufacturing companies are requesting that the discharge limit be further relaxed.
[0006] Specifically, current technologies cannot treat such refractory wastewater at satisfactory levels. Furthermore, because biological treatment is insufficient for treatment of such wastewater, physical and chemical pretreatment is performed before biological treatment, and thus in most cases, sludge is caused by precipitation of large amounts of chemicals. In addition, a severe offensive odor occurs during the treatment process, and it is difficult to treat sludge generated during the treatment process. Accordingly, a fundament solution to these problems and an effective method for treatment of wastewater are been urgently required.
SUMMARY OF THE INVENTION
Technical Problem
[0007] Accordingly, the present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is to propose a possibility of biologically treating high-concentration refractory wastewater such as livestock manure or tannery wastewater and to a method for biologically treating refractory wastewater, which can reduce the generation of sludge during wastewater treatment.
[0008] Another object of the present invention is to provide a wastewater treatment agent for treating high-concentration refractory wastewater such as livestock manure or tannery wastewater.
Technical Solution
[0009] In order to accomplish the above objects, the present invention provides a method for biologically treating refractory wastewater, the method comprising the steps of: maintaining a mixture of 0.01-1 wt % of microorganism BM-S-1 (accession number: KCTC 11789BP), 0.1-1 wt % of powdery chaff, 0.1-1 wt % of powdery peat moss, 1-5 wt % of molasses, 0.01-1 wt % of shiitake mushroom waste wood powder and 92-98 wt % of water at 15 to 28° C. to prepare a liquid microbial agent; mixing 50-90 wt % of a medium with 5-50 wt % of the liquid microbial agent to prepare a mixed material; inoculating 100 parts by weight of the mixed material with 0.01-1 part by weight of the microbial mixture (BM-S-1) at a high temperature of 65° C. to 85° C., incubating the mixed material inoculated at a high temperature; drying the incubated mixed material; incubating the dried mixed material in a liquid state to prepare a microbial solution; and proliferating and activating microorganisms of the microbial solution before introducing the microbial solution into wastewater.
[0010] According to a preferred embodiment of the present invention, the wastewater is selected from among livestock manure, tannery wastewater and refractory wastewater, and the microbial solution is fixed on a carbohydrate medium.
[0011] A wastewater treatment agent according to a preferred embodiment of the present invention is prepared by mixing 0.01-1 wt % of microorganism BM-S-1 (accession number: KCTC 11789BP), 0.1-1 wt % of powdery chaff, 0.1-1 wt % of powdery peat moss, 1-5 wt % of molasses, 0.01-1 wt % of shiitake mushroom waste wood powder and 92-98 wt % of water.
Advantageous Effects
[0012] According to the present invention, the following effects can be provided.
[0013] According to the present invention, livestock manure and tannery wastewater, known as high-concentration refractory wastewater, are treated by the biological method only. The treatment efficiency of the biological method of the present invention is higher than that of a conventional physical/chemical process, and the method of the present invention significantly reduces the generation of offensive odors and the generation of sludge.
[0014] In addition, environmental improvement charges of farmhouses or enterprises can be reduced, thus reducing production costs.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 is a flowchart showing the biological treatment of refractory wastewater according to a preferred embodiment of the present invention.
[0016] FIG. 2 shows a configuration for the biological treatment of refractory wastewater according to a preferred embodiment of the present invention.
[0017] FIG. 3 shows T-N measurement values obtained in Test Example 1 of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0018] Hereinafter, the present invention will be described in further detail.
[0019] The present invention is directed to a biological treatment method for efficiently purifying tannery wastewater, livestock manure or the like, which has a high degree of contamination and contains large amounts of poorly degradable materials, unlike general river sewage.
[0020] A microbial mixture (BM-S-1) that is used in the present invention was deposited at the Korean Collection for Type Culture (KCTC) of the Korea Research Institute of Bioscience and Biotechnology under accession number KCTC 11789BP on Oct. 20, 2010. The results of analysis of the microbial mixture (BM-S-1) showed that the microbial mixture is composed of about 130 bacterial strains (see Table 1), including Prevotellaceae_uc_s, Lactobacillus _uc, Lactobacillus parabuchneri , Lactobacillaceae_uc_s, Lactobacillus paracasei, Lactobacillus parafarraginis, Lactobacillus camelliae, Lactobacillus manihotivorans, Acetobacter lovaniensis, Ethanoligenens _uc, Veillonellaceae_uc_s, Lactobacillus similis, Lactobacillus harbinensis and Rhodospirillales _uc_s, and yeast ( Candida boidinii ).
[0021] Table 1 below shows the distribution of species in the microbial mixture (BM-S-1), analyzed by pyrosequencing.
[0000]
TABLE 1
Name of species
Ratio (%)
Prevotellaceae_uc_s
22.2
Lactobacillus_uc
17.7
Lactobacillus parabuchneri
6.9
Lactobacillaceae_uc_s
6.5
Lactobacillus paracasei
5.8
Lactobacillus parafarraginis
4.3
Lactobacillus camelliae
3.0
Lactobacillus manihotivorans
2.4
Acetobacter lovaniensis
2.3
Lactobacillus collinoides
2.2
Lactobacillus vini
2.0
Lactobacillus hilgardii
1.8
Lactobacillus pentosus
1.7
Lactobacillus rapi
1.5
Lactobacillus pantheris
1.3
Ethanoligenens_uc
1.2
Veillonellaceae_uc_s
1.2
Lactobacillus similis
1.2
Lactobacillus harbinensis
1.0
Rhodospirillales_uc_s
0.5
Others
13.8
Total
100.0
[0022] In this table, the data are results of analysis of a total of 6801 clones, and “uc_s” means unclassified species.
[0023] Lactobacillus sp. inhibits the growth of harmful microorganisms such as pathogenic microorganisms by making the surrounding environment acidic or generating hydrogen peroxide. It lives mainly in waste plant matter and is also found in the bowels of humans or animals while showing probiotic activity. The Rhodospirillales order is divided into Acetobacteraceae and Rhodospirillaceae. Acetobacteraceae includes Acetobacter lovaniensis shown in Table 1, and Acetobacter lovaniensis is an aerobic microorganism that forms acetic acid from alcohol and lives in the root, stem, leaf and the like of various plants (sugar canes, sweet potatoes, coffee trees, tea plants, bananas, etc.).
[0024] Rhodospirillaceae includes purple non-sulfur bacteria and green non-sulfur bacteria, which either grow using various organic acids or ethanol, produced by Lactobacillus sp., Acetobacter sp. and other anaerobic bacteria ( Ethanoligenens sp.), which are present in the microbial agent of the present invention, or fix CO2 through a photosynthetic process and play a major role in the purification of wastewater contaminated with organic materials. Prevotellaceae which is present in the microbial agent of the present invention at a significant density is present in the bowels of normal warm-blooded mammals (humans, animals, etc.), and is believed to function to convert sugars to succinic acid or acetic acid and contribute to the rapid decomposition of organic materials.
[0025] It was found that the dominant yeast identified in the microbial agent of the present invention was Candida boidinii , which is believed to make physiologically active substances such as vitamins or amino acids, which contribute to the growth of the microbial mixture (BM-S-1) and the decomposition of organic matter.
[0026] This microbial mixture (BM-S-1) was isolated in the following manner.
[0027] A soil sample (bamboo humus, ruminant non-digested material, or broad-leaved tree humus) was collected and mixed with a culture medium (rice bran, chaff, sawdust, egg shells, other shells, or peat moss) crushed to a size of 80-120 mesh, and the mixture was adjusted to a water activity of 40-60% and cultured on soil in a semi-shade condition for 90 days.
[0028] A medium obtained by mixing 10 wt % of rice bran, 40 wt % of chaff, 25 wt % of peat moss and 25 wt % of sawdust was adjusted to a water activity of 60%, and then the above-cultured sample was inoculated onto the medium in an amount of 0.01 parts by weight based on 100 parts by weight of the medium and was fermented while shaking at a temperature of 80 to 90° C. for 4 hours, and after 3 weeks it was fermented, thereby preparing a powdery microbial mixture having a water concentration of 8% or less. The isolated microbial mixture (BM-S-1) that is used in the present invention was deposited at the Korean Collection for Type Culture (KCTC) of the Korea Research institute of Bioscience and Biotechnology under accession number KCTC 11789BP on Oct. 20, 2010.
[0029] The method for biologically treating refractory wastewater using the isolated microbial mixture comprises the steps of preparing a liquid microbial agent, preparing a mixed material, inoculating the mixed material at a high temperature, incubating the mixed material, drying it, preparing a microbial solution, and activating microorganisms.
[0030] In the step of preparing the liquid microbial agent, a mixture of 0.01-1 wt % of microorganism BM-S-1 (accession number: KCTC 11789BP), 0.1-1 wt % of powdery chaff, 0.1-1 wt % of powdery peat moss, 1-5 wt % of molasses, 0.01-1 wt % of shiitake mushroom waste wood powder and 92-98 wt % of water is maintained at a temperature of 15 to 28° C. while air is introduced therein at a rate of 6×103 to 8×103 L/min for 2-4 (aeration process), and the aeration process is stopped for a period of 2-4 days. The aeration process and the non-aeration process are repeatedly performed for 18-36 days, thereby preparing the liquid microbial agent. The conditions of the aeration process and the like are the optimum results determined based on the results of studies conducted by the present inventors, and the above culture conditions can be somewhat modified without departing from the scope of the present invention.
[0031] After preparing the liquid microbial agent, 50-95 wt % of at least one medium selected from the group consisting of pre-fermented peat moss and chaff is mixed with 5-50 wt % of the liquid microbial agent to prepare a mixed material.
[0032] Then, the step of inoculating 0.01-1 part by weight of the microbial mixture (BM-S-1) onto 100 parts by weight of the mixed material is performed.
[0033] The microbial agent of the present invention comprises, as a medium, chaff or peat moss, which is relatively easily available and inexpensive. In addition, forest byproducts, agricultural byproducts or food waste may be used as the medium. As the medium, chaff, peat moss, forest byproducts and agricultural byproducts may be used alone or in combination, but the medium is preferably used in a powdery state after it is crushed to a size of about 80-160 mesh and pre-fermented before use.
[0034] The mixed and crushed materials are placed in a shaking incubator, and the water content is adjusted to provide an environment suitable for microbial fermentation, after which the microbial mixture (BM-S-1) is inoculated.
[0035] The microbial mixture can be prepared in a powdery state by collecting a microbial phase from soil having seasonal and environmental diversities without filtration, and adapting the collected microbial phase to the environment on a carbohydrate medium for 6-9 months to remove harmfulness from the microbial phase.
[0036] In the preparation of the microbial agent according to the present invention, the microbial mixture (BM-S-1) is preferably inoculated in an amount of 0.01-1 part by weight based on 100 parts by weight of the mixed material.
[0037] The step of inoculating the mixed material at a high temperature of 65° C. to 85° C. for 4-6 hours is performed. In view that the fact that common microbial inoculation is generally performed at a temperature ranging from 20° C. to 40° C., it can be seen that the inoculation in the method of the present invention is performed at a high temperature. Particularly, in an embodiment of the present invention, the medium inoculated with the microbial mixture is stirred at a temperature of 65° C. to 85° C. for 4-6 hours at a speed of 60-180 rpm. The stirring is performed at 65° C. or higher in order to induce the thermal denaturation of the medium components to induce the proliferation of soil microorganisms, but is performed at 85° C. or lower in order to induce the activation of the microbial mixture according to the present invention.
[0038] The reason why the high-temperature inoculation is selected is because the diversity of strains in culture at a high temperature of 65 to 85° C. is 3-5 times higher than that in culture at a middle/low temperature of 20 to 40° C.
[0039] After the high-temperature inoculation step, the cultured material is optionally naturally cooled to room temperature, and is then placed in a porous container and cultured for 28-45 days, followed by drying. The dried material may be ground to a size of 120 mesh or less to maximize water affinity, thereby preparing a microbial fine powder product having high water affinity. In addition, the method of the present invention may further comprise a step of adding 13-16 parts by weight of the liquid microbial agent to the post-fermented powder and molding the mixture using a molding device.
[0040] Although the drying or grinding process may also be performed to provide powder, the molding process may be performed if necessary, and the water is supplied for molding. The molding process is not specifically limited, but in an example of the present invention, the cultured microbial agent was molded using a molding machine having a treatment capacity of 500-700 kg per hour, thereby obtaining pellets.
[0041] After the culture or molding step, an aging step of post-fermenting the cultured microbial agent may also be performed. The drying step may be performed using any known drying method that does not cause thermal denaturation of microorganisms, and is not specifically limited. In an example of the present invention, hot-air drying at 40 to 60° C. was performed.
[0042] In addition, the method of the present invention comprises a step of culturing the dried material in a liquid state to prepare a microbial solution, and a step of proliferating and activating the microorganisms of the microbial solution before adding the microbial solution to wastewater.
[0043] This is because it is effective to add microorganisms activated in situ to a wastewater treatment tank so that the function of the microorganisms can be exhibited rapidly, compared to adding the microorganisms directly to the wastewater treatment tank. In order to activate the microorganisms as described above, it is more advantageous to induce the activation of the microorganisms by dilution to activate the microorganisms in a liquid medium containing 10-20 wt % of effluent wastewater to which the microbial solution is to be applied. In other words, the use of the activation medium is more preferable because it increases the activity of the microorganisms and shortens the degradation period.
[0044] The method of adding the microorganisms after activation is performed in order to stably and continuously maintain the activity of the microorganisms, and specific examples of this method are already known in the art.
[0045] According to the wastewater treatment method of the present invention, tannery wastewater or livestock manure, which have high COD values and contain high concentrations of nitrogen compounds, can be treated using the microbial agent of the present invention so that the values are reduced below standard limits. In addition, the microbial agent of the present invention may, if necessary, contain various additives, for example, minerals (flocculants), alginic acid and its salts, organic acids, a protective colloidal thickener, an agent that is used in molding, and the like. The microbial agent that is prepared as described above may be added using any method that can uniformly disperse the microbial agent in a treatment tank. For example, the microbial agent in a storage container may be manually added directly to wastewater in a treatment tank while air is introduced or stirring is performed using a stirrer. The total capacity of a plurality of wastewater treatment tanks and the retention time vary depending on the amount of wastewater, but the retention time of wastewater in the plurality of treatment tanks is generally adjusted to the range from about 0.3 days to about 28 days. Particularly, the retention time is preferably adjusted to a range of about 0.5 days to about 11 days. Also, the number of treatment tanks is not limited, but is preferably 3-5 from the viewpoint of efficiency and equipment cost.
[0046] Treatment with the microbial agent is controlled by measuring pH, dissolved oxygen (DO), the COD values before and after treatment, and the like. The pH is 4.0-8.5, and preferably 5.5-8.0, and a narrower pH range can be selected depending on the nature of the wastewater. The DO is 3.0 mg/l-13.0 mg/l, and preferably 5.0 mg/l-9.0 mg/l. The pH can be controlled by addition of an acid or alkali, and the DO can be controlled by adding air to sewage to control water drainage and purification. The concentration of a specific compound can be measured by direct quantification, but CODmn corresponding to concentration is actually used. The measurement of CODmn is preferably performed by measuring concentrations in both an inlet of a first wastewater treatment tank and an outlet of a final treatment tank. In the wastewater treatment process, a carbon source, a nitrogen source, an organic nutrient source or an inorganic salt, which is suitable for growth of microorganisms, can be introduced. Examples of the organic nutrient source include polypeptone, yeast extract, meat extract, molasses and the like, and examples of the inorganic nutrient source include various phosphates, magnesium salts and the like. The organic nutrient source is added in an amount of about 0.001-0.005 wt %, and preferably about 0.001-0.002 wt %, based on the weight of wastewater, and the inorganic nutrient source is added in an amount of about 0.01-0.1 wt % based on the weight of the organic nutrient source. These amounts are not limited and are suitably selected depending on the nature or state of wastewater.
[0047] The method for treating wastewater using the microbial agent obtained as described above satisfies current wastewater discharge limits. In addition, when the method was applied for 6 months, a daily sludge generation of about 40-50 tons before treatment was reduced by about 85% on average, which corresponds to a decrease in cost of 40-50 million Won (Korean currency). Furthermore, it is expected that an astronomical cost for treatment of sludge will be incurred after the year 2011 from which the ocean dumping of sludge is prohibited.
[0048] 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 only and are not intended to limit the scope of the present invention.
Example 1
Culture of Microbial Mixture
[0049] A microorganism-containing soil sample (bamboo humus, pine tree humus, oak waste, or broad-leaved tree humus) was heat-treated at 60° C. for 30 minutes, and then ground finely with a mortar and pestle. Then, 1 g of the sample was taken, suspended in 9 ml of 0.85% NaCl and diluted by a factor of 100 to 10-6. 100 μl of each of the diluted suspensions was plated on TSA, BL, and BBL media (DIFCO) and cultured at 28° C., thereby culturing the microbial mixture.
Example 2
Preparation of Wastewater Treatment Agent
[0050] 0.05 kg of the microbial mixture (BM-S-1) cultured as described above, 0.2 kg of powdery chaff, 0.2 kg of powdery peat moss, 2.5 kg of molasses and 0.1 kg of shiitake mushroom waste wood powder were mixed with potable water to a total weight of 100 kg. The mixture was maintained at 15 to 28° C. while air was introduced therein at a rate of 60 cm 3 /min for 3 days (aeration) and the aeration process was stopped for a period of 3 days. The aeration process and the non-aeration process were repeatedly performed for 30 days, thereby preparing a liquid microbial agent. The total cell count of the liquid microbial agent was 2.8×109 cfu/g.
[0051] Meanwhile, 45 kg of crushed chaff and 45 kg of peat moss powder were placed in a shaking incubator and mixed for 30 minutes. 10 kg of the liquid microbial agent was added to the mixed material to obtain a culture medium, and the culture medium was adjusted to a water activity of 50-60%, after which the soil microbial mixture was inoculated onto the culture medium in an amount of 0.02 wt % based on the total weight of the culture medium. The inoculated culture medium was incubated in an incubator at a temperature of 65 to 80° C. for 5 hours while it was rotated at a speed of 120 rpm. The incubated material was cooled to 20° C. and dried in hot air at 60° C., thereby preparing 90 kg of a powdery microbial agent having a water content of less than 10%.
Test Example 1
Application to Tannery Wastewater
[0052] The microbial agent prepared in the example of the present invention was applied to a public wastewater treatment system of the Pusan Shinpyung Janglim Leather Industry Association (Korea).
[0053] First, 5 kg of a seed, 15 kg of the powdery microbial agent and 25 kg of molasses were placed in a 1-ton tank, and the content of the tank was aged for 24 hours while stirring. 1 ton of the content was diluted in 10 tons of water and activated for 24 hours, after which the dilution was placed in a 30-ton tank.
[0054] When the safety inventory of the 30-ton tank was 20 tons, 10 tons of the dilution was added thereto. The liquid microbial agent in the 30-ton tank was controlled at a flow rate of 5 tons per day, and no chemical treatment process was performed. As a result, there was little or no generation of sludge, and the generation of offensive odors was reduced.
[0055] As shown in Tables 2 and 3 below (test example for tannery wastewater treatment using the microbial agent), the quality of effluent water was significantly improved as can be seen from the results of measurement of BOD, COD and T-N.
[0000]
TABLE 2
July
August
September
October
COD
SS
T-N
COD
SS
T-N
COD
SS
T-N
COD
SS
T-N
Raw water
2100
2500
700
2200
2400
680
2150
2550
710
2200
2400
800
Primary
250
1000
240
260
980
231
210
931
210
220
930
210
settling
tank
Secondary
90
100
93
88
96
91
82
91
91
91
120
96
settling
tank
Tertiary
15
12
25
18
15
29
23
12
21
10
15
12
settling
tank
Treatment
95.7
96.0
86.7
96.0
96.0
86.6
96.2
96.4
87.2
95.9
95.0
88.0
efficiency
(%)**
Treatment
99.3
99.5
96.4
99.2
99.4
95.7
98.9
99.5
97.0
99.5
99.4
98.5
efficiency
(%)***
[0000]
TABLE 3
November
December
COD
SS
T-N
COD
SS
T-N
Raw water
2500
2600
800
2400
2300
650
Primary
230
1020
250
270
1100
270
settling
tank
Secondary
96
99
102
110
121
108
settling
tank
Tertiary
27
25
30
45
27
50
settling
tank
Treatment
96.2
96.2
87.3
95.4
94.7
83.4
efficiency
(%)**
Treatment
98.9
99.0
96.3
98.1
98.8
92.3
efficiency
(%)***
[0056] In Tables 2 and 3, unit: mg/; ** treatment efficiency of the secondary settling tank relative to raw water; *** treatment efficiency of the tertiary secondary settling tank relative to raw water.
[0057] 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.
INDUSTRIAL APPLICABILITY
[0058] The present invention relates to a method for biologically treating sewage, wastewater, tannery wastewater and livestock manure, and more particularly to a method for biologically treating refractory wastewater, which can biologically treat refractory wastewater without performing physical or chemical pretreatment and can also reduce the generation of various offensive odors and sludge in a wastewater treatment process, and to an agent for treating wastewater.
|
The biological treatment method for refractory wastewater of the present invention includes: a step of producing a complex microbial liquid by maintaining, at between 15 and 28° C., a complex microbial liquid obtained by mixing between 0.01 and 1 percent by weight of mixed microorganisms BM-S-1 (Repository Deposit No. KCTC 11789BP), between 0.1 and 1 percent by weight of powdered chaff, between 0.1 and 1 percent by weight of powdered peat moss, between 1 and 5 percent by weight of molasses, between 0.01 and 1 percent by weight of shiitake mushroom waste wood dust and between 92 and 98 percent by weight of water; a mixed stock production step; a high-temperature inoculation step; a culturing step; a drying step; a microbial starting broth production step; and a microbe activation step.
| 2
|
CROSS-RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application No. 60/837,770, filed on Aug. 15, 2006. The content of which is hereby incorporated by reference in its entirety.
BACKGROUND
[0002] Tumor necrosis factor alpha (TNFα), a mononuclear cytokine, possesses various biological activities, such as killing cancer cells or inhibiting growth of cancer cells, enhancing the phagocytosis of neutrophilic granulocyte, and up-regulating the production of peroxide region. Interleukin-1 beta (IL-1β), a cytokine secreted by monocyte macrophages and dendritic cells, mediates immune and inflammatory responses. Nuclear factor-kappa B (NF-κB), a pro-inflammatory transcription factor, upregulates cytokines (e.g., TNFα and IL-1β) and thereby mediates the inflammatory response. Inducible nitric oxide synthase (iNOS) is induced by endotoxins or cytokines (e.g., TNFα and IL-1β). It catalyzes the production of nitric oxide, an important pleiotropic molecule, from L-arginine and oxygen.
[0003] TNFα, IL-1β, NF-κB, and iNOS all play critical roles in important physiological and pathological processes. A wide range of diseases, e.g., autoimmune disease, cancer, atherosclerosis, or diabetes, can be treated by modulating their expression or activity. See, e.g., Ogata H, Hibi T. et al Curr Pharm Des. 2003; 9(14): 1107-13; Taylor P C. et al Curr Pharm Des. 2003; 9(14): 1095-106; Fan C., et al. J. Mol. Med 1999, 77, 577-592; and Alcaraz et al., Current Pharmaceutical Design, 2002: 8, 215.
SUMMARY
[0004] This invention is based on an unexpected finding that a number of costunolide derivatives inhibited effect on the expression of TNFα, IL-1β, and iNOS, and the activity of NF-κB.
[0005] One aspect of this invention features costunolide derivatives having the following formula:
in which X is CH 2 and Y is NR 1 R 2 , OCONR 1 R 2 , SR 1 , or OR 3 ; or X is C(O) and Y is NR 1 R 2 , OR 1 , or SR 1 ; in which each of R 1 and R 2 , independently, is H, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, or R 1 , R 2 , and N to which they are attached, taken together, form a saturated or unsaturated 3-8 membered ring, optionally substituted with R 1 ′, OR 2 ′, NR 2 ′R 3 ′, SR 2 ′, C(O)R 2 ′, CO 2 R 2 ′, or C(O)NR 2 ′R 3 ′, R 1 ′ being alkyl, cycloalkyl, heterocycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, and each of R 2 ′ and R 3 ′, independently, being H, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl; and R 3 is alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl; and Z is a bond or O.
[0006] Referring to the compounds of the above formula, a subset features that Y is NR 1 R 2 , in which R 1 and R 2 , independently, is H, alkyl, or aryl; or NR 1 R 2 , together, is a morpholinyl or piperidinyl. Another subset features that X is C(O) and Y is OR 1 , in which R 1 is H or alkyl; or X is CH 2 and Y is OR 3 , in which R 3 is alkyl. A further subset features Z is a double bond.
[0007] Shown below are exemplary compounds of this invention:
No. Name Structure 1 (3aR,6Z,10E,11aR)-10-methyl-3-methylene-2- oxo-2,3,3a,4,5,8,9,11a-octahydrocyclodeca [b]furan-6-carboxylic acid 2 (3aR,6Z,10E,11aR)-N,10-dimethyl-3- methylene-2-oxo-2,3,3a,4,5,8,9,11a- octahydrocyclodeca[b]furan-6-carboxamide 3 (3aR,6Z,10E,11aR)-N,N-diethyl-10-methyl-3- methylene-2-oxo-2,3,3a,4,5,8,9,11a- octahydrocyclodeca[b]furan-6-carboxamide 4 (3aR,6Z,10E,11aR)-10-methyl-3-methylene-2- oxo-N-propyl-2,3,3a,4,5,8,9,11a- octahydrocyclodeca[b]furan-6-carboxamide 5 (3aR,6Z,10E,11aR)-10-methyl-3-methylene-6- (piperidine-1-carbonyl)-3,3a,4,5,8,9- hexahydrocyclodeca[b]furan-2(11aH)-one 6 (3aR,6Z,10E,11aR)-10-methyl-3-methylene-6- (morpholine-4-carbonyl)-3,3a,4,5,8,9- hexahydrocyclodeca[b]furan-2(11aH)-one 7 (3aR,6Z,10E,11aR)-10-methyl-3-methylene-6- ((propylamino)methyl)-3,3a,4,5,8,9- hexahydrocyclodeca[b]furan-2(11aH)-one 8 (3aR,6Z,10E,11aR)-6-((2- hydroxyethylamino)methyl)-10-methyl-3- methylene-3,3a,4,5,8,9- hexahydrocyclodeca[b]furan-2(11aH)-one 9 (3aR,6Z,10E,11aR)-10-methyl-3-methylene-6- (morpholinomethyl)-3,3a,4,5,8,9- hexahydrocyclodeca[b]furan-2(11aH)-one 10 (3aR,6Z,10E,11aR)-10-methyl-3-methylene-2- oxo-N-(4-fluoro-benzyl)-2,3,3a,4,5,8,9,11a- octahydrocyclodeca[b]furan-6-carboxamide 11 (3aR,6Z,10E,11aR)-10-methyl-3-methylene-2- oxo-N-(4-phenoxyphenyl)-2,3,3a,4,5,8,9,11a- octahydrocyclodeca[b]furan-6-carboxamide 12 (3aR,6Z,10E,11aR)-10-methyl-3-methylene-2- oxo-N-(2-methoxyethyl)-2,3,3a,4,5,8,9,11a- octahydrocyclodeca[b]furan-6-carboxamide 13 (3aR,6Z,10E,11aR)-10-methyl-3-methylene-2- oxo-N-(3-(N-methylbenzamide)- 2,3,3a,4,5,8,9,11a-octahydrocyclodeca[b]furan- 6-carboxamide 14 (3aR,6Z,10E,11aR)-methyl-10-methyl-3- methylene-2-oxo-2,3,3a,4,5,8,9,11a- octahydrocyclodeca[b]furan-6-carboxylate 15 ((3aR,6Z,10E,11aR)-10-methyl-3-methylene-2- oxo-2,3,3a,4,5,8,9,11a- octahydrocyclodeca[b]furan-6-yl)methyl cyclopropylcarbamate 16 ((3aR,6Z,10E,11aR)-10-methyl-3-methylene-2- oxo-2,3,3a,4,5,8,9,11a- octahydrocyclodeca[b]furan-6-yl)methyl benzylcarbamate 17 ((3aR,6Z,10E,11aR)-10-methyl-3-methylene-2- oxo-2,3,3a,4,5,8,9,11a- octahydrocyclodeca[b]furan-6-yl)methyl ethylcarbamate
[0008] The term “alkyl,’ unless stated otherwise, refers to a straight or branched hydrocarbon containing 1-20 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and t-butyl.
[0009] The term “alkenyl” refers to a straight or branched hydrocarbon having one or more carbon-carbon double bonds. The term “alkynyl” refers to a straight or branched hydrocarbon having one or more carbon-carbon triple bonds. Alkenyl and alkynyl, unless stated otherwise, contain 1-20 carbon atoms.
[0010] The term “cycloalkyl,” unless stated otherwise, refers to a saturated and partially unsaturated cyclic hydrocarbon group having 3 to 12 carbon atoms. Examples of cyclyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, and cyclooctyl. The term “heterocycloalkyl” refers to a saturated or partially unsaturated cyclic hydrocarbon group having 2 to 12 carbon atoms and at least one heteroatom selected from N, O, and S.
[0011] The term “aryl,” unless stated otherwise, refers to a 6-carbon monocyclic, 10-carbon bicyclic, 14-carbon tricyclic aromatic ring system wherein each ring may have 1 to 4 substituents. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, and anthracenyl.
[0012] The term “heteroaryl” refers to an aromatic 5-8 membered monocyclic, 8-12 membered bicyclic, or 11-14 membered tricyclic ring system having one or more heteroatoms (such as O, N, or S). Examples of heteroaryl groups include pyridyl, furyl, imidazolyl, benzimidazolyl, pyrimidinyl, thienyl, quinolinyl, indolyl, and thiazolyl.
[0013] Alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl can be either substituted or unsubstituted. For examples, these moieties can be substituted with groups containing zero to six heteroatoms selected from halogen, oxygen, sulfur, and nitrogen. Possible substituents on alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl include alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, amino, alkylamino, dialkylamino, arylamino, diarylamino, hydroxyl, halogen, thio, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, acylamino, aminoacyl, amidino, guanidino, ureido, cyano, nitro, acyl, acyloxy, carboxyl, and carboxylic ester. Possible substituents on alkyl include all of the above-said substituents except alkyl.
[0014] The compounds described above include their pharmaceutically acceptable salts and prodrugs, if applicable. Such a salt can be formed between a positively charged ionic group in the compounds (e.g., ammonium) and a negatively charged counterion (e.g., trifluoroacetate). Likewise, a negatively charged ionic group in the compounds (e.g., carboxylate) can also form a salt with a positively charged counterion (e.g., sodium, potassium, calcium, or magnesium). The compounds may contain a non-aromatic double bond and one or more asymmetric centers. Thus, they can occur as racemic mixtures, single enantiomers, individual diastereomers, diastereomeric mixtures, and cis- or trans-isomeric forms. All such isomeric forms are contemplated. As an example, the compounds of this invention can be isomers having the stereochemistry as shown in the following formula:
[0015] Another aspect of this invention features a method of inhibiting the expression of TNFα, IL-1β, or iNOS, or inhibiting the activity of NF-κB. More specifically, the method includes administering to a subject in need thereof an effective amount of the compound of the following formula:
In which X is CH 2 or C(O); Y is NR 1 R 2 , OCONR 1 R 2 , OR 1 , or SR 1 ; in which each of R 1 and R 2 , independently, is H, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, or R 1 , R 2 , and N to which they are attached, taken together, form a saturated or unsaturated 3-8 membered ring, optionally substituted with R 1 ′, OR 2 ′, NR 2 ′R 3 ′, SR 2 ′, C(O)R 2 ′, CO 2 R 2 ′, C(O)NR 2 ′R 3 ′, R 1 ′ being alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, and each of R 2 ′ and R 3 ′, independently, being H, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl; and Z is a bond or O; or a pharmaceutically acceptably salt or a stereoisomer thereof.
[0016] Still another aspect of this invention features a method of treating disease associated with TNFα, IL-1β, iNOS, or NF-κB (e.g., autoimmune disease, cancer, atherosclerosis, or diabetes) by administering to a subject in need thereof an effective amount of one or more the just-described compounds.
[0017] Also within the scope of this invention is a composition containing the above-described compound and a pharmaceutically acceptable carrier for use in treating autoimmune disease, cancer, atherosclerosis, or diabetes, as well as the use of such a composition for the manufacture of a medicament for treating such a disease.
[0018] The details of one or more embodiments of the invention are set forth in the description below. Other features, objects, and advantages of the invention will be apparent from the description and from the claims.
DETAILED DESCRIPTION
[0019] The compounds of this invention can be synthesized by synthetic methods well known in the art. An exemplary synthetic route is shown in Scheme 1 below.
[0020] In Scheme 1, the starting costunolide aldehyde and chloro derivatives of costunolide can be prepared by the method described in Macias F. A., et al. Tetra. Lett., 2004, 60, 8477-8488. They are transformed to an amino compound by reductive amination or an ether (thioether) compound by substitution.
[0021] As another example, carboxy, amide, or ester derivatives of costunolide can be prepared from costunolide aldelhyde. As shown in Scheme 2 below, the aldehyde compound can be readily oxidized to give a carboxylic acid. The carboxylic acid is reacted with an amino compound to form an amide compound.
[0022] Scheme 3 below illustrates an example of synthesizing costunolide carbamate compounds from costunolide alcohol. Costunolide alcohol can be prepared by the method described in Macias F. A., et al. Tetra. Lett., 2004, 60, 8477-8488.
[0023] The above-described synthetic methods demonstrate the synthesis of only certain costunolide derivatives of this invention. A skilled person in the art, in view of these examples, would be able to modify the methods to synthesize other costunolide derivatives of this invention. Alternatively, the skilled person can use other methods well known in the art to synthesize the costunolide derivatives of this invention. The compounds thus synthesized can be further purified by column chromatography, high performance liquid chromatography, or crystallization.
[0024] Synthetic chemistry transformations and protecting group methodologies (protection and deprotection) useful in synthesizing applicable compounds are known in the art and include, for example, those described in R. Larock, Comprehensive Organic Transformations, VCH Publishers (1989); T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, 3 rd Ed., John Wiley and Sons (1999); L. Fieser and M. Fieser, Fieser and Fieser's Reagents for Organic Synthesis, John Wiley and Sons (1994); and L. Paquette, ed., Encyclopedia of Reagents for Organic Synthesis, John Wiley and Sons (1995) and subsequent editions thereof.
[0025] The costunolide derivatives described above show effective inhibition against expression of TNFα, IL-1β, and iNOS and activity of NF-κB. Thus, this invention relates to a method of inhibiting expression of TNFα, IL-1β, and iNOS and activity of NF-κB by contacting it with an effective amount of one or more costunolide derivatives. Also included in this invention is a method of treating autoimmune disease, cancer, atherosclerosis by administering to a subject who needs the treatment an effective amount of one or more of the costunolide derivatives described above. Examples of the autoimmune disease includes, but are not limited to, rheumatoid arthritis, osteoarthritis, inflammatory bowels diseases, psoriasis, multiple sclerosis, sepsis, or diabetes. The term “treating” refers to application or administration of one or more of the costunolide derivatives to a subject, who has autoimmune disease, cancer, or atherosclerosis, a symptom of the disease, or a predisposition toward the disease, with the purpose to cure, heal, alleviate, relieve, alter, remedy, ameliorate, improve, or affect the disease, the symptom, or the predisposition. “An effective amount” refers to the amount of the costunolide derivative which is required to confer the desired effect on the subject. Effective amounts vary, as recognized by those skilled in the art, depending on route of administration, excipient usage, and the possibility of co-usage with other therapeutic treatments such as use of other active agents.
[0026] To practice the methods of this invention, a composition having one or more of the costunolide derivatives described above can be administered parenterally, orally, nasally, rectally, topically, or buccally. The term “parenteral” as used herein refers to subcutaneous, intracutaneous, intravenous, intramuscular, intraarticular, intraarterial, intrasynovial, intrasternal, intrathecal, intralesional, or intracranial injection, as well as any suitable infusion technique.
[0027] A sterile injectable composition can be a solution or suspension in a non-toxic parenterally acceptable diluent or solvent, such as a solution in 1,3-butanediol. Among the acceptable vehicles and solvents that can be employed are mannitol and water. In addition, fixed oils are conventionally employed as a solvent or suspending medium (e.g., synthetic mono- or diglycerides). Fatty acids, such as oleic acid and its glyceride derivatives, are useful in the preparation of injectables, as are natural pharmaceutically acceptable oils, such as olive oil or castor oil, especially in their polyoxyethylated versions. These oil solutions or suspensions can also contain a long chain alcohol diluent or dispersant, carboxymethyl cellulose, or similar dispersing agents. Other commonly used surfactants such as Tweens or Spans or other similar emulsifying agents or bioavailability enhancers which are commonly used in the manufacture of pharmaceutically acceptable solid, liquid, or other dosage forms can also be used for the purpose of formulation.
[0028] A composition for oral administration can be any orally acceptable dosage form including capsules, tablets, emulsions and aqueous suspensions, dispersions, and solutions. In the case of tablets, commonly used carriers include lactose and corn starch. Lubricating agents, such as magnesium stearate, are also typically added. For oral administration in a capsule form, useful diluents include lactose and dried corn starch. When aqueous suspensions or emulsions are administered orally, the active ingredient can be suspended or dissolved in an oily phase combined with emulsifying or suspending agents. If desired, certain sweetening, flavoring, or coloring agents can be added.
[0029] A nasal aerosol or inhalation composition can be prepared according to techniques well known in the art of pharmaceutical formulation. For example, such a composition can be prepared as a solution in saline, employing benzyl alcohol or other suitable preservatives, absorption promoters to enhance bioavailability, fluorocarbons, and/or other solubilizing or dispersing agents known in the art. A composition having an active costunolide derivative can also be administered in the form of suppositories for rectal administration.
[0030] The carrier in the pharmaceutical composition must be “acceptable” in the sense that it is compatible with the active ingredient of the composition (and preferably, capable of stabilizing the active ingredient) and not deleterious to the subject to be treated. One or more solubilizing agents can be utilized as pharmaceutical excipients for delivery of an active costunolide derivative. Examples of other carriers include colloidal silicon oxide, magnesium stearate, cellulose, sodium lauryl sulfate, and D&C Yellow #10.
[0031] The costunolide derivatives of this invention can be preliminarily screened by an in vitro assay for one or more of their desired activities, e.g., inhibiting expression of TNFα, IL-1β, or iNOS, or activity of NF-κB. Compounds that demonstrate high activities in the preliminary screening can further be screened for their efficacy by in vivo assays. For example, a test compound can administered to an animal model (e.g., a mouse having autoimmune disease, cancer, or atherosclerosis) and its therapeutic effect is then accessed. Based on the results, an appropriate dosage range and administration route can also be determined.
[0032] The specific examples below are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. Without further elaboration, it is believed that one skilled in the art can, based on the description herein, utilize the present invention to its fullest extent. All of the publications cited herein are hereby incorporated by reference in their entirety.
EXAMPLE 1
Synthesis of (3aR,6Z,10E,11aR)-10-methyl-3-methylene-2-oxo-2,3,3a,4,5,8,9,11a-octahydrocyclodeca[b]furan-6-carboxylic acid
[0033] To a solution of costunolide aldehyde (1 mmol) in t-BuOH (30 mL) and 2-methyl-2-butene (7 mL) was added a buffer solution of NaClO 2 (10 mmol) and NaH 2 PO 4 (7.4 mmol) in 9 mL of H 2 O. The reaction mixture was stirred at room temperature for 2 hours. After removal of the solvent in vacuo and addition of H 2 O, the mixture was extracted with EtOAc. The organic layers were combined, washed with a saturated sodium chloride solution, dried with anhydrous sodium sulfate, and concentrated in vacuo.
[0034] 1 H NMR (CDCl 3 , 300MHz): 6.862 (t, J=9.0 Hz, 1H), 6.180 (d, J=3.3 Hz,1H), 5.458 (d, J=3.3 Hz,1H), 5.118 (t, J=10.2 Hz,1H),4.627 (t, J=9.6 Hz,1H), 2.813-2.690 (m,1H), 2.420-2.044 (m,8H), 1.275(s,3H);
[0035] MS: 263.0(M+1).
EXAMPLE 2
Synthesis of (3aR,6Z,10E,11aR)-N,10-dimethyl-3-methylene-2-oxo-2,3,3a,4,5,8,9,11a-octahydrocyclodeca[b]furan-6-carboxamide
[0036] To a solution of the acid product of Example 1 (0.1 mmol) in CH 2 Cl 2 (5 mL) was added C 2 O 2 Cl 2 (0.12 mmol) and DMF (in a catalytic amount). The reaction mixture was stirred for 2 hours. The solvent was removed in vacuo.
[0037] The resultant residue was dissolved in CH 2 Cl 2 (2 mL) and was added dropwise to a mixture of methylamine hydrochloride (0.1 mmol) and pyridine (0.1 mmol) in CH 2 Cl 2 (5 mL) and stirred for another 30 mins. H 2 O was added and the mixture was extracted with EtOAc. The organic layers were combined, washed with a saturated sodium chloride solution, dried with anhydrous sodium sulfate, and concentrated in vacuo to provide the desired product at the yield of 70%.
[0038] 1 H NMR (CDCl 3 , 300 MHz): 6.137 (t, J=3.3 Hz, 1H), 5.962 (t, J=7.2 Hz, 1H), 5.440 (d, J=3.3 Hz, 1H), 5.094 (d, J=10.5 Hz, 1H), 4.605 (t, J=9.0 Hz, 1H), 2.849 (d, J=5.1 Hz, 3H), 2.586-2.412 (m, 3H), 2.281-2.187 (m, 2H), 2.088-1.894 (m, 3H), and 1.854 (s, 3H);
[0039] MS: 276.3 (M+1).
EXAMPLE 3
Synthesis of (3aR,6Z,10E,11aR)-N,N-diethyl-10-methyl-3-methylene-2-oxo-2,3,3a,4,5,8,9,11a-octahydrocyclodeca[b]furan-6-carboxamide
[0040] The compound was prepared at the yield of 65% following the procedure described in Example 2 except that diethylamine (0.1 mmol) was used in place of methylamine hydrochloride.
[0041] 1 H NMR (CDCl 3 , 300 MHz): 6.131 (t, J=3.3 Hz, 1H), 5.542 (t, J=7.2 Hz, 1H), 5.342 (d, J=3.3 Hz, 1H), 5.266 (d, J9.6 Hz, 1H), 4.621 (t, J=9.6 Hz, 1H), 3.389 (br, 4H), 3.177-3.102 (m, 1H), 2.328-1.979 (m, 8H), 3.035-2.973 (m, 1H), 1.594 (s, 3H), 1.165 (t, J=7.2 Hz, 6H);
[0042] MS: 318.3 (M+1).
EXAMPLE 4
Synthesis of (3aR,6Z,10E,11aR)-10-methyl-3-methylene-2-oxo-N-propyl-2,3,3a,4,5,8,9,11a-octahydrocyclodeca[b]furan-6-carboxamide
[0043] The compound was prepared following the procedure described in Example 2 except that propylamine (0.1 mmol) was used in place of methylamine hydrochloride. The yield is 65%.
[0044] 1 H NMR (CDCl 3 , 300 MHz): 6.158 (d, J=3.3 Hz, 1H), 5.955 (t, J=7.2 Hz, 1H), 5.439 (d, J=2.7 Hz, 1H), 5.088 (d, J=10.2 Hz, 1H), 4.625 (t, J=10.2 Hz, 1H), 3.304-3.228 (m, 3H),2.579-2.455 (m, 3H), 2.300-2.202 (m, 2H), 1.917-1.868 (m, 3H),1.590-1.495 (m, 5H), 0.934 (t, J=7.2 Hz, 3H);
[0045] MS: 304.4 (M+1).
EXAMPLE 5
Synthesis of (3aR,6Z,10E,11aR)-10-methyl-3-methylene-6-(piperidine-1-carbonyl)-3,3a,4,5,8,9-hexahydrocyclodeca[b]furan-2(11aH)-one
[0046] The compound was prepared following the procedure described in Example 2 except that piperidine (0.1 mmol) was used in place of methylamine hydrochloride. The yield is 55%.
[0047] 1 H NMR (CDCl 3 , 300 MHz): 6.144(d, J=3.3 Hz, 1H), 5.586 (t, J=7.2 Hz, 1H), 5.384 (d,.J=3.3 Hz, 1H), 5.244 (d, J=10.5 Hz, 1H), 5.628 (t, J=10.2 Hz, 1H), 3.517 (m, 4H), 2.999 (m, 1H), 2.260-1.869 (m, 8H), 1.660-1.504 (m,10H);
[0048] MS: 330.3 (M+1).
EXAMPLE 6
Synthesis of (3aR,6Z,10E,11aR)-10-methyl-3-methylene-6-(morpholine-4-carbonyl)-3,3a,4,5,8,9-hexahydrocyclodeca[b]furan-2(11aH)-one
[0049] The compound was prepared following the procedure described in Example 2 except that morpholine (0.1 mmol) was used in place of methylamine hydrochloride. The yield is 58%.
[0050] 1 H NMR (CDCl 3 , 300 MHz): 6.159 (d, J=3.6 Hz,1H), 5.591 (t, J=8.7 Hz,1H), 5.393 (d, J=3.3 Hz, 1 H), 4.629 (d, J=10.2 Hz, 1H), 4.629 (t, J=10.2 Hz, 1H), 3.644-3.522 (m, 8H), 2.986 (br, 1H), 2.273-1.917 (m, 8H), 1.610 (s, 3H);
[0051] MS: 332.3(M+1).
EXAMPLE 7
Synthesis of (3aR,6Z,10E,11aR)-10-methyl-3-methylene-6-((propylamino)methyl)-3,3a,4,5,8,9-hexahydrocyclodeca[b]furan-2(11aH)-one
[0052] To a solution of costunolide aldehyde (0.1 mmol) and propylamine (0.1 mmol) in CH 2 Cl 2 (2 mL) was added NaHCO 3 (0.5 mmol). The mixture was stirred at room temperature for 3 hours. NaB(O 2 CCH 3 ) 3 H (1 mmol) was added. The resultant mixture was stirred overnight, filtered, and evaporated under reduced pressure. The residue was purified by chromatography column using CH 2 Cl 2 /CH 3 OH to produce the title compound at the yield of 50%.
[0053] 1 H NMR (CDCl 3 , 300 MHz): 6.166 (d, J=3.6 Hz, 1H), 5.428 (d, J=3.3 Hz, 1H), 5.402 (t, J=8.4 Hz, 1H), 5.072 (d, J=10.2 Hz, 1H), 4.616 (d, J=9.6 Hz, 1H), 3.254 (d, J=13.2 Hz, 1H), 3.089(d, J=13.2 Hz, 1H), 2.556-2.480 (m, 4H),2.388-2.286(m,1H), 2.181-1.899 (m,6H), 1.550-1.453 (m, 2H), 1.245 (s, 3H), 0.926 (t, J=7.2 Hz,3H);
[0054] MS: 290.3 (M+1).
EXAMPLE 8
Synthesis of (3aR,6Z,10E,11aR)-6-((2-hydroxyethylamino)methyl)-10-methyl-3-methylene-3,3a,4,5,8,9-hexahydrocyclodeca[b]furan-2(11aH)-one
[0055] The compound was prepared following the procedure described in Example 7 except that hydroxyethylamine (0.1 mmol) was used in place of propylamine. The yield is 60%.
[0056] 1 H NMR (CDCl 3 , 300 MHz): 6.179 (d, J=2.4 Hz, 1H), 5.450-5.400 (m, 2H), 5.063 (d, J=10.2 Hz, 1H), 4.624 (d, J=9.6 Hz, 1H), 3.663 (br, 2H), 3.309 (d, J=13.5 Hz, 1H), 3.096 (d, J=13.5 Hz, 1H), 2.909-2.738 (m, 6H), 2.197-1.908 (m, 5H), 0.871 (s, 3H);
[0057] MS: 292.2 (M+1).
EXAMPLE 9
Synthesis of (3aR,6Z,10E,11aR)-10-methyl-3-methylene-6-(morpholinomethyl)-3,3a,4,5,8,9-hexahydrocyclodeca[b]furan-2(11aH)-one
[0058] The compound was prepared following the procedure described in Example 7 except that morpholine (0.1 mmol) was used in place of propylamine. The yield is 50%.
[0059] 1 H NMR (CDCl 3 , 300 MHz): 6.181 (d, J=3.6 Hz, 1H), 5.424 (d, J=3.0 Hz, 1H), 5.365 (t, J=7.8 Hz, 1H), 5.059 (d, J=9.9 Hz, 1H), 4.632 (d, J=9.9 Hz, 1H), 3.680-3.650 (m, 4H), 3.095 (d, J=11.7 Hz, 1H), 2.617 (d, J=12.6 Hz, 1H),2.392-1.851 (m, 9H), 1.251 (s, 3H);
[0060] MS: 318.2 (M+1).
EXAMPLE 10
Synthesis of (3aR,6Z,10E,11aR)-10-methyl-3-methylene-2-oxo-N-(4-fluoro-benzyl)-2,3,3a,4,5,8,9,11a-octahydrocyclodeca[b]furan-6-carboxamide
[0061] The compound was prepared following the procedure described in Example 2 except that 4-fluorobenzylamine (0.1 mmol) was used in place of methylamine hydrochloride. The yield is 80%.
[0062] 1 H NMR (CDCl 3 , 300 MHz): 7.246-7.201 (t, J=8.4 Hz, 2H), 7.018-6.961 (t, J=8.4 Hz, 2H), 6.175 (d, J=3.0 Hz, 1H), 6.030 (t, J=7.5 Hz, 1H), 5.406 (d, J=2.7 Hz, 1H), 5.076 (d, J=10.5 Hz, 1H), 4.625 (t, J=9.3 Hz,1H), 4.470 (d, J=4.8 Hz, 2H), 2.980-2.426 (m, 3H), 2.288-1.876 (m, 6H), 1.876 (s, 3H);
[0063] MS: 368.1 (M−1).
EXAMPLE 11
Synthesis of (3aR,6Z,10E,11aR)-10-methyl-3-methylene-2-oxo-N-(4-phenoxyphenyl)-2,3,3a,4,5,8,9,11a-octahydrocyclodeca[b]furan-6-carboxamide
[0064] The compound was prepared following the procedure described in Example 2 except that 4-phenoxyphenylamine (0.1 mmol) was used in place of methylamine hydrochloride. The yield is 80%.
[0065] 1 H NMR (CDCl 3 , 300 MHz): 7.682 (s, 1H), 7.522 (d, J=7.2 Hz, 2H), 7.354 (d, J=7.5 Hz, 2H), 7.300 (d, J=8.1 Hz, 2H), 7.118 (t, J=7.5 Hz, 1H), 7.005 (d, J=7.5 Hz, 2H), 6.197 (t, J=7.5 Hz, 1H), 6.132 (d, J=3.3 Hz, 1H), 5.435 (d, J=3.3 Hz, 1H), 5.198 (d, J=10.2 Hz, 1H), 4.652 (t, J=9.0 Hz, 1H), 2.650-2.568 (m,3H), 2.326-2.294 (m,3H), 2.089-2.041 (m, 3H), 1.902(s, 3H);
[0066] MS: 430.5 (M−1).
EXAMPLE 12
Synthesis of (3aR,6Z,10E,11aR)-10-methyl-3-methylene-2-oxo-N-(2-methoxyethyl)-2,3,3a,4,5,8,9,11a-octahydrocyclodeca[b]furan-6-carboxamide
[0067] The compound was prepared following the procedure described in Example 2 except that 2-metlioxyethylamine (0.1 mmol) was used in place of methylamine hydrochloride. The yield is 70%.
[0068] 1 H NMR (CDCl 3 , 300 MHz): 6.090 (d, J=3.6 Hz, 1H), 5.950 (t, J=7.5 Hz, 1H), 5.373 (d, J=3.3 Hz, 1H), 5.043 (t, J=10.2 Hz, 1H), 4.533(t, J=10.2 Hz, 1H), 3.397-3.373 (m, 4H), 3.261 (s, 3H), 2.478-2.406 (m,3R), 2.216-2.144 (m,2H),2.003-1.894 (m, 4H), 1.894(s,3H);
[0069] MS: 320.4 (M+1).
EXAMPLE 13
Synthesis of (3aR,6Z,10E,11aR)-10-Methyl-3-methylene-2-oxo-N-(3-(N-methylbenzamide)-2,3,3a,4,5,8,9,11a-octahydrocyclodeca[b]furan-6-carboxamide
[0070] The compound was prepared following the procedure described in Example 2 except that 3-amino-N-methylbenzamide (0.1 mmol) was used in place of methylamine hydrochloride. The yield is 75%.
[0071] 1 H NMR (CDCl 3 , 300 MHz): 7.859 (s, 1H), 7.698 (br, 1H), 7.396 (d, J=7.2 Hz, 1H), 7.209-7.205 (m, 1H), 6.165 (m, 1H), 6.077 (d, J=3.3 Hz, 1H), 5.320 (d, J=3.3 Hz, 1H), 5.185 (d, J=6.9 Hz, 1H), 4.536 (t, J=9.9 Hz, 1H), 2.960 (s, 3H), 2.484-1.956 (m, 9H), 1.815 (s, 3H).
[0072] MS: 395.5 (M+1).
EXAMPLE 14
Synthesis of methyl (3aR,6Z,10E,11aR)-10-methyl-3-methylene-2-oxo-2,3,3a,4,5,8,9,11a-octahydrocyclodeca[b]furan-6-carboxylate
[0073] Concentrated sulfuric acid (2 mL) was added slowly to a solution of the acid product of Example 1 (0.1 mmol) in 20 mL absolute methanol. The mixture was refluxed overnight, cooled to room temperature, and diluted with brine. The resultant solution was extracted with 3×20 mL CHCl 3 . The combined organic layers were washed with a saturated sodium bicarbonate solution and brine, dried over magnesium sulfate, and concentrated in vacuo. The residue was purified by column chromatography to provide the desired product in a yield of 82%.
[0074] 1 H NMR(CDCl 3 , 300 MHz): 6.714 (t, J=7.8 Hz, 1H), 6.176 (d, J=3.0 Hz, 1H), 5.458 (d,J=3.0 Hz, 1H), 5.117 (d, J=10.2 Hz, 1H), 4.625 (t, J=9.9 Hz, 1H), 3.747 (s, 3H), 2.760-2.638 (m, 1H), 2.483-2.025 (m, 8H), 1.879 (s, 3H);
[0075] MS: 277.4 (M+1).
EXAMPLE 15
Synthesis of ((3aR,6Z,10E,11aR)-10-methyl-3-methylene-2-oxo-2,3,3a,4,5,8,9,11a-octahydrocyclodeca[b]furan-6-yl)methyl cyclopropylcarbamate
[0076] To costunolide alcohol (0.1 mmol) in 5 mL anhydrous methylene chloride were added p-nitrophenyl chloroformate (0.1 mmol) and triethylamine (0.1 mmol). The reaction mixture was stirred at room temperature for 2 hours. After addition of cyclopropylamine (0.1 mmol), the mixture was stirred overnight and then diluted with water (5 mL). It was extracted three times with methylene chloride. The combined organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. After concentration in vacuo, the residue was purified by column chromatography to provide the desired product in a yield of 38%.
[0077] 1 H NMR(CDCl 3 , 300 MHz): 6.178 (d, J=3.6 Hz, 1H), 5.560-5.512 (m, 1H), 5.447 (d, J=3.2 Hz, 1H), 5.076 (d, J=6.4 Hz,1 Hz), 4.839 (br,1H), 4.612-4.587 (t, J=10.0 Hz, 2H), 4.456 (br,1H), 2.578-1.843 (m, 12H), 1.571 (m,1H), 0.724 (br, 2H), 0.504 (br, 2H);
[0078] MS: 332.2 (M+1).
EXAMPLE 16
Synthesis of ((3aR,6Z,10E,11aR)-10-methyl-3-methylene-2-oxo-2,3,3a,4,5,8,9,11a-octahydrocyclodeca[b]furan-6-yl)methyl benzylcarbamate
[0079] To costunolide alcohol (0.1 mmol) in 5 mL methylene chloride were added benzyl isocyanate (0.1 mmol), 4-N,N′dimethylamino pyridine (0.1 mmol) and triethylamine (0.1 mmol). The mixture was stirred overnight, diluted with 5 mL water, and extracted three times with methylene chloride. The combined organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. After concentration in vacuo, the residue was purified by column chromatography to provide the desired product in a yield of 70%.
[0080] 1 H NMR (CDCl 3 , 400 MHz): 7.347-7.253 (m,5H), 6.153 (d, J=3.6 Hz, 1H), 5.557 (t, J17.2 Hz, 1H), 5.411 (d,.J=2.0 Hz, 1H), 5.070 (m, 2H), 4.643 (d, J=12.0,1H), 4.611 (t, J=7.5 Hz, 1H), 4.499 (d, J=12.0 Hz, 1H), 4.364 (d, J=6.0 Hz, 1H), 2.621-2.571 (m, 1H), 2.194-1.840 (m, 11H);
[0081] MS: 382.3 (M+1).
EXAMPLE 17
Synthesis of ((3aR,6Z,10E,11aR)-10-methyl-3-methylene-2-oxo-2,3,3a,4,5,8,9,11a-octahydrocyclodeca[b]furan-6-yl)methylethylcarbamate
[0082] The compound was prepared following the procedure described in Example 16 except that ethyl isocyanate was used in place of benzyl isocyanate. The yield is 39%.
[0083] 1 H NMR(CDCl 3 , 400 MHz): 6.154 (d, J=3.2 Hz, 1H), 5.531 (t, J=7.6 Hz, 1H), 5.424 (d, J=3.6 Hz, 1H), 5.057 (d, J=10.0 Hz, 1H), 4.590 (m, 2H), 4.433(d, J=12.4 Hz, 1H), 3.203-3.170(m, 2H), 2.604-2.542(m, 1H), 2.360-2.296(m, 1H), 2.148-1.821(m, 10H), 1.118(t, J=7.2Hz, 3H);
[0084] MS: 319.9 (M+1).
EXAMPLE 18
Inhibition of NF-κB Activity
[0085] An in vitro assay was conducted to evaluate the efficacy of the above-obtained compounds in inhibiting TNFα-induced NF-κB activation in 293 HEK cells.
[0086] Human Embryonic Kidney (HEK) 293 cells were purchased from American Tissue Culture Collection (Manassas, Va.) and cultured in DMEM media containing 10% FBS at 37° C. with 5% CO 2 . The cells were cotransfected with pNFκB-luc and pcDNA3.1. Stably transfected pNFKB-luc-293 clones were selected in the presence of 0.6 mg/ml G418. These cells were seeded in a 96-well plate at 3×10 4 cells/well.
[0087] A series of dilute DMEM solutions were prepared for each of the above-synthesized compounds and were subsequently added to wells containing the selected HEK 293 cells. The final concentrations of the compound in the wells were 0.1, 0.3, 1, 3, and 10 μM. After incubated for 15 minutes, the cells were stimulated with 10 ng/ml recombinant human TNFα for 4 hours. Wells containing 0.1 μg/mL Triptolide and 10 ng/ml recombinant human TNFα were used as positive control. Cells containing 10 μl DMEM media and 10 ng/ml recombinant human TNFα were used as negative control. Cells containing 10 μl DMEM media, not TNFα and the tested compounds were used as the background.
[0088] The treated cells were lysed, and luciferase activity was measured with the Luciferase Assay System (Promega, WI, USA) using a Perkin-Elmer Victor 3 plate reader.
Inhibition Ratio (%)=[1−(drug treatment−background)/(negative control−background)]×100%
[0089] The results show that compounds 1-17 all inhibited TNFα-induced NF-κB activation.
EXAMPLE 19
Inhibition of TNFα, IL-1β, and iNOS Expression
[0090] In vitro assays were conducted to evaluate the efficacy of the above-obtained compounds in inhibiting expression of TNFα, IL-1β, and iNOS.
[0091] THP-1 cells (human monocytic cell line) and RAW 264.7 cells (Mouse leukaemic monocyte macrophage cell line) were purchased from American Tissue Culture Collection. The cells were cultured in RPMI 1640 or DMEM media containing 10% FBS at 5×10 3 cells/well).
[0092] A series of dilute DMEM solutions were prepared for each of the above-synthesized compounds and subsequently added to the wells. The final concentrations of the compound in the wells were 0.1, 0.3, 1, 3, and 10 μM. Wells containing 10 μM dexamethason were used as positive control. Wells containing 10 μl media were used as background. The plate was incubated at 37° C. under 5% CO 2 for 15 minutes. For cytokines induction, 10 μl of 10 μg/ml LPS was added to each well except for the wells having background and the cells were placed in a 37° C., 5% CO 2 incubator for 1 hour. For iNOS mRNA induction, 10 μl of 10 μg/ml LPS and 200 ng/mL mIFN-γ were added to each well except for the background wells and the cells were placed in a 37° C., 5% CO 2 incubator for 8 hours. Finally, THP-1 cells were treated with a lysis buffer containing TNFα or IL-1β target probes at 53° C. for 0.5 hour and RAW264.7 cells were treated with a lysis buffer containing iNOS target probes at 53° C. for 0.5 hour.
[0093] The lysate of cells were analyzed using bDNA assay kits (QuantiGene™, GenoSpectra, US) according to the manufacturer's protocol. The oligonucleotide probes derived from human TNFα (GenBank NM — 000594), human IL-1β (GenBank NM — 000576), and mouse inducible nitric oxide synthase 2 (iNOS, GenBank NM — 010927) were synthesized by Invitrogen Biotechnology Company (Shanghai, China). Briefly, 100 μl of the cell lysate from each well was transferred to a well of a capture plate and incubated at 53° C. for 16 to 20 hours. After washing the capture plate with washing buffer, 100 μl of an Amplifier Working Reagent was added to each well and the plate was incubated at 53° C. for 1 hour. Following a wash, 100 μl of a Label Working Reagent was added to each well before being incubated at 53° C. for 1 hour. Finally, after washing the plate, 100 μl of a Substrate Working Reagent was added to each well. After incubation at 46° C. for 0.5 hour, the luminescence of each well was measured using a Perkin-Elmer Victor 3 plate reader.
Inhibition Ratio (%)=[1−(compound treatment−background)/(stimuli treatments−background)]×100%
[0094] The results show that compounds 1-17 all inhibited the mRNA expression of TNFα, IL-1β, and iNOS. Some compounds exhibited IC 50 values as low as 0.1 μM.
Other Embodiments
[0095] All of the features disclosed in this specification may be combined in any combination. Each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, each feature disclosed is only an example of a generic series of equivalent or similar features.
[0096] From the above description, one skilled in the art can easily ascertain the essential characteristics of the present 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. For example, compounds structurally analogous to the costunolide derivatives of this invention can be made and used to practice this invention. Thus, other embodiments are also within the claims.
|
A compound of the following formula:
wherein X, Y, and Z are as defined herein. Also disclosed are methods for inhibiting TNFα expression, IL-1β expression, iNOS expression, and NF-κB activity and methods for treating autoimmune disease, cancer, or atherosclerosis with such a compound.
| 2
|
This is a division of application Ser. No. 796,953, filed May 16, 1977, now U.S. Pat. No. 4,127,234.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention related to multiorifice structures and a method of fabrication and, more particularly, to a multiorifice structure spray disc for use in conjunction with an automotive type fuel injector valve for atomizing the fuel being injected into an internal combustion engine.
2. Prior Arts
The use of multiorifice structures in connection with nozzles for dispersing or atomizing an exiting fluid is well known in the art. Such multiorifice structures are found in a wide variety of applications ranging from old fashion sprinkling cans for watering a garden to sophisticated fuel injector valves for internal combustion engines. Whether the multiorifice structure merely disperses the fluid as with the sprinkling can or atomizes the fluid as in the fuel injector nozzle application depends upon several factors, one of which is the size of the apertures, as well as force with which the fluid is ejected. Atomization is best accomplished when fluid is ejected from relatively small apertures with relatively high forces. For automotive fuel injector applications, small apertures having effective diameters in the range from several hundred to less than one hundred microns appear to give the desired atomization without the need of having the fuel pressurized above tolerable limits. Unfortunately, multiorifice structures having apertures in ths size range are difficult to manufacture and their cost is prohibitive to meet the high volume, low cost needs for the automotive market.
Various techniques for making the desired multiorifice structure, such as drilling or punching, are impractical. Photoetching or chemical machining appear as a better approach but due to the depth of the apertures required, the desired uniformity of the apertures is difficult to achieve. Alternatively, the fusion of small diameter tubes disclosed by Roberts et al in U.S. Pat. No. 3,737,367 (June 1973) appears as the best approach taught by the prior art. The disadvantage of this approach is that the resultant aperture passages are parallel to each other and therefore the spray cone of the emitted fuel is limited. The divergence of the spray pattern emitted by the Roberts type structure can be increased by coining the structure to produce a curved surface. Alternatively, the parallel tubes in various sections of the structure may be angularly disposed as taught by Roberts et al in U.S. Pat. No. 3,713,202 (January 1973).
Atomization may also be obtained by twisting the individual rows of tubes, as taught by A. L. R. Ellis in U.S. Pat. No. 1,721,381 (June 1929). In this patent the alterante rows are twisted in the opposite direction to incease the turbulance thereby enhancing the mixing and combustion of the emitted gases. Ellis further teaches the use of the interstices between the tubes to pass the oxidizing gas which supports the combustion of the fuel gas passing through the tubes. E. E. Fassler in U.S. Pat. No. 3,602,620 (August 1971) teaches a thermal lance in which the oxidizing gas is fed to the tip of the lance through the interstices formed by twisting solid wires about a core. The twisted rods in this patent provide a tortuous path to impede the gas flow.
SUMMARY OF THE INVENTION
The invention is a multiorifice wafer structure having a plurality of angularly disposed passages and a method for making the multiorifice structure.
The structure is made by fusing concentric layers of solid rods interspaced with cylindrically shaped members wherein each successive layer of rods is disposed at a progressively larger angle with respect to the axis of the fused assembly. The fused assembly of cylinders and rods is then cut into relatively thin wafers wherein the interstices formed between the fused layers of rods and the cylindrical members form a plurality of angularly disposed passageways in which angles of the passageways increase progressively as a function of their distance from the center of the structure. The thickness of the wafer is determined by the effective aperture of the interstices and is sufficient to impart to the fluid passing through the interstices a directional component parallel to the angular displacement of the rods with respect to the common axis of the structure.
The object of the invention is a multiorifice structure having a plurality of passageways angularly disposed with respect to a common axis.
Another object of the invention is a multiorifice structure in which the angular displacement of the passageways increases as a function of the displacement of the passageway from the center of the structure.
Another object of the invention is a flat multiorifice spray plate for a fuel injector valve in which the fuel passing through the spray plate is ejected at an angle which is a function of orifices distance from the center of the structure.
Still another object is a method for making a multiorifice structure which comprises fusing concentric layers of alternating cylindrical members and angularly disposed rods into an integral assembly, and slicing such integral assembly in a direction normal to the axis of said cylindrical members to produce a plurality fo multiorifice structures wherein the interstices between said rods and cylinders form a plurality of angularly disposed passageways.
These and other advantages of the invention will become apparent from a reading of the following detailed description in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective of the disclosed multiorifice structure.
FIG. 2 is an exploded side view showing the angular disposition of the sequential layers of rods.
FIG. 3 is an enlarged section of the multiorifice structure.
FIG. 4 is an exploded view illustrating the structure of the internal layers of a composite assembly.
FIG. 5 is an enlarged partial section showing a structure fabricated from coated rods and coated cylindrical members.
FIG. 6 is a side view of a fused composite and the resultant multiorifice structures cut therefrom.
DETAILED DESCRIPTION OF THE INVENTION
An exemplary embodiment of the invention is illustrated in FIG. 1. The multiorifice structure, designated generally by the numeral 10, is a wafer comprising alternating concentric layers of solid rods 12 and cylindrical members 14 fused or sintered into an integral assembly. Each layer of rods 12 comprises a plurality of individual rods 16 angularly disposed with respect to the axis of the concentric cylindrical members. In the preferreed embodiment, each concentric layer of rods 12, starting from the center of the structure is disposed a greater angle with respect to a core rod 18 than the preceding layer as illustrated in FIG. 2. In FIG. 2, Row A designates the core rod 18 which is axially disposed with respect to the wafer. Row B is a side view of just the first or innermost layer of rods 16. Row C designates the next sequential layer of rods and Rows D and E represent the next sequential layers of rods. It is to be understood that only four layers of rods are used to illustrate the concept, and that in actual practice the structure may have from two or three layers to well over 100 layers. Further, the angles at which the rods 16 are disposed with reference to the core rod 18 may be different than the angles shown. The angles shown are illustrative and the actual angular disposition of each layer or rods with respect to the axis of the multiorifice structure depends ultimately on the end use of the structure including the desired dispersion angle or spray cone of the fluid emitted from the structure. As is obvious, increasing the angular displacement of the rods will increase the resultant dispersion capabilities of the structure.
Referring now to FIG. 3, there is shown an enlarged section of a portion of the multiorifice structure. As previously described, the structure comprises a plurality of layers 12 of rods 16 separated by cylindrical members 14. The interstices or interstitial spaces 20 between the individual rods 16 and the cylindrical members 14 form a plurality of generally triangularly shaped passageways through the structure. These interstices 20 constitute the orifices through which the fluid to be dispersed or atomized flows.
The thickness of the structure is a function of the effective aperture of the interstices and is selected such that the fluid passing therethrough will, upon exiting the structure, have a directional component parallel to the axis of the interstices. Normally, the thickness of the multiorifice structure will be about 10 or more times the size of the individual orifices.
One advantage of the disclosed structure is that the triangular shaped orifices are more effective in the atomization of the exiting fluid than the circular orifices of the prior art. As is well known, surface tension forces acting on the exiting fluid tend to cause the exiting fluid stream to oscillate which eventually cause the exiting stream of fluid to break up in small droplets. The greater the distortion of the exiting stream from the natural spherical configuration of a free fluid, the greater will be the surface tension forces acting on the exiting fluid. As a result, the exiting fluid will be caused to vibrate more vigorously and break up into smaller particles than would be achieved with circular orifices having the same effective aperture.
Another factor to be considered is the overall uniformity of the apertures formed by this method over conventional drilling and/or photoetching techniques. The rods 16 are normally made by extruding techniques which result in very precise tolerances on its diameter, therefore, the triangular apertures resulting from the disclosed configuration will have a very uniform size.
FIGS. 4 and 5 illustrate a very simple and economical method for fabricating the disclosed multiorifice structure. Referring to FIG. 4, a central or core rod 18 is circumscribed by six or more rods or wires 16'. The first layer of rods 16' are twisted about the core and rod 18, so that their axis are disposed at a predetermined angle with respect to the axis of core rod 18. The angle α may be 5° as indicated in FIG. 2-B or any other desired angle. Core rod 18 and twisted rods 16' are then sheathed in a cylindrical member 14' whose internal diameter is equal to diameter of the core rod 18 plus two times the diameter of the rods 16' so that the rods 16' are in physical contact with the external surface of the core rod 18 and the internal surface of the cylindrical member 14'. The external diameter of cylindrical member 14' is seleced so that an integral number of rods 16" of the same diameter as rods 16' completely surround member 14' with their external surfaces in contact with each other. A second layer of rods or wires 16" are also twisted about the external surface of the cylindrical member 14' and sheated in a second cylindrical member 14". The twisted rods on the second layer are angularly disposed with regard to the core rod 18 at an angle β which may be the same as α or may be different as shown in FIG. 2. The internal diameter of the cylindrical member 14" is selecetd so that the rods 16" will be encased between and in contact with the external surface of member 14' and the internal surface of member 14". The external diameter of member 14" is again selected so that an integral number of rods 16" of the same diameter as rods 16' will completely surround member 14 with their external surfaces in contact with the adjacent rods. In a like manner, the layer of rods 16" will be sheathed in a cylindrical member 14"' and so on until the composite structure of rods and cylindrical members has a diameter equal to the diameter of the desired multiorifice structure 10. The composite structure is then fused or sintered to form an integral structure 22 in which each rod is fused to each adjacent rod and to the surfaces of the bounding cylindrical members 14.
To facilitate the fusion of the rods and the cylindrical members, the rods and cylindrical members may be coated with a thin layer of material having a lower melting temperature than the materials of the rods and cylindrical members, as shown in FIG. 5. This coating material may be deposited on the surface of the rods and cylindrical members by electroplating, dipping, vapor deposition or any other way known in the art. FIG. 5 is an enlarged section of the multiorifice structure in which the thickness of the coatings are exaggerated for illustrative purposes. Referring to FIG. 5, each rod 16 and cylindrical member 14 is coated with a thin layer of a material 24. For example, the rods 16 and cylindrical member may be made from a stainless or carbon steel and the coating material may be copper, nickel, tin, or any other suitable material having a lower melting temperature. It is recognized that the multiorifice structure need not be made from metals, and glass as well as plastic materials may be used. Further, it is not always necessary that both rods 16 and cylindrical members 14 be coated with the lower melting temperature material and alternatively, only one or other needs to be coated.
Referring now to FIG. 6, the fused assembly 22 is sliced or cut using any of the known methods to produce a plurality of thin multiorifice structures 10 having the desired thickness. The sliced surfaces 26 of the multiorifice structures may subsequently be ground or polished to produce required surface finish or uniformity of thickness.
Although the invention has been described and illustrated with reference to a particular configuration and method of manufacture, it is not contemplated that the invention be limited to the structure shown or the particular method of making discussed. It is recognized that those skilled in the art could conceive alternate embodiments wherein the cylindrical members could take alternate shapes or the single layer of rods be replaced by rods having noncircular cross-sections or even multiple layers of rods between the cylndrical members without departing from the spirit of the invention.
|
The invention is a multiorifice structure and method of manufacuture. The structure comprises a plurality of triangularly shaped orifices angularly disposed with respect to a common axis. The structure is formed by fusing together concentric alternating layers of cylindrical members and parallel rods angularly disposed with respect to the axis of the cylindrical members. The fused structure is sliced generally normal to its axis to produce a plurality of multiorifice wafers or discs. The interstices between the rods and the cylindrical members form a plurality of small triangularly shaped orifices particularly well suited to use as an atomizer for an internal combustion engine fuel injector valve.
| 8
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a surgical implement, and more particularly, to a surgical implement used to simultaneously retract and view bodily tissues. Even more particularly, the invention relates to an endoscopic retractor equipped with an imaging unit to form images of bodily tissues which are exposed from operation of the endoscopic retractor.
2. Description of the Related Art
Many surgical procedures done today typically include the use of an endoscopic device to aid surgeons and medical staff to visualize bodily tissues exposed during a surgical procedure. An endoscopic procedure may even be carried out to merely view bodily tissues (e.g., a colonoscopy). Basically, an endoscope is inserted through the skin of a patient into a prepared opening in the body which is typically called a cavity. The cavity is often filled with air or other gasses to expand the cavity for better viewing. See U.S. Pat. No. 4,608,965 to Anspach, Jr., et. al. The '965 patent teaches an endoscope retainer that does not slip out of a cavity and also retracts soft tissue around the opening in the cavity away from the cavity to provide a better view of the cavity.
Typically, the endoscopes of the type contemplated herein, include a probe part which is inserted into an bodily organ. Generally, the probe part includes a charge coupled device (CCD) on its end to form images of the object of interest (e.g., a heart or other bodily organ), an illuminating member such as light channel to supply light to the object of interest, a lens though which the CCD captures a reflection of the light illuminated by the illuminating member from the object of interest and a receiving channel member to receive and transmit the electric signals produced by the CCD to a main system which converts the electric signals into image signals (e.g., NTSC signals or other signals which are displayable on a television tube device or on another type of cathode ray device--e.g., a computer terminal screen). See e.g., U.S. Pat. No. 4,872,446 to Nudelman et al. The '446 patent, in particular, discloses a probe carrying a single fiber optics channel including a flexible coherent fiber optics bundle for both transmitting illumination light and receiving reflected light from the object. An endoscope of such a configuration can be used in very small diameter applications, such as those required in the imaging of coronary arteries.
Procedures currently being done with an endoscope include gall bladder surgery, knee surgery, hernia surgery, insertion of breast implants through a long tube through the navel, brow lift surgery, and colon resection. Additionally, OB/GYN surgeons have been using endoscopy for many years to treat various problems of the pelvic area. Orthopedic surgeons use endoscopic procedures to treat and access joint cavities.
The benefits which result from using an endoscope are not, however, available to all types of medical procedures. This is because many procedures that exist today and that require a relatively small opening of the skin of a subject to allow for direct visualization and/or insertion of implantable material are not being done endoscopically due to the impracticality of current technologies. For example in breast augmentation in women, an incision of approximately 3 to 4 centimeters (cm) is made under a women's breast. Through this relatively small incision, a relatively large implant needs to be inserted into an even larger pocket, which pocket needs to be created through the small incision. To help facilitate this type of procedure, there are currently available lighted retractors. See e.g., U.S. Pat. No. 4,226,228 to Shin et al. and U.S. Pat. No. 5,035,232 to Lutze et al.
Generally, a retractor is a hand-held rod-like structure which is curved in such a way as to allow a surgeon to pull tissue away from an incision in order to open the incision to provide for direct visualization of the operative sight or location. A surgeon may more easily visualize the pocket with a lighted retractor of the type contemplated above. However, problems still exist when visualizing deep pockets. For example, the operating surgeon often must contort her body and neck in order to strain to see the depths of the wound made by a relatively small incision. A surgeon often encounters similar problems when doing face lifts, particularly in the area of the neck.
U.S. Pat. No. 5,039,198 to VanBeek attempts to alleviate some of the problems mentioned above with a stereoscopic microsurgery system. In the system of the '198 patent, a head mounted viewing assembly, including dual optical viewers, is used for depth of field viewing of an operative sight or location. Problematically, however, the system of the '198 patent is bulky and inconvenient to use and it does not provide a clear and complete view of the operative site as would and imaging device of the type used in endoscopes.
SUMMARY OF THE INVENTION
In view of the foregoing and other problems associated with the art to which the present invention relates, it is therefore an object of the present invention to solve such problems.
It is yet a further object of the present invention to provide a surgical implement for easily and clearly visualizing a bodily cavity formed through a relatively small opening in a skin surface.
It is still another object of the present invention to provide a single surgical implement for simultaneously performing a minimal opening tissue retracting procedure and providing endoscopic visualization of a pocket formed through a relatively small incision made as a result of the minimal opening procedure.
It is yet a further object of the present invention to provide a single surgical implement for performing a minimal opening tissue retracting procedure, simultaneously providing endoscopic visualization of a deep pocket formed through a relatively small incision made by the minimal opening procedure and also simultaneously providing suction to evacuate smoke and other matter (e.g., gasses or liquids) which are produced by an electrocautery device.
It is still a further object of the present invention to enable assistants of an operating surgeon to easily and clearly visualize an operative site while the surgeon performs a tissue retracting procedure.
It is still another object of the present invention to facilitate teaching a tissue retracting procedure.
It is still a further object of the present invention to reduce the number of instruments, and therefore the number of hands, required to perform a given surgical procedure.
These and other objects of the present invention are achieved by providing a retractor device for simultaneously retracting and viewing bodily tissues during a medical procedure. The retractor includes a blade member for retracting bodily tissues and an imaging device to form an image of the bodily tissues which are exposed from operation of the blade member. The imaging device is coupled to a display device so that the image of the bodily tissues is displayed thereby.
Moreover, the present invention provides a method for endoscopically performing a tissue retracting procedure using a retractor device. The method includes the steps of retracting bodily tissues using a retractor device to form a cavity and imaging the cavity using an imaging device mounted on said retractor to form an image of the cavity and to provide the image of the cavity to a display device that is coupled to the imaging device.
BRIEF DESCRIPTION OF THE DRAWINGS
The above-listed and other features and advantages of the present invention will become apparent and readily appreciated from the following detailed description of the preferred embodiments, taken in conjunction with the attached drawing figures, of which like elements are represented by like reference numerals and of which:
FIG. 1 is a top view of an endo-retracting device according to a first embodiment of the present invention;
FIG. 2 is a cross-sectional view of the endo-retracting device of FIG. 1 taken along the line 2--2;
FIG. 3 is a cross-sectional view of the endo-retracting device of FIG. 1 taken along the line 3--3.
FIG. 4 illustrates a modification to the endo-retracting device of FIG. 1.
FIG. 5 illustrates a further modification to the endo-retracting device of FIG. 1.
FIG. 6 is a top view of an endo-retracting device according to a second embodiment of the present invention;
FIG. 7 illustrates a modification of the second embodiment depicted in FIG. 6.
FIG. 8 is a top view of a suction-retracting device according to a third embodiment of the present invention;
FIG. 9 illustrates an example of an alternative configuration of the retracting devices of the first, second and third embodiments depicted in FIGS. 1-8; and
FIG. 10 illustrates a fourth embodiment according to the present invention which employs a wireless signal transmission system.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention is now described with regard to the exemplary embodiments shown in FIGS. 1-10. Like parts will be referred to with like reference numerals where appropriate within the drawings.
Referring now to FIG. 1, a preferred embodiment of a surgical implement in accordance with the present invention is designated generally by the reference numeral 10. Surgical implement 10 includes handle 12, shaft 14, blade 16 and endoscope 18. Elements 12, 14 and 16 form a conventional retractor of various configurations. With reference to FIG. 9, therein shown is an example of an alternative configuration of a conventional retractor 200 including elements 12, 14, and 16. In particular, endoscope 18 includes scope (i.e. probe) 20, fiber-optics bundle 22 disposed within fiber-optics channel 24 and standard interfacing equipment 26 for receiving and processing signals from the fiber-optics bundle and displaying an image based on the received and processed signals under the display device of the interfacing equipment.
Shaft 14 has a first end portion 28 and a second end portion 30. Handle 12 is rigidly and integrally formed with shaft 14 at first end portion 28. Blade 16 is rigidly and integrally formed with shaft 14 at second end portion 30. Retracting elements 12, 14 and 16 are preferably made from a rigid material such as metal, but may be made from other materials such as hard plastics, rubber or the like. All that is required of the material from which retracting elements 12, 14 and 16 are formed is that such material be suited to surgical uses.
Endoscope 18 is shown as being encased with a strong plastic or metal material to withstand sterilization techniques, i.e., an autoclave, along with retractor elements 12, 14 and 16. Endoscope 18 may be disconnected from equipment 26 at approximately 32 for sterilization and storage. Scope 20 is insertable into a body cavity along with blade 16 and a top surface 46 of scope 20 is approximately even with a top surface 48 of blade 16. Scope 20 has a conventional internal configuration, such as that disclosed in the Nudelman et al. or the Murata patent as such were mentioned above. That is, referring now to FIG. 2, which illustrates a cross sectional view taking along the line 2--2 of FIG. 1, scope 20 includes a signal fiber-optics channel 24 containing fiber-optics bundle 22, as disclosed in Nudelman et al.
It should be noted that with regard to the embodiment shown in FIG. 1 and with regard to the other embodiments discussed herein, that the endoscope part of the retractor device is configured to form images of bodily tissues. In particular, the endoscope should be configured to generate electrical signals which can be processed to form image or video signals for display on a display device. For example, an endoscope can be used which generates television (TV) signals which can be processed in conventional ways to be displayed on a television set or monitor. For a discussion of the use of cameras and fiber-optic bundles to achieve the video-optical characteristics of the endoscope and its features of the present invention, the reader is directed to the above-mentioned Nudelman et al. patent (U.S. Pat. No. 5,109,276). Additionally, it should be noted that the signals generated by the endoscope structure of the present invention can be digitally processed to aid in visualizing special image characteristics and like (e.g., visually detecting radioactive coloring agents in bodily tissues). Such digital processing techniques for television and video signals are generally discussed in R. H. Stafford, DIGITAL TELEVISION (Bandwidth Reduction and Communication Aspects), John Wiley & Sons Press, Copyright 1980.
With reference now to FIG. 3 on the other hand, which illustrates a cross-sectional view taking along the line 3--3 of FIG. 1, scope 20 includes at least one illuminating channel 34 and a receiving channel 36 including a lens (not shown) and a CCD device (not shown) for transmitting light reflected from an object, as disclosed in Murata.
Referring again to FIG. 1, endoscope 18 is arranged along either side (the opposite side illustrated by broken lines) of retractor elements 12, 14 and 16, along the longitudinal direction of the retractor elements. Endoscope 18 is securely adhered to the retractor elements along surface 38 (or surface 40) with conventional bonding techniques such as glue. Instead, endoscope 18 may be securely connected to the retractor elements with conventional connecting elements such a screws or clamps (not shown). Similarly, endoscope 18 may be adhered or connected to a top surface 42 (see FIG. 4) or a bottom surface 44 (see FIG. 5) of the retractor elements. Referring again to FIGS. 1, 2 and 3, surgical implement 10 may further include a suction tube 50 located within endoscope 18, to simultaneously evacuate smoke produced by an electrocautery device while retracting tissue with implement 10.
FIG. 1 further shows a knob or joystick 52 attached to the endoscope near the handle, to allow the surgeon to control a rotation of scope 20 to adjustably visualize the entire cavity while gripping handle 12 and retracting tissue. See e.g., the Murata patent which teaches a control knob for controlling vertical and horizontal movements of a head portion of a probe. See also, U.S. Pat. No. 5,159,466 to Hibino et al., which teaches a distal end of the endoscope provided with a bendable portion. Moreover, the Hibino et al. patent teaches both a knob for manually operating the bendable portion and a joystick for vertically and horizontally bending the bendable portion in conjunction with a motor. The Hibino et al. patent also teaches a straight switch for straightening the bendable portion and a vibration switch for minutely vibrating the bendable portion.
With reference now to FIG. 6, therein illustrated is a second embodiment of a surgical implement 100 of the present invention. In this embodiment, endoscope 18 is located within hollow portion 54 of the retractor elements 12, 14 and 16. Hollow portion 54 runs through handle 12, shaft 14 and blade 16. Endoscope 18 fits securely within hollow portion 54 and includes the same channel(s) as illustrated in either FIGS. 2 or 3. Top surface 46 of the scope is aligned with the top surface 48 of blade 16. Top surface 46 of blade 16 is either transparent to allow imaging by scope 20 or has an aperture of width X equal to the width of scope 20 or the width of channel 54, to allow imaging by scope 20. FIG. 7 shows scope 20 slightly above top surface 48 of blade 16, such that scope 20 protrudes slightly from aperture X. The surgical implement 100 of the embodiment shown in FIG. 6, as well as the modification to second embodiment shown in FIG. 7, may further include knob/joystick 52, attached to an outer surface of handle 12 and internally to endoscope 18 to control a movement of probe 20 as discussed above with regard to the first preferred embodiment. As furthest discussed above, implement 100 of FIGS. 6 and 7 may additionally include a suction channel and illuminating channel within endoscope 18.
With reference now to FIG. 8, therein depicted is a third embodiment of a surgical implement, in accordance with the present invention and is designated generally by reference numeral 100. Similar to the embodiment of FIG. 1, surgical implement 100 includes handle 112, shaft 114, blade 116 and suction channel 50. Elements 12, 14 and 16 form a conventional retractor of various configurations. Suction channel 150 may be connected to either side of the retractor elements, similar to the endoscope of FIG. 1, or may be connected on either the top or bottom surface of the retractor elements, similar to the endoscope of FIGS. 4 and 5. The retractor is a conventional lighter retractor in combination with a suction device. Alternatively, suction channel 150 may be located within the hollow portion 54 of the retractor, similar to the endoscope of FIG. 6, with the hollow portion also including a conventional illumination channel. The embodiment of FIG. 8 illustrates a hand held retractor and a suction device to facilitate the suction of smoke of a tissue retraction operation that a accumulates in a large pocket with a small opening.
Referring now to FIG. 10, therein depicted is yet another embodiment of the present invention. For the most part, this embodiment is exactly the same as the embodiment depicted in FIG. 1. However, the embodiment depicted in FIG. 10 employs commonly used and understood wireless transmission technology to transmit a video or other signal(s) from a transmitter 200 located on surgical implement 10 to corresponding receiver 201. The signals transmitted by transmitter 200 and which are received by receiver 201 can processed by interfacing equipment 26 and displayed in a conventional manner. For example, if the transmitter 200 is configured to process a video signal of the television variety (i.e., a raster type signal which originates from detections by a CCD type device and which are converted to an NTSC signal) such a signal may then be transmitted by well-known and used FM radio transmission devices to receiver 201 for processing so that interface equipment 26 can display the same in a conventional way. A typical wireless video signal transmission system comprising a transmitter for processing a video signal to produce an FM radio broadcast in the FM radio range of about 900 Mhz which can be received by a corresponding radio receiver is one manufactured by RECOTON Corporation having Model No. V900SX. The V900SX system is designed so that a video source (e.g., a NTSC video source) connects to a transmitter which transmits FM broadcasts at either 914 or 922 Mhz and which are received by receiver which is typically connected to a video signal display device (e.g., a television set or monitor).
It is believed that the use of such wireless systems within the context of the present invention and, in particular, the embodiment depicted in FIG. 10, will now allow surgeons to effectively use an endo-scopic retracting device without having to be burdened with messy wire and cable arrangements which are typically referred to a "spaghetti wires." That is, the embodiment depicted in FIG. 10 will now allow surgeons to have a single, hand-held endo-scopic retracting device which is free of any tethering device such as a cable which connects the device to a display system. The details of coupling a radio or other wireless signal transmitter to a corresponding radio or wireless signal receiver in the context of the present invention will be readily appreciated by those skilled in the art of wireless signal transmission systems. Moreover, while enabling disclosure has been provided with reference to FM or radio based transmission systems, other forms of wireless transmission systems (e.g., Infra-Red, etc.) can be employed. Finally, it should be noted that in the case of the embodiment depicted in FIG. 10, power systems such as batteries or the like would need to be maintained within implement 10 so as to provide operational energy to the components of the imaging system and the signal transmission system; such power and battery systems, especially in the field of medical devices, are well known to those skilled in the art of medical electronic devices.
Although a few preferred embodiments of the invention have been shown and described, it will be readily appreciated by those skilled in the art that many changes and modifications may be made to such embodiments without departing from the principles and spirit and scope of the present invention, the scope of which is defined in the appended claims.
|
A reactor device for simultaneously retracting and viewing bodily tissues during a medical procedure. The retractor includes a blade member for retracting bodily tissues and an imaging device to form an image of the bodily tissues which are exposed by the operation of the blade member. The imaging device is coupled to a display device so that the image of the bodily tissues formed by the imaging device is displayed by the display device. Moreover, a method is provided for endoscopically performing a tissue retracting procedure using a retractor device. The method includes the steps of retracting bodily tissues using a retractor to form a cavity and imaging the cavity using an imaging device mounted on said retractor to form an image of the cavity and to provide the image of the cavity to a display device that is coupled to the imaging device.
| 0
|
RELATED PATENT APPLICATIONS
The present application is a continuation of U.S. patent application Ser. No. 12/215,232, and is co-pending with U.S. patent application Ser. No. 12/215,233, the disclosures of which are incorporated herein by reference.
FIELD OF INVENTION
The field of invention relates to a system for channeling wind to one or more wind turbines in order to increase the productivity of the wind turbines.
BACKGROUND OF THE INVENTION
Wind turbines harness the kinetic energy of the wind and convert it into mechanical or electric power. Traditional wind turbines have a horizontal spinning axis that allowed blades of the wind turbine to rotate around the axis. As wind engages the blades, the blades move around the horizontal spinning axis of the wind turbine. The relative rotation of the blades to the horizontal axis may then be converted into energy.
Wind turbines only capture wind that engages the blades. Thus, only the wind directly passing the in line with the wind turbine is converted into energy.
SUMMARY OF THE INVENTION
In the method of this invention, the force of wind acting on a wind turbine is increased thereby increasing the resulting energy output of the wind turbine. This method is achieved by positioning one or more wind compressors proximate a first side of a wind turbine and one or more wind compressors proximate the second side of the wind turbine, where the second side is distal from the first side. The wind compressors comprise an obstruction configured to redirect a wind flow from each of the wind compressors toward the wind turbine. The one or more wind compressors should be arranged proximate to the wind turbine in a configuration that creates a Venturi effect on the wind flow aimed at the wind compressors so that the redirected wind flows converge toward the wind turbine at an increased velocity and force.
The wind directing system of this invention comprises one or more wind compressors which are proximate to a first side of the wind turbine and one or more wind compressors which are proximate a second side of the wind turbine. The second side is distal from the first side. Each of the wind turbines of this invention comprise an obstruction which is configured to redirect wind flow from each of the wind compressors toward the wind turbines so that the converged wind flow creates a Venturi effect. The redirected wind flow has an increased velocity and force. The system also comprises a plurality of transporters with one or more wind compressors coupled to at least one transporter. The transporters are configured to move at least one wind compressor to a location that maximizes the force of the wind encountered by the wind compressor and directed by the wind compressor to the wind turbine.
In one embodiment, the wind compressor system for directing wind toward one or more wind turbines of this invention comprises one or more riggings with a sail coupled to each one which is configured to engage and redirect the wind so that the wind converges toward the one or more wind turbines in a Venturi effect. A transporter is also coupled to the riggings and is configured to maintain a first location of the sail while the sail redirects wind toward the one or more wind turbines. The system also comprises a controller which is configured to move the transporter to a second location in response to a change in the wind direction.
This invention also entails a wind powered generator system for generating electrical power from wind power which comprises a vertical turbine rotor, a vertical turbine support, and one or more blades coupled to the turbine rotor which are configured to move the turbine rotor relative to the turbine support. One or magnet sets are located between the turbine support and the turbine rotor. There is also a space between a portion of the turbine rotor and the turbine support, where the space is created by the magnetic force from the one or more magnet sets. One or more generators are configured to generate electric power from the rotating movement of the turbine rotor. The one or more wind compressors are proximate to a first side of the turbine support and one or more compressors are also proximate to a second side of the turbine support, where the second side is distal from the first side. Each of the wind compressors have an obstruction which is configured to redirect wind flow from each of the wind compressors toward the turbine rotors so that the converged wind flow from the wind compressors creates a Venturi effect. The converged wind flow results in an increased velocity and wind force on the turbine rotors.
The method of this invention for generating electricity comprises attaching a set of dipolar magnets to a turbine rotor and a turbine support. In one aspect, the magnets are located between the turbine rotor and the turbine support, creating an opposing magnetic force that reduces friction and creates a space between the turbine rotor and the turbine support. As one or more blades engage with wind, the vertical turbine rotor is rotated relative to the turbein support. A generator converts the mechanical energy of the moving vertical turbine into electric power. One or more wind compressors are proximate to a first side of a turbine support and to a second side of the turbine support where the second side is distal from the first side. The wind compressors comprise an obstruction configured to redirect wind flow from each of the wind compressors towards the turbine rotor. The wind compressors proximate to the turbine support create a Venturi effect on the wind flow aimed at the wind compressors so that the redirected wind flow converges toward the turbine rotor at an increased velocity and force. The mechanical energy of the moving turbine rotor is converted into electric power by the use of a generator.
BRIEF DESCRIPTION OF THE DRAWINGS
While the specification concludes with claims particularly pointing out and distinctly claiming the subject matter that is regarded as forming the present invention, it is believed that the invention will be better understood from the following description taken in conjunction with the accompanying DRAWINGS, where like reference numerals designate like structural and other elements, in which:
FIG. 1A is a schematic cross-sectional view of a wind turbine according to one embodiment of the present invention;
FIG. 1B is a schematic top view of a wind turbine according to one embodiment of the present invention;
FIG. 2 is a schematic cross-sectional view of a wind turbine according to one embodiment of the present invention;
FIG. 3 is a schematic side view of a wind turbine according to one embodiment of the present invention;
FIG. 4 is a schematic top view of a wind turbine with wind compressors according to one embodiment of the present invention;
FIG. 5 is a schematic top view of wind turbines with wind compressors according to one embodiment of the present invention;
FIG. 6 is a front view of a wind compressor according to one embodiment of the present invention; and
FIG. 7 is a side view of a wind compressor according to one embodiment of the present invention.
DETAILED DESCRIPTION
The following detailed description is presented to enable any person skilled in the art to make and use the invention. For purposes of explanation, specific nomenclature is set forth to provide a thorough understanding of the present invention. However, it will be apparent to one skilled in the art that these specific details are not required to practice the invention. Descriptions of specific applications are provided only as representative examples. Various modifications to the preferred embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be applied to other embodiments and applications without departing from the scope of the invention. The present invention is not intended to be limited to the embodiments shown, but is to be accorded the widest possible scope consistent with the principles and features disclosed herein.
FIG. 1A is a schematic cross sectional view of a wind turbine 100 , according to one embodiment. The wind turbine 100 , as shown, is a vertical axis wind turbine. Therefore, a core axis 102 of the wind turbine 100 is substantially in a vertical plane relative to the Earth. The wind turbine 100 may have a turbine rotor 104 and a turbine support 106 within and concentric to the turbine rotor 104 . The turbine rotor 104 rotates around the core axis 102 of the turbine support 106 in response to wind engaging one or more blades 108 , shown schematically. The kinetic energy from the wind is captured by the blades 108 thereby rotating the turbine rotor 104 . The turbine core support 106 may remain stationary as the turbine rotor 104 rotates around the axis 102 . In order to reduce the effects of friction between the rotating turbine rotor 104 and the turbine support 106 , one or more sets of magnets 110 are used to reduce the weight force of the turbine rotor 104 acting on the turbine support 106 . A generator 112 may be located proximate the wind turbine 100 in order to convert the mechanical energy of the rotating turbine rotor 104 into electric power.
The turbine rotor 104 , as shown in FIG. 1A , comprises a central axis 113 that is substantially centered around the axis 102 . The turbine rotor 104 , may include a top 114 and a bottom 116 extending out from the central axis 113 . As shown, the central axis 113 supports the top 114 and the bottom 116 . The top 114 and/or the bottom 116 , as shown, extends radially away from the central axis 113 . In FIG. 1B a top view of the wind turbine 100 is shown. The top view shows the top 114 extending a first radius R 1 away from the axis 102 . The bottom 116 may extend the same distance as the top 114 from the axis 102 ; however, it should be appreciated that the distance the top 114 and bottom 116 extend from the axis 102 may vary depending on design conditions. The top 114 , as shown in FIGS. 1A and 1B , extends over the top of a support shaft 118 of the turbine support 106 ; however, it should be appreciated that other suitable configurations for the top 114 may be used.
The turbine rotor 104 may have alternative designs to the one shown in FIG. 1 . For example, the turbine rotor 104 may not cover the top of the support shaft 118 , as shown in FIG. 2 . Further, the turbine rotor 104 may simply include the top 114 and the bottom 116 and be held together by the blades 108 . Further still, the top 114 and/or the bottom 116 may not be shaped in a circular pattern, but instead may extend as supports over each of the blades 108 in an effort to save money on materials and reduce the weight of the turbine rotor 104 . The turbine rotor 104 may have any suitable design capable of supporting the blades 108 and rotating around the axis 102 .
The bottom 116 of the turbine rotor 104 may include one or more of the magnets 110 . The one or more magnets 110 located in the bottom 116 of the turbine rotor 104 provide an opposing force against one or more magnets 110 located on the turbine support 106 . The opposing force created by the one or more magnets 110 reduces the weight load of the turbine rotor 104 on the turbine support 106 , as will be discussed in more detail below.
The turbine support 106 may be any suitable shape capable of supporting the weight of the turbine rotor 104 and stabilizing the turbine rotor 104 as it rotates about the axis 102 . The turbine support 106 , as shown in FIG. 1A , includes a base 120 and the support shaft 118 . The base 120 may rest under the bottom 116 of the turbine rotor 104 . The base 120 typically acts as a support between a surface 124 , such as the ground or bed rock, and the turbine rotor 104 . The base 120 may include a platform 122 adjacent the turbine rotor 104 and a bottom member 123 adjacent the surface 124 . The base 120 may be any suitable shape so long as the base is capable of supporting the weight of the turbine rotor 104 .
The surface 124 , as shown in FIG. 1A , is the ground; however, it should be appreciated that the surface 124 may be any suitable surface for supporting the base 120 including, but not limited to, a trailer, a boat, a rail car as illustrated in FIG. 3 , a top of a building, a top of a parking garage, a top of a stadium, and the like.
The platform 122 typically provides the support for the weight of the turbine rotor 104 . The platform 122 may include one or more magnets 110 B which provide an opposing force against the one or more magnets 110 A located on the bottom 116 of the turbine rotor 104 , as will be described in more detail below. The base 120 and/or the platform 122 may extend the same radial distance from the axis 102 as the turbine rotor 104 . Alternatively, the base 120 may extend a shorter radial distance from the axis 102 than the turbine rotor 104 , or, in another alternative embodiment, may extend a longer radial distance from the axis 102 than the turbine rotor 104 . It should be appreciated that the platform 122 may be any suitable shape capable of providing a vertical support surface for the turbine rotor 104 .
The support shaft 118 of the turbine support 106 may provide for stabilization of the turbine rotor 104 . The support shaft 118 , as shown in FIGS. 1A and 1B is located radially inside the central axis 113 of the turbine rotor 104 . FIG. 1A shows the support shaft 118 as a substantially solid shaft which is slightly smaller than the interior of the central axis 113 of the turbine rotor 104 . Alternatively, as shown in FIG. 2 , the support shaft 118 may define an opening that allows for an interior access way 202 . The support shaft 118 allows the turbine rotor 104 to rotate in response to the wind while preventing the turbine rotor 104 from moving substantially in the direction perpendicular to the core axis 102 . The support shaft 118 may include one or more magnets 110 C which provide an opposing force against one or more magnets 110 D located on the central axis 113 of the turbine rotor 104 . The magnet 110 C located on the support shaft 118 may act to stabilize the turbine rotor as will be discussed in more detail below.
The wind turbine 100 may include a connector 126 , shown schematically in FIGS. 1A and 3 . The connector 126 may secure the turbine rotor 104 to the turbine support 106 while allowing the turbine rotor 104 to rotate. FIG. 1A shows the connector 126 as a pin type connection which is secured to the support shaft 118 and penetrates an opening in the top 114 of the turbine rotor 104 . A head of the pin may rest on the top 114 of the turbine rotor 104 . The opening may be large enough to not engage the pin as the turbine rotor 104 rotates about the turbine support 106 . The head may simply provide an upward travel limit for the turbine rotor 104 . Thus, typically the turbine rotor 104 may not engage the connector 126 ; however, in the event that the turbine rotor 104 lifts off of the turbine support 106 , the head will stop it from becoming detached from the wind turbine 100 . It should be appreciated that any suitable arrangement for securing the turbine rotor 104 to the turbine support 106 may be used.
The one or more sets of magnets 110 C, 110 D reduce friction between the turbine support 104 and the turbine rotor 106 by creating a space between the turbine support 104 and the turbine rotor 106 . The magnets replace the role of roller bearings in prior wind turbines. The one or more magnets 110 A, 110 B positioned on the bottom 116 of the turbine rotor 104 and the platform 122 of the turbine support may include one or more levitation magnets and one or more stabilization magnets. The levitation magnets supply an opposing force between the bottom 116 of the turbine rotor 104 and the platform 122 . The opposing force created by the levitation magnets may create a force on the turbine rotor 104 substantially opposite to a gravitational force on the turbine rotor 104 . The levitation magnets can provide a large enough opposing force to lift the turbine rotor 104 off of the platform 122 thereby eliminating friction between the platform 122 and the turbine rotor 104 . Specifically, a space may be created between the platform 122 and the bottom 116 of the turbine rotor 104 as a result of the opposing force. Alternatively, the opposing force created by the levitation magnets may only negate a portion of the gravitational force, so that the friction force between the platform 122 and the turbine rotor 104 is reduced.
The stabilization magnets 110 D, 110 C, as shown in FIG. 1A , are designed to provide an opposing force between the central axis 113 and the support shaft 118 . The stabilization magnets may be located directly on the interior of the central axis 113 and the exterior of the support shaft 118 . The stabilization magnets may maintain a space between the inner diameter of the central axis 113 and the outer diameter of the support shaft 118 . Therefore, during rotation of the turbine rotor 104 there may be no friction between the central axis 113 of the turbine rotor 104 and the support shaft 118 . It should be appreciated that other means of reducing the friction between central axis 113 and the support shaft 118 may be used including, but not limited to, a bearing.
Friction may be eliminated between the turbine rotor 104 and the turbine support 106 using both the levitation magnets and stabilization magnets. The one or more sets of magnets 110 may be any magnets suitable for creating an opposing force including but not limited to a permanent magnet, an electromagnet, permanent rare earth magnet, ferromagnetic materials, permanent magnet materials, magnet wires and the like. A permanent rare earth magnet may include samarium cobalt (SmCo) and/or neodymium (NdFEB). Further, the one or more magnets 110 may be arranged in any suitable manner so long as they reduce the friction between the turbine rotor 104 and the turbine support 106 . FIGS. 1A , 2 , and 3 show the one or more sets of magnets 110 as a series of permanent magnets spaced apart from one another; however, it should be appreciated that an electromagnet may be used in order to magnetize a portion of the turbine rotor 104 and the turbine support 106 . Further, in an alternative embodiment, a portion of the turbine rotor 104 and the turbine support 106 may be magnetized to provide the opposing force. Thus in an alternative embodiment, the entire platform 122 and/or base 120 may be magnetized to provide an opposing force on the bottom 116 of the turbine rotor 104 which may also be magnetized.
The blades 108 may be any suitable blade capable of converting the kinetic energy of the wind into mechanical energy. In one embodiment, the blades 108 are made from a thin metal material, however, it should be appreciated that blades may be any suitable material including, but not limited to, a poly-carbon, a fabric, a synthetic material.
The blades 108 may be fixed to the turbine rotor 104 in a static position. Alternatively, the blades 108 may be moveably attached to the turbine rotor 104 . For example, a connection between the blades 108 and the turbine rotor 104 may allow the angle of the blades 108 to adjust in relation to the turbine rotor 104 . The angle may adjust manually or automatically in response to the wind conditions at the location.
The turbine rotor 104 provides mechanical energy for the one or more generators 112 as the turbine rotor 104 rotates about the axis 102 . In one embodiment, a generator gear 128 is moved by a portion of the turbine rotor 104 as the turbine rotor 104 rotates. As shown in FIG. 1A , an outer edge 130 of the gear 128 may be proximate an edge of the turbine rotor 104 . In one embodiment, the gear 128 engages the turbine rotor 104 with a traditional gear and/or transmission device capable of transferring rotation to the gear 128 .
In an additional or alternative embodiment, the gear 128 may be a magnetic gear. The magnetic gear is a gear that moves in response to a magnetic force between the turbine rotor 104 and the magnetic gear. At least one of the gear 128 and/or the proximate portion of the turbine rotor 104 may be magnetized. Thus, as the turbine rotor 104 rotates proximate the gear 128 the magnetic force moves the gear 128 in response to the turbine rotor 104 rotation. The magnetic gear allows the turbine rotor 104 to rotate the gear 128 without any friction between the two components.
FIG. 3 shows the magnetic gear according to one embodiment. A rotor gear component 300 may protrude from the outer surface of the turbine rotor 104 . The rotor gear component 300 may extend beyond the outer diameter of the turbine rotor 103 and rotate with the turbine rotor 104 . As shown, the rotor gear component 300 is a plate extending around an outer diameter of the turbine rotor 104 ; however, it should be appreciated that any suitable configuration for the rotor gear component 300 may be used. The gear 128 may include one or more gear wheels 302 which extend from the gear to a location proximate the rotor gear component 300 . As shown in FIG. 3 , there are two gear wheels 302 which are located above and below a portion of the rotor gear component 300 . As the turbine rotor 104 rotates, the rotor gear component 300 rotates. A portion of the rotor gear component 300 may pass in between two portions of one or more gear wheels 302 . Any of the rotor gear component 300 , and the one or more gear wheels 302 may be magnetized. The type of magnet used to produce the magnetic force for the magnetic gear may be any magnet described herein. The magnetic force between the components of the magnetic gear move the gear 128 , thereby generating electricity and/or power in the generator 112 .
The generators 112 may be located at various locations proximate the turbine rotor 104 . FIG. 1B shows three generators 112 located around the perimeter of the turbine rotor 104 . It should be appreciated that any suitable number of generators 112 may be used around the perimeter of the turbine rotor 104 . Further, the generator 112 may be located at other locations proximate the turbine rotor including, but not limited to, proximate the shaft 102 of the turbine rotor, in line with the axis 102 above and/or below the turbine rotor 104 , and the like.
The generator 112 may be any suitable generator for converting mechanical energy into power including, but not limited to, electric generators, motors, linear generators, and the like.
In one embodiment, one or more of the generators 112 is a linear synchronous motor (LSM). The LSM motor may advance the turbine support 120 and may double as a braking system.
The power generated by the generator may be fed directly to a power grid. Further, it should be appreciated that the power may alternatively or additionally be used on site or stored. The stored power may be used at a later date when demand for the power is higher. Examples of power storage units include, but are not limited to, batteries and generating stored compressed air, a flywheel system, a magnetically levitated flywheel system, hydraulic accumulators, capacitors, super capacitors, a combination thereof, and the like.
The one or more magnets 110 reduce and potentially eliminate friction between the turbine rotor 104 and the turbine support 106 . This friction reduction allows the scale of the wind turbine 100 to be much larger than a conventional wind turbine. In a conventional wind turbine the larger the wind turbine, the more friction is created between the moving parts. The amount of friction eventually limits the effective size of a conventional wind turbine. In one example, the wind turbine may have an outer diameter of 1000 ft. In a preferred embodiment, a fixed wind turbine 200 , as shown in FIG. 2 , has an outer diameter of about 600 ft. and is capable of producing more than 1 GWh of power. A smaller portable wind turbine 304 , shown in FIG. 3 , may be adapted to transport to remote locations. The portable version may have a diameter of greater than 15 ft. and a height of greater than 15 ft. In a preferred embodiment, the portable version has an outer diameter of about 30 ft. and a height of about 25 ft. and is capable of producing 50 MWh of power. It should be appreciated that the size and scale of the wind turbine may vary depending on a customers need. Further, it should be appreciated that more than one wind turbine may be located on the same portable transports system, and/or at one fixed location.
Although, the overall size of the wind turbine 100 may be much larger than a traditional wind turbine, the amount of power one wind turbine 100 produces is much larger than a traditional wind turbine. Therefore, the total land use required for the wind turbine 100 may be reduced over that required for a traditional wind farm.
The embodiment shown in FIG. 2 shows the fixed wind turbine 200 , according to one embodiment. The fixed wind turbine 200 may have a turbine support 106 which extends over the turbine rotor 104 . The one or more magnets 110 may be on an upper portion 201 of the turbine support 106 in addition to the locations described above.
The fixed wind turbine 200 may include an interior access way 202 , according to one embodiment. It should be appreciated that any of the wind turbines 100 , 200 and 304 may include an interior access way 202 . The interior access way 202 allows a person to access the interior of the turbine support 106 . The interior access way 202 may extend above and/or below the turbine rotor 104 in order to give the person access to various locations in the fixed wind turbine 200 . The interior access way 202 may allow a person to perform maintenance on the magnets 110 and other components of the wind turbine 100 , 200 , and 304 . Further, the interior access way 202 may have a means for transporting persons up and down the interior access way 202 . The means for transporting persons may be any suitable item including, but not limited to, an elevator, a cable elevator, a hydraulic elevator, a magnetic elevator, a stair, a spiral staircase, an escalator, a ladder, a rope, a fireman pole, a spiral elevator, and the like. The spiral elevator is an elevator that transports one or more persons up and down the interior access way 202 in a spiral fashion around the interior of the interior access way 202 . For example, the spiral elevator may travel in a similar path to a spiral staircase. The elevator and/or spiral elevator may use magnetic levitation to lift the elevator up and down.
The upper portion 201 of the turbine support 106 may include an observation deck 204 . The observation deck 204 may extend around the perimeter of the wind turbine 100 , 200 and/or 304 , thereby allowing a person to view the surrounding area from the observation deck 204 . The observation deck 204 may also serve as a location for an operator to control various features of the wind turbine, as will be discussed in more detail below.
The upper portion 201 of the turbine support 106 may further include a helipad 206 . The helipad 202 allows persons to fly to the wind turbine 100 , 200 , and/or 304 and land a helicopter (not shown) directly on the wind turbine. This may be particularly useful in remote locations, or locations with limited access including, but not limited to, the ocean, a lake, a industrial area, a tundra, a desert, and the like.
The upper portion 201 of the turbine support 106 may further have one or more cranes 208 . The cranes 208 allow an operator to lift heavy equipment. The crane 208 may be a tandem crane capable of rotating around the diameter of the wind turbine. The crane may assist in the construction of the wind turbine 100 .
FIG. 4 shows a top view of the wind turbine 100 in conjunction with one or more wind compressors 400 . The wind compressors 400 are each an obstruction configured to channel the wind toward the wind turbine 100 . As illustrated in FIG. 5 , a wind compressor 400 is positioned on either side of the wind turbine 500 so as to redirect the flow of wind towards the wind turbine 500 . The wind compressor 400 funnels the wind 506 into the wind turbine 500 . The convergence of the winds towards the wind turbine 500 creates a Venturi effect thereby increasing the speed and force of the winds upon the wind turbine 500 . This Venturi effect on the wind turbines increases the rpms or rotation speed of the rotors which translates into increased electrical energy produced by the generators 112 ( FIG. 1A ). This increase in wind energy and force upon the turbine blades 108 is thus translated from the wind turbine 500 to the generator 112 resulting in an increased output of electricity. This invention 400 increases the efficiency and ultimate output of the wind turbine 100 , 500 up to, beyond 1000-2000 megawatts (MGW) per hour or 1 gigawatt (GW) per hour. Known wind turbines produce between 2-4 MGW/hour.
The wind compressor 400 may be any suitable obstruction capable of re-channeling the natural flow of wind towards the wind turbines 100 , 400 . Suitable wind compressors include, but are not limited to, a sail, a railroad car, a trailer truck body, a structure, and the like. Structurally, the obstructions comprise a shape and size to capture and redirect a body of wind towards the wind turbine. In one embodiment, an obstruction, such as a sail, which comprises a large area in two dimensions but is basically a flat object, must be anchored to avoid displacement by the force of the wind. Other obstructions, such as the rail road car or trailer truck, should have enough weight to avoid wind displacement.
Each of the wind compressors 400 may be moveably coupled to a transporter 403 , or transport device to move the compressor 400 to a location or position that captures the wind flow as the direction of wind changes and directs the wind flow towards the wind turbine. The transporter may be any suitable transporter 403 capable of moving the wind compressor 400 including, but not limited to, a locomotive to move a rail car, an automobile, a truck, a trailer, a boat, a Sino trailer, a heavy duty self-propelled modular transporter 403 and the like. Each of the transporters 403 may include an engine or motor capable of propelling the transporter 403 . The location of each of the wind compressors 400 may be adjusted to suit the prevailing wind pattern at a particular location. Further, the location of the wind compressors 400 may be automatically and/or manually changed to suit shifts in the wind direction. To that end, the transporter 403 may include a drive member for moving the transporter 403 . The transporter 403 may be in communication with a controller, for manipulating the location of each of the transporters 403 in response to the wind direction. A separate controller may be located within each of the transporters 403 .
One or more pathways 402 , shown in FIG. 4 , may guide transporters 403 as they carry the wind compressors 400 to a new location around the wind turbine 100 . The one or more pathways 402 may be any suitable pathway for guiding the transporters including, but not limited to, a railroad, a monorail, a roadway, a waterway, and the like. As shown in FIG. 4 , the one or more pathways 402 are a series of increasingly larger circles which extend around the entire wind turbine 100 . It should be appreciated that any suitable configuration for the pathways 402 may be used. As described above, the size of the wind turbine 100 may be greatly increased due to the minimized friction between the turbine rotor 104 and the turbine support 106 . Thus, the pathways 402 may encompass a large area around the wind turbine 100 . The wind compressors 400 as a group may extend out any distance from the wind turbine 100 , only limited by the land use in the area. Thus, a large area of wind may be channeled directly toward the wind turbine 100 thereby increasing the amount of wind engaging the blades 108 .
In one aspect of this invention, the controller may be a single controller 404 capable of controlling each of the transporters 403 from an onsite or remote location. The controller(s) 404 may be in wired or wireless communication with the transporters 403 . The controller(s) 404 may initiate an actuator thereby controlling the engine, motor or drive member of the transporter 403 . The controller(s) may comprise a central processing unit (CPU), support circuits and memory. The CPU may comprise a general processing computer, microprocessor, or digital signal processor of a type that is used for signal processing. The support circuits may comprise well known circuits such as cache, clock circuits, power supplies, input/output circuits, and the like. The memory may comprise read only memory, random access memory, disk drive memory, removable storage and other forms of digital memory in various combinations. The memory stores control software and signal processing software. The control software is generally used to provide control of the systems of the wind turbine including the location of the transporters 403 , the blade direction, the amount of power being stored versus sent to the power grid, and the like. The processor may be capable of calculating the optimal location of each of the wind compressors based on data from the sensors.
One or more sensors 310 , shown in FIGS. 3 and 5 , may be located on the wind turbines 100 , 200 , 304 and/or 500 and/or in the area surrounding the wind turbines. The sensors 310 may detect the current wind direction and/or strength and send the information to a controller 312 . The sensors 310 may also detect the speed of rotation of the turbine rotor 104 . The controller 312 may receive information regarding any of the components and/or sensors associated with the wind turbines. The controller 312 may then send instructions to various components of the wind turbines, the wind compressors and/or the generators in order to optimize the efficiency of the wind turbines. The controller 312 may be located inside the base of the tower, at the concrete foundation, a remote location, or in the control room at the top of the tower.
It should be appreciated that the wind compressors may be used in conjunction with any number and type of wind turbine, or wind farms. For example, the wind compressors 400 may be used with one or more horizontal wind turbines, traditional vertical wind turbines, the wind turbines described herein and any combination thereof.
FIG. 5 shows a schematic top view of two wind compressors 400 used in conjunction with multiple wind turbines 500 . The wind compressors 400 are located on two sides of the wind turbines 500 . The wind turbines 500 represent any wind turbine described herein. The wind compressors 400 engage wind 504 which would typically pass and not affect the wind turbines 500 . The wind 504 engages the wind compressors 400 and is redirected as a directed wind 506 . The directed wind 506 leaves the wind compressor 400 at a location that optimally affects at least one or the wind turbines 500 . The wind compressors 400 may shield a portion of the wind turbines 500 from an engaging wind 508 in order to increase the affect of the wind on the wind turbines 500 . The engaging wind 508 is the wind that would directly engage the wind turbines 500 . For example, the wind compressors 400 shown in FIG. 5 shield a portion 509 of a vertical wind turbine which would be moving in the opposite direction to the wind 504 . The redirected wind 506 and the engaging wind 506 then engage an upstream side 510 of each of the wind turbines 500 . This arrangement may greatly increase the effectiveness of the wind turbines 500 .
Although the wind compressors 400 are shown on each side of the wind turbines 500 , it should be appreciated that any arrangement that increases the productivity of the wind turbine 500 may be used.
FIG. 6 shows a front view of the wind compressor 400 according to one embodiment. The transporter supporting the wind compressor is shown as a trailer 600 . The trailer supports a rigging 602 . The rigging 602 supports a sail 604 . FIG. 7 shows a side view of the wind compressor 400 , according to one embodiment. The sail 604 is full blown and shown in a mode of the wind engaging the sail 604 .
The rigging 602 , as shown in FIGS. 6 and 7 includes multiple poles extending in a substantially vertical direction from the transporter. The multiple poles are configured to couple to the sail 604 . The poles may couple to the sail 604 proximate two sides of the sail 604 . In one embodiment, two poles may be spaced apart from one another in order to allow the sail to extend a large distance between the poles. As shown, the poles vary in height; however, it should be appreciated that any arrangement of the poles may be used. Further, the rigging may be any suitable structure capable of supporting the sail 604 .
The sail 604 is any suitable surface intended to deflect wind. As shown, the sail is a flexible material held by the rigging. The flexible material may be any flexible material including, but not limited to, a canvass, a cloth, a polycarbon, a metal, a glued and molded sail, a mylar, and the like. Further, the sail may be a solid non-flexible material which deflects wind that engages the sail. The non-flexible material may not require the rigging.
Preferred methods and apparatus for practicing the present invention have been described. It will be understood and readily apparent to the skilled artisan that many changes and modifications may be made to the above-described embodiments without departing from the spirit and the scope of the present invention. The foregoing is illustrative only and that other embodiments of the integrated processes and apparatus may be employed without departing from the true scope of the invention defined in the following claims.
|
A wind compressor system having one or more wind turbines and a plurality of wind compressors located proximate the one or more wind turbines. The wind compressors optimize the energy created by the wind turbines by redirecting and converging the wind from the wind compressor to the wind turbines. Each of the wind compressors comprises an obstruction having a size and shape adapted to converge the wind currents by means of a Venturi effect toward the one or more turbines thereby increasing the velocity and force of the wind hitting the wind turbine. A plurality of transporters coupled to the wind compressors. The transporters configured to move at least one wind compressors to a location that maximizes the force of the wind encountered by the turbine.
| 5
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to an end block for a battery and, more particularly, to an end block with a composite structure having a low density, high strength core enveloped by a light weight inert material.
2. Description of the Prior Art
Electrochemical cells utilizing bipolar cell designs having reactive electrodes are well known. Conventional flowing electrolyte bipolar batteries are typically comprised of "stack" of cells, an electrolyte pump, an electrolyte reservoir, a cooling element, and external studs in electrical communication with the terminal electrodes. Each cell is comprised of an electrode upon which the anodic reaction takes place and an electrode upon which the cathodic reaction takes place.
In a typical bipolar battery, each electrode comprises two "poles", such that the anodic reaction occurs on one side of the electrode and the cathodic reaction occurs on the opposite side of the same electrode. Thus, in contrast to a monopolar battery, which requires two separate electrodes per cell, a bipolar battery is comprised of bipolar electrodes upon which both the anodic and cathodic reactions occur. As with a monopolar battery, the cells in a bipolar battery are electronically connected in series. Unlike a monopolar battery, where the cells are hydraulically isolated, the cells of a flowing electrolyte bipolar battery are hydraulically connected in parallel. Application Ser. No. 189,363 filed May 2, 1988, now abandoned entitled "Terminal Electrode" and having the same assignee as the present application, describes the current flow and structure of a bipolar battery of the zinc-bromine type and is incorporated by way of reference herein for such detail.
Generally, however, flowing electrolyte bipolar batteries require, in addition to cell stack components, electrolyte manifolds and fluid anolyte/catholyte pumps, and end blocks at each end of the battery which sandwich the cell stack therebetween. The end blocks serve as a supporting structure for the cell stack and provide the framework for duct and shunt tunnels to communicate with interiorly disposed elements of the battery. Additionally, the blocks support the various terminal studs which electrically communicate with the end or terminal electrodes of the cell stack. Not only must the blocks necessarily be inert relative to the various chemical constituencies comprising the fluid anolyte/catholyte, it is important that end blocks resist bending or bowing caused primarily by the different pressures which exist between the atmosphere and internal operating environments of the battery. For example, in a zinc-bromine battery environment, operating pressures may reach 15 pounds per square inch. Bowing of end plates may result in nonuniform electrolyte distribution in end cells. Nonuniform flow distribution may then cause a significant reduction in voltage and/or discharge capacity during discharge in, those cells relative to other cells.
Additionally, in zinc-bromine batteries, bowing of end blocks may result in poor zinc plating at the other end cell causing undesirable dendritic zinc growth to occur through the pore structure of the separator of the adjacent end cell. If dendritic growth reaches a cathode surface, it would provide a short circuit for current in that cell and eliminate its voltage contribution.
Various attempts have been made in the prior art to provide end plates which minimize bowing and resulting problems. For example, steel plates coated with an inert plastic material have been employed as end blocks largely at the sacrifice of another important consideration, namely weight. Still other attempts have considered the use of plastic materials ribbed in various patterns to provide additional strength to withstand the internal operating pressures to provide the required rigidity. It is often necessary, however, to have ribs which may approach a thickness of nearly an inch, resulting in an unnecessary increase in the overall volume of the assembly.
SUMMARY OF THE INVENTION
A light weight, deflection-resistant end block for a battery comprising a base member made of a light weight, chemically inert and electrically resistive material which has one or more cavities for housing low density, substantially rigid inserts such as honey-combed aluminum. The inserts are encapsulated by a cover welded or otherwise secured to the walls of the base member defining the cavities. The base member may also extend beyond the walls to provide a means for receiving the various ducts carrying the flowing electrolyte to and from the interior of the battery, thereby isolating the inserts from possible exposure to the electrolyte.
BRIEF DESCRIPTION OF THE DRAWING
A preferred exemplary embodiment of a composite end block in accordance with the present invention will hereinafter be described in conjunction with the appended drawing, wherein like designations denote like elements, and:
FIG. 1 is a perspective view of the various components of a bipolar battery sandwiched between a pair of end blocks in accordance with the present invention;
FIG. 2 is an exploded perspective of an end block in accordance with the present invention;
FIG. 3 is a front view of an assembled end block as shown in FIG. 2;
FIG. 4 is a back view of an assembled end block as shown in FIG. 2; and
FIG. 5 is a sectional view of an end block taken along line 5--5 of FIG. 3.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
Referring to FIG. 1, bipolar battery 100 comprises a pair of end blocks 130, in accordance with the present invention, disposed exterior to a series of alternating separators 112 and electrodes 114, and sealed together to form a stack 120 of electrochemical cells. A pair of terminal electrodes 110 are shown separated from end blocks 130 and stack 120.
To provide the aqueous anolyte and catholyte to the respective half cells, anolyte and catholyte inlet ducts 35 and 20, respectively, and respective anolyte and catholyte discharge ducts 45 and 40 are positioned to facilitate passage of the aqueous anolyte and catholyte. Channels 116 are provided on each side of electrodes 114 or separators 112 as desired for the proper flow of the fluid electrolyte. The various details involving the structures of the various internal components and movement of the aqueous anolyte and catholyte are not necessary for understanding of the present invention but may be found in the aforementioned application Ser. No. 189,363. The technique of fabricating electrodes with the desired surface configurations for the appropriate flow of the aqueous electrolyte is disclosed in commonly assigned application Ser. No. 247,035 entitled "Friction Welded Battery Component and Method", filed Sept. 20, 1988, now U.S. Pat. No. 4,945,019 which is incorporated by way of reference herein.
Battery 100 is further provided with a pair of shunt tunnels 60 and 65 and preferably a removable shunt terminal 70 which helps minimize the effect of parasitic currents which often plague bipolar batteries of the zinc-bromine type. Commonly assigned application Ser. No. 241,714 entitled "Removable Protective Electrode in a Bipolar Battery", filed Sept. 8, 1988, now U.S. Pat. No. 4,929,325 sets forth in detail such a removable terminal 70 and is therefore incorporated by way of reference herein.
Referring now to FIG. 2, end block 130 is depicted in exploded perspective with the three major parts thereof separated: a base member 132, a pair of end block inserts 134 and 136, and cover 138. Base member 132 is essentially a thin planar member having a first "major surface" 140, as seen in FIG. 4. On the opposite side, a second "major surface" 142 is seen in FIGS. 2 and 5. A "major surface" may be defined as those surfaces on a flat object having the greatest area as opposed to the relatively small areas on the connecting sides. Major surface 140 is essentially flat while major surface 142 is totally circumscribed by a wall 144 projecting outwardly from surface 142 except for corners 152. A dividing wall 146 essentially bisects the area on surface 142 within the perimeters of wall 144 such that wall 146, together with wall 144 and surface 142, define a pair of cavities 148 and 150. Wall 146, which may have a width of about 0.5 inches, acts as a reinforcing rib to provide desired rigidity to base 132 and end block 130.
Inserts 134 and 136 are housed within and have configurations complimentary to the dimensions of respective cavities 148 and 150. To facilitate complete enclosure, i.e. encapsulation, of inserts 134 and 136, walls 144 and 146 preferably extend outward from major surface 142 a distance equal to or slightly greater than the thickness of inserts 134 and 136.
Flat cover member 138 has a configuration which is preferably substantially identical to that defined by the outside edge of wall 144. Thus, respective corners 152 of base member 132 remain exposed even after cover 138 is positioned on and secured to wall 144, thereby encapsulating inserts 134 and 136. As best seen in FIG. 1, corners 152 serve as the supporting structure for the various anolyte/catholyte ducts and shunt tunnels. Additionally, as will become more apparent from the ensuing description, by providing corners 152 separated by wall 144 from cavities 148 and 150, inserts 134 and 136 are completely isolated from the electrolyte ducts and tunnels. This provides a further safeguard against any contact by the fluid electrolyte with the material comprising the inserts.
As described in referenced application Ser. No. 189,163, the number of studs extending from terminal electrode 120 is a matter of choice. In the embodiment of FIG. 1, two rectangularly shaped studs 50 and 55 are shown extending through each block 130. As seen in FIG. 2, each component of end block 130 is provided with a pair of openings through which respective studs 50 and 55 may extend when the components thereof are assembled. Base member 132 has a pair of rectangular shaped openings 158 and 160 circumscribed by respective rectangular shaped extensions or protrusions 159, 161 extending outward from major surface 142 centrally located within respective cavities 148 and 150. Complimentary openings 162 and 164 are formed within respective inserts 134, 136 such that protrusions 159 and 161 extend therethrough in a snug fit relationship. Protrusions 159 and 161 thus serve to electrically insulate studs 50 and 55 from inserts 134 and 136. The length of the extension of protrusions 159, 161 should be about the same or slightly greater than the thickness of inserts 134, 136, i.e. about the same as the extension of wall 144 and 146, such that the top surface of each protrusion abuts cover 138 about complimentary openings 154, 156 formed in cover 138.
Base member 132 and cover 138 are preferably fabricated from polyethylene, although other polyolefins such as polypropylene or polyolefin copolymers may be used as well. Various fillers and reinforcers may be incorporated into the selected material to increase its strength. Fillers may be selected from any compatible materials, such as, for example, glass fibers, glass beads, or titanium dioxide. It has been determined that fillers up to about forty percent by weight of the selected material may be used without detrimentally affecting other desired characteristics of the base and cover.
Inserts 134 and 136 are fabricated from low density materials, for example, less than 8 pounds per cubic foot, having significant resistance to bending over the longest "linear dimension" of the end block. The term "linear dimension" is defined herein to mean the length or width measured along major surface 132 of the end block. A preferred material is honey-combed aluminum laminated on either side with aluminum sheet, commercially available under the registered trademark Hexcel, from the Hexcel Company. Other materials having a density and weight approaching that of aluminum may also be utilized so long as the combined resistance against bending of the composite comprising end block 130 limits bending to less than about 0.005" under internal pressures within said battery of about 12 to 15 psi. For example, certain other materials like polyurethane, polypropylene, polyethylene, ceramics and graphite may also be employed.
Both base 132 and cover 138 are preferably made through an injection molding process, although compression molding techniques may be employed as well. Once base 132 is formed, inserts 134, 136 may be placed within respective cavities 148, 150. Cover 138 then is positioned in place and friction welded to the abutting parts of base 132. In fabrication of base 132 and cover 138, a weld bead (not shown) flanked by two flash traps may be positioned about the circumference of cover 138 or, alternatively, on wall 144 to facilitate friction welding of cover 138 to base 132. Additionally, a weld line (not shown) may extend down wall 146 and a weld seal (not shown) about the cover abutting the top surfaces of protrusions 159, 161 may be used to provide additional support against bending.
When assembling battery 100, major surface 140 of each end block 130 faces inwardly toward the various battery components. As described in the previously referenced application Ser. No. 247,035, each substrate of the various battery components is made from a material such as polethylene, polypropylene, other polyolefins, or copolymers thereof, such that the components may be friction welded together about the entire peripheries thereof thereby forming an integral structure. Similarly, the end blocks of the present invention may each be friction welded along the periphery of major surface 140 to an adjacent terminal electrode 110 to again provide the desired integral structural frame.
Thus, it is apparent that there has been provided, in accordance with the invention, a composite end block for use in a battery that fully satisfies the aims and advantages set forth above. While the invention has been fully described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art. Accordingly, it is intended to embrace all such alternatives, modifications and variations as fall within the spirit and scope of the appended claims.
|
A light weight deflection-resistant end block is provided for a battery and comprises a base member of a light weight, chemically inert and electrically resistive material which has one or more cavities adapted to receive low density, substantially rigid inserts such as honey-combed aluminum.
| 8
|
The invention described herein was made in the course of work under a grant or award from the Department of Health, Education, and Welfare.
DESCRIPTION
1. Technical Field
This invention relates to a method for preparing compounds having vitamin D-like activity and to compounds which are key intermediates in such method.
More specifically, this invention relates to a method for preparing compounds having vitamin D-like activity which contain an oxygen function at carbon 1 in the molecule.
Still more specifically, this invention relates to a method for preparing 1α-hydroxylated compounds which are characterized by vitamin D-like activity via a cyclovitamin D intermediate.
It is well known that the D vitamins exhibit certain biological effects, such as stimulation of intestinal calcium absorption, stimulation of bone mineral resorption and the prevention of rickets. It is also well known that such biological activity is dependent upon these vitamins being altered in vivo, i.e. metabolized, to hydroxylated derivatives. For example, current evidence indicates that 1α,25-dihydroxyvitamin D 3 is the in vivo active form of vitamin D 3 and is the compound responsible for the aforementioned biological effects.
The synthetic 1α-hydroxyvitamin D analogs, such as 1α-hydroxyvitamin D 3 , and 1α-hydroxyvitamin D 2 also exhibit pronounced biological potency and such compounds as well as the natural metabolites show great promise as agents for the treatment of a variety of calcium metabolism and bone disorders, such as osteodystrophy, osteomalacia and osteoporosis.
2. Background Art
The discovery that in vivo metabolism of vitamin D leads to 1α-hydroxylated forms and the demonstration that the presence of a 1α-hydroxy function imparts high biological potency to vitamin D compounds has lead to many processes for the chemical synthesis of such 1-hydroxylated derivatives. Most processes involve 1-hydroxylation of a suitable steroid precursor followed by conversion of 1-hydroxy steroid to the 1-hydroxyvitamin D compound. Recently a novel general scheme for the production of 1-hydroxylated vitamin D compounds has been proposed which differs radically from the methods previously known. This new process, developed by Paaren et al (Proc. Nat. Acad. Sci. U.S.A. 75, 2080-2081) involves the direct hydroxylation of a vitamin D precursor to give the corresponding 1α-hydroxy compound in high yield.
For purposes of discussion this process may be illustrated by the following schematic (Process Schematic A). ##STR1##
In reference to the foregoing schematic the process steps are:
Step (1): Tosylation of a β-hydroxyvitamin D starting material (e.g. vitamin D 3 , vitamin D 2 , 25-hydroxyvitamin D 3 , etc.) to give the corresponding 3-O-tosyl derivative which is subjected directly to
Step (2): Solvolysis in an alcohol solvent (ZOH, where Z may be methyl, ethyl, propyl, etc. or H) to give the cyclovitamin intermediate (2)
Step (3): Introduction of 1α-hydroxyl by allylic oxidation using SeO 2 to give intermediate (3)
Step (4): Protection of the 1α-hydroxy function as the 1α-O-acyl derivative (4A) where acyl may be any convenient acyl group such as formyl, acetyl, benzoyl, etc.
Step (5): Solvolysis of intermediate (4A) using p-toluene sulfonic acid, a catalyst, to form a mixture of 1α-O-acyl-3β-hydroxyvitamin D compound (5A) and the corresponding 5,6-trans isomer (6A)
Step (6): Separation of this mixture by chromatography and alkaline hydrolysis (or reductive cleavage) of the acyl function to produce the 1α-hydroxyvitamin D compound (7) and if desired, the corresponding 5,6-trans compound (8)
This process offers a highly convenient and efficient route to 1α-hydroxyvitamin D compounds (and/or their 5,6-trans isomers) from appropriate vitamin D starting materials. Furthermore, the method is extremely general in that the side chain R of the starting material may be any of the common side chains which may also be substituted by a wide spectrum of functional groups including hydroxy, alkyl, O-acyl, halo, keto, carboxy, amido, or unsaturation.
DISCLOSURE OF INVENTION
A new process has now been found which improves and shortens the Paaren et al process described above.
Specifically, it has been found that under suitable conditions the 1α-hydroxycyclovitamin D intermediate (structure 3 in the above schematic) can be solvolyzed directly--without prior protection of the 1-hydroxy group as 1-O-acyl function--to yield a mixture of 5,6-cis and 5,6-trans 1α-hydroxy-3-O-acyl vitamin D compounds, which can be separated and converted to the desired 1α-hydroxyvitamin D compounds (or the corresponding 5,6-trans isomer).
It is evident that Paaren et al protected the 1α-hydroxy function group by conversion to a 1α-O-acyl group, because of the reasonable expectation that the sensitive allylic 1α-hydroxy function would be subject to degradative reaction during solvolysis using a fairly strong acid such as p-toluene sulfonic acid. Experience has, in fact, shown that solvolysis of an unprotected 1α-hydroxycyclovitamin D compound under such conditions leads to much decomposition and a complex product mixture containing undesired products. Paaren et al indicate also that after protection of the 1α-hydroxyl as a 1α-O-acyl group the desired solvolysis product is obtained in good yield but such protection does not completely prevent undesired decomposition reaction during solvolysis using a p-toluene sulfonic acid catalyst. They further found that decomposition can be minimized by solvolyzing the 1α-O-acyl-protected cyclovitamin compound in acetic or formic acid. However, under such conditions they obtained the 5,6-cis and 5,6-trans mixture of the 1,3-di-O-acyl vitamin D compounds which is very difficult to separate, and the advantage of minimizing decomposition reactions is negated by the losses incurred due to the requirement for elaborate chromatography. Whenever the substituents at C-1 and C-3 are of like character (e.g. both are hydroxy or O-acyl) separation of the 5,6-cis and trans forms of such vitamin D derivatives is difficult. To overcome this separation problem, Paaren et al suggested a scheme in which a 1α-O-acyl cyclovitamin D compound (where acyl may represent any acyl group but not formyl) is solvolyzed in formic acid to produce the 5,6-cis and 5,6-trans mixture of the 1α-O-acyl-3β-O-formyl-vitamin D compounds. The formyl group is then removed by selective hydrolysis to yield the 5,6-cis and 5,6-trans mixture of the 1α-O-acyl-3β-hydroxy compounds, which may then be separated conveniently and processed according to step 6 of the above schematic. Such modification, however, introduces still another reaction step (the selective hydrolysis of the formyl group).
It is a particularly advantageous feature of the present process that it eliminates both the undesired decomposition reactions and the necessity for the hydroxy protection/deprotection steps. The process of this invention can be illustrated by the following schematic (Process Schematic B). ##STR2## In the new process illustrated above, steps 1, 2 and 3 are identical to the corresponding steps in Process Schematic A.
Step 4 is the key new step which involves direct solvolysis of the 1α-hydroxycyclovitamin D intermediate (3) in the presence of low-molecular weight organic carboxylic acids (such as formic or acetic acids) to yield the 1α-hydroxy-3-O-acyl vitamin D derivative (5B) as well as the corresponding 1α-hydroxy-3-O-acyl-5,6-transvitamin D compound (6B) (where the acyl group corresponds, of course, to the acyl moiety of the acid used in the solvolysis reaction).
Step 5 is analogous to step 6 of Process Schematic A and involves the separation of the cis and trans 1α-hydroxy-3-O-acyl compounds and subsequent hydrolytic or reductive removal of the 3-acyl group to yield the 1α-hydroxyvitamin D compound (7) or, if desired, the 5,6-trans-1α-hydroxyvitamin D compound (8).
The process of this invention offers significant practical advantages over that of Paaren et al. Thus,
(a) the overall synthesis is accomplished in fewer steps, since the hydroxy protection step and/or the formate hydrolysis step, or both, are omitted.
(b) direct solvolysis yields a product mixture containing the 1α-hydroxy-3-O-acyl vitamin D compound and the corresponding 5,6-trans product, without the contamination by various degradation products that results from the use of p-toluene sulfonic acid as a catalyst in the solvolysis reaction described by Paaren et al.
(c) because undesired degradation products are eliminated, separation of the cis and trans forms resulting from solvolysis is simplified.
(d) the brevity of the scheme and the ease of separation of cis and trans isomers makes the new scheme the preferred process for large-scale synthesis of 1α-hydroxyvitamin D compounds.
(e) the elimination of one process step and the absence of undesired degradation products leads to improved yields of desired 1α-hydroxylated compounds.
In the present process the steps up to the formation of the 1α-hydroxy cyclovitamin D intermediate (steps 1, 2, 3 in Process Schematic B) are, as already pointed out above, identical with the corresponding steps in the Paaren et al process (Process Schematic A) and are conducted as described by these authors.
The key new step, direct solvolysis of the 1α-hydroxy cyclovitamin D intermediate (step 4 of Process Schematic B) is conveniently accomplished by dissolving the cyclovitamin in a low-molecular weight organic carboxylic acid and briefly warming the resulting mixture. Preferred acids are, for example, formic or acetic acid and the reaction is conveniently conducted at a temperature of 40°-60° C. over a period of 15-30 minutes. If convenient, or required, an inert co-solvent may be used in conjunction with the organic carboxylic acid to improve the solubility of the 1-hydroxycyclovitamin. Suitable co-solvents are, for example, tetrahydrofuran or dioxane. Solvolysis of 1α-hydroxycyclovitamin D compounds in organic carboxylic acids results in a product mixture (ratio of ca. 3:1) consisting of 1α-hydroxy-3-O-acyl vitamin D and 1α-hydroxy-3-O-acyl-5,6-trans-vitamin D, where the acyl group derives from the organic acid used for solvolysis. For example, solvolysis of 1α-hydroxy-3,5-cyclovitamin D 3 in glacial acetic acid yields 1α-hydroxyvitamin D 3 3-acetate and 1α-hydroxy- 5,6-trans-vitamin D 3 3-acetate. Similarly, solvolysis of 1α,25-dihydroxy-3,5-cyclovitamin D 3 in formic acid leads to 1α,25-dihydroxyvitamin D 3 3-formate and the corresponding 5,6-trans isomer. The introduction of a 3-O-acyl function during solvolysis is a highly desirable and advantageous feature of the process, because the 5,6-cis and 5,6-trans isomers of 1α-hydroxy-3-O-acyl-vitamin D compounds are easily separated by chromatography. Suitable chromatographic methods include silica gel thin-layer chromatography, high pressure liquid chromatography and (for larger scale preparations) silica gel column chromatography or high pressure liquid chromatography using preparative columns, all of which are well known in the art.
After separation of the cis and trans isomers the 3-O-acyl group can be removed by hydrolysis under basic conditions, or by reduction using hydride reagents. For example treatment of a methanol solution of a 1α-hydroxy-3-O-acyl-vitamin D compound with 5% aqueous NaOH, for 1-2 hours at 25°-50° C., removes the acyl group quantitatively and yields the desired 1,3-dihydroxyvitamin D product. The same result is achieved by treatment of an ether solution of a 1α-hydroxy-3-O-acyl derivative with an excess of LiAlH 4 at room temperature for 30 minutes. The same methods applied to a 1α-hydroxy-3-O-acyl-5,6-trans vitamin D compound provide the 1α-hydroxy-5,6-trans-vitamin D product. Reductive or hydrolytic methods for acyl removal are equally convenient and a choice between them would depend on the nature of other functionalities that may be present in the molecule.
The 5,6-trans-1α-hydroxyvitamin D compounds obtained by this process can, of course, be converted to the 5,6-cis compounds by irradiation with ultraviolet light, according to the general procedures of Inhoffen et al (Chem. Ber. 90, 2544 (1957)). Anaologously the 5,6-trans-1α-hydroxyvitamin D 3-O-acyl intermediates resulting from solvolysis can be converted to the corresponding 5,6-cis-derivatives, which upon acyl removal, as described above, yield the 1α-hydroxyvitamin D compounds.
A noteworthy feature which the present process shares with the original Paaren et al process is its generality. The process may be applied to vitamin D compounds bearing any of the common steroid side chains. More specifically, the side chain R in any of the compounds in Schematic B, may be hydrogen or lower alkyl (such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl), or R may have any of the structures depicted below: ##STR3## wherein each of R 1 , R 2 and R 3 can be hydrogen, hydroxy, lower alkyl O-lower alkyl, O-lower acyl, O-aromatic acyl, or fluoro, and
where,
R 4 is hydrogen or lower alkyl
Another noteworthy feature of this invention is that direct solvolysis yield vitamin D compounds and 5,6-trans vitamin D compounds in which the C-3 hydroxy group is specifically aceylated in a more facile manner. Such compounds have considerable utility, particularly in cases where modification (e.g. oxidation, substitution, etc.) at the C-1 hydroxy is desired without affecting the C-3 hydroxy group, the preparation of which by other methods has been generally more cumbersome and difficult.
Wherever in this application and in the claims the term "lower alkyl" is used it is intended to designate a hydrocarbon radical having from 1 to about 5 carbon atoms and which may be of branched or unbranched structure. The term "lower acyl" signifies an acyl group having from 1 to about 4 carbon atoms (e.g. formyl, acetyl, butyryl) and the term "aromatic acyl" means a benzoyl or substituted benzoyl unit (e.g. p-nitro benzoyl).
The following Examples are intended to be illustrative only and are not to be construed as limiting the appended claims.
EXAMPLE 1
A solution of 10 mg of 1α-hydroxy-6-methoxy-3,5-cyclovitamin D 3 in 1.0 ml of glacial acetic acid is heated to 55° C. for 15 min. The cooled reaction mixture is added dropwise to a stirring solution of ice/sat NaHCO 3 and the resulting neutralized mixture is extracted with ether. The organic extracts are washed once with sat NaHCO 3 , once with H 2 O, dried over MgSO 4 and the solvent removed in vacuo. The resulting crude oily residue is applied to a 20 cm×20 cm silica gel TLC plate (750μ thick) which is developed in Skellysolve B:ethyl acetate (3:1) to yield 5.8 mg of 1α-hydroxyvitamin D 3 3-acetate [UVλ max 264 nm; mass spectrum, m/e: 442 (M + , 40), 382 (65), 364 (15), 269 (20), 134 (100); NMR, δ, 0.54 (3H, s, 18-H 3 ), 0.86 (6H, d, J=6.6 Hz, 26-H 3 and 27-H 3 ), 0.92 (3H, d, J=6.0 Hz, 21-H 3 ), 2.04 (3H, s, 3-OCOCH 3 ), 4.41 (1H, m, 1-H), 5.02 (1H, m (sharp), 19(Z)-H), 5.21 (1H, m, 3-H), 5.34 (1H, m (sharp), 19(E)-H), 6.02 (1H, d, J=11.1 Hz, 7-H), 6.34 (1H, d, J=11.1 Hz, 6-H)] and 2.0 mg of 5,6-trans-1α-hydroxyvitamin D 3 3-acetate [UVλ max 273 nm; mass spectrum, m/e: 442 (M + , 10), 382 (80), 269 (23), 134 (100); NMR, δ, 0.54 (3H, s, 18-H 3 ), 0.87 (6H, d, J=6.3 Hz, 26-H 3 and 27-H 3 ), 0.92 (3H, d, J=6.1 Hz, 21-H 3 ), 2.03 (3H, s, 3-OCOCH 3 ), 4.49 (1H, m, 1-H), 4.99 (1H, m (sharp), 19(Z)-H), 5.13 (1H, m (sharp), 19(E)-H), 5.25 (1H, m, 3-H), 5.80 (1H, d, J=11.4 Hz, 7-H), 6.57 (1H, d, J=11.4 Hz, 6-H)]. Treatment of 1α-hydroxyvitamin D 3 3-acetate with 10% methanolic NaOH in ethanol for 1.0 Hr at 50° C. yields 1α-hydroxyvitamin D 3 which is identical to an authentic sample. Similar treatment of 5,6-trans-1α-hydroxyvitamin D 3 3-acetate gives 5,6-trans-1α-hydroxyvitamin D 3 [UVλ max 273 nm, mass spectrum; m/e: 400 (M + , 12), 382 (8), 152 (42), 134 (100); 0.56 (3H, s, 18-H 3 ), 0.87 (6H, d, J=6.6 Hz, 26-H 3 and 27-H 3 ), 0.93 (3H, d, J=6.02 Hz, 21-H 3 ), 4.24 (1H, m, 3-H), 4.50 (1H, m, 1-H), 4.97 (1H, m (sharp), 19(Z)-H), 5.12 (1H, m (sharp), 19(E)-H), 5.89 (1H, d, J=11.4 Hz, 7-H), 6.58 (1H, d, J=11.4 Hz, 6-H).]
EXAMPLE 2
A solution of 8 mg of 1α-dihydroxy-6-methoxy-3,5-cyclovitamin D 3 in 800 μl of glacial HOAc is heated to 55° C. for 15 min, cooled, and added dropwise to a stirring mixture of ice/sat NaHCO 3 . This mixture is extracted with ether and the organic extract is washed once with sat NaHCO 3 , once with H 2 O, dried over MgSO 4 and concentrated in vacuo. The resultant oil is chromatographed on a 20 cm×20 cm silica gel plate (750μ thickness) which is developed in Skellysolve B:ethyl acetate (3:2) to yield 4.0 mg of 1α,25-dihydroxyvitamin D 3 3-acetate [UVλ max ; mass spectrum, m/e: 458 (M + , 30), 398 (70), 380 (15), 134 (100), 59 (80); NMR, δ, 0.55 (3H, s, 18-H 3 ), 1.22 (6H, s, 26-H 3 and 27-H 3 ), 0.92 (3H, d, J=6.0 Hz, 21-H 3 ), 2.04 (3H, s, 3-OCOCH 3 ), 4.38 (1H, m, 1-H), 5.00 (1H, m (sharp), 19(Z)-H), 5.20 (1H, m, 3-H), 5.34 (1H, m (sharp), 19(E)-Z), 6.06 (1H, d, J=11.6 Hz, 7-H), 6.42 (1H, d, J=11.6 Hz, 6-H)] and 1.7 mg of 5,6-trans-1α,25-dihydroxyvitamin D 3 3-acetate [UVλ max 273 nm; mass spectrum, m/e: 458 (M + , 10), 398 (85), 380 (25), 134 (100), 59 (85); NMR, δ, 0.54 (3H, s, 18-H 3 ), 1.23 (6H, s, 26-H 3 and 27-H 3 ), 0.92 (3H, d, J=6.0 Hz, 21-H 3 ) 2.03 (3H, s, 3-OCOCH 3 ), 4.50 (1H, m, 1-H), 4.96 (1H, m (sharp), 19(Z)-H), 5.10 (1H, m (sharp), 19(E)-H), 5.28 (1H, m, 3-H), 5.80 (1H, d, J=11.4 Hz, 7-H)° 6.55 (1H, 3, J=11.4 Hz, 6-H).] Hydrolysis of 5,6-cis-1α,25-dihydroxyvitamin D 3 3-acetate with 10% NaOH in methanol for 1.0 hr at 55° C. gives 1α,25-dihydroxyvitamin D 3 which is identical in all respects to an authentic sample. By treating 5,6-trans-1α,25-dihydroxyvitamin D 3 3-acetate as above, 5,6-trans-1α,25-dihydroxyvitamin D 3 is obtained; [UVλ max 273 nm; mass spectrum; m/e 416 (15), 398 (8), 152 (40), 134 (100), 59 (95); NMR, δ, 0.55 (3H, s, 18-H 3 ), 1.23 (6H, s, 26-H 3 and 27-H 3 ), 0.92 (3H, d, J=6.0 Hz, 21-H 3 ), 4.22 (1H, m, 3-H), 4.53 (1H, m, 1-H), 4.95 (1H, m (sharp), 19(Z)-H), 5.12 (1H, m (sharp), 19(E)-H), 5.85 (1H, d, J=11.4 Hz, 7-H) and 6.55 (1H, d, J=11.4 Hz, 6-H).]
EXAMPLE 3
To a solution of 12 mg of 1α-hydroxy-6-methoxy-3,5-cyclovitamin D 3 in 1.0 ml of dry THF is added 1.0 ml of 98% HCO 2 H. The reaction is heated to 55° C. for 10 min, then quenched with ice/sat. NaHCO 3 . The aqueous suspension is quickly extracted with ether and the organic extracts are washed with H 2 O, dried over MgSO 4 and concentrated in vacuo. The crude oil is applied to a 20 cm×20 cm silica gel TLC plate (750μ thick) which is developed in Skellysolve B:ethyl acetate (4:1) to yield 6.3 mg of 1α-hydroxyvitamin D 3 3-formate [UVλ max 264 nm; mass spectrum, m/e: 428 (M + )] and 2.2 mg of 5,6-trans-1α-hydroxyvitamin D 3 3-formate [UVλ max 273; mass spectrum, m/e: 428 (M + )]. Hydrolysis of the formate esters with KHCO 3 in aqueous methanol at 45° C. for 0.5 hr gives 1α-hydroxyvitamin D 3 and the corresponding 5,6-trans isomer which were identical in all respects to the compounds reported in Example 1.
EXAMPLE 4
A solution of 7.5 mg of 1α,25-dihydroxy-6-methoxy-3,5-cyclovitamin D 3 in 1.0 ml of dry THF is treated with 1.0 ml of 98% HCO 2 H. After heating for 10 min at 55° C. the reaction is quenched over ice sat NaHCO 3 and quickly extracted with ether. The ether extracts are washed with water, dried over MgSO 4 and concentrated in vacuo. The crude oil is chromatographed on a 20 cm×20 cm silica gel TLC plate (750μ thick) in Skellysolve B:ethyl acetate (3:2) to yield 3.6 mg of 1α,25-dihydroxyvitamin D 3 3-formate [UVλ max =264 nm; mass spectrum, m/e: 444 (M + )] and 1.3 mg of 5,6-trans-1α,25-dihydroxyvitamin D 3 3-formate: [UVλ max =273 nm; mass spectrum m/e: 444 (M + )]. Simple KHCO 3 hydrolysis of the 5,6-cis and 5,6-trans analog which are identical to the compounds described in Example 2.
EXAMPLE 5
A solution of 380 mg of 1α-hydroxy-6-methoxy-3,5-cyclovitamin D 2 in 8 ml of glacial acetic acid is heated to 60° C. for 15 min. The reaction mixture is cooled and slowly added to a stirring solution of ice/sat NaHCO 3 . After neutralization the aqueous suspension is extracted with ether and the organic phase is washed once with water and then dried over MgSO 4 . After removing the solvent in vacuo, the crude oily product is applied to a 1.5 cm×60 cm column packed with 45 g of silica gel in hexanes. Batch elution with 100 ml of 4% ethyl acetate, 100 ml of 8% ethyl acetate and 100 ml of 12% ethyl acetate followed by 400 ml of 16% ethyl acetate which was collected in 6.0 ml fractions. Fractions 23-32 contained 180 mg of pure 1α-hydroxyvitamin D 2 3-acetate [UVλ max =264 nm; mass spectrum, m/e; 454 (M + , 70), 394 (60), 376 (20), 269 (35), 134 (100)] while fractions 33-45 contained a cis-trans mixture and fractions 46-60 contained 60 mg of 5,6-trans-1α-hydroxyvitamin D 2 3-acetate [UVλ max 273 nm; mass spectrum, m/e: 454 (M + , 20), 394 (80), 376 (10), 269 (25), 134 (100)]. Hydrolysis of 1α-hydroxy-vitamin D 2 3-acetate with 10% methanolic NaOH in ethanol at 50° C. for 1.0 hr produced 5,6-cis-1α-hydroxyvitamin D 2 which is identical in all respects to an authentic sample prepared by another method [Lam et al, Steroids, 30, 671-677 (1977)] and identical hydrolysis of the 5,6-trans isomer gives 5,6-trans-1α-hydroxyvitamin D 2 [UVλ max 273 nm; mass spectrum, m/e: 412 (25, M + ), 394 (60), 376 (10), 269 (20), 152 (60), 134 (100)].
EXAMPLE 6
A solution of 6.8 mg of 1α,25-dihydroxy-6-methoxy-3,5-cyclovitamin D 2 (which is prepared from 25-hydroxyvitamin D 2 , by following the procedures given by Paaren et al (Proc. Nat. Acad. Sci, U.S.A. 75, 2080 (1978)) for the preparation of the corresponding 1α,25-dihydroxy-cyclovitamin D 3 analog) in 0.5 ml of glacial acetic acid is heated to 60° for 10 min then added dropwise to an ice/sat NaHCO 3 solution. This aqueous mixture is extracted with ether and the organic extracts are washed once with water, dried over MgSO 4 and concentrated in vacuo. HPLC of the oily residue on micro-particulate silica gel (Zorbax-SIL, a product of DuPont, Wilmington, Del.) with 10% isopropanol in hexane as the solvent yields 3.5 mg of 1α,25-dihydroxyvitamin D 2 3-acetate (UVλ max 264 nm; mass spectrum, m/e, 472 (M + ) and 412 (M + -60)) and 1.3 mg of 5,6-trans-1α,25 -dihydroxyvitamin D 2 3-acetate (UVλ max 273 nm; mass spectrum, m/e; 472 (M + ), 412 (M + -60)). Hydrolytic cleavage of the 3β-acetoxy functions (5% NaOH/MeOH, 45°, 45 min) provides 1α,25-dihydroxyvitamin D 2 which is identical in all respects to an authentic sample and 5,6-trans-1α,25-dihydroxyvitamin D 2 (UV,λ max 273 nm; mass spectrum, m/e, 428 (M + ).
EXAMPLE 7
A solution of 4.5 mg of 1α,25-trihydroxy-6-methoxy-3,5-cyclovitamin D 3 (which is prepared from 24,25-dihydroxyvitamin D 3 , by tosylation at C-3, solvolysis to the 3,5-cyclovitamin, and SeO 2 -oxidation to the 1α-hydroxy compound, according to the procedures of Paaren et al, Proc. Nat. Acad. Sci 75, 2080 (1978)) in 0.3 ml of glacial acetic acid is heated to 55° for 10 min and then quenched over ice/sat. NaHCO 3 . The aqueous solution is extracted with ether and the organic extracts are washed once with water, dried over MgSO 4 and concentrated in vacuo. High performance liquid chromatography (HPLC) on micro-particulate silica gel (Zorbax-SIL/DuPont) with 12% isopropanol in hexane as the solvent yields 2.0 mg of 1α,24,25-trihydroxyvitamin D 3 3-acetate (UVλ max 264 nm), and 0.8 mg of the corresponding 5,6-trans-1α,24,25-trihydroxyvitamin D 3 -acetate isomer (UV,λ max 273 nm). Basic hydrolysis (5% NaOH/MeOH, 45°, 1.0 hr.) of 1α,24,25-trihydroxy-vitamin D 3 3-acetate yields 1α,24,25-trihydroxyvitamin D 3 which is identical in all respects to an authentic sample. Hydrolysis of 1α,24,25-trihydroxy-5,6-trans-vitamin D 3 under the same conditions give 5,6-trans-1α,24,25-trihydroxyvitamin D 3 (UVλ max 273 nm; mass spectrum, m/e, 432 (M + )).
|
An improved method for the preparation of 1α-hydroxylated vitamin D compounds involving directly introducing an oxygen function at carbon 1 of the vitamin D molecule or precursors or derivatives thereof, wherein the 1α-hydroxycyclovitamin D intermediate is solvolyzed directly, without first converting the 1-hydroxy group to a 1-O-acyl function as a protective measure.
| 2
|
TECHNICAL FIELD
[0001] The invention relates to a dose delivery device, wherein a dose can be set by rotating a dose setting member, whereby a push button is elevated from one end of the device, and the set dose can then be injected by pressing the push button back to its non-elevated position, thereby moving a piston rod co-operating with the piston in a cartridge and expelling a medicament out of the cartridge through a needle.
BRIEF DISCUSSION OF RELATED ART
[0002] From EP 0 327 910 is known an injection device in which a dose is set in the classic way by rotating a tubular injection button engaging a threaded piston rod, thereby causing the injection button to elevate from the end of the injection device. By pressing down the injection button until abutment with a fixed stop, the threaded piston rod is moved a distance corresponding to the movement of the injection button. The piston rod mates a piston in a cartridge and medicine is expelled from the cartridge. This kind of injection device transmits the injection force directly to the piston of the cartridge but provides no gearing, i.e. the linear movement of the injection button corresponds exactly to the linear movement of the piston rod.
[0003] However, the above described device does not comprise a numbered scale drum, and the amount of a set dose has to be calculated by adding a one digit scale with a ten digit scale. As all parts of the dose setting mechanism are reset by linear movements when a set dose is injected, the increment size of a unit in the dose setting mechanism is very small, and a dose can only be set to every second unit.
[0004] EP 1 003 581 describes a number of methods to achieve a dose setting providing a gearing between the axial movement of the piston rod and the dose setting member to allow a scale drum with sufficient space for numbers to be added. In one embodiment a dose setting member is rotated in a thread in the housing having a higher pitch than the pitch on the piston rod. When pressure is added to an injection button, the piston rod is being rotationally coupled to the dose setting member and as the piston rod is rotated in a nut fixed to the housing it is moved forward until the dose setting member abuts a fixed stop. This embodiment provides a gearing in movement, but does not reduce the needed injection force, as the transmission from linear movement to rotational movement and back from rotational to linear movement eats up most of the obtained force reduction due to friction.
[0005] The unit increment size in the dose setting mechanism for above mentioned embodiments is rather big and plenty of space for numbers are provided. However, for people with small hands and fingers it might be a problem to inject a set dose without changing the grip during injection due to the long movement of the pushbutton, especially if a user wants to use the index finger for injection
[0006] In WO 2008/058667 a piston rod is provided with a first thread which is engaging a driver and a second thread handed in the opposite direction which is engaging the housing. A numbered scale drum is rotating together with the driver when setting a dose and is decoupled from the driver, when the dose is injected. When a dose is set the driver is rotated up along the piston rod in a helical movement, due to the coupling with the scale drum, and the piston rod is thereby prevented from rotating in the dose setting situation. When the dose is injected, the driver, which is now prevented from rotating, is pressed down and consequently it is pushing the piston rod forward. As the piston rod is also engaged with the housing in an opposite handed thread, it will rotate and thereby move a shorter distance than the driver.
[0007] WO 2005/018721 describes a pen with a gearing mechanism based on two threads handed in the same direction and a third thread on the piston rod which is not directly a part of the gearing mechanism. A piston rod is connected with a nut. A non-rotational driver is engaging a scale drum via a first thread and the nut via a second thread. The pitch of the first thread is bigger than the pitch of the second pitch and the difference between them is equal to the pitch of the piston rod. When a dose is set, the nut is rotationally locked to the scale drum, and is thereby rotated and elevated a distance corresponding to the elevation of the driver. When the set dose is to be injected, the nut disengages the scale drum to engage the non-rotational driver. As the scale drum is pushed into the device, the rotation of the scale drum will cause the non-rotational driver to retract into the scale drum and the resulting displacement of the driver to be equal to the set dose. The nut is now pushed back to zero position bringing the piston rod along causing insulin to be expelled. It should be noted however that the pitches of the threads are dependent of number of increments per revolution and unit size etc. and the dose force will be relatively high due to the low driving pitch.
[0008] In WO 2009/039851 a gearing nut is provided with a first thread which is engaging a driver and a second thread handed in the opposite direction which is engaging the housing and is axially locked to a dosing nut. A dosing nut is engaged with a non-rotating piston rod in a thread connection. The driver and the housing are relatively locked against rotation. A numbered scale drum is rotating together with a dose setting grip when setting a dose and is decoupled from the dose setting grip, when the dose is injected. When a dose is set the dosing nut is rotated one distance up along the piston rod in a helical movement and the driver is pushed another distance by the scale drum. When the dose is injected, the non-rotating driver is pressed down via the dose setting grip and the relative axial and non-rotating movement between the driver and the housing will cause the gearing nut to move a shorter distance due to the two opposite handed threads. As the gearing nut is axially locked to the dosing nut, the dosing nut will be pressed down the same distance. The dosing nut is prevented from rotating during injection and it will therefore bring along the non-rotating piston rod.
[0009] The three above mentioned devices provides a smaller push-button movement pro unit, but for users taking large doses and having small hands, it might still be a challenge to carry out an injection. At the same time they comprise additional parts to provide a gearing.
[0010] The invention provides an injection device comprising a numbered scale drum, a few and simple parts and with a short movement of the injection button during injection.
BRIEF SUMMARY
[0011] The invention relates to a dose delivery device comprising a housing, a dose selector, a push-button, a piston rod not rotating during dose setting and rotating during injection, a driver threadedly engaged with the piston rod and a numbered scale drum rotationally locked to the driver,
[0012] wherein a dose can be set by rotating the dose selector, whereby the push-button is elevated from one end of the device a distance proportional to the set dose from a position fixed relative to the housing, and
[0013] wherein the set dose can then be injected by pressing the push-button back to its non-elevated position, through which motion of the push-button the piston rod will move the same distance,
[0014] characterised by
[0015] the driver is rotated an angle in one direction when setting the dose, and together with the piston rod the same angle in the opposite direction when injecting the set dose.
[0016] By letting the driver rotate one way during dose setting and the other way together with the scale drum during injection, it is possible to rotate a numbered scale drum in such a way, that it will display the amount of a set or remaining dose correctly in any situation.
[0017] In an embodiment of the invention, the dose setting member and the push-button is formed as one integral part. Hereby it is achieved that the number of parts and, thus, the complexity and production costs of the device are reduced.
[0018] In another embodiment of the invention a numbered scale drum displaying the amount of a set dose is rotationally locked to the driver and axially locked to the push-button. Hereby a scale drum without any thread engagements with other parts causing loss of energy is provided.
[0019] In a further embodiment of the invention a numbered barrel is engaging a first thread in the housing having a first pitch and a second thread on the driver having a second pitch the second pitch being higher than the first pitch. In this way it is possible to let the numbered barrel rotates a bigger angle than the driver and at the same time to elevate more than the driver, and thereby it is possible to print bigger numbers and increase readability.
[0020] In a further embodiment of the invention a ratchet arm is provided on the numbered scale drum and wherein the ratchet arm cooperates with a protrusion in the housing in such a way, that when a dose is injected and the push-button is moved the initial distance the ratchet arm will pass over the protrusion in end of the injection, but when the pressure is removed from the push-button and the push-button is no longer moved the initial distance, the ratchet arm can pass the protrusion in the housing and a new dose can be set. This makes it more clearly for the user when the injection is fulfilled.
[0021] In a further embodiment of the invention, the dose selector is rotationally coupled to the driver during dose setting and decoupled during injection. This has the advantage, that the dose selector does not rotate during injection and a separate pushbutton can be avoided.
[0022] In a further embodiment of the invention, the dose selector is indexed on certain positions on a revolution in the housing producing a clicking and tactile feed-back due to an interaction between the dose selector and the housing. In this way a separate item for producing a clicking sound is avoided and the dose-selector is prevented from rotating during dose injection.
[0023] In an even further embodiment of the invention a ratchet is provided between the dose selector and the driver to cause the dose selector to rotationally bring along the driver when a dose is set. This makes it unnecessary to couple and decouple the dose selector from the driver, as the torque produced in the thread engagement between the piston rod and the housing when injecting a dose will overcome the torque from the ratchet, and therefore the driver will rotate relative to the dose selector as the dose selector is prevented from rotating due to the dose setting clicks.
[0024] In yet another embodiment of the invention, the dose delivery device comprises a one-way ratchet which is rotational coupled to the piston rod. This has the function that it together with the friction in the piston helps preventing the piston rod from moving when a dose is set and at the same time it produces a clicking sound when injecting the dose.
[0025] In yet another embodiment of the invention, the dose delivery device comprises an item which is rotational coupled to the piston rod and which is rotational coupled to the housing during dose setting and decoupled during injection. This has the advantage that it in a more rigid way prevents the piston rod from moving when a dose is set.
[0026] In a further embodiment of the invention, the numbered scale drum moves axially together with the push-button and the scale drum couples rotationally to the ratchet when the push-button is pushed. This provides a very simple way to make the driver, the scale drum, the piston rod and the ratchet to rotate together when the dose is injected.
[0027] In yet another embodiment of the invention, the dose delivery device further comprises a non-rotationally window which is axially movable and which is engaged with the scale drum via a thread in such a way, that it moves axially in the opposite direction of the driver when setting and injecting a dose. This makes it possible to use a bigger area of the scale drum for the numbers and thereby to make the numbers bigger.
[0028] In yet another embodiment of the invention, a magnifier which enlarges the displayed number corresponding to the set dose is provided. In this way the readability and thereby the convenience in using the device is enhanced.
[0029] The invention provides a dose delivery device comprising a threaded piston rod engaged with a thread in an opening in a housing and engaged with a thread on a driver. A unidirectional ratchet is rotational locked to the piston rod and is axial but not rotational coupled to the driver. To set a dose the driver is rotated up along the piston rod in the locking direction of the ratchet. To correct a set dose, the driver is rotated back and the resistance in the ratchet prevents the ratchet and the piston rod from rotating. To inject the set dose the driver is coupled rotationally to the ratchet via a scale drum and pushed forward toward the needle end (this will be explained further). This will force the piston rod and the ratchet and the driver to rotate due to the thread engagement with the housing, and the resistance in the ratchet will be overruled and the ratchet will produce a clicking sound when the piston rod moves forward.
[0030] The dose delivery device is of the gearless kind where the movement of the pushbutton corresponds to the movement of the piston rod, which has the advantage that users having small fingers doesn't have to change grip during injection, and that injection using the index finger is possible. To display the amount of a set dose, a numbered scale drum is provided, which is rotational locked to the driver. The scale drum will display the amount of a set dose in a window in the housing. The scale drum is capable of moving axial a small distance relative to the driver. A dose selector is releasable coupled to the driver and is axial mating the scale drum via a gliding bearing. When the set dose is to be injected the dose selector which also acts as push-button is pushed a little forward which will disconnect it from the driver, and at the same time the scale drum is pushed a little forward which will lock the scale drum rotational to the ratchet. In this way a package comprising the piston rod, the driver, the scale drum and the ratchet are locked together rotationally. Further push on the push-button/dose selector will cause the package to rotate and move forward due to the thread connection between the housing and the piston rod. A spring between the scale drum and the driver will push the dose selector back in engagement with the driver after ending or interrupting the injection, and the scale drum and the ratchet will at the same time be disengaged.
[0031] The dose selector also acts as a bidirectional ratchet against the housing, to provide increments of a specified size around the length axis of the device and to provide a tactile and audible feed back. When the dose is injected, the dose selector does not rotate. However, an unintentional rotation during injection will cause no harm, as the dose selector and the driver are decoupled.
[0032] A window can be added to the housing to protect the user from touching the scale drum or a magnifier can be added to more clearly display the amount of a set dose. A window or a magnifier can also act as a stop for the maximum settable dose by having an inward reaching protrusion cooperating with the scale drum or another part of the device.
[0033] In another embodiment the scale drum has an outer thread having a pitch of e.g. the double of the pitch of the piston rod. A window item which might also comprise a magnifier and which is axial but not rotational movable relative to the housing is engaging the thread of the scale drum. When the scale drum rotates up along the piston rod, the window item moves down a bigger distance, and in that way more space on the scale drum is available for displaying numbers. A prolonged hole in the housing should allow the window item to display the number in different positions.
[0034] It should be noted, that the dose delivery device can be designed to be either disposable or rechargeable and to contain one, two or multiple cartridges at the time. If the dose delivery device is designed to be rechargeable, the piston rod must be able to rotate when the cartridge holder is disconnected.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] In the following the invention is described in further details with reference to the drawings, wherein
[0036] FIG. 1 shows a perspective view of a device according to the invention,
[0037] FIG. 2 shows an exploded view of a device according to the invention,
[0038] FIG. 3 shows a partly exploded view of the dose setting mechanism of a device according to the invention,
[0039] FIG. 4 schematically shows a vertical sectional view of a device according to the invention ready to set a dose,
[0040] FIG. 5 schematically shows a vertical sectional view of a device according to the invention where a dose has been set,
[0041] FIG. 6 schematically shows a vertical sectional view of a device according to the invention where the dose setting member has been pushed and the driver is disengaged,
[0042] FIG. 7 schematically shows a vertical sectional view of a device according to the invention where a dose has been injected but the dose setting member is still depressed,
[0043] FIG. 8 schematically shows a vertical sectional view of an embodiment of a device according to the invention with an axial movable window where a dose has been set
[0044] FIG. 9 shows a perspective view of the movable window according to the invention
[0045] FIG. 10 schematically shows a vertical sectional view of an embodiment of a device according to the invention with an axial movable window where a dose has been set
[0046] FIG. 11 shows a perspective view of the scale drum with an “end of dose” ratchet arm
[0047] FIG. 12 shows a perspective view of the scale drum with an “end of dose” ratchet arm acting in the housing in a position where the push button is still depressed
[0048] FIG. 13 shows a perspective view of the scale drum with an “end of dose” ratchet arm acting in the housing in a position where the push button is released
DETAILED DESCRIPTION
[0049] FIG. 1 shows a device according to the invention in an oblique view. Visible is the housing 2 comprising a window 39 , where the amount of a set dose can be displayed, the dose selector 4 by which a dose is set and injected and the cartridge holder 3 comprising a thread 16 for the attachment of a double-ended needle. The cartridge holder 3 also contains the medicine-filled cartridge 10 (visible on FIG. 2 ). The cartridge 10 comprises a piston, which cooperates with the piston rod 7 (visible on FIG. 4 ) of the injection system to expel a set dose of medicine from the cartridge 10 out through the needle. The cooperation between the different elements of the device will be described in the following.
[0050] The dose selector of the shown embodiments is to be comprehended as an element by which a dose can be both set and injected. In other embodiments of the invention, the functions of the dose selector 4 could be divided into two elements—a dose setting button and an injection button.
[0051] The dose delivery device according to the invention has a gearing ratio of 1:1 which means that the axial movement of the dose selector 4 during injection is equal to the axial movement of the piston rod 8 and the piston 40 . In addition the dose selector 4 moves a little distance to engage/disengage from the driver 6 in the teeth connection 17 / 28 and to cause scale drum 5 and the ratchet 7 to engage in the teeth connection 24 / 30 .
[0052] The dose setting and the dose injection mechanisms are highly integrated and the change from dose setting mode to dose injection mode is due to an initial movement of the integrated push-button and dose selector 4 before the actual injection starts. The mechanism comprises the following moving parts: a dose selector 4 , a piston rod 8 , a ratchet 7 , a driver 6 , a scale drum 5 , the dose selector 4 and these parts cooperates with the housing 2 . The piston rod 8 has a thread 35 and is engaged with the housing 2 via a thread 13 in a narrowing and at the same time the piston rod 8 is engaged with a thread 26 on the driver 6 . A unidirectional ratchet 7 is axial locked to the driver 6 and is rotational locked to the piston rod 8 via a key/groove connection and allows rotation of the piston rod 8 in only one direction due to the ratchet arms 33 which interacts with teeth 12 in the housing 2 . A scale drum 5 displaying the amount of a set dose is rotational locked to the driver 6 and is capable of moving a small axial distance relative to the driver 6 which allows it to be rotational connected with the ratchet 7 due to teeth on both items 24 / 30 during injection. A dose selector 4 is mating the scale drum 5 via gliding surfaces 21 / 38 on the two items. The dose selector 4 is coupled to the driver 6 via sets of teeth 17 / 28 when a dose is set, and decoupled by a small initial axial movement when a dose is injected and to allow this connection, the scale drum 5 has a pair of openings 22 for the teeth 28 on the driver 6 . The dose selector 4 furthermore comprises knobs 20 (visible on FIG. 3 ) on the outer surface which cooperates with grooves 11 in the housing 2 in such a way that they act as bidirectional ratchet which will index the dose selector 4 and thereby the driver 6 and the scale drum 5 in positions equally spaced around the main axis of the device, and the distance between two increments corresponding to a unit of the drug to be injected. This bidirectional ratchet also gives the user an audible and tactile feed-back which allows the user to count the units when setting a dose.
[0053] Between the driver 6 and the scale drum 5 a spring mechanism is provided. Two flexible arms 29 on the driver 6 are sliding over slanted ribs 27 in the scale drum 5 near the top. When the driver 6 and the scale drum 5 are pressed together, the flexible arms 29 will bend and act with a force on the slanted ribs 27 perpendicular to the axis of the device and along the axis of the device. The force along the axis of the device will try to take apart the parts as the flexible arms 29 try to straighten out and regain their original form. A flange 18 on the dose selector 4 mates the lower surface of the teeth segments 28 of the driver 6 and prevents the parts from going a part.
[0054] The housing 2 has an opening to allow the user to read a set dose and this opening is equipped with a window which is preferably formed as a magnifier to ease the readability of the set dose.
[0055] In the following all sequences related to having an injection are described with references to FIGS. 4-7 .
[0056] FIG. 4 shows a device according to the invention ready to set a dose. As it can be seen the spring function 27 / 29 between the driver 6 and the scale drum 5 is in its relaxed position and the dose selector 4 and the scale drum 5 are in their non depressed position. Consequently the dose selector 4 is engaging the driver 6 via the teeth connection 17 / 28 and the scale drum 5 is decoupled 24 / 30 from the ratchet 7 . The piston rod 8 is locked against rotation in the dose setting direction due to the ratchet arms 33 on the ratchet 7 , and the rotational position of the scale drum 5 and the driver 6 is well defined due to thread engagement 26 / 35 between the driver 6 and the piston rod 8 and due to the rotational stop 15 in the housing 2 which cooperates with the stop surface 23 on the scale drum 5 . The scale drum 5 displays 0 through the window 39 in the housing 2
[0057] FIG. 5 shows a device according to the invention where a dose has been set. To set the dose the dose selector 4 has been rotated clockwise which will cause it to produce a clicking and tactile feed-back due to the knobs 20 (see FIG. 3 ) on the outside of the dose selector 4 and the grooves 11 inside the housing 2 . Due to the teeth engagement 17 / 28 between the dose selector 4 and the driver 6 the driver will be rotated as well and both items will at the same time elevate away from the needle end. The piston rod 8 is locked against rotation in the dose setting direction due to the ratchet arms 33 on the ratchet 7 . The scale drum 5 will follow the driver 6 due to the spring connection 27 / 29 and the rotational connection formed by the cuts 22 in the scale drum 5 and the teeth sections 28 on the driver 6 and display the amount of the set dose through the window 39 . If a dose has been wrongly set and consequently has to be corrected, the dose selector 4 is simply rotated anti-clockwise until the correct amount is displayed in the window 39 . The rotational resistance in the ratchet 7 and the axial resistance between the piston 40 and the cartridge 10 will ensure that the piston rod 8 does not rotate during correction of the dose.
[0058] In FIG. 6 the dose selector 4 has been moved a small distance by a push on the upper surface 42 on the dose selector 4 , just enough to decouple the teeth connection 17 / 28 (see FIG. 3 ) between the dose selector 4 and the driver 6 and to engage the teeth connection 24 / 30 between the scale drum 5 and the ratchet 7 , but not enough to actually start the injection. It is clear that the flexible arms 29 on the driver 6 has been bended due to the interaction with the slanted surfaced 27 on the ribs inside the scale drum 5 , and they now apply an axial force between the scale drum 5 and the driver 6 , when they try to straighten out and gain there initial form. The piston rod 8 , the driver 6 , the scale drum 5 and the ratchet 7 are now coupled together and will move as one part as long as the dose selector 4 has been pushed. Because the surface 41 in the cut 22 in the scale drum 5 now mates the upper side of the teeth sections 28 on the driver 6 further push on the dose selector 4 will cause the piston rod 8 , the driver 6 , the scale drum 5 and the ratchet 7 to rotate causing a very little rotational resistance due to the gliding bearing 21 / 38 between the dose selector 4 and the scale drum 6 and the gliding bearing 36 / 37 between the piston rod 8 and the piston washer 9 . They will now move axial toward the needle end due to the thread engagement 32 / 35 between the piston rod 8 and the housing 2 , which again will move the piston 40 via the piston washer 9 and expel the medicament. Due to the disengagement from the driver 6 the dose selector 4 will not rotate due to further pushing, and any unintended rotation of the dose selector 4 during injection will not have any influence on the accuracy of the injected dose. During injection the ratchet arms 33 on the ratchet 7 will produce a clicking sound when jumping in and out in the grooves 12 in the housing 2 .
[0059] FIG. 7 shows a device according to the invention, where the injection of a set dose has just been accomplished and it is clear, that the piston rod 8 , piston washer 9 and piston 40 has moved a distance corresponding to the amount of the set dose. The piston rod 8 , the driver 6 , the scale drum 5 and the ratchet 7 has all been rotated until the stop surface 23 on the scale drum 6 has mated the stop rib 15 in the housing 2 and the number “0” is displayed through the window 35 in the housing 2 . The dose selector 4 is still depressed and to prepare the device for a new dose setting, the pressure on the dose selector 4 must be removed, which will engage the teeth connection 21 / 38 between the dose selector 4 and the driver 5 and decouple the teeth engagement 24 / 30 between the scale drum 5 and the ratchet 7 due to the spring function 27 / 29 between the driver 6 and the scale drum 5 .
[0060] FIG. 8 shows another embodiment of a device according to the invention. The scale drum 5 b is provided with an outer thread 34 with a pitch which is handed the opposite way of the thread 35 on the piston rod 8 . As the pitch of the thread 35 on the piston rod 8 is left handed, the pitch of the thread on the scale drum 5 is right handed. A sliding window 19 (see also FIG. 9 ) which is non rotational but axial movable in an elongated hole in the housing 2 b has a thread segment which engages the thread 34 of the scale drum 5 . The pitch of the thread 34 and the thread segment of the sliding window 19 should be higher than the pitch 35 of the piston rod 8 e.g. the double, so that the sliding window 19 will move towards the needle end, when the scale drum 5 moves away from the needle end. This makes it possible to provide the scale drum 5 with bigger numbers to ease the readability. The sliding window 19 can further form a magnifier to further increase the readability.
[0061] In FIG. 10 a dose has been set, and it is now obviously that the window 19 moves down when the scale drum 5 moves up, and that more space for numbers thereby is provided.
[0062] FIG. 11 shows a scale drum 5 b with an “end of dose” ratchet arm 43 in a housing 2 . When a dose is being injected, the ratchet is in an area where it is allowed to rotate freely, but in the end of the injection it has moved down to the level of the stop rib 15 and just before the injection stops, the “end of dose” ratchet arm will pass the stop rib 15 and this passage will cause the “end of dose” ratchet arm to be pushed and to fall down behind the stop rib 15 creating a clicking sound, which should be designed to be different from the sound of the injection clicks. When the pressure on the push-button is released, the “end of dose” ratchet arm 43 will move to a level relative to the stop rib 15 where it is capable of moving in the stop direction of the ratchet 43 and a new dose can be set.
|
A dose delivery device is disclosed wherein a dose can be set by rotating a dose setting member, whereby a push button ( 4 ) is elevated from one end of the device a distance proportional to the set dose from a position fixed relative to the housing, and wherein the set dose can then be injected by pressing the push button back to its non- elevated position, through which motion a piston rod will move approximately the same distance. The invention provides a method of forcing a numbered scale drum to rotate both during dose setting and injection to allow the user to read the remaining dose at any time during setting and injecting a dose.
| 0
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to medical devices and more particularly pertains to various connectors designed to facilitate the healing of broken bones or torn tissue in the human body.
2. Description of the Prior Art
There is a plethora of well known devices used in the medical field for the purpose of temporarily connecting broken bones and torn tissue. Most of these devices rely upon implantable rods positionable within a broken bone, bone and tissue plates attachable to external surfaces of the bones and tissue, and surgical steel screws designed to attach plates or otherwise hold broken bones together by a threaded attachment arrangement. These various devices are constructed out of conventional materials such as stainless steel, titanium, and chrome cobalt alloys. These rigid materials will often cause atrophy of a broken bone which frequently then results in the necessity of having a second medical operation.
A typical example of a bone implant is to be found in U.S. Pat. No. 4,787,378 which issued to Jitendra Sodhi on Nov. 29, 1988. This patent discloses a self-retaining nail which is inserted inside a broken femur so as to urge the two bone halves together, thereby facilitating a healing by a natural growth process.
Another patent of interest as disclosing a bone implant is U.S. Pat. No. 4,955,911 which issued to Frey et al. on Sep. 11, 1990. This patent is of interest inasmuch as the bone implant is formed of a plastic body having a multi-layer wire fabric secured to an outside surface. As such, some flexible movement of the bone implant is facilitated and this is a desirable characteristic in the healing process. However, this type of implant would most likely be difficult and costly to manufacture which perhaps accounts for its unavailability at the present time in the commercial market.
U.S. Pat. No. 4,943,292, which issued to Amnon Foux on Jul. 24, 1990, is of interest as disclosing a plate positionable on an external surface of a broken bone and which utilizes the aforediscussed surgical screws. These screws are positioned in elongated holes filled with an elastically deformable material whereby the plate is utilized to stabilize the bone pieces but permits the screws, and hints the bone pieces, to move a short distance back and forth in the direction of the axis of the bone in order to promote healing.
A typical example of a plate for broken bone fixation is disclosed in U.S. Pat. No. 4,429,690 which issued to Giancarlo Angelino-Pievani on Feb. 7, 1984. This patent is representative of a plurality of prior art patents which disclose various configurations for rigid bone-holding plates.
Another patent which is of interest and which relates to a bone plate is U.S. Pat. No. 4,905,680 which issued to Degar Tunc on Mar. 6, 1990. This patent discloses an absorbable bone plate which is constructed totally of materials that will eventually be absorbed in the body.
As can be appreciated, all of the above-discussed bone fixation devices are functional for their intended purposes and there is a distinct possibility that all are now being used at various times. However, as can also be appreciated, there is a continuing need for new and improved bone and tissue fixation devices which represent a simpler and less costly construction while facilitating an enhanced degree of reliability. In this respect, the various embodiments of the present invention substantially fulfill this need.
SUMMARY OF THE INVENTION
In view of the foregoing disadvantages inherent in the known types of bone and tissue fixation devices now present in the prior art, the present invention provides various embodiments of improved bone and tissue fixation devices to thus reduce the cost of manufacture and difficulty of use thereof. As such, the general purpose of the present invention, which will be described subsequently in greater detail, is to provide new and improved bone and tissue fixation devices which have all the advantages of the prior art bone and tissue fixation devices and none of the disadvantages.
To attain this, the present invention essentially comprises bone and tissue connectors which are designed for use on or in the human body for the purpose of connecting bone or soft tissue to promote a healing process. Various embodiments are in the form of bands, straps, braids, or rods and are secured by fasteners such as pegs, plates, screws and cable ties. All of the connectors are formed from materials having a similar of elasticity as bone and include, among others, polyethylene, polysulfone, collagen and polymer-carbon fiber composites.
In this regard, the bone and tissue fixation devices comprising the present invention are non-toxic and biocompatible, while also being strong, lightweight and flexible as opposed to the aforediscussed conventional materials (stainless steel, titanium and chrome cobalt alloys) currently used for the same purpose. All of these fixation devices can be produced at a reasonable cost, and their applications in world wide orthopedic surgery are unlimited.
There has thus been outlined, rather broadly, the more important features of the invention in order that the detailed description thereof that follows may be better understood, and in order that the present contribution to the art may be better appreciated. There are, of course, additional features of the invention that will be described hereinafter and which will form the subject matter of the claims appended hereto.
In this respect, before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purpose of description and should not be regarded as limiting.
As such, those skilled in the art will appreciate that the conception, upon which this disclosure is based, may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention.
Further, the purpose of the foregoing abstract is to enable the U.S. Patent and Trademark Office and the public generally, and especially the scientists, engineers and practitioners in the art who are not familiar with patent or legal terms or phraseology, to determine quickly from a cursory inspection the nature and essence of the technical disclosure of the application. The abstract is neither intended to define the invention of the application, which is measured by the claims, nor is it intended to be limiting as to the scope of the invention in any way.
It is therefore an object of the present invention to provide new and improved bone and tissue fixation devices which have all the advantages of the prior art bone and tissue fixation devices and none of the disadvantages.
It is another object of the present invention to provide new and improved bone and tissue fixation devices which ay be easily and efficiently manufactured and marketed.
It is a further object of the present invention to provide new and improved bone and tissue fixation devices which are of a durable and reliable construction.
An even further object of the present invention is to provide new and improved bone and tissue fixation devices which are susceptible of a low cost of manufacture with regard to both materials and labor, and which accordingly are then susceptible of low prices of sale to the consuming public, thereby making such bone and tissue fixation devices economically available to the buying public.
Still yet another object of the present invention is to provide new and improved bone and tissue fixation devices which provides in the apparatuses and methods of the prior art some of the advantages thereof, while simultaneously overcoming some of the disadvantages normally associated therewith.
Still another object of the present invention is to provide new and improved bone and tissue fixation devices which are constructed of material having similar modulus of elasticity as a human bone.
These together with other objects of the invention, along with the various features of novelty which characterize the invention, are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and the specific objects attained by its uses, reference should be had to the accompanying drawings and descriptive matter in which there is illustrated preferred embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein:
FIG. 1 is a front elevation view of a flat cable tie comprising a first embodiment of the present invention.
FIG. 2 is an enlarged detail view taken from FIG. 1.
FIG. 3 is a perspective view illustrating a use of the first embodiment of the invention.
FIG. 4 is an elevation view illustrating a plate and cable tie combination which comprise a second embodiment of the invention.
FIG. 5 is a front elevation view of a round cable tie comprising a third embodiment of the invention.
FIG. 6 is an enlarged detail view of the invention taken from FIG. 5.
FIG. 7 is a perspective view illustrating a manner of forming an aperture to facilitate a use of the third embodiment of the invention.
FIG. 8 is a perspective view illustrating a first use of the third embodiment of the invention.
FIG. 9 is a perspective view illustrating a second use of the third embodiment of the invention.
FIG. 10 is an elevation view illustrating a round cable tie comprising a fourth embodiment of the invention.
FIG. 11 is a perspective view of a round cable tie comprising a fifth embodiment of the invention.
FIG. 12 is a perspective view illustrating a use of the fourth and fifth embodiments of the invention.
FIG. 13 is an elevation view illustrating a cable tie having a deployable head which comprises a sixth embodiment of the invention.
FIG. 14 is an elevation view illustrating the sixth embodiment of the invention in a deployed condition.
FIG. 14A is a top plan view of the sixth embodiment of the invention as viewed along the line 14A--14A in FIG. 14.
FIG. 15 is a front elevation view of a peg comprising a seventh embodiment of the invention.
FIG. 16 is a cross-sectional view of the peg shown in FIG. 15 as viewed along the lines 16--16 thereof.
FIG. 17 is a cross-sectional view of the peg shown in FIG. 15 illustrating a modified embodiment thereof which effectively comprises the eighth embodiment of the invention.
FIG. 18 is a cross-sectional view illustrating a use of the seventh and eighth embodiments of the invention.
FIG. 19 is a perspective view illustrating a further use of the seventh and eighth embodiments of the invention.
FIG. 20 is an elevation view, partly in cross-section, illustrating a peg and rod combination which comprises a ninth embodiment of the present invention.
FIG. 21 is a perspective view illustrating a plate and screw combination which comprises a tenth embodiment of the present invention.
FIG. 22 is a perspective view illustrating a flexible braid utilizable as a substitute for a human ligament and effectively comprising a eleventh embodiment of the present invention.
FIG. 23 is a perspective view illustrating a flexible chinese trap utilized for tendon repair with such trap comprising a twelfth embodiment of the present invention.
FIG. 24 is an exploded perspective view, partially in cross-section, illustrating an intramedullary rod comprising a thirteenth embodiment of the present invention.
FIG. 25 is a cross-sectional view of the invention as viewed along the line 25--25 in FIG. 24.
FIG. 26 is a cross-sectional view as viewed along the line 26--26 in FIG. 24.
FIG. 27 is a cross-sectional view illustrating a use of the thirteenth embodiment of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference now to the drawings, and in particular to FIGS. 1-3 thereof, a first embodiment of a new and improved bone and tissue fixation device embodying the principles and concepts of the present invention and generally designated by the reference numeral 10 will be described.
More specifically, it will be noted that the first embodiment 10 of the invention comprises a flat, flexible band 12 formed from a material having similar modulus of elasticity as a human bone. These materials include but are not limited to polyethylene, polysulfone, collagen and polymer-carbon. In this regard, all embodiments of the invention as will be subsequently described will include a use of these modulus-matching materials to the fullest extent possible.
The flat flexible band 12 has a plurality of upstanding integral teeth 14 molded into a first free end 16, and the second end of the band includes an integral upstanding curvilinearly-shaped member 18 which has first and second openings 20, 22 through which the end 16 of the band 12 can be positioned as best illustrated in FIGS. 2 and 3. Attached to an interior top portion of the member 18 is an angulated, downwardly positioned spring member 24 having a serrated end 26 which is symmetrically positionable within the teeth 14. The spring member 24 is of a fail proof construction and might in a preferred embodiment be constructed from surgical steel.
The spring member 24 can flexibly bend to allow the teeth 14 to be pulled through the opening 20, 22 so as to effect a tightening of the clamp around a broken bone 28 as best illustrated in FIG. 3. The angulated forward positioning of the spring 24 facilitates the flexible movement of the teeth 14 as they slide through the openings 20, 22 while at the same time preventing a reverse movement of the teeth and a subsequent loosening of the band 12 after a desired degree of tightening has been achieved. The member 18 effectively comprises a low profile head so that the cable tightener 10 is of a desirable medical grade and as shown in FIG. 3, an optional composite rod 30 might be positioned within a broken bone 28 prior to the use of one or more of the flat cable ties 10.
FIG. 4 of the drawings illustrates a modified embodiment of the flat cable tie 10 wherein the same is utilized with a flat bar member 32 constructed from the above-mentioned material. The bar member 32 is particularly useful when a prosthesis 34 is used to construct a hip joint or the like and threaded screws 36 cannot be employed to attach the bar in the area of the prosthesis. More particularly, threaded fasteners 36 would come into contact with the prosthesis 34 as can be seen in FIG. 4, so this form of the invention is combined with a plurality of flexible cable ties 10 to effectively hold the broken bone together.
FIGS. 5 and 6 of the drawings illustrate a third embodiment of the invention that effectively comprises a flexible round cable tie which is generally designated by the reference numeral 38. The tie 38 includes a notched round band 40 having a fixed head 42 attached thereto. A moveable head 44 is selectively moveable by advancement along the band member 40, and upstanding spring locks 46 positioned within the concavely shaped moveable head 44 serve to hold the moveable head in fixed engagement with the shank 40 after the desired position has been achieved. More specifically, the spring locks 46 can be constructed from a fail proof material, such as stainless steel or the like, and are sloped to allow movement of the moveable head 44 on the shank 40 while then serving to frictionally engage the shank by spring lock to prevent a loosening movement of the moveable head.
FIGS. 7, 8 and 9 illustrate a manner of usage of the flexible round cable tie 38. In this respect, FIG. 7 shows a broken humerus bone, and a semi-rigid awl 48 is used to hone out a drilled aperture extending through the two broken, mating pieces of bone 50, 52. The flexible tie 38 can then be positioned through the curvilinearly-directed aperture as shown in FIG. 9 and the excess shank 40 can be clipped off proximate the moveable head 44 which is now locked in position. Of course, as illustrated in FIG. 8, the flexible round tie member 38 can be used on any type of bone break such as the head of an ulna.
FIG. 10 illustrates a modified embodiment of the flexible round cable tie 38 with this modified embodiment being generally designated by the reference numeral 54. As illustrated, the embodiment 54 is identical in all respects to the embodiment 38 of the invention with the exception that the notched shank member 40 is provided with an integral pointed end 56 which facilitates its forced movement through a drilled aperture in a bone. Depending upon the rigidity of the shank 40 in the embodiment 54 of the invention, the pointed end 56 could be utilized to expand an existing aperture or even create a new one.
FIGS. 11 and 12 of the drawings illustrate a fifth embodiment of the invention which is generally designated by the reference numeral 58. The embodiment 58 also comprises a round cable tie similar to the embodiment 54, with the exception that the notched shank 40 has been replaced with a shank 60 having a plurality of circumferentially extending detents 62, and the moveable head 64 is then forcibly positioned over each of the cup-shaped detents. More specifically, the circumferentially extending detents 62 are flexibly mendable in response to a forced movement of the moveable head 64 thereover and are provided with enough elasticity to return to their normal shape thereafter so as to prevent a reverse movement of the moveable head 64 down the shank 60. This type of fastener 58 is particularly useful, as shown in FIG. 12, in those areas of a bone break where it is difficult to effect a threadable movement of either the fixed head associated with the tie 58 or the moveable head 64 attached thereto.
Another alternative to those situations where a moveable head cannot be threadably attached to a shank 40 is illustrated in FIGS. 13, 14 and 14A. In this regard, the shank 40 is provided with a deployable head 66 which effectively comprises a stainless sleeve-shaped spring and which may be forced through an opening 68 in a bone 70 as best shown in FIG. 13 by use of some type of deploying instrument 72. Once the deployable head 66 has cleared the opening 68, a reverse movement of the shank 40 will result in the head collapsing into the cross-shaped position 74 as illustrated in both FIGS. 14 and 14A. As can be appreciated, the deployable head 66 is fixedly secured to a free end of the shank 40, and the reverse movement force effectively collapses the head into the position 74 best illustrated in FIG. 14.
The present invention also envisions the use of force fittable pegs 76 of the type illustrated in FIGS. 15 and 16. Recognizing that the peg 76 is of a somewhat flexible construction and possesses similar modulus of elasticity of a human bone, a "plus" shaped cross-section facilitates a tight fit of such a peg between mating bone halves. While the peg 76 is shown as having four axially aligned ridges 78, 80, 82, 84 in FIG. 16, it could also have substantially flexible, curvilinearly shaped ridges 86, 88, 90, 92 as shown in FIG. 17. This embodiment shown in FIG. 17 is generally designated by the reference numeral 94 and facilitates a more easily placed positioning of a peg in a manner which can now be well understood. In this regard, FIGS. 18 and 19 illustrate two preferred uses of the pegs 76, 94. Specifically, either of the peg embodiments 76, 94 can be used in a broken patella (knee cap) as shown in FIG. 18 or, for example, in a broken femur wherein the pegs would be inserted with an arthroscope as best illustrated in FIG. 19.
FIG. 20 of the drawings illustrates a modified embodiment of the invention which is generally designated by the reference numeral 96. In this embodiment 96, any combination of the pegs 76, 94 can be employed with a composite rod 98 positionable within a broken bone 100. As shown, the pegs 76, 94 can be positioned through a plurality of laterally extending apertures 102 formed in the composite rod 98, and such positioning of the pegs prevent a shortening of the rod or associated bone, as well as rotation of the rod within the bone during the healing process.
FIG. 21 of the drawings illustrates a further embodiment of the invention 104 wherein screws 106 formed of a material having a similar modulus of elasticity as the bone are positionable through a plate 108 also formed of that material. In this embodiment 104, the plate 108 may be contoured to a selected shape to match the bone structure, and it is envisioned that a microwave oven or some similar heater could be utilized to soften the plate prior to its being molded to such a desired shape.
FIG. 22 of the drawings illustrates a further embodiment of the invention 106 wherein the selected material is braided to effectively create a very flexible band 108 having threaded fasteners 110, 112 attached to the free ends thereof. The braid 106 is illustrated as being utilized to repair ligament damage in a knee joint. The braided band 108 can function as a primary ligament or augment the strength of an existing ligament. It is envisioned that the braid 108 would be attached proximate to an existing or missing ligament in a now well understood manner.
FIG. 23 of the drawings illustrates a use of the same flexible braid material 108 with it being formed into a chinese trap structure 114. A connection loop 116 is positionable at one end of the chinese trap 114 and a circular band 118 is located at the other end. The band 118 is positionable over a torn ligament or tendon 120, and a chinese trap structure 114 is then collapsed to grasp the tendon or ligament. A plurality of sutures 122 may also be employed to keep the chinese trap structure 114 in position, and it can then be fastened to a bone through the use of an appropriate connector positioned through the opening 116.
FIGS. 24, 25 and 26 illustrate a specially designed intramedullary rod concept which is generally designated by the reference numeral 124 and which essentially comprises a nonmetallic rod of a slightly flexible construction formed from the same materials as the previous embodiments of the invention. The rod 126 is of a general I-beam construction so as to provide strength, and threadable fasteners 128 may be drilled through the rod at desired locations. Integral or separable rings 130 may be positioned at various points along the rod 126 to provide further strength, and the ends 132, 134 of the rod are smoothly curved to allow easy insertion within a hollow bone as best illustrated in FIG. 27. This rod structure 134 is used to link fragments or segments of bone, and the rod effectively acts as a "core" to which other devices may be attached, i.e., the aforementioned pegs, screws, nails, straps, etc.
As to the manner of usage and operation of the present invention, the same should be apparent from the above description. Accordingly, no further discussion relating to the manner of usage and operation will be provided.
With respect to the above description then, it is to be realized that the optimum dimensional relationships for the parts of the invention, to include variations in size, materials, shape, form, function and manner of operation, assembly and use, are deemed readily apparent and obvious to one skilled in the art, and all equivalent relationships to those illustrated in the drawings and described in the specification are intended to be encompassed by the present invention.
Therefore, the foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention.
|
Bone and tissue connectors are designed for use on or in the human body for the purpose of connecting bone or soft tissue to promote a healing process. Various embodiments are in the form of bands, straps, braids, or rods and are secured by fasteners such as pegs, plates, screws and cable ties. All of the connectors are formed from materials having a similar modulusof elasticity as bone and include, among others, polyethylene, polysulfone, collagen and polymer-carbon fiber composites.
| 8
|
[0001] The present patent document claims the benefit of the filing date of DE 10 2006 051 881.0 filed on Oct. 31, 2006, which is hereby incorporated by reference.
BACKGROUND
[0002] The present embodiments relate to a patient positioning apparatus.
[0003] A patient positioning apparatus positions a person lying on a patient bed in the effective range of a medical diagnosis or therapy device. The effective range for a medical diagnostic imaging device, such as a computer tomography device or an x-ray device, is the scan range in which the person must be positioned in order to create a diagnostic image of a region of the body. The effective range for a therapy device is the region of the body able to be detected by the therapy device. For example, the effective range for a radiation therapy device is the region of the body able to be detected by x-ray radiation generated by the radiation therapy device.
[0004] A control device is used to change the position of the patient bed. The control devices uses a control signal to activate a drive for motorized movement of the patient bed. A computer program or an input aid (device) may be used to position the patient bed. The input aid (device) may include a joystick, with a computer keyboard, a touch screen or a computer mouse. The input aid transfers the positioning information to the control device. Using the input aid, the person lying on the patient bed is able to be positioned without any force being exerted. Movement to a number of positions, one after the other, may be automated. This is, for example, of significance in computer tomography if a number of images are first to be recorded as a type of image sequence and are subsequently to be computed jointly to form merged image information.
[0005] The positioning information is entered indirectly via the input aid. An operator checks the positioning information entered via the input aid with reference to the actual position to which the bed is moved to make sure that it is correct, for example, by constant visual contact with the patient bed. Multiple attempts may be needed to arrive at the desired position.
[0006] The patient bed may be moved manually. The manual movement may be easy, such as when it is only necessary to move the patient bed to one individual position, for example, for the measurement of individual medical x-ray image information by an x-ray device, For manual movement, however, an operator must overcome the resistance of the drive, especially the resistance of the motor and transmission.
[0007] DE 199 29 654 C1 discloses an electromagnetic or manual clutch for coupling the drive to the patient bed. The electromagnetic or manual clutch is used to facilitate manual movement of the patient bed despite the drive being coupled to the bed. If the patient bed is to be moved manually, the bed is decoupled from the drive by the clutch, so that only the frictional forces of, for example, a patient bed support embodied as a linear guide have to be overcome. The clutch must be released by a manual activation. The clutch involves a considerable additional constructional outlay.
[0008] DE 10 2004 047 615 B3 discloses coupling the motorized drive and the patient bed elastically to each other. A position sensor compares the actual position of the patient bed and the position of the motorized drive with each other. If the two positions differ and the motorized drive is simultaneously switched off, the patient bed has been moved by an operator.
SUMMARY
[0009] The present embodiments may obviate one or more of the drawbacks or limitations inherent in the related art. For example, in one embodiment, a patient positioning apparatus supports manual movement of the patient bed by the motorized drive and can be implemented in a simple and cost-effective way.
[0010] In one embodiment, a patient positioning apparatus includes a sensor device that detects a manual force acting on the patient bed to move the patient bed. A control device controls the drive as a function of the force detected. The sensor device may include a force transducer that measures the force operating on the transducer by strain gage technology.
[0011] The strain gage technology may include a force transducer having an elastic sprung body. One or more strain gages are applied to the elastic sprung body. The one or more strain gages detect a deformation of the sprung body as a result of the effect of a force. When acted on by a force, one or more strain gages generate a measuring signal in the form of an electrical voltage. The measuring signal may be tapped off in a simple manner.
[0012] A force transducer has a low cost. The strain gage technology is widely developed. Force transducers with almost any measurement range and with almost any given sensitivity are available on the market as standard devices.
[0013] The control device may be detect and process the electrical measuring signal. The control device may generate a control signal with reference to stored program logic, which drives the motorized drive to support the force applied to the patient bed.
[0014] The patient bed may be moved by the drive and moved manually. No separate clutch for decoupling of patient bed and drive is necessary. When moving a patient bed manually, an operator only has to overcome the frictional forces of a guide assigned to the patient bed. Manual movement is assisted by the drive. The drive may be a self-arresting linear drive, for example, a threaded spindle. Even with the self-arresting linear drive, a manual movement may be implemented. In contrast to the conventional clutch, the resistance to movement of the drive elements, for example, of toothed belts or spindles, is removed.
[0015] In one embodiment, the sensor device detects a relative force between the drive and the patient bed. If a relative force is measured, no separate calculation of the forces acting on the drive and on the patient bed is necessary.
[0016] The sensor device may be disposed between the drive and the patient bed. The force sensors may be equally loaded for tensile and compressive forces, which have two threaded connections for introduction of forces. The force sensors may be positioned by screw connections in an interference fit between the motor drive and the patient bed. Since the force transducer may be subjected to tensile and compressive forces, the force transducer may be mounted at almost any location. The force transducer is operable to measure the relative force between motorized drive and patient bed.
[0017] In one embodiment, the control unit controls the drive only when the threshold of a force acting on the patient bed is exceeded. Light and accidental (minimal) contacts with the patient bed by the operator or movements of the person lying on the patient bed do not lead to a change in the position of the patient bed. When the operator lets go of the patient bed the patient bed comes to a halt because the force falls below the threshold value.
[0018] The control unit may control the drive so that the force between a drive axis driven by the drive and the patient lies (maintained) below a predetermined tolerance value. The drive axis involves a toothed belt drive, for example. The sensitivity in the control of the motorized drive may be attenuated. The measurement signal may vary slightly as a result of uneven application of manual force by the operator or because of movement of the person lying on the patient bed during the movement do not lead to a change of direction of movement or speed of movement of the patient bed.
[0019] In one embodiment, the force is measured and the drive activated iteratively, for example, at regular intervals. A closed-loop control circuit may be checked iteratively with the program logic. The program logic may determine a change of the force is present and how the drive is to be controlled to support a movement of the patient bed in a specific direction.
[0020] The force may be measured and averaged at a high measurement cycle (frequency). Fluctuations of the measurement signal and of the manual force acting on the patient bed may be compensated for because of the high measurement cycle. The control of the motorized drive may be undertaken with a lower cycle, to avoid abrupt changes with respect to the speed of movement and the direction of movement. This allows an even movement of the patient bed to be achieved despite an uneven effect of the force.
[0021] The patient bed may include a guide. The guide may be a linear guide. A linear guide enables a one-dimensional or two-dimensional displacement movement. The ease of movement of the patient bed may be predetermined via the choice of linear guide. Linear guides may be combined with one another in accordance with the building block principle. Linear guides are available on the market in a variety of versions at a low cost.
[0022] In one embodiment, a patient positioning apparatus includes a positioning robot as a guide for the patient bed. The positioning robot may include a number of pivot arms linked by swivel joints. The pivot arms may move the patient bed to almost any position in the space. The pivot arms may adjust the patient bed in the vertical direction and tilt the patient bed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] FIG. 1 illustrates one embodiment of a patient positioning apparatus, and
[0024] FIG. 2 illustrates the timing of one embodiment of a measurement signal and a control signal in a time-force diagram
DETAILED DESCRIPTION
[0025] In one embodiment, as shown in FIG. 1 , a patient positioning apparatus 2 includes a patient bed 4 that can be moved by a linear guide 6 in the longitudinal direction 8 and the transverse direction 10 . The patient positioning apparatus 2 may be used to position a person 12 lying on the patient bed 4 in the effective range of a medical diagnosis or therapy device.
[0026] A motorized drive 14 is used to position the person 12 . The motorized drive 14 includes an electric motor 16 , a transmission 17 and drive axis 18 driven by the transmission 17 . As shown in the exemplary embodiment shown in FIG. 1 , the drive axis 18 is a toothed belt. To move the patient bed 4 , the transmission 17 is coupled by a coupling element 20 to the linear guide 6 . A control device 22 controls the electric motor 14 . The control device 22 may predetermine speed of travel and direction of travel of the patient bed 4 using a control signal S.
[0027] The patient bed 4 may be positioned automatically by the control device 22 . Using the automatic positioning, a medical diagnosis device, such as a computer tomography, may measure successive two-dimensional image information and merge in an evaluation unit the two-dimensional image information into three-dimensional image information.
[0028] In one embodiment, the patient positioning apparatus 2 includes input aids. The input aids may be used to manually position the patient bed 4 . The input aids may include, for example, a joystick 24 . The movement of the joystick 24 in a longitudinal direction 8 or transverse direction 10 is converted into a corresponding movement of the patient bed 4 .
[0029] In one embodiment, a sensor device 26 is coupled to the coupling element 20 in an interference fit. The sensor device 26 detects a manual force K acting on the patient bed 4 . Since the sensor device 26 is arranged between the drive axis 18 and the linear guide 6 , the sensor device 26 may measure the relative force arising between the transmission 16 and the linear guide 6 during manual movement of the patient bed 4 . The sensor device 26 generates a measuring signal M, which is detected and processed by the control device 22 . The sensor device 26 is, for example, a force transducer with strain gage technology.
[0030] In one embodiment, the patient bed 4 is positioned automatically. The measuring signal M is not processed in the control device 22 if the patient bed 4 is positioned automatically. The measurement signal M is only processed if the patient positioning apparatus 2 is in a standby position. Accordingly, the patient bed 4 , for example, can be positioned using the joystick 24 . If a manual force is exerted on the patient bed 4 , the relative force is measured between the drive axis 18 and the linear guide 6 . The relative force has amount and direction information. If the amount information exceeds a threshold value SCH, for example, as shown in FIG. 2 , the control device 26 generates a control signal S for activation of the electrical drive 14 . The threshold value SCH may be used to pre-specify the sensitivity of the control.
[0031] The control device 22 may detect iteratively the measuring signal M at defined intervals. The electrical drive 14 is activated until the measuring signal M for the relative force falls below the threshold value SCH. The measuring signal M for the relative force falls below the threshold value SCH occurs when the operator lets go of the patient bed 4 . The displacement process is ended and the new position of the patient bed 4 is reached.
[0032] During the displacement process, the control signal S may be iteratively adapted to the measuring signal M for the measured relative force in a type of closed-loop control procedure. A differing control signal may be only generated if the relative force lies above a tolerance threshold T. Even displacement of the patient bed 4 may be achieved. An operator may be assisted by the drive 14 when exerting the manual force K.
[0033] The manual force K acting on the patient bed 4 includes a longitudinal direction 8 component and a transverse direction 10 component. The resultant relative force is measured by the sensor device 26 and transmitted as a measuring signal M to the control device 22 . The measuring signal M includes a longitudinal direction 8 component and a transverse direction 10 component. To control the drive 14 , the control device generates a control signal S having a longitudinal direction 8 component and a transverse direction component.
[0034] FIG. 2 shows one embodiment of a diagram for a displacement process. In FIG. 2 , the absolute amounts for the measuring signal M proportional to the manual force K and the control signal S generated by the control device 22 are represented as functions of time. The measuring signal M is plotted as a solid line and the control signal S is a dashed line.
[0035] The manual force K acts on the patient bed 4 , which causes the measuring signal M to increase from time t 1 up to a final value M 1 at time t 4 . The threshold value SCH is exceeded at time t 2 . The delay Δt corresponds to the speed of processing of the control device 22 for detection and calculation of the measurement signal M and the generation of the control signal S. With the delay Δt, the control device 22 generates the control signal S for activating the drive 14 from time t 3 onwards. From the beginning, the control signal S has the threshold value SCH and follows the measuring signal M for the manual force K until it reaches the final value S 1 at time t 5 , with the time delay Δt in relation to the final value M 1 of the measurement signal M at time t 4 .
[0036] At time t 6 , the manual force K increases. The measuring signal M increases to the value M 2 . This value will be reproduced by the control unit 22 as signal value S 2 with the time delay Δt at time t 7 .
[0037] From time t 8 to time t 9 , the manual force K and the measuring signal M fluctuate. In FIG. 2 this time interval is labeled M 3 . The fluctuation of the measurement signal M lies in the positive and in the negative tolerance threshold T, so that no change to the control signal S occurs. An even displacement movement of the patient bed 4 may be achieved.
[0038] At time t 10 and beyond, the manual force K falls, for example, since the operator lets go of the patient bed 4 . The measuring signal M falls from its momentary value M 4 at time t 10 to the value 0 at time t 14 . The control device 22 generates a corresponding signal S which falls with the time delay Δt from time t 11 from its momentary value S 4 . At time t 12 , the value falls below threshold value SCH. With the time delay Δt the amount of the control signal S is equal to 0 at time t 13 , for example, the drive 14 is no longer activated. The patient bed 4 stops although a relative force which differs from 0 is still measured until time t 14 .
[0039] Various embodiments described herein can be used alone or in combination with one another. The forgoing detailed description has described only a few of the many possible implementations of the present invention. For this reason, this detailed description is intended by way of illustration, and not by way of limitation. It is only the following claims, including all equivalents that are intended to define the scope of this invention.
|
The patient positioning apparatus features a patient bed able to be moved by a motorized drive under the control of a control device. A sensor device is provided for detection of a manual force acting on the patient bed to move it. The control device is configured so that it activates the drive as a function of the force detected. In this way a simple method of supporting the manual movement of the patient bed by the drive is achieved.
| 0
|
This is a continuation of application Ser. No. 810,956, filed on June 29, 1977, now abandoned.
FIELD OF THE INVENTION
This invention relates to fluid flow transfer devices using pleated membranes.
BACKGROUND OF THE INVENTION
In constructing a fluid flow transfer device using a pleated membrane such as a hemodialyzer, it is desirable to anchor the membrane tips on the blood (or other fluid to be dialyzed) side to the apparatus housing interior to direct the blood flow into the spaces between the membrane folds and prevent shunting of blood from inlet to outlet without being dialyzed between the folds. One problem has been development of a simple but effective method of anchoring the tips. One proposed method of anchoring the membrane tips is that invented by Thomas E. Goyne and involves injecting liquid adhesive potting material into a housing that is positioned horizontally, as are the membrane tips, to produce uniformity of potting.
Even with uniform potting, however, the problem of achieving a bond that will not fail has persisted, including in the situation in which the pleated membrane is treated with a plasticizer such as glycerin. One basis for the problem is that in normal operation a dialyzer will have a higher pressure on the blood side of the membrane, a pressure that will tend to force the membrane away from the potting. One way of strengthening the bond is by increasing the membrane tip surface area embedded in the potting. However, if one simply allows the potting to flow freely to cover more of the tip surface area, the potting may flow too far into the spaces between the membrane folds and block the fluid flow passages therein, thus impairing the efficiency of the device.
SUMMARY OF THE INVENTION
I have discovered that a strong bond between the housing interior and the pleated membrane tips of a fluid flow transfer device can be produced without undesirably interfering with fluid flow passages by carrying out the following steps: positioning support spacers in the membrane folds on the membrane side opposite the side to be bonded, closing the entrances to the spaces between the folds on the bonding side of the membrane, introducing flowable adhesive between the membrane tips and the housing interior while the entrances remain closed, applying a pressure differential across the membrane, with the higher pressure being on the bonding side of the membrane and the differential being large enough to force the membrane folds against their respective support spacers so that the spacers support the membrane, and curing the adhesive to harden it.
The bond produced is a strong one, including in the case in which the membrane has been treated with a plasticizer.
In particular aspects the invention includes applying positive pressure to the membrane side opposite the side to be bonded to close the entrances to the spaces between the folds, partially curing the adhesive for a time long enough to make it more viscous but not long enough to render it unable to flow, and applying negative pressure to the membrane side opposite the side to be bonded to produce the pressure differential and draw adjacent membrane folds away from each other, thereby reopening the entrances to permit the adhesive to flow partly into the spaces. The partial curing step is done long enough to prevent adhesive from flowing into and thus undesirably blocking fluid flow passages between membrane folds but not too long to prevent sufficient flow of adhesive into the spaces to increase the bonding surface of the tips. The tendency of the membrane folds to pull away from the potting under transmembrane pressure (higher on the blood side) is resisted by both the increased bonding area of the membrane and the support provided by the support spacers.
PREFERRED EMBODIMENT
I turn now to description of the presently preferred embodiment of the invention.
Drawings
FIG. 1 is a perspective view of a dialyzer utilizing the presently preferred embodiment;
FIG. 2 is a somewhat diagrammatic sectional view along 2--2 of FIG. 1;
FIG. 3 is an exploded view of a portion of the membrane and support netting of the dialyzer of FIG. 1;
FIG. 4 is an enlarged perspective view of a portion of the support netting of FIG. 3;
FIG. 5 is a sectional view along 5--5 of FIG. 1; and
FIG. 6 is a greatly enlarged vertical sectional view like that of FIG. 2 of a portion of the membrane and support netting of the dialyzer of FIG. 1.
DESCRIPTION
The embodiment shown in the drawings and its operation are now described.
1. Embodiment
FIGS. 1 and 2 show dialyzer 10, which includes a two-part housing comprising trough-shaped polycarbonate casing 12 and interfitting polycarbonate casing 14, which is open at both longitudinal ends and has a pair of longitudinal fins 16. Casing 12 includes inlet 18 and outlet 20, both integrally molded therewith. Casing 14 includes integrally molded inlet 22 and outlet 24. Inlets 18 and 22 and outlets 20 and 24 become channels of steadily decreasing cross section when they enter their respective casings. A pair of stub shafts 26, formed by mating semicircular portions on casings 12 and 14, and a pair of cooperating stops 28 (only one is shown in FIG. 2), spaced equidistantly longitudinally from the right stub shaft, permit rotatable, vertical mounting of the dialyzer on a bracket, for degassing and normal operation.
Dialysis membrane 30, a Cuprophan (trademark of Enka Glanzstoff AG) cuprammonium cellophane sheet having a generally accordion pleated configuration and to which glycerin has been added as a plasticizer and humectant for smooth processing, is squeezed between fins 16, and is sealed with polyurethane potting 32 along its outermost flaps to the outer faces of the fins. The folded upper tips of membrane 30, shown somewhat rounded in FIG. 2, are affixed to casing 12 by being anchored in polyurethane potting 32, thereby forming a series of separate parallel fluid flow passages, indicated by B in FIG. 3, in the valleys above the membrane. Potting of the upper tips prevents shunting of fluid directly from inlet 18 to outlet 20 without entering passages B. Support netting 34, a nonwoven polypropylene mesh (see the arrangement of its strands 35 in FIG. 4) sold under the Du Pont trademark Vexar, is also in the form of an accordion pleated sheet, and is positioned within membrane 30 on the membrane side adjacent casing 14 (FIG. 3). By this configuration, support netting 34 spaces apart the underside faces of adjacent membrane walls with two layers of the netting shown in FIG. 4, and provides parallel fluid flow passages underneath the membrane, indicated by D in FIG. 3. Netting 34 is not bonded to either casing, except at its longitudinal ends, as will be described hereinafter, and unlike membrane 30 does not fold over fins 16.
Both membrane 30 and netting 34 are pleated along generally parallel lines, and strands 35 run at 45° to those lines.
Casing 12 has a continuous peripheral ridge 50 that seats in continuous peripheral groove 52 of shelf portion 54, which surrounds casing 14. When casing 12 and casing 14 are so interfitted, the tips of fins 16 are vertically spaced from the adjacent inner surface of casing 12 and from ribs 36 running transversely on that surface, to avoid cutting of membrane 30 between the pointed fin tip and casing 12.
Longitudinal ends of membrane 30 and netting 34 are bonded to casings 12 and 14 by potting 32 (FIG. 5). Transverse ribs 36 (one shown in FIGS. 2 and 5) of casing 12 space the folded tips of membrane 30 from the casing ceiling to provide channels for flow of potting 32 during construction of dialyzer 10, described hereinafter. Ribs 36 have arcuate portions 56 which laterally space fins 16 from the angled and vertical sidewalls of casing 12 by tangential contact with fins 16 through membrane 30; portions 56 permit the flow channels to extend from the central fluid chamber between fins 16 to the side compartments between each fin and the corresponding sidewall of casing 12. A continuous ridge of General Electric RTV 108 thixotropic silicone rubber adhesive 38 adjacent casing ribs 40 surrounds the channel portion of outlet 20 (and in the same way inlet 18, though not shown) and bonds to the membrane tips, to act as a formed-in-place gasket in order to prevent flow of potting 32 into the channel area during construction. The adhesive needs to be thixotropic so that it will not itself wick across the membrane folds in the manifold area and thus block entrances to passages B. Inlet 18 and outlet 20 thus cooperate along their channel portions with membrane 30 to form inlet and outlet manifolds into and out of the fluid passages indicated at B in FIG. 3. Likewise inlet 22 and outlet 24 cooperate along their channel portions with membrane 30 on its underside to form inlet and outlet manifolds into and out of the fluid passages indicated at D in FIG. 3.
In constructing dialyzer 10, one pleats a sheet of membrane 30, pleats a sheet of netting 34, and combines the two by placing each fold of netting within a corresponding fold of membrane (FIG. 3). The resultant membrane-netting stack is squeezed together and placed in a casing 14 between fins 16, with each of the two outermost flaps of membrane 30 folded over its respective fin. Each outermost flap is then sealed to the outer face of the adjacent fin 16 with polyurethane potting 32. Casing 12 is then provided, and two ridges of silicone rubber adhesive 38, each having a weight of approximately one gram, are then applied around the outer edges of the channel portions of inlet 18 and outlet 20 of casing 12, adjacent ribs 40 and on end shoulders 41 (one shown in FIG. 5). Casing 14 is then interfitted with casing 12. Ridge 50 is wetted with solvent and then pressed into groove 52, to which it bonds on drying. A ramp portion 48 running along the base of each fin 16 serves to guide ridge 50 into groove 52. The interfitting is done while the silicone adhesive 38 is still wet so that it will seep a short way (about 1/16 to 1/8 inch) into the membrane folds to prevent wicking of polyurethane potting in the folds in the manifold area and consequent undesirable blockage of fluid flow into or out of the folds. The membrane and netting longitudinal ends are then potted in polyurethane 32, which is applied through holes 42 in casing 14 at each end thereof by a needle inserted through tapes (not shown) placed on raised portions 58 and covering the holes 42 (only one hole is shown in FIG. 5). Dialyzer 10 is held vertical during this process, with the end to be potted at the bottom. After curing of the potting at the end, the dialyzer is rotated 180°, with the other end at the bottom, ready to receive its potting. Potting seeps into the netting side of the membrane but not generally into the other side (FIG. 5). Holes 42 are sealed with the hardened potting, and the tapes are removed.
The potting of the membrane tips and flaps to casing 12 now takes place. Dialyzer 10 is positioned horizontally with the membrane tips to be potted below the membrane body and horizontally aligned, with casing 12 on the bottom (inverted from FIG. 2). Plugs (not shown) are placed in inlet 22 and outlet 24, and a needle is inserted through one of the plugs to apply 300 mmHg positive pressure from a pressure source through netting 34 against the face of membrane 30 adjacent casing 14. The pressure source is removed after pressurization is complete, and a pressure gauge is used to check for leaks. The plug maintains the pressure. Inlet 18 and outlet 20 are open to atmospheric pressure. Approximately 60 cc of polyurethane potting 32, which comprises an initially liquid mixture of Polyol 936 and Vorite 689, a urethane prepolymer, both manufactured by N.L. Industries, Bayonne, New Jersey, is then pumped into a dialyzer 10 through hole 44 (FIG. 2) in one sidewall of casing 12. The potting flows into the side compartment formed between the sidewall of casing 12 and one fin 16 through channels between arcuate rib portions 56, down into the trough of casing 12, transversely through channels formed by 0.06 inch deep transverse ribs 36 (FIG. 5), and again through channels between arcuate portions 56 up into the other side compartment between the other sidewall of casing 12 and the other fin 16. Arcuate portions 56 prevent fins 16 from flaring outward to contact the sidewalls of casing 12 and thereby block potting flow into or out of the side compartments. A pair of pinholes (now shown) in casing 14, one adjacent inlet 22 and the other adjacent outlet 24, let air escape as the potting is pumped in. The potting settles uniformly on the inner surface of casing 12 and reaches the same level in each side compartment. Because of the positive pressure maintained on the opposite side of membrane 30, passages B are closed up, and the potting cannot wick or otherwise flow up between the folds. After a curing time of 60 minutes, one of the plugs is removed to permit a vacuum to be applied to the membrane side that initially received the higher pressure. Ten dialyzers 10 are connected in parallel to a vacuum pump through a 25 gauge one inch long needle acting as a pneumatic resistor, and the evacuation produces a negative pressure from 20 to 24 inches of mercury. The resistor chosen gives a desirable rate of evacuation. If evacuation is either too fast or too slow, unwanted bubbles will form in the polyurethane potting.
As a result of the evacuation, the folds of membrane 30 are drawn back from each other, enlarging the spaces between the folds, and are drawn tightly and even crushed against the folds of netting 34 (FIG. 6), which then support the membrane and prevent it from pulling away from the inner surface of casing 12. The now more viscous potting can seep up through the entrances to the spaces between the membrane folds and into those spaces to increase the bonding surface area provided by the membrane tips and thereby further improve the casing-membrane bond effected by the potting. However, the potting is too viscous to seep undesirably far into those spaces so as to interfere with flow passages B. Curing time between the pressure and evacuation steps is important; if the time chosen for the particular potting compound is too short, the potting will not be viscous enough and will seep too far into the spaces between the membrane folds when the vacuum is applied, thus interfering with fluid flow passages B. If the time is too long, unwanted bubbles will form in the potting because of its increased viscosity.
After further curing, dialyzer 10 is ready for use.
Dimensions of dialyzer 10 are as follows. Its housing is approximately 12 inches by 35/8 inches by 2 inches. Membrane 30 has a dry thickness of 13.5 microns and an actual surface area of approximately 1.54 m 2 . Netting 34 has 16 strands per inch and a mean thickness of 0.022 inch. Both membrane and netting have 66 folds ("folds" meaning adjacent pairs of membrane or netting walls joined along a crease), which is equivalent to the number of upper tips of membrane 30 affixed to casing 12 (far fewer folds are shown in the somewhat diagrammatic view of FIG. 2). There are 65 fluid flow passages B along the folds. The channel portions of inlet 18 and outlet 20 are approximately 23/4 inches long, 3/8 inch wide and 5/32 inch deep adjacent the tubular portion of the inlet or outlet, which acts as a port, and 3/8 inch wide and 1/16 inch deep at the narrower channel tip. There are seventeen ribs 36, spaced about 1/2 inch apart, and seventeen corresponding pairs of arcuate portions 56. Additionally, there is a pair of arcuate portions 56 (not shown) between each longitudinal end of casing 12 and inlet 18 and outlet 20.
2. Operation
When used as a hemodialyzer, dialyzer 10 operates as follows. Blood tubing is connected to inlet 18 and outlet 20, and dialysate tubing is connected to inlet 22 and outlet 24. Dialyzer 10 is mounted vertically, with inlet 18 and outlet 24 on top. Blood is introduced into inlet 18, flows along its channel portion, and then, partly because of the potting 32, flows into the spaces B between the folds of membrane 30 and in the general direction indicated by arrows in FIG. 3, until it is collected in the channel portion of outlet 20 and then passes out of dialyzer 10. Dialyzing fluid or dialysate is introduced into inlet 22 and flows along its channel portion where it is distributed into all of the dialysate flow passages D (FIG. 3), and flows in the general direction indicated by arrows in FIG. 3, countercurrently with blood flow. It has been found that the membrane tips adjacent casing 14 do not need to be potted to it, when dialysate is introduced on this side. Dialysate is collected in the channel portion of outlet 24 and then passes out of dialyzer 10, from which it is collected for regeneration or disposal. Dialysis occurs across membrane 30. Blood is introduced into its inlet port with use of a pump while dialysate is introduced into its inlet port at a lower pressure. Thus in addition to removal of unwanted substances from the blood by dialysis, dialyzer 10 effects removal of water from the blood through membrane 30 because of the pressure difference across the membrane.
In normal operation dialysate flows upward because of the vertical positioning of dialyzer 10, and the dialysate flow paths D (FIG. 3) are constantly being degassed as dialysate flows in that direction. The blood flow paths B (FIG. 3) are degassed prior to dialysis by inverting dialyzer 10, introducing a saline priming solution, and having that solution flow upward for a predetermined time.
An enlarged view of the arrangement of support netting 34 and membrane 30 is shown in FIG. 6. Potting 32 has seeped somewhat into the space between the folds shown, to increase the bonding area and hence improve the bond between membrane tips and the potting. The pleated sheet configuration of netting 34 provides a spacer between adjacent membrane folds that is two layers thick. The effect is to increase the dialysate flow passages and to lower the dialysate pressure drop through the dialyzer. The double layer of netting tends not to entrap air bubbles, which on accumulating would impede dialysate flow and increase the pressure drop. Instead the bubbles desirably wash on through. As to blood flow, strands 35 tend to pinch adjacent folds of membrane 30 at spaced points designated P in FIG. 6. Between points P portions of folds of membrane 30 sag into inter-strand spaces of netting 34 to create separate blood flow passages 46. Pressure from the blood helps keep the membranes apart for blood flow.
Dialyzer 10 provides the following specifications and results when used in hemodialysis:
______________________________________Pressure DropsBlood (at flow rate,Q.sub.B, of 200 ml/min. and 15 mmHgTransmembrane Pressure (TMP)of 100 mmHg) (Hematocrit = 30%)Dialysate (at flow rate,Q.sub.D, 500 ml/min. and 2 mmHgTMP of 100 mmHg)In Vitro Clearances*(Q.sub.B = 200 ml/min.Q.sub.D = 500 ml/min. TMP = 100 mmHg)Urea 140 ml/min.Creatinine 120 ml/min.B-12 31 ml/min.Ultrafiltration Rate (in vitro)* 3.6 ml/hr/mmHg TMPBlood Volume100 mmHg TMP 85 ml200 mmHg TMP 120 mlDialysate Volume 730 mlMaximum TMP 500 mmHg______________________________________ *Performance subject to variations in Cuprophan membrane.
Variations and Modifications
The invention has other uses beside that in hemodialysis; for example, it can be used in laboratory dialysis.
Regarding variations, I note that the curing time can be reduced or virtually eliminated by increasing the viscosity of the potting material when it is first pumped in so that it will be viscous enough for the evacuation step much sooner. Using an initially more viscous potting material will require greater pumping pressures (and, consequently, higher initial positive pressures on the dialysate side to keep the fold entrances closed) or larger flow channels in the casing.
A second variation is to paint an adhesive primer on the membrane tips and allow the primer to cure in order to bond adjacent tips to each other and thereby close the fold entrances. This can replace or supplement the use of positive pressure to close these entrances. With this variation no curing of the potting is necessary prior to the evacuation step because the entrances will not reopen as a result of evacuation and thus there will advantageously be no seepage of potting into the spaces between the membrane folds during evacuation. Rather, the membrane stack as a whole will be forced against the support netting and receive support therefrom. One chooses for the primer one that will improve the bond between the potting and the membrane.
A third variation is simply to substitute application of a positive pressure on the blood side of the membrane higher than that on the dialysate side for application of negative pressure on the dialysate side, to draw the membrane against the netting.
Other embodiments of the invention will be obvious to those skilled in the art.
Other Inventions
The method of injecting liquid potting material into a housing for uniform potting of the membrane tips to the housing was the invention of Thomas E. Goyne, and is the subject matter of U.S. Pat. No. 4,165,287, entitled "Potting Pleated Membrane".
The fin-membrane sealing construction was the invention of Donn D. Lobdell, and is the subject matter of U.S. Pat. No. 4,163,721, entitled "Edge Sealed Pleated Membrane".
The method of sealing off fluid inlets and outlets from seepage of potting thereinto was the joint invention of Dennis Hlavinka and Frank Corbin and is the subject matter of U.S. Pat. application Ser. No. 961,618.
|
The tips of a pleated membrane are bonded to the interior of the housing of a fluid flow transfer apparatus by positioning support spacers in the membrane folds on the membrane side opposite the side to be bonded, closing the entrances to the spaces between the folds on the bonding side of the membrane, introducing flowable adhesive between the membrane tips and the housing interior while the entrances remain closed, applying a pressure differential across the membrane, with the higher pressure being on the bonding side of the membrane and the differential being large enough to force the membrane folds against their respective support spacers so that the spacers support the membrane, and curing the adhesive to harden it.
| 1
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates in general to a method of fiber scouring. More particularly, it relates to a method for removing oil agents from fibers using supercritical carbon dioxide as an extraction media.
2. Description of the Related Arts
As known in the art, spinning oils and finishing oils are respectively applied to the surface of artificial fibers when they are subjected to spinning and false twisting. The most commonly used spinning oils are ethylene oxide/propylene oxide (EO/pO) copolymer ester, while finishing oils are commonly coning oils. The spinning and finishing oils must be scoured from the fibers before they are subjected to subsequent processing, i.e., dyeing.
Referring to FIG. 1, the conventional scouring for artificial fibers includes three successive steps. The artificial fibers with oils agents are scoured with strong bases and scouring agents, neutralized with weak acids, and finally, rinsed by hot water. The major drawback of such method is that it necessitates a large quantity of rinsing agents including water, scouring agents, strong bases, and weak acids, thus making the practice of this method costly. Moreover, a substantial quantity of wastewater will be produced from the rising agents, whose treatment also raises the costs. Another drawback of the conventional scouring is its low efficiency. In general, it takes about 45 minutes to complete the scouring process.
SUMMARY OF THE INVENTION
It is therefore an object of the invention to provide a method of scouring fibers which reduces costs and improves efficiency, and does not produce wastewater.
To attain the above object, the present invention provides a method for scouring fibers by flowing carbon dioxide through the fibers under pressure and temperature conditions such that the carbon dioxide is a supercritical fluid and removes a substantial portion of the oil content from the fibers, which can be either natural fibers or artificial fibers such as polyester or nylon fibers.
The method using carbon dioxide to remove oils from fibers operates at moderate pressures between 90 and 350 bar and at temperature levels ranging from 40 to 120° C. The extraction efficiency can be modulated by varying the operating pressures and temperatures.
The present method is superior to the conventional method in several ways. The most important advantage of this method is its low cost. Referring to FIG. 2, this method significantly reduces the production cost by obviating the need for using large quantities of rinsing agents. Accordingly, the need for treating wastewater is also eliminated. It is also financially advantageous that the carbon dioxide can be recycled and the oil extract can be recovered. Another advantage of this method is its high efficiency. The scouring time of the present method is about ten minutes, whereas that of conventional scouring is about 45 minutes. A further advantage of this method is that the extraction efficiency can be simply controlled by regulating the operating pressures and temperatures. In addition, by using the supercritical carbon dioxide, the integration of the scouring process into the supercritical carbon dioxide dyeing process is made possible.
Other objects, features, and advantages of the present invention will become apparent from the following detailed description which makes reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flow chart showing the process steps of the conventional scouring method.
FIG. 2 is a flow chart showing the scouring method of the invention by using supercritical carbon dioxide.
FIG. 3 illustrates representative equipment which can be used in the practice of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 3 shows representative apparatus for practicing the invention, in which 31 - 39 are valves ( 31 - 33 are check valves), 40 - 42 are filters, 43 is a pressure gauge, and 44 - 45 are thermal couples. It should be noted that apparatus other than that shown in FIG. 3 can be used to practice the invention. In the system of FIG. 3, liquid carbon dioxide from cylinder 11 is fed through water absorber 12 to cooling coil 13 which decreases the temperature of the liquid carbon dioxide. Water absorber 12 is a column filled up with molecular sieves which absorbs moisture in the liquid carbon dioxide. The cooled carbon dioxide is then passed through pump 14 which raises the pressure of the carbon dioxide. The pressure is maintained at a setting value by back pressure regulator 15 ; when the system pressure is greater than the setting value, the carbon dioxide is drawn back through back pressure regulator 15 to water absorber 12 . The carbon dioxide is then passed through oven 10 where it is heated above its critical temperature. The supercritical carbon dioxide then enters extraction vessel 16 which has been previously loaded with fibers which are to be scoured. Extraction vessel 16 is made of stainless steel and has a capacity of about 22 ml. As shown in the FIG., vessel 16 is enclosed in oven 10 to maintain the temperature of the carbon dioxide above its critical temperature.
As the supercritical carbon dioxide passes through vessel 16 it extracts oil agents from the fibers. The supercritical carbon dioxide with its load of oils leaves vessel 16 and passes through pressure reduction valves 38 , 39 , which reduce the pressure of the carbon dioxide. As a result, the oil agents precipitate out of the carbon dioxide and are captured by a solvent of ethanol/n-hexane. After the oil agents have been removed, the carbon dioxide passes through flow meter 17 and wet gas meter 18 . Wet gas meter 18 is used to measure accumulative gas flow and flow meter 17 is used to measure the flow rate of carbon dioxide through the system. According to the invention, the overall solvent-to-feed ratio is preferably between 0.5 to 10 grams CO 2 per gram of fiber.
Without intending to limit it in any manner, the present invention will be further illustrated by the following examples.
EXAMPLE 1
Polyester fibers with an oil content of 1.2-2.5% by weight were scoured at varying pressures and temperatures using the apparatus shown in FIG. 3 . The oil agents consisted essentially of coning oils and EO/PO copolymers. Carbon dioxide was passed through the system at the rate of approximately 150 ml/min. The overall solvent-to-feed ratio was about 8.85 grams CO 2 per gram of fiber. The operating pressures were varied in a range from 96 to 345 bar and the operating temperatures were varied in a range from 40 to 120° C. The results of the experiment are shown in Table 1.
TABLE 1
Extraction Efficiencies of SC—CO 2 in Removing
Oil Agents from Polyester Fibers
Pressure
96.5
137.9
241.4
275.9
310.3
344.8
Tempe.
bar
bar
bar
bar
bar
bar
120° C.
39%
—
88%
88%
92%
96%
100° C.
—
—
88%
92%
97%
—
80° C.
—
—
91%
94%
98%
—
60° C.
—
83%
96%
95%
99%
—
40° C.
86%
—
99%
99%
100%
100%
As shown in the above Table, extraction efficiencies ranging from 39 to 100% were attained by employing different pressures and temperatures. It can be seen that for a given temperature, the extraction efficiency increases with the operating pressure. On the contrary, for a given pressure, the extraction efficiency decreases with the operating temperature.
EXAMPLE 2
Nylon fibers were scoured by supercritical carbon dioxide at a pressure and temperature of 276 bar and 60° C. using the apparatus shown in FIG. 3 . The overall solvent-to-feed ratio was 5.30 grams CO 2 per gram of fiber. The results of the experiment are shown in Table 2. As shown therein, a high level of extraction were achieved by using supercritical carbon dioxide scouring.
TABLE 2
Extraction Efficiencies of SC—CO 2 in Removing
Oil Agents from Nylon Fibers
Oil Pick Up
Extraction
Rate (OPU)
Efficiency
Nylon 66
Before scouring
2.13%
—
After scouring
0.14%
93%
Nylon 6
Before scouring
1.18%
—
After scouring
0.13%
89%
EXAMPLE 3
In this example, supercritical carbon dioxide scouring and conventional scouring were employed on polyester fibers individually to compare their effects on fibers' physical properties. In the conventional scouring, the polyester fibers were first scoured by a strong-base solution at 100° C. for 25 minutes, which was an aqueous solution containing 2 g of scouring agent and 3 g of sodium hydroxide per liter of water. The fibers were then neutralized with a weak-base solution at 50° C. for 10 minutes, which contained 0.5 g of acetic acid per liter of water. Finally, hot water of 85° C. was used to rinse the neutralized fibers for 10 minutes. The operating conditions of the supercritical carbon dioxide scouring are listed in Table 3. The scoured fibers were tested for their tensile properties and the results are also summarized in Table 3.
TABLE 3
Physical Effects on Fibers After Scouring
Operating conditions of
Tensile property
SC—CO 2 Scouring
Tensile
Temp.
Pressure
strength
C.V.
Elongation
C.V.
(° C.)
(bar)
m co 2
(gm/denier)
(%)
(%)
(%)
120
345
8.85
4.52
4.05
37.41
5.6
40
241
8.85
4.34
5.59
41.15
9.06
Polyester fibers
4.59
2.67
25.52
7.94
(before scouring)
Polyester fibers
4.19
8.60
30.21
19.0
(conventional scouring)
m co 2 : the ratio of grams of CO 2 used per gram of fibers
C.V.: coefficient of variation
The above Table indicates that the conventional scouring adversely affected the fibers on both the tensile strength and the elongation. On the contrary, the supercritical carbon dioxide scouring had little effects on the tensile strength and coefficient of variation; moreover, it actually improved the elongation.
EXAMPLE 4
In this example, the supercritical carbon dioxide was performed at a fixed pressure and temperature of 310 bar and 80° C., and the amount of carbon dioxide used was varied in a stepwise manner to regulate the extraction efficiency. The scouring was carried out for a period of ten minutes and the results are shown in Table 4. As shown therein, a 90% extraction was attained in ten minutes by using less than 2 grams of carbon dioxide per gram of fibers. Furthermore, since the extraction efficiency increases with the amount of carbon dioxide, a complete removal was accomplished by using a greater amount of carbon dioxide.
TABLE 4
m co 2
Extraction efficiency
0.29
86%
0.59
87%
1.77
90%
3.54
95%
5.31
97%
7.08
95%
8.85
100%
10.62
100%
m co 2 : the ratio of grams of CO 2 used per gram of fibers
In summary, the supercritical carbon dioxide scouring of the invention has the following advantages:
1. Carbon dioxide is non-toxic and easy to handle.
2. Aqueous rinsing agents are not necessary, thus avoiding the need for wastewater treatment and reducing the production costs.
3. A higher throughput can be obtained since the scouring time is shortened from 45 to 10 minutes on the average.
4. The carbon dioxide can be recycled for use, and the recovery of the oils agents is possible.
5. The integration of the scouring process into the supercritical carbon dioxide dyeing process is made possible.
While the invention has been particularly shown and described with the reference to the preferred embodiment thereof, it will be understood by those skilled in the art that various changes in form and details may be made without departing from the spirit and scope of the invention.
|
A method of removing spinning and finishing oils from fibers using supercritical carbon dioxide as an extraction media is provided. This process using carbon dioxide to remove oils from fiber surface operates at moderate pressures between 90 and 350 bar and at temperature levels ranghng from 40 to 120° C. The treated fibers have improved strength and elongation properties compared to those treated by conventional scouring. The treated fibers can be directly subjected to the subsequent dyeing processing.
| 3
|
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This claims priority to and the benefit of U.S. Patent Provisional Application No. 61/046,878, filed Apr. 22, 2008, the entirety of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] For load-bearing structures, we normally need materials with high compressive strength. However, in order to use these materials effectively, large masses are required. A filament, a wire, or a cable of the material would be useless in the compressive mode. There are materials that have very high tensile strengths that can support large loads as a cable, if the support is supplied from above the load. Unfortunately in practice, most loads are supported from below. I propose herein a method for using the high tensile strengths of some materials to support loads in the compressive mode. This means that building blocks could be much lighter than the standard load-bearing materials such as masonry bricks, concrete, or steel beams. (Since “wire” connotes a metal, “string” connotes a collection of fibers, “yarn” means a large string, and “cable” is usually applied to a large metal rope, “filament” will be used in this document refer to the elongated support member).
[0003] U.S. Patents such as U.S. Pat. Nos. 3,854,253, 4,004,380, 4,676,032, 5,675,938, and 6,584,732 show inflatable structures that have interior braces, cables, and films to maintain the geometry of the structure, but they are not constructed to form building blocks for larger structures. Between the connecting points of the cables to the outer surfaces, the outer surface material typically bulges out, due to the air pressure. If these were used as building blocks, when one block is placed upon another, the bulges would be springy and would compress so that there would not be sufficient rigidity for effective building blocks.
[0004] This description also includes the use of the building blocks for the construction of convection towers, for which I have four patents with the U.S. Pat. Nos. 5,284,628, 5,395,598, 5,477,684, and 5,483,798.
SUMMARY OF THE INVENTION
[0005] High air pressure in an air bag can support heavy loads, but they are very compressible (spongy). Now suppose that we have a bag in the shape of a rectangular box and each face of the box is maintained in position by air pressure and an array of high tensile strength, high modulus filaments that run from one face to the opposite face. The load-bearing surfaces can be rigid or can have external washers that connect to the filaments. The air pressure pushes outward, while the filaments pull in. The pressure can be high inside such a box since the forces on the faces are borne by the filaments. When a heavy load is placed on the top face, the tension on the filaments that run from the top face to the bottom face of the box is reduced, and the load is supported by the air pressure. Since the filaments are made of a high modulus material such as Vectran, S-glass, graphite yarn, carbon-reinforced plastic, or even steel, there will be almost no depression of the box. It would be quite rigid as long as the external pressure on the top face did not exceed the pressure of the air inside the box.
[0006] This invention provides a method of utilizing the high tensile strength of some materials to provide large compression forces to support loads.
[0007] A box shape is appropriate for many building blocks, but the use of air pressure in an enclosed surface with internal filaments or thin films to maintain the shape can take many shapes. This invention concerns pressurized containers that can be stacked to make larger structures. They would be quite rigid as long as the external pressure on the top face did not exceed the pressure of the air inside the box. We may call it a “Compressed-Air Rigid Building Block” (CARBB), and it may be much larger than a standard brick or a building block.
[0008] To prevent gradual deflation by possible small leaks, each CARBB could have a small-diameter hose attached to it through a one-way valve. The hose is attached to a pressure tank. Actually, if it is properly built, it should hold its pressure for years, just like car tires. If one CARBB is accidentally damaged, it can be deflated and removed, and another one can be inserted and inflated. The CARBB's are laid like ordinary bricks with the middle of each brick placed over the joint of the two bricks below it. See FIG. 8 . For applications in which a narrow column is required, the CARBB's can be stacked one above the other.
[0009] Large CARBB's would be useful in building large structures such as convection towers, cooling towers, housings for blimps, airplanes, military equipment, and farm products such as wheat, and temporary buildings for special events. Since they are light and foldable, they can be shipped in the deflated state and inflated at the site where they will be used. They could be used as temporary bridge supports in dry streambeds in military applications.
[0010] To give an idea of the kind of load that can be borne by a CARBB, suppose it is constructed in the form of a cube that is 10 feet on each side and then a pressure of 100 psi is applied inside. The filaments can be made of Vectran, which has a tensile strength of 3.2 Giga Pascals (464,000 psi). It would require 235 lbs. of Vectran for the filaments (with a safety factor of 4) and 600 lbs of other materials, for a total of 835 lbs. Yet it could support 700 tons (1.4 million pounds) of weight on top of it. Imagine stacking 14 military tanks on top of an 835 lb. box! Of course, the compressed air inside the air box weighs 490 lbs., so the total weight is 1,325 lbs. Its average density of the CARBB is 0.021 gm/cc, including the air. That compares to 0.69 for cardboard and 0.12 gm/cc for balsa wood. The CARBB is much stronger than cardboard or balsa.
[0011] We could stack such boxes on top of each other to a height of about 11,000 feet, before the bottom box would begin to collapse. By tapering the weight (that is, by having the higher boxes have less mass and less air pressure), they could theoretically be stacked to over 30,000 feet. We can also increase the air pressure and put in heavier filaments in order to support heavier loads. Replacing air with helium allows the construction of taller towers. For the moment, we are neglecting such things as wind forces and guy wires.
[0012] For many applications, the CARBB would be much smaller than 10 feet on each side. The advantage of having them large is the fact that their density is less. A 10 by 10 by 10 foot CARBB would occupy 1,000 cubic feet. It would require 125 blocks that were two feet on each side to construct a building block that that occupied 1,000 cubic feet. It would weigh much more, because there would be much more face material.
[0013] To provide a perspective, we can make a comparison to a steel cable. An ordinary steel cable, one square inch in cross sectional area, can safely support 10 tons of weight. If it is suspended from a crane 100 meters high, the cable will weigh 1,116 lbs. It can support 17.9 times its own weight. Compare this with the 10 by 10 by 10 foot CARBB. The unit can support 1,080 times its own weight.
[0014] The U.S. military could use CARBB's as structural material, since military units often have to move quickly into an area to set up large temporary buildings. For military purposes, the boxes might be six feet on each side and weigh 240 lbs. The CARBB's are transported flat and then inflated on site. They can be stacked to make walls. What about the roof? Calculations show that if the CARBB's are designed with sufficient diagonal filaments, they can be placed on top of the walls to stretch across a 200-foot opening on the top to form a roof. Rather than having to build CARBB's that are 200 feet long, shorter bodies can be designed so that they can be placed end-to-end, and sliding connectors can hold them together.
[0015] Of course, for building moderate size structures, such as the military might need, it is not necessary to design the CARBB's for 100 psi. For example, a CARBB that is 6 by 6 by 12 feet long that has only 10 psi pressure inside would be able to support 50 tons. If the CARBB's were used to build a wall 60 feet tall, the weight on the top of each bottom CARBB due to the CARBB's above it would be a little over one ton. The extra support capacity can be used to support the roof and possibly intermediate floors. If heavier loads are required, the pressure can be increased.
[0016] Another application would be tall convection towers. A company in Australia plans to build a 1,000-meter tall solar power tower to produce electricity. The tower would be 130 meters in diameter and would be built of reinforced concrete that is one meter thick at the bottom. The glass-covered greenhouse around the base is to be 7 kilometers in diameter, incorporating 38 square kilometers (15 square miles) of glass to heat the air with solar energy. The tower will be very heavy (requiring a massive foundation) and expensive. By stacking CARBB's around in a circle at the base and continuing to stack CARBB's on top of those, the tower could be less expensive and far lighter. The proposed concrete tower would weigh more than 600,000 tons. A tower built of CARBB's (3 meter wide walls at the bottom) would weigh about 25,000 tons.
[0017] Downdraft convection towers that spray water across the open top to cool the air can clean air pollution from the atmosphere while producing electric power. They can be built with CARBB's. These will be discussed below.
[0018] For wind turbines in the U.S. and around the world, taller heights mean higher wind speeds and greater power production. CARBB's could be used to inexpensively build taller wind turbine towers. The towers could be constructed by laying the CARBB's like bricks in a circular fashion, or they could be built with circular CARBB's like that shown in FIG. 10 .
[0019] Homes, factories, warehouses, and office buildings can be built with CARBB's that are especially designed for the purpose. Hangers at airports represent another application.
[0020] It is therefore an object of the present invention to provide a rigid box-like structure that is caused to retain its shape by internal air pressure (or other gas pressure) and by high strength, high modulus filaments that are attached to opposite faces of the structure.
[0021] It is another object of the present invention provide a rigid cylindrical structure that is caused to retain its shape by internal air pressure (or other gas pressure) and by high strength, high modulus filaments that are attached to the top and bottom of the structure and by filaments attached to the outside of the structure.
[0022] It is another object of the present invention to provide a rigid box-like structure that is caused to retain its shape by internal air pressure (or other gas pressure) and by high strength, high modulus films that are attached to the interior faces of the structure.
[0023] It is another object of the present invention to utilize rigid structures for inexpensive construction of convection towers for the generation of electric power.
[0024] Other objects, advantages and novel features, and further scope of applicability of the present invention will be set forth in part in the detailed description to follow, taken in conjunction with the accompanying drawings, and in part will become apparent to those skilled in the art upon examination of the following, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] The accompanying drawings illustrate embodiments of the present invention and, together with the description, serve to explain the principles of the invention. The drawings are only for the purpose of illustrating preferred embodiments of the invention and are not to be construed as limiting the invention. In the drawings:
[0026] FIG. 1 is a cross-sectional side-view schematic of one embodiment of the present invention showing a structure that is held rigid by air pressure pushing outward and tension filaments pulling inward.
[0027] FIG. 2 is an isometric drawing of the CARBB invention showing a structure that is held rigid by air pressure and internal tension filaments and showing diagonal filaments on the outside faces that resist shearing forces.
[0028] FIG. 3 is a schematic side view showing a method of inserting filaments between the top and bottom faces of a CARBB.
[0029] FIG. 4 is a schematic side view showing a method of inserting filaments between the side faces of a CARBB.
[0030] FIG. 5 is a cross-sectional side-view schematic of a single frame on which tension filaments are wound.
[0031] FIG. 6 is an end view and a top view of part of the frame of FIG. 5 .
[0032] FIG. 7 illustrates a method of inserting filaments into a CARBB.
[0033] FIG. 8 shows how the CARBB's are laid to form a wall.
[0034] FIG. 9A is a cross-sectional side-view schematic of another embodiment of the present invention showing a structure that is cylindrical.
[0035] FIG. 9B is an isometric view of the cylindrical embodiment of FIG. 9A .
[0036] FIG. 10 is an isometric view of another embodiment of the present invention, which provides a circular geometry with a cylindrical hollow inside.
[0037] FIG. 11 is a top view schematic showing how the circular configurations of FIGS. 9A and 9B or FIG. 10 can be arranged on a flat sheet.
[0038] FIG. 12 is a cross-sectional side-view schematic of another embodiment of the present invention showing a structure that contains horizontal sheets and vertical filaments as tension members.
[0039] FIG. 13 is an isometric schematic of another embodiment of the present invention showing a structure that contains horizontal, vertical, and diagonal sheets as tension members.
[0040] FIG. 14 is a cross-sectional side-view schematic of a convection tower that uses CARBB modules to construct the walls of the tower.
DETAILED DESCRIPTION OF THE INVENTION
[0041] FIG. 1 shows one design of a CARBB 1 in cross sectional side view. The faces 2 , 3 , 4 and 5 of the CARBB can be made of thin, tough composite plastic material or other airtight material. The top face 2 and bottom face 4 can be somewhat rigid. Side faces 3 and 5 , as well as the front and back faces (not shown) should be flexible so that the box can be folded down for shipping. Horizontal filaments 8 and vertical filaments 9 are shown. The dots 10 represent filaments that run in the third dimension (perpendicular to the page). The filaments hold the faces in place against the inside air pressure. In this design, the filaments 9 and 10 run through the side faces and are attached to rectangular plastic or metal washers, which distribute the force from the filaments to the face material. Filaments 8 pass through the top and bottom faces and are attached to the outside of those faces. On the side faces 3 and 5 (as well as the front and back faces), there should be small gaps between the rectangular washers so that the side faces can fold inward to allow the box to be collapsed.
[0042] FIG. 2 shows a perspective view of the box. The encasing composite material on the faces has diagonal filaments 12 cemented to the outside of the faces to resist shear forces.
[0043] In order to fabricate such a building block, one method would be to construct a plastic CARBB with the six faces sealed together at the edges of each face sheet and hold it in place by slight inside air pressure against the inside a jig. A rod passes a filament through holes in one face and continues on to holes in opposite faces of the box, and the filament is fastened to the rectangular, tapered washers on the outside of the faces. An appropriate adhesive seals the washers to the box. This would work for small boxes, but it would be difficult for large boxes.
[0044] The question is, how are the filaments installed in the box of FIG. 1 and FIG. 2 , if the box is large? There are several ways in which it may be done. One method is described here. The top face 2 and the bottom face 4 have small holes drilled in them at appropriate locations for the filaments to pass through. Both faces are placed in a jig with the top face 2 lying on the bottom face 4 , as shown in FIG. 3 . This is just a schematic drawing, showing only a few spools and filaments. A machine 13 that has many spools 14 of filaments across top area of the top face 2 and needles (not shown) pointed downward toward the holes in the top and bottom faces with the filaments 9 threaded through the eyes of the needles, which descend so that the needles pass through the holes in the top and bottom faces. Mechanisms below the bottom face 4 would intercept the needles and filaments and attach the filaments to the bottom face, similar to the operation of a sewing machine. The upper part of the machine would then rise. The top sheet would be raised the appropriate distance.
[0045] We now have two rigid sheets at the top and bottom and rows of vertical filaments 9 extending between the two sheets. The whole assembly is then rotated 90 degrees to the left, and the faces 2 and 4 are separated further. See FIG. 4 . Note that the machine 13 is now on the left. Face 3 is placed below the filaments 9 , and face 5 is placed above the filaments 9 . Face 3 is raised as face 5 is lowered. The filaments 9 are pressed between the two faces 3 and 5 as the spools 14 allow the filaments to be extended. Faces 3 and 5 have holes in them for the passage of the filaments. Face 3 has rectangular washers cemented to its bottom matching the position of the holes. Face 5 has rectangular washers cemented to its top over the holes. While faces 3 and 5 are pressed together, machine 15 , which is similar to machine 13 , and spools 16 holding filaments pass the filaments 8 through holes in faces 3 and 5 by needles (not shown). The filaments are attached to the bottom of face 3 . Then face 3 is lowered while machine 15 and face 5 are raised.
[0046] The process of the preceding paragraph is repeated, except that the whole assembly is rotated into the page of the drawing, and the front and back faces of the CARBB are placed above and below all the filaments. The front and back faces are moved together to press all the filaments 8 and 9 between them. Another machine then passes filaments through the front and back faces, the filaments are connected to one of the faces, and the faces are moved apart. All of the faces are moved into the appropriate positions, and all the filaments are tightened and cemented to the outside of the faces. The faces are sealed along all the edges. The finished BARBB can then be inflated.
[0047] Each CARBB has an inflation connection and valve, and a connection for a small diameter hose to maintain pressure (not shown).
[0048] Another way of positioning the filaments is to wind the filaments onto a plastic (or metal) frame 20 as shown in FIG. 5 . The frames are constructed of narrow strips that might be two inches wide (in the direction normal to the page of the drawing) and perhaps 3/16 of an inch thick. Vertical 9 , horizontal 8 , and diagonal filaments 7 are wound around the frames. Many of these frames are then placed adjacent to each other. The top, bottom, and sides of the plastic casing (faces) of the CARBB are then epoxied to the outside of the frames and sealed at the corners. That will take care of four faces of the box. Filaments will need to be passed through the other faces by rods. If each rod has a streamlined body at its front end, it will be guided through rows and columns of filaments as it presses against those filaments. Finally the end plastic sheets are sealed to the side sheets. The whole process can be automated in a factory.
[0049] The advantage of having the diagonal filaments is that they provide resistance to shear forces about the axis normal to the page. The CARBB's can be oriented so that the probable direction of greatest shear forces will be resisted. Shear forces in other directions can be resisted by diagonal filaments on the outside of the box.
[0050] The frames 20 have hinges 21 on side strips 25 and 26 so that the CARBB's can be folded down for transporting to the location of use or for storage. The side encasing material must be flexible in order to permit the folding of the box. The top and bottom of the box can be rigid. Alternatively, in order to make side strips easily foldable, side strips 25 and 26 can be made of flexible material that have rigid rectangular washers where the filaments are attached.
[0051] FIG. 6 shows detail of part of the frame. The filaments 7 , 8 , and 9 are wrapped into slots 22 in the frames and tightened to specified tension while the frames are held in a jig. When the frames are stacked adjacent to each other, they fit together with overlaps 23 and 24 .
[0052] Another way to put the filaments into the CARBB is illustrated in FIG. 7 . The top face 2 and the bottom face 4 of CARBB can be put together as shown in FIG. 3 . The filaments are passed through and attached to the bottom face. Then the two faces are moved to their normal finished positions, and the filaments 9 are cemented to the outside of the top face. In FIG. 7 , the left face 3 is then placed on the left. A vertical row of shuttles 80 attached to rods 82 are inserted from the right and pass down between the rows of vertical filaments 9 . The rods 82 are moved by support 83 . For the first pass through, horizontal filaments 8 are attached to the first vertical catch rod 84 . There is one vertical catch rod 84 at the right of each row of vertical filaments 9 . From there filaments 8 pass through the eye of the needles 81 and then go back to spools 87 . Alternatively, the shuttles 80 could contain the spools of filaments. The shuttles 80 are supported by supports 86 and roller 89 .
[0053] When the shuttles 80 reach the left side, an inserted guide 85 guides the needles into the holes 88 in the left face 3 . After the needles pass through left face, a mechanism (not shown) seizes the filament above the needle and attaches it to the surface of face 3 . Then the shuttles are withdrawn to the right. The support 83 , along with the rods, shuttles, and the spools, move one row toward the viewer in the drawing. As it moves toward the viewer, the filament passes around the next catch rod 84 . On the left, the guide 85 , which has slots in the side to let the filaments pass through, also moves toward the viewer to line up with the next row of holes 88 . Then the shuttles move again to the left to install the next row of horizontal filaments 8 . This process continues until all the horizontal filaments are installed. The guide 85 is removed, and the left face 3 is moved into contact with the top face 2 and bottom face 4 and cemented to them.
[0054] On the right, the shuttle mechanism ( 80 , 82 , 83 , and 87 ) is removed. The right face 5 (shown in FIG. 1 ) is put into place, and a mechanism from the right side of the right face inserts hooks through the holes and seizes the filaments that are held by the catch rod 84 and pulls them through the holes. The catch rods have grooves in the right side so that it is easy to snag the filaments. After all the filaments 8 have been drawn through the holes, the catch rods 84 are removed, and the right face 5 is moved against the top face 2 and bottom face 4 and sealed into place. The filaments 8 are drawn tight and attached to the right surface of face 5 .
[0055] The assembly is then rotated about the vertical axis 90 degrees counterclockwise. The back face is placed to the left along with the guide 85 . The supports 86 are removed from between the shuttles, because they would interfere with the filaments 8 . The shuttles are guided by moving down the channels, which are surrounded by the vertical and horizontal filaments. The catch rods 84 are put in place on the right. The shuttles are inserted from the right, and the process described in the proceeding paragraphs insert the remaining filaments. Finally the front and back faces are cemented in place.
[0056] This method would work for the design shown in FIG. 1 . It would also work for the design in which filaments 7 , 8 , and 9 are put in place by the frames of FIG. 5 . In some cases, the diagonal filaments would be pushed out of the way by the shuttles.
[0057] FIG. 8 shows one method of building a wall or other supporting structure with CARBB's. The CARBB's 1 can be stacked like bricks.
[0058] Another embodiment ( 30 ) of a CARBB is shown in FIG. 9A and FIG. 9B . FIG. 9A shows a cross sectional side view of a cylindrical enclosure that has filaments 9 running in the axial direction to support the circular faces 33 and 34 against internal air pressure. FIG. 9B gives an isometric view of the outside of this embodiment. Filaments 32 are wrapped around the cylinder 35 in a circumferential direction to support the side pressure. Diagonal filaments (not shown) cemented to the outside of cylinder 35 resist shear forces. The cylinder 35 should be made of flexible material so that the CARBB can be folded down for shipping. Cylinder 35 is sealed to the rigid top 33 and the rigid bottom 34 .
[0059] This cylindrical embodiment can be easily fabricated in a factory. The top face 33 and the bottom face 34 should have small holes for the filaments at appropriate locations. Both are placed in a jig with the top face lying on the bottom face. A machine that has many spools of filaments across a circular area and needles pointed downward toward the holes in the top and bottom faces with the filaments threaded through the eyes of the needles can descend so that the needles pass through the holes in the top and bottom faces. Mechanisms below the faces would intercept the needles and filaments and attach the filaments to the bottom face. The upper part of the machine would then rise. The top sheet would be raised the appropriate distance, and the filaments would be attached to the top face. The holes would be sealed and the filaments would be cemented to the top face 33 and bottom face 34 . The side enclosure 35 would then be sealed to the top and bottom sheets.
[0060] For narrow towers, like those that support wind turbines, the CARBB's could be constructed in a circular design 36 as shown in FIG. 10 . The interior would be constructed of frames like that in FIG. 5 , but the outer part of each frame would be wider than the inner part, since the radius and the circumference of the circular design are larger on the outside. There would be vertical, horizontal, and diagonal filaments inside. The horizontal filaments run radially. Since the outside cylinder 37 has a larger area than the inside cylinder 38 , there might be concern that the radial filaments would pull more strongly towards the outside, but there will be filaments wrapped circumferentially around the outside cylinder 37 that will counter this extra force.
[0061] FIG. 11 shows a method of grouping CARBB modules such as design 30 in FIG. 9 or design 36 in FIG. 10 . The modules can be attached to a bottom rigid sheet 39 . In this way, the circular CARBB's can be assembled to function as building blocks similar to those of FIG. 2 and can be stacked like those of FIG. 8 .
[0062] Another design that makes it easy to fold the CARBB flat is shown in side view cross section in FIG. 12 . The air pressure on the CARBB's sides is countered by horizontal thin film sheets 41 of material with high tensile strength. The internal air pressure on the top 44 and bottom 45 are supported by filaments 42 . The outer edges of the sheets are sealed together by end sheets 43 that are cemented to the horizontal sheets 41 . Air pressure forces them to curve outward. This design is fabricated by laying the bottom face 45 of the CARBB on the factory assembly mechanism and then laying the first horizontal sheet 41 on the bottom face 45 and sealing the first sheet 41 to the bottom face with the end sheets 43 . While that sheet lays flat on the bottom, the second horizontal sheet 41 is laid on top of the first sheet 41 and sealed to the first horizontal sheet with other end sheets 43 . This process is continued until the last horizontal sheet 41 is sealed to the top face 44 of the CARBB with end sheets 43 . The top face 44 and the bottom face 45 can be somewhat rigid and have many small holes in them for the attachment of the filaments 42 . With the whole assembly lying flat, needles pass through the holes in the top face 44 and are forced down through the horizontal sheets 41 with filaments 42 in the eyes of the needles. Mechanisms below the bottom face catch the filaments 42 and attach them to the bottom face 45 . When this process is finished, air pressure raises the top to full height while spools reel out the filaments. The filaments are then attached to the top, and the holes where the filaments pass through are sealed.
[0063] An alternative to the design shown in FIG. 12 would be to use sets of filaments in place of the horizontal sheets. The sets of filaments would be laid upon the bottom face 45 and attached to the end sheets 43 in a manner similar to the description in the previous paragraph. An advantage of the horizontal sheets 41 is that they provide resistance to shear forces about the vertical axis.
[0064] Another alternative embodiment similar to FIG. 12 is shown in FIG. 13 . The tension support is provided by vertical 51 , horizontal 52 , and diagonal sheets 53 of strong plastic film. This configuration of sheets can be formed by extrusion of the plastic through a die. The isometric drawing shows the direction of extrusion. When the plastic exits the die, it already has the vertical, horizontal, and diagonal sheets. Only two diagonal sheets are shown, but diagonal sheets can actually be placed to meet all the intersections of the vertical and horizontal sheets. The extrusion units are cemented to the top rigid face 55 and bottom rigid face 56 . If the end sheets 54 are not part of the extrusion, they can be added by cementing onto the horizontal sheets 51 .
[0065] For large assemblies, the extrusions can be made in smaller units and can then be cemented together. For example, each extrusion unit might be one foot square in cross section with two-inch spacing between the vertical sheets and two-inch spacing between the horizontal sheets. If the CARBB is to be six feet long by three feet wide by three feet tall, it would require nine of the extruded units (each six feet long) to fill the interior. Holes in the interior sheets would allow air to flow throughout the interior.
[0066] The advantage of the design of FIG. 13 is that, in addition to the strong tension forces applied to the outside faces of the box by the interior sheets, there are strong forces to resist any shear stresses. The end sheets 54 on the side allow the unit to collapse downward when the air pressure is removed. To attach end sheets to the front (nearest the viewer in the drawing) and back, the extrusion is allowed to extend a little beyond the intended face of the box, the vertical and the diagonal sheets are cut back slightly, and end sheets are cemented to the horizontal sheets. Since interior sheets are thin, heavier and more rigid sheets 55 and 56 are cemented to the top and bottom. The end sheets should be thicker and tough to prevent abrasive objects from damaging the unit.
[0067] If the sheets in a 6 by 3 by 3 feet CARBB are 5 mils thick with two-inch spacing between sheets and the material has a density similar to Spectra 2000, the weight on the interior sheets would be 41 lbs. If the tensile strength is 30,000 psi, the maximum allowable air pressure would be 150 psi. With a safety factor of three (air pressure=50 psi), the CARBB could support 129,600 lbs. A warehouse wall 120 feet long could support 1,296 tons. The complete 6 by 3 by 3 foot CARBB would weigh 100 lbs. With the compressed air at 60 psi, it would weigh 120 lbs. It can support 1,300 times its own weight.
[0068] Since the CARBB's are so light, there might be a concern that CARBB's might be blown off a wall built with CARBB's by the wind. For some applications, Velcro could be applied to the top, bottom, and ends of the CARBB's to secure them together. For other applications, straps can tie them together and anchor them to a concrete foundation.
[0069] Rigid CARBB's that use air pressure to provide support and internal filaments that have high tensile strength and high modulus can be used to build towers, such as those that support wind turbines.
[0070] One of the important applications of CARBB technology is the construction of convection towers, either downdraft or updraft. A downdraft convection tower, such as that shown schematically in side view cross-section in FIG. 14 , works well in low-humidity areas where water is available. Water is sprayed across the open top of the tower by a water spraying system 61 . That cools the air and makes it dense. The air falls down the inside of the tower and turns air turbines 62 at the bottom of the tower to generate electricity. The diffuser 63 improves the efficiency of the turbines.
[0071] The cylindrical wall 60 is made by stacking CARBB's in brick-like manner ( FIG. 8 ). Guy wires 65 and radial cables 66 add to the rigidity of the tower wall. These can be steel cables, or they can be made of some of the new lightweight, high-strength filament materials. Structural supports 67 are built to support the wall above the turbines.
[0072] A downdraft convection tower that is 1,000 meters tall and 500 meters in diameter can generate 1,000 megawatts of electric power when the relative humidity is 20% or less. But building a tower of that size is quite expensive by using the standard materials and methods. The value of CARBB can be illustrated by comparing it with concrete and steel construction. Consider the CARBB's to be 10 by 10 by 10-foot cubes, as described above with air pressure of 100 psi. The cube would weigh 1,325 lbs, including the compressed air. A cube of the same size made of concrete would weigh 150,000 lbs. The foundation for a 1,000-meter tall concrete tower would be enormous.
[0073] As mentioned above, with a CARBB top face force of 1,440,000 lbs, it could support CARBB's that are stacked to a height of 10,000 feet. Since the tower is only 3,280 feet tall, the pressure can be lowered considerably.
[0074] Whereas a 1,000 meter tall concrete and steel tower would require several years to complete. Such a tower that is built with CARBB would require about five months. The blocks can be inflated at the base of the tower. Lightweight lifting units on top of the wall can raise the CARBB to the top and quickly place it on top of the wall. A number of crews of three workers each can make the tower grow rapidly. When one row is finished, the lifting unit can be placed on an uninflated CARBB, and the inflation of the CARBB will lift the lifting unit to the next level. For concrete towers, it requires a lot of energy to lift the concrete, and then after the concrete is poured, time must be allowed for it to harden. After that, the concrete forms must be dismantled and reset.
|
The outstanding tensile strength of some materials are used in compression applications by using air pressure to supply the outward force on an enclosure and by using interior tension members to maintain the geometry of the air-pressurized structure. The air pressure on each face of the structure is balanced by the tension in the tension members. Due to the high modulus of the tension members, the air-pressurized structures are very rigid. It is the air pressure that actually supports any load placed on the structure, but it is the tension members that maintain the geometry when the load is removed, and the strength of the tension members determine how much air pressure can be sustained. The mass of tension material required in such a structure is roughly equivalent to the amount of filament material required in a cable to support the same load. The Compressed-air Rigid Building Blocks can be stacked like bricks to form strong, lightweight walls, buildings, towers, and other structures.
| 4
|
RELATED APPLICATIONS
This application is a divisional application of U.S. application Ser. No. 11/205,764, filed on Aug. 17, 2005, which claims the benefit of U.S. Provisional Application No. 60/676,727, filed on May 2, 2005 and U.S. Provisional Application No. 60/696,622, filed on Jul. 5, 2005. The entire teachings of the above applications are incorporated herein by reference.
TECHNICAL FIELD
The present invention relates generally to the processes and intermediates useful in the preparation O-(6-pyrazol-1-yl-pyridin-3-ylmethyl)-hydroxylamine which is a reagent in the synthesis of certain bridged erythromycin and ketolide derivatives described in U.S. Pat. No. 6,878,691, U.S. Pat Pub. No. 2005037982 and PCT Application WO 03/097659 A1.
BACKGROUND OF THE INVENTION
Macrolide antibiotics play a therapeutically important role, particularly with the emergence of new pathogens. Structural differences are related to the size of the lactone ring and to the number and nature (neutral or basic) of the sugars. Macrolides are classified according to the size of the lactone ring (12, 14, 15 or 16 atoms). The macrolide antibiotic family (14-, 15- and 16-membered ring derivatives) shows a wide range of characteristics (antibacterial spectrum, side-effects and bioavailability). Among the commonly used macrolides are erythromycin, clarithromycin, and azithromycin. Macrolides possessing a 3-oxo moiety in place of the 3-cladinose sugar are known as ketolides and have shown enhanced activity towards gram-negative bacteria and macrolide resistant gram-positive bacteria. The search for macrolide compounds which are active against MLS B -resistant strains (MLS B =Macrolides-Lincosamides-type B Streptogramines) has become a major goal, together with retaining the overall profile of the macrolides in terms of stability, tolerance and pharmacokinetics.
Recently PCT Application WO 03/095466 A1, published Nov. 20, 2003 and PCT Application WO 03/097659 A1, published Nov. 27, 2003 disclose a series of bicyclic erythromycin derivatives.
SUMMARY OF THE INVENTION
The present invention provides methods for preparing compounds of Formula I:
A most preferred embodiment of a compound of formula I is O-(6-pyrazol-1-yl-pyridin-3-ylmethyl)-hydroxylamine having the formula Ia:
In one embodiment of the invention, pyridyl derivatives of formulae I are reacted with pyrazole in the presence of acids, bases or metallic catalysts. The invention further relates to increasing product yield and decreasing process steps for intermediate and large scale production O-(6-pyrazol-1-yl-pyridin-3-ylmethyl)-hydroxylamine. Compounds of Formula I and particularly, O-(6-pyrazole-1-yl-pyridin-3-ylmethyl)-hydroxylamine is particularly useful as a reagent in the synthesis of EP13420 which has the following formula:
DETAILED DESCRIPTION OF THE INVENTION
In a first embodiment, the present invention provides a process for the preparation of compounds of formulae (I);
wherein R 1 and R 2 are each independently selected from:
(a) hydrogen; or
(b) NH 2 ;
or one of R 1 or R 2 is a hydrogen and the other is selected from:
(a) C(O)R 3 , where R 3 is C 1 -C 6 alkyl, optionally substituted with one or more substituents selected from aryl, substituted aryl, heteroaryl, or substituted heteroaryl;
(b) C(O)OR 3 , where R 3 is as previously defined; or.
wherein A and B are each independently hydrogen, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted heteroaryl group; or A and B taken together with the carbon to which they are attached form a cyclic moiety selected from: aryl, substituted aryl, heterocyclic, substituted heterocyclic, alicyclic, or substituted alicyclic;
alternatively, R 1 and R 2 are taken together with the nitrogen atom to which they are attached to form N═C(R 4 )(R 5 ), where R 4 and R 5 are each independently selected from a substituted or unsubstituted aliphatic group, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted heteroaryl group;
said process comprising one or more of the following steps:
(1) treating 2-chloro-5-chloromethyl-pyridine with compounds of formula R 1 R 2 NOH wherein R1 and R2 are as previously defined in the presence of base to yield compounds of formulae (II):
(2) reacting pyrazole with compound of formulae (II) in the presence of acid, base and metallic catalyst to provide compound of formula (I):
Optionally, the process may further comprise the step of hydrolyzing the compound of formula I with a base or an acid in a protogenic organic solvent or aqueous solution, to yield a preferred compound of the invention, O-(6-pyrazol-1-yl-pyridin-3-ylmethyl)-hydroxylamine, having the formulae (Ia):
In a second embodiment, the present invention provides a process for the preparation of a compound of formulae (I);
wherein R 1 and R 2 are each independently selected from
(a) hydrogen; or
(b) NH 2 ;
or one of R 1 or R 2 is a hydrogen and the other is selected from:
(a) C(O)R 3 , where R 3 is C 1 -C 6 alkyl, optionally substituted with one or more substituents selected from aryl, substituted aryl, heteroaryl, or substituted heteroaryl;
(b) C(O)OR 3 , where R 3 is as previously defined; or
wherein A and B are each independently hydrogen, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted heteroaryl group; or A and B taken together with the carbon to which they are attached to form a cyclic moiety selected from: aryl, substituted aryl, heterocyclic, substituted heterocyclic, alicyclic, or substituted alicyclic;
alternatively, R 1 and R 2 are taken together with the nitrogen atom to which they are attached to form N═C(R 4 )(R 5 ), where R 4 and R 5 are each independently selected from a substituted or unsubstituted aliphatic group, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted heteroaryl group;
said process comprising one or more of the following steps:
(1) treating (6-chloro-pyridin-3-yl)-methanol with a suitable hydroxyl protecting reagent to form compounds of formulae (IV):
where Rp is a hydroxyl protecting group;
(2) reacting pyrazole with compounds of formulae (IV) in the presence of base to give compound of the following formula V:
(3) deprotecting the hydroxyl protecting group of formula (V) and halogenating the corresponding compound with a chlorinating reagent to provide a compound of formula (VI):
(4) treating compounds of formulae (VI) with compounds of formula R 1 R 2 NOH wherein R1 and R2 are as previously defined, in the presence of base, followed by hydrolysis to provide compounds of formula (I).
Optionally, the process may further comprise the step of hydrolyzing the compound of formula I with a base or an acid in a protogenic organic solvent or aqueous solution, to yield a preferred compound of the invention, O-(6-pyrazol-1-yl-pyridin-3-ylmethyl)-hydroxylamine, having the formulae (Ia):
In yet another embodiment of the invention a process is provided that comprises one or more of the following steps:
(1) treating (6-chloro-pyridin-3-yl)-methanol with pyrazole in the presence of any of the following: an acid catalyst in organic solvent, preferably in an aprotic solvent; a neat organic acid; or a base with a catalyst such as copper(I) salt or other transition metal derivatives combined with 1,2-diamino derivatives, preferably in an aprotic solvent; to form a compound of formula III, (6-Pyrazole-1-yl-pyrind-3-yl)-methanol:
(2) halogenating the compound of formula III with a chlorinating reagent to provide a compound of formula (VI):
(3) reacting at least one compound of the formula R 1 R 2 NOH wherein R 1 and R 2 are as previously defined, with the compound of formula VI to form a compound of formula I.
Optionally, the process may further comprise the step of hydrolyzing the compound of formula I with a base or an acid in a protogenic organic solvent or aqueous solution, to yield a preferred compound of the invention, O-(6-pyrazol-1-yl-pyridin-3-ylmethyl)-hydroxylamine, having the formulae (Ia):
The above processes, as well as other processes depicted in this application react either a pyrazole, hydroxylamine or other compound with a chloropyridine or a substituted chloroalkane (e.g., a substituted pyridinylmethyl chloride). In these reactions, the chloride acts as a leaving group. In yet another set of embodiments of the invention, other leaving groups can be used in place of the chlorine. Examples of leaving groups include, without limitation, halo groups, e.g., bromine, or sulfonates, e.g., tosylate, mesylate, nosylate, and triflate. In this embodiment, the Cl of the formula set forth above can be replaced with a LG wherein LG is a leaving group.
DEFINITIONS
Listed below are definitions of various terms used to describe this invention. These definitions apply to the terms as they are used throughout this specification and claims, unless otherwise limited in specific instances, either individually or as part of a larger group.
An “aliphatic group” is non-aromatic moiety that may contain any combination of carbon atoms, hydrogen atoms, halogen atoms, oxygen, nitrogen or other atoms, and optionally contain one or more units of unsaturation, e.g., double and/or triple bonds. An aliphatic group may be straight chained, branched or cyclic and preferably contains between about 1 and about 24 carbon atoms, more typically between about 1 and about 12 carbon atoms. In addition to aliphatic hydrocarbon groups, aliphatic groups include, for example, polyalkoxyalkyls, such as polyalkylene glycols, polyamines, and polyimines, for example. Such aliphatic groups may be further substituted.
Suitable aliphatic or aromatic substituents include, but are not limited to, —F, —Cl, —Br, —I, —OH, protected hydroxy, aliphatic ethers, aromatic ethers, oxo, —NO 2 , —CN, —C 1 -C 12 -alkyl optionally substituted with halogen (such as perhaloalkyls), C 2 -C 12 -alkenyl optionally substituted with halogen, —C 2 -C 12 -alkynyl optionally substituted with halogen, —NH 2 , protected amino, —NH—C 1 -C 12 -alkyl, —NH—C 2 -C 12 -alkenyl, —NH—C 2 -C 12 -alkenyl, —NH—C 3 -C 12 -cycloalkyl, —NH-aryl, —NH-heteroaryl, —NH-heterocycloalkyl, -dialkylamino, -diarylamino, -diheteroarylamino, —O—C 1 -C 12 -alkyl, —O—C 2 -C 12 -alkenyl, —O—C 2 -C 12 -alkynyl, —O—C 3 -C 12 -cycloalkyl, —O-aryl, —O-heteroaryl, —O-heterocycloalkyl, —C(O)—C 1 -C 12 -alkyl, —C(O)—C 2 -C 12 -alkenyl, —C(O)—C 2 -C 12 -alkynyl, —C(O)—C 3 -C 12 -cycloalkyl, —C(O)-aryl, —C(O)-heteroaryl, —C(O)-heterocycloalkyl, —CONH 2 , —CONH—C 1 -C 12 -alkyl, —CONH—C 2 -C 12 -alkenyl, —CONH—C 2 -C 12 -alkynyl, —CONH—C 3 -C 12 -cycloalkyl, —CONH-aryl, —CONH-heteroaryl, —CONH-heterocycloalkyl, —CO 2 —C 1 -C 12 -alkyl, —CO 2 —C 2 -C 12 -alkenyl, —CO 2 —C 2 -C 12 -alkynyl, —CO 2 —C 3 -C 12 -cycloalkyl, —CO 2 -aryl, —CO 2 -heteroaryl, —CO 2 -heterocycloalkyl, —OCO 2 —C 1 -C 12 -alkyl, —OCO 2 —C 2 -C 12 -alkenyl, —OCO 2 —C 2 -C 12 -alkynyl, —OCO 2 —C 3 -C 12 -cycloalkyl, —OCO 2 -aryl, —OCO 2 -heteroaryl, —OCO 2 -heterocycloalkyl, —OCONH 2 , —OCONH—C 1 -C 12 -alkyl, —OCONH—C 2 -C 12 -alkenyl, —OCONH—C 2 -C 12 -alkynyl, —OCONH—C 3 -C 12 -cycloalkyl, —OCONH-aryl, —CONH-heteroaryl, —OCONH-heterocycloalkyl, —NHC(O)—C 1 -C 12 -alkyl, —NHC(O)—C 2 -C 12 -alkenyl, —NHC(O)—C 2 -C 12 -alkynyl, —NHC(O)—C 3 -C 12 -cycloalkyl, —NHC(O)-aryl, —NHC(O)-heteroaryl, —NHC(O)-heterocycloalkyl, —NHCO 2 —C 1 -C 12 -alkyl, —NHCO 2 —C 2 -C 12 -alkenyl, —NHCO 2 —C 2 -C 12 -alkynyl, —NHCO 2 —C 3 -C 12 -cycloalkyl, —NHCO 2 -aryl, —NHCO 2 -heteroaryl, —NHCO 2 -heterocycloalkyl, —NHC(O)NH 2 , NHC(O)NH—C 1 -C 12 -alkyl, —NHC(O)NH—C 2 -C 12 -alkenyl, —NHC(O)NH—C 2 -C 12 -alkynyl, —NHC(O)NH—C 3 -C 12 -cycloalkyl, —NHC(O)NH-aryl, —NHC(O)NH-heteroaryl, —NHC(O)NH-heterocycloalkyl, NHC(S)NH 2 , NHC(S)NH—C 1 -C 12 -alkyl, —NHC(S)NH—C 2 -C 12 -alkenyl, —NHC(S)NH—C 2 -C 12 -alkynyl, —NHC(S)NH—C 3 -C 12 -cycloalkyl, —NHC(S)NH-aryl, —NHC(S)NH-heteroaryl, —NHC(S)NH-heterocycloalkyl, —NHC(NH)NH 2 , NHC(NH)NH—C 1 -C 12 -alkyl, —NHC(NH)NH—C 2 -C 12 -alkenyl, —NHC(NH)NH—C 2 -C 12 -alkynyl, —NHC(NH)NH—C 3 -C 12 -cycloalkyl, —NHC(NH)NH-aryl, —NHC(NH)NH-heteroaryl, —NHC(NH)NH-heterocycloalkyl, NHC(NH)—C 1 -C 12 -alkyl, —NHC(NH)—C 2 -C 12 -alkenyl, —NHC(NH)—C 2 -C 12 -alkynyl, —NHC(NH)—C 3 -C 12 -cycloalkyl, —NHC(NH)-aryl, —NHC(NH)-heteroaryl, —NHC(NH)-heterocycloalkyl, —C(NH)NH—C 1 -C 12 -alkyl, —C(NH)NH—C 2 -C 12 -alkenyl, —C(NH)NH—C 2 -C 12 -alkynyl, —C(NH)NH—C 3 -C 12 -cycloalkyl, —C(NH)NH-aryl, —C(NH)NH-heteroaryl, —C(NH)NH-heterocycloalkyl, —S(O)—C 1 -C 12 -alkyl, —S(O)—C 2 -C 12 -alkenyl, —S(O)—C 2 -C 12 -alkynyl, —S(O)—C 3 -C 12 -cycloalkyl, —S(O)-aryl, —S(O)-heteroaryl, —S(O)-heterocycloalkyl-SO 2 NH 2 , —SO 2 NH—C 1 -C 12 -alkyl, —SO 2 NH—C 2 -C 12 -alkenyl, —SO 2 NH—C 2 -C 12 -alkynyl, —SO 2 NH—C 3 -C 12 -cycloalkyl, —SO 2 NH-aryl, —SO 2 NH-heteroaryl, —SO 2 NH-heterocycloalkyl, —NHSO 2 —C 1 -C 12 -alkyl, —NHSO 2 —C 2 -C 12 -alkenyl, —NHSO 2 —C 2 -C 12 -alkynyl, —NHSO 2 —C 3 -C 12 -cycloalkyl, —NHSO 2 -aryl, —NHSO 2 -heteroaryl, —NHSO 2 -heterocycloalkyl, —CH 2 NH 2 , —CH 2 SO 2 CH 3 , -aryl, -arylalkyl, -heteroaryl, -heteroarylalkyl, -heterocycloalkyl, —C 3 -C 12 -cycloalkyl, polyalkoxyalkyl, polyalkoxy, -methoxymethoxy, -methoxyethoxy, —SH, —S—C 1 -C 12 -alkyl, —S—C 2 -C 12 -alkenyl, —S—C 2 -C 12 -alkynyl, —S—C 3 -C 12 -cycloalkyl, —S-aryl, —S-heteroaryl, —S-heterocycloalkyl, or methylthiomethyl. It is understood that the aryls, heteroaryls, alkyls and the like can be further substituted.
The terms “C 2 -C 12 alkenyl” or “C 2 -C 6 alkenyl,” as used herein, denote a monovalent group derived from a hydrocarbon moiety containing from two to twelve or two to six carbon atoms having at least one carbon-carbon double bond by the removal of a single hydrogen atom. Alkenyl groups include, but are not limited to, for example, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl, alkadienes and the like.
The term “substituted alkenyl,” as used herein, refers to a “C 2 -C 12 alkenyl” or “C 2 -C 6 alkenyl” group as previously defined, substituted by one, two, three or more aliphatic substituents.
The terms “C 2 -C 12 alkynyl” or “C 2 -C 6 alkynyl,” as used herein, denote a monovalent group derived from a hydrocarbon moiety containing from two to twelve or two to six carbon atoms having at least one carbon-carbon triple bond by the removal of a single hydrogen atom. Representative alkynyl groups include, but are not limited to, for example, ethynyl, 1-propynyl, 1-butynyl, and the like.
The term “substituted alkynyl,” as used herein, refers to a “C 2 -C 12 alkynyl” or “C 2 -C 6 alkynyl” group as previously defined, substituted by one, two, three or more aliphatic substituents.
The term “C 1 -C 6 alkoxy,” as used herein, refers to a C 1 -C 6 alkyl group, as previously defined, attached to the parent molecular moiety through an oxygen atom. Examples of C 1 -C 6 -alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, neopentoxy and n-hexoxy.
The terms “halo” and “halogen,” as used herein, refer to an atom selected from fluorine, chlorine, bromine and iodine.
The terms “aryl” or “aromatic” as used herein, refer to a mono- or bicyclic carbocyclic ring system having one or two aromatic rings including, but not limited to, phenyl, naphthyl, tetrahydronaphthyl, indanyl, idenyl and the like.
The terms “substituted aryl” or “substituted aromatic,” as used herein, refer to an aryl or aromatic group substituted by one, two, three or more aromatic substituents.
The term “arylalkyl,” as used herein, refers to an aryl group attached to the parent compound via a C 1 -C 3 alkyl or C 1 -C 6 alkyl residue. Examples include, but are not limited to, benzyl, phenethyl and the like.
The term “substituted arylalkyl,” as used herein, refers to an arylalkyl group, as previously defined, substituted by one, two, three or more aromatic substituents.
The terms “heteroaryl” or “heteroaromatic,” as used herein, refer to a mono-, bi- or tri-cyclic aromatic radical or ring having from five to ten ring atoms of which at least one ring atom is selected from S, O and N; zero, one or two ring atoms are additional heteroatoms independently selected from S, O and N; and the remaining ring atoms are carbon, wherein any N or S contained within the ring may be optionally oxidized. Heteroaryl includes, but is not limited to, pyridinyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, thiophenyl, furanyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzooxazolyl, quinoxalinyl, and the like. The heteroaromatic ring may be bonded to the chemical structure through a carbon or hetero atom.
The terms “substituted heteroaryl” or “substituted heteroaromatic,” as used herein, refer to a heteroaryl or heteroaromatic group, substituted by one, two, three, or more aromatic substituents.
The term “alicyclic,” as used herein, denotes a monovalent group derived from a monocyclic or bicyclic saturated carbocyclic ring compound by the removal of a single hydrogen atom. Examples include, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclo[2.2.1]heptyl, and bicyclo[2.2.2]octyl.
The term “substituted alicyclic,” as used herein, refers to an alicyclic group substituted by one, two, three or more aliphatic substituents.
The term “heterocyclic,” as used herein, refers to a non-aromatic 5-, 6- or 7-membered ring or a bi- or tri-cyclic group fused system, where (i) each ring contains between one and three heteroatoms independently selected from oxygen, sulfur and nitrogen, (ii) each 5-membered ring has 0 to 1 double bonds and each 6-membered ring has 0 to 2 double bonds, (iii) the nitrogen and sulfur heteroatoms may optionally be oxidized, (iv) the nitrogen heteroatom may optionally be quaternized, (iv) any of the above rings may be fused to a benzene ring, and (v) the remaining ring atoms are carbon atoms which may be optionally oxo-substituted. Representative heterocycloalkyl groups include, but are not limited to, [1,3]dioxolane, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, piperidinyl, piperazinyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiazolidinyl, isothiazolidinyl, quinoxalinyl, pyridazinonyl, and tetrahydrofuryl.
The term “substituted heterocyclic,” as used herein, refers to a heterocyclic group, as previously defined, substituted by one, two, three or more aliphatic substituents.
The term “heteroarylalkyl,” as used herein, to an heteroaryl group attached to the parent compound via a C 1 -C 3 alkyl or C 1 -C 6 alkyl residue. Examples include, but are not limited to, pyridinylmethyl, pyrimidinylethyl and the like.
The term “substituted heteroarylalkyl,” as used herein, refers to a heteroarylalkyl group, as previously defined, substituted by independent replacement of one, two, or three or more aromatic substituents.
The term “alkylamino” refers to a group having the structure —NH(C 1 -C 12 alkyl).
The term “dialkylamino” refers to a group having the structure —N(C 1 -C 12 alkyl) (C 1 -C 12 alkyl), where C 1 -C 12 alkyl is as previously defined. Examples of dialkylamino are, but not limited to, dimethylamino, diethylamino, methylethylamino, piperidino, and the like.
The term “alkoxycarbonyl” represents an ester group, i.e., an alkoxy group, attached to the parent molecular moiety through a carbonyl group such as methoxycarbonyl, ethoxycarbonyl, and the like.
The term “carboxaldehyde,” as used herein, refers to a group of formula —CHO.
The term “carboxy,” as used herein, refers to a group of formula —COOH.
The term “carboxamide,” as used herein, refers to a group of formula —C(O)NH(C 1 -C 12 alkyl) or —C(O)N(C 1 -C 12 alkyl)(C 1 -C 12 alkyl), —C(O)NH 2 , NHC(O)(C 1 -C 12 alkyl), N(C 1 -C 12 alkyl)C(O)(C 1 -C 12 alkyl) and the like.
The term “hydroxy protecting group,” as used herein, refers to a labile chemical moiety which is known in the art to protect a hydroxyl group against undesired reactions during synthetic procedures. After said synthetic procedure(s) the hydroxy protecting group as described herein may be selectively removed. Hydroxy protecting groups as known in the are described generally in T. H. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, 3rd edition, John Wiley & Sons, New York (1999). Examples of hydroxyl protecting groups include benzyloxycarbonyl, 4-nitrobenzyloxycarbonyl, 4-bromobenzyloxycarbonyl, 4-methoxybenzyloxycarbonyl, methoxycarbonyl, tert-butoxycarbonyl, isopropoxycarbonyl, diphenylmethoxycarbonyl, 2,2,2-trichloroethoxycarbonyl, 2-(trimethylsilyl)ethoxycarbonyl, 2-furfuryloxycarbonyl, allyloxycarbonyl, acetyl, formyl, chloroacetyl, trifluoroacetyl, methoxyacetyl, phenoxyacetyl, benzoyl, methyl, t-butyl, 2,2,2-trichloroethyl, 2-trimethylsilyl ethyl, 1,1-dimethyl-2-propenyl, 3-methyl-3-butenyl, allyl, benzyl, para-methoxybenzyldiphenylmethyl, triphenylmethyl (trityl), tetrahydrofuryl, methoxymethyl, methylthiomethyl, benzyloxymethyl, 2,2,2-trichloroethoxymethyl, 2-(trimethylsilyl)ethoxymethyl, methanesulfonyl, para-toluenesulfonyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, and the like. Preferred hydroxyl protecting groups for the present invention are acetyl (Ac or —C(O)CH 3 ), benzoyl (Bz or —C(O)C 6 H 5 ), and trimethylsilyl (TMS or —Si(CH 3 ) 3 ).
The term “protected hydroxy,” as used herein, refers to a hydroxy group protected with a hydroxy protecting group, as defined above, including benzyloxycarbonyl, 4-nitrobenzyloxycarbonyl, 4-bromobenzyloxycarbonyl, 4-methoxybenzyloxycarbonyl, methoxycarbonyl, tert-butoxycarbonyl, isopropoxycarbonyl, diphenylmethoxycarbonyl, 2,2,2-trichloroethoxycarbonyl, 2-(trimethylsilyl)ethoxycarbonyl, 2-furfuryloxycarbonyl, allyloxycarbonyl, acetyl, formyl, chloroacetyl, trifluoroacetyl, methoxyacetyl, phenoxyacetyl, benzoyl, methyl, t-butyl, 2,2,2-trichloroethyl, 2-trimethylsilyl ethyl, 1,1-dimethyl-2-propenyl, 3-methyl-3-butenyl, allyl, benzyl, para-methoxybenzyldiphenylmethyl, triphenylmethyl (trityl), tetrahydrofuryl, methoxymethyl, methylthiomethyl, benzyloxymethyl, 2,2,2-trichloroethoxymethyl, 2-(trimethylsilyl)ethoxymethyl, methanesulfonyl, para-toluenesulfonyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, and the like. Preferred hydroxyl protecting groups for the present invention are acetyl (Ac or —C(O)CH 3 ), benzoyl (Bz or —C(O)C 6 H 5 ), and trimethylsilyl (TMS or —Si(CH 3 ) 3 ).
The term “amino protecting group,” as used herein, refers to a labile chemical moiety which is known in the art to protect an amino group against undesired reactions during synthetic procedures. After said synthetic procedure(s) the amino protecting group as described herein may be selectively removed. Amino protecting groups as known in the are described generally in T. H. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, 3rd edition, John Wiley & Sons, New York (1999). Examples of amino protecting groups include, but are not limited to, t-butoxycarbonyl, 9-fluorenylmethoxycarbonyl, benzyloxycarbonyl, and the like.
The term “protected amino,” as used herein, refers to an amino group protected with an amino protecting group as defined above.
The term “acyl” includes residues derived from acids, including but not limited to carboxylic acids, carbamic acids, carbonic acids, sulfonic acids, and phosphorous acids. Examples include aliphatic carbonyls, aromatic carbonyls, aliphatic sulfonyls, aromatic sulfinyls, aliphatic sulfinyls, aromatic phosphates and aliphatic phosphates.
The term “aprotic solvent,” as used herein, refers to a solvent that is relatively inert to proton activity, i.e., not acting as a proton-donor. Examples include, but are not limited to, hydrocarbons, such as hexane and toluene, for example, halogenated hydrocarbons, such as, for example, methylene chloride, ethylene chloride, chloroform, and the like, heterocyclic compounds, such as, for example, tetrahydrofuran and N-methylpyrrolidinone, and ethers such as diethyl ether, bis-methoxymethyl ether. Such compounds are well known to those skilled in the art, and it will be obvious to those skilled in the art that individual solvents or mixtures thereof may be preferred for specific compounds and reaction conditions, depending upon such factors as the solubility of reagents, reactivity of reagents and preferred temperature ranges, for example. Further discussions of aprotic solvents may be found in organic chemistry textbooks or in specialized monographs, for example: Organic Solvents Physical Properties and Methods of Purification, 4th ed., edited by John A. Riddick et al, Vol. II, in the Techniques of Chemistry Series , John Wiley & Sons, NY, 1986.
The term “protogenic organic solvent,” as used herein, refers to a solvent that tends to provide protons, such as an alcohol, for example, methanol, ethanol, propanol, isopropanol, butanol, t-butanol, and the like. Such solvents are well known to those skilled in the art, and it will be obvious to those skilled in the art that individual solvents or mixtures thereof may be preferred for specific compounds and reaction conditions, depending upon such factors as the solubility of reagents, reactivity of reagents and preferred temperature ranges, for example. Further discussions of protogenic solvents may be found in organic chemistry textbooks or in specialized monographs, for example: Organic Solvents Physical Properties and Methods of Purification, 4th ed., edited by John A. Riddick et al., Vol. II, in the Techniques of Chemistry Series , John Wiley & Sons, NY, 1986.
The term “oxidizing agent(s),” as used herein, refers to reagents useful for oxidizing the 3-hydroxyl of the macrolide ring to the 3-carbonyl. Oxidizing agents suitable in the present process are either Swern oxidation reagents (dimethyl sulfoxide and an electrophilic compound selected from dicyclohexylcarbodiimide, acetic anhydride, trifluoroacetic anhydride, oxalyl chloride, or sulfur trioxide), Dess Martin oxidation reagents, or Corey-Kim oxidation reagents. A preferred method of oxidation is the use of the Corey-Kim oxidation reagents N-chlorosuccinimide-dimethyl sulfide complex.
Combinations of substituents and variables envisioned by this invention are only those that result in the formation of stable compounds. The term “stable”, as used herein, refers to compounds which possess stability sufficient to allow manufacture and which maintains the integrity of the compound for a sufficient period of time to be useful for the purposes detailed herein.
The synthesized compounds can be separated from a reaction mixture and further purified by a method such as column chromatography, high pressure liquid chromatography, or recrystallization. As can be appreciated by the skilled artisan, further methods of synthesizing the compounds of the formulae herein will be evident to those of ordinary skill in the art. Additionally, the various synthetic steps may be performed in an alternate sequence or order to give the desired compounds. Synthetic chemistry transformations and protecting group methodologies (protection and deprotection) useful in synthesizing the compounds described herein are known in the art and include, for example, those such as described in R. Larock, Comprehensive Organic Transformations , VCH Publishers (1989); T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, 2d. Ed., John Wiley and Sons (1991); L. Fieser and M. Fieser, Fieser and Fieser's Reagents for Organic Synthesis , John Wiley and Sons (1994); and L. Paquette, ed., Encyclopedia of Reagents for Organic Synthesis , John Wiley and Sons (1995).
The compounds of this invention may be modified by appending appropriate functionalities to enhance selective biological properties. Such modifications are known in the art and may include those which increase biological penetration into a given biological system (e.g., blood, lymphatic system, central nervous system), increase oral availability, increase solubility to allow administration by injection, alter metabolism and alter rate of excretion.
The compounds described herein contain one or more asymmetric centers and thus give rise to enantiomers, diastereomers, and other stereoisomeric forms that may be defined, in terms of absolute stereochemistry, as (R)- or (S)-, or as (D)- or (L)- for amino acids. The present invention is meant to include all such possible isomers, as well as their racemic and optically pure forms. Optical isomers may be prepared from their respective optically active precursors by the procedures described above, or by resolving the racemic mixtures. The resolution can be carried out in the presence of a resolving agent, by chromatography or by repeated crystallization or by some combination of these techniques which are known to those skilled in the art. Further details regarding resolutions can be found in Jacques, et al., Enantiomers, Racemates, and Resolutions (John Wiley & Sons, 1981). When the compounds described herein contain olefinic double bonds, other unsaturation, or other centers of geometric asymmetry, and unless specified otherwise, it is intended that the compounds include both E and Z geometric isomers or cis- and trans-isomers. Likewise, all tautomeric forms are also intended to be included. The configuration of any carbon-carbon double bond appearing herein is selected for convenience only and is not intended to designate a particular configuration unless the text so states; thus a carbon-carbon double bond or carbon-heteroatom double bond depicted arbitrarily herein as trans may be cis, trans, or a mixture of the two in any proportion.
As used herein, the term “pharmaceutically acceptable salt” refers to those salts which are, within the scope of sound medical judgment, suitable for use in contact with the tissues of humans and lower animals without undue toxicity, irritation, allergic response and the like, and are commensurate with a reasonable benefit/risk ratio. Pharmaceutically acceptable salts are well known in the art. For example, S. M. Berge, et al. describes pharmaceutically acceptable salts in detail in J. Pharmaceutical Sciences, 66: 1-19 (1977). The salts can be prepared in situ during the final isolation and purification of the compounds of the invention, or separately by reacting the free base function with a suitable organic acid. Examples of pharmaceutically acceptable include, but are not limited to, nontoxic acid addition salts are salts of an amino group formed with inorganic acids such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid and perchloric acid or with organic acids such as acetic acid, maleic acid, tartaric acid, citric acid, succinic acid or malonic acid or by using other methods used in the art such as ion exchange. Other pharmaceutically acceptable salts include, but are not limited to, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bisulfate, borate, butyrate, camphorate, camphorsulfonate, citrate, cyclopentanepropionate, digluconate, dodecylsulfate, ethanesulfonate, formate, fumarate, glucoheptonate, glycerophosphate, gluconate, hemisulfate, heptanoate, hexanoate, hydroiodide, 2-hydroxy-ethanesulfonate, lactobionate, lactate, laurate, lauryl sulfate, malate, maleate, malonate, methanesulfonate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, propionate, stearate, succinate, sulfate, tartrate, thiocyanate, p-toluenesulfonate, undecanoate, valerate salts, and the like. Representative alkali or alkaline earth metal salts include sodium, lithium, potassium, calcium, magnesium, and the like. Further pharmaceutically acceptable salts include, when appropriate, nontoxic ammonium, quaternary ammonium, and amine cations formed using counterions such as halide, hydroxide, carboxylate, sulfate, phosphate, nitrate, alkyl having from 1 to 6 carbon atoms, sulfonate and aryl sulfonate.
As used herein, the term “pharmaceutically acceptable ester” refers to esters which hydrolyze in vivo and include those that break down readily in the human body to leave the parent compound or a salt thereof. Suitable ester groups include, for example, those derived from pharmaceutically acceptable aliphatic carboxylic acids, particularly alkanoic, alkenoic, cycloalkanoic and alkanedioic acids, in which each alkyl or alkenyl moiety advantageously has not more than 6 carbon atoms. Examples of particular esters include, but are not limited to, formates, acetates, propionates, butyrates, acrylates and ethylsuccinates.
The term “pharmaceutically acceptable prodrugs” as used herein refers to those prodrugs of the compounds of the present invention which are, within the scope of sound medical judgment, suitable for use in contact with the tissues of humans and lower animals with undue toxicity, irritation, allergic response, and the like, commensurate with a reasonable benefit/risk ratio, and effective for their intended use, as well as the zwitterionic forms, where possible, of the compounds of the present invention. “Prodrug”, as used herein means a compound which is convertible in vivo by metabolic means (e.g. by hydrolysis) to a compound of Formula I. Various forms of prodrugs are known in the art, for example, as discussed in Bundgaard, (ed.), Design of Prodrugs, Elsevier (1985); Widder, et al. (ed.), Methods in Enzymology, vol. 4, Academic Press (1985); Krogsgaard-Larsen, et al., (ed). “Design and Application of Prodrugs, Textbook of Drug Design and Development, Chapter 5, 113-191 (1991); Bundgaard, et al., Journal of Drug Deliver Reviews, 8:1-38(1992); Bundgaard, J. of Pharmaceutical Sciences, 77:285 et seq. (1988); Higuchi and Stella (eds.) Prodrugs as Novel Drug Delivery Systems, American Chemical Society (1975); and Bernard Testa & Joachim Mayer, “Hydrolysis In Drug And Prodrug Metabolism: Chemistry, Biochemistry And Enzymology,” John Wiley and Sons, Ltd. (2002).
Prodrugs include compounds wherein an amino acid residue, or a polypeptide chain of two or more (e.g., two, three or four) amino acid residues is covalently joined through an amide or ester bond to a free amino, hydroxy or carboxylic acid group of a bridged erythromycin or ketolide derivative synthesized using the reagents prepared in accordance with the invention. The amino acid residues include but are not limited to the 20 naturally occurring amino acids commonly designated by three letter symbols and also includes 4-hydroxyproline, hydroxylysine, demosine, isodemosine, 3-methylhistidine, norvalin, beta-alanine, gamma-aminobutyric acid, citrulline homocysteine, homoserine, ornithine and methionine sulfone. Additional types of prodrugs are also encompassed. For instance, free carboxyl groups can be derivatized as amides or alkyl esters. Free hydroxy groups may be derivatized using groups including but not limited to hemisuccinates, phosphate esters, dimethylaminoacetates, and phosphoryloxymethyloxycarbonyls, as outlined in Advanced Drug Delivery Reviews, 1996, 19, 115. Carbamate prodrugs of hydroxy and amino groups are also included, as are carbonate prodrugs, sulfonate esters and sulfate esters of hydroxy groups. Derivatization of hydroxy groups as (acyloxy)methyl and (acyloxy)ethyl ethers wherein the acyl group may be an alkyl ester, optionally substituted with groups including but not limited to ether, amine and carboxylic acid functionalities, or where the acyl group is an amino acid ester as described above, are also encompassed. Prodrugs of this type are described in J. Med. Chem. 1996, 39, 10. Free amines can also be derivatized as amides, sulfonamides or phosphonamides. All of these prodrug moieties may incorporate groups including but not limited to ether, amine and carboxylic acid functionalities.
Suitable concentrations of reactants used in the synthesis processes of the invention are 0.01M to 10M, typically 0.1M to 1M. Suitable temperatures include −10° C. to 250° C., typically −78° C. to 150° C., more typically −78° C. to 100° C., still more typically 0° C. to 100° C. Reaction vessels are preferably made of any material which does not substantial interfere with the reaction. Examples include glass, plastic, and metal. The pressure of the reaction can advantageously be operated at atmospheric pressure. The atmospheres include, for example, air, for oxygen and water insensitive reactions, or nitrogen or argon, for oxygen or water sensitive reactions.
The term “in situ,” as used herein, refers to use of an intermediate in the solvent or solvents in which the intermediate was prepared without removal of the solvent.
Unless otherwise defined, all technical and scientific terms used herein are accorded the meaning commonly known to one with ordinary skill in the art. All publications, patents, published patent applications, and other references mentioned herein are hereby incorporated by reference in their entirety.
ABBREVIATIONS
Abbreviations which may be used in the descriptions of the scheme and the examples that follow are:
Ac for acetyl;
AIBN for azobisisobutyronitrile;
Bu 3 SnH for tributyltin hydride;
CDI for carbonyldiimidazole;
dba for dibenzylidene acetone;
dppb for diphenylphosphino butane or 1,4-bis(diphenylphosphino)butane;
DBU for 1,8-diazabicyclo[5.4.0]undec-7-ene;
DEAD for diethylazodicarboxylate;
DMAP for dimethylaminopyridine;
DMF for dimethyl formamide;
DPPA for diphenylphosphoryl azide;
EtOAc for ethyl acetate;
HPLC for high-pressure liquid chromatography;
MeOH for methanol;
NaN(TMS) 2 for sodium bis(trimethylsilyl)amide;
NMMO for N-methylmorpholine N-oxide;
Rp for hydroxyl protecting group;
TEA for triethylamine;
THF for tetrahydrofuran;
TPP or PPh 3 for triphenylphosphine;
MOM for methoxymethyl;
Boc for t-butoxycarbonyl;
Bz for benzyl;
Ph for phenyl;
POPd for dihydrogen dichlorobis(di-tert-butylphosphinito-κP)palladate(II);
TBS for tert-butyl dimethylsilyl; or
TMS for trimethylsilyl.
All other abbreviations used herein, which are not specifically delineated above, shall be accorded the meaning which one of ordinary skill in the art would attach.
Synthetic Schemes
The present invention will be better understood in connection with Schemes 1-3. It will be readily apparent to one of ordinary skill in the art that the process of the present invention can be practiced by substitution of the appropriate reactants and that the order of the steps themselves can be varied.
As outlined in Scheme 1, Step A, a compound of formula (II) is prepared by adding the compound of formula (1-2) to a compound of formula (1-1), wherein R 1 and R 2 are as previously defined. The present conversion preferably takes place in the presence of a base in an aprotic solvent.
A compound of formula (I) is prepared, as illustrated in Step B of Scheme 1, by reacting 2-chloro-5-methyl-hydroxyamine derivatives (II) with pyrazole in the presence of an acid catalyst in organic solvent, preferably in an aprotic solvent or without solvent, to provide a compound of the formula (I). In a preferred embodiment of the reaction, the reaction temperature is between 75° C. and 200° C. and the duration of the reaction is 6 to 48 hours. In a particularly preferred embodiment of the reaction, the acid is organic acid, such as acetic acid, toluene solufonic, methyl sulfonic acid, or camphorsulfonic acid without additional solvent.
In another embodiment of Scheme 1, a compound of formula (I) is prepared, as illustrated in Step B of Scheme 1, by reacting 2-chloro-5-methyl-hydroxyamine derivatives (II) with pyrazole in a neat organic acid, to provide a compound of the formula (I). In a preferred embodiment of the reaction, the reaction temperature is under a reflux temperature of the chosen acid, and the duration of the reaction is 12 to 48 hours. In a particularly preferred embodiment of the reaction, the acid is acetic acid, and the temperature is acetic acid reflux temperature.
In another embodiment of Scheme 1, a compound of formula (I) is prepared as illustrated in Step B, by reacting 2-chloro-5-methyl-hydroxyamine derivatives (II) with pyrazole in the presence of a base with catalyst, such as copper(I) salt or other transition metal derivatives combined with a 1,2-diamino derivatives, preferably in an aprotic solvent, to provide a compound of the formula (I). In a preferred embodiment of the reaction, the reaction temperature is between 25° C. and 150° C. and the duration of the reaction is less than 6 to 48 hours. In a particularly preferred embodiment of the reaction, the base is potassium carbonate and the aprotic solvent is neat pyrazole, the catalyst is copper(II) iodide and racemic-trans-N,N′-dimethylcyclohexane-1,2-diamine.
As outlined in Scheme 1, Step C, a compound of formula (Ia) is prepared by removal of the protecting group of R 1 and R 2 in the formula (I) under either basic or acidic conditions, depending on the nature of R 1 and R 2 , wherein R 1 and R 2 are as previously defined.
Scheme 2 describes another process of preparing compounds I and Ia,
As outlined in Scheme 2, Step A, a compound of formula (III) is prepared by adding the compound of formula (2-2) to a compound of formula (2-1). The present conversion preferably takes place in the presence of acid catalyst or a basic catalytic system, in an aprotic solvent.
A compound of formula (III) is prepared, as illustrated in Step A of Scheme 1, by reacting 2-chloro-5-hydroxymethyl-pyridine (2-1) with pyrazole in the presence of acid catalyst in organic solvent, preferably in an aprotic solvent, to provide a compound of the formula (III). In a preferred embodiment of the reaction, the reaction temperature is between 75° C. and 200° C. and the duration of the reaction is 6 to 48 hours. In a particularly preferred embodiment of the reaction, the acid is organic acid, such as acetic acid, toluene solufonic, methyl sulfonic acid, or camphorsulfonic acid and the aprotic solvent is toluene.
Alternatively, a compound of formula (III) is prepared, as illustrated in Step A of Scheme 2, by reacting 2-chloro-6-hydroxymethyl-pyridine (2-1) with pyrazole in a neat organic acid, to provide a compound of the formula (III). In a preferred embodiment of the reaction, the reaction temperature is under a reflux temperature of the chosen acid, and the duration of the reaction is 12 to 48 hours. In a particularly preferred embodiment of the reaction, the acid is acetic acid, and the temperature is acetic acid reflux temperature.
Alternatively, a compound of formula (III) is prepared, as illustrated in Step A of Scheme 2, by reacting 2-chloro-5-hydroxymethyl-pyridine (2-1) with pyrazole in the presence of a base with catalyst, such as copper(I) salt or other transition metal derivatives combined with a 1,2-diamino derivatives, preferably in an aprotic solvent, to provide a compound of the formula (III). In a preferred embodiment of the reaction, the reaction temperature is between 25° C. and 150° C. and the duration of the reaction is less than 6 to 48 hours. In a particularly preferred embodiment of the reaction, the base is potassium carbonate and the aprotic solvent is neat pyrazole, the catalyst is copper(I) iodide and racemic-trans-N,N′-dimethylcyclohexane-1,2-diamine.
As outlined in Scheme 2, Step B, a compound of Formula (VI) is prepared by reacting of compound (III) with a chlorinating reagent.
A compound of formula (I) is prepared by adding a compound of formula (2-3), to a compound of formula (VI), as illustrated in Step C, wherein R 1 and R 2 are as previously defined. The present conversion preferably takes place in an aprotic solvent in the presence of a base.
A compound of formula Ia may be prepared from a compound of formula I as outlined in Scheme 1.
Scheme 3 describes an additional process of preparing compounds I and Ia.
As illustrated in Scheme 3, Step A, a compound of formula (IV) is prepared by first reacting 2-chloro-5-hydroxymethyl-pyridine (3-1) with a hydroxyl protecting reagent Rp-X, wherein, Rp is previously defined and X is a leaving group, in the presence of a base, preferably in an aprotic solvent, to provide a compound of the formula (IV).
As outlined in Scheme 3, Step B, a compound of formula (V) is prepared by adding pyrazole to a compound of formula (IV). The present conversion preferably takes place in the same conditions as described in Scheme 2, Step A, with different starting material of formula (IV).
A compound of formula (III) is prepared, as illustrated in Step C of Scheme 3, by deprotecting the compound of formula (V) with acid or base in an aprotic organic solvent or an aqueous mixture thereof.
The compound of formula VI is prepared by reacting the compound of formula III with a chlorinating reagent. The compound of formula I is prepared from the compound of formula VI by reacting the compound of formula VI with at least one compound of formula R 1 R 2 NOH wherein R 1 and R 2 are as previously defined, in the presence of base, optionally followed by hydrolysis to provide compounds of formula Ia.
All references cited herein, whether in print, electronic, computer readable storage media or other form, are expressly incorporated by reference in their entirety, including but not limited to, abstracts, articles, journals, publications, texts, treatises, internet web sites, databases, patents, and patent publications.
EXAMPLES
The compounds and processes of the present invention will be better understood in connection with the following examples, which are intended as an illustration only and not limiting of the scope of the invention. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art and such changes and modifications including, without limitation, those relating to the chemical structures, substituents, derivatives, formulations and/or methods of the invention may be made without departing from the spirit of the invention and the scope of the appended claims.
Example 1
Preparation of 2-chloro-5-pyridyl-N-methoxy succinimide (IIb)
To a 5 L-three neck flask equipped with a mechanic stirrer, heating mantle with temperature controller and a gas outlet, were charged N-hydroxysuccinimide (426 g, 3.7 mol), 2-chloro-5-chloromethylpyridine (500 g, 3.1 mol) and anhydrous DMF (1 L). The mixture was stirred for 5 min when inner temperature dropped to 8.5° C. Anhydrous K 2 CO 3 (640 g, 4.6 mol) was charged in one portion followed by anhydrous DMF (0.5 L). It was stirred for 5 min when inner temperature raised to 15.5° C. The mixture was heated to 70° C. (preset) within 30 min but the temperature continued to rise to 89° C. over 1 h of reaction period, during which a lot of gas was evolved and the reaction was finished as judged by MS and TLC, or simply the termination of gas-evolving. It was cooled down to room temperature, poured into water (6 L) with mechanic stirring. The insoluble was collected by filtration and washed with water (1.5 L), air-dried for 60 h to give the desired product as an off-white powder (364 g, 49%). ESIMS m/e (M+H) + : 241. 1 H NMR (500 MHz, CDCl 3 ): 8.44 (s, 1H), 7.95 (d, 1H, 3 J=8.5 Hz), 7.41 (d, 1H, 3 J=8.0 Hz), 5.14 (s, 2H), 2.73 (s, 4H) ppm. 13 C NMR (125 MHz, CDCl 3 ): δ 170.8, 152.6, 150.2, 140.2, 128.2, 124.4, 74.9, 25.4.
Example 2
Preparation of 2-chloro-5-pyridyl-N-methoxy acetonimide (IIc)
Sodium hydride (60 wt %, 485 mg, 12 mmol, 1.2 eq) was added portion-wise to a DMF (6 ml) solution of propan-2-one oxime (886 mg, 12 mmol, 1.2 eq). To the resulting white foaming suspension was added a DMF (3.5 ml) solution of 2-chloro-5-chloromethyl-pyridine (1.64 g, 10 mmol). After stirring for 4 hours at room temperature, the reaction mixture was diluted with 30 ml ethyl acetate. The organic solution was washed with water (3×50 ml), dried over sodium sulfate and concentrated. Column chromatography (hexanes) of the residue afforded the product as a light yellow oil 1.8 g (yield: 90%). MS-ESI m/z 198.98 (M+H) + ; 1 H NMR (CDCl 3 ) δ 8.39 (s, 1H), 7.67 (d, 1H), 7.33 (d, 1H), 5.05 (s, 2H), 1.92 (s, 3H), 1.90 (s, 3H) ppm.
Example 3
Preparation of 2-(1-pyrazolyl)-5-pyridyl-N-methoxy succinimide (Ib)
Procedure-1
Starting material (IIa, 2.4 g, 10 mmol) and pyrazole (2.0 g, 29.4 mmol, 2.9 eq) were mixed with p-toluenesulfonic acid (190 mg, 1.0 mmol, 10 mol %). The resulting mixture was heated to 110° C. stirred for 10 hours. After cooling down, the residue was dissolved in CH 2 Cl 2 (150 ml) and washed with half saturated aqueous sodium bicarbonate (50 ml). The organic phase was separated, dried over sodium sulfate and concentrated. Crystallization (CH 2 Cl 2 :hexanes, 1:2, 100 ml) afforded the product as a white crystalline solid 2.4 g (yield: 89%, purity>95% by 1 H NMR). MS-ESI m/z 273.08 (M+H) + ; 1 H NMR (CDCl 3 ) δ 8.58 (s, 1H), 8.46 (s, 1H), 8.03 (s, 2H), 7.76 (s, 1H), 6.45 (s, 1H), 5.18 (s, 2H), 2.68 (s, 4H) ppm, 13 C NMR (CDCl 3 ) δ 171.2, 149.4, 142.7, 140.7, 127.5, 127.0, 112.5, 108.3, 75.7, 25.7 ppm.
Example 4
Preparation of 2-(1-pyrazolyl)-5-pyridyl-N-methoxy succinimide (Ib)
Procedure-2
Starting material (224 mg, 0.93 mmol), pyrazole (74.5 mg, 1.09 mmol) were dissolved in acetic acid (1.4 ml) and stirred at 105° C. for 65 hours. After cooling down, the mixture was diluted with 10 ml ethyl acetate and carefully basified with saturated aqueous sodium bicarbonate solution to pH 8-9. The organic phase was separated, dried over sodium sulfate and concentrated. Column chromatography (EtOAc:hexanes, 1:1) of the residue afforded the product as an off-white solid 203 mg (yield: 80%). MS-ESI m/z 273.08 (M+H) + ; 1 H NMR (CDCl 3 ) δ 8.58 (s, 1H), 8.46 (s, 1H), 8.03 (s, 2H), 7.76 (s, 1H), 6.45 (s, 1H), 5.18 (s, 2H), 2.68 (s, 4H) ppm, 13 C NMR (CDCl 3 ) δ 171.2, 149.4, 142.7, 140.7, 127.5, 127.0, 112.5, 108.3, 75.7, 25.7 ppm.
Example 5
Preparation of 2-(1-pyrazolyl)-5-pyridyl-N-methoxy acetonimide (Ic)
Copper(I) iodide (30 mg, 0.16 mmol, 13 mol %), pyrazole (290 mg, 4.26 mmol, 3.5 eq), potassium carbonate (496 mg, 3.60 mmol, 3.0 eq), starting material (240 mg, 1.20 mmol) and rac-trans-N,N′-dimethylcyclohexane-1,2-diamine (65 mg, 0.46 mmol, 38 mol %) were mixed together and stirred at 110° C. for 36 hours. After cooling down, the mixture was dissolved in ethyl acetate and water (1:1, v/v, 10 ml). The organic phase was separated, dried over sodium sulfate and concentrated. Column chromatography (EtOAc:hexanes, 1:1) of the residue afforded the product as a light brown oil 220 mg (yield: 80%). MS-ESI m/z 231.05 (M+H + .
Example 6
Preparation of (6-Pyrazol-1-yl-pyridin-3-yl)-methanol (III)
Copper(I) iodide (65 mg, 0.34 mmol, 22 mol %), pyrazole (411 mg, 6.04 mmol, 3.8 eq), potassium carbonate (705 mg, 5.10 mmol, 3.2 eq), (6-Chloro-pyridin-3-yl)-methanol (227 mg, 1.58 mmol) and rac-trans-N,N′-dimethylcyclohexane-1,2-diamine (92 mg, 0.65 mmol, 41 mol %) were mixed together and stirred at 110° C. for 44 hours. After cooling down, the mixture was dissolved in ethyl acetate and water (1:1, v/v, 10 ml). The organic phase was separated, dried over sodium sulfate and concentrated. Column chromatography (EtOAc:hexanes, 1:1) of the residue afforded the product as a light brown oil 292 mg (corrected yield: 95%), which was good for the next reaction although containing 10 wt % pyrazole by 1 H NMR. MS-ESI m/z 175.97 (M+H) + ; 1 H NMR (CDCl 3 ) δ 8.58 (s, 1H), 8.39 (s, 1H), 7.95 (d, 1H), 7.84 (d, 1H), 7.73 (s, 1H), 6.46 (s, 1H), 3.74 (s, 2H) ppm.
Example 7
Preparation of 5-Chloromethyl-2-pyrazol-1-yl-pyridine (IV)
To a solution of alcohol (III) (10.5 g, 59.9 mmol) in CH 2 Cl 2 (150 ml), SOCl 2 (36 g, 22 ml, 299.6 mmol) was added and the resulting reaction mixture was stirred at room temperature for a period of between 12 to 18 hours. The excess SOCl 2 was quenched with saturated aqueous NaHCO 3 . The resulting mixture was extracted with CH 2 Cl 2 and washed with brine. Removal of solvent gave a compound of formulae (11.15 g, 95% yield) as a white solid. MS-ESI=194.06, 196.06, 1 H NMR (ppm): 8.59 (H3′, d), 8.43 (H6, d), 8.03 (H2, d), 7.89 (H3, dd), 7.78 (H5′, s), 6.50 (H4′, t), 4.65 (—CH2-).
Example 8
Preparation of 2-(1-pyrazolyl)-5-pyridyl-N-methoxy succinimide (Ib) via 5-Chloromethyl-2-pyrazol-1-yl-pyridine (IV)
DBU (1.55 mL, 10.36 mmol) was added to a solution of N-hydroxysuccinimide (894 mg, 7.77 mmol) in 26 mL of DMF at 0° C. and stirred for 10 min followed by the addition chlorinated pyrazole-pyridine (compound IV, 1 g, 5.18 mmol). The reaction mixture was stirred for 4 hrs at room temperature. The resulting mixture was diluted with EtOAc; washed with saturated aqueous NaHCO 3 and brine. The combined organic layers dried over Na 2 SO 4 , filtered and evaporated in vacuo to yield 1.36 g (96%) of compound (Ib) as off-white powder. MS-ESI m/z 273.08 (M+H) + ; 1 H NMR (CDCl 3 ) δ 8.58 (s, 1H), 8.46 (s, 1H), 8.03 (s, 2H), 7.76 (s, 1H), 6.45 (s, 1H), 5.18 (s, 2H), 2.68 (s, 4H) ppm, 13 C NMR (CDCl 3 ) δ 171.2, 149.4, 142.7, 140.7, 127.5, 127.0, 112.5, 108.3, 75.7, 25.7 ppm.
The compound (Ib) can also be prepared according to the experimental procedure described in example 1.
Example 9
Preparation of 2-(1-pyrazolyl)-5-pyridyl-N-methoxy acetonimide (Ic)
The experimental procedure is similar to the procedure described in example 2. MS-ESI m/z 231.05 (M+H) + .
Example 10
Preparation of O-(6-Pyrazol-1-yl-pyridin-3-ylmethyl)-hydroxylamine (Ia) via 2-(1-pyrazolyl)-5-pyridyl-N-methoxy succinimide (Ib)
Starting material (2.0 kg, 7.3 mol) was dissolved in methanol (30 L). Hydrazine monohydrate (0.72 L, 14.9 mol, 2.0 eq) was added and the reaction mixture was stirred at 45° C. for 2.5 hours. After cooling down, the reaction mixture was diluted with water (8 L) and then was extracted with IPAC (3×8 L). The organic phase was combined, washed with half saturated aqueous sodium bicarbonate and concentrated. Crystallization (IPAC:heptane, 3:4, 7 L) afforded the product was a white crystalline solid (yield: 84%). MS-ESI m/z 191.09 (M+H) + ; 1 H NMR (CDCl 3 ) δ 8.56 (d, 1H), 8.39 (d, 1H), 7.98 (d, 2H), 7.83 (dd, 1H), 7.74 (d, 1H), 6.47 (dd, 1H), 5.48 (s, 2H), 4.70 (s, 2H) ppm; 13 C NMR(CDCl 3 ) δ 151.4, 148.4, 142.3, 139.3, 131.1, 127.3, 112.2, 108.1, 74.8 ppm.
Although the invention has been described in detail with respect to various preferred embodiments it is not intended to be limited thereto, but rather those skilled in the art will recognize that variations and modifications may be made therein which are within the spirit of the invention and the scope of the appended claims.
|
The present invention relates generally to novel methods for the synthesis of O-(6-pyrazol-1-yl-pyridin-3-ylmethyl)-hydroxylamine which is an essential reagent in the synthesis of one of the bridged erythromycin derivatives and their respective pharmaceutically acceptable salts in PCT Application WO 03/097659 A1. In particular, the present invention relates to processes and intermediates for the preparation of a compound of formula (Ia):
| 2
|
BACKGROUND
[0001] Networks enable computers and other devices to communicate. For example, networks can carry data representing video, audio, e-mail, and so forth. Typically, data sent across a network is divided into smaller messages. The structure and contents of the messages depend on the networking technology being used. For example, Internet Protocol (IP) datagrams include a destination address that is much like an address written on the outside of an envelope. Devices, known as routers, receive datagrams and can determine how to forward the datagram further toward its destination based on the destination address. Another network technology is known as Asynchronous Transfer Mode (ATM). In ATM, data messages, known as cells, include identification of a “circuit” that leads from the sender to the receiver. That is, rather than identifying a destination, an ATM cell identifies a path connecting the sender and receiver.
[0002] To complicate matters conceptually, IP and ATM can both be used to support the other technology. For example, an IP datagram can be divided across different ATM cells. A receiver can reassemble the IP datagram after receiving the ATM cells.
[0003] IP datagrams and ATM cells are examples of protocol data units (PDUs). A PDU includes a payload and header. The data in the header is often used by network protocols in handling the PDU (e.g., determining where to forward the PDU, whether transmission errors occurred, and so forth). Other examples of PDUs include frames (e.g., Ethernet and Synchronous Optical Network (SONET) frames) and segments (e.g., Transmission Control Protocol (TCP) segments).
[0004] A sender can send data to a single receiver. This is known as “unicasting”. Alternately, a sender (or multiple senders) can send the same data to multiple members of a group. For example, a sender can send streaming video data to many different group members located at different points in the network. This is known as “multicasting”.
[0005] Different protocols support multicasting in different ways. For example, in the Internet Protocol, instead of specifying a single destination, an IP datagram can specify a group address. ATM networks may also support multicasting in a variety of ways. For example, multicasting may be provided by a “tree” of circuits where a given circuit may feed diverging circuits downstream. Again, the above is merely a sampling of a wide variety of approaches to multicasting.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] [0006]FIG. 1 is a diagram illustrating handling of multicast data.
[0007] [0007]FIG. 2 is a diagram illustrating control and multicast data.
[0008] [0008]FIG. 3 is a diagram illustrating data identifying different multicast group sub-groups.
[0009] [0009]FIG. 4 is a diagram of logic to transmit multicast data via egress interfaces.
[0010] [0010]FIG. 5 is a diagram illustrating interface scheduling.
[0011] [0011]FIG. 6 is a flow-chart of a process for multicasting data.
[0012] [0012]FIG. 7 is a diagram of a network processor.
DETAILED DESCRIPTION
[0013] Multicasting can increase traffic handled by network devices. For example, where paths to different multicast group members diverge, a device may need to construct multiple protocol data units (PDUs) (e.g., IP datagrams or ATM cells) having copies of the same multicast data, but destined for different group members. FIG. 1 illustrates a technique that can potentially reduce traffic associated with multicasting. In particular, the technique shown can delay replication of multicast data to reduce traffic between a device 100 and a downstream device 106 . As shown, instead of carrying multiple PDUs storing copies of the same multicast data 104 between devices 100 and 106 , FIG. 1 depicts a scheme where device 100 transmits one copy of the multicast data 104 with control data 102 . The downstream device 106 , in turn, generates PDUs carrying the multicast data and transmits the generated PDUs via the appropriate egress interfaces (e.g., links to remote network devices). The technique illustrated in FIG. 1 may not only reduce traffic between devices 100 and 106 , but may also offload duties from device 100 . For example, construction of the out-bound PDUs by the downstream device 106 can conserve resources of device 100 .
[0014] In greater detail, the sample system of FIG. 1 includes a device 100 , such as a network processor or an Application-Specific Integrated Circuit (ASIC), that processes PDUs received over a network. The processing can include a determination of how to forward a PDU. For example, a network processor may be programmed to determine which egress interface(s) (labeled “port 1”-“port n”) of a downstream device 106 to send out received multicast data. The downstream device 106 shown in FIG. 1 may be local to device 100 . For example, the device 106 may be a medium access controller (MAC) (e.g., an Ethernet MAC), SONET framer, or other link layer device. Alternately, the downstream device 106 may be a remote device (i.e., one separated from device 100 by one or more network connections).
[0015] As shown in FIG. 1, the device 100 transmits multicast data 104 (e.g., the payload(s) of one or more received multicast PDUs) to the downstream device 106 . The device 100 also transmits control information 102 that instructs the downstream device 106 how to handle multicast data 104 . For example, as shown, the control information 102 includes forwarding information such as identification of the downstream device 106 egress interfaces that should be used to transmit the multicast data. In the example shown, the control information 102 also includes PDU header data. The downstream device 106 can generate multiple out-bound PDUs 108 by adding (e.g., pre-pending) the headers to copies of the multicast data 104 . The downstream device 106 can then transmit the generated PDUs 108 via the identified egress interfaces.
[0016] The network device 100 can store the control information 102 for a multicast group to speed PDU processing. For example, the device 100 may store a table of headers and interfaces to be used for members of different multicast groups (or sub-groups). Thus, determining the control information 102 becomes a matter of a fast table lookup. The network device 100 may be statically provisioned with the control information 102 or may update the control information 102 as members join and leave a multicast group. For example, the network device 100 may receive group membership data transmitted via IGMP (Internet Group Management Protocol) messages from group members and multicast routers or switches. Additionally, the device 100 may also dynamically modify the control information 102 based on changing network characteristics (e.g., as network connections become congested or go off-line).
[0017] Network device 100 may perform other operations beyond determining the control information 102 for given multicast data. For example, the device 100 can facilitate multicasting of an IP datagram over an ATM network by segmenting the datagram data across different ATM cells. Techniques for associating ATM circuits with IP multicast groups is described in greater detail in Request For Comments (RFC) 2022 (G. Armitage, Support for Multicast over UNI 3.0/3.1 based ATM Networks, November 1996).
[0018] In the sample scheme depicted in FIG. 1, the limited responsibilities of the downstream device 100 enable the device to be implemented relatively inexpensively (e.g., as a Field Programmable Gate Array (FPGA) or other circuitry). The division of duties can also conserve resources of the network device 100 . That is, instead of expending resources replicating PDUs, the device 100 can devote greater resources to other PDU processing tasks. Again, the technique illustrated above can also reduce traffic between device 100 and 106 as the multicast data 104 may be transmitted, at most, once for a given multicast group or sub-group.
[0019] [0019]FIG. 2 illustrates an example of control 120 and multicast data 122 messages sent to the downstream device 106 . As-shown, both messages 120 , 122 include a “type” identifier to distinguish data messages 122 from control messages 120 . Both messages also include a multicast group identifier that enables the downstream device 106 to pair the messages 120 , 122 together.
[0020] The data message 122 includes the data being multicast. This data can include the payload of a multicast PDU received by device 100 and may or may not include portions of the received PDU header. The control message 120 can include data for the different paths to be taken by copies of the multicast message. For example, as shown, the message 120 includes pairs of headers/egress interfaces. For example, the pairs may include Virtual Path Identifiers (VPI) and a Virtual Channel Identifiers (VCI) of an ATM header and port or virtual port identifiers. After receiving the messages 120 , 122 the downstream device 106 can construct the out-bound PDUs by copying the multicast data and adding the header data. The device 120 can then output the constructed PDUs via the identified egress interfaces.
[0021] The messaging scheme shown in FIG. 2 is merely illustrative and many variations of the above can be implemented. For instance, instead of sending two different messages 120 , 122 , a single message can be used that includes both control and multicast data.
[0022] Potentially, members of a multicast group may have different associated data rates. For example, some multicast group members may have a data rate associated with Digital Subscriber Loop (DSL) connections while others have data rates associated with T1 connections. As shown in FIG. 3, the device 100 can categorize different multicast group 112 members according to their different data rates 114 . In the example illustrated, multicast group 112 x includes data rate sub-groups 114 a , 114 n . As shown, the control data stored for members of a sub-group 114 a , 114 n can include identification (e.g., port numbers or Ethernet addresses) of the downstream egress interfaces used to transmit a multicast message to the sub-group 114 members and/or header data used to prepare the out-bound PDUs at the downstream device 106 . For instance, for sub-group 114 a , multicast data 110 should be output via downstream ports “2”, “1”, and “3”.
[0023] As shown, device 100 can transmit control data 114 a to the downstream device 106 for individual data rate sub-groups. Transmitting control information 114 a and multicast 110 data, at most, once per sub-group enables the downstream device 106 to efficiently handle transmission of the multicast data. Additionally, when multicast data is being sent to multiple sub-groups, the device 100 can flag the multicast data for storage by the downstream entity 106 . This can eliminate retransmission of the multicast data to the downstream entity 106 for each sub-group. As described below, grouping members by data rate can also potentially ease transmission scheduling and can reduce system complexity.
[0024] [0024]FIG. 4 illustrates a scheme that device 100 can implement to coordinate efficient handling of multicast data via the downstream device 106 . As shown, when data arrives at the device, receive logic 130 determines whether the data is a unicast or multicast transmission and enters a request to transmit the data in the appropriate queue 132 , 134 . For multicast data, an entry can be queued in a multicast queue 134 for each multicast sub-group.
[0025] A scheduler 138 determines when the set of egress interfaces used to multicast to a sub-group are available. At the time scheduled, transmit logic 136 sends the multicast and control data to the downstream device. The downstream device 106 can then generate the specified PDUs and output them via the egress interfaces.
[0026] [0026]FIG. 5 illustrates an example of a scheduling scheme that synchronizes availability of the egress interfaces used by a particular multicast group or sub-group. The scheme includes a interface vector for each multicast group or data rate sub-group receiving multicast data. A bit (labeled “intf #”) within the vector identifies the availability of an egress interface. Initially, the vector may be setup so that bits corresponding to the egress interfaces to be used to transmit multicast data are set to “0” while the remaining vector bits are set to “1”. In the example shown, the multicast data will be transmitted via interfaces “1” and “3”.
[0027] The scheme also includes an interface “wheel” that identifies when egress interfaces will become available for a transmission. As shown, in a given time-period (e.g., a set of downstream device cycles), illustrated as a pie-slice of the wheel, one or more interfaces may be scheduled for availability. For instance, in time-period “2” 144 b egress interface “1” will become available, for example, after completing transmission of a previously scheduled PDU and awaiting some minimum gap time between transmissions. Thus, for time-period “2”, the bit for interface “1” is set to “1” and the use of interface “1” is reserved (e.g., the interface cannot be scheduled for other unicast or multicast use until the multicast data is transmitted). Finally, in time-period “3” 144 c , egress interface “3” will become available and the bit for interface “3” is set to “1”. Thus, at time-period “3”, all bits in the vector are set. Thus, the needed interfaces have been reserved for the multicast sub-group. A schedule entry (e.g., the multicast ID) can be made for the sub-group at the specified time. Other entries identify other scheduled multicast groups/sub-groups and unicast transmissions. When time-period “3”, arrives, the schedule entry causes the device 100 to transmit the control and multicast data to the downstream device.
[0028] The interface wheel is continually updated to reflect the future availability of interfaces. Thus, entries for interfaces “1” and “3” can be re-inserted into the wheel after time-period “3” based on the size and data rate of the transmission. Since the sub-groups may be based on data rate, the technique described above can keep the interfaces synchronized after the initial synchronization. That is, since the interfaces are operated at the same rate and may transmit the same amount of data, the interfaces may be scheduled at the same future time-periods. This can ease scheduling operations.
[0029] The scenarios illustrated above assumed that a given set of interfaces could be reserved within a given period of time. However, such scheduling may not always be possible. In such cases, the multicast transmissions to the different interfaces may be enqueued in unicast queues.
[0030] Provisioning bandwidth for the multicast traffic may be performed. Since the constituent ports in the multicast group may be of different rates, apportioning bandwidth for the multicast group can ensure the minimum bandwidth requirement at each port to process the multicast stream. The definition of minimum bandwidth for multicast traffic may be defined in cases where such traffic contains real-time data (video). For multicast traffic that is processed at best-effort priority, the scheduler performs a different set of operations compared to multicast groups that have bandwidth associated with it. The scheduler distinguishes between unicast and multicast traffic. For multicast traffic, if a minimum bandwidth is assigned to a multicast group, a unique ID associated with the multicast group will be used to populate the scheduler wheel. A schedule entry for unicast traffic will contain an index to the unicast queue and for multicast traffic, a schedule entry will index into a table of bit-vectors. The significance of the bit-vector is to be able to identify the physical ports that are eligible for transmission. To determine the eligibility of each physical port in the multicast group, the scheduler will use the physical port's inter-packet/cell gap along with other schedule information of other packets/cells on that port. The scheduler then reconciles the time when the multicast packet/cell needs to be sent to meet the minimum bandwidth (of the multicast group's bandwidth) criteria with the physical port bandwidth. For ports that are eligible, the bit-vector associated with the multicast group will be updated. For ports that cannot be reconciled, the multicast packet will be en-queued into the unicast queue since such ports will not be able to transmit that multicast packet along with other ports in the multicast group.
[0031] If multicast packets/cells are sent with a best-effort priority, the scheduler will determine when ports in the multicast group become eligible and, based on this information, it will group a subset of multicast group physical ports for transmission. If such an alignment of transmission time among some subset of the physical ports in the multicast group is not possible, the multicast packet is replicated and copied into the respective unicast queues.
[0032] Packet/cell replication may be avoided by using a virtual queue concept, where a packet is not removed from a queue until the packet is transmitted among all the members of the multicast group.
[0033] [0033]FIG. 6 depicts a flow-chart illustrating operation of the sample system described above. After receiving 152 data to multicast to a multicast group, forwarding information for the message is determined 154 (e.g., egress interfaces of the downstream device and PDU headers). After receiving 160 the transmitted multicast 156 and control data 158 , the downstream device can construct PDUs and forward 162 the PDUs via the appropriate egress interfaces based on the control information.
[0034] The techniques described above may be used in a wide variety of systems. For example, FIG. 7 depicts a programmable network processor 200 that features multiple packet processors 204 . The network processor 200 shown is an Intel® Internet eXchange network Processor (IXP). Other network processors feature different designs.
[0035] As shown, the network processor 200 features an interface 202 (e.g., an Internet eXchange bus interface) that can carries PDUs between the processor 200 and network components. For example, the bus may carry PDUs received via physical layer (PHY) components (e.g., wireless, optic, or copper PHYs) and link layer component(s) 222 (e.g., MACs and framers). The processor 200 also includes an interface 208 for communicating, for example, with a host. Such an interface may be a Peripheral Component Interconnect (PCI) type interface such as a PCI-X bus interface. The processor 200 also includes other components such as memory controllers 206 , 212 , a hash engine, and scratch pad memory.
[0036] The network processor 200 shown features a collection of packet processors 204 . The packet processors 204 may be Reduced Instruction Set Computing (RISC) processors tailored for network PDU processing. For example, the packet processors may not include floating point instructions or instructions for integer multiplication or division commonly provided by general purpose central processing units (CPUs).
[0037] An individual packet processor 204 may offer multiple threads. The multi-threading capability of the packet processors 204 is supported by context hardware that reserves different general purpose registers for different threads and can quickly swap instruction and status data for the different threads between context registers and context storage.
[0038] The processor 200 also includes a core processor 210 (e.g., a StrongARM® XScale®) that is often programmed to perform “control plane” tasks involved in network operations. The core processor 210 , however, may also handle “data plane” tasks and may provide additional datagram processing threads.
[0039] The network processor 200 may implement the techniques described above in a variety of ways. For example, the control data may be stored as an array in DRAM while different packet processor 204 and core 210 threads process received PDUs and implement scheduling logic.
[0040] The techniques may be implemented in hardware, software, or a combination of the two. For example, the techniques may be implemented by programming a network processor or other processing system. The programs may be disposed on computer readable mediums and include instructions for causing processor(s) to execute instructions implementing the techniques described above.
[0041] Other embodiments are within the scope of the following claims.
|
In general, in one aspect, the disclosure describes a technique of determining forwarding information for at least a sub-set of members of a multicast group, and sending, toward a downstream entity, at most a single copy of data to be multicasted to the sub-set of members and the determined forwarding information.
| 7
|
FIELD OF THE INVENTION
[0001] The present invention relates to dovetail joinery and more particularly, to dovetail dowels split into wedge shape halves longitudinally for joinery with dovetail shaped channels.
BACKGROUND OF THE INVENTION
[0002] Dovetail shaped channels are used as attachment points for hanging utilities from ceilings and walls, and in wood joinery. Dovetail shaped dowels slide into dovetail channels to join two separate pieces together or to act as an attachment point for accessories.
[0003] Dovetail dowels must be slid in from the end of a dovetail channel along the channel until the dowel is positioned in the proper location along the channel. A dovetail dowel split longitudinally into two wedge shaped halves can each be placed directly into a dovetail channel without sliding them down from the ends. The two halves can then be positioned together to act as one piece.
[0004] Dovetail dowels must be glued or screwed in place to prevent the dowel from moving along the length of the dovetail channel. A dovetail dowel split longitudinally into two wedge shaped halves can together be sized to be slightly wider than the width of the dovetail channel. The two halves when positioned together will be compressed in the dovetail channel locking the dovetail dowel in place through friction.
[0005] Through this mechanism the dovetail dowel can tie two separate pieces together that have matching dovetail channel indentations. Through this mechanism the dovetail dowel can become an attachment point for finishes and accessories.
[0006] Split wedge dovetail dowels can be used in wood joinery such as furniture production and metal attachment channels for utilities. Split wedge dovetail dowels can be used in dovetail channels formed in plastics, concrete, masonry, metals, and woods.
[0007] The following example is one possible use in one possible combination of materials for this split wedge dovetail dowel configuration. This example is not to be taken in a limiting sense but as one possible use that illustrates the concept involved with split wedge dovetail dowels. The scope of the invention is best defined by the appended claims.
[0008] Masonry walls are made of cementitious materials. When used in home construction, masonry block walls must have furring strips applied at 16 inch centers to allow for the attachment of drywall to the interior of the walls. Drywall screws do not penetrate into masonry blocks but they do attach to wood furring strips. When drywall comes in direct contact with masonry blocks that are damp, the drywall can absorb moisture and mold can form.
[0009] While wood furring strips do not transfer heat as fast as masonry, wood does transfer heat from the drywall to the masonry reducing the energy efficiency of the home.
[0010] Masonry walls can resist the pressures from wind events such as tornadoes and hurricanes much better than walls constructed of 2×6 wood members. A more efficient, energy conserving, and mold resistant manor of attaching drywall finishes on the interior of masonry construction is needed. Wood furring strips are also used for exterior finishes on masonry walls and the same concepts apply.
[0011] Plastic split wedge dovetail dowels spaced in a 16 inch by 8 inch pattern on the face of a wall constructed of masonry blocks can replace wood furring strips that run from floor to ceiling at 16 inch centers used for the attachment of drywall. Masonry block is manufactured in molds and dovetail channels running full height from top to bottom at 8 inch centers can easily be formed in the face of these block using current block mold technology.
[0012] Two halves of a plastic split wedge dovetail dowel can be placed in from the face of a masonry wall with dovetail channels without having to slide the two pieces down from the top. The two pieces can be slid together to form one combined attachment point for drywall. The plastic pieces can be formed to extend out from the face of the masonry wall the same distance as a wood furring strip.
[0013] Tapping the two halves of the dowel together with a hammer expands the width of the two halves further compressing the two pieces against the sides of the dovetail channel locking the combination in place through friction. These steps are repeated over and over creating the required 16 inch by 8 inch grid pattern of dowels that would replace the wood furring strips.
[0014] Plastic furring attachment points would reduce heat transfer from the drywall or finish material to the masonry wall compared with wood furring strips.
[0015] Plastic split wedge dovetail dowels are resistant to mold unlike wood furring strips.
[0016] Plastic split wedge dovetail attachment points require no drilling and screwing into the masonry unlike wood furring strips.
[0017] The present invention solves many of the problems associated with wood furring strips and expands the uses of dovetail channels formed in construction materials.
[0018] Building Codes will soon require continuous insulation as energy efficiency becomes more of an issue in our society. Masonry walls with wood furring strips and discontinuous insulation between the furring strips will not meet these future requirements. Masonry walls construction with furring strips will become obsolete when these requirements are added to the code.
[0019] As can be seen, there is a need for simpler furring strips made of an insulating material such as plastic that will meet the requirements of continuous insulation.
[0020] Split wedge dovetail dowels expand the uses for dovetail channels by providing a way to lock the dowels into place without the need for glue or screws.
[0021] Split wedge dovetail dowels expand the uses for dovetail channels by providing a way to insert the dowel into the dovetail channel without having to slide the dowel in from the end of the channel.
SUMMARY OF THE INVENTION
[0022] In one aspect of the present invention, a configuration of dovetail dowels where the dowels are split longitudinally into two halves such that the two halves of the dowel can fit past the front smaller width face of a dovetail channel.
[0023] The two halves are split at a wedge shaped angle such that when the two halves are slid together within the dovetail channel the wedge shape expands the two halves to a width wider than the dovetail channel compressing the two halves together locking them in place through friction within the restraining dovetail channel.
[0024] The contacting edges of the two halves of the dovetail dowel are fashioned with a ridge on one edge and a matching groove on the opposing edge such that the split edge is held in alignment when compressed through wedging action.
[0025] The two halves of the dovetail dowel are placed in the dovetail channel separately, slid together at their desired location, and tapped together with a hammer to expand the two halves within the dovetail channel locking the dovetail dowel in place. The combination of the two halves of the dovetail dowel can then be used as an attachment point and/or the two halves can span across two separate matching dovetail channels to act as a connector.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] FIG. 1A is an orthogonal side view of a dovetail shaped dowel before it is fashioned into two halves for insertion into a dovetail channel.
[0027] FIG. 2A is an orthogonal top view of a dovetail channel
[0028] FIG. 3A is an orthogonal side view of a dovetail shaped dowel split in half longitudinally with the two halves together
[0029] FIG. 3B is an orthogonal side view of a dovetail shaped dowel split in half longitudinally with the two halves separated
[0030] FIG. 4A is a close up top view of a matching ridge and groove fashioned along the split surface of two halves of a dovetail dowel
[0031] FIG. 5A is a front view of two halves of a dovetail dowel inserted into a dovetail channel before the two halves of the dowel are positioned together
[0032] FIG. 5B is a front view of two halves of a dovetail dowel inserted into a dovetail channel after the two halves of the dowel are positioned together
[0033] FIG. 6A is an orthogonal view of dovetail dowels spaced in a grid pattern in dovetail channels to provide attachment points for drywall
DETAILED DESCRIPTION OF THE INVENTION
[0034] The following detailed description is of one currently contemplated mode of carrying out exemplary embodiments of the invention. The description is not to be taken in a limiting sense, but is made merely for the purpose of illustrating the general principles of the invention, since the scope of the invention is best defined by the appended claims.
[0035] Broadly, an embodiment of the present invention provides a dovetail dowel that expands within a dovetail channel. The dovetail dowels can be used for any purpose that can benefit from a locked dowel attachment point. The dovetail dowels are split in a longitudinal wedge shape such that when the wedge shapes are moved past each other the two halves of the dowel widen.
[0036] Dowels are fashioned to a width slightly wider than the widest width of a board or member with a dovetail channel formed in it. The opposing sides of the dowel are mitered to match the dovetail shape of the channel where the attachment is required such that the front face of the dowel is not as wide as the back face of the dowel.
[0037] The dowel is split in two longitudinally at an angle no greater than 45 degrees with a groove fashioned on one edge and a matching ridge fashioned on the opposing edge. The dowel is split to a width such that the largest width of each half of the dowel when separated is smaller that the smaller front width of the dovetail channel.
[0038] One half of the split wedge dovetail dowel is inserted into the dovetail channel at one location and the other half is inserted into the same dovetail channel at another location. The two halves are moved up and down the channel respectively such that the split longitudinal edges with matching ridge and groove come in contact. Moving the two halves together even further results in the two halves together become wider than the dovetail channel. Tapping with a hammer creates the force necessary to wedge and compress the two halves of dowel inside the restraining confinement of the dovetail channel.
[0039] The front face of the dowel is held flush as the compressed dowel forces the ridge into the matching groove. The dowel is locked in place by friction as the compressed dowel is forced against the side of the dovetail channel made of a material strong enough to resist the applied compression forces.
[0040] The dowel can span across two separate pieces with matching dovetail channels and can tie those two pieces together as the dowel acts as one piece when compressed together.
[0041] The dowel can act as an attachment point for drywall or utilities or other construction accessories that normally would have difficulty otherwise attaching to the member with the dovetail channel formed in it.
[0042] Referring now to the Figures, a dovetail shape dowel 10 is fashioned to a plan view shape that matches the outline shape of dovetail channel 30 . The side slope of the dowel 11 on both sides closely matches the side slope of the channel 31 . The width of the dowel 15 is about the same width of the channel 35 except it 15 is slightly larger. See FIG. 1A for a view of the dowel 10 and FIG. 2A for a view of the channel 30 .
[0043] Referring now to FIG. 3A and 3B , the dowel 10 is split into two halves 20 in a longitudinal fashion 24 such that each half is a width 25 smaller than the front face of the dovetail channel 30 . When slid together the two halves 20 are expanded to the original dowel width. 15
[0044] Referring now to FIG. 4A , the contacting edges of the two halves of the dowel 20 are fashioned with groove 28 and matching ridge 27 such that the face of the dowels remain flush when the two halves are compressed together.
[0045] The dowels can extend out from the face of the member 39 with the dovetail channel 30 by extending the face of the dowel out 23 .
[0046] Referring now to FIG. 5A and 5B , the two halves of the dovetail dowel 20 can be inserted past the front face of the dovetail channel 30 in member 39 at separate locations. When slid together the two dowels 20 will be compressed in the dovetail channel 30 and locked in place.
[0047] Referring now to FIG. 6A , shows one possible use for split wedge dovetail dowels used as an attachment point for drywall with the attachment points arranged in a 16 inch by 8 inch grid pattern. A wall made of concrete masonry block 39 with dovetail channels 30 molded into the block for their full height at 8 inch centers has dovetail dowel halves 20 made of molded polypropylene locked together in a 16 inch by 8 inch pattern within the dovetail channels 30 . ½ inch drywall 40 is placed against the dovetail dowels and can be permanently screwed into place with standard drywall screws.
[0048] In one embodiment, strips of EPS foam insulation matching the width and depth of the dowels are placed in the channels between the lines of spaced dowels.
[0049] Drywall 40 can not be attached directly to concrete masonry block 39 with drywall screws. Drywall 40 can absorb moisture from concrete masonry block 39 which is not desirable. Dovetail dowels 20 provide an easy way to apply attachment point for drywall to concrete masonry walls. Drywall screws will attach directly to polypropylene dovetail dowels. 20 Drywall 40 will not absorb moisture from dovetail dowels. 20
[0050] Wood furring strips must be drilled and screwed in concrete masonry masonry block 39 . Dovetail dowels 20 are easily tapped into place in pairs with a hammer. Wood furring strips transmit more energy from the drywall into the concrete masonry block than does polypropylene dovetail dowels. Polypropylene dovetail dowels 20 would increase the energy efficiency of a wall system over wood furring strips.
[0051] The above shows just one possible use for split wedge dovetail dowels. The dowels and the member with the dovetail channel can be made of any rigid construction material. Another example of a use for split wedge dovetail dowels would be wood dovetail dowels connecting together two pieces of wood with matching dovetail channels fashioned in them such as in furniture manufacturing.
[0052] This process creates a split wedge dovetail shaped dowel that can lock in a dovetail shaped channel for connection purposes.
[0053] It should be understood, of course, that the foregoing relates to exemplary embodiments of the invention and that modifications may be made without departing from the spirit and scope of the invention as set forth in the following claims.
|
A configuration for split wedge dovetail dowels that provide attachment points along dovetail channels where wedge action locks the dovetail dowels in place through compression and friction without the need for glue or screws. This configuration can also be used to connect two members with matching dovetail channels by positioning the split wedge dovetail dowel across the joint between the two members.
| 4
|
[0001] This application is a Continuation of U.S. Ser. No. 10/752,146 filed Jan. 6, 2004, which is a Continuation of U.S. Ser. No. 09/994,292 filed Nov. 26, 2001, which claims the benefit of U.S. Provisional Applications 60/275,023; 60/274,996; 60/275,047; and 60/274,995, all filed Mar. 12, 2001.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention relates to the field of estrogen receptors and particularly, though not exclusively, to the effect of estrogen receptors and ligands for estrogen receptors, particularly those ligands which are agonists, and on the use of those ligands for prevention or treatment of obesity. The invention also relates to the effect of estrogen receptors and their ligands on lipoprotein levels in mammals.
[0004] 2. Description of the Related Art
[0005] The cloning of the novel estrogen receptor, ERβ, suggested that there may exist alternative mechanisms of action for estrogen (Kuiper, G. G., et al (1996) Proc. Natl. Acad. Sci. USA 93, 5925-5930). For example, ERβ is expressed in growth plate chondrocytes and osteoblasts, indicating a possible role for ERβ in the regulation of longitudinal bone growth and/or adult bone metabolism (Onoe, Y., et al (1997) Endocrinology 138, 4509-4512; Arts, J., and/or adult bone metabolism (Onoe, Y., et al (1997) Endocrinology 138, 4509-4512; Arts, J., Kuiper, G. G., et al (1997) Endocrinology 138, 5067-5070; Vidal, O., et al (1999) J Bone Miner Res In press; Nilsson, L. O., et al (1999) J Clin Endocrinol Metab 84, 370-373; Windahl own unpublished results). We have recently generated mice devoid of functional ERβ protein and reported that ERβ is essential for normal ovulation efficiency, but is not essential for female or male sexual development, fertility, or lactation (Krege, J. H., et al (1998) Proc Natl Acad Sci USA 95, 15677-15682).
[0006] The molecular mechanisms of action for ERα compared to ERβ have recently been investigated. ERα and ERβ have almost identical DNA-binding domains and studies in vitro have demonstrated that the two receptors have similar affinities for estrogenic compounds (Kuiper, G. G. et al (1996) Proc Natl Acad Sci USA 93, 5925-5930; Kuiper, G. G., et al (1997) Endocrinology 138, 863-870; Tremblay, G. B., et al (1997) Mol Endocrinol 11, 353-365). The amino-acid sequence of ERβ differs from ERα in the N- and C-terminal trans-activating regions. Therefore the transcriptional activation mediated by ERβ may be distinct from that of ERα (Paech, K., et al (1997) Science 277, 1508-1510). Considering the great similarities in ligand- and DNA-binding specificity, it has been speculated that a differential tissue distribution of estrogen receptors may be important for mediating tissue specific responses to estrogens (Kuiper, G. G., and Gustafsson, J. A. (1997) FEBS Lett 410, 87-90). Thus, the unique transactivating domains of the two receptor subtypes, in combination with differential tissue-distribution, or differential cell-type distribution within a tissue, could be important factors to determine the estrogen response in target tissues.
[0007] It is well known that estrogen exerts atheroprotective effects in women. The incidence of atherosclerotic disease is low in premenopausal women, rises in postmenopausal women, and is reduced in postmenopausal women who receive estrogen therapy (Mendelsohn M E, Karas R H, N Engl J Med (1999) 340, 1801-1811; Stampfer M J et al (1991) N Engl J Med 325, 756-762; Grady D et al (1992) Ann Intern Med 117, 1016-1027; Barrett-Connor E (1997) Circulation 95, 252-264). The protective effect of estrogen depends both on estrogen induced alterations in serum lipids and on direct actions of estrogen on blood vessels (Mendelsohn M E, Karas R H, (1999) supra). The possible protective effects of estrogen in males are less well documented. However, recent clinical findings in males with either aromatase deficiency (estrogen deficient) or estrogen resistance (estrogen receptor mutation) have indicated that estrogen exerts important effects on carbohydrate and lipid metabolism in males as well (Smith E P et al (1994) N Engl J Med 331, 1056-1061; Morishima A et al (1995) J Clin Endocrinol Metab 80, 3689-3698; Grumbach M M et al (1999) J Clin Endocrinol Metab 84, 4677-4694). The clinical features of these patients include glucose intolerance, hyperinsulinemia and lipid abnormalities (MacGillivray M H et al (1998) Horm Res 49 Suppl 1, 2-8). Furthermore, estrogen resistance in a male subject was associated with premature coronary atherosclerosis (Grumbach M M et al (1999) supra).
[0008] Orchidectomy (orx) results both in a decreased activation of the androgen receptor and decreased estrogen levels, leading to decreased activation of estrogen receptors. We have previously demonstrated that orx of male mice results in a decreased weight gain during sexual maturation (Sandstedt J et al (1994) Endocrinology 135, 2574-2580). Similarly, orx of rats also results in a decreased body weight (Vanderschueren D et al (1996) Caldif Tissue Int 59 179-183; Vanderschueren D et al (1997) Endocrinology 138 2301-2307; Zhang X Z et al (1999) Bone Miner Res 14 802-809). However, the decreased body weight in orchidectomized mice and rats was accompanied by a decreased size of the skeleton, indicating that it is a growth related effect rather than an effect related to the fact that the animals became leaner. The effect of estrogen on fat content, carbohydrate metabolism and lipid metabolism in male mice is largely unknown. However, it was recently reported that aromatase deficient (ArKO) male mice, with decreased serum levels of estrogen, had a 50% increase of the gonadal fat pads (Fisher C R et al (1998) Proc Natl Acad Sci USA 95 6965-6970). No information about carbohydrate and lipid metabolism in these mice was given in that publication.
[0009] Possible effects of estrogen on fat mass may, for instance, include direct effects on the fat tissue and indirect central effects on food intake, food efficiency and activity. Furthermore, it is known that estrogen exerts liver specific effects on lipid and carbohydrate metabolism. The two estrogen receptor subtypes, ERα and ERβ, bind estrogen with similar affinity but are believed to differ in their transactivating properties. The relative importance of ERα and ERβ in adipose tissue is not known. Some previous studies have reported ERα protein (Mizutani T et al (1994) J Clin Endocrinol Metab 78, 950-954; Pedersen S B et al (1996) Eur J Clin Invest 26, 1051-1056) as well as specific estrogen binding and ERα mRNA to be present in human subcutaneous adipose tissue (Pedersen S B et al (1996) supra). However, others have failed to detect estrogen receptors in human adipose tissue (Bronnegard M et al (1994) J Steroid Biochem Mol Biol 51, 275-281; Rebuffe-Scrive M et al (1990) J Clin Endocrinol Metab 71, 1215-1219). More recently, ERβ mRNA has been detected in human subcutaneous adipose tissue, suggesting that direct effects of estrogen may involve both receptor subtypes (Crandall D L et al (1998) Biochem Biophys Res Commun 248, 523-526).
[0010] Mice lacking a functional ERα gene, ERα Knockout mice (ERKO), have been generated (Couse, J. F. et al (1995) Mol. Endocrinol. 9, 1441-1454) and more recently ERβ Knockout mice (BERKO) have also been described (Krege, J. H. et al (1998) Proc. Natl. Acad. Sci. USA 95, 15677-15682). We have also generated Double-ER-Knockout mice (DERKO) i.e. mice having no estrogen receptors.
SUMMARY OF THE INVENTION
[0011] The aim of the present study was to investigate the function of the estrogen receptors and in particular their effects on body fat and serum levels of leptins in mammals. These parameters were studied in ERα knockout (ERKO), ERβ knockout (BERKO) and ERα/β double knockout (DERKO) mice before during and after sexual maturation.
[0012] Surprisingly, it was found that neither the total body fat nor serum leptin levels were altered in any group before or during sexual maturation. However, after sexual maturation, ERKO and DERKO but not BERKO demonstrated a markedly increased amount of total body fat as well as increased serum levels of leptin. Serum levels of corticosterone were decreased whereas serum cholesterol was increased in adult mice with ERα inactivated. Interestingly, a qualitative change in the lipoprotein profile, including smaller and denser LDL particles, was also observed in ERKO and DERKO mice. In conclusion, ERα but not ERβ inactivated male mice develop obesity after sexual maturation. This obesity is associated with a disturbed lipoprotein profile.
[0013] It is well known that ovariectomy (ovx) in the rat results in weight gain, which, at least in part, is due to an increase in food intake (Bennett P A et al (1998) Neuroendocrinology 67, 29-36; Richter C et al (1954) Endocrinology 54, 323-337). Conversely, estrogen is well known to suppress food intake and reduce body weight in female rats (Couse, J. F. & Kovach K. S. (1999) Science, 286, 2328; Mook D G et al (1972) J Comp Physiol Psychol 81, 198-211). A weight reducing effect of estrogen in female rodents is supported by the fact that female ArKO mice, with undetectable levels of estrogen, develop increased weight of the mammary- and the gonadal-fat pads after sexual maturation (Fisher C R et al (1998 supra). It is unknown whether or not estrogen reduces body weight in male rodents. We have in the present study demonstrated that adult male mice, devoid of all known estrogen receptors, develop obesity, indicating that estrogen reduces body weight in male rodents as well. A physiological fat reducing effect of estrogen in males is supported by a recent observation that the weight of the gonadal fat pads is increased in male ArKO mice. Furthermore, the estrogen receptor specificity for this obese phenotype in DERKO and ArKO mice was investigated. In the present study, ERα but not ERβ inactivated mice developed a similar obese phenotype as did the DERKO mice, demonstrating that ERα inactivation is responsible for the obese phenotype in DERKO mice. In contrast, a non significant tendency of reduced weight of the retroperitoneal fat pads was found in male BERKO mice. We are currently feeding BERKO and wild type mice with high fat diet in order to investigate whether or not BERKO mice actually are less obese than wild type mice. The mechanism behind the adult obesity in ERα-inactivated mice is unknown and may include both peripheral and central effects.
[0014] Serum levels of IGF-I are decreased in ERKO and DERKO mice and clinical studies have demonstrated that male obesity is associated with low serum levels of IGF-I (Vidal O et al (2000) Proc Natl Acad Sci USA in press; Bennett P A et al (1998) supra; Richter C et al (1954) supra; Mook D G et al (1972) supra; Marin P et al (1993) Int J Obes Relat Metab Disord 17, 83-89). Thus, one possible mechanistic explanation for the increased fat mass in ERKO and DERKO mice might be a reduction of serum IGF-I levels, resulting in obesity.
[0015] Estrogen therapy reduces the risk of developing cardiovascular disease (Psaty B M et al (1993) Arch Intern Med 153 1421-1427; The writing group for the PEPI t 1995) JAMA 273 199-208; Grodstein F et al (1996) N Engl J Med 335 453-461; Henriksson P et al (1989) Eur J Clin Invest 19 395-403; Wagner J D et al (1991) J Clin Invest 88 1995-2002; Haabo J et al (1994) Arterioscler Thromb 14 243-247; Herrington D M et al (1994) Am J Cardiol 73 951-952; Zhu X D et al (1997) Am J Obstet Gynecol 177 196-209). The ability of estrogen to lower plasma levels of total cholesterol and to reduce plasma level of LDL-particles is of importance for the cardioprotective effect of estrogen since elevated levels of cholesterol are strongly associated with cardiovascular disease (Gordon T et al (1981) Arch Intern Med 141, 1128-1131). The higher exposure to estrogens in females than males has been proposed as being the protective factor explaining the lower risk for cardiovascular disease that women have compared with men (Kannel W B et al (1976) Ann Intern Med 85, 447-452; Bush T L et al (1990) Ann N Y Acad Sci 592, 263-71). The protective effects of estrogen in preventing atherosclerosis have also been described in animal models (Henriksson P et al (1989) supra; Kushwaha R S et al (1981) Metabolism 30, 359-366). At least some of the effects of estrogens on cholesterol metabolism have been shown to be dependent on ERs (Parini, P et al (1997) Arterioscler Thromb Vasc Biol 17, 1800-1805; Scrivastava R A et al (1997) J Biol Chem 272, 33360-33366). However, the physiological role exerted by ERs in the regulation of cholesterol and lipoprotein metabolism is still unclear.
[0016] Clinical case reports have described that estrogen resistance results in metabolic effects including disturbed lipid profile (Smith E P et al (1994) supra). In the present study, the levels of total cholesterol were increased in ERα but not in ERβ inactivated male mice. Furthermore, the disruption of the ERα gene, alone or in association with the disruption of the ERβ gene, resulted in an atherogenic lipoprotein profile characterized by an increase in the smaller and denser LDL particles. This atherogenic lipoprotein profile was not present in male BERKO mice, denoting a clear phenotype associated with the ERα and suggesting a physiological role for ERα in the regulation of lipoprotein metabolism in male mice.
[0017] The mechanism behind the altered lipoprotein profile in male ERα-inactivated mice cannot be decided from the present study, but may for instance include alterations in serum levels of apolipoprotein E, hepatic lipase activity and LDL-receptor expression. It has previously been described that wild type mice, but not ERKO mice, display an estrogen induced increase in serum levels of apolipoprotein E. In contrast, the basal apolipoprotein E levels were not significantly decreased in ERKO mice compared with wild type mice (Scrivastava R A et al (1997) J Biol Chem 272, 33360-33366). Estrogen administration to mice does not affect the activity of hepatic lipase (Scrivastava R A et al (1997) Mol Cell Biochem 173, 161-168). However, this finding does not rule out the possibility that ER-inactivation may regulate hepatic lipase activity. Difference in LDL-receptor expression should also be considered. High dose estrogen treatment increases LDL-receptor expression in rats (Kovanen P T et al (1979) J Biol Chem 254, 11367-11373; Chao Y S et al (1979) J Biol Chem 254, 11360-11366), rabbits (Henriksson P et al (1989) supra; Ma P T et al (1986) Proc Natl Acad Sci USA 83, 792-796) and human (Angelin B et al (1992) Gastroenterology 103, 1657-1663). In contrast, treatment of rats with antiestrogens does not reduce hepatic LDL-receptor expression (Parini P et al (1997) Arterioscler Thromb Vasc Biol 17, 1800-1805) and LDL-receptors are not upregulated by estrogen in mice (Scrivastava R A et al (1997) supra; Scrivastava R A et al (1994) Eur J Biochem 222, 507-514), suggesting that LDL-receptor expression is not dependent on ERs in mice.
[0018] ERKO and DERKO but not BERKO mice had increased levels of cholesterol in the HDL-fraction, supporting previous reports that administration of estrogen decreases HDL-cholesterol levels in mice (Tang J J et al (1991) 32, 1571-1585). In contrast, estrogen increases HDL-cholesterol in humans. Furthermore, the insulin×glucose as well as the insulin×free fatty acid products were increased in the ERα inactivated mice, indicating that these mice are insulin resistant. Clinical studies have demonstrated that men with defective estrogen synthesis or action also have a propensity for both insulin resistance and dyslipidemia (Smith E P et al (1994) supra; Morishima A et al (1995) supra; Grumbach M M et al (1999) supra). These men, as well as DERKO and ArKO mice, have increased serum levels of testosterone (Fisher C R et al (1998) supra; Vortkamp A et al (1996) Science 273, 613-622). The role of a high concentration of testosterone (or its action in the absence of estrogen) is uncertain. Estrogen therapy reverses the lipid abnormalities seen in men with estrogen deficiency (Grumbach M M et al (1999) J Clin Endocrinol Metab 84, 4677-4694). Correction of the lipid abnormalities could either be a direct effect of estrogen or an indirect effect via normalization of the high serum androgen concentration.
[0019] Selective estrogen receptor modulators (SERMs) have been shown to maintain estrogen's positive bone and cardiovascular effects while minimizing several of the side-effects of estrogen (Delmas P D et al 1997) N Engl J Med 337, 1641-1647). It has been well documented that SERMs decrease total serum cholesterol in ovx female rats (Bryant H et al (1996) Jounral of Bone and Mineral Metabolism 14, 1-9; Black L J et al (1994) J Clin Invest 93, 63-69; Ke H Z et al (1997) Bone 20, 31-39) and total serum cholesterol and low density lipoprotein in postmenopausal women (Delmas P D et al (1997) supra; Cosman F et al (1999) Endocr Rev 20, 418-434). Furthermore, oral estrogen treatment improves serum lipid levels in elderly men (Giri S et al (1998) Atherosclerosis 137, 359-366). A recent study demonstrated that the SERM lasofoxifene decreased total serum cholesterol in orx male rats, indicating that lasofoxifene acts as an estrogen agonist for serum lipoproteins in male rats, similar to that seen in ovx female rats (Ke H Z et al (2000) Endocrinology 141, 1338-1344). Lasofoxifene treated orx male rats demonstrated decreased food intake and body weight, which may result in the decreased total serum levels of cholesterol. The result that lasofoxifene decreases body weight and serum levels of cholesterol in male mice is consistent with the present study in which male ER-inactivated mice develop obesity and increased serum levels of cholesterol.
[0020] It has recently been demonstrated that mice devoid of all known ERs are viable (Vidal O et al (2000) supra; Couse J F et al (1999) Science 286, 2328-2331). However, loss of both receptors leads to an ovarian phenotype that is distinct from that of the individual ER mutants indicating that both receptors are required for the maintenance of germ and somatic cells in the postnatal ovary (Couse J F et al (1999) supra). Furthermore, the skeletal growth is inhibited in male DERKO mice, associated with decreased serum levels of IGF-I (Vidal O et al (2000) supra). Dissection of the estrogen receptor specificity clearly demonstrated that ERα but not ERβ was responsible for the inhibited growth seen in DERKO mice (Vidal O et al (2000) supra). The present data represents the first information about the metabolic phenotype of DERKO mice. Similar to the growth related effects, the metabolic effects, including the reduction of fat described in the present study, seem to be mediated via ERα and not ERβ. Therefore, one may speculate that ERα specific agonists could be useful in the treatment of some males with obesity and/or disturbed lipoprotein profile. In conclusion, ERα inactivated male mice develop obesity after sexual maturation. This obesity is associated with a disturbed lipoprotein profile.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] The invention will now be described, by way of example only, with reference to the accompanying drawings FIGS. 1 to 6 in which:
[0022] FIG. 1 shows total body fat levels in wild type (WT), ERKO, BERKO and DERKO mice before sexual maturation, during sexual maturation and after sexual maturation;
[0023] FIG. 2 shows serum leptin levels in wild type (WT), ERKO, BERKO and DERKO mice before sexual maturation, during sexual maturation and after sexual maturation;
[0024] FIG. 3 shows fat content in sexually mature male wild type (WT) ERKO, BERKO and DERKO mice;
[0025] FIG. 4 shows dissected retroperitoneal and gonadal fat levels in sexually mature male wild type (WT), ERKO, BERKO and DERKO mice;
[0026] FIG. 5 shows serum lipoprotein levels in sexually mature male wild type (WT) mature male wild type (WT) ERKO, BERKO, and DERKO mice; and
[0027] FIG. 6 shows the effect of estrogen on fat levels in wild type (WT) ERKO, BERKO and DERKO mice.
DETAILED DESCRIPTION OF THE INVENTION
[0028] According to one aspect of the invention, there is provided the use of an ERα selective compound in the preparation of a medicament for the treatment or prevention of obesity in a mammalian subject. The invention also provides a method of treating or preventing obesity in a mammalian subject comprising supplying an ERα selective compound to the subject. Preferably, the ERα selective compound is an ERα agonist. The mammalian subject may preferably be adult although the treatment of sexually maturing mammals is contemplated. The mammalian subject may be human, but the treatment of other species, especially domesticated species, is also contemplated. Gonadal fat levels may be reduced as a percentage of body weight to about 1.25% or below.
[0029] The invention also provides a pharmaceutical composition for the treatment or prevention of obesity, the composition comprising an ERα selective compound, preferably an ERα agonist. Pharmaceutical compositions of this invention comprise any of the compounds of the present invention, and pharmaceutically acceptable salts thereof, with any pharmaceutically acceptable carrier, adjuvant or vehicle. Pharmaceutically acceptable carriers, adjuvants and vehicles that may be used in the pharmaceutical compositions of this invention include, but are not limited to, ion exchangers, alumina, aluminum stearate, lecithin, serum proteins, such as human serum albumin, buffer substances such as phosphates, glycine, sorbic acid, potassium sorbate, partial glyceride mixtures of saturated vegetable fatty acids, water, salts or electrolytes, such as protamine sulfate, disodium hydrogen phosphate, potassium hydrogen phosphate, sodium chloride, zinc salts, colloidal silica, magnesium trisilicate, polyvinyl pyrrolidone, cellulose-based substances, polyethylene glycol, sodium carboxymethylcellulose, polyacrylates, waxes, polyethylene-polyoxypropylene-block polymers, polyethylene glycol and wool fat.
[0030] The pharmaceutical compositions of this invention may be administered orally, parenterally, by inhalation spray, topically, rectally, nasally, buccally, vaginally or via an implanted reservoir. We prefer oral administration or administration by injection. The pharmaceutical compositions of this invention may contain any conventional non-toxic pharmaceutically-acceptable carriers, adjuvants or vehicles. The term parenteral as used herein includes subcutaneous, intracutaneous, intravenous, intramuscular, intra-articular, intrasynovial, intrasternal, intrathecal, intralesional and intracranial injection or infusion techniques.
[0031] The pharmaceutical compositions may be in the form of a sterile injectable preparation, for example, as a sterile injectable aqueous or oleaginous suspension. This suspension may be formulated according to techniques known in the art using suitable dispersing or wetting agents (such as, for example, Tween 80) and suspending agents. The sterile injectable preparation may also be a sterile injectable solution or suspension in a non-toxic parenterally-acceptable diluent or solvent, for example, as a solution in 1,3-butanediol. Among the acceptable vehicles and solvents that may be employed are mannitol, water, Ringer's solution and isotonic sodium chloride solution. In addition, sterile, fixed oils are conventionally employed as a solvent or suspending medium. For this purpose, any bland fixed oil may be employed including synthetic mono- or diglycerides. Fatty acids, such as oleic acid and its glyceride derivatives are useful in the preparation of injectables, as are natural pharmaceutically-acceptable oils, such as olive oil or castor oil, especially in their polyoxyethylated versions. These oil solutions or suspensions may also contain a long-chain alcohol diluent or dispersant such as Ph. Helv or a similar alcohol.
[0032] The pharmaceutical compositions of this invention may be orally administered in any orally acceptable dosage form including, but not limited to, capsules, tablets, and aqueous suspensions and solutions. In the case of tablets for oral use, carriers which are commonly used include lactose and corn starch. Lubricating agents, such as magnesium stearate, are also typically added. For oral administration in a capsule form, useful diluents include lactose and dried corn starch. When aqueous suspensions are administered orally, the active ingredient is combined with emulsifying and suspending agents. If desired, certain sweetening and/or flavoring and/or coloring agents may be added.
[0033] The pharmaceutical compositions of this invention may also be administered in the form of suppositories for rectal administration. These compositions can be prepared by mixing a compound of this invention with a suitable non-irritating excipient which is solid at room temperature but liquid at the rectal temperature and therefore will melt in the rectum to release the active components. Such materials include, but are not limited to, cocoa butter, beeswax and polyethylene glycols.
[0034] Topical administration of the pharmaceutical compositions of this invention is especially useful when the desired treatment involves areas or organs readily accessible by topical application. For application topically to the skin, the pharmaceutical composition should be formulated with a suitable ointment containing the active components suspended or dissolved in a carrier. Carriers for topical administration of the compounds of this invention include, but are not limited to, mineral oil, liquid petroleum, white petroleum, propylene glycol, polyoxyethylene polyoxypropylene compound, emulsifying wax and water. Alternatively, the pharmaceutical composition can be formulated with a suitable lotion or cream containing the active compound suspended or dissolved in a carrier. Suitable carriers include, but are not limited to, mineral oil, sorbitan monostearate, polysorbate 60, cetyl esters wax, cetearyl alcohol, 2-octyldodecanol, benzyl alcohol and water. The pharmaceutical compositions of this invention may also be topically applied to the lower intestinal tract by rectal suppository formulation or in a suitable enema formulation. Topically-transdermal patches are also included in this invention.
[0035] The pharmaceutical compositions of this invention may be administered by nasal aerosol or inhalation. Such compositions are prepared according to techniques well-known in the art of pharmaceutical formulation and may be prepared as solutions in saline, employing benzyl alcohol or other suitable preservatives, absorption promoters to enhance bioavailability, fluorocarbons, and/or other solubilizing or dispersing agents known in the art.
[0036] In a pharmaceutical composition of the invention the ERα selective compound is preferably an ERα agonist.
[0037] The invention also provides a method of screening compounds for efficiacy in the treatment or prevention of obesity, the method including determining the ER binding properties of the components. The compounds are preferably selected on the basis of being ERα selective compounds. Most preferably compounds are selected which are ERα agonists.
[0038] According to another aspect of the invention there is provided an ERα selective compound in the preparation of a medicament for the reduction or lowering of serum lipoprotein levels in a mammalian subject. The ERα selective compound is preferably an ERα agonist. The ERα agonist is preferably ERα selective. The subject is preferably adult, most preferably human.
[0039] The invention also provides pharmaceutical composition for the reduction of serum lipoprotein levels, the composition comprising an ERα selective compound. The ERα selective compound is preferably an ERα agonist. The invention also provides a method of screening compounds for efficiacy in the reduction of serum lipoprotein levels, the method including determining the ER binding properties of the compounds. Compounds are preferably selected on the basis of being ERα agonists. Preferably the agonists are selective for ERα.
[0000] Definitions
[0040] “ER Agonism”: An ER agonist is a compound that displays ≧50% of the activity of the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol, activity defined as e.g the increased expression of a gene product that is transcriptionally controlled by an estrogen-response-element (ERE)-promoter-gene construct (ERE-reporter vector) in the presence of an ER.
[0041] “ER antagonism”: An ER antagonist is a compound that displays ≦5% or no agonist activity compared to the activity displayed by the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol, or a compound that decrease the activity of E2 or the synthetic estrogen moxestrol down to ≦5% of the activity displayed by E3 or the synthetic estrogen moxestrol alone, activity defined as e.g the increased expression of a gene product that is transcriptionally controlled by an estrogen-response-element (ERE)-promoter-gene construct (ERE-reporter vector) in the presence of an ER.
[0042] “Compound with mixed agonist/antagonist activity”. (SERM: Selective Estrogen Receptor Modulator): An ER-binding compound that displays ≦50% but ≧5% of the activity of the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol, activity defined as e.g the increased expression of a gene product that is transcriptionally controlled by an estrogen-response-element (ERE)-promoter-gene construct (ERE-reporter vector) in the presence of an ER.
[0043] “ERα selective compound”: An ERα selective compound is a compound that displays ≧1 0-fold higher binding affinity for ERα than for ERβ as determined by a standard receptor-ligand competition binding assay, and/or that displays ≧10-fold higher potency via ERα than via ERβ in the transcriptional regulation of an estrogen sensitive gene in the presence or absence of the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol. Estrogen sensitive gene defined by an estrogen-response-element (ERE)-promoter-gene construct (ERE-receptor vector).
[0044] “ERβ selective compound”: An ERβ selective compound is a compound that displays ≧10-fold higher binding affinity for ERβ than for ERα as determined by a standard receptor-ligand competition binding assay, and/or that displays ≧10-fold higher potency via ERβ than via ERα in the transcriptional regulation of an estrogen sensitive gene in the presence or absence of the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol. Estrogen sensitive gene defined by an estrogen-response-element (ERE)-promoter-gene construct (ERE-reporter vector).
[0045] “ERα selective agonist”: An ERα selective agonist is a compound that displays ≧50% of the activity of the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol, mediated by ERα, but ≦50% of the activity of the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol, mediated by ERβ. Activity defined as e.g the increased expression of a gene product that is transcriptionally controlled by an estrogen-element (ERE)-promoter-gene construct (ERE-reporter vector) in the presence of ERα or ERβ.
[0046] “ERβ selective agonist”: An ERβ selective agonist is a compound that displays ≧50% of the activity of the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol, mediated by ERβ, but ≦50% of the activity of the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol, mediated by ERα. Activity defined as e.g the increased expression of a gene product that is transcriptionally controlled by an estrogen-response-element (ERE)-promoter-gene construct (ERE-reporter vector) in the presence of ERβ or ERα.
[0047] “ERα selective compound with mixed agonist/antagonist activity (SERM: Selective Estrogen Receptor Modulator)”: An ER-binding compound that displays≦50% but ≧5% of the activity of the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol, mediated by ERα: but ≧50% or ≦5% of the activity of the natural estrogen 17β-estradial (E2) or the synthetic estrogen moxestrol, mediated by ERβ. Activity defined as e.g the increased expression of a gene product that is transcriptionally controlled by an estrogen-response-element (ERE)-promoter-gene construct (ERE-reporter vector) in the presence of ERα or ERβ.
[0048] “ERβ selective compound with mixed agonist/antagonist activity (SERM Selective Estrogen Receptor Modulator)”: An ER-binding compound that displays ≦50% but ≧5% of the activity of the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol, mediated by ERβ, but ≧50% or ≦5% of the activity of the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol, mediated by ERα. Activity defined as e.g the increased expression of a gene product that is transcriptionally controlled by an estrogen-response-element (ERE)-promoter-gene construct (ERE-reporter vector) in the presence of ERβ or ERα.
[0049] “ERα selective antagonist”: An ER-binding compound that displays ≦5% or no agonist activity compared to the activity displayed by the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol, mediated by ERα, but that displays ≧5% of the activity of the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol, mediated by ERβ. Activity defined as e.g, the increased expression of a gene product that is transcriptionally controlled by an estrogen-response-element (ERE)-promoter-gene construct (ERE-reporter vector) in the presence of ERα or ERβ.
[0050] “ERβ selective antagonist”: An ER-binding compound that displays ≦5% or no agonist activity compared to the activity displayed by the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol, mediated by ERβ, but that displays ≧5% of the activity of the natural estrogen 17β-estradiol (E2) or the synthetic estrogen moxestrol, mediated by ERα. Activity defined as e.g the increased expression of a gene product that is transcriptionally controlled by an estrogen-response-element (ERE)-promoter-gene construct (ERE-reporter vector) in the presence of ERβ or ERα.
EXAMPLES
[0051] The invention is further described by the following Examples, but is not intended to be limited by the Examples. All parts and percentages are by weight and all temperatures are in degrees Celsius unless explicitly stated otherwise.
[0000] 1. Methods
[0000] a) Animals
[0052] Male double heterozygous (ERα +/− β +/− ) mice were mated with female double heterozygous (ERα +/− β +/− ) mice, resulting in WT, ERKO, BERKO and DERKO offspring. All mice were of mixed C57BL/6J/129 backgrounds. Genotyping of tail DNA was performed at 3 weeks of age. The ERα-gene was analyzed with the following primer pairs: Primers AACTCGCCGGCTGCCACTTACCAT (SEQ ID NO:1) and CATCAGCGGGCTAGGCGACACG (SEQ ID NO:2) for the WT gene correspond to flanking regions in the targeted exon no. 2. They produce a fragment of approximately 320 bp. Primers TGTGGCCGGCTGGGTGTG (SEQ ID NO: 3) and GGCGCTGGGCTCGTTCTC (SEQ ID NO:4) for the KO gene correspond to part of the NEO-cassette and the flanking exon no. 2. They produce a 700 bp fragment. Genotyping of the ERβ-gene has been previously described (Windahl S. H. et al (1999) J Clin Invest 104: 895-901). Animals were maintained in polycarbonate plastic cages (Scanbur A S, Køge, Denmark) containing wood chips. Animals had free access to fresh water and food pellets (B&K Universal AB, Sollentuna, Sweden) consisting of cereal products (76.9% barley, wheat feed, wheat and maize germ), vegetable proteins (14.0% hipro soya) and vegetable oil (0.8% soya oil).
[0000] b) Dual X-Ray Absorptiometry (DXA)
[0053] We have previously developed a combined Dual X-Ray Absorptiometry (DXA) Image analysis procedure for the in vivo prediction of fat content in mice (Sjogren et al manuscript). The DXA measurements were done with the Norland pDEXA Sabre (Fort Atkinson, Wis.) and the Sabre Research software (3.9.2). Three mice were analysed in each scan. A mouse, which was sacrificed at the beginning of the experiment, was included in all the scans as an internal standard in order to avoid inter-scan variations. The software % fat procedure was used with a setting so that areas with more than 50% fat was made white on the image. The accuracy of this setting was checked daily with a standard consisting of a gradient with 0-100% fat. The image was then printed, scanned and imported to the software Scion Image (Scion Corporation, Frederick, Md.). The imported image was then threshold to a setting of 50 arbitrary units, making lean mass and bone black while the fat area appeared as white holes in the mice. Therafter, the “analyse particle” procedure was performed first with white areas in mice included (=A1=total mouse area) and then without the white area included (=A2=lean area +bone area). The % fat area was then calculated as ((A1−A2)/A1)×100. The inter-assay CV for the measurements of % fat area was less than 3%.
[0000] c) Serum Levels of Leptin, Insulin, Corticosterone, Cholesterol, Triglycerides, Glucoso and Free Fatty Acids
[0054] Serum leptin levels were measured by a radio immuno assay (Chrystal Chem Inc, IL, USA) with an intra-assay and interassay coefficient of variations (CVs) of 5.4 and 6.9%, respectively. Serum insulin levels were measured by a radio immuno assay (Chrystal Chem Inc, IL, USA) with an intra-assay and interassay coefficient of variations (CVs) of 3.5 and 6.3%, respectively. Serum corticosterone levels were measured by a radio immuno assay (ImmunoChem ICN Biomedicals, Inc CA USA) with an intra-assay and interassay coefficient of variations (CVs) of 6.5 and 4.4%, respectively. Serum total cholesterol, triglycerides and glucose were assayed using the respective commercially available assay kit from Boehringer Mannheim (Mannheim, Germany). Free fatty acids were measured by an enzymatic calorimetric method (ACS-ACOD; Wako Chemicals Inc, VA, USA) with an intra-assay coefficient of variations (CV) of less than 3%.
[0000] d) Lipoprotein Cholesterol Determination
[0055] Size fractionation of lipoproteins by miniaturized on-line FPLC was performed using a micro-FPLC column (30×0.32 cm Superose 6B) coupled to a system for on-line detection of cholesterol. In brief, 10 μl of serum from each animal was injected and the cholesterol content in the lipoproteins was determined on-line using a cholesterol assay kit (Boehringer Mannheim, Mannheim, Germany), which was continuously mixed with the separated lipoproteins. Absorbance was measured at 500 nm and the signals collected using EZ CROM software (Scientific Software, San Ramon, Calif.).
[0000] e) Effects of Estrogen Exposure
[0056] Male double heterozygous (ERα +/− β +/− ) mice were mated with female double heterozygous (ERα +/− β +/− ) mice, resulting in ERα +/+ β +/+ wildtype (WT); ERα −/− β +/+ =ERKO, ERα +/+ β −/− =BERKO and ERα −/− β −/− =DERKO offsprings (Vidal O et al (2000) Proc Natl Sci USA, 97, 5474). The diet, housing and genetic background was as previously described in Vidal O et al (2000) supra. In the estrogen exposure experiments all mice were ovariectomized. Ovaries were removed after a flank incision and the incisions were closed with metallic clips. Mice were left to recover for four days after ovariectomy before start of experiments. After recovery mice were injected s.c with 2.3 μg/mouse/day of 17β-estradiol benzoate (Sigma, St Louis, Mo., USA) for 5 days/week during three weeks time. Control mice received injections of vehicle oil (olive oil, Apoteksbolaget, Göteborg, Sweden).
[0000] 2) Results
[0000] A) Measurement of Body Fat Levels
[0057] We have previously demonstrated that male ERKO and DERKO mice develop a retarded longitudinal bone growth concomitantly with a reduced body weight gain during sexual maturation (Vidal O et al (2000) Proc Natl Acad Sci USA in press). However, two months after sexual maturation, no significant effect on body weight was seen in ERKO and DERKO (4 months of age; WT 33.0±1.1 g, ERKO 31.6±0.9 g, BERKO 31.1±0.6 g, DERKO 33.0±1.6 g). Thus, the 4 months old ERKO and DERKO mice had decreased size of the skeleton while their body weight was unchanged, indicating that they had become obese. Therefore, the serum levels of leptin and total body fat content, as measured with DXA, were followed before, during and after sexual maturation in male wt, ERKO, BERKO and DERKO mice. Neither the total body fat nor serum leptin levels were altered in any group before (1 months of age) or during (2 months of age) sexual maturation ( FIGS. 1-2 ). Specifically FIG. 1 shows total body fat, as measured using dual energy X-ray absorptiometry, in wild type (WT), ERKO, BERKO and DERKO mice before sexual maturation (Prepubertal, 1 month of age), during sexual maturation (Pubertal, 2 months of age) and after sexual matruation (Adult, 4 months of age; n=5-9). Values are given as means±SEM. Data were first analysed by a one-way analysis of variance followed by Student-Neuman-Keul's multiple range test. In FIG. 1 *p<0.05 versus WT, **p<0.01 versus WT. FIG. 2 shows serum leptin levels in wild type (WT), ERKO, BERKO and DERKO mice before sexual maturation (Prepubertal, 1 month of age), during sexual maturation (Pubertal, 2 months of age) and after sexual maturation (Adult, 4 months of age; n=5.9). Values are given as means±SEM. Data were first analysed by a one-way analysis of variance followed by Student-Neuman-Keul's multiple range test *p<0.05 versus WT. In FIG. 2 **p<0.01 versus WT. However, after sexual maturation (4 months of age), ERKO and DERKO but not BERKO demonstrated a markedly increased amount of total body fat as well as increased serum levels of leptin ( FIGS. 1-3 ). FIG. 3 shows DXA/Image analysis of fat content in mice. Four months old male wild type (WT), ERKO, BERKO and DERKO mice were scanned in a DXA, followed by Image analysis as described above. Areas with more than 50% fat are shown as white areas while areas with learn mass and bone are shown as black areas. The increased amount of fat in adult (four month old) ERKO and DERKO mice was also reflected in a pronounced increase in the weight of dissected retroperitoneal and gonadal fat ( FIG. 4 ). In FIG. 4 values are given as means±SEM. Data were first analysed by a one-way analysis of variance followed by Student-Newman-Keul's multiple range test. *p<0.05 versus WT, **p<0.01 versus WT. In contrast a non significant tendency of reduced weight of the retroperitoneal fat pads was found in ERβ inactivated male mice (−37%, p=0.02, FIG. 4 ).
[0000] b) Measure of Metabolic Serum Parameters
[0058] No significant effect in any group was seen on serum levels of insulin, free fatty acids or triglycerides (Table 1).
TABLE 1 Metabolic Serum Parameters 2-way WT ERKO BERKO DERKO ANOVA (n = 6) (n = 9) (n = 6) (n = 5) ERα−/− Corticosterone (ng/ml) 135 ± 34 67 ± 8 139 ± 15 96 ± 35 P < 0.05 NS Insulin (pg/ml) 389 ± 42 352 ± 33 308 ± 12 454 ± 40 NS NS Glucose (mM) 27.9 ± 1.0 30.3 ± 1.0 23.5 ± 0.9* 31.6 ± 2.0 P < 0.01 NS Free Fatty Acids 1.09 ± 0.08 1.32 ± 0.08 1.05 ± 0.12 1.15 ± 0.08 NS NS (mEq/l) Insulin × Glucose 10.9 ± 1.4 11.2 ± 0.9 7.2 ± 0.3* 15.2 ± 1.4* P < 0.01 NS FFA × Insulin 420 ± 44 473 ± 61 323 ± 39 505 ± 32 P < 0.05 NS Cholesterol (nM) 3.22 ± 0.16 3.52 ± 0.23 2.85 ± 0.22 3.55 ± 0.20 P < 0.05 NS Triglycerides (nM) 1.49 ± 0.17 2.18 ± 0.23 1.70 ± 0.35 1.83 ± 0.13 NS NS
[0059] Values are given as means±SEM. Data were first analysed by a one-way analysis of variance followed by Student-Neuman-Keul's multiple range test *p<0.05 versus WT. Furthermore, a 2-way analysis of variance followed by Student-Neuman-Keul's multiple range test was performed, in which ERα−/− and ERβ−/− was regarded as separate treatments. The p-value versus respective +/+allele is indicated. NS=non significant.
[0060] However, the insulin×glucose as well as the insulin×free fatty acid products were increased in the ERα inactivated mice (2 way-ANOVA; Table 1), indicating that these mice are insulin resistant. Furthermore, the serum levels of corticosterone were decreased while serum levels of glucose and cholesterol were increased in mice with ERα inactivated (2 way-ANOVA; Table 1). In order to study the effects on serum cholesterol in more detail, lipoproteins were separated by micro-FPLC and their cholesterol content was determined on-line in 4 months old male wild type (WT), ERKO, BERKO and derko MICE (N=5-9). After separation of 10 μl serum from each animal, cholesterol content in lipoproteins was determined on-line and the absorbance measured at 500 nm. Mean profiles are shown. ( FIG. 5 ). An increased high density lipoprotein (HDL) peak was found in adult male ERKO and DERKO but not in BERKO mice. Interestingly, the ERKO and DERKO mice had a qualitative alteration in the low density lipoprotein (LDL) peak, resulting in an increase of cholesterol in the smaller LDL particles.
[0000] c) Measurement of Gonadal Fat
[0061] Ovariectomized (ovx) mice, lacking one or both of the two known ERs, were given estrogen and the effects on gonadal fat was studied. The effects of estrogen in mice with both ERα and ERβ inactivated (DERKO) were compared with the effects of estrogen in wild type (WT) mice. Estrogen treatment of ovx WT mice resulted in a reduction of gonadal fat mass (Table 1) (Windahl S. H. et al (1999) supra; Daci E. et al (2000) supra; Turner R. T., et al (1994) Endocr Rev, 15, 275; Turner R. T., (1999) supra; Bucher N. L. (1991) J Gastroenterol Hepatol, 6, 615; Clarke A. G. & Kendall M. D. (1994) supra; Couse J. F. & Korach K. S. (1999) supra).
TABLE 2 Effects of Estrogen on Fat Levels Effect of Estrogen (%) ERα/β Parameter WT DERKO Dependent Independent Fat Weight −29.8 ± 333** −2.0 ± 5.2++ 93% 7%
[0062] In Table 2, the left part describes the effects of estrogen on fat in ovx wild type (WT) and DERKO mice. Three months old ovx mice were treated for three weeks with 2.3 μg/mouse/day of 17β-estradiol 5 days/week or olive oil as control (=vehicle). n=7 for WT vehicle, n=7 for WT estrogen, n=7 for DERKO vehicle, n=8 for DERKO estrogen. Values are given as means±SEM and expressed as % increase over vehicle treated animal. **=p<0.01 compared with vehicle treated mice. ++=p<0.01 effect of estrogen in DERKO compared with the effect of estrogen in WT, Student t-test. The right part of Table 2 describes the calculation of estrogen receptor α/β dependent and independent effects of estrogen. The effects of estrogen in WT and DERKO mice, as described in the left part of the table, were used for the calculation of the proportion of ERα/β dependent and independent effects of estrogen. The values are given as % of the total effect seen in WT mice.
[0063] In the present invention, the gonadal fat mass was reduced by estrogen in WT and BERKO mice, but not in ERKO or DERKO mice, demonstrating that ERα is responsible for this effect ( FIG. 6 ). The estrogen hyperresponsiveness in BERKO mice, regarding fat reduction ( FIG. 6 ) may be the result of an unopposed ERα activity.
[0064] While the invention has been described in combination with embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications and variations as fall within the spirit and broad scope of the appended claims. All patent applications, patents, and other publications cited herein are incorporated by reference in their entireties.
|
This invention relates to the field of estrogen receptors and particularly though not exclusively on the effect of estrogen receptors and ligands for estrogen receptors on the prevention or treatment of obesity. The invention also relates to the effect of estrogen receptors and their ligands on lipoprotein levels in mammals.
| 2
|
BACKGROUND
[0001] While wounds heal more effectively in moist environments, bacterial infection poses increased risk. Use of antibiotics to treat bacterial infections can build bacterial resistance. Silver compounds are known to impart antimicrobial effects to a surface with minimal risk of developing bacterial resistance. Silver is delivered to the surface by sustained release of silver ions from the surface when in contact with moist environments, such as a wound bed.
[0002] Silver compositions, such as silver nitrate and silver sulfadiazine, are effective antimicrobials used in a variety of applications. However, they are typically not light stable, leave a stain on skin with which they come into contact, and in the case of silver nitrate, can be quickly depleted in an aqueous environment. Use of silver salts as antimicrobials have included the use of stabilizing agents to increase light stability such as those described in U.S. Pat. No. 2,791,518 (Stokes et al.) (using a first solution of ammonia, silver nitrate and barium nitrate; and a second solution of sodium chloride and sodium sulfate); and in U.S. Pat. No. 6,669,981 (Parsons et al.) (a silver salt in water/organic solvent followed by one or more stabilizing agents (e.g., ammonium salts, thiosulphates, chlorides and/or peroxides)).
SUMMARY
[0003] The present invention is directed to methods of making antimicrobial articles, particularly packaged antimicrobial articles, methods of whitening antimicrobial articles, and packaged antimicrobial articles.
[0004] In one embodiment, the present invention provides a method of making a packaged antimicrobial article. The method includes: preparing a composition comprising silver sulfate; coating the silver sulfate composition on a substrate; drying the coated substrate to form an antimicrobial article; placing the antimicrobial article in packaging material having a volatile organic content of no greater than 100 mg per square meter, and sealing the packaging material with the antimicrobial article therein.
[0005] In another embodiment, the present invention provides a method of whitening at least a portion of an antimicrobial article. The method includes: providing a packaged antimicrobial article having at least a portion colored other than white, wherein the article includes a substrate coated with a silver salt composition including at least a portion of the silver in the zero-valent state, and wherein the antimicrobial article is sealed within packaging material having a volatile organic content of greater than 100 milligrams per square meter (100 mg/m 2 ); and irradiating the packaged antimicrobial article to whiten at least a portion of the antimicrobial article.
[0006] In other embodiments, the present invention provides packaged antimicrobial articles. In one embodiment, a packaged antimicrobial article includes: an antimicrobial article including a substrate coated with a silver sulfate composition; and packaging having the antimicrobial article sealed therein; wherein the packaging comprises material having a volatile organic content of no greater than 100 mg/m 2 .
[0007] In certain preferred embodiments of the present invention, antimicrobial articles are color stable, particularly during and/or after irradiation. In this context, “color stable” means that the color of the dried silver sulfate composition coated on a substrate does not exhibit a significant change in color and/or color homogeneity to the human eye over time (preferably at least 4 hours, more preferably at least 8 hours, even more preferably at least 48 hours, and even more preferably at least 1 week) when compared to the same coated composition on a substrate that has not been exposed to light (e.g., fluorescent, natural, UV). Preferably, “color stable” means that the color of the dried silver sulfate composition coated on a substrate does not exhibit a perceptible change to the human eye over time (preferably at least 4 hours, more preferably at least 8 hours, even more preferably at least 48 hours, and even more preferably at least 1 week) when compared to the same coated composition on a substrate that has not been exposed to light (e.g., fluorescent, natural, UV).
[0008] Color change can be evaluated in a number of ways using a number of grading scales. For example, color change can be evaluated by visual ranking under fluorescent lighting. Samples are compared to color standards and given a rating based on that visual comparison. In this ranking scale, 0, 1, and 2 are classified as “whitish” including white to cream, 3 through 5 are classified as “yellowish” including light yellow to golden yellow, and 6 through 10 are classified as rust to dark brown. Color change is the difference in ratings obtained by subtracting the initial rating from the rating after treatment. Positive ratings represent a darkening in appearance and negative ratings represent a lightening in appearance. A color change on this scale of 1 or less is acceptable as long as the color is substantially homogeneous. If the color is non-homogeneous, even a color change of 0.5 is considered a “significant” and unacceptable change.
[0009] Color change can also be measured using a colorimeter such as a Minolta Chroma Meter (CR-300, manufactured by Konica Minolta Photo Imaging U.S.A., Inc., Mahwah, N.J.) using tristimulus values. A color change on this scale in the “Y” value of 15% or less is acceptable as long as the color is homogeneous. If the color is non-homogeneous, even a color change of 5% in the “Y” value is considered a “significant” and unacceptable change.
[0010] Color change can also be measured using a calorimeter according to ASTM D2244. The resulting CIELAB color difference (DE*), between the sample after exposure for the indicated period of time and the unexposed sample can be determined. For purposes of reference only, a DE*, or color change of about 2 units is just detectable by the naked eye whereas a DE* of 20 or greater represents a substantial or “significant” and unacceptable color change.
[0011] In certain preferred embodiments of the present invention, antimicrobial articles are maintained in an environment of no more than 50% RH (i.e., a water activity of 0.5) at room temperature. In certain preferred embodiments of the present invention, antimicrobial articles are maintained in an environment of no more than 30% RH at room temperature. In this context “room temperature” means an average room temperature, typically 23° C.+/−2° C. “Relative humidity” the ratio of the quantity of water vapor present in the atmosphere to the quantity that would saturate the atmosphere at the given temperature.
[0012] As used herein, “a,” “an,” “the,” “at least one,” and “one or more” are used interchangeably. Also herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).
[0013] The terms “comprises” and variations thereof do not have a limiting meaning where these terms appear in the description and claims.
[0014] The words “preferred” and “preferably” refer to embodiments of the invention that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
[0015] The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. The description that follows more particularly exemplifies illustrative embodiments.
DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS OF THE INVENTION
[0016] The present invention is directed to methods of making antimicrobial articles, particularly packaged antimicrobial articles, methods of whitening antimicrobial articles, and packaged antimicrobial articles.
[0017] In certain embodiments, the antimicrobial articles are prepared using a composition including silver sulfate (e.g., an aqueous-based composition), coating the silver sulfate composition on a substrate, and drying the coated substrate to form an antimicrobial article. The antimicrobial article is placed in packaging material and the packaging material sealed with the antimicrobial article therein. Accordingly, the present invention provides a packaged antimicrobial article that includes an antimicrobial article that includes a substrate coated with a silver sulfate composition, and packaging having the antimicrobial article sealed therein. In certain embodiments, the antimicrobial article sealed in the packaging material is irradiated.
[0018] In certain embodiments, the packaging includes material having a volatile organic content of no greater than 100 milligrams per square meter (mg/m 2 ). In other embodiments, the volatile organic content is no greater than 50 mg per square meter. In this context, the “volatile organic content” is defined by the equation: (mass of packaging material before oven exposure−mass of packaging material after oven exposure)/surface area. This can be determined using ASTM D 2369-03 as described in the Examples Section.
[0019] Useful packaging materials for the present invention may be porous or nonporous, as long as it maintains sterility of the product after sterilization. Useful packages may include one or more layers of materials. There may be one or more packages surrounding a substrate. For example, there may be one or more inner pouches within an outer pouch. In such a situation, the innermost pouch (i.e., the one in direct contact with the antimicrobial article) is preferably porous. Sufficient porosity can allow for transfer of gases released during irradiation of the packaged antimicrobial article. Typically, in such a situation where the innermost pouch is porous, the outermost pouch of the packaging material is nonporous or of very low porosity, particularly with respect to oxygen permeability and moisture vapor permeability.
[0020] In certain embodiments, the packaging includes material having an oxygen permeability of less than 0.01 cubic centimeter per 645 square centimeters per 24 hours. In this context, “oxygen permeability” is defined as the volume of oxygen gas that diffuses through 645 square centimeters (100 square inches) of packaging film during 24 hours. This can be determined using ASTM D3985.
[0021] In certain embodiments, the packaging includes material having a moisture vapor transmission rate (MVTR) of less than 0.01 gram per 645 square centimeters per 24 hours. In this context, the MVTR is the mass of water that diffuses through 645 square centimeters (100 square inches) of packaging film during 24 hours. This can be determined using ASTM F1249.
[0022] Packaging materials having such properties include TPC-0765B/TPC-0760B construction (Tolas Health Care; Feasterville, Pa.) and Techni-Pouch package (Technipaq, Inc., Crystal Lake, Ill.) with a PET (polyester)/Aluminum Foil/LLDPE (linear low density polyethylene) material construction.
[0023] In certain embodiments, the packaging includes a porous material having a Gurley Hill porosity of less than 100 seconds per 100 cubic centimeters of air (100 s/100 cc air). In certain embodiments, the porosity is at least 5 seconds per 100 cubic centimeters of air. Porous packaging materials having this property include those commercially available under the tradename TYVEK such as TYVEK 1073B/TPF-0501A (a TYVEK/film construction) available from Tolas Health Care Packaging, Feasterville, Pa.; and paper/film type packaging construction such as that available under the tradename CONVERTERS Sterilization Pouches (e.g., 3 inch×8 inch (7.5 cm×20 cm) size; Catalog 90308) distributed by Cardinal Health of McGaw Park, Ill.
[0024] In certain embodiments, the packaging material includes an inner pouch and an outer pouch, wherein the inner pouch has a Gurley Hill porosity of less than 100 s/100 cc of air (preferably of 5 s to 100 s/100 cc of air), and the outer pouch has an oxygen permeability of less than 0.01 cubic centimeter per 645 square centimeters per 24 hours and/or a moisture vapor transmission rate of less than 0.01 gram per 645 square centimeters per 24 hours.
[0025] In certain embodiments, an antimicrobial article is made by dissolving silver sulfate in an aqueous-based composition, coating the composition on a substrate, and drying the coated substrate. In certain embodiments, the substrate coated with silver sulfate remains stable to light (e.g., visible, UV) and heat without the addition of traditional stabilizing agents such as ammonia, ammonium salts (e.g., ammonium acetate, ammonium sulfate, and ammonium carbonate), thiosulfates, water insoluble salts of metals (e.g., halides such as chlorides), peroxides, magnesium trisilicate, and/or polymers.
[0026] Preferably, any component that would function as a stabilizing agent is present in amounts less than 100 parts per million (ppm), more preferably less than 50 ppm, most preferably less than 20 ppm, based on the total weight of the silver sulfate composition.
[0027] Alternatively, any component that would function as a stabilizing agent is present in amounts less than 1000 ppm, more preferably less than 500 ppm, most preferably less than 100 ppm, based on the total weight of the antimicrobial article comprising a dried silver sulfate composition coated on a substrate.
[0028] The resultant solution containing the silver sulfate solution can be coated on a substrate, preferably an absorbent substrate, although nonabsorbent substrates can also be used. The coated substrate is dried to drive off the volatile components, such as water and organic solvents (e.g., methanol, ethanol, isopropanol, acetone, or other organic solvents that are miscible with water). Drying can be accomplished at room temperature or by heating the coated substrate. Heat will speed the drying process. In a preferred embodiment, the coated substrate is dried at temperatures below 190° C., more preferably below 170° C., even more preferably below 140° C., to minimize reduction of the silver compounds, and also prevent the oxidation of a cellulosic material, when used as a substrate.
[0029] Further, tensile strength of an oxidizable substrate (such as cotton) is maximized when the silver sulfate composition on the substrate is dried at a low temperature, preferably less that 140° C., more preferable at less than 100° C., and most preferably at less than 70° C.
[0030] Once dried, the substrate remains coated with the silver sulfate. The coated composition typically contains silver sulfate in a major amount. Low levels of silver metal (i.e., zero-valent silver) may be present in amounts, preferably less than 20 wt %, and more preferably, less than 10 wt %, based on the total weight of the silver components in the composition. In some embodiments, the choice of starting materials and drying temperatures results in a coating that leaves no residue with essentially only the silver sulfate remaining on the substrate, and all other components of the silver solution removed from the substrate upon drying.
[0031] When applied, the silver sulfate solution penetrates and impregnates the interior of the substrate. For example, when gauze is used, the silver solution impregnates between the fibers of the gauze.
[0032] The concentration of silver sulfate on the substrate is a function of the amount of silver sulfate in solution, the total amount of solution applied onto a unit area of the substrate, and the drying temperature. The silver sulfate concentration on the substrate is typically less than 30 mg/cm 2 , and in certain embodiments less than 5 mg/cm 2 . In a preferred embodiment, the silver sulfate concentration on the substrate ranges from 0.001 mg/cm 2 to 5 mg/cm 2 , and in certain embodiments from 0.001 mg/cm 2 to 1 mg/cm 2 .
[0033] The substrate can be a woven or nonwoven material (e.g., a gauze) made of natural or synthetic compounds. The substrate can be a porous or nonporous film. It can be a knitted fabric, a foam, or a hydrocolloid, for example.
[0034] In certain embodiments, the substrate is a silver nitrate oxidizable substrate. In certain embodiments, the substrate includes a cellulosic material. Examples of cellulosic materials include polysaccharides or modified polysaccharides, regenerated cellulose (such as rayon), paper, cotton, those materials available under the tradename TENCEL, carboxymethyl cellulose, and the like.
[0035] Other materials may be used, including for example, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl ether, polyacrylate, polyacrylamide, collagen, gelatin, may be used. Non-absorbent substrates may also be used including, but not limited to, nylon, polyester, polyethylene, and polypropylene.
[0036] Other suitable materials for the substrate include polyacrylonitrile, polyvinylidene difluoride, polytetrafluoroethylene, polyoxymethylene, polyvinyl chloride, polycarbonate, styrene-ethylenebutylene-styrene elastomer, styrene-butylene-styrene elastomer, styrene-isoprene-styrene elastomer, and combinations thereof. Other substrate materials are disclosed herein below. Various combinations of materials may be included within the substrate. In certain embodiments, the substrate includes a material selected from the group consisting of a cellulosic material, nylon, polyester fiber, and combinations thereof. In certain embodiments, the substrate includes a cellulosic material. In certain embodiments, the cellulosic substrate includes cotton.
[0037] The method provides a silver sulfate solution for coating on a substrate without using an acid. The presence of acid can hydrolyze the cellulosic material. This aspect of the process allows the coating to be applied without weakening the cellulosic substrate. Preferably the coating solution has a pH of at least 4, more preferably at least 5. Preferably, the coating solution has a pH of no greater than 9.
[0038] Elevated temperatures can also accelerate the oxidation of cellulose by a silver salt, resulting in such affects as lowering the tensile strength and changing the color of the silver sulfate composition on the substrate. The color change on a cellulosic material, such as cotton, is likely due to the reduction of silver salt to silver metal with an accompanying oxidation of the cellulose substrate. The oxidized cotton has lower tensile strength.
[0039] If silver sulfate is coated on a cellulosic substrate or other easily oxidizable substrate (e.g., a silver nitrate oxidizable substrate), the article will change color in proportion to the drying temperature and the time in the drying device, such as an oven. Generally, no color change is observed when the substrate coated with the silver sulfate composition is dried below approximately 100° C. for 15 minutes. For example, when wetted cotton is dried at an oven temperature greater than approximately 100° C., the cotton substrate darkens in proportion to the oven temperature and turns yellow then brown then dark brown.
[0040] If a synthetic substrate such as polyester, which is not easily oxidized, is coated with silver sulfate coating solution and dried, the polyester will remain white even when dried at temperature above 100° C. Similarly, when polyester or other substrate material such as polyester, nylon, polyethylene, polypropylene, polyvinylidene difluoride, polytetrafluoroethylene, polyoxymethylene, polyvinyl chloride, polycarbonate, styrene-ethylenebutylene-styrene elastomer, styrene-butylene-styrene elastomer, or styrene-isoprene-styrene elastomer, is irradiated after being coated with silver sulfate coating solution and dried, the material does not typically change color.
[0041] The silver compositions, once coated, are preferably color stable (i.e., stable to light as defined herein). In addition, preferably the compositions are also stable to at least one of the following: heat and/or moisture. Regardless of substrate choice, preferably the coated silver sulfate composition is color stable. The initial color that the silver sulfate solution develops after drying at a particular temperature will remain without appreciable change over time (e.g., preferably at least 4 hours, more preferably at least 8 hours, even more preferably at least 48 hours, and even more preferably at least 1 week) either with or without exposure to light.
[0042] In certain situations, however, coated silver sulfate will change color. For example, in certain situations, irradiating an antimicrobial article after the article is placed in packaging and the packaging material is sealed will cause a color change. This often occurs when the substrate of the antimicrobial article includes a cellulosic material. The radiation typically includes gamma radiation and/or electron beam radiation. Such radiation is typically used to sterilize the antimicrobial articles. Thus, typical radiation levels include that which is necessary to assure a Sterility Assurance Level of 10 −6 , based on the AAMI Method of Sterility Assurance.
[0043] It has been discovered that this color change upon irradiation can occur in certain situations in standard packaging with a relatively high volatile organic content (i.e., one with a volatile organic content (VOC) of greater than 100 mg/m 2 ). Examples of such standard packaging include that available from Phoenix Healthcare Products, LLC, Milwaukee, Wis., and VP Group, Feuchtwangen, Germany. The use of packaging material having a volatile organic content of no greater than 100 mg/m 2 as described herein, however, in certain situations will reduce, and often eliminate, such a radiation-induced color change.
[0044] Low VOC packaging can be particularly useful when the color of the article is changed from the initial color (e.g., whitish) to a yellowish color, or some color other than a whitish color. Heat can cause a color change to a state that is more stable to irradiation than the initial color. For example, a silver sulfate composition that is dried to a whitish state will darken when irradiated in packaging regardless of the volatile organic content; however, when it is heated to a temperature that causes the color to change to yellowish, this state is generally more stable to irradiation and will typically not change color when irradiated in a low VOC package (i.e., one with no greater than 100 gm/m 2 VOC), particularly when low humidity conditions are used to package the article, although it will in a high VOC package (unless large amounts of substrate material are used relative to the amount of packaging material). For certain embodiments, the present invention provides a method of making a packaged antimicrobial article that includes drying the coated substrate at a temperature that causes the silver sulfate composition to develop a yellowish color (typically due to the formation of silver in the zero valence state during drying), which is color stable during and/or after irradiation (typically, after irradiation, and preferably during and after irradiation). This is particularly true for yellowish articles in low VOC packaging (i.e., no greater than 100 gm/m 2 VOC) during and after e-beam irradiation, or with yellowish articles in low VOC packaging after gamma irradiation (although there may be a color change during gamma irradiation), or with yellowish articles in low VOC packaging during and after gamma irradiation when low humidity packaging conditions are used (e.g., 30% RH or lower).
[0045] Whitish articles are not necessarily as color stable as yellowish articles under similar conditions; however, whitish articles can be color stable in low VOC packaging with activated carbon in the packaging, particularly after e-beam or gamma irradiation. Thus, the present invention provides a method of making a packaged antimicrobial article that includes: preparing a composition including silver sulfate; coating the silver sulfate composition on a substrate; drying the coated substrate occurs at a temperature that causes the silver sulfate composition to develop a whitish color; placing the antimicrobial article in packaging material having a volatile organic content of no greater than 100 mg per square meter; and sealing the packaging material with the antimicrobial article therein; wherein activated carbon is present in the packaging, and further wherein the antimicrobial article is color stable during and after irradiation.
[0046] Low VOC packaging, however, is not necessarily required with a yellowish article when the amount of substrate of the article is greater than 2 mg per interior square centimeter of packaging material. Thus, the present invention provides a color stable packaged antimicrobial article (and a method of making) that includes: an antimicrobial article including a substrate coated with a silver sulfate composition; and packaging having the antimicrobial article sealed therein; wherein the packaging includes material having a volatile organic content of greater than 100 mg per square meter; and wherein the ratio of antimicrobial article substrate to packaging material is greater than 2 mg substrate per interior square centimeter packaging material. The dried coated substrate includes silver in the zero-valent state, has a yellowish color, and preferably is color stable after irradiation.
[0047] The color stability of the coated silver sulfate composition provides several advantages. The color stability provides an indication to the end user that the product is of consistent high quality. Further, the color stability indicates that the form of silver on the substrate has not appreciably changed which indicates that its performance (i.e., silver release, antimicrobial activity) is essentially constant over time in the package (e.g., preferably, at least 1 month, more preferably at least 2 months, even more preferably at least 6 months, and even more preferably at least 1 year). Thus, the use of packaging as described herein is desirable when antimicrobial articles of the present invention are irradiated and such color stability is desirable.
[0048] Such compositions are useful in medical articles, particularly wound dressings and wound packing materials, although a wide variety of other products can be coated with the silver sulfate compositions.
[0049] Stability of the silver sulfate coated substrate is prolonged and/or increased when the relative humidity (RH) at room temperature (particularly during the packaging process) is maintained at 50% or lower; more preferably at 30% or lower; and most preferably at 20% or lower. Relative humidity can be reduced to 30%, and preferably to 20%, or lower, for the silver sulfate coated substrate by a number of methods including: 1) placing the coated substrate in an environment that has a relative humidity of 30% or lower, and preferably 20% or lower, and then packaging the product in the same environment; 2) drying the mesh in an oven, then immediately packaging the mesh; and 3) addition of a desiccant within the package. Preferably, to maintain a low relative humidity in the dried silver sulfate composition, the article should be packaged in a package with a low moisture vapor transmission rate (MVTR) such as a Techni-Pouch package (Technipaq, Inc., Crystal Lake, Ill.) with a PET/Aluminum Foil/LLDPE material construction. Low relative humidity increases the thermal stability of silver sulfate treated cotton.
[0050] In certain situations, it may be desirable to take advantage of the color change irradiation (e.g., gamma radiation and/or electron beam radiation) can cause in packaging with a volatile organic content of greater than 100 mg/m 2 . Thus, the present invention also provides a method of whitening at least a portion of an antimicrobial article. For example, if an antimicrobial article has at least a portion colored other than whitish, wherein the article includes a substrate coated with a silver salt composition including at least a portion of the silver in the zero-valent state, irradiating can whiten the colored portion.
[0051] Silver compounds, including silver sulfate, provide sustained release of silver ions over time based in part on their limited solubility and inherent dissociation equilibrium constants. The silver sulfate composition may have other silver salts, including those that are not color stable, in varying amounts, as long as the composition when coated on the substrate remains color stable. In addition to silver sulfate, other silver compounds that may be coated on a substrate in addition to the silver sulfate include silver oxide, silver acetate, silver nitrate, silver citrate, silver chloride, silver lactate, silver phosphate, silver stearate, silver thiocyanate, silver carbonate, silver saccharinate, silver anthranilate, silver benzoate, and combinations thereof. Silver metal may also be present on the substrate. Preferably, the amount of silver compounds other than silver sulfate is less than 20 wt %, more preferably less than 10 wt %, based on the total weight percentage (wt %) of the silver components in the silver sulfate composition coated on the substrate.
[0052] The silver sulfate coated substrate remains stable when it contains silver sulfate in combination with other silver salts with limited color stability. Preferably, the amount of silver sulfate is at least 60 wt %, more preferably at least 75 wt %, and most preferably at least 90 wt %, based on the total weight percentage (wt %) of the silver components in the silver sulfate composition coated on the substrate.
[0053] Articles can be prepared using the silver solution described herein according to a variety of coating methods. When a porous substrate is coated, the process used typically allows the yarns, filaments, or film such as perforated or microporous film, to be coated, while leaving most of the apertures unobstructed by the composition. Depending on the structure of the support used, the amount of solution employed will vary over a wide range.
[0054] The silver sulfate coating solution can be prepared by mixing silver sulfate and distilled water. The silver sulfate coating solution can have a range of concentrations up to a water solubility of about 0.6% at room temperature. Optionally, higher concentrations of silver sulfate can be obtained by dissolving silver sulfate in hot water. Optionally sulfate in other forms may be added, such as sodium sulfate.
[0055] The process can be accomplished as a continuous process, or it can be done in a single step or with a single coating solution. The process to apply the coating does not require elevated temperatures, and can be applied at temperatures less than 70° C. The coating solution can be maintained below a pH of 9, and preferably less than 7, to minimize adverse effects to the substrate. The coating solution can be maintained at a pH above 4.
[0056] According to a variant of this process, a substrate can be passed through a bath of the silver composition. The substrate covered with the silver sulfate composition is then dried, for example in an oven at a temperature sufficient to evaporate constituents of the solution. The temperature is preferably less than 190° C., more preferably less than 170° C., and most preferably less than 140° C.
[0057] The silver sulfate solution can also be coated onto a carrier web or a backing (described below) using a known coating technique such as gravure coating, curtain coating, die coating, knife coating, roll coating, or spray coating. A preferred coating method is gravure coating.
Medical Articles
[0058] The silver compositions of the present invention can be used in a wide variety of products, although they are preferably used in medical articles. Such medical articles can be in the form of a wound dressing, wound packing material, or other material that is applied directly to or contacts a wound. Other potential products include clothing, bedding, masks, dust cloths, shoe inserts, diapers, and hospital materials such as blankets, surgical drapes and gowns.
[0059] The silver compositions can be coated on various backings (i.e., a support substrate). The backing or support substrate can be porous or nonporous. The composition of the present invention can be coated on the support substrate or impregnated into it, for example.
[0060] Suitable materials are preferably flexible, and may be fabric, non-woven or woven polymeric webs, polymer films, hydrocolloids, foam, metallic foils, paper, and/or combinations thereof. More specifically, cotton gauze is useful with the silver compositions of the present invention. For certain embodiments it is desirable to use a permeable (e.g., with respect to moisture vapor), open apertured substrate (i.e., a scrim). For certain embodiments, the substrate may be a hydrocolloid, such as a hydrophilic polymer, or hydrophobic polymer matrix containing hydrophilic particles, as described in U.S. Pat. App. Pub. Nos. 2004/0180093 and 2005/0124724.
[0061] The substrates (i.e., backings) are preferably porous to allow the passage of wound fluids, moisture vapor, and air. In certain embodiments, the substrates are substantially impervious to liquid, especially wound exudate. In certain embodiments, the substrates are capable of absorbing liquid, especially wound exudate. In certain embodiments, the substrate is an apertured liquid permeable substrate.
[0062] Suitable porous substrates include knits, wovens (e.g., cheese cloth and gauze), nonwovens (including spun-bonded nonwovens, and BMF (blown micro fibers), extruded porous sheets, and perforated sheets. The apertures (i.e., openings) in the porous substrates are of sufficient size and sufficient number to facilitate high breathability. For certain embodiments, the porous substrates have at least 1 aperture per square centimeter. For certain embodiments, the porous substrates have no greater than 225 apertures per square centimeter. For certain embodiments, the apertures have an average opening size (i.e., the largest dimension of the opening) of at least 0.1 millimeter (mm). For certain embodiments, the apertures have an average opening size (i.e., the largest dimension of the opening) of no greater than 0.5 centimeter (cm).
[0063] For certain embodiments, the porous substrates have a basis weight of at least 5 grams/meter 2 . For certain embodiments, the porous substrates have a basis weight of no greater than 1000 grams/meter 2 , and in some embodiments no greater than 200 grams/meter 2 .
[0064] The porous substrates (i.e., backings) are preferably flexible yet resistant to tearing. For certain embodiments, the thickness of the porous substrates is at least 0.0125 millimeter (mm). For certain embodiments, the thickness of the porous substrates is no greater than 15 mm, and for certain embodiments no greater than 3 mm.
[0065] Materials of the backing or support substrate include a wide variety of materials including paper, natural or synthetic fibers, threads and yarns made from materials such as cotton, rayon, wool, hemp, jute, nylon, polyesters, polyacetates, polyacrylics, alginates, etbylene-propylene-diene rubbers, natural rubber, polyesters, polyisobutylenes, polyolefins (e.g., polypropylene polyethylene, ethylene propylene copolymers, and ethylene butylene copolymers), polyurethanes (including polyurethane foams), vinyls including polyvinylchloride and ethylene-vinyl acetate, polyamides, polystyrenes, fiberglass, ceramic fibers, and/or combinations thereof.
[0066] The backing can also be provided with stretch-release properties. Stretch-release refers to the property of an adhesive article characterized in that, when the article is pulled from a surface, the article detaches from the surface without leaving significant visible residue. For example, a film backing can be formed from a highly extensible and highly elastic composition that includes elastomeric and thermoplastic A-B-A block copolymers, having a low rubber modulus, a lengthwise elongation to break of at least 200%, and a 50% rubber modulus of not above 2,000 pounds/square inch (13.8 megapascals (MPa)). Such backings are described in U.S. Pat. No. 4,024,312 (Korpman). Alternatively, the backing can be highly extensible and substantially non-recoverable such as those described in U.S. Pat. No. 5,516,581 (Kreckel et al,).
[0067] In certain embodiments, the coated substrates of the present invention are nonadherent, although it should be understood that an adhesive (e.g., a pressure sensitive adhesive) could be added to an article coated with the solution. As used herein, the silver compositions of the present invention when coated on a substrate do not adhere significantly to wound tissue such that they do not cause pain and/or destruction of the wound tissue upon removal and display a 180° peel strength of less than 1 N/cm from steel, as described in U.S. Pat. App. Pub. No. 2005/0123590.
[0068] In certain embodiments, substrates coated with the silver composition can be covered on one or both sides by a permeable nonadherent outside layer to reduce adhesion and attachment to the wound. The nonadherent layer can be attached to the substrate, such as by coating or laminating. Alternatively, the coated substrate can be enclosed within a nonadherent layer, such as sleeve. The nonadherent layer can be made from nonadherent woven or nonwoven fabrics such as nylon or perflourinated-material coatings on cotton gauze. The nonadherent layer prevents attachment of materials from the enclosed silver coated substrate. At the same time, the nonadherent layer does not adversely affect the sustained release of silver from the coated substrate.
[0069] In another embodiment, the backing or support substrate can be composed of nonadherent material. For example, a nonadherent hydrophilic polymer can be used as the backing or support material, or coated on a permeable porous substrate, as described in U.S. Pat. Pub. Nos. 2004/0180093, 2005/0123590, and 2005/0124724.
[0070] If desired, the coated substrate can be covered with two protective films (for example, thin polyester films). These films optionally may include a nonstick treatment and can function to facilitate extraction from a package and in handling the article. If desired, the coated substrate can be cut into individual compresses, of sizes suitable for the use, packaged in sealed sachets, and sterilized.
[0071] Pressure sensitive adhesives used in medical articles can be used in articles of the present invention. That is, a pressure sensitive adhesive material could be applied to the article of this invention, for example, around the periphery, to adhere the article to the skin.
EXAMPLES
[0072] Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. Unless otherwise indicated, all parts and percentages are on a weight basis, all water is distilled water, and all molecular weights are weight average molecular weight.
Test Protocols
Volatile Organic Content
[0073] Volatile organic content (VOC) can be determined using ASTM D 2369-03. Three pouches were placed in a constant temperature, constant humidity (CTH) room (50% RH 23° C.) for 48 hours (hrs). Six samples were punched out with an 8.9 cm by 8.9 cm die punch for each pouch material. Each sample was weighed with a Mettler balance. Samples were placed polyethylene-side-up on aluminum trays and put in a forced air oven at 110±5° C. for 60 minutes (min). Samples were re-equilibrated in the CTH room for 48 hours and then reweighed.
Color Change
[0074] Color change was evaluated by visual ranking under fluorescent lighting (Philips, F32T8/TL735, Universal/Hi-Vision, E4). Samples were compared to color standards and given a rating based on that visual comparison. Color change was the difference in ratings obtained by subtracting the initial rating from the rating after treatment. Positive ratings represent a darkening in appearance and negative ratings represent a lightening in appearance.
[0075] Samples having color ratings (1-10) of the silver coated cotton samples were also measured using a Minolta Chroma Meter (CR-300, manufactured by Konica Minolta Photo Imaging U.S.A., Inc., Mahwah, N.J.) and gave the following results.
[0000]
TABLE 1
Color Ratings and Measured Color
CIE Tristimulus values
Visual color rating
X
Y
Z
White standard
92.98
94.95
108.54
1
71.9
72.97
52.43
3
59.74
59.48
33.84
4
50.77
50.00
23.68
5
41.92
39.87
23.07
7
28.88
26.82
18.78
8
26.90
24.81
17.22
10
26.4
24.88
19.42
Silver Measurements
Total Silver
[0076] Silver content of dressing was measured using EPA Procedure, EPA 6010B with ICP-AES detection.
Dressing Silver Ion Release
[0077] Silver ion release from dressing after 30 minutes immersion in distilled water was determined using an Ag ion selective electrode (Orion, available VWR International, Batavia, Ill.). Two 3.175 cm diameter discs were cut from the web, weighed, and placed in 98 milliliter (mL) of distilled water and 2 mL of 5M NaNO 3 was added to the amber bottle. The bottle was capped with a TEFLON lined lid and placed on ajar roller. After 30 minutes an ion selective electrode and double junction reference electrode were placed in the solution. The temperature was 21.20° C. The voltage across the electrodes was measured. A standard curve was determined by plotting log (silver ion concentration) versus millivolts (mV) for two standards, 1 microgram (μg) Ag + /mL and 10 μg Ag + /mL and using this curve to determine sample silver ion release by converting mV to silver ion concentration.
Substrate Anion Content
[0078] Anion content of the substrates was made using the following procedure. Extraction: The samples were weighed into 50 mL polypropylene centrifuge tubes, with 25 mL of 18 MΩ water pipetted. The samples were extracted for 24 hours at room temperature, at which time the cotton was removed. The sample was analyzed in triplicate with triplicate blanks using Ion Chromotography(IC).
[0079] IC: Solutions were transferred to 0.7 mL autosampler vials. Next, one 30 μL aliquot was injected from each autosampler vial into a DIONEX DX500 ion chromatograph using an AS3500 autosampler. The DIONEX chromatograph used a GP40 Gradient Pump and EG40 Eluent Generator to establish an eluent (gradient KOH 10-54 mM in 18MΩ water) flow rate of 1 mL per minute. A conductivity detector (ED40), self-regenerating suppressor and columns AS18 (analytical) and AG18 (guard) were used.
[0080] Concentration of extractable anions in units of parts per million (ppm, μg/g) were determined using standard solutions to calibrate the system for fluoride, acetate, formate, chloride, sulfate, bromide nitrate and phosphate.
[0081] Various substrates were evaluated for anion content before coating with silver salts. The anion content was determined using ion chromatography by the procedure described above gave the results in Table 2.
[0000]
TABLE 2
Concentration of extractable anions in units of parts per million (ppm, μg/g).
Sample
Fluoride
Acetate
Formate
Chloride
Sulfate
Bromide
Nitrate
Phosphate
Spuntech
2
31.3
32
588
124
1.2
11.8
ND
Cotton
(±1)
(±0.3)
(±2)
(±6)
(±2)
(±0.2)
(±0.4)
<10 ppm
Unitika
0.9
5.7
11.5
6.9
11.0
3.4
9.7
ND
Cotton-
(±0.3)
(±0.6)
(±0.3)
(±0.1
(±2)
(±0.4)
(±1.0)
<10 ppm
COTTOASE
Example
1.7
11.7
42
44.5
30.8
4.2
5.9
ND
4 non-
(±0.2)
(±1.2)
(±2)
(±0.6)
(±0.9)
(±0.8)
(±0.7)
<10 ppm
woven
Nisshinbo
0.28
32
ND
42
23.8
0.9
13.5
22.9
Cotton
(±0.02)
(±4)
<1 ppm
(±3)
(±0.7)
(±0.2)
(±3.6)
(±0.2)
[0000]
TABLE 3
MATERIALS
DESIG-
NATION
DESCRIPTION
SOURCE/ADDRESS
P-1
Non-peelable pouch
Pheonix
Top: Paper/LDPE (low density
Healthcare
polyethylene)/aluminum/adhesive/
Products, LLC,
LDPE
Milwaukee, WI
Bottom:
Paper/LDPE/aluminum/adhesive/
LDPE
VOC content 166 mg/m 2
To-1
Peelable Foil pouch
Tolas Health Care
Top: TPC-0765B
Packaging,
PET/LDPE/Foil/Ionomer
Feasterville, PA
Bottom: TPC-0760B
PET/LDPE/Foil/LDPE/Peelable
Sealant
VOC content 23 mg/m 2
To-2
Non-Peelable Pouch
Tolas Health Care
Polyester/LDPE/Foil/Ionomer
Packaging,
Top: TPC-0765B
Feasterville, PA
PET/LDPE/Foil/Ionomer
Bottom: TPC-0765B
PET/LDPE/Foil/Ionomer
VOC content 15 mg/m 2
Te-1
Peelable Foil Pouch
Technipaq;
Top: PET/White Opaque PP/
manufactured by
Foil/PE
Technipaq Inc.,
Bottom: PET/White Opaque
Crystal Lake, IL
PP/Foil/Peelable PE
VOC content 25 mg/m 2
Te-2
Non-Peelable Foil Pouch
Technipaq;
Top: PET/White Opaque PP/
manufactured by
Foil/PE
Technipaq Inc.,
Bottom: PET/White Opaque PP/
Crystal Lake, IL
Foil/PE
VOC content 22 mg/m 2
V-1
Peelable Pouch
VP Group,
Top:
Feuchtwangen,
Paper/LDPE/aluminum/adhesive/
Germany
LDPE
Bottom:
Paper/LDPE/aluminum/adhesive/
LDPE/Full Peel Coating
VOC content 258 mg/m 2
ACC
Activated carbon canister
SorbiCap;
Multisorb
Technologies, Inc.
Buffalo, NY; part
number 02-
01803BG02
Example 1
Silver Sulfate Coated High Anion Containing Cotton Substrate
[0082] A silver sulfate coating solution was made by mixing silver sulfate (Colonial Metals Inc., Elkton, Md.) and water to make a 0.1333 gram (g or gm) AgSO 4 per 100 grams water solution. Spunlaced 100% cotton web (50 g/m 2 ; 30.48 cm wide, manufactured by Spuntech Industries, Upper Tiberius, Israel) was coated with a slot die. The pump speed was 316 mL/min. The coated web was dried at 356° F. (180° C.). The oven length was 15.24 meters (m). The web speed was 3.049 m/min. The dried web was golden yellow. It was rolled up and placed in a heat sealable foil pouch. There was 4.7 mg total silver per gram dressing (Method: EPA 6010B using ICP-AES). Silver ion release was determined to be 4.2 milligrams (mg) Ag + /g dressing by the method defined.
[0083] Dressings were die cut and placed into the various packaging materials at a water activity=0.5 and the package heat sealed. The packaged silver dressings were electron beam irradiated at 30 kGy or gamma irradiated at 38 kGy. The samples were stored at room temperature for 1 to 8 weeks before evaluating color change. Table 4 has the results of those evaluations.
[0000]
TABLE 4
Color change of Example 1.
Time
after
Treatment
Pouch Material
Treatment
(weeks)
P-1
Te-1
Te-2
To-1
To-2
E-beam
1
1*
0
1
0
0.5
E-beam
8
0.5*
1
1
0.5
1
Gamma
1
1*
1*
2
1
0.5
Gamma
8
2*
1*
2*
2*
2*
*indicates that the post irradiation dressing was not homogenous in color due to either streaks or edge whitening; pre-irradiation color = 4
Example 2
Silver Sulfate Coated Low Anion Containing Cotton Substrate
[0084] Example 2 dressing was made as in Example 1 except that the spunlaced 100% cotton web was manufactured by Unitika Ltd., Osaka, Japan; under the trade designation COTTOASE, 280 millimeters (mm) wide; grams per square meter (50 gm/m 2 ). This resulted in a dressing with 5.5 mg total silver per gram dressing (Method: EPA 6010B using ICP-AES) and a silver ion release of 3.6 mg Ag + /g dressing was measured by the method in the Test Protocols. The dried dressing was yellow in color.
[0085] Dressings were die cut and placed into the various packaging materials at a water activity=0.5 and the package heat sealed. The packaged silver dressings were electron beam irradiated at 30 kGy or gamma irradiated at 38 kGy. The samples were stored at room temperature for 1 to 8 weeks before evaluating color change. Table 5 has the results of those evaluations.
[0000]
TABLE 5
Color change of Example 2.
Time
after
Treatment
Pouch Material
Treatment
(weeks)
P-1
Te-1
Te-2
To-1
To-2
E-beam
1
0*
0
0
0
0
E-beam
8
−0.5*
0
0.5
0.5
0
Gamma
1
−0.5*
1
1*
2*
0*
Gamma
8
−0.5*
2*
3*
1*
1*
*indicates that the post irradiation dressing was not homogenous in color due to either streaks or edge whitening; pre-irradiation color = 3.
Example 3
Silver Sulfate Coated Low Anion Containing Cotton Substrate
[0086] Example 3 dressing was prepared as in Example 2 except that the drying temperature was 175° F. (79° C.). The dried silver sulfate coated cotton was white. There was 5.3 mg total silver per gram dressing (Method: EPA 60101B using ICP-AES) and the dressing had a silver ion release of 3.5 mg Ag + /g dressing measured by the method in the Test Protocol. Dressings were die cut and placed into the various packaging materials at a water activity=0.5 and an activated carbon canister (ACC) insert was then added and the package heat sealed, packaging with dressing and without insert were also prepared. The packaged silver dressings were electron beam irradiated at 30 kGy or gamma irradiated at 38 kGy. The samples were stored at room temperature for 1 to 8 weeks before evaluating color change. The table shows the effect that the activated carbon present in the packaging has on the white Example 3 dressing material in various packaging materials.
[0000]
TABLE 6
Color change of Example 3.
Time after
Treatment
Pouch Material
Treatment
Insert
(weeks)
P-1
Te-1
Te-2
To-1
To-2
E-beam
None
1
2*
1.5
1.75
1
1.75
E-beam
ACC
1
0.75*
0.5
0.5
0.5
0.5
E-beam
None
8
2*
2
1.5
2
1
E-beam
ACC
8
1*
0.5
0.5
1
0.5
Gamma
None
1
3.5*
4*
5.75*
3
2.75
Gamma
ACC
1
0.75*
1
0.75
0.75
0.75
Gamma
None
8
4*
7*
6*
4*
3*
Gamma
ACC
8
1*
0.5
1
1
0.5
*indicates that the post irradiation dressing was not homogenous in color due to either streaks or edge whitening; pre-irradiation color = 0
Example 4
Silver Sulfate Coated Multi Component Non-Woven
[0087] Silver sulfate coated on substrate was prepared as in Example 1 except that the web was a multicomponent web composed of TENCEL lyocell fiber/Type 254 CELBOND Bicomponent Fiber (PET/Copolyester, 2.0 denier): 95/5. The TENCEL lyocell fiber was manufactured by Lenzing AG. The Type 254 CELBOND Bicomponent Fiber was manufactured by Trevira, Spartanburg, S.C. There was 4.0 mg total silver per gram dressing (Method: EPA 6010B using ICP-AES). The silver ion release was measured as 2.5 mg Ag + /g dressing by the test procedure described in the Test Protocol section.
[0088] The Example 4 dressings were not stable at 8 weeks in the P-1 packaging after electron beam or gamma irradiation at a water activity of 0.5 or at a water activity near 1.
[0089] The Example 4 dressings were stable at 50% RH or 100% RH in the To-1 packaging after electron beam.
Example 5
[0090] A silver sulfate coating solution was prepared by placing 0.289 g silver sulfate and 200 g distilled water in a glass bottle and capping the bottle and shaking at room temperature overnight. The resulting silver sulfate (approximately 1000 μg Ag/g) solution was coated on 100% cotton spunlaced non-woven mesh (COTTOASE, containing less than 20 ppm chloride) by transferring the solution by pipet to saturate the mesh that was contained in a polystyrene dish. Each piece of non-woven mesh (50 grams per square meter (gsm)) was treated with approximately 5.5 g of the solution on a 4.375 inch by 4.375 inch (11.11 cm×11.11 cm) piece of mesh. Approximately one gram of coating solution dripped off of the mesh before the mesh was suspended in the oven for drying. Some additional solution dripped off the mesh in the oven (estimated at 1 g). The coated mesh was dried in a forced air oven (Memmert Universal Oven, available from Wisconsin Oven Company, East Troy, Wis.) by heating at 170° C. for 12 minutes. The color of the samples after drying was golden yellow. The samples were placed in a foil pouch (Tolas Health Care Packaging, TPC-0765B/TPC-0760B construction) after drying and maintained at a relative humidity inside the pouch of less than 25%. Samples were also sealed in the foil pouch after drying and then exposed to gamma irradiation (32.9-33.5 kGy). The samples were removed from the pouches for color measurement at 2 and 29 days after irradiaton. Color CIE tristimulus values of the samples were measured using a Minolta Chroma Meter (CR-300, manufactured by Konica Minolta Photo Imaging U.S.A., Inc., Mahwah, N.J.). The results are shown in Table 7.
[0000]
TABLE 7
Color of Example 5.
Gamma
Days after
Color of
CIE Tristimulus Values
irradiated
Irradiation
Sample
X
Y
Z
No
—
golden yellow
50.6
49.42
21.09
Yes
2
golden yellow
47.21
45.57
20.87
Yes
29
golden yellow
53.53
53.89
28.78
Example 6
[0091] Samples were prepared in same way as Example 5, except substrate was 100% cotton non-woven from Suntec Union, Japan (Nissinbo, AN20601050, 60 gsm). The color of the samples was a uniform golden yellow. The results are shown in Table 8.
[0000]
TABLE 8
Color of Example 6.
Gamma
Days after
Color of
CIE Tristimulus Values
irradiated
irradiation
Sample
X
Y
Z
No
—
golden yellow
42.6
41.3
16.48
Yes
2
golden yellow
45.08
44.29
19.35
Yes
29
golden yellow
38.25
36.58
15.32
Example 7
[0092] Samples were prepared in the same way as Examples 5 and 6 and were then measured for silver release into a solution of distilled water and sodium nitrate using a silver ion selective electrode (Orion, available VWR International, Batavia, Ill.). Sodium nitrate is used as an ionic strength adjustor. The release was measured as described in the Test Protocol Section. The results of these measurements are in Table 9.
[0000]
TABLE 9
Silver Ion Release.
Silver Release
mg Ag+/g
Example
Gamma
Days after
Color of
sample in 30
Number
irradiated
irradiation
Sample
minutes
5
No
—
golden yellow
7.9
5
Yes
2
golden yellow
5.7
5
Yes
29
golden yellow
6.6
6
No
—
golden yellow
4.1
6
Yes
2
golden yellow
4.0
6
Yes
29
golden yellow
3.5
Example 8
[0093] A 40 gram/m 2 spunlaced 100% cotton non-woven substrate was dip coated in a continuous manner into an approximately saturated solution of silver sulfate, squeezed to remove excess coating solution, and then dried at approximately 175° C. The resulting coated substrate contained 6 mg total silver per gram substrate and was golden yellow in color. Four-inch by 8-inch (10 cm×20 cm) samples were cut from the coated substrate, and then folded into 4-inch×4-inch (10 cm×10 cm) two-ply samples. These two-ply samples were then placed into porous packaging (5.75″×9.75″ (14.6 cm×24.8 cm) unprinted Chevron peel pouch; uncoated TYVEK 1073B/TPF-0501A construction; Tolas Health Care Packaging, Feasterville, Pa.; containing a VOC content of less than 50 mg/m 2 ), and the package was heat sealed. Some of these packaged samples were then e-beam irradiated at 21.5-28.9 kGy by Steris Isomedix in Libertyville, Ill., and some of these packaged samples were not irradiated.
[0094] Three packaged samples (either e-beam irradiated or not) were then placed into a second non-porous package (custom made from Technipaq Inc. Crystal Lake, Ill.; zipper pouch with bottom gusset/unprinted; 12.5-inch×10.5-inch×2.5-inch OD (31.8 cm×26.7 cm×6.4 cm); 60 ga Biax Orientated Nylon/A/0.00035 Foil/A/3.5 mil (0.009 cm) Linear Low Density Polyethylene construction) along with one 3.0 gram activated carbon/silica gel (50/50) absorbent sachet (Multisorb Technologies, Inc., Buffalo, N.Y.). After the addition of the packaged samples and the absorbent sachet, the second non-porous package was heat sealed, and then aged at room temperature.
[0095] The samples were removed from both pouches for color measurement at specified aging times as described in Table 10. Color CIE tristimulus values of the samples were measured using a Minolta Chroma Meter (CR-300, manufactured by Konica Minolta Photo Imaging U.S.A., Inc., Mahwah, N.J.). Results are shown in Table 10.
[0000]
TABLE 10
Color of Example 8.
E-beam
Months of
Color of
CIE Tristimulus Values
irradiated
Aging study
Sample
X
Y
Z
No
initial
golden yellow
57.72
57.58
36.63
No
initial
golden yellow
54.79
54.43
31.85
No
initial
golden yellow
56.20
56.00
33.03
Yes
initial
golden yellow
52.16
51.41
29.58
Yes
initial
golden yellow
58.23
58.10
35.88
Yes
initial
golden yellow
56.14
55.85
32.53
No
3
golden yellow
54.65
54.24
32.58
No
3
golden yellow
58.66
58.71
38.30
No
3
golden yellow
58.04
58.07
37.77
Yes
3
golden yellow
56.27
55.99
35.65
Yes
3
golden yellow
59.11
59.10
35.92
Yes
3
golden yellow
58.37
58.27
35.92
[0096] The complete disclosures of the patents, patent documents, and publications cited herein are incorporated by reference in their entirety as if each were individually incorporated. Various modifications and alterations to this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention. It should be understood that this invention is not intended to be unduly limited by the illustrative embodiments and examples set forth herein and that such examples and embodiments are presented by way of example only with the scope of the invention intended to be limited only by the claims set forth herein as follows.
|
A silver composition comprising silver sulfate, methods of making antimicrobial articles, particularly packaged antimicrobial articles, methods of whitening antimicrobial articles, and packaged antimicrobial articles.
| 0
|
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of and claims priority from U.S. application Ser. No. 13/446,275 filed on Apr. 13, 2012, which in turn claims priority under 35 U.S.C. §119 from Chinese Patent Application No. 201110097928.2 filed Apr. 19, 2011, the entire contents of both applications are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention generally relates to information processing technical field, and more particularly, to a method and system for revising user input position.
[0004] 2. Description of Related Art
[0005] With the development of the information technology, the forms of information terminals are numerous. For example, cell phone, navigator, hand computer, pad computer, kiosk, handheld game machine and the like have become popular. However, when a user uses these information apparatuses, there are some bad user experiences. For example, sometimes the user wants to click on an application, but since the position pressed by the finger or the position pressed by the inputter is shifted, undesired applications are clicked on. The time of the user is wasted and thus, creates a bad user experience. It normally needs the user to repeat or carefully click on the desired application, to make the user enters into the correct application. With the wide usage of touch screens, the inconvenient experience of the user becomes an important problem to solve.
[0006] The prior art attempts to improve such experience of the user. In U.S patent application publication No. U.S. 2010/0302212A1, the invention proposes obtaining and setting a series of finger characters from different users' fingers, and then performing characterized operations on the screen according to these characters, such as providing big icons for big fingers, and providing small icons for small fingers, and so on. However, the method needs the user and the software to make a relatively big change, and is not convenient when using it.
[0007] Thus, a method and system for revising user input position is needed.
SUMMARY OF THE INVENTION
[0008] One aspect of the invention provides a method for revising user input position. The method includes detecting input position of a user, revising the input position of the user based on a predefined revising model, to obtain an accurate position, where, a wrong input position of the user is at least analyzed in advance to obtain the revising model, and in response to obtaining the accurate position, triggering an application corresponding to the accurate position.
[0009] Another aspect of the invention provides a system for revising user input position. The system includes a detecting unit, to detect input position of a user, a revising unit, to revise the input position of the user based on a predefined revising model, to obtain an accurate position, where, a wrong input position of the user is at least analyzed in advance by an analyzing unit to obtain the revising model, and a triggering unit, to, in response to obtaining the accurate position, trigger an application corresponding to the accurate position.
[0010] In yet another aspect of the invention provides a computer readable storage medium. The computer readable storage medium tangibly embodies a computer readable program code having computer readable instructions which, when implemented, cause a computer to carry out the steps of a method including detecting input position of a user, revising the input position of the user based on a predefined revising model, to obtain an accurate position, where, a wrong input position of the user is at least analyzed in advance to obtain the revising model, and in response to obtaining the accurate position, triggering an application corresponding to the accurate position.
[0011] With the technology for automatically revising the input position of the user on the touch screen provided by the invention, it is possible to help the user more conveniently locate the needed content, so as to save the time of the user and improve the user experience.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The features and advantages of the embodiments of the invention will be particularly explained with reference to the appended drawings. If possible, the same or like reference number denotes the same or like component in the drawings and the description. In the drawings:
[0013] FIG. 1 shows a first embodiment for revising user input position of the invention;
[0014] FIGS. 2 and 3 show embodiments for analyzing a wrong input position of the user to obtain a revising model;
[0015] FIG. 4 shows a embodiment for analyzing a correct input position of the user to obtain a revising model;
[0016] FIGS. 5 and 6 show distributions of positive and negative samples relative to buttons;
[0017] FIG. 7 shows a preferred embodiment for obtaining the revising model of the invention;
[0018] FIGS. 8 and 9 show a second embodiment for revising user input position of the invention; and
[0019] FIG. 10 shows a structural diagram of a system for revising user input position of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] Below, the exemplary embodiments of the invention will be described in detail with reference to the drawings in which the embodiments of the invention are illustrated, and like reference number always indicates the same element. It should be understood that the invention is not limited to the disclosed exemplary embodiments. It should be also understood that not every feature of the method and apparatus is necessary for implementing the invention to be protected by any claim. In addition, in the whole disclosure, when displaying or describing the process or the method, the steps of the method can be executed in any order or simultaneously, unless it is clear from the context that one step depends on another previously-executed step. In addition, there can be prominent time interval between the steps.
[0021] Every user has a unique fixed usage habit. For example, some users have thick fingers, and in the case of small buttons, in order to clearly see the application corresponding to the accurate position, their input positions to be clicked on often shift down and make errors. This habit is difficult to correct in a short time period. Based on this finding, it is proposed a first embodiment for revising user input position of the invention.
[0022] As shown in FIG. 1 , in step 101 , the input position of the user is detected. The input apparatus can be the information apparatus such as cell phone, navigator, hand computer, pad computer, kiosk, and handheld game machine and so on. Preferably, the input interface is a touch screen of the related apparatus. In these apparatuses, software or hardware for detecting the user's input position has already been installed, which will not be described again. In step 103 , the input position of the user is revised based on a predefined revising model to obtain an accurate position, wherein, a wrong input position of the user is at least analyzed in advance to obtain said revising model. Said revising model is the one which undergoes a sample training in advance, and is stored in a related storage device to correct the input of the user.
[0023] This embodiment obtains shown revising model by at least analyzing the wrong input position of the user in advance, which will be descried in detail in the subsequent preferred embodiments. Due to relative fixed feature of the user's usage habit, such revising model is relatively effective. In step 105 , in response to obtaining the accurate position, an application corresponding to the accurate position is triggered. The adjusted accurate position is used as the input of the user to trigger the application which is desired by the user to launch. The bad user experience due to wrongly clicking can be avoided. The original clicking habit of the user is remained in order to make the user's input natural and smooth.
[0024] FIGS. 2 and 3 show embodiments for analyzing a wrong input position of the user to obtain a revising model. In step 201 , a wrong input position of the user is obtained. In step 203 , a sample set is formed based on an association between the wrong input position of the user and the accurate position. In step 205 , based on the sample set, the revising model is formed. As shown in FIG. 3 , wrong input of the user will follow a certain pattern. The sub-diagram ( 1 ) of FIG. 3 shows a common webpage link list, i.e., (application) Title 1 to Title 7 . The sub-diagram ( 2 ) shows a touch behavior of the user, with the touching area between Title 2 and Title 3 . The sub-diagram ( 3 ) shows a back behavior of the user, that is, after the user finds the response by the system is Title 3 , he re-clicks Back button. The sub-diagram ( 4 ) shows a retouch behavior of the user, that is, after the user learns the lesson of the last touch, the touch of the user is closer to Title 2 . The sub-diagram ( 5 ) shows a loading process of the Title 2 , and the sub-diagram ( 6 ) shows a particular content viewing behavior of the Title 2 .
[0025] Thus, it can be seen that the wrong click of the user follows the pattern of: wrong input position →undesired application→back→accurate position→desired application, in which the accurate position refers to a response area corresponding to the application which is truly desired by the user to use. Such pattern can be used to determine the actions of the wrong input position of the user: obtaining an input position of the user; and in response to obtaining a back action and an action for re-determining the accurate position of the user, determining the input position of the user as a wrong input position. The method for detecting the wrong input position of the user can be realized to monitor the input position path of the user in real time, and can be preferably realized to store the input position path of the user as a log which can be analyzed offline after a certain data is accumulated.
[0026] In order to assure more accurate and complete revising model, FIG. 4 shows a embodiment for analyzing a correct input position of the user to obtain a revising model. In step 401 , a correct input position of the user is obtained. The correct input position should be understood as the input position of the user falling on the accurate position with the user using the related application according to normal operations, according to the above pattern.
[0027] In step 403 , based on an association between the correct input position of the user and the accurate position, a sample set is formed. Such sample set can include samples related to wrong input positions of the embodiment as shown in FIG. 3 (which can be called as negative samples) and samples related to correct input positions (which can be called as positive samples); and in step 405 , based on the sample set, the revising model is formed.
[0028] Below, the method for how the revising model is obtained based on the sample set will be described in detail in combination with FIGS. 5 and 6 . For every button which meets a condition (available triggering area), such as B 1 , B 2 , B 3 and B 4 in FIG. 5 , some positive samples and negative samples are obtained to learn. Here, taking the button B 1 as an example, the example of the positive samples is that the user desires to click on B 1 , and in fact the user clicks on B 1 , such as solid points within the area of the accurate position of B 1 in FIGS. 5 and 6 .
[0029] The example of the negative samples is that the user desires to click on B 1 , but in fact the user does not click on B 1 , but on adjacent area around B 1 , such as hollow points in FIGS. 5 and 6 . It is to be noted that the negative samples can be used only to obtain the revising model, to realize the corresponding technical effect. A rectangular coordinate as shown in FIG. 6 can be built for the button B 1 , and assuming that the set of all the sample points related to the button B 1 is A, the screen coordinate area covered by the button B 1 is R, and the coordinate of a certain sample point p is shown as (x p , y p ), the positive sample coordinates and the negative sample coordinates are defined as follows:
[0000] the positive sample coordinates: P ={( x p , y p )| p ∈A ∪ ( x p , y p ) ∈ R}
[0000] the negative sample coordinates: N ={( x p , y p )| p ∈A ∪ ( x p , y p ) ∉ R}
[0030] The learning process of the revising model is divided into two steps of:
Step 1: Bias Learning of a Single Button
[0031] The learning of this step can be realized by many existing methods, and two particular learning methods are exemplified as follows:
1. Mathematical Expectation
[0032] For the B 1 button as shown in FIGS. 5 and 6 , the simplest mathematical expectation can be used to learn, with the process as follows:
[0033] Input: A=P∪N , i.e., the coordinates of all the positive and negative samples; the coordinate of the centroid point of the button B 1 is
[0000]
(
x
c
,
y
c
)
=
(
1
2
x
b
1
,
1
2
y
b
1
)
,
[0000] x b1 and y b1 are length and width of the button B 1 respectively.
[0034] Output: Δx & Δy.
[0035] The calculation formula is:
[0000]
Δ
x
=
1
A
∑
p
∈
A
(
x
p
x
c
)
Δ
y
=
1
A
∑
p
∈
A
(
y
p
y
c
)
[0036] |A| indicates the number of the sets in the set A. Δx indicates the x coordinate shift of the sequential user input positions to be rectified for the button B 1 . Δy indicates the y coordinate shift of the sequential user input positions to be rectified for the button B 1 .
2. Mean Value Function
[0037] For the B 1 button as shown in FIGS. 5 and 6 , in the case of unchanged input and output, the simple mean value function can be used to learn, with the process as follows:
[0038] Input: A=P∪N , i.e., the coordinates of all the positive and negative samples; the coordinate of the centroid point of the button B 1 is
[0000]
(
x
c
,
y
c
)
=
(
1
2
x
b
1
,
1
2
y
b
1
)
,
[0000] x b1 and y b1 are length and width of the button B 1 respectively.
[0039] Output: Δx & Δy.
[0040] The calculation formula is:
[0000] Δ x =med { x p −x c |p ∈A}
[0000] Δ y =med { y p −y c |p ∈A}
[0041] med indicates taking the mean value of the set.
Step 2: Average Bias Learning of All the Buttons
[0042] Within one screen, there are several available triggering area for several buttons, each available triggering are corresponding to a group of Δx & Δy . The adjustment for the whole screen can take the mean value as follows:
[0000]
Δ
X
=
1
num
(
buttons
)
∑
(
Δ
x
)
Δ
Y
=
1
num
(
buttons
)
∑
(
Δ
y
)
[0043] ΔX indicates the x coordinate adjustment of the sequential user input positions within the scope of the whole screen. ΔY indicates the y coordinate adjustment of the sequential user input positions within the scope of the whole screen. Num (buttons) indicates the number of the buttons which undergo the sample learning in the whole screen. Thus, the samples of a limited number of buttons in the whole screen can be learned, to apply for the whole input screen, thereby improving the efficiency of learning. The revising model can be obtained based on the above obtained adjustment values: (x, y)=(x+ΔX, y+ΔY) , that is, for a sequential user input position (x, y) , it can be revised as its accurate position (x+ΔX, y+ΔY) by the revising model.
[0044] It is to be noted, the person skilled in the art can easily obtain said revising model based on the application and according to other suitable learning model. In addition, the above rectangle “button” from is only exemplary, and the “button” can also be in a form of a line of words or other patterns and so on.
[0045] FIG. 7 shows another preferred embodiment for obtaining the revising model of the invention. In step 701 , an input position path record is received. The input position path record records the input history of the user in a form of log, such as correct inputs and wrong inputs. The input history of one day, one week and even longer can be record as the input position path record. It can be the input position of the user and the time sequence for the function/application. For example, one record is <time n, input position, corresponding function n or application n>, wherein, n is a sequential number.
[0046] In steps 703 and 705 , correct position inputs and wrong position inputs are recognized. Since the determined corresponding function or application has determined accurate position, it only needs to compare the input position with the accurate position to obtain whether the input position of the user is correct or wrong. The respective input positions as samples form a sample set. In step 708 , the revising model is obtained based on said sample set.
[0047] FIGS. 8 and 9 show a third embodiment for revising user input position of the invention. The embodiment is based on the input manner of a screen of an information apparatus. The embodiment is divided into two stages. One stage is the stage for pre-generating revising model, in which in step 801 , the user performs a touch operation by the touch screen, to use various (program) application. In step 803 , the operation of the user is detected, for example in real time or in a form of log, to record the input position path of the user.
[0048] In step 805 , the input position path of the user is quantization-analyzed, to obtain a sample set including positive samples and negative samples. In step 807 , a revising model is obtained based on the sample set. The revising model as shown in FIG. 8 is obtained in advance, and preferably, the revising model can be updated in real time or regularly according to the addition of new samples (new inputs of the user), to adapt to the change of the user's habit.
[0049] The second stage is the stage for revising the input position of the user. In step S 809 , the user performs a new touch operation, in step 811 , the new touch position of the user is detected, in step 803 , the detected touch position is revised as an accurate position according to the obtained revising model, and based on the determined accurate position, in step 815 , the information apparatus triggers the corresponding application according to the accurate position to respond to the new touch operation of the user. As shown in FIG. 9 , the actual touch area of the user is sensed by the information apparatus as Title 3 , and the adjusted touch target is Title 2 .
[0050] Another aspect of the invention provides a system for revising user input position as shown in FIG. 10 . The system includes: a detecting means 1003 , configured to detect input position of a user; a revising means 1005 , configured to revise the input position of the user based on a predefined revising model, to obtain an accurate position, wherein, a wrong input position of the user is at least analyzed in advance by an analyzing means 1001 to obtain said revising model; and a triggering means 1007 , be configured to, in response to obtaining the accurate position, trigger an application corresponding to the accurate position.
[0051] Preferably, said analyzing means 1001 is further configured to obtain the revising model by analyzing a correct input position of the user in advance.
[0052] Preferably, said analyzing means 1001 includes: a wrong position obtaining means, configured to obtain the wrong input position of the user; a sample set forming means, configured to, based on an association between the wrong input position of the user and the accurate position, form a sample set; and a revising model forming means, configured to, based on said sample set, form said revising model.
[0053] Preferably, wrong position obtaining means includes: an user input position obtaining means, configured to obtain an input position of the user; and a wrong input position determining means, configured to, in response to obtaining a back action and an action for re-determining the accurate position of the user, determine the input position of the user as a wrong input position.
[0054] Preferably, the analyzing means 1005 further includes: a user correct input position obtaining means, configured to obtain the correct input position of the user; a sample set forming means, configured to, based on an association between the correct input position of the user and the accurate position, form a sample set; and a revising model forming means, configured to, based on said sample set, form said revising model.
[0055] Preferably, the revising model is formed based on the sample set, and according to one of the Mathematical Expectation Model and the Mean Value Model.
[0056] Preferably, the system further includes: a recorder, for recording an input path of the user.
[0057] Preferably, the system has a touch screen.
[0058] Although the exemplary embodiments of the invention are described here with reference to the drawings, it should be understood that the invention is not limited to these precise embodiments, and the person skilled in the art can make various modifications to the embodiments without departing from the scope and the principle of the invention. All these variations and modifications are intended to be contained in the scope of the invention defined by the appended claims.
[0059] According to the above description, the person skilled in the art will know that the invention can be embodied as a system, a method or a computer program product. Thus, the invention can be implemented in particular in following forms, i.e., a whole hardware, a whole software (including firmwares, residing softwares, microcodes), or a combination of the software parts normally called “circuit”, “module” or “system” in the text and the hardware parts. In addition, the invention can also adopt the form of computer program product in any medium of expression, with computer-usable program codes included in the medium.
[0060] Any combination of one or more computer-usable or computer-readable mediums can be used. The computer-usable or computer-readable mediums can be, but not limited to for example, electric, magnetic, optic, electro-magnetic, infrared, or semiconductor system, apparatus, device or transmission medium. More particular examples of the computer-readable mediums include: electric connection with one or more wires, portable computer disk, hard disk, Random Access Memory (RAM), Read Only Memory (ROM), Erasable Programmable Read Only Memory (EPROM or flash memory), optical fiber, portable Compact Disk Read Only Memory (CD-ROM), optical storage device, such as transmission medium supporting Internet or Intranet, or magnetic storage device.
[0061] It is appreciated that, the computer-usable or computer-readable mediums can be even papers or other suitable mediums with programs printed thereon, because such paper or other mediums can be for example, electrically scanned to electrically obtain the program, and then compiled, interpreted or processed in a suitable manner, and stored in a computer memory as necessary. In the context of this document, the computer-usable or computer-readable medium can be any medium for containing, storing, transferring, transporting, or transmitting programs to be used by instruction execution system, apparatus or device, or to be associated with the instruction execution system, apparatus or device. The computer-usable medium can include data signal embodying the computer-usable program codes, transmitted in the base band or as a part of the carrier. The computer-usable program codes can be transmitted by any suitable medium, including, but not limited to, wireless, wired, cable, RF and so on.
[0062] The computer program codes for performing the operations of the invention can be composed in any combination of one or more programming languages including Object-Oriented programming languages, such as Java, Smalltalk, C++ and so on, and normal process programming languages, such as “C” programming language or like programming languages. The program codes can be executed entirely on the user's computer, partially on the user's computer, as one independent software package, partially on the user's computer and partially on a remote computer, or entirely on the remote computer or a Web server. In the latter case, the remote computer can be connected to the user's computer by any type of network, including Local Area Network (LAN) or Wide Area Network (WAN), or to external computers (by for example the Internet web service provider using Internet).
[0063] In addition, each block of the flowchart and/or block diagram, and the combinations of blocks in the flowchart and/or block diagram of the invention can be realized by computer program instructions, which can be provided to processors of general computers, dedicated computers or other programmable data processing apparatus to produce one machine to enable generating the means for the functions/operations prescribed in blocks in the flowchart and/or block diagram by these instructions executed by the computers or other programmable data processing apparatus.
[0064] These computer program instructions can also be stored in computer-readable mediums capable of instructing computers or other programmable data processing apparatus to operate in a particular manner. Thus, the instructions stored in the computer-readable medium generate a manufacture of instruction means for realizing the functions/operations prescribed in blocks in the flowchart and/or block diagram.
[0065] The computer program instructions can also be loaded into a computer or other programmable data processing apparatus, to enable the computer or other programmable data processing apparatus to execute a series of operation steps, to generate the process realized by the computer, thereby providing a process of realizing the functions/operations prescribed in blocks in the flowchart and/or block diagram in the instructions executed on the computer or other programmable apparatus.
[0066] The flowcharts and the block diagrams in the drawings illustrate the possible architecture, the functions and the operations of the system, the method and the computer program product according the embodiments of the invention. In this regard, each block in the flowcharts or block diagrams can represent a portion of a module, a program segment or a code, and said portion of the module, the program segment or the code includes one or more executable instructions for implementing the defined logical functions.
[0067] It should be also noted that in some implementations as alternatives, the functions labeled in the blocks can occur in an order different from the order labeled in the drawings. For example, two sequentially shown blocks can be substantially executed in parallel in fact, and they sometimes can also be executed in a reverse order, which is defined by the referred functions. It also should be also noted that, each block in the flowcharts and/or the block diagrams and the combination of the blocks in the flowcharts and/or the block diagrams can be implemented by a dedicated system based on hardware for executing the defined functions or operations, or can be implemented by a combination of the dedicated hardware and computer instructions.
|
A method and system for revising user input position. The method for revising user input position includes, detecting input position of a user, revising the input position of the user based on a predefined revising model, to obtain an accurate position, where, a wrong input position of the user is at least analyzed in advance to obtain the revising model and in response to obtaining the accurate position, triggering an application corresponding to the accurate position. With the technology for automatically revising the input position of the user on the touch screen provided by the invention, it is possible to help the user more conveniently locate the needed content, so as to save the time of the user and improve the user experience.
| 6
|
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to the food product art and more particularly to a snack food product combining a pretzel type snack food with a cinnamon bun type snack food.
[0003] 2. Description of the Prior Art
[0004] Snack foods are one of the common type of food products enjoyed by many people as between meal snacks, with meals or in place of meals, as the case may be. Among the many varieties of snack foods are pretzels and cinnamon buns. Both of these types of snack foods have in the past and now are two of the most popular snack foods demanded by the purchasing public. Many shopping malls, strip malls, shopping centers, discount merchandisers and the like often feature separate stores or locations which dispense pretzels and others which dispense cinnamon buns.
[0005] However, there has not heretofore been a single food product which combines the taste composition and configuration of both a pretzel and a cinnamon bun.
SUMMARY OF THE INVENTION
[0006] Accordingly, it is an object of the present invention to provide an improved snack food.
[0007] It is another object of the present invention to provide a snack food having the configuration and composition of both a pretzel and a cinnamon bun.
[0008] It is yet another object of the present invention to provide an improved snack food that may be economially fabricated and configured in the conventional shapes of both a cinnamon bun and a pretzel.
[0009] The above and other objects of the present invention are achieved, in preferred embodiments of the invention, by providing a first elongated dough member which has a first preselected composition such aa a pretzel dough and is formed into the conventional pretzel shape in which there are provided three openings between adjacent portions of the pretzel. It will be understood that other configurations of the first elongated dough member may be utilized in the practice of the present invention. The preferred embodiments described herein are described with reference to the conventional pretzel configuration for convenience of description.
[0010] A second elongated dough member is also provided and the second elongated dough member may have a second composition which maybe, for example, be a cinnamon bun dough. The second elongated dough member is formed in the configuration of a spiral and is positioned within one of the openings formed by the pretzel configuration of the first elongated dough member. The second elongated dough member is retained in the one of the openings of the first elongated dough member's pretzel configuration by frictional forces or by adhesion to the adjacent portions of the first elongated dough member. The adhesion may be accomplished by surface treatment such as the based coating often employed on cinnamon buns or any other desired type of coating utilized on cinnamon buns.
[0011] In other embodiments of the present invention there may be provided both a second elongated dough member and a third elongated dough member positioned, individually, in a first and a second of the openings provided by the pretzel configuration of the first elongated dough member. The third elongated dough member may have the same cinnamon bun composition as the second elongated dough member or, alternatively, the composition of the first elongated dough member.
[0012] In other embodiments of the present invention there may be provided both a second elongated dough member, a third elongated dough member and a fourth elongated dough member positioned in, respectively the first, second and third openings defined by the pretzel configuration of the first elongated dough member. At least one of the first, second and third elongated dough members is composed of a cinnamon bun dough to provide the desired combination of a pretzel and a cinnamon bun.
BRIEF DESCRIPTION OF THE DRAWING
[0013] The above and other objects of the present invention my be more fully understood from the following detailed description taken together with the accompanying drawing wherein similar reference characters refer to similar elements throughout and in which:
[0014] FIG. 1 illustrates a first embodiment of the present invention;
[0015] FIG. 2 illustrates a second embodiment of the present invention;
[0016] FIG. 3 illustrates a third embodiment of the present invention;
[0017] FIG. 4 illustrates a fourth embodiment of the present invention;
[0018] FIG. 5 illustrates a fifth embodiment of the present invention;
[0019] FIG. 6 illustrates a sixth embodiment of the present invention; and,
[0020] FIG. 7 illustrates a seventh embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0021] Referring now to the drawing, there is illustrated in FIG. 1 a first embodiment, generally designated 10 of the present invention. The embodiment 10 is a food product, generally designated 12 . The food product 12 is made from a first elongated dough member 14 . The first elongated dough member 14 has a first preselected composition which may be a pretzel dough. The first elongated dough member 14 is made into the conventional pretzel configuration to define three openings 16 , 18 and 20 between portions of the first elongated dough member 14 . The first elongated dough member 14 has a first end 22 and a second end 24 .
[0022] Positioned within opening 22 is a second elongated dough member 26 having a second preselected composition. The second preselected composition may be a cinnamon bun composition. The second elongated dough member is formed into a spiral configuration for nesting in the opening 20 . The second elongated dough member 26 may be retained in the opening 20 by surface treatment such as by a sugar type coating thereon and/or by frictional forces between the first elongated dough member 14 and the second elongated dough member 26 .
[0023] In a modified form of the embodiment 10 , the second elongated dough member may be made from the same pretzel dough composition as the first elongated dough member 14 . As a further modification, if desired, to the embodiment 10 , the first end 22 , or the second end 24 of the first elongated dough member 14 may be further elongated and twisted into the spiral configuration shown for the second elongated dough member 26 .
[0024] Referring now to FIG. 2 , there is shown an embodiment 50 of the present invention which is similar to the embodiment 10 described above. There is provided a food product 52 having a first elongated dough member 54 similar to the first elongated dough member 14 described above which may be of a pretzel dough composition and is in the configuration of a pretzel and forms the three openings 56 . 58 and 60 . The first elongated dough member 54 also has a first end 55 and a second end 57 . In the embodiment 50 there is a second elongated dough member 62 similar to the second elongated dough member 26 described above and is positioned in the opening 60 . The second elongated dough member 62 may be of the same composition as the first elongated dough member 54 or a different composition such as a cinnamon dough. The second elongated dough member 62 may, if desired be formed from a further elongation of the first end 55 of the first elongated dough member 54 .
[0025] Referring now to FIG. 3 , there is shown an embodiment 70 of the present invention which is similar to the embodiments 10 and 50 described above. There is provided a food product 72 having a first elongated dough member 74 similar to the first elongated dough member 14 described above which may be of a pretzel dough composition and is in the configuration of a pretzel and forms the three openings 76 , 78 and 80 . The first elongated dough member 74 also has a first end 82 and a second end 84 . In the embodiment 70 there is a second elongated dough member 86 similar to the second elongated dough member 26 described above and is positioned in the opening 80 . The second elongated dough member may be of the same composition as the first elongated dough member 54 or a different composition such as a cinnamon dough. The second elongated dough member 86 may, if desired be formed from a further elongation of the second end 84 of the first elongated dough member 54 .
[0026] Referring now to FIG. 4 , there is shown an embodiment 90 of the present invention which is similar to the embodiment 10 , 50 and 70 described above. There is provided a food 92 having a first elongated dough member 94 similar to the first elongated dough member 14 described above which may be of a pretzel dough composition and is in the configuration of a pretzel and forms the three openings 96 , 98 and 100 . The first elongated dough member 94 also has a first end 102 and a second end 104 . In the embodiment 90 there is a second elongated dough member 106 similar to the second elongated dough member 26 described above and is positioned in the opening 96 . The second elongated dough member 106 may be of the same composition as the first elongated dough member 94 or a different composition such as a cinnamon dough. The second elongated dough member 106 may, if desired be formed from a further elongation of the first end 102 of the first elongated dough member 94 . In the embodiment 90 there is also provided a third elongated dough member 108 which may be similar to the second elongated dough member 106 . The third elongated dough member 108 may be of the same composition as the first elongated dough member 94 or a different composition such as a cinnamon dough. The third elongated dough member 108 may, if desired be formed from a further elongation of the second end 104 of the first elongated dough member 94 .
[0027] Referring now to FIG. 5 , there is shown an embodiment 110 of the present invention which is similar to the embodiments 10 , 50 , 70 and 90 described above. There is provided a food 112 having a first elongated dough member 114 similar to the first elongated dough member 94 described above which may be of a pretzel dough composition and is in the configuration of a pretzel and forms the three openings 116 , 118 and 120 . The first elongated dough member. 114 also has a first end 122 and a second end 124 . In the embodiment 110 there is a second elongated dough member 128 similar to the second elongated dough member 108 described above and is positioned in the opening 120 . The second elongated dough member 128 may be of the same composition as the first elongated dough member 114 or a different composition such as a cinnamon dough. The second elongated dough member 128 may, if desired be formed from a further elongation of the second end 124 of the first elongated dough member 114 . In the embodiment 110 there is also provided a third elongated dough member 108 which may be similar to the second elongated dough member 106 . The third elongated dough member 126 which may be of the same composition as the first elongated dough member 114 or a different composition such as a cinnamon dough. The third elongated dough member 126 may, if desired be formed from a further elongation of the first end 122 or the second end 124 of the first elongated dough member 114 .
[0028] Referring now to FIG. 6 , there is shown an embodiment 130 of the present invention which is similar to the embodiment 10 , 50 , 70 , 90 , and 110 described above. There is provided a food 132 having a first elongated dough member 134 similar to the first elongated dough member 114 described above which may be of a pretzel dough composition and is in the configuration of a pretzel and forms the three openings 136 , 138 and 140 . The first elongated dough member 134 also has a first end 142 and a second end 144 . In the embodiment 130 there is a second elongated dough member 146 similar to the second elongated dough member 128 described above and is positioned in the opening 136 . The second elongated dough member 146 may be of the same composition as the first elongated dough member 134 or a different composition such as a cinnamon dough. The second elongated dough member 146 may, if desired be formed from a further elongation of the second end 142 of the first elongated dough member 134 . In the embodiment 130 there is also provided a third elongated dough member 148 which may be similar to the second elongated dough member 146 . The third elongated dough member 148 which may be of the same composition as the first elongated dough member 134 or a different composition such as a cinnamon dough. The third elongated dough member 148 may, if desired be formed from a further elongation of the first end 142 or the second end 144 of the first elongated dough member 114 .
[0029] Referring now to FIG. 7 , there is shown an embodiment 150 of the present invention which is similar to the embodiments 10 , 50 , 70 , 90 , 110 and 130 described above. There is provided a food product 152 having a first elongated dough member 154 similar to the first elongated dough member 134 described above which may be of a pretzel dough composition and is in the configuration of a pretzel and forms the three openings 156 , 158 and 160 . The first elongated dough member 154 also has a first end 162 and a second end 164 . In the embodiment 150 there is a second elongated dough member 166 similar to the second elongated dough member 128 described above and is positioned in the opening 158 . The second elongated dough member 166 may be of the same composition as the first elongated dough member 154 or a different composition such as a cinnamon dough. The second elongated dough member 166 may, if desired be formed from a further elongation of the second end 164 of the first elongated dough member 154 . In the embodiment 150 there is also provided a third elongated dough member 108 which may be similar to the second elongated dough member 106 . The third elongated dough member 168 which may be of the same composition as the first elongated dough member 154 or a different composition such as a cinnamon dough. The third elongated dough member 168 may, if desired be formed from a further elongation of the first end 162 of the first elongated dough member 114 . In the embodiment 150 there is also provided a fourth elongated dough member 170 which may be similar to the second elongated dough member 166 and the third elongated dough member 168 . The fourth elongated dough member 170 may be of the same composition as the first elongated dough member 154 or a different composition such as a cinnamon dough. The fourth elongated dough member 170 may, if desired be formed from a further elongation of the first end 162 or the second end 164 of the first elongated dough member 114 .
[0030] Although specific embodiments of the present invention have been described above with reference to the various Figures of the drawing, it should be understood that such embodiments are by way of example only and merely illustrative of but a small number of the many possible specific embodiments which can represent applications of the principles of the present invention. Various changes and modifications obvious to one skilled in the art to which the present invention pertains are deemed to be within the spirit, scope and contemplation of the present invention as further defined in the appended claims.
|
A food product composed of a first elongated dough member formed into the shape of a pretzel and defining three open spaces and a second elongated dough member formed into a spiral and positioned into at least one of said open spaces and the first dough member is pretzel dough and the second dough member is cinnamon bun dough.
| 0
|
[0001] This application claims the benefit of U.S. Provisional Patent Application No. 60/594,925, filed May 19, 2005.
FIELD OF THE INVENTION
[0002] The invention relates to an air supported impact section for air supported belt conveyors. Specifically, it relates to an improved impact section that minimizes damage to the conveyor belt.
BACKGROUND OF THE INVENTION
[0003] Conventional belt conveyors use idlers to support the length of the belt. The trough formed by the idlers and belt typically has a V-shape cross section for holding the material being carried along the belt conveyor. The V-shape cross section disadvantageously creates a pinch point at the bottom of the V-shape. Conventional belt conveyors also disadvantageously have belt sag between idlers and idler bumping causing material to be thrown up every time it goes over an idler, resulting in dust generations, product separation and degradation.
[0004] At the loading zones where material are loaded onto a belt conveyor, impact resulting from lump size, material density and height of material free fall could seriously damage the belt. In a conventional belt conveyor system, at the impact section, impact idlers are used. Impact idlers are generally cushioned to sustain the impacting force of dropped objects.
[0005] The vertical velocity of the material dropped from various heights above the belt surface and the horizontal belt speed will be different than the speed of the material when it contacts the belt, resulting in greater impact and shearing forces on the belt. Lumpy materials can cause appreciable impact on the belt. The heavier the lump, the greater height of fall or the greater its angular velocity when it contacts the belt, the greater will be the energy tending to rupture the belt. When the material strikes the belt directly over a conventional belt conveyor with idlers, damages to the carcass can result from the crushing action of the lump against the idlers.
[0006] Air supported belt conveyors (ASBC) overcome many of the disadvantages of conventional belt conveyors. As shown in FIG. 1 , an ASBC 1 includes a large air chamber 2 with a curve plenum plate 3 forming the upper section of the air chamber 2 . Along the length of the plenum plate 3 are a plurality of holes 4 . A plenum bed 5 (i.e. belt) rests on top of the plenum plate 3 for holding the material 6 being carried along the ASBC. An ASBC may optionally include a roof cover (not shown). When air is blown into the air chamber 2 , air travels through the holes 4 forming a film of air between the plenum plate 3 and plenum bed 5 . The entire length of the plenum bed 5 and load of the ASBC is fully supported by a thin cushion of air and advantageously prevent belt sag and idler bumping of conventional belt conveyors. The curvature of the plenum plate 3 and plenum bed 5 also advantageously avoid pinching as in conventional belt conveyors. Further, the lack of idlers produces less friction than conventional belt conveyors. Because impact idlers are not used, there is a need for an improved impact section at the loading zone of an ASBC to minimize damage to the ASBC.
SUMMARY OF THE INVENTION
[0007] The present invention is an improved impact section that minimizes damage to the conveyor belt. In particular, an air supported impact section for ASBC.
[0008] The impact section of the present invention includes a cushioned pad incorporated into the plenum plate to cushion the impact force and minimize damage to the plenum plate, plenum bed, roof cover and carcass. The pad may be cast directly into the plenum plate during the manufacturing process. The pad may be made of urethane and absorbs most of the energy from the falling material. The pad has the same catenary curve profile as the plenum plate. A plurality of holes similar in size and spacing as those along the plenum plate are provided along the pad to provide continuous air film to support the plenum bed and load. Materials falling into the improved impact section of the present invention is immediately lifted and exited from the loading zone because the plenum bed is supported by a cushion of air and eliminates damages to both the plenum bed and plenum plate.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] Preferred embodiments of the present invention have been chosen for purposes of illustration and description and are shown in the accompanying drawings forming a part of the specification wherein:
[0010] FIG. 1 shows a cross sectional view of an air supported belt conveyor (ASBC).
[0011] FIG. 2 shows a perspective view of the air supported impact section of the present invention.
[0012] FIG. 3 shows a cross sectional view of the air supported impact section of the present invention.
[0013] FIG. 4 shows a top view of the air supported impact section of the present invention.
[0014] FIG. 5 shows a side view of the air supported impact section of the present invention.
[0015] FIG. 6 shows a perspective view of a removable air supported impact section of the present invention.
[0016] FIG. 7 shows a top view of the removable air supported impact section of the present invention.
[0017] FIG. 8 shows a side view of the removable air supported impact section of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0018] With reference to the drawing wherein the same reference number illustrates the same element throughout, FIGS. 2-5 show an air supported impact section 10 of the present invention for an air supported belt conveyor (ASBC) such as that shown in FIG. 1 . The air supported impact section 10 includes an air chamber 12 with a plenum plate 14 forming the upper section of the air chamber 12 . The plenum plate 14 has a curved profile, e.g. 20, 35, or 45 degrees. The plenum plate 14 has a plurality of equally-spaced holes 16 along the centerline where air is forced from the air chamber 12 . A plenum bed, i.e. belt (not shown), rests on top of the plenum plate 3 for holding the material being carried along the ASBC.
[0019] A section of the plenum plate 14 incorporates a rectangular shaped pad 18 that cushions the impact force from material dropped at the loading zone. The pad 18 may be made from a urethane, neoprene, or polymer material, etc. The pad 18 has the same catenary curve profile as the plenum plate 14 . Similar to the plenum plate 14 , the pad 18 has a plurality of equally-spaced holes 16 along the centerline to allow air to travel through to lift the plenum bed that rests on top of the pad 18 . The pad 18 may be molded directly into an opening of the plenum plate 14 during the manufacturing process. During the molding process of the pad 18 , a cover plate with pins that have the same diameter and spacing as the holes 16 on the plenum plate 14 is used.
[0020] Materials entering the ASBC are first directed to the air supported impact section 10 . The materials are channeled and directed to the pad 18 of the impact section 10 . Immediately after the materials fall onto the plenum bed, the cushion of air between the pad 18 and plenum bed lifts the material to allow the material to exit from the loading zone onto the ASBC, which eliminates damages to both the plenum bed and plenum plate 14 .
[0021] As shown in FIGS. 6-8 , the air supported impact section 10 ′ has a pad 18 ′ that may be removably attached to the plenum plate 14 to facilitate replacement of a damaged or worn pad 18 ′. The pad 18 ′ has a circumferential edge 20 where a plurality of fastening means 22 are provided for removable attachment to an opening 24 of the plenum plate 14 . Fastening means 22 can be rivets, nuts and bolts, clamps, etc.
[0022] The size, shape and location of the pad 18 or 18 ′ on the plenum plate 14 may vary based on the particular application of the ASBC. The air supported impact section 10 or 10 ′ can be used for belt widths from 12″ to 120″.
[0023] Although certain features of the invention have been illustrated and described herein, other better modifications and changes will occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modification and changes that fall within the spirit of the invention.
|
An improved air supported impact section for air supported belt conveyors that includes a cushioned pad incorporated into the plenum plate to cushion the impact form and minimize damage to the air supported belt conveyors.
| 1
|
FIELD OF THE INVENTION
[0001] The present invention relates to materials that are waterproof, insulated and breathable. Such a covering may be used to form sports clothing, such as fishing waders and boots.
BACKGROUND OF THE INVENTION
[0002] Technical developments in the sports clothing industry have resulted in the use of engineered textiles for specialized performances in different sports. With high-functional and smart materials providing a strong focus in the textile industry generally, companies are increasingly looking for ‘value added’ textiles and functional design in sportswear.
[0003] Traditionally, materials that require water resistance plus insulation against the cold include or are entirely comprised of a solid rubber layer, such as neoprene rubber, which is the name for a family of synthetic rubbers based on polychloroprene. This neoprene material, although waterproof cannot ‘breathe’ or vent water vapor, such as warm body moisture (perspiration) of a wearer to the outside.
[0004] When excess body moisture cannot escape, it accumulates within the garment and creates a clammy feeling, can soak the garment (and/or user) with perspiration that leads to discomfort and potential heat loss.
[0005] The following are other known waterproof materials used to manufacture sports clothing, such as waders: expanded PTFE film, i.e. GORE-TEX, and eVENT. While these materials are waterproof, they provide little or no thermal insulation and a user must wear one or more layers of fabric (such as thermal underwear and/or socks) under the material to attempt to stay warm.
SUMMARY OF THE INVENTION
[0006] The invention is a breathable, insulated, waterproof composite material that includes an insulating layer that allows body moisture to escape, or vent from, the material. The material is comprised of more than one layer and preferably includes (1) an insulated layer of open cell foam, (2) a waterproof layer on one side of the insulating layer, and (3) an optional protective layer on the side of the insulating layer opposite the waterproof layer. There may be one or more layers in addition to these layers, and any layer may either be a material, such as natural or synthetic cloth, or a coating applied to a membrane, such as a spray coating. Layers may or may not be attached to adjacent layers.
[0007] Each of the layers utilized in a composite material according to the invention is breathable to allow moisture to escape through the composite material to the outside. At least the waterproof layer is waterproof to prevent penetration by liquid water.
[0008] The insulating layer is an open cell foam and is preferably a polyurethane. Most preferably, the insulating layer is a thermoplastic polyurethane that can be re-shaped (preferably by a thermal molding process) after being formed. The waterproof layer is positioned on a side of the insulting layer towards the outside of the composite material, and is comprised of any suitable material, such as GORE-TEX. The optional protective layer is any suitable, breathable material that offers some protection to the insulating layer, and may be a fleece that wicks moisture.
[0009] In one preferred embodiment, the insulating layer is HYPUR-CEL polyurethane foam, the waterproof layer is expanded PTFE—GORE-TEX (positioned on one side of the insulating layer) and the protective layer is polyester fleece (positioned on the other side of the insulating layer). The resulting composite material could be used in place of neoprene in certain applications. The invention may be used in numerous outdoor covering applications (such as for fishing, biking, backpacking, hiking, or camping). Additional potential markets are military applications (e.g., uses for the Navy) and other commercial or consumer clothing applications such as for offshore oil and gas rigs, underwater salvage, sport and commercial diving, commercial logging, sport and commercial fishing, boating, shipping, emergency response, homeland security and other such applications in which the finished product (whether it is a garment, covering, or other product) are subject to water, cold and/or generally inclimate weather. The composite material may be used in end products such as, but not limited to, fishing waders, waterfowl hunting waders, hunting gear, boots, shoes, socks, hats, gloves, outerwear (such as jackets, coats, pants, bib-overalls, or shells), dive suits, scuba suits, oil rig garments, sailing gear and clothing, horse blankets, dog coats, dog beds, kayak/canoe gear, waterproof mattress pads, tent and/or shelter fabrics, or seating cushions (for example, industrial, vehicle, automotive, office interior, or residential seating.)
[0010] Depending upon the particular embodiment of the invention, the invention may have additional benefits, such as an ergonomic fit because the foam utilized as the insulator can preferably be formed into shapes and may be stretchable, particularly if a thermoplastic (rather than thermoset) foam is utilized.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a cross-sectional view of an embodiment of the invention.
[0012] FIG. 2 is a cross-sectional view of an alternative embodiment of the invention.
[0013] FIG. 3 is a cross-sectional view of an alternative embodiment of the invention.
[0014] FIG. 4 is a cross-sectional view of an alternative embodiment of the invention.
[0015] FIG. 5 includes charts showing the features of some layers that may be included in the invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0016] The term “membrane” or “layer” as used herein means any one of a natural or synthetic fabric, foam, polymer, sheet, film and/or coating. The term “composite material” as used herein means a material constructed of a plurality (i.e., two or more) layers. Each of the various layers in a composite material may or may not be attached to an adjacent layer.
[0017] The term “breathable” as used herein means a membrane comprising a microporous substance that includes pores large enough to allow water vapor molecules (such as in the form of perspiration) to pass through, thus allowing them to move from one side of the membrane to the other (e.g., from the side closest to the user to the outside in order to vent perspiration). Quantatively, breathability is defined herein as any membrane with a water vapor flux greater than 800 gm/m 2 per 24 hours, using a Dynamic Moisture Permeation Cell (DMPC), per test method ASTM F2298. For some applications a vapor flux as high as 10,000 gm/m 2 per 24 hours may be desired.
[0018] The term “waterproof” as used herein means a membrane having micropores (up to millions per square foot) wherein the micropores are smaller than, and usually many times smaller than, a water droplet, thus preventing liquid water molecules from passing through the membrane. Quantatively, waterproof is defined herein as any membrane, such as a natural or synthetic fabric, that resists water penetration at a hydrostatic head of 1500 mm or greater. For some applications, a hydrastatic head rating of 10,000 mm or greater, or 28,000 mm or greater, or 45,000 mm or greater is desirable.
[0019] The invention comprises at least an insulating layer and a waterproof layer. Optionally, a protective layer and/or other layers may be included.
Insulating Layer
[0020] The breathable, insulating layer (sometimes referred to herein simply as “insulating layer”) is an open cell foam that insulates and allows for the transmission of water vapor (such as perspiration) through the open-cell foam. The breathable, insulating layer is preferably constructed from an open-cell foam of a thickness ranging from 0.30 mm to 25.0 mm, although any suitable thickness may be used, depending upon the type of foam and the application for which the resulting composite material will be used.
[0021] The breathable, insulating layer may optionally be of a type that, after being formed, could be molded or otherwise reformed into a 3-dimensional or 2-dimesional configuration to provide added function such as better fit, added or improved functionality, or ease of manufacturing a finished product including the insulating layer. For example, if the composite material were to be used in waders, insulating layer could be first manufactured in sheets and later reformed) to the proper configuration for the boot portion of the wader. If reformed after first being manufactured, the insulating layer may be reformed using any suitable process, such as, but not limited to, thermoforming, thermal-molding, vacuum forming, and/or pressure forming.
[0022] Alternatively, the insulating layer could be initially manufactured (rather than being reformed) in the proper configuration, such as the configuration of a boot or padded knee articulation (pre-creased for ease of bending), or after being initially manufactured could be cut and/or pieced into the proper configuration.
[0023] The breathable, insulating layer is an open-cell foam that is preferably, but not necessarily, a thermoplastic. The layer could also be or include an open cell thermoset material. The most preferred material is a polyurethane (either thermoplastic or thermoset) foam. In preferred embodiments, the breathable, insulating layer comprises one or more of the following: (a) HYPUR-CEL T-Series open-cell polyether-based, thermal formable polyurethane foam from Rubberlite, Inc. (Huntington, W. Va.); (b) HYPUR-CEL S-Series open-cell polyester-based, high elongation thermal formable polyurethane foam from Rubberlite, Inc. (Huntington, W. Va.); (c) HYPUR-CEL H-Series open-cell hybrid polymer, high temperature, non-thermal formable polyurethane foam from Rubberlite, Inc. (Huntington, W. Va.); (d) VISCO-CEL (to include grades VO517, VO525, VO533) open-cell non-thermal formable, visio-elastic polyurethane foam from Rubberlite, Inc. (Huntington, W. Va.); (e) Estane polyether-based open-cell, thermoplastic polyurethane (TPU) foam from Noveon, Inc., a subsidiary of The Lubrizol Corporation (Wickliffe, Ohio); (f) Estane polyester-based open-cell, thermoplastic polyurethane (TPU) foam from Noveon, Inc., a subsidiary of The Lubrizol Corporation (Wickliffe, Ohio); (g) an open-cell polyurethane foam from E-A-R Specialty Composites, Inc., a subsidiary of the Aeraro Company, Inc. (Indianapolis, Ind.); (h) an open-cell polyurethane foam (series 10000, 12000, 19000) from Pro-Tac Industries, Inc. (Quebec, Calif.).
[0024] Following are the properties of some open-cell foams that may be used to practice the invention:
TYPICAL PROPERTIES OF HYPUR-CEL - T0503 (Polyurethane Foam) Flammability FMVSS-302 PASS (.078″ OR THICKER) 1 TEST UNIT OF PHYSICAL PROPERTY METHOD MEASURE RESULT DENSITY ASTM D3574 PCF 3.5-6.5 HARDNESS ASTM D2240 SHORE 0 4 TENSILE STRENGTH ASTM D3574 PSI 45 ELONGATION ASTM D3574 PSI 100 TEAR STRENGTH ASTM D624 LB/IN 5 (Min) COMPRESSION SET ASTM D1056 % 3 (Max) 50% - 22 HRS @ 73° F. COMPRESSION SET ASTM D3574 % — 50% - 22 HRS @ 158° F. COMPRESSION FORCE ASTM D3574 PSI 1-5 DEFLECTION 25% COMPRESSION ASTM D1056 PSI 1-5 DEFLECTION @25% COLOR N/A N/A GREY
[0025]
TYPICAL PROPERTIES OF HYPUR-CEL - T0812
(Polyurethane Foam)
Flammability
FMVSS-302
PASS (.078″ OR THICKER) 1
TEST
UNIT OF
PHYSICAL PROPERTY
METHOD
MEASURE
RESULT
DENSITY
ASTM D3574
PCF
6.5-9.5
HARDNESS
ASTM D2240
SHORE 0
20
TENSILE STRENGTH
ASTM D3574
PSI
75 (MIN)
ELONGATION
ASTM D3574
%
50 (MIN)
TEAR STRENGTH
ASTM D624
LB/IN
5 (MIN)
COMPRESSION SET
ASTM D1056
%
3 (MAX)
50% - 22 HRS @ 73° F.
COMPRESSION SET
ASTM D3574
%
—
50% - 22 HRS @ 158° F.
COMPRESSION FORCE
ASTM D3574
PSI
5-9
DEFLECTION 25%
COMPRESSION
ASTM D1056
PSI
9-15
DEFLECTION
@ 25%
COLOR
N/A
N/A
BLACK
[0026]
TYPICAL PROPERTIES OF HYPUR-CEL - T2040
(Polyurethane Foam)
Flammability
FMVSS-302
PASS (.063″ OR THICKER) 1
TEST
UNIT OF
PHYSICAL PROPERTY
METHOD
MEASURE
RESULT
DENSITY
ASTM D3574
PCF
17-23
HARDNESS
ASTM D2240
SHORE 0
40
TENSILE STRENGTH
ASTM D3574
PSI
150 (MIN)
ELONGATION
ASTM D3574
%
120 (MIN)
TEAR STRENGTH
ASTM D624
LB/IN
25 (MIN)
COMPRESSION SET
ASTM D1056
%
3 (MAX)
50% - 22 HRS @ 73° F.
COMPRESSION SET
ASTM D3574
%
—
50% - 22 HRS @ 158° F.
COMPRESSION FORCE
ASTM D3574 2
PSI
19-25
DEFLECTION 25%
COMPRESSION
ASTM D1056
PSI
30-50
DEFLECTION
@ 25%
COLOR
N/A
N/A
BLACK
[0027]
TYPICAL PROPERTIES OF HYPUR-CEL - T0805
(Polyurethane Foam)
Flammability
FMVSS-302
PASS (.078″ OR THICKER) 1
TEST
UNIT OF
PHYSICAL PROPERTY
METHOD
MEASURE
RESULT
DENSITY
ASTM D3574
PCF
6.5-9.5
HARDNESS
ASTM D2240
SHORE 0
7
TENSILE STRENGTH
ASTM D3574
PSI
65 (MIN)
ELONGATION
ASTM D3574
%
100 (MIN)
TEAR STRENGTH
ASTM D624
LB/IN
6 (MIN)
COMPRESSION SET
ASTM D1056
%
3 (MAX)
50% - 22 HRS @ 73° F.
COMPRESSION SET
ASTM D3574
%
—
50% - 22 HRS @ 158° F.
COMPRESSION FORCE
ASTM D3574
PSI
2-6
DEFLECTION 25%
COMPRESSION
ASTM D1056
PSI
3-7
DEFLECTION
@ 25%
COLOR
N/A
N/A
Grey
[0028]
TYPICAL PROPERTIES OF HYPUR-CEL - S0702
(Polyurethane Foam)
Flammability
FMVSS-302 (TESTED AT .500″)
PASS
TEST
UNIT OF
PHYSICAL PROPERTY
METHOD
MEASURE
RESULT
DENSITY
ASTM D3574
PCF
5.5-8.5
HARDNESS
ASTM D2240
SHORE 0
0
TENSILE STRENGTH
ASTM D3574
PSI
60 (MIN)
ELONGATION
ASTM D3574
%
250 (MIN)
TEAR STRENGTH
ASTM D624
LB/IN
8 (MIN)
COMPRESSION SET
ASTM D1056
%
5 (MAX)
50% - 22 HRS @ 73° F.
COMPRESSION SET
ASTM D3574
%
—
50% - 22 HRS @ 158° F.
COMPRESSION FORCE
ASTM D3574
PSI
.5-3
DEFLECTION 25%
COMPRESSION
ASTM D1056
PSI
.5-3.5
DEFLECTION
@ 25%
COLOR
N/A
N/A
Dark
Blue
[0029]
TYPICAL PROPERTIES OF HYPUR-CEL - S1203
(Polyurethane Foam)
Flammability
FMVSS-302 (TESTED AT .500″)
PASS
TEST
UNIT OF
PHYSICAL PROPERTY
METHOD
MEASURE
RESULT
DENSITY
ASTM D3574
PCF
10-14
HARDNESS
ASTM D2240
SHORE 0
5
TENSILE STRENGTH
ASTM D3574
PSI
90 (MIN)
ELONGATION
ASTM D3574
%
300 (MIN)
TEAR STRENGTH
ASTM D624
LB/IN
15 (MIN)
COMPRESSION SET
ASTM D1056
%
3 (MAX)
50% - 22 HRS @ 73° F.
COMPRESSION SET
ASTM D3574
%
—
50% - 22 HRS @ 158° F.
COMPRESSION FORCE
ASTM D3574
PSI
1-5
DEFLECTION 25%
COMPRESSION
ASTM D1056
PSI
1-5
DEFLECTION
@ 25%
COLOR
N/A
N/A
BLACK
[0030]
TYPICAL PROPERTIES OF HYPUR-CEL - T1515
(Polyurethane Foam)
Flammability
FMVSS-302
PASS (.063″ OR THICKER) 1
TEST
UNIT OF
PHYSICAL PROPERTY
METHOD
MEASURE
RESULT
DENSITY
ASTM D3574
PCF
13-17
HARDNESS
ASTM D2240
SHORE 0
22
TENSILE STRENGTH
ASTM D3574
PSI
120 (MIN)
ELONGATION
ASTM D3574
%
150 (MIN)
TEAR STRENGTH
ASTM D624
LB/IN
15 (MIN)
COMPRESSION SET
ASTM D1056
%
3 (MAX)
50% - 22 HRS @ 73° F.
COMPRESSION SET
ASTM D3574
%
—
50% - 22 HRS @ 158° F.
COMPRESSION FORCE
ASTM D3574
PSI
5-11
DEFLECTION 25%
COMPRESSION
ASTM D1056
PSI
12-18
DEFLECTION
@ 25%
COLOR
N/A
N/A
BLACK
[0031] Some differences of the afore-mentioned HYPUR-CEL foams and some other foams are as follows:
[0032] (1) Thermoplastic vs. thermoset—HYPUR-CEL can be thermoformed or molded into custom shapes, as compared with typical thermoset foam that is often only available as sheet stock, cut from a larger bun;
[0033] (2) open cell foam vs. closed cell—HYPUR-CEL can be manufactured to be breathable due to its open cell structure;
[0034] (3) HYPUR-CEL foam can utilize a polyurethane-based adhesive that is porous and may be used to bond, or laminate the foam to other materials without inhibiting the breathability of the resulting composite. In this manner a foam insulating layer can be bonded to Lycra, polyester, nylon, PTFE, and/or other materials, while maintaining breathability.
[0035] The breathable, insulating layer may be attached to other layers in any manner such as by ultrasonic welding, stitching, chemical lamination, thermal lamination, thermal welding, or a cross-linking lamination. Further, the insulating layer need not be attached to an adjacent layer.
[0036] The insulating layer of open-cell foam may also serve as an energy absorbing layer due to inherent properties of specific foam selected. The insulating layer might serve to protect against shock, vibration, impacts, and in general, absorb energy. The insulating layer could optionally be perforated with one or more openings to provide greater flow of air and water vapor and/or to create a lighter weight construction.
[0037] The insulating layer described herein could be constructed of multiple sub-layers of open-cell foam (thermoplastic and/or thermoset in any combination), wherein each sub-layer could provide a specific characteristic, such as providing thermal performance, a certain porosity or density, or being energy absorbing. One possible construction of such an insulating layer comprising sub-layers would be an insulating layer with two sub-layers of Rubberlite open-cell polyurethane foam, e.g., HYPUR-CEL (thermoplastic/thermoformable) and one sub-layer of VISCO-CEL (thermoset/non-thermoformable). In this embodiment, the HYPUR-CEL would provide a formability characteristic, since after it is manufactured it can be re-shaped (hereafter, “reformed”) utilizing thermoforming techniques. The VISCO-CEL sub-layer would provide the characteristic of being energy absorbing and shock attenuating. By combining the two, the VISCO-CEL sub-layer may be retained in a shape to which the HYPUR-CEL sub-layer is reformed. Both of these foams are open-cell and provide an insulating function. However, the HYPUR-CEL layer would be the major insulator and the VISCO-CEL would be the major energy absorber. These sub-layers could be bonded via an adhesive that is itself open-cell and hence air permeable, or otherwise be retained as part of a material according to the invention in any suitable manner.
Waterproof Layer
[0038] The breathable, waterproof layer may be a single layer of a uniform substance or may be comprised of sub-layers of different substances to provide enhanced function or a combination of functions, e.g., being waterproof while under immersion, stretchable to provide elasticity, lightweight, and/or extended performance under demanding applications.
[0039] The breathable, waterproof layer utilized in the composite material might comprise, but is not limited to, one or more of (a) Musto HPX from Musto Ltd. (Essex, England, UK); (b) Hydrodry P3, or similar formulation, a hydrophilic laminate from Sprayway, Inc. (Manchester, England, UK); (c) Drilite Extreme (DLE), a monolithic, hydrophilic, highly waterproof/breathable and stretchable laminate from Mountain Equipment; (d) HyVent, a polyurethane waterproof/breathable membrane from The North Face, Inc. (San Leandro, Calif.); (e) eVENT, a hydrophobic expanded Polytetrafluoroethylene (ePTFE) and oleophobic membrane from Pearl Izumi, Inc., a subsidiary of Nautilus, Inc. (Vancouver, Wash.); (f) a polymer membrane made from expanded Polytetrafluoroethylene (ePTFE); (g)GORE-TEX ePTFE from W.L. Gore & Associates, Inc. (Newark, Del.); (h) GORE-TEX WINDSTOPPER ePTFE from W.L. Gore & Associates, Inc. (Newark, Del.); (i) GORE-TEX XCR ePTFE; GORE-TEX Classic 2-Layer ePTFE; 0) GORE-TEX Classic 3-Layer ePTFE; (k) GORE-TEX PacLite ePTFE; (1) GORE-TEX Immersion Technology ePTFE; (m) GORE-TEX Ocean Technology ePTFE; (n) H2No waterproof/breathable coating from Patagonia, Inc.; (o) Teslin waterproof/breathable silica-filled porous synthetic film from PPG Industries, Inc.; (p) Breeze Dry-Tec, a waterproof/breathable microporous membrane from Mont-Bell (Osaka, Japan); (q) Dry-Tec, a waterproof/breathable microporous membrane from Mont-Bell (Osaka, Japan); (r) Dry Lite Tec, a waterproof/breathable microporous polyurethane coating from Mont-Bell (Osaka, Japan); or (s) Hydro Breeze, a waterproof/breathable multi-layer microporous polyurethane coating from Mont-Bell (Osaka, Japan), Super Hydro Breeze, a waterproof/breathable multi-layer microporous polyurethane coating from Mont-Bell (Osaka, Japan).
[0040] The breathable, waterproof function may also be derived from the use of a breathable coating, such as a thin layer of resin, applied to a fabric. The breathable coating could be of any suitable type (such as microporous or hydrophilic) or types. Such a breathable, waterproof coating may be TriplePoint Ceramic, a multi-layer waterproof microporous coating from Lowe Alpine, Hydrodry P2, a mixture of hydrophilic coatings and laminates from Sprayway, Inc. (Manchester, England, UK), Entrant II, a multi-layer microporous waterproof coating, or Aquadry (a hydrophobic, multi-layer microporous waterproof coating from Craghopper.)
Optional Protective Layer
[0041] The invention also includes an optional protective layer between the insulating layer and the inner surface of the product that utilizes a composite material according to the invention. The protective layer is preferably a fabric, such as fleece, or could be flocking adhesively bonded to the insulating layer, or could be a spray coating on the insulating layer. One purpose of the protective layer is to protect the insulating layer against abrasion while a finished product including a composite material according to the invention is in use. Optionally, the protective layer could provide a moisture management function by wicking, or transporting, excess water vapor (perspiration) away from the user's body through the multi-layer composite material to the outside, and/or provide added comfort to the user. In that case, if the invention were used as a garment, the protective layer would be on the inside next to the user. Further, the purpose of a layer next to the user could simply be to wick moisture and/or provide added comfort, rather than protect the insulating layer. A wicking layer would provide and assist in transporting water vapor (such as perspiration) away from the user's body and through the composite to the outside of the material. Such a layer, whether used to protect the insulating layer or simply to provide a wicking function and/or comfort may include a moisture-wicking material such as a polyester fleece, for example, PolarTec (manufactured by Malden Mills Industries, Inc.). In that case, this layer would preferably be the surface closest to the user's body.
[0042] For some applications, the protective layer is not required. Further, the open cell foam used as the insulating layer could be durable enough such that a separate protective layer is not required.
Optional Phase Change Materials and Other Optional Agents
[0043] The composite material may include any number of layers other than the insulating layer and waterproofing layers. As previously described, the composite material might include a protective layer or simply a layer to provide moisture wicking and/or comfort to a user.
[0044] Additionally, the composite material according to the invention could include an outer face layer to provide or add abrasion protection and/or a specific appearance. The outer face layer could be of a specific color and/or pattern to meet a specific look or function and may be dye sublimation printed to add a specific color, and or pattern to the outer shell for the purposes of decoration, aesthetics or functions such as camouflage. For example, the outer layer of the composite material may be printed with a RealTree camouflage pattern from Jordan Outdoor Enterprises, Ltd. (Columbus, Ga.), an Advantage camouflage pattern from Jordan Outdoor Enterprises, Ltd. (Columbus, Ga.), or a MossyOak camouflage pattern from Haas Outdoors, Inc. (West Point, Mass.), a Predator camouflage pattern from Predator, Inc. (LaCrosse, Wis.), or a Tru-Woods camouflage pattern from Miller Outdoors, Inc. (Stowe, Pa.).
[0045] The outer, or face, layer may, after being applied, be treated with a durable water repellent (DWR) coating, which could be a polymer coating.
[0046] The outer layer could also be a synthetic fabric comprised of nylon, nylon blend, nylon weave, ballistic nylon, polyester, and/or aramid polymer fiber such as, but not limited to, KEVLAR.
[0047] The composite material may also incorporate phase change material (PCM) for the purpose of thermal management. The PCM could act as a heat reservoir, by absorbing and storing excess body heat as it is generated and then releasing the excess heat when it is needed. The PCM could be incorporated as a coating or in situ to the fibers of any suitable layer. Such a PCM could be Outlast from Outlast Technologies, Inc. (Boulder, Colo.), or Smart Fabric Technology from Outlast Technologies, Inc. (Boulder, Colo.).
[0048] The multi-layer composite construction could also incorporate antimicrobial agents, organic or inorganic, integral to the materials, as a coating or in situ to fabric fibers for the purposes of controlling bacteria.
Conclusion
[0049] The present invention provides a new level of functionality in material construction that can be incorporated in a wide variety of applications.
[0050] Having thus described different embodiments of the invention, other variations and embodiments that do not depart from the spirit of the invention will become apparent to those skilled in the art. The scope of the present invention is thus not limited to any particular embodiment, but may be instead set forth in the appended claims and the legal equivalents thereof. Unless expressly stated in the written description or claims, the steps of any method recited in the claims may be performed in any order capable of yielding the desired product.
|
A composite material that may be used to form, among other things, sports clothing, such as jackets, gloves, boots or fishing waders, is waterproof, breathable and insulated. The composite material includes at least an insulating layer of open-cell foam a waterproof layer on one side of the insulating layer. The composite material also preferably includes a protective layer on the side of the insulating layer opposite the waterproof layer. The composite material may have additional layers on either side or both sides of the insulating layer. The open-cell foam of the insulating layer is preferably, but not necessarily, a thermoplastic that can be re-shaped through the use of a thermal forming process.
| 1
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a polyester composition containing, in a substantially homodisperse distribution, finely divided crosslinked polymer particles which have been prepared in an emulsion-polymerization process and exhibit a narrow grain-size distribution. The polymer particles are incorporated into the polyester during the synthesis thereof.
The invention also relates to molded articles comprising the above-mentioned polyester composition and preferably being in the form of a stretched film, particularly a biaxially stretched film, which may even form part of a multilayer film.
The invention furthermore relates to fibers or filaments formed from the polyester composition according to the invention or comprising an addition of this composition to other polymers.
Moreover, the invention pertains to the use of the film, particularly as a support material for magnetic recording elements or as a capacitor film, and also to the use of the fibers or filaments, preferably in the production of tire cord.
Due to their outstanding properties, polyesters, in particular polyethylene terephthalate or polyester copolymers, which are especially in the form of oriented films, preferably biaxially oriented films, are used in many technical fields, for example, as a dielectric in capacitors, as a support material for video, audio and computer tapes, as stamping foils and the like.
For the various fields of application, polyester films should possess a number of specific properties, and these properties must either be systematically adjusted in the production process or must be pre-formed already in the raw material. Above all, a systematic adjustment of surface properties, particularly of the roughness structure of the surface and of the slip and abrasion behaviors which are connected therewith, must be taken into account, in view of the high processing speeds which are presently employed and in view of the permanent stresses occurring in use.
If the films are intended for use, for example, as supports for magnetic recording elements in audio, video and computer techniques, they must have a uniform and good slip behavior and a high abrasion resistance and, in particular, they must meet especially high requirements in respect of uniformity of surface structure. In particular, relatively large particles should not be present on the film surface, since these will form undesirable elevations, for example, upon coating with a magnetizable layer. When the film is, for example, used as an information carrier, these elevations result in a loss of information and thus limit or affect the usability of the film. Similarly, indesirable elevations produced by coarse particles give rise to difficulties in the metallization of capacitor films. For this purpose, good surface properties are required, which are diminished to a considerable extent by nonuniformity of the pigment.
High requirements regarding uniformity of surface must also be met, when polyester films are used as stamping foils. In other technical applications good transparency of the films is required in the first place.
2. Description of the Prior Art
It has been disclosed in the prior art to overcome or at least alleviate the disadvantages by adding pigments of a very broad grain-size distribution to polymers, in such a way that, for example, the inorganic particles are classified or catalyst precipitation is influenced by the choice of catalysts and by the choice of catalysts and by the choice of the type and quantity of the phosphorus stabilizers which are added in the polyester production.
A detailed summary of the prior art and of the methods employed to overcome the disadvantages in the structuring of film surfaces, by catalyst precipitation or by the addition or inorganic particles, is given in U.S. Pat. No. 4,320,207. U.S. Pat. No. 4,320,207 has proposed to incorporate crosslinked particles into polyester films, in order to improve, in particular, the affinity between the added particles and the polymer matrix, the crosslinked particles being formed by pulverizing a crosslinked polymer having a specific surface area of at least 1 m 2 /g and a pore volume of at least 0.1 ml/g. The described improvements which are achievable with these particles, due to an improved affinity for the polyester--either by filling pre-formed cavities with matrix polymer or by true covalent bond of the particles with the polymer matrix--require great technical expenditure in the preparation of the particles. As disclosed, a porous crosslinked copolymer must be polymerized in an emulsion-polymerization process with the addition of linear polymers and solvents to produce the polymer particles which are described as additives for film-forming polyesters.
Moreover, the organic solvent added and the straight-chain polymeric compound must be extracted to obtain a good grindability and to prevent disturbing foams. It is also necessary to pre-grind the polymer to a grain size of approximately 10 μm in a jet mill. The desired grain-size distribution must, in addition, be adjusted by at least one grinding operation in a pearl mill.
It is still a fundamental disadvantage of this prior art process that--in addition to the great techncial expenditure--the kind of adjusting the grain size of the particles inevitably results in a particular grain-size distribution, involving the problem of oversize grain, i.e. particles which have sizes exceeding the average size.
It is therefore an object of the present invention to provide a polyester raw material containing, in a substantially homodisperse distribution, finely divided crosslinked polymer particles which show a narrow grain-size distribution in the polyester material and possess a good affinity for the raw material; which result in a good distribution upon incorporation into the raw material; and which give a structured surface without any undesirable excessive structures (in the positive and/or negative region), agglomerates or coarse surface elevations, when they are used for the production of molded articles, particularly films which are preferably in a stretched form.
SUMMARY OF THE INVENTION
The object of the invention is achieved by a composition comprising a polyester polymer modified with from 0.005 to 5.0 percent by weight, based upon the total weight of said composition, of crosslinked polymer particles covalently bonded to and substantially homogeneously distributed thoughout said polyester, said particles having a grain size distribution of from 0.02 to 2.0 μm, wherein the quotient of the weight average particle diameter and the number average particle diameter is less than 1.1. The polyester composition of the present invention may be fabricated into heat-set and/or oriented films useful in magnetic recording tape and capacitor film applications. Fibers formed from the polyester composition may be useful as a tire cord.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph of particle grain size distribution.
FIG. 2 is a graph of surface roughness in biaxially oriented polyester film surfaces.
FIG. 3 is a diagram of the surface roughness of a biaxially oriented polyester film surface of the prior art.
FIG. 4 is a diagram of the surface roughness of another biaxially oriented polyester film surface of the prior art.
FIG. 5 is a diagram of the surface roughness of another biaxially oriented polyester film surface of the prior art.
FIG. 6 is a diagram of the surface roughness of another biaxially oriented polyester film surface of the prior art.
FIG. 7 is a diagram of the surface roughness of a biaxially oriented polyester film of the present invention.
FIG. 8 is a photograph of the surface of a biaxially oriented polyester film of the prior art.
FIG. 9 is a photograph of the surface of a biaxially oriented polyester of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Surprisingly, it has been found that crosslinked polymer particles which are appropriate for incorporation into polyester compositions can be produced in a suitable size distribution by an emulsion-polymerization process. It has also been found that the particles used according to the present invention are attained in the emulsion polymerization in a nearly monodisperse distribution, practically free of oversize grain. The emulsions obtained in the preparation process can be added directly in the polyester synthesis, without the need for an expensive grinding or classifying operation, and they result in an excellent distribution in the polymer.
It has furthermore appeared that the molded articles, for example films which preferably are in a stretched form, particularly in a biaxially stretched form, and for the production of which particles according to the invention have been used, have very uniformly structured surfaces showing unform elevations and being free of disturbing elevations which are greater than those determinable by the uniform grain size of the added particles.
Moreover, it has been found that, due to the spherical shape of the crosslinked particles, which is determined by the preparation process, the elevations protruding from the surface of the preferably stretched films, in which these particles have been employed, are also substantially spherically shaped. As a result, an exactly defined surface roughness and an excellent abrasion behavior are obtained.
The crosslinked, covalently incorporated particles make it possible--by the choice of particle concentration in the polyester and by the choice of grain size of the added particles--to structure a surface of a molded article, preferably an oriented film, in such a way that the ratio between the contact area formed by the elevations, e.g. when a film is contacted by rolls, and the area formed by the free space between the elevations can, in any case, be accurately adjusted and that also the distance between the level of the contact area and the level of the free space is adjustable within close limits.
It is, for example, possible to achieve a very high density of peaks at an extremely narrow distribution of heights of peaks. and it is also possible to produce a desired distribution of particle sizes by mixing particles of different sizes, however, in that case, the below-indicated conditions must be complied with.
According to the invention, the polyester composition contains from 0.005 to 5.0 percent by weight of polymeric particles, which have a grain-size distribution in the range from 0.02 to 2.0 μm, the quotient of the weight average particle diameter (D w ) and the number average diameter (D n ) less than 1.1, particularly preferably<1.05. For the determination of D w and D n see U. E. Woods, J. S. Dodge, I. M. Krieger, P. Pierce in "Journal of Paint Technology", Vol. 40, No. 527, 1968, page 545, the disclosure of which is hereby incorporated by reference.
Polyester compositions are to be understood as including polymers which are preferably substantially built up of ethylene terephthalate units and/or preferably up to 30 mole percent of comonomer units, with a possible variation in the glycol component and/or the acid component of the comonomer units. The polyesters can be prepared according to the transesterification process, using conventional catalysts such as, for example, zinc, calcium, lithium and manganese salts and they can also be prepared according to the direct esterification process.
Processes which are known per se and which need not be described in detail, can be employed for the production of polyester films from the above-described raw materials or from a combination of the above polyester polymers with further polymers or additives. The films may be in the form of single layer and also multilayer films which are optionally coextruded and have identically structured surfaces or differently structured surfaces, in which one surface is pigmented and the other surface does not contain any pigment.
Particularly in a multi-stage stretching process involving high stretching ratios in one preferred direction or both in the longitudinal (machine) and transverse directions, for example, in the production of films which meet very high mechanical requirements, the advantages of the covalently incorporated particles according to the invention become especially effective. It is also possible to employ stretching processes which include the following stretching sequences: longitudinal-transverse-longitudinal, simultaneous (longitudinal/transverse) and multiple stretching in one or both directions.
In the present invention, the nearly monodisperse, crosslinked polymer particles corresponding to the above-indicated data, which have been prepared in an emulsion-polymerization reaction and carry incorporated reactive groups, are particularly advantageously introduced, as early as possible, into the polyester synthesis, for example, advantageously at the beginning of the transesterification reaction or, in the case of direct esterification, at the beginning of the esterification reaction.
It is particular advantage of the present invention that the crosslinked polymer particles which are present in the dispersion obtained in the emulsion polymerization can directly be introduced into the polymer synthesis, without the need for expensive size-reduction, classification, filtration and purification processes. For this purpose, ethylene glycol is, for example, added to the aqueous dispersion from the polymerization reaction or is added at the beginning or during the polymer-production process.
The crosslinked particles can be prepared in an emulsion-polymerization process in such a way that a crosslinked or non-crosslinked latex is initially present or is produced in situ, and the primary particles are increased to the desired particle size in one or several stages, by causing to swell and polymerizing a further monomer or a monomer mixture.
The emulsion polymerization can be conducted with or without the addition of an emulsifying agent. The conventionally used emulsifiers can be employed for emulsifying and stabilizing the latex, for example, anionic emulsifiers, such as alkyl sulfates, alkylaryl sulfates, alkylaryl sulfonates, alkali metal salts and/or ammonium salts of alkyl or alkylarylpolyglcolether sulfonates, as well as non-ionic emulsifiers, such as oxethylated fatty alcohols and alkyl and alkylaryl phenols.
Preferably, the amount of emulsifier is kept as low as possible. Particularly preferred production processes are those which can be carried out without emulsifiers and protective colloids.
Examples of comonomers which can optionally be used in the polyester include unsaturated non-ionic monomers, such as the ester of acrylic and methacrylic acids, for example, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, preferably methyl methacrylate and butyl acrylate, the diesters of unsaturated dicarboxylic acids, such as maleic acid dialkyl ester, unsaturated vinyl compounds, such as styrene and vinyl toluene, unsaturated nitriles, such acrylonitrile and methacrylonitrile, functional monomers, such as unsaturated carboxylic acids, for example, methacrylic acid, acrylic acid, maleic acid, crotonic acid, itaconic acid, monomers containing hydroxyl groups, such as hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, n-methylol methacrylamide, monomers containing epoxy groups, for example, glycidyl methacrylate and allylglycidyl ether, unsaturated sulfonic acids, such as ethane sulfonate or acrylamidopropane sulfonic acid.
The crosslinked particles are obtained by polymerizing ethylenically unsaturated monomers in an aqueous system in the absence of emulsifiers and protective colloids, using free-radical initiators which are partly or completely soluble in water, it being necessary, at least at the start of polymerization, for a polyethylenically unsaturated compound to be present in the polymerization mixture in an amount of more than 0.01% by weight, based on the total amount of monomer. It is possible to obtain thereby polymer dispersions which are free from emulsifiers and protective colloids and have an average particle diameter between 0.05 and 2.0 μm and and a particle size distribution D w /D n <1.05.
The emulsion polymers can be obtained from the aqueous polymer dispersions in a dry powder form free from emulsifiers and protective colloids by removal of water. The removal of water can be effected, for example, by spray drying, freeze-drying or thin-film evaporation. Spray drying is preferred.
Corresponding non-aqueous polymer dispersions which are free from emulsifiers and protective colloids can be obtained either by carrying out the polymerization in a homogeneous mixture of water and a water-miscible non-aqueous phase as the dispersing medium, or by mixing the water-miscible, non-aqueous phase with the aqueous dispersion when polymerization is complete, and in either case subsequently removing the water more or less completely from the mixture. This can be effected, for example, by distillation. Vacuum distillation is particularly preferred.
Crosslinked particles free from emulsifiers and protective colloids may be prepared by the free-radical initiated emulsion polymerization of ethylenically unsaturated, copolymerizable monomers, which comprises first subjecting to preliminary polymerization, in the absence of emulsifiers and protective colloids and using one or more water-soluble, free-radical forming initiators in an aqueous emulsion, an amount or partial amount of the polyethylenically unsaturated, copolymerizable monomer of at least 0.01% by weight, preferably 0.01 to 20% by weight, particularly preferentially 0.02 to 10% by weight and especially 0.1 to 5% by weight, based on the total amount of monomers, if appropriate on its own or, preferably, together with a partial amount of the monoethylenically unsaturated monomers of preferably 0.5 to 40% by weight, particularly preferentially 1 to 30% by weight and especially 1.5 to 15% by weight, based on the total quantity of monomers, and then metering in the residual amount of the monoethylenically unsaturated monomer and, if appropriate, the residual amount of the polyethlenically unsaturated monomer and, if appropriate, the residual amount of initiator, completing the polymerization of the mixture and, if appropriate, subsequently isolating the polymers from the resulting dispersion.
The content of disperse, polymeric solids in the resulting polymer dispersions is preferably 20 to 55% by weight, especially 25 to 45% by weight, based on the dispersion.
The process can be carried out discontinuously or continuously.
The particles are preferably in the form of a dispersion or a dry powder. They can, however, also constitute shaped articles, especially film.
Examples of crosslinking components which may be used for the particles which are to be incorporated are polyethylenically unsaturated compounds, such as diallyl phthalate, divinyl benzene, butanediol dimethacrylate, ethanediol dimethacrylate, hexanediol dimethacrylate, ethanediol diacrylate, butanediol diacrylate, hexanediol diacrylate, pentaerythritol triacrylate, trimethylol propane triacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate and trimethylol propane trimethacrylate.
The use of the polyethylenically unsaturated compounds discussed above surprisingly makes it possible, inter alia, to achieve high solids contents during the emulsion copolymerization, and, at the same time, to achieve, in the finished dispersion, a very good stability against coagulation of the batch. A content of at least 0.01% by weight, based on the total quantity of monomers, of one of the crosslinking components discussed above in the quantity of monomer initially taken is required for this purpose, at least during the starting phase of the polymerization. The amount of polyethylenically unsaturated monomers, based on the total amount of monomers, should, in general, preferably be between 0.01 and 20% by weight, particularly preferentially 0.02-10% by weight and especially 0.02-5% by weight.
Hydroxyethyl methacrylate, acrylic acid and methacrylic acid are particularly suitable examples of the components which carry functional groups and which are incorporated by polymerization into the particles, in order to form covalent bonds between the polyester matrix and the crosslinked particles, preferably in the polyester synthesis.
The degree of crosslinking of the particles can be varied within wide limits, by the composition and particularly by the amount of the crosslinking component. It is thus possible to produce particles which have a soft, rubber elastic consistency and also particles which have a hard, brittle, highly crosslinked structure.
Examples of preferred monomer combinations are acrylate or methacrylate monomers as monoolefinically unsaturated compounds, and divinylbenzene as a poly-unsaturated compound. Examples of particularly preferred combinations are those comprising methyl methacrylate, butyl acrylate and divinylbenzene; or styrene, butyl acrylate and divinylbenzene; or styrene, methyl methacrylate and divinylbenzene; or methyl methacrylate, butyl acrylate, divinylbenzene, methacrylic acid and/or acrylic acid; or styrene and divinylbenzene; or styrene, acrylonitrile and divinylbenzene; or vinyl acetate and butanediol dimethacrylate; or methyl methacrylate, butyl acrylate and butanediol dimethacrylate; or acrylonitrile and divinylbenzene; or vinyl chloride and divinylbenzene.
The composition of the monomers should preferably be selected so that the content of hydrophilic monomers, such as, for example, acrylic acid, methacrylic acid, acrylonitrile, hydroxyethyl methacrylate, glycidyl methacrylate, maleic acid, maleic acid half-ester and the like is not more than 25% by weight, preferably <15% by weight, based on the total amount of monomers. The polymerization liquor is stirred at the stirring speeds customary for emulsion polymerizations, for example at 10-200, preferably 3-100, r.p.m.
Dispersions of organic polymer particles can, for example, preferably be prepared in the following manner: 0.01 to 10% by weight of a water-soluble, radical-forming initiator, preferably 0.02-5% by weight and particularly preferentially 0.05-3.0% by weight, based on the total amount of monomers in the batch, is added to an aqueous system containing one or more types of ethylenically unsaturated monomers, of which 0.1-100% by weight, preferably 0.5-60% by weight and particularly preferentially 1-40% by weight, based on the amount of monomers initially taken, must be polyethylenically unsaturated monomers, and the polymerization is started, for example by thermolytic decomposition of the free-radical initiator. Instead of initially taking the total amount of the initiator, it is also possible initially to take, in the aqueous liquor, only a fraction of the initiator, preferably 1-90% by weight, particularly preferentially 5-70% by weight and especially 10-60% by weight, based on the total amount of the initiator, and to meter in the residual amount subsequently as an aqueous solution together with the still outstanding amount of monomers.
The proportion of monomers in the polymerization mixture initially taken, at the start of the polymerization reaction in this mixture which is designated as preliminary polymerization, is preferably 0.01-30% by weight, particularly preferentially 0.1-25% by weight and especially 1-20% by weight, based on the total amount, initially introduced, of aqueous phase and non-aqueous monomer phase.
The duration of the preliminary polymerization is between 0.1 minute and 3 hours, preferably 0.5 minute to 2 hours and particularly preferentially 1 minute to 1 hour. The polymerization temperature is usually within a temperature range at which the initiator or the initiator system has a half-life time of decomposition between 20 minutes and 15 hours. After the completion of the preliminary polymerization, the amounts still outstanding of the monomer(s) and, if appropriate, the residual initiator are metered into the polyerization batch. The rate of metering in the monomer(s) and, if appropriate, the residual initiator should be adjusted to match the decomposition rate of the initiator or the initiator system in such a way that monomer does not float or settle out during the polymerization.
The emulsion polymerizations according to the invention are preferably carried out within an acid pH range of less than pH 7, preferably at pH 1 to 5.
The molecular weight of the polymers can be reduced in a known manner by the use of molecular weight regulators. Mercaptans, halogen-containing compounds and other radical-transferring substances are preferably used for this purpose. Butyl mercaptan, octyl mercaptan, dodecyl mercaptan, tetrakismercaptoacetylpentaerythritol, chloroform, carbon tetrachloride, trichloroethylene, trichlorobromomethane, bromoform and toluene are particularly preferred. Water-soluble peroxides, azo compounds or redox systems are preferably employed as radical-forming initiators. Examples of particularly preferred systems are sodium, potassium or ammonium peroxydisulfate or sodium, potassium or ammonium peroxydisulfate redox systems containing sulfides, sulfites or other reducing agents. Radical-forming initiators which are readily and completely soluble in water are preferred. The amount of the radical-forming initiator is preferably 0.01 to 10% by weight, particularly preferentially 0.02-5% by weight and especially 0.05-3.0% by weight, based on the total amount of monomers.
The particle size of the polymer particles can, inter alia, be influenced by the nature of the monomers used and their solubility behavior in water, and also by the nature and amount of the water-soluble, radical-forming initiator used or by the mode in which it is metered in, and also by the nature and the amount used of the polyethylenically unsaturated comonomers which result in polymeric crosslinking reactions, and also the nature and amount of the monoethylencially unsaturated compounds which may be copolymerized with these comonomers in the preliminary polymerization and, in some cases, also in the main polymerization.
In order to obtain non-aqueous dispersions according to the invention which are free from emulsifiers and protective colloids, either the polymerization described above is carried out in a mixture of water and an inert, non-aqueous organic compound, or, after polymerization has been carried out in an aqueous phase, an adequate quantity of a non-aqueous organic compound or a mixture of such compounds is added and the water is removed. These water-soluble organic compounds are preferably organic compounds containing OH groups or mixtures of such compounds. Glycolic compounds or mixtures thereof with water-miscible organic compounds, or in some cases also with water-immiscible further organic compounds, are very particularly preferred. Thus dispersing media composed of ethylene glycol or of mixtures containing ethyene glycol are very particularly preferred for the use of the polymer dispersions for pigmenting, for example, polyester compositions which can be used, for example, for the production of films, fibers or filaments.
The water-miscible, non-aqueous dispersing medium or the water-miscible, non-aqueous, liquid phase preferably contains inert, water-soluble organic compounds which contain hydroxyl groups and in which the OH groups can be completely or partly substituted, preferably etherified or esterified. Compounds containing unsubstituted OH groups are preferred. Polyhydric alcohols, in particular dihydric alcohols, such as glycols or polyglycols, and also polyglycol ethers in which the free hydroxyl groups can in some cases be substituted, are particularly preferred.
As inert, non-aqueous constituents, the dispersing medium can contain, for example, the following: monoalcohols, such as methanol, ethanol, isopropanol, butanol, amyl alcohols, iso-C 13 alcohol, lauryl alcohol, oleyl alcohol or butyldiglycol, monoesters or diesters of glycol or polyglycols with lower carboxylic acids, ethylene glycol, propylene glycol, glycerol, glycerol esters or partial esters, glycerol ethers, butylene glycol, phenol or alkylphenols. In removing the water of the dispersion by distillation it is preferable to use non-aqueous constituents having a boiling point higher than the boiling point of water. Ethylene glycol is particularly preferred.
Water is preferably expelled from mixtures containing ethylene glycol by distillation under normal pressure or in vacuo. The use of entraining agents or ternary mixtures can be particularly advantageous when removing water by distillation. The water content remaining in the resulting dispersion depends on the end use of the dispersion, for example on the water-sensitivity of the system which is to be pigmented with the polymer particles. However, as the water content rises, both the viscosity and the density of the resulting dispersion can fall which in both cases promotes the tendency to settle out and thus can have an adverse effect on the stability to storage.
The water content aimed at in the "non-aqueous" polymer dispersion is, therefore, preferably less than 20% by weight, particularly preferentially less than 10% by weight and very particularly preferentially less than 5% by weight, based on the dispersion.
It is an advantage of the present invention that the crosslinked particles are not soluble or fusible during the polymer synthesis and retain their original volume, even when the polyester is subjected to repeated melting operations in the production of molded articles, in particular in the production of films, or in the reworking of scrap.
If crosslinking is sufficient, the spherical shape of the particles, which has substantially been obtained in the preparation process is generally maintained and, as a result, the molded articles, preferably films, also have spherical elevations on their surfaces, particularly in the case of balanced stretching. With the aid of less crosslinked, i.e. ductile particles, it is, however, also possible to produce a surface with flattened elevations.
The advantages of the raw materials according to the present invention and of the molded articles, preferably films, produced therefrom reside in the fact that it is possible to obtain, in a simple manner, highly uniform surface structures without disturbing, relatively large elevations which might cause difficulties in the further processing and/or use.
A good abrasion resistance of molded articles is especially achieved by the covalent incorporation of the structuring particles. Due to the excellent, nearly homodisperse distribution of the crosslinked particles in the polyester, very regularly structured surfaces can be attained at high concentrations of the added particles. The dense packing and uniform height of the elevations result in a honeycombe-type structure, in which the depressions existing between the elevations enclose small air cushions and thus produce a favorable slip behavior, when the molded articles, preferably films, slide at high speed.
The high quality films which are, for example, produced according to the present invention can thus be employed in many technical fields. They are, for example, particularly suitable for use as support materials to which metal is applied by vapor-deposition or which are provided with thin coatings and which are used in video, audio and computer techniques, or as capacitor films, stamping foils and separating films.
The Figures which accompany the specification clearly illustrate the advantage of the present invention over the prior art.
EXAMPLES
The Examples which follow illustrate the practice and advantage of the present invention in comparison to the prior art. As Examples they are illustrative only, and do not limit the scope of the invention in any manner
Measurements were made as follows:
Grain-size distribution:
1. Using a Coulter Counter, Model IIA, manufacturer Coulter Electronics,
2. by means of an aerosol-spectrometer for extremely finely divided particles.
In each case, the distribution of mass=distribution of volume was recorded, taking the spherical shape as a basis.
d 50 =central value of grain-size distribution
GS 1 =grain size determined for 1% residue or 99% passed, respectively
GS 10 =grain size determined for 10% residue
GS 10 /GS 90 =narrowness of the curve of grain-size distribution.
Surface roughness of the films:
1. By Gould measurements,
2. using a Perthometer for measuring the R z value (average peak-to-valley roughness, determined as the mean value of the individual peak-to-valley roughnesses of five mutually adjoining individual measurement lengths, cf. DIN 4768),
R t value (maximum peak-to-valley roughness between the highest and lowest points of the roughness profile).
By an interference method it is possible to control in a simple manner, whether coarse elevations are present.
Surface structure of the films:
Photographs taken by transmitted light,
Microphotographs taken with the aid of a scanning electron microscope.
FIG. 1 shows the extremely narrow grain-size distribution of the polymer particles used according to the present invention, in comparison to ground particles according to the state of the art.
FIG. 2 shows the R z distribution in biaxially stretched polyethylene terephthalate film and thus also the uniformity of surfaces, compared to the prior art.
FIGS. 3 to 6 depict Gould recordings of biaxially stretched polyethylene terephthalate films according to the state of the art (U.S. Pat. No. 4,32,207). These diagrams were recorded by means of an instrument which mechanically scans the surface of the film to be examined, producing electrical pulses in the process, which are passed on to an amplifier and from there to a recorder. Amplification was adjusted in such a way that 1 cm in the direction of the curves proceeding from left to right corresponds to a measurement length of 100 μm on the the film surface; vertically, in the direction of the distance between the curves which are arranged one beneath the other, 1 cm in the figures similarly corresponds to a measurement length of 100 μm on the film surface; in the direction normal to the plane of the recording, i.e. in the direction of the elevations shown, 1 cm in the figures corresponds to an elevation of 0.5 μm on the measured film surface. The figures clearly show the irregularities on the surfaces, which are caused by extremely protruding peaks (oversize grain).
FIG. 7 shows the particular uniformity of a biaxially stretched polyethylene terephthalate film produced from a raw material of the present invention. Amplification is identical to that chosen in the measurements of FIGS. 3 to 6.
FIG. 8 is a copy of a photograph showing the surface of a biaxially stretched polyethylene terephthalate film produced from a raw material containing pulverized polymer particles according to the state of the art (U.S. Pat. No. 4,320,207). In the photograph, the coarse peaks of the pigment are clearly recognizable.
FIG. 9 is a copy of a photograph showing the surface of a biaxially stretched polyethlyene terephthalate film produced from a waw material of the present invention. In comparison to the film according to FIG. 8, this photograph displays the uniformity of the surface of the film of the invention, which is free of oversize grain.
While the examples recited above illustrate a polyester composition comprising polyethylene terephthalate, the present invention is not so limited since--as is explained herein--the particles prepared by emulsion polymerization can also be used in other polyesters.
|
This invention pertains to a polyester composition containing finely divided polymer particles in a substantially homodisperse distribution. The polymer particles are prepared in an emulsion-polymerization process and are crosslinked.
The polymer particles exhibit an extremely narrow grain-size distribution and are incorporated into the polyester during the synthesis thereof.
The invention also relates to films, particularly stretched films, which are produced from the polyester composition and which can also be used as base films for the production of composite films.
It is additionally also possible to produce filaments and fibers from the composition according to the invention or with the addition of this composition to other polymers.
The films are preferably used as bases for magnetic recording elements or for capacitors, and fiber or filaments are employed in the production of tire cord.
| 8
|
TECHNICAL FIELD
[0001] This invention relates generally to flexible expansion joints and, more particularly, to a method and apparatus for limiting the axial extension and compression thereof.
BACKGROUND OF THE INVENTION
[0002] Expansion joints are commonly installed in piping systems such as those used in the chemical processing industry, and in the air conditioning, heating, plumbing, refrigerating and ventilating fields. The purposes of such a joint are to provide flexibility for accommodating expansion and contraction due to pressure and temperature variations, and for damping vibrations to thereby reduce noise. In the absence of such an expansion joint in a piping or ducting system, the vibrations and the pressure and thermal changes can produce stress on the system at fixed points such as at vessels and rotating equipment, as well as in the piping or ductwork system itself.
[0003] Typically, an expansion joint includes a fluid conducting flexible body member secured between a pair of spaced flanges, with the combination then being interposed within a length of pipe or duct. The flexible body member may be in the form of a metal bellows, a Teflon bellows or an elastomeric spherical arch.
[0004] Recognizing that under certain conditions, the assembly can be expanded or contracted beyond the allowable limits of safe operation, provision has been made to axially restrain such motion. This has customarily been accomplished by a pair of limit rods that are axially mounted on opposite sides of the joint and connected at their opposite ends to the flanges or to gusset plates attached to and extending radially outwardly from the coupling flanges. Overextension was prevented by fasteners attached to the limit rods on the axially outer sides of the flanges. Compression of the unit was limited by fasteners located on the axially inner sides of the flanges or by way of a pipe sleeve disposed over each of the tie rods.
[0005] Because of the rigidity of the tie rods, and the relative inflexibility of the combination during installation within a system, some expansion joints are now being assembled without tie rods but with a flexible link, such as a cable, interconnecting the spaced flanges. One such arrangement is shown in U.S. Pat. No. 5,273,321. While such an arrangement provides for limited expansion of the joint, it does not prevent the joint from being compressed beyond the allowable limits. Further the need to secure the cables to the flanges complicates the process.
[0006] What is needed is an expansion joint that is flexible for installation purposes but which is limited in its axial movement in operational conditions of both expansion and contraction.
DISCLOSURE OF THE INVENTION
[0007] Briefly, in accordance with one aspect of the invention, a cable is secured between two gussets by simply extending the cable through one opening in each gusset and then back through another opening therein, with the ends being secured together by a single crimping device.
[0008] In accordance with another aspect of the invention, compression of the assembly is limited by a sleeve which is disposed over one strand of the cable, with the other strand being outside of the sleeve to facilitate the crimping process.
[0009] In the drawings as hereinafter described, a preferred embodiment is depicted; however, various other modifications and alternate constructions can be made thereto without departing from the true spirit and scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is an elevational view of a typical piping installation with expansion joints in accordance with the prior art.
[0011] FIG. 2 is a front view, partially in cross section, of an expansion joint in accordance with the prior art.
[0012] FIG. 3 is a perspective view of one embodiment of the present invention.
[0013] FIG. 4 is an alternative embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0014] A typical fluid flow pumping and piping arrangement is shown in FIG. 1 which includes a pump 11 fluidly connected to an intake pipe 12 by a flange connection 13 and to a discharge pipe 14 by way of a flange connection 16 . The pump 11 , although securely fastened to the foundation 17 will tend to transmit some motion to the intake pipe 12 and discharge pipe 14 by vibrations and the like. Support for the piping is provided by way of anchor structures 18 and 19 which are supported by the foundation 17 and by anchor structures 21 and 22 which are securely fastened to vertical support structures within the building.
[0015] In addition to the movement as caused by vibrations as discussed hereinabove, thermal and pressure differences will tend to cause the piping system to expand or contract. That is, as the temperature and/or pressure of the fluid being pumped through the system rises, the piping system will tend to expand, and as they are lowered, the piping system will contract. To accommodate that expansion and contraction, a pair of expansion joints 23 and 24 are installed within the piping system, on either side of the pump 11 . The structure of the expansion joints 23 and 24 is set forth in more detail in FIG. 2 .
[0016] Fluidly interconnected between sections of pipe 12 is a fluid conducting flexible body member 26 with appropriate end fittings to match the adjoining pipe fittings. The particular member as shown is a so called bellows design which is formed as a thin walled tubing to form a corrugated cylinder with a plurality of convolutions as shown. Such a member is commonly made from metal (e.g. stainless steel) or Teflon, for example.
[0017] The present invention is also applicable to other types of expansion joints. For example, one type of flexible joint commonly used with plastic piping systems is not bellows shaped as shown but rather is formed of a molded spherical flowing arch that is made from an elastomeric material. Although different in structure, these expansion joints also require some type of structure to limit the expansion and contraction of the joint.
[0018] The flexible body member 26 is disposed between and connected to a pair of axially spaced flanges 27 and 28 with the interconnection between the flexible body member 26 and the flanges 28 being such that, as the body member 26 expands or contracts, the flanges 27 and 28 are accordingly caused to move toward or away from each other.
[0019] Disposed near the radially outer edges of the flanges 27 and 28 are a pair of radially, circumferentially spaced axially disposed tie rod pins 29 and 31 and their associated nuts 32 and 33 . The tie rods pins 29 and 31 pass through holes formed in the respective flanges 27 and 28 and the respective nuts 32 and 33 are so positioned on the respective pins 29 and 31 , such that clearance spaces 34 and 36 allow for some axial (i.e. outward) movement of the flange 28 but limit the extent to which this can occur. This distance can be selectively adjusted to meet the requirements of the particular expansion joint and application.
[0020] In order to limit the movement of the flanges 27 and 28 toward each other, and therefore limit the compression of the expansion joint, a pair of nuts, similar to the nuts 32 and 33 , can be selectively placed on the inner sides of the respective flanges 27 and 28 . Another approach is to place a pair of sleeves 37 and 38 over the respective tie rods pins 29 and 31 as shown, with the lengths of the sleeves 37 and 38 being generally shorter than the distance between the two flanges 27 and 28 . In this way, the flanges 27 and 28 are free to move inwardly, toward each other, to thereby allow for contraction of the body member 26 but this movement is limited when the inner surfaces of the flanges 27 and 28 begin to impinge on the ends of the sleeves 37 and 38 .
[0021] A variation of the FIG. 2 approach is to provide for two or more radially outwardly extending gussets to be attached to the flanges 27 and 28 and, rather than extending the pins 29 and 31 through the flanges 27 and 28 , extending the pins 29 and 31 through openings in the gussets.
[0022] Use of tie rod pins 29 and 31 as discussed hereinabove is problematic in some situations. For example, since the tie rod pins are installed on the assembly at the factory and shipped to the site for installation, even though the pins 29 and 31 and their associated nuts 32 and 33 are not adjusted to their final position, the assembly is very rigid in nature and presents difficulties in the process of aligning the expansion joint and securing it in its installed position between two pipe sections. Further, there is often very little space in which to work such that final adjustments and the selective positioning of the nuts 32 and 33 can be difficult.
[0023] Referring now to FIG. 3 , a pair of axially spaced flanges 39 and 41 are shown with radially outwardly extending gussets 42 and 43 attached thereto. The gussets 42 and 43 are secured by way of a plurality of bolts 44 passing through openings 46 . For illustrative purposes, the gusset 42 is shown to be installed on the inner side of the flange 39 , and the gusset 43 is shown to be attached on the outer side of the flange 41 . Although this is a possible arrangement, a more likely installation would be for the two gussets to be on the inner sides of their respective flanges or on the outer sides thereof.
[0024] Near the radially outer end of the gusset 42 is a pair of spaced holes 47 and 48 . Similarly, near the radially outer end of the gusset 43 is a pair of spaced holes 49 and 51 . These holes are used for attachment purposes.
[0025] Rather than the use of tie rod pins, the gussets 42 and 43 are interconnected by a cable 52 having two strands 53 and 54 . The first strand 53 passes into holes 48 and 51 , wraps around the outer surfaces of the respective gussets 42 and 43 , and then comes back through holes 47 and 49 . The second strand 54 results from the two ends being fastened together by one or more fastening devices 56 such as a crimping device. The result is a double stranded cable which is easy to install either at the factory or on the installation site and which functions to limit the axial separation of the two flanges 39 and 41 , and thus the expansion of the expansion joint.
[0026] As will be understood, the FIG. 3 embodiment does not provide any protection against over compression of the system. Accordingly, the FIG. 4 embodiment is substantially the same except that a sleeve 57 is disposed over the strand 53 such that in a non-compressed condition, there is a space between the one end of the sleeve 57 and the inner side of the gusset 43 . When compression occurs, the two gussets 42 and 43 tend to be moved toward each other, but that movement is limited when the ends of the sleeve 57 become engaged with the inner sides of the gussets 42 and 43 . Such an arrangement allows for the strand 54 to be freely accessible for purposes of joining the two ends of the cable 52 for the purpose of installing the crimping device 56 .
[0027] While the present invention has been particularly shown and described with reference to preferred and modified embodiments as illustrated by the drawings, it will be understood by one skilled in the art that various changes in detail may be made thereto without departing from the spirit and scope of the invention as defined by the claims.
|
Provision is made to limit the degree of expansion of an expansion joint having a flexible body interposed between a pair of axially spaced flanges. The flanges or radial extensions thereof are interconnected by two or more circumferentially spaced cables, with the cables being unitary in form but having a pair of parallel strands, with the two ends of the cable being interconnected such that the two stands limit the expansion of the joint. Compression of the assembly is limited by way of a sleeve disposed on one strand and adapted to have its ends engage the inner surfaces of the flanges or radial extensions thereof upon reaching the limit of intended compression.
| 5
|
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
[0001] This application claims the priority of Korean Patent Application No. 10-2005-0024076, filed on Mar. 23, 2005, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This application relates to semiconductor memory devices, and more particularly, to semiconductor memory devices with a shared open bit line sense amplifier architecture.
[0004] 2. Description of the Related Art
[0005] In a dynamic random access memory (DRAM), design considerations such as the arrangement of memory cells, each including a transistor and a capacitor, and the arrangement of sense amplifiers that sense and amplify data output from each memory cell are significant in determining the area and the performance of the DRAM. In general, a memory cell array including a sense amplifier is arranged according to an open bit line method or a folded bit line method.
[0006] FIG. 1 illustrates the open bit line method, in which a memory cell MC is positioned at each intersection of a word line WL and a bit line BL to maximize the density of each memory cell MC and minimize the area of a chip. If the minimum design dimension is F, it is possible to manufacture a memory cell with an area of 4F 2 . However, since each sense amplifier SA must be designed to be arranged inside the pitch of a bit line BL, the design rules for sense amplifiers SA are tight, reducing flexibility in the design of the layout of the sense amplifiers SA. Furthermore, since a pair of bit lines BL connected to the sense amplifier SA are not arranged in the same cell array block, one side of the pair of the bit lines BL may be affected by noise generated in one cell array block, while the other side of the pair is not. Thus, a semiconductor memory device fabricated according to the open bit line method is vulnerable to noise.
[0007] FIG. 2 illustrates a relaxed open bit line method in which a memory cell MC is positioned at each intersection of a word line WL and a bit line BL and each sense amplifier SA is arranged inside the pitch of two bit lines BL. It is easier to design the layout of the sense amplifier SA using the relaxed open bit line method than using the open bit line method. However, it is still difficult to design the layout of the sense amplifier SA using the relaxed open bit line method. In addition, a semiconductor memory device manufactured according to the relaxed open bit line method is vulnerable to noise similar to one manufactured according to the open bit line method.
[0008] FIG. 3 illustrates a folded bit line method in which a sense amplifier SA is arranged inside the pitch of four bit lines BL, and thus, it is easier to design than a sense amplifier using the open bit line method. In addition, since a pair of bit lines BL connected to the sense amplifier SA are installed in the same cell array block, both sides of the pair of the bit lines BL are affected by noise generated in the cell array. Thus, a semiconductor memory device manufactured using the folded bit line method is more immune to noise. However, a memory cell MC manufactured according to the folded bit line method has an area of 8F 2 . The area of the memory cell MC may be double that of the memory cell MC manufactured according to the open bit line method, increasing the required chip area.
[0009] As described above, the area of a memory cell array manufactured according to the open bit line method is reduced, but the memory cell array is vulnerable to noise. In contrast, a memory cell array manufactured according to the folded bit line method is more immune to noise, but the area of a memory cell array is increased.
[0010] Since the trend in DRAMs is to increase capacity, the open bit line method has been used in arranging memory cells to reduce the area of each memory cell array. Accordingly, a method of arranging sense amplifiers that reduces noise is required.
SUMMARY OF THE INVENTION
[0011] An embodiment includes a memory device including memory cell arrays, each memory cell array including bit lines, and a sense amplifier configured to couple to at least two bit lines a memory cell array and configured to couple to at least two bit lines of a different memory cell array.
[0012] A further embodiment includes a method of operating a memory device including selecting a pair of bit lines from at least four bit lines coupled to a sense amplifier, and sensing the two bit lines using the sense amplifier.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The above and other aspects and advantages of the invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which:
[0014] FIG. 1 illustrates a dynamic random access memory (DRAM) fabricated according to the open bit line method;
[0015] FIG. 2 illustrates a DRAM fabricated according to the relaxed open bit line method;
[0016] FIG. 3 illustrates a DRAM fabricated according to the folded bit line method;
[0017] FIG. 4 illustrates a DRAM with a shared open bit line sense amplifier architecture according to an embodiment;
[0018] FIGS. 5 through 7 illustrate connection of sense amplifiers to bit lines in the DRAM illustrated in FIG. 4 ;
[0019] FIG. 8 is a circuit diagram of circuits of bit lines connected to a first sense amplifier illustrated in FIG. 4 ;
[0020] FIG. 9 illustrates a layout of the circuit diagram of FIG. 6 ;
[0021] FIG. 10 illustrates the operating sequence of a sense amplifier in the DRAM illustrated in FIG. 4 ;
[0022] FIG. 11 is a timing diagram of the sensing operation of a sense amplifier according to an embodiment; and
[0023] FIG. 12 illustrates equalization of bit lines in the DRAM illustrated in FIG. 4 .
DETAILED DESCRIPTION OF THE INVENTION
[0024] Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings. Like reference numerals denote like elements in the drawings.
[0025] FIG. 4 illustrates a dynamic random access memory (DRAM) 400 with a shared open bit line sense amplifier architecture according to an embodiment. Referring to FIG. 4 , the DRAM 400 includes first through third memory cell arrays 410 A, 410 B, and 410 C, each having cells arranged in the form of a matrix. In the first through third memory cell arrays 410 A, 410 B, and 410 C, DRAM cells MC, each including a transistor and a capacitor, are arranged at intersections of word lines WLi and bit lines BLj (i denotes a number from 0 to 11, and j denotes a number from 0 to 3). That is, the first through third memory cell arrays 410 A, 410 B, and 410 C are manufactured according to the open bit line method. If the minimum design dimension is F, the memory cell MC may have an area of 4F 2 or 6F 2 .
[0026] A first sense amplifier 420 is arranged inside the pitch of four bit lines BL 0 through BL 3 between the first and second memory cell arrays 410 A and 410 B, and a second sense amplifier 430 is arranged inside the pitch of four bit lines BL 0 through BL 3 between the second and third memory cell arrays 410 B and 410 C. Thus, the first sense amplifier 420 is shared by the first and second memory cell arrays 410 A and 410 B, and the second sense amplifier 430 is shared by the second and third memory cell arrays 410 B and 410 C.
[0027] FIG. 4 illustrates that first through fourth word lines WL 0 through WL 3 are in the first memory cell array 410 A, fifth through eighth word lines WL 4 through WL 7 are in the second memory cell array 410 B, and ninth through twelfth word lines WL 8 through WL 11 are in the third cell array 410 C. However, the number of word lines in each memory cell array is not limited to four. Referring to FIG. 4 , one of the first and second amplifiers 420 and 430 is positioned inside the pitch of the four bit lines BL 0 through BL 3 in the first through third memory cell arrays 410 A, 410 B, and 410 C. However, one of the first and second amplifiers 420 and 430 may also be positioned inside the pitch of every 4N bit lines (N≧1).
[0028] In this embodiment, the four bit lines BL 0 through BL 3 in the first through third memory cell arrays 410 A, 410 B, and 410 C, and the first and second sense amplifiers 420 and 430 connected to the four bit lines BL 0 through BL 3 are collectively labeled a unit of layout 440 . It is possible to manufacture a large-capacity DRAM 400 by using the unit of layout 440 repeatedly.
[0029] The bit lines BL 0 through BL 3 of the first and second memory cell arrays 410 A and 410 B adjacent the ends of the first sense amplifier 420 are connected to the first sense amplifier 420 . Specifically, a first bit line BL 0 A and a third bit line BL 2 A of the first memory cell array 410 A are connected to the left side of the first sense amplifier 420 , and a first bit line BL 0 B and a third bit line BL 2 B of the second memory cell array 410 B are connected to the right side of the first sense amplifier 420 .
[0030] The bit lines BL 0 through BL 3 of the second and third memory cell arrays 410 B and 410 C which are positioned at the ends of the second sense amplifier 430 , respectively, are connected to the second sense amplifier 430 . Specifically, a second bit line BL 1 B and a fourth bit line BL 3 B of the second memory cell array 410 B are connected to the left side of the second sense amplifier 430 , and a second bit line BL 1 C and a fourth bit line BL 3 C of the third memory cell array 410 C are connected to the right side of the second sense amplifier 430 .
[0031] The first sense amplifier 420 uses the third bit line BL 2 B of the second memory cell array 410 B as a reference in sensing the first bit line BL 0 A of the first memory cell array 410 A, and the first bit line BL 0 B of the second memory cell array 410 B as a reference in sensing the third bit line BL 2 A of the first memory cell array 410 A. Similarly, as illustrated in FIG. 5 , the first sense amplifier 420 uses the third bit line BL 2 A of the first memory cell array 410 A as a reference in sensing the first bit line BL 0 B of the second memory cell array 410 B, and the first bit line BL 0 A of the first memory cell array 410 A as a reference in sensing the third bit line BL 2 B of the second memory cell array 4101 B.
[0032] In other words, to sense one of the bit lines BL 0 A and BL 2 A of the first memory cell array 410 A as a data line, the first sense amplifier 420 uses one of the bit lines BL 2 B and BL 0 B of the second memory cell array 410 B that is diagonal to the sensed bit line as a reference line. To sense one of the bit lines BL 0 B and BL 2 B of the second memory cell array 410 B as a data line, the first sense amplifier 420 uses one of the bit lines BL 2 A and BL 0 A of the first memory cell array 410 A that is diagonal to the sensed bit line as a reference line.
[0033] Referring to FIG. 6 , the second sense amplifier 430 uses the fourth bit line BL 3 C of the third memory cell array 410 C as a reference in sensing the second bit line BLIB of the second memory cell array 410 B, and the second bit line BL 1 C of the third memory cell array 410 C as a reference in sensing the fourth bit line BL 3 B of the second memory cell array 410 B. Similarly, referring to FIG. 7 , the second sense amplifier 430 uses the fourth bit line BL 3 B of the second memory cell array 410 B as a reference in sensing the second bit line BL 1 C of the third memory cell array 410 C, and the second bit line BL 1 B of the second memory cell array 410 B as a reference in sensing the fourth bit line BL 3 C of the third memory cell array 410 C.
[0034] That is, to sense one of the bit lines BL 1 B and BL 3 B of the second memory cell array 410 B as a data line, the second sense amplifier 430 uses one of the bit lines BL 3 C and BL 1 C of the third memory cell array 410 C that is diagonal to the sensed bit line as a reference line. Also, to sense one of the bit lines BL 1 C and BL 3 C of the third memory cell array 410 C as a data line, the second sense amplifier 430 uses one of the bit lines BL 3 B and BL 1 B of the second memory cell array 410 B that is diagonal to the sensed bit line as a reference line.
[0035] FIG. 8 is a circuit diagram of circuits of bit lines connected to the first sense amplifier 420 . Referring to FIG. 8 , first and second equalization circuits 610 and 630 , first and second isolation units 620 and 640 (also referred to as switching units), a column selection unit 650 , and a second sense amplifier 420 are installed between first and third bit lines BL 0 A and BL 2 A of a first memory cell array 410 A, and first through third bit lines BL 0 B and BL 2 B of the second memory cell array 410 B.
[0036] The first equalization circuit 610 is connected between the first and third bit lines BL 0 A and BL 2 A of the first memory cell array 410 A. The first equalization circuit 610 equalizes the voltages of the first and third bit lines BL 0 A and BL 2 A of the first memory cell array 410 A with a voltage of Vcc/2 in response to an equalization signal EQ.
[0037] The first isolation unit 620 selectively connects the first and third bit lines BL 0 A and BL 2 A of the first memory cell array 410 A to the first sense amplifier 420 in response to a first isolation signal ISO_A and a second isolation signal ISO_B. The first isolation unit 620 includes a first isolation transistor 621 and a second isolation transistor 622 . The first isolation transistor 621 transmits a signal of the first bit line BL 0 A of the first memory cell array 410 A to a first sensing node 421 of the first sense amplifier 420 in response to the first isolation signal ISO_A. The second isolation transistor 622 transmits a signal of the third bit line BL 2 A of the first memory cell array 410 A to a second sensing node 422 of the first sense amplifier 420 in response to the second isolation signal ISO_B.
[0038] The second equalization circuit 630 is connected between the first and third bit lines BL 0 B and BL 2 B of the second memory cell array 410 B, and equalizes the voltages of the first and third bit lines BL 0 B and BL 2 B of the second memory cell array 410 B with a voltage of Vcc/2 in response to the equalization signal EQ.
[0039] The second isolation unit 640 includes a third isolation transistor 641 which transmits a signal of the first bit line BL 0 B of the second memory cell array 410 B to the first sensing node 421 of the first sense amplifier 420 in response to the second isolation signal ISO_B, and a fourth isolation transistor 642 which transmits a signal of the third bit line BL 2 B of the second memory cell array 410 B to the second sensing node 422 of the first sense amplifier 420 in response to the first isolation signal ISO_A.
[0040] The first sense amplifier 420 includes a first PMOS transistor 423 connected between a power supply voltage Vcc and the first sensing node 421 , with a gate connected to the second sensing node 422 ; a second PMOS transistor 424 connected between the power supply voltage Vcc and the second sensing node 422 , with a gate connected the first sensing node 421 ; a first NMOS transistor 425 connected between the first sensing node 421 and a ground voltage Vss, with a gate connected to the second sensing node 422 ; and a second NMOS transistor 426 connected between the second sensing node 422 and the ground voltage Vss, whose gate is connected to the first sensing node 421 .
[0041] The column selection unit 650 applies a voltage of the first sensing node 421 sensed by the first sense amplifier 420 and a voltage of the second sensing node 422 to a data line DIO in response to a column selection signal CSL.
[0042] In the circuits illustrated in FIG. 8 , the first isolation unit 620 transmits a signal of the first bit line BL 0 A of the first memory cell array 410 A to the first sensing node 421 of the first sense amplifier 420 in response to the first isolation signal ISO_A. The second isolation unit 640 transmits a signal of the third bit line BL 2 B of the second memory cell array 410 B to the second sensing node 422 of the first sense amplifier 420 also in response to the first isolation signal ISO_A. Accordingly, the first sense amplifier 420 performs a sensing operation using the first bit line BL 0 A of the first memory cell array 410 A and the third bit line BL 2 B of the second memory cell array 410 B as a data line and a reference, or a reference line and a data line, respectively.
[0043] Alternatively, the first isolation unit 620 transmits a signal of the third bit line BL 2 A of the first memory cell array 410 A to the second sensing node 422 of the first sense amplifier 420 in response to the second isolation signal ISO_B. The second isolation unit 640 transmits a signal output from the first bit line BL 0 B of the second memory cell array 410 B to the first sensing node 421 of the first sense amplifier 420 in response to the second isolation signal ISO_B. Thus, the first sense amplifier 420 performs a sensing operation using the third bit line BL 2 A of the first memory cell array 410 A and the first bit line BL 0 B of the second memory cell array 410 B as a data line and a reference line, respectively, or a reference line and a data line, respectively.
[0044] The operation of the first isolation unit 620 matches the above operation of the first sense amplifier 420 that uses, as a reference line, the bit line BL 2 B or BL 0 B of the second memory cell array 410 B that is diagonal to the bit line BL 0 A or BL 2 A of the first memory cell array 410 A to be sensed as a data line, and uses, as a reference line, the bit line BL 2 A or BL 0 A of the first memory cell array 410 A that is diagonal to the bit line BL 0 B or BL 2 B of the second memory cell array 410 B to be sensed as a data line.
[0045] FIG. 9 illustrates a layout of the circuits of FIG. 8 . Referring to FIG. 9 , the first equalization circuit 610 , the first isolation unit 620 , the column selection unit 650 , the second sense amplifier 420 , the second isolation unit 640 , and the second equalization circuit 630 are arranged inside the pitch of the four bit lines BL 0 through BL 3 between the first memory cell array 410 A and the second memory cell array 410 B.
[0046] FIG. 10 illustrates an operating sequence of each sense amplifier with the shared open bit line architecture sense amplifier, illustrated in FIG. 4 . Referring to FIG. 10 , first, the first sense amplifier 420 performs a sensing operation using the first bit line BL 0 A of the first memory cell array 410 A and the third bit line BL 2 B of the second memory cell array 410 B as a data line and a reference line, respectively, or as a reference line and a data line, respectively ({circle around (1)}). Second, the second sense amplifier 430 performs a sensing operation using the second bit line BL 1 B of the second memory cell array 410 B and the fourth bit line BL 3 C of the third memory cell array 410 C as a data line and a reference line, respectively, or as a reference line and a data line, respectively ({circle around (2)}). Third, the first sense amplifier 420 performs a sensing operation using the third bit line BL 2 A of the first memory cell array 410 A and the first bit line BL 0 B of the second memory cell array 410 B as a data line and a reference line, respectively, or as a reference line and a data line, respectively ({circle around (3)}). Fourth, the second sense amplifier 430 performs a sensing operation using the fourth bit line BL 3 B of the second memory cell array 410 B and the second bit line BL 1 C of the third memory cell array 410 C as a data line and a reference line, respectively, or as a reference line and a data line, respectively ({circle around (4)}).
[0047] The reason why a sensing operation is performed in the sequence from the first sensing operation {circle around (1)} to the fourth sensing operation {circle around (4)} will now be described. In the first sensing operation {circle around (1)}, the first sense amplifier 420 senses the first bit line BL 0 A of the first memory cell array 410 A and the third bit line BL 2 B of the second memory cell array 410 B to fully swing the voltage of the first bit line BL 0 A of the first memory cell array 410 A and the voltage of the third bit line BL 2 B of the second memory cell array 410 B to a power supply voltage Vcc and the ground voltage Vss, respectively. Therefore, the second bit line BL 1 B and the fourth bit line BL 3 B , which are adjacent to the third bit line BL 2 B of the second memory cell array 410 B, are coupled to the third bit line BL 2 B and thus affected by noise.
[0048] To reduce problems of the second bit line BL 1 B of the second memory cell array 410 B caused by noise in the second sensing operation {circle around (2)}, the second sense amplifier 430 senses the second bit line BL 1 B of the second memory cell array 410 B and the fourth 4 bit line BL 3 C of the third memory cell array 410 C. As a result of the second sensing operation {circle around (2)}, the voltage of the second bit line BL 1 B of the second memory cell array 410 B and the voltage of the fourth bit line BL 3 C of the third memory cell array 410 C fully swing to the power supply voltage Vcc and the ground voltage Vss, respectively. Thus, the first bit line BL 0 B adjacent to the second bit line BL 1 B of the second memory cell array 410 B is coupled to the second bit line BL 1 B , thus affected by noise.
[0049] To reduce problems of the first bit line BL 0 B of the second memory cell array 410 B caused by noise in the third sensing operation {circle around (3)}, the first bit line BL 0 B of the second memory cell array 410 B and the third bit line BL 3 A of the first memory cell array 410 A are sensed. Lastly, in the fourth sensing operation {circle around (4)}, the second sense amplifier 430 senses the fourth bit line BL 3 B of the second memory cell array 410 B and the second bit line BL 1 C of the third memory cell array 410 C.
[0050] As described with reference to FIG. 8 , similar to the first and second isolation units 620 and 640 connected to the first sense amplifier 420 , third and fourth isolation units (not shown) that operate in response to the first and second isolation signals ISO_A and ISO_B, respectively, can be installed between the second and fourth bit lines BL 1 B and BL 3 B of the second memory cell array 410 B and the second sense amplifier 430 and between the second sense amplifier 430 and the second and fourth bit lines BL 1 C and BL 3 C of the third memory cell array 410 C. In this case, referring to FIG. 11 , the first sensing operation {circle around (1)} and the second sensing operation {circle around (2)} are simultaneously performed at a point of time t 1 , and then, the third sensing operation {circle around (3)} and the fourth sensing operation {circle around (4)} are simultaneously performed at a point of time t 2 .
[0051] FIG. 12 illustrates equalization of bit lines of the DRAM 400 of FIG. 4 . Referring to FIGS. 8 and 12 , the first and second isolation units 620 and 640 turn off the first and second isolation transistors 621 , 622 , 641 , and 642 when the first and second isolation signals ISO_A and ISO_B are deactivated. Then, the first bit line BL 0 A and the third bit line BL 2 A of the first memory cell array 410 A, and the first bit line BL 0 B and the third bit line BL 2 B of the second memory cell array 410 B are separated from the first sense amplifier 420 . Likewise, the second bit line BL 1 B and the fourth bit line BL 3 B of the second memory cell array 410 B, and the second bit line BL 1 C and the fourth bit line BL 3 C of the third memory cell array 410 C are separated from the second sense amplifier 430 .
[0052] The first equalization unit 610 equalizes the voltages of the first bit line BL 0 A and the third bit line BL 2 A of the first memory cell array 410 A, which are separated from the first sense amplifier 420 , with a voltage of Vcc/2 in response to the equalization signal EQ. The second equalization circuit 630 equalizes the voltages of the first bit line BL 0 B and the third bit line BL 2 B of the second memory cell array 410 B, which are separated from the first sense amplifier 420 , with the voltage of Vcc/2 in response to the equalization signal EQ. Also, the voltages of the second bit line BL 1 B and the fourth bit line BL 3 B of the second memory cell array 410 B and the second bit line BL 1 C and the fourth bit line BL 3 C of the third memory cell array 410 C, which are separated from the second sense amplifier 430 , are equalized with the voltage of Vcc/2 in response to the equalization signal EQ. The voltages of all the bit lines of the DRAM 400 are equalized to the voltage of Vcc/2 in response to the equalization signal EQ.
[0053] Accordingly, in a DRAM according to an embodiment, one memory cell is arranged at each intersection of a word line and a bit line, a sense amplifier is arranged inside the pitch of four bit lines in an open bit line architecture with each memory cell having an area of 4F 2 , and a sense amplifier is arranged to be shared by a first memory cell array and a second memory cell array on opposite sides of the sense amplifier. In the sense amplifier, two bit lines are connected to a first memory cell array and two bit lines are connected to a second memory cell array. Also, to sense a bit line of the first memory cell array as a data line, a sense amplifier uses, as a reference line, a bit line of the second memory cell array that is diagonal to the data line.
[0054] Although embodiments have been described with reference to three memory cell arrays and two sense amplifiers, one of ordinary skill in the art will understand that embodiments may include any number of memory cell arrays or sense amplifiers.
[0055] Although a sense amplifier having isolation units have been described with reference to selectively connecting one bit line from two bit lines to one side of the sense amplifier, one of ordinary skill in the art will understand that an isolation unit may selectively connect one bit line from more than two bit lines to one side of the sense amplifier.
[0056] While this invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
|
Provided is a memory device with a shared open bit line sense amplifier architecture. The memory device includes memory cell arrays, each memory cell array including bit lines, and a sense amplifier configured to couple to at least two bit lines a memory cell array and configured to couple to at least two bit lines of a different memory cell array.
| 6
|
CROSS REFERENCE TO RELATED APPLICATION
This is an application under 35 U.S.C. Section 119(e) based upon a previously filed provisional application, Ser. No. 60/116,771 filed Jan. 22, 1999, which is incorporated herewith by reference, and which is co-pending, and which is believed to disclose adequately and sufficiently subject matter claimed herein.
This invention was made with U.S. Government support under SBIR grant Number N0022-C-4120 awarded by the Naval Sea Systems Command. Further description of the present invention is provided in the Report (dated Feb. 27, 1998), under contract N00024-97-C-4130, sponsored by the Naval Sea Systems Command. The Government has certain rights in the invention described herein.
BACKGROUND OF THE INVENTION
1. Technical Field of the Invention
The present invention relates to continuous composite coextrusion methods, apparatus for coextrusion, and compositions for preparing composites, such as continuous fiber reinforced ceramic matrix composites, using dense fibers and green matrices as well as to methods for the preparation of composites having interfaces between dense fibers and green matrices.
2. Background of the Invention
Composites are combinations of two or more materials present as separate phases and combined to form desired structures so as to take advantage of certain desirable properties of each component. The materials can be organic, inorganic, or metallic, and in various forms, including but not limited to particles, rods, fibers, plates and foams. Thus, a composite, as defined herein, although made up of other materials, can be considered to be a new material have characteristic properties that are derived from its constituents, from its processing, and from its microstructure.
Composites are made up of the continuous matrix phase in which are embedded: (1) a three-dimensional distribution of randomly oriented reinforcing elements, e.g., a particulate-filled composite; (2) a two-dimensional distribution of randomly oriented elements, e.g., a chopped fiber mat; (3) an ordered two-dimensional structure of high symmetry in the plane of the structure, e.g., an impregnated cloth structure; or (4) a highly-aligned array of parallel fibers randomly distributed normal to the fiber directions, e.g., a filament-wound structure, or a prepreg sheet consisting of parallel rows of fibers impregnated with a matrix.
Monolithic ceramic materials are known to exhibit certain desirable properties, including high strength and high stiffness at elevated temperatures, resistance to chemical and environmental attack, and low density. However, monolithic ceramics have one property that limits their use in stressed environments, namely their low fracture toughness. While significant advances have been made to improve the fracture toughness of monolithic ceramics, mostly through the additions of whisker and particulate reinforcements or through careful control of the microstructural morphology, they still remain extremely damage intolerant. More specifically, they are susceptible to thermal shock and will fail catastrophically when placed in severe stress applications. Even a small processing flaw or crack that develops in a stressed ceramic cannot redistribute or shed its load on a local scale. Under high stress or even mild fatigue, the crack will propagate rapidly resulting in catastrophic failure of the part in which it resides. It is this inherently brittle characteristic which can be even more pronounced at elevated temperatures, that has not allowed monolithic ceramics to be utilized in any safety-critical designs.
Research and development for these high temperature and high stress applications have focused on the development of continuous fiber reinforced ceramic matrix composites, hereafter referred to as CFCCs. The use of fiber reinforcements in the processing of ceramic and metal matrix composites is known in the prior art, and has essentially provided the fracture toughness necessary for ceramic materials to be developed for high stress, high temperature applications. See J. J. Brennan and K. M. Prewo, “High Strength Silicon Carbide Fiber Reinforced Glass-Matrix Composites,” J. Mater. Sci., 15 463-68 (1980); J. J. Brennan and K. M. Prewo, “Silicon Carbide Fiber Reinforced Glass-Ceramic Matrix Composites Exhibiting High Strength Toughness,” i J. Mater. Sci., 17 2371-83 (1982); P. Lamicq, G. A. Gernhart, M. M. Danchier, and J. G. Mace, “SiC/SiC Composite Ceramics,” Am. Ceram. Soc. Bull., 65 [2] 336-38 (1986); T. I. Mah, M. G. Mendiratta, A. P. Katz, and K. S. Mazdiyasni, “Recent Developments in Fiber-Reinforced High Temperature Ceramic Composites,” Am. Ceram. Soc. Bull., 66 [2] 304-08 (1987).; K. M. Prewo, “Fiber-Reinforced Ceramics: New Opportunities for Composite Materials,” Am. Ceram. Soc. Bull., 68 [2] 395-400 (1989); H. Kodama, H. Sakamoto, and T. Miyoshi, “Silicon Carbide Monofilament-Reinforced Silicon Nitride or Silicon Carbide Matrix Composites,” J. Am. Ceram. Soc., 72 [4] 551-58 (1989); and J. R. Strife, J. J. Brennan, and K. M. Prewo, “Status of Continuous Fiber-Reinforced Ceramic Matrix Composite Processing Technology,” Ceram. Eng. Sci. Proc., 11 [7-8] 871-919 (1990).
Under high stress conditions, the fibers are strong enough to bridge the cracks which form in the ceramic matrix allowing the fibers to ultimately carry the load, and catastrophic failure can be avoided. This type of behavior has led to a resurgence of CFCCs as potential materials for gas turbine components, such as combustors, first-stage vanes, and exhaust flaps. See D. R. Dryell and C. W. Freeman, “Trends in Design in Turbines for Aero Engines,” pp. 38-45 in Materials Development in Turbo-Machinery Design; 2nd Parsons International Turbine Conference, Edited by D. M. R. Taplin, J. F. Knott, and M. H. Lewis, The Institute of Metals, Parsons Press, Trinity College, Dublin, Ireland, 1989. CFCCs have also been given serious consideration for heat exchangers, rocket nozzles, and the leading edges of next-generation aircraft and reentry vehicles. See M. A. Karnitz, D. F. Craig, and S. L. Richlin, “Continuous Fiber Ceramic Composite Program,” Am. Ceram. Soc. Bull., 70 [3] 430-35 (1991), and Flight Vehicle Materials, Structures and Dynamics—Assessment and Future Directions, Vol. 3, edited by S. R. Levine, American Society of Mechanical Engineers, New York, 1992. In addition, CFCCs with a high level of open porosity are currently being utilized as filters for hot-gas cleanup in electrical power generation systems, metal refining, chemical processing, and diesel exhaust applications. See L. R. White, T. L. Tompkins, K. C. Hsieh, and D. D. Johnson, “Ceramic Filters for Hot Gas Cleanup,” J. Eng. for Gas Turbines and Power, Vol. 115, 665-69 (1993).
CFCCs are currently fabricated by a number of techniques. The simplest and most common method for their fabricating has been the slurry infiltration technique whereby a fiber or fiber tow is passed through a slurry containing the matrix powder; the coated fiber is then filament wound to create a “prepreg”; the prepreg is removed, cut, oriented, and laminated into a component shape; and the part undergoes binder pyrolysis and a subsequent firing cycle to densify the matrix. See J. J. Brennan and K. M. Prewo, “High Strength Silicon Carbide Fibre Reinforced Glass-Matrix Composites,” J. Mater. Sci., 15 463-68 (1980); D. C. Phillips, “Fiber Reinforced Ceramics,” Chapter 7 in Fabrication of Composites, edited by A. Kelly and S. T. Mileiko, North-Holland Publishing Company, Amsterdam, The Netherlands, 1983; and K. M. Prewo and J. J. Brennan, “Silicon Carbide Yarn Reinforced Glass Matrix Composites,” J. Mater. Sci., 17 1201-06 (1982).
Other techniques for fabricating CFCCs also typically involve an infiltration process in order to incorporate matrix material within and around the fiber architecture, e.g. a fiber tow, a preformed fiber mat, a stack of a plurality of fiber mats, or other two dimensional (2D) or three dimensional (3D) preformed fiber architecture. These techniques include the infiltration of sol-gels. See J. J. Lannutti and D. E. Clark, “Long Fiber Reinforced Sol-Gel Derived Alumina Composites”, pp. 375-81 in Better Ceramics Through Chemistry, Material Research Society Symposium Proceedings, Vol. 32, North-Holland, New York, 1984; E. Fitzer and R. Gadow, “Fiber Reinforced Composites Via the Sol-Gel Route”, pp. 571-608 in Tailoring Multiphase and Composite Ceramics, Materials Science Research Symposium Proceedings, Vol. 20, edited by R. E. Tressler et al., Plenum Press, New York, 1986. Other techniques include polymeric precursors which are converted to the desired ceramic matrix material through a post-processing heat treatment. See J. Jamet, J. R. Spann, R. W. Rice, D. Lewis, and W. S. Coblenz, “Ceramic-Fiber Composite Processing via Polymer-Filler Matrices,” Ceram. Eng. Sci. Proc., 5 [7-8] 677-94 (1984); and K. Sato, T. Suzuki, O. Funayama, T. Isoda, “Preparation of Carbon Fiber Reinforced Composite by Impregnation with Perhydropolysilazane Followed by Pressureless Firing,” Ceram. Eng. Sci. Proc., 13 [9-10] 614-21 (1992).
Other research and development has involved molten metals that are later nitrided or oxidized. See M. S. Newkirk, A. W. Urquhart, H. R. Zwicker, and E. Breval, “Formation of Lanxide Ceramic Composite Materials,” J. Mater. Res., 1 81-89 (1986); and M. K. Aghajanian, M. A. Rocazella, J. T. Burke, and S. D. Keck, “The Fabrication of Metal Matrix Composites by a Pressureless Infiltration Technique,” J. Mater. Sci., 26 447-54 (1991). Other research and development has involved molten materials that are later carbided to form a ceramic matrix. See R. L. Mehan, W. B. Hillig, and C. R. Morelock, “Si/SiC Ceramic Composites: Properties and Applications,” Ceram. Eng. Sci. Proc., 1 405 (1980). Still other research and development has involved molten silicates that cool to form a glass or glass-ceramic matrix (see M. K. Brun, W. B. Hillig, and H. C. McGuigan, “High Temperature Mechanical Properties of a Continuous Fiber-Reinforced Composite Made by Melt Infiltration,” Ceram. Eng. Sci. Proc., 10 [7-8] 611-21 (1989)), and chemical vapors which decompose and condense to form the ceramic matrix (See A. J. Caputo and W. J. Lackey, “Fabrication of Fiber-Reinforced Ceramic Composites by Chemical Vapor Infiltration,” Ceram. Eng. Sci. Proc., 5 [7-8] 654-67 (1984); and A. J. Caputo, W. J. Lackey, and D. P. Stinton, “Development of a New, Faster, Process for the Fabrication of Ceramic Fiber-Reinforced Ceramic Composites by Chemical Vapor Infiltration,” Ceram. Eng. Sci. Proc., 6 [7-8] 694-706 (1985).
Two U.S. patents have issued which involve a method for the fabrication of a fiber reinforced composite by combining an inorganic reinforcing fiber with dispersions of powdered ceramic matrix in organic vehicles, such as thermoplastics. The first patent, U.S. Pat. No. 5,024,978, discloses a method for making an organic thermoplastic vehicle containing ceramic powder that can form the matrix of a fiber reinforced composite. This patent also discloses that the ceramic powder/thermoplastic mixtures can be heated to above the melt transition temperature of the thermoplastic and then applied as a heated melt to an inorganic fiber. This patent further discloses that the process may be used to make composite ceramic articles. The second patent, U.S. Pat. No. 5,250,243, discloses a method for applying a dispersion of ceramic powder in a wax-containing thermoplastic vehicle to an inorganic fiber reinforcement material to form a prepreg material such as a prepreg tow. This patent further discloses that the prepreg tow may be subjected to a binder pyrolysis step to partially remove the wax binder vehicle prior to consolidation of the prepreg tow into the preform of a composite ceramic article.
To summarize, the continuous fiber reinforced ceramic composites (“CFCCs”) prior to the present invention have traditionally been fabricated using methods and apparatuses to infiltrate the matrix or matrix-forming material around a preformed architecture of dense fibers or fiber tows or by passing the fibers through a powder/melt slurry. While these methods and apparatuses provide a fiber reinforced composite structure, there is no control over the thickness of the matrix forming vehicle, and rarely will the matrix uniformly surround the fibers. In such methods, the fibers often contact each other which is detrimental to the mechanical behavior of such composites. In addition, these infiltration processes are quite slow, sometimes requiring weeks or months to fabricate components, and are severely limited in the matrix/fiber combinations that can be produced.
Thus, there exists a need for more efficient methods and apparatuses for applying the matrix to the fiber reinforcement. There exists a further need for methods and apparatuses that are versatile enough to allow almost limitless combinations of matrix and fiber reinforcement.
It is therefore an object of the present invention to provide methods and apparatuses for efficient fabrication of ceramic composites that exhibit non-catastrophic behavior when used as a fiber reinforcement for a green ceramic matrix.
Another object of the present invention is to provide relatively efficient methods and apparatuses for applying the green matrix material to the fiber reinforcement such that it completely surrounds the fiber reinforcement prior to composite layup.
A further object of the present invention is to provide relatively efficient methods and apparatuses for preparing and applying the green matrix material to the fiber reinforcement, regardless of the composition from which the matrix is prepared or the composition of the fiber reinforcement.
Yet another object of the present invention is to provide relatively efficient methods and apparatuses for preparing both a green ceramic matrix and a green matrix/fiber interfacial layer that can be applied to the fiber reinforcement regardless of the composition of the matrix, interface, or fiber reinforcement.
These and other objects and advantages of the present invention, as well as additional inventive features, will be apparent to those of skill in the art from the description of the invention provided herein.
SUMMARY OF THE INVENTION
The present invention comprises novel continuous composite coextrusion methods and apparatus for fabricating fiber reinforced composite materials. Specifically, the present invention comprises novel methods and apparatus to fabricate composite materials via an economical, versatile, and controlled continuous composite coextrusion processes. In a particular preferred embodiment of the present invention, a dense fiber or dense fiber tow (bundles of fibers) is introduced during melt extrusion of a ceramic (or metal)/binder feed-rod. The result of this coextrusion process is a coextruded “green” filament containing an in-situ dense fiber or tow of fibers.
More specifically, the present invention relates to processes for the fabrication of a fiber reinforced composite, i.e., a composite which is comprised of a matrix of a material, such as a ceramic or metallic material, and having fibers of a ceramic material dispersed within the matrix as a reinforcement. A preferred method of the present invention comprises: (a) forming a material-laden composition comprising a thermoplastic polymer and at least about 40 volume % of a ceramic or metallic particulate in a manner such that the composition has a substantially cylindrical geometry and thus can be used as a substantially cylindrical feed rod; (b) forming a hole down the symmetrical axis of the feed rod; (c) inserting the start of a continuous spool of ceramic fiber, metal fiber or carbon fiber through the hole in the feed rod; (d) extruding the feed rod and fiber reinforcement simultaneously to form a continuous filament consisting of a “green” matrix material completely surrounding a dense fiber reinforcement and said filament having an average diameter that is less than the average diameter of the feed rod; and (e) arranging the continuous filament into a desired architecture to provide a green fiber reinforced composite. The green matrix may be subsequently fired, i.e., heated, to provide a fiber reinforced composite with non-brittle failure characteristics.
The present invention also provides a process for the fabrication of a fiber reinforced composite having an interlayer, i.e., a composite that is comprised of a matrix of material, such as a ceramic or metallic material, having fibers of a ceramic material dispersed within the matrix as a reinforcement, and having an interlayer that is between the matrix and fiber reinforcement. This method is the same as that described in the preceding paragraph, but further comprises forming a feed rod that contains two dissimilar particulate-laden compositions wherein during the extrusion process the second particulate-laden composition forms a green interlayer between the fiber reinforcement and the green matrix in a continuous filament. This filament can be arranged as described in the previous paragraph and both the green interlayer and the green matrix may be subsequently fired to provide a fiber reinforced composite having substantially improved non-brittle failure characteristics compared to a fiber reinforced composite in the absence of an interlayer.
The present invention further provides methods for the fabrication of continuous filaments used in preparing fiber reinforced composites wherein the architecture of the filaments can be readily controlled.
Yet another aspect of the present invention is the ability to take the continuous filaments and form a shaped green-body. Typically, the extruded filament is molded by pressing into an appropriate mold at temperature of at least about 80° C. The molding operation joins the fiber reinforced green filaments together, creating a solid, shaped green body. Any shape that can be compression molded or otherwise formed by plastic deformation can be obtained with extruded filament. The green body so molded has the desired texture created by the arrangement of the extruded filaments. For example, a uniaxially aligned fiber reinforced composite can be obtained by a uniaxial lay-up of the extruded filaments prior to molding, or a woven architecture can be obtained by molding a shape from previously woven extruded filaments. The extruded filament product permits a wide variety of composite architectures to be fabricated in a molded green body.
In a preferred method of the present invention, a co-axial filament is produced with a fiber tow surrounded by a “green” ceramic. In a further preferred embodiment of the present invention, the process has been demonstrated utilizing carbon fiber tows in a hafnium carbide (“HfC”) matrix and the resulting product can be used in extreme high temperature environments. The fiber imparts the necessary thermal shock resistance and toughness that HfC lacks as a monolithic ceramic.
The processing techniques of the invention readily allows for control of the fiber volume fraction and changes to the matrix composition. This technology is readily applicable to other matrix/fiber combinations and will significantly enhance manufacturing capability for low cost, high-performance and high temperature ceramic composites.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 illustrates a cross-section of a preferred apparatus of the present invention.
FIG. 2 illustrates a cross-section of another preferred apparatus of the present invention.
FIGS. 3A and 3B are schematic illustrations respectively of the matrix feedrod with and without the graphite interface feedrod in accordance with the present invention.
FIG. 4 is flow chart illustrating a preferred method of the present invention.
FIG. 5B is a schematic illustration of a “green” coaxial filament with a graphite interface layer and FIG. 5A is a schematic illustration of a “green” coaxial filament without a graphite interface layer in accordance with the present invention.
FIG. 6 is a perspective view of a guide tube that may be used in the apparatus shown in FIG. 2 .
FIG. 7 illustrates the self-propagating, high temperature synthesis for producing hafnium carbide matrix.
FIG. 8 further illustrates the self-propagating, high temperature synthesis method using poly(acrylonitrile-co-butadiene), i.e., “PAB”, for producing hafnium carbide matrix.
FIG. 9 illustrates the x-ray diffraction of the reaction of hafnium and carbon using PAB.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 illustrates a cross-section of a preferred apparatus of the present invention. The apparatus 40 is an extrusion die comprising an extrusion barrel 41 , an extrusion ram 42 , a heating jacket 43 , a transition block 44 , a spinnerette 45 , an extrusion orifice 46 , and a motor driven winding spool 47 , a motor driven ram screw 48 , and an inlet 49 .
FIG. 4 depicts a flow chart of a preferred method of the present invention. In accordance with a preferred method and apparatus of the present invention, as shown in FIGS. 1 — 3 , a graphite rod or graphite interface layer 50 can be prepared by blending graphite material and pressing the graphite material into a rod shape. In addition, a matrix feedrod 60 can be prepared by blending a suitable matrix feedrod material, pressing the matrix feedrod material into a rod shape, and drilling a core hole 61 through the longitudinal axis of the matrix feedrod 60 . The core hole 61 should have a diameter just large enough for the insertion of the graphite rod 50 there through.
The blending steps for the matrix feedrod 60 and graphite rod 50 as shown in FIG. 1-3 can comprise milling and batching of matrix feedrod and graphite powders individually with thermoplastic binders and additives in a mixer, e.g., a Brabender Plasticorder high shear mixer. In a preferred embodiment, the matrix feedrod material comprises hafnium carbide (“HfC”) or zirconium carbide (“ZrC”). Preferably the carbide powder/thermoplastic blend is pressed into a “green” rod having a diameter of about 0.885 inches, i.e., about 2.248 cm.
After preparation of the matrix feedrod 60 and the graphite rod 50 , graphite rod 50 can then be inserted into and through core hole 61 of matrix feedrod 60 . If desired, graphite rod 50 and surrounding matrix feedrod 60 can then be repressed to maintain their rod shapes. A cylindrical hole 80 can next be drilled through the longitudinal axis of graphite rod 50 . In a preferred embodiment, cylindrical hole 80 has a diameter of about 0.125 inches, i.e., 0.318 cm.
The resulting combination of graphite rod 50 and surrounding matrix feedrod 60 can then be inserted into inlet 49 and extrusion barrel 41 , until it stops at location 54 . If desired, a guide tube 20 , an example of which is shown in detail in FIG. 6, can be inserted through cylindrical hole 80 , as shown in FIG. 3 B.
Extrusion ram 42 can next be placed on top of the combination of graphite rod 50 and surrounding matrix feedrod 60 . Extrusion ram 42 has a bore 52 having a diameter of sufficient size to receive the carbon fiber tow 51 and slide over the guide tube 20 , if such guide tube is used (as shown in FIG. 6 ).
Carbon fiber tow 51 can then be inserted through bore 52 of extrusion ram 42 and cylindrical hole 80 of graphite rod 50 , until the inserted end reaches extrusion orifice 46 .
As shown in FIGS. 1-2, heating jacket 43 heats the matrix feedrod 60 to melt the matrix feedrod material. Extrusion ram 42 pushes the matrix feedrod 60 through heating jacket 43 to the soften zone 56 . Preferably, soften zone 56 has a frusto-conical shape, with the extrusion orifice 46 located at the bottom of soften zone 56 .
Co-axial filament 70 is extruded from extrusion orifice 46 and wound on the motor driven spinnerette or winding spool 47 . As shown in FIG. 1, co-axial filament 70 thus comprises carbon fiber tow 51 , surrounded by graphite rod or graphite interface layer 50 and matrix feedrod 60 . Co-axial filament 70 can also be called a green ZrC/C F filament, if ZrC is used as the matrix feedrod material, and the tow comprises a carbon fiber material.
The graphite interface layer 50 surrounding the carbon fiber tow 51 as shown in FIG. 5B has been found to reduce and eliminate matrix cracking in composites caused by the large CTE mismatch between the matrix feedrod and the fiber materials. By pressing the graphite rods to different diameters, the graphite interface layer 50 can be varied as desired.
Notably, the carbon fiber tow 51 is centered in the green co-axial filament 70 . Design choices to achieve the desired product include varying the viscosities of ZrC powder/thermoplastic and graphite powder/thermoplastic blends, eliminating the guide tube 20 , and changing the composite fiber extrusion conditions. These choices can lead to a uniform interfacial coating.
FIG. 4 is a flow chart illustrating a preferred method of the present invention.
FIG. 5B is a schematic illustration of a “green” coaxial filament with a graphite interface layer and FIG. 5A is a schematic illustration of a “green” coaxial filament without a graphite interface layer in accordance with the present invention.
FIG. 6 is a perspective view of a guide tube that may be used in the apparatus shown in FIG. 2 .
FIG. 7 illustrates the self-propagating, high temperature synthesis for producing hafnium carbide matrix.
FIG. 8 further illustrates the self-propagating, high temperature synthesis method using poly(acrylonitrile-co-butadiene), i.e., “PAB”, for producing hafnium carbide matrix.
FIG. 9 illustrates the x-ray diffraction of the reaction of hafnium and carbon using PAB.
A wide variety of fibers can be used in accordance with the present invention. The type of fiber to use is a design choice, as are types of fiber tows. For example, ceramic fibers can comprise silicon carbide, and metal fibers can comprise tungsten, tantalum, steel, aluminum, and copper fibers. In choosing a fiber tow, factors to consider include fiber tow diameter, tow strength, tow elastic modulus, and the coefficient of thermal expansion (CTE). Three examples of fibers that can be used in accordance with the present invention are as follows in Table 1:
TABLE 1
Carbon Fiber Tow Properties
Tow
Tensile
Tensile
Diameter
Strength GPa
Modulus GPa
Axial CTE
Supplier
Fiber Type
(mm)
(ksi)
(Msi)
ppm/K
Hexcel
AS4 3K
0.387
5.93 (570)
221 (32)
−0.7
Hexcel
UHMS-G 3K
0.242
3.48 (500)
441 (64)
−0.5
Amoco
T-300 3K
0.393
3.65 (530)
231 (33.5)
−0.6
The above fibers from Hexcel comprise polyacrylonitrile (“PAN”). The above fiber from Amoco comprises a petroleum extract, referred to as “pitch.”
The starting carbon fiber tow diameter is a factor in determining the fiber volume fraction of final composite parts. The tow strength and tow stiffness governs mechanical properties such as flexural and tensile strength in the final composite. The CTE of the fiber will determine the compatibility of the fiber/matrix and the size/type of interface. The reported CTE value of the ZrC matrix is 6.9 ppm/K, while axial CTE of carbon fiber is less than 0 ppm/K. In order to minimize this CTE mismatch, a graphite interfacial coating is placed between the carbon fiber and ZrC matrix during co-extrusion.
The wound up co-axial filament can be weaved and/or laid up into a part. The part can then be laminated by heating and/or squeezing out the thermoplastic. The part can then be placed into a furnace and subjected to heat to burn out any remaining thermoplastic. The resulting product of these steps is a co-axial filament having a carbon fiber tow, a graphite interface, and a matrix, and thus comprises a fiber reinforced matrix composite.
The fiber reinforced matrix composite can be further consolidated using any suitable method, including but not limited to, hot pressing, hot isostatic pressing, pressureless sintering, and self propagating high temperature synthesis, all of which are known to those skilled in the art. The consolidation step is to form a fully dense fiber reinforced composite.
Pressureless sintering can be an alternative to the consolidation of composites by hot pressing. In a typical uniaxial hot-pressing process, the monolithic ceramic or composite is consolidated in a graphite die at high temperatures and pressures. While this process is amenable to the production of two-dimensional parts, it is often difficult to produce complicated three-dimensional parts. Also, the uniaxial hot-pressing process is typically not a high volume manufacturing process since only few samples can be pressed in a single run.
In pressureless sintering processes, samples are heated to high temperatures without high pressure in a large volume, high temperature furnace. This allows the production of complex three-dimensional parts in large quantities. Thus, the development of a pressureless sintering process can lead to low cost, fully dense composite parts.
ZrC may be pressureless sintered using sintering additives, for example, zirconium metal. The following examples show the density and flexural strength of composites wherein the consolidation was accomplished by pressureless sintering.
EXAMPLE 1
NCE-BR01
Description: Core Material
Brabender Size: small
Batch Size: 42 cc
Batch Temperature: 150° C.
Batch Speed: 60 rpm
Ingredients
Material
Density (g/cc)
Volume %
Volume (cc)
Weight (g)
ZrC (10% SiC)
6.35
53.65%
22.53
143.08
EEA
0.93
30.00%
12.60
11.72
Wax
0.92
3.75%
1.58
1.45
B-67
1.06
5.27%
2.23
2.35
Butyl Oleate
0.87
7.33%
3.09
2.69
NCE-BR02
Description: Graphite Interlayer Material
Brabender Size: small
Batch Size: 42 cc
Batch Temperature: 150° C.
Batch Speed: 60 rpm
Ingredients
Material
Density (g/cc)
Volume %
Volume (cc)
Weight (g)
Graphite
1.80
53.65%
22.53
37.04
EEA
0.93
30.00%
12.60
11.72
Wax
0.92
6.75%
2.84
2.61
B-67
1.06
5.27%
2.23
2.35
Butyl Oleate
0.87
8.98%
3.78
3.29
Thermal stresses and associated fractures were reduced in the production of relatively crack-free ZrC composites. Further reduction of thermal stresses and degradation of the carbon fibers was achieved during consolidation. This was accomplished by using Hexcel UHMS-G carbon fiber tow. It is believed that the higher elastic modulus of this fiber would help reduce the clamping forces on the fibers produced by the CTE mismatch and thereby eliminate microcracks. In addition, the fiber architecture was varied to better distribute the residual stresses. Two billets were prepared using ZrC (10 vol % SiC) powder.
In preparing the material-laden compounds used in the inventive methods, the raw material powders are typically blended with an organic polymer and, advantageously, one or more processing aids. Most thermoplastic polymers can be used in the compositions of the present invention, but preferred polymer systems are the highly flexible polymers and copolymers, advantageously ethylene polymers and copolymers, and preferably polyethylene, ethylene-ethyl acetate copolymers (“EEA”) e.g., ELVAX 470, from E. I. Dupont Co., and acryloid resin, e.g., B-67, from Rohm and Haas.
A wide variety of powder ceramics may also be used in the material-laden compositions, affording a wide flexibility in the composition of the final fiber reinforced composite. Advantageously, powders which may be used in the first material-laden composition to provide the feed rod include ceramic oxides, ceramic carbides, ceramic nitrides, ceramic borides, ceramic suicides, metals, and intermetallics. Preferred powders for use in that composition include aluminum oxides, barium oxides, beryllium oxides, calcium oxides, cobalt oxides, chromium oxides, dysprosium oxides and other rare earth oxides, lanthanum oxides, magnesium oxides, manganese oxides, niobium oxides, nickel oxides, aluminum phosphate, yttrium phosphate, lead oxides, lead titanate, lead zirconate, silicon oxides and silicates, thorium oxides, titanium oxides and titanates, uranium oxides, yttrium oxides, yttrium aluminate, zirconium oxides and their alloys; boron carbides, iron carbides, hafnium carbides, molybdenum carbides, silicon carbides, tantalum carbides, titanium carbides, uranium carbides, tungsten carbides, zirconium carbides; aluminum nitrides, cubic boron nitrides, silicon nitrides, titanium nitrides, uranium nitrides, yttrium nitrides, zirconium nitrides; aluminum boride, hafnium boride, molybdenum boride, titanium boride, zirconium boride; molybdenum disilicide; magnesium and other alkali earth metals and their alloys; titanium, iron, nickel and other transition metals and their alloys; cerium, ytterbium and other rare earth metals and their alloys; aluminum; carbon; and silicon.
The process of the present invention can be accomplished using various suitable materials, such as ceramic powders (having different particle sizes), thermoplastics, and plasticizers. The present invention can also incorporate various modifications to various steps, including the steps of compounding, maling feed rods, passing the fiber/fiber tow through the feed rod, and using spinnerettes for extrusion. Further, the present invention can be used to achieve more than one coating on a fiber/fiber tow (interlayers), and that the coated fibers/fiber tows of the present invention can be used to form fiber reinforced ceramic articles.
Among the materials that can be used in the present invention for a source of carbon in the self propagating high temperature synthesis process are:
Poly(arylacetylene) (PAA)
Phenolic Resin
Furfuryl Resin
Mesophase Pitch
Petroleum Pitch
Acrylonitrile
Poly(acrylonitril-co-butadiene)
Self-propagating, high temperature synthesis (“SHS”) has been used in test batches of Al 2 O 3 with:
Poly(acrylonitril-co-butadiene) (“PAB”)
A-240 Petroleum pitch
After the tests showing suitable blending between Al 2 O 3 and PAB, Hf/C was then blended with PAB as follows.
1. Hf/C with PAB, air stabilized
2. HF/C with PAB, air stabilized
3. HF/C with PAB, nitrogen pyrolysis, slow ramp
4. Hf/C with PAB, air stabilized, slow ramp
wherein Hf/C is hafnium carbide matrix.
The continuous composite coextrusion process of the present invention has been used to make a hafnium carbide matrix/no interface/carbon fiber reinforcement, and to make a hafnium carbide matrix/graphite interface/carbon fiber reinforcement, as well as zirconium carbide and silicon carbide matrices with graphite interfaces and carbon fiber reinforcement.
The following examples further illustrate preferred embodiments of the present invention but are not be construed as in any way limiting the scope of the present invention as set forth in the appended claims.
EXAMPLE 1
Hafnium Carbide Matrix/No Interface/Carbon Fiber Reinforcement
VPCA-BR00
Description: Core Material
Brabender Size: small
Batch Size: 42 cc
Batch Temperature: 150° C.
Batch Speed: 60 rpm
Ingredients
Material
Density (g/cc)
Volume %
Volume (cc)
Weight (g)
HfC
12.67
54.0%
22.66
287.36
EEA
0.93
32.4%
13.608
12.66
B-67
0.94
3.6%
1.512
1.42
HMO
0.881
10.0%
4.2
3.70
In the above-cited formulation, HfC is hafnium carbide powder from Cerac, Inc., designated as H-1004, B-67 is acryloid resin from Rohin and Haas, EEA is ethylene-ethyl acetate copolymers, and HMO is heavy mineral oil which is a plasticizer. A “Brabender” mixing machine (from C. W. Brabender of South Hackensack, N.J.) was used to mix the above-cited materials. The mixture of materials can then be formed into a feed rod with a hole through the symmetrical axis of the feed rod. After mixing, the mixture was formed into a feed rod-like shape like that shown in FIG. 1 and in detail in FIG. 3 . The carbon fiber reinforcement can be inserted into the hole of the matrix as desired. Following coextrusion, the result is a “green” material that still contains binder, like that shown in FIG. 5 . This green material can now be formed in a desired manner, such as a billet. The billet can then be subjected to lamination in a warm pressing operation to fill remaining voids, and the result is a green billet. The green billet can then be subjected to pyrolysis and then the resulting part can be hot pressed, hot isostatic pressed, or pressureless sintered to densify the matrix.
EXAMPLE 2
Hafnium Carbide Matrix/Graphite Interface/Carbon Fiber Reinforcement
The hafnium carbide matrix made in accordance with Example 1 is the same matrix for Example 2. The only difference in Example 2 is that the hole through the symmetrical axis of the feed rod is made larger so that a graphite interface can be inserted through the hole of the feed rod. The graphite interface defines a hole through its symmetrical axis, and the carbon fiber reinforcement can be inserted into the hole of the graphite interface, resulting in the product illustrated in FIG. 3 . Following coextrusion, desired formation (such as a billet), lamination, pyrolysis, and firing as described in Example 1 and 2 the result is a fully dense composite formation. The formulation for the graphite interface is as follows.
VPCA-BR06
Description: Core Material
Brabender Size: small
Batch Size: 42 cc
Batch Temperature: 150° C.
Batch Speed: 60 rpm
Ingredients
Material
Density (g/cc)
Volume %
Volume (cc)
Weight (g)
Graphite-4929
2.25
49.0%
113.19
254.68
EEA
0.93
49.0%
113.19
105.27
MPEG-550
1.104
2.0%
4.62
5.10
In the above formation, MPEG-550 is methoxy polyethylene glycol 550 (i.e., having an average molecular weight of 550). As previously noted, graphite interface has a hole through its symmetrical axis so that the carbon fiber reinforcement can be inserted through that axis as desired.
Various grades of materials can be used in accordance with the present invention, including various grades of HfC and graphite.
The present invention can be used to make other reinforcements, including but not limited to:
Zirconium Carbide Matrix/Graphite Interface/Carbon Fiber Reinforcement;
Zirconium Carbide Matrix/No Interface/Carbon Fiber Reinforcement or Silicon Carbide Reinforcement;
Silicon Carbide Matrix/No Interface/Carbon Fiber Reinforcement;
Hafnium Diboride Matrix/Graphite Interface/Carbon Fiber Reinforcement;
Silicon Carbide Matrix/Boron Nitride Interface/Silicon Carbide Reinforcement; and
Silicon Nitride Matrix/Boron Nitride Interface/Silicon Carbide Reinforcement.
The continuous composite coextrusion process of the present invention can be used to make a wide range of hafnium carbide matrix (“HfC”) and C f (“carbon fiber reinforcement”) products, including:
1. HfC/C f (25 vol. %), 18 μm carbon black interlayer
2. HfC/C f (25 vol. %),32 μm carbon black interlayer.
3. HfC/C f (12.5 vol. %)45 μm carbon black interlayer.
Thermal Expansion Considerations
Material
CTE (× 10 −6 K −1 )
C f
−0.1 (axial)
HfC
7.2-8.2*
TaC
7.3
HfB 2
7.9
ZrB 2
8.2
SiC
5.8
*Coors Analytical Laboratory
To summarize, the continuous composite coextrusion process of the present invention can be used for ceramic matrix composites (“CMCs”) and metal matrix composites (“MMCs”). Further, the use of interlayers helps to control stresses due to mismatches among the coefficients of thermal expansion (“CTE”), including those set forth above. Further, the present invention reduces microcracking. In addition, the self-propagating, high temperature synthesis is versatile, although it requires an additional densification step.
The present invention can be used for HfC/C f (“carbon fiber reinforced hafnium carbide matrix”) continuous composite coextrusion process cylinders and processes; quantitative fiber volume loading effects; combinations of self-propagating, high temperature synthesis with continuous composite coextusion process; and HfC CVD (“chemical vapor deposition”) coatings.
Many modifications and variations may be made in the techniques and structures described and illustrated herein without departing from the spirit and scope of the present invention. Accordingly, the techniques and structures described and illustrated herein should be understood to be illustrative only and not limiting upon the scope of the present invention.
|
A process for continuous composite coextrusion comprising: (a) forming first a material-laden composition comprising a thermoplastic polymer and at least about 40 volume % of a ceramic or metallic particulate in a manner such that the composition has a substantially cylindrical geometry and thus can be used as a substantially cylindrical feed rod; (b) forming a hole down the symmetrical axis of the feed rod; (c) inserting the start of a continuous spool of ceramic fiber, metal fiber or carbon fiber through the hole in the feed rod; (d) extruding the feed rod and spool simultaneously to form a continuous filament consisting of a green matrix material completely surrounding a dense fiber reinforcement and said filament having an average diameter that is less than the average diameter of the feed rod; and (e) arranging the continuous filament into a desired architecture to provide a green fiber reinforced composite.
| 3
|
TECHNICAL FIELD
The technology relates to the utilization of radio-frequency identification (RFID) tags, and more specifically, to the usage of RFID for object recognition and localization services.
BACKGROUND
People are storing lots of valuable tools and equipment in their basements, shacks and attics. After a couple of months/years they lose track and don't remember where they have put the tool or it is even forgotten, that it exists at all. This is true for professional companies as well as private households.
What is needed is to combine RFID technology and additional data of customer property and manage the resultant data so as to provide improved functionality for management and control of their goods and tools. Customers are everyday consumers with their household goods (all their tools and goods in their basement) as well as professional users, which will benefit from the additional functionality for better control over their property, tools, and inventory.
SUMMARY
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 determining the scope of the claimed subject matter.
A method of creating and managing a database of meta_data sets for a plurality of objects is provided. The meta-data set is configured to characterize an object. The plurality of objects can be enumerated by using an index “j”, wherein “j” is an integer equal or greater than 1. Thus, any object can be identified as a “j”-object, without specifying its particular nature. The meta_data set for a “j”-object is selected from the group consisting of: a first item; a second item; an “i”-th item; and ID-j tag; wherein “i” is an integer equal or greater than.
The method comprises: (A) identifying a meta-data set for at least one object; (B) collecting a meta-data set for at least one object; (C) creating the database of meta-data sets for the plurality of objects; (D) storing the database of meta-data sets for the plurality of objects; and (E) accessing the database of meta-data sets for the plurality of objects.
DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and form a part of this specification, illustrate embodiments of the technology and, together with the description, serve to explain the principles below:
FIG. 1 illustrates a block diagram of an apparatus for creating and managing a database of meta-data sets for a plurality of objects for the purposes of the present technology.
FIG. 2 is a block diagram of a meta-data set collector including a plurality of sensors for the purposes of the present technology.
FIG. 3 depicts a block diagram of an access and manipulation engine configured to access a database of meta-data sets for a plurality of objects to provide service related to at least one object for the purposes of the present technology.
FIG. 4 is a block diagram of an object recognition engine for the purposes of the present technology.
FIG. 5 illustrates the functioning of an object recognition engine for the purposes of the present technology.
FIG. 6 is a flow chart of a method for creating and managing a database of meta-data sets for a plurality of objects for the purposes of the present technology.
DETAILED DESCRIPTION
Reference now is made in detail to the embodiments of the technology, examples of which are illustrated in the accompanying drawings. While the present technology will be described in conjunction with the various embodiments, it will be understood that they are not intended to limit the present technology to these embodiments. On the contrary, the present technology is intended to cover alternatives, modifications and equivalents, which may be included within the spirit and scope of the various embodiments as defined by the appended claims.
Furthermore, in the following detailed description, numerous specific-details are set forth in order to provide a thorough understanding of the presented embodiments. However, it will be obvious to one of ordinary skill in the art that the presented embodiments may be practiced without these specific details. In other instances, well known methods, procedures, components, and circuits have not been described in detail as not to unnecessarily obscure aspects of the presented embodiments.
In an embodiment of the present technology, FIG. 1 illustrates the block diagram 10 of an apparatus for creating and managing a database of meta-data sets for a plurality of objects 11 for the purposes of the present technology.
In an embodiment of the present technology, at least one object 11 is characterized by a meta-data set comprising a plurality of items selected from the group consisting of: a 2-D picture of an object; position coordinates of location of the object; a material of which the object has been made; an explicit functional value of the object; an implicit functional value of the object; a purpose of the object; a brand of the object; an age of the object; weight of the object; and dimensions of the object.
Customers with a large variety of tools kept in shops or in trucks, or in the field, may benefit from having an online database of the tools, along with various ancillary types of data. This online database can contain much more than just the name and model of the tool, making the database extremely useful in terms of obtaining updates, determining warranty periods, consulting on uses of a specific tool, etc.
Example I
The customer takes a picture of the object he wants to archive and track location in the future (alternately he could also scan the bar-code, or write a description) and puts an RFID tag on it. He uploads the picture/information to a “Trimble object recognition service”, along with the unique ID of this RFID tag. The service identifies the type of object (e.g. by pattern matching with pictures in the Internet), sends this information back to the customer's database. From then on the customer can add his own information about the object into the database (initial price, time of purchase, etc.). Also he can locate the object easily with a detector device, when it has been misplaced.
In an embodiment of the present technology, a special Object Recognition Engine can be used to provide an integrated platform for the Asset Management & Visibility. Please, see the detailed disclosure below.
As it is disclosed below in more details, the Object Recognition Engine utilizes a summarized language of Identities to automate the recognition function. Indeed, an object can have a plurality of identities including, but not limited to,: (a) Visual identity—including brand identity etc. that can be looked up using visual recognition; (b) Electronic identity—Barcodes, RFID, tags, QR codes that needs either local or remote recognizers; (c) Engineering identity—drawings, an Application Program, Interface; a source code, accessories, data sheets, application notes etc. that can be looked up; (d) Material identity—what this object is made of.
Referring still to FIG. 1 , in an embodiment of the present technology, the input engine 12 provides to the meta-data set identifier 14 all items that are relevant to the object 11 .
In an embodiment of the present technology, the input engine 12 is implemented by using a data input device selected from the group consisting of: a laptop computer; a netbook; and a smart phone.
In an embodiment of the present technology, the meta-data set identifier 14 is configured to store all items of the meta-data set that are relevant to the object 11 .
In an embodiment of the present technology, the meta-data set identifier 14 is implemented by using a memory storage device selected from the group consisting of: a memory stick; a laptop computer; a netbook; and a smart phone.
In an embodiment of the present technology, the meta-data set identifier 14 transmits to the meta-data set collector 16 all items that are relevant to the object 11 .
As it is shown in FIG. 2 , in an embodiment of the present technology, the meta-data set collector 40 comprises a plurality of sensors that are used to determine each item relevant to the object 11 .
In an embodiment of the present technology, at least one item relevant to object 11 comprises a 3-D picture of the object 11 .
In an embodiment of the present technology, the image-capturing sensor 50 (of FIG. 2 ) is used to capture 3-D picture of the object 11 .
In an embodiment of the present technology, the image-capturing sensor 50 (of FIG. 2 ) configured to capture the 3-D picture of the object 11 is selected from the group consisting of: a digital camera; a digital video camera; a digital camcorder; a stereo digital camera; a stereo video camera; a motion picture camera; a television camera; and a non-photometric 3D scanner.
In an embodiment of the present technology still video and digital cameras store the images in a solid-state memory, or on magnetic media or optical disks.
In an embodiment of the present technology, the image-capturing sensor 50 further comprises a stereo digital camera. A stereo camera is a type of camera with two or more lenses. This allows the camera to simulate binocular vision, and therefore gives it the ability to capture three-dimensional images, a process known as stereo photography. Stereo cameras may be used for making stereo views and 3D pictures for movies, or for range imaging. 3-D Images Ltd., located in UK, produces a 3-D Digital Stereo camera—a fully automatic, time synchronized, digital stereo camera. Point Grey Research Inc., located in Canada produces binoculars or multiple array cameras that can provide full field of view 3 D measurements ion an unstructured environment.
In an embodiment of the present technology, the image-capturing sensor 50 further comprises a non-photometric 3D scanner 46 . 3D scanner is a device that analyzes a real-world object or environment to collect data on its shape and possibly its appearance (i.e. color). The collected data can then be used to construct digital, three dimensional models.
Many different technologies can be used to build these 3D scanning devices; each technology comes with its own limitations, advantages and costs. Many limitations in the kind of objects that can be digitized are still present, for example, optical technologies encounter many difficulties with shiny, mirroring or transparent objects. Collected 3D data is useful for a wide variety of applications. These devices are used extensively by the entertainment industry in the production of movies and video games. Other common applications of this technology include industrial design, orthotics and prosthetics, reverse engineering and prototyping, quality control/inspection and documentation of cultural artifacts.
In an embodiment of the present technology, at least one item relevant to object 11 comprises a 2-D picture of the object 11 . In an embodiment of the present technology, the image-capturing sensor 50 (of FIG. 2 ) is used to capture a 2-D picture of the object 11 .
In an embodiment of the present technology, the image-capturing sensor 50 (of FIG. 2 ) configured to capture the 2-D picture of the object 11 is selected from the group consisting of: a digital camera; a digital video camera; a digital camcorder; a motion picture camera; a television camera; and a non-photometric 2D scanner. (Please see the discussion above).
In an embodiment of the present technology, at least one item relevant to object 11 comprises position coordinates of the object 11 .
In an embodiment of the present technology, the position sensor 48 (of FIG. 2 ) is used to obtain position coordinates of the object 11 .
In an embodiment of the present technology, the position sensor 48 (of FIG. 2 ) configured to obtain position coordinates of the object 11 is selected from the group consisting of: a radio-based position sensor; an image-capturing position sensor; a laser sensor; and a contact and proximity sensor.
In an embodiment of the present technology, the radio-based position sensor 48 (of FIG. 2 ) configured to obtain position coordinates of the object 11 is implemented by using a Trimble Total Station (not shown) to determine precise position coordinates of the object 11 .
In an embodiment of the present technology, the position sensor 48 (of FIG. 2 ) configured to obtain position coordinates of the object 11 is implemented by using a range measuring device (not shown) selected from the group consisting of: a point laser beam; a sonar; a radar; and a laser scanner.
In an embodiment of the present technology, a point laser beam range measuring device can be implemented by using blue solid-state lasers, red diode lasers, IR lasers which maybe continuously illuminated lasers, or pulsed lasers, or sequenced lasers.
In an embodiment of the present technology, a laser scanner range measuring device can be implemented by using positioning sensors offered by Sensor Intelligence website www.sick.com. For instance, the Laser Scanner Model Name S10B-9011DA having compact housing and robust IP 65 design may be used. This laser scanner has the following data sheet: dimensions: (W×H×D)=102×152×105 mm, the scan angle of 270°, and the switching field range of 10 meters. It has the following functionality: a stand-by mode, a 7-segment input display, an integrated parameter memory in-system, a plug CANopen interface, and low energy consumption.
In an embodiment of the present technology, a sonar range measuring device can be implemented by using active sonar including sound transmitter and a receiver.
Active sonar creates a pulse of sound, often called a “ping”, and then listens for reflections (echo) of the pulse. This pulse of sound is generally created electronically using a sonar projector consisting of a signal generator, power amplifier and electro-acoustic transducer/array, possibly with a beam former. To measure the distance to the object 11 the time from transmission of a pulse to reception is measured and converted into a range by knowing the speed of sound. The pulse may be at constant frequency or a chirp of changing frequency (to allow pulse compression on reception). Pulse compression can be achieved by using digital correlation techniques.
In an embodiment of the present technology, a radar range measuring device (not shown) can be implemented by using a transmitter that emits either microwaves or radio waves that are reflected by the scene (not shown) and detected by a receiver, typically in the same location as the transmitter.
In an embodiment of the present technology, at least one item relevant to object 11 comprises material of which the object 11 has been made.
In an embodiment of the present technology, the material probing sensor 44 (of FIG. 2 ) is used to determine the material of which the object 11 has been made.
In an embodiment of the present technology, the material probing sensor 44 (of FIG. 2 ) is selected from the group consisting of: a probe material analyzer; a bio organic sensor; a bio inorganic sensor; a nano organic sensor; a nano inorganic sensor; a micro-electrochemical sensor; a bio-electrochemical sensor; and an integrated analytical system.
Probe Material Analyzer manufactured by Chemsultants International, Inc., located in Mentor, Ohio 44060 can be used as a versatile and user-friendly testing device. The ChemInstruments Probe Material Analyzer is configured to characterize a variety of materials through the insertion, dwell and retraction of custom probe sensors. Those materials include viscoelastic polymers, adhesives and compounds. Data management is made easier with the included EZ-Lab software.
A biosensor is an analytical device that can convert a biological reaction into an electrical (voltage) signal. Biosensors consist of a biological element (e.g. enzyme, whole cell, etc.) that is immobilized on a membrane and connected to a transducer (probe). The reaction occurs at the membrane where the substrate of interest is converted to a product that causes an electrical response. This response is measured by the transducer and then amplified, processed and displayed using a meter and PowerLab data acquisition system. The PowerLab is a high-performance data acquisition unit capable of recording at speeds of up to 400,000 samples per second continuously to disk (aggregate). PowerLab units are compatible with instruments, signal conditioners and transducers supplied by ADInstruments, as well as many other third-party companies. In addition to standard single-ended BNC inputs, 4 differential Pod ports are also available for direct connection of Pod signal conditioners and appropriate transducers. Research PowerLab is manufactured by ADInstruments, Inc., Colorado Springs, Colo. 80906.
The Nanochemistry and Nanoengineering group from the University of Dayton Research Institute located in Dayton, Ohio, has developed numerous bio sensors.
A XYZ-on-a-chip MEMS Fuel Sensor is a portable all-in-one functional sensor for combat in-field fuel testing for specific hydrocarbon content, oxygen, water, conductivity, etc.
Opto-Chemical Sensors is a CdS nanoparticle-based thin film for opto-chemical sensor applications. Opto-chemical sensing is based on the unique ability of nanostructured semiconductors to alter their optical response in the presence of a “recognition element,” the chemical adsorbent on the surface. Such sensors can be calibrated for detection of specific chemicals, including toxic species in both liquids and gases.
Nanobiomagnetic Sensors utilize functionalized magnetic nanoparticles.
A variety of electrochemical sensors are being used extensively in many stationary and portable applications. Electrochemical sensors operate by reacting with the gas of interest and producing an electrical signal proportional to the gas concentration. A typical electrochemical sensor consists of a sensing electrode (or working electrode), and a counter electrode separated by a thin layer of electrolyte.
Sandia National Laboratories research team has developed an electrochemical sensor that uses a unique surface chemistry to reliably and accurately detect thousands of differing biomolecules on a single platform.
The University of Texas at Austin has developed a self-powered micro electrochemical sensor in which pressure-driven flow alone (no external electrical energy) can be used to drive faradaic electrochemical reactions.
Referring still to FIG. 1 , in an embodiment of the present technology, at least one item relevant to object 11 comprises a purpose of the object 11 .
In an embodiment of the present technology, the purpose of the object 11 could be entered manually by an owner of object 11 at the time the local database of meta-data sets 18 has been created.
In an embodiment of the present technology, the purpose of the object 11 could be recovered from the inventory records.
Referring still to FIG. 1 , in an embodiment of the present technology, at least one item relevant to object 11 comprises a brand of the object 11 .
In an embodiment of the present technology, the brand of the object 11 could be entered manually by an owner of object 11 at the time the local database of meta-data sets 18 has been created.
In an embodiment of the present technology, the brand of the object 11 could be recovered from the inventory records.
Referring still to FIG. 1 , in an embodiment of the present technology, at least one item relevant to object 11 comprises an age of the object 11 .
In an embodiment of the present technology, the age of the object 11 could be entered manually by an owner of object 11 at the time the local database of meta-data sets 18 has been created.
In an embodiment of the present technology, the age of the object 11 is relevant for the purposes of evaluating the value of the object.
Referring still to FIG. 1 , in an embodiment of the present technology, at least one item relevant to object 11 comprises the weight of the object 11 .
In an embodiment of the present technology, the weight of the object 11 could be entered manually by an owner of object 11 at the time the local database of meta-data sets 18 has been created.
In an embodiment of the present technology, the weight of the object 11 could be recovered from the inventory records.
Referring still to FIG. 1 , in an embodiment of the present technology, at least one item relevant to object 11 comprises the dimensions of the object 11 .
In an embodiment of the present technology, the dimensions of the object 11 could be entered manually by an owner of object 11 at the time the local database of meta-data sets 18 has been created.
In an embodiment of the present technology, the dimensions of the object 11 could be recovered from the inventory records.
Referring still to FIG. 1 , in an embodiment of the present technology, at least one item relevant to object 11 comprises the explicit (objective) functional value of the object 11 .
In an embodiment of the present technology, the explicit (objective) functional value of the object 11 could be entered manually by an owner of object 11 at the time the local database of meta-data sets 18 has been created.
In an embodiment of the present technology, the explicit functional value of the object 11 could be recovered from the inventory records.
In an embodiment of the present technology, the explicit functional value of the object 11 could be determined by using the functional intelligent engine 42 of FIG. 2 .
Referring still to FIG. 1 , in an embodiment of the present technology, at least one item relevant to object 11 comprises the implicit (subjective) functional value of the object 11 .
In an embodiment of the present technology, the implicit (subjective) functional value of the object 11 could be entered manually by an owner of object 11 at the time the local database of meta-data sets 18 has been created.
In an embodiment of the present technology, the implicit functional value of the object 11 could be determined by using the functional intelligent engine 42 of FIG. 2 .
Referring still to FIG. 1 , in an embodiment of the present technology, the object 11 is identified by an ID tag 13 attached to it.
Referring still to FIG. 1 , in an embodiment of the present technology, the ID tag 13 is selected from the group consisting of: a quick response code (QR code) attached to the object; an RFID tag; a low power RFID tag; a barcode; an infra-red tag; and an ultra sound tag.
QR Code (abbreviated from quick response code) is the trademark for a type of matrix barcode (or two-dimensional code) first designed for the automotive industry. More recently, the system has become popular outside of the industry due to its fast readability and large storage capacity compared to standard UPC barcodes. The code consists of black modules arranged in a square pattern on a white background. The information encoded can be made up of four standardized kinds (“modes”) of data (numeric, alphanumeric, byte/binary, Kanji), or through supported extensions, virtually any kind of data. Invented by the Toyota subsidiary Denso Wave in 1994 to track vehicles during the manufacturing process, the QR Code is one of the most popular types of two-dimensional barcodes. It was designed to allow its contents to be decoded at high speed.
Formerly confined to industrial uses, they have in recent years become common in consumer advertising and packaging, because the dissemination of smartphones “has put a barcode reader in everyone's pocket” for the first time. As a result, the QR code has become a focus of advertising strategy, since it provides quick and effortless access to the brand's website. Beyond mere convenience to the consumer, the importance of this capability is that it increases the conversion rate (that is, increase the chance that contact with the advertisement will convert to a sale), by coaxing qualified prospects further down the conversion funnel without any delay or effort, bringing the viewer to the advertiser's site immediately, where a longer and more targeted sales pitch may continue.
Referring still to FIG. 1 , in an embodiment of the present technology, the ID tag 13 can be implemented by using Radio-frequency identification (RFID) technology that uses communication through the use of radio waves to exchange data between a reader and an electronic tag attached to an object, for the purpose of identification and tracking.
It is possible in the near future, RFID technology will continue to proliferate in our daily lives the way that bar code technology did over the forty years leading up to the turn of the 21st century bringing unobtrusive but remarkable changes when it was new.
RFID makes it possible to give each product in a grocery store its own unique identifying number, to provide assets, people, work in process, medical devices etc. all with individual unique identifiers—like the license plate on a car but for every item in the world. This is a vast improvement over paper and pencil tracking or bar code tracking that has been used since the 1970s. With bar codes, it is only possible to identify the brand and type of package in a grocery store, for instance.
Furthermore, passive RFID tags (those without a battery) can be read if passed within close enough proximity to an RFID reader. It is not necessary to “show” them to it, as with a bar code. In other words it does not require line of sight to “see” an RFID tag, the tag can be read inside a case, carton, box or other container, and unlike barcodes RFID tags can be read hundreds at a time. Bar codes can only read one at a time.
Some RFID tags can be read from several meters away and beyond the line of sight of the reader. The application of bulk reading enables an almost simultaneous reading of tags.
Radio-frequency identification involves the hardware known as interrogators (also known as readers), and tags (also known as labels), as well as RFID software or RFID middleware. The novel RFID tags are selected from the group including, but not limited to, a High Frequency (HF) RFID tag; and an Ultra High Frequency (UHF) RFID tag, Ultra-Wideband (UWB) tags, and Chipless RFID tags.
Most RFID tags 13 contain at least two parts: one is an integrated circuit for storing and processing information, modulating and demodulating a radio-frequency (RF) signal, and other specialized functions; the other is an antenna (not shown) for receiving and transmitting the RF signal.
RFID can be either passive (using no battery), active (with an on-board battery that always broadcasts or beacons its signal) or battery assisted passive “BAP” which has a small battery on board that is activated when in the presence of an RFID reader. Passive tags in 2011 start at $0.05 each and for special tags meant to be mounted on metal, or withstand gamma sterilization go up to $5. Active tags for tracking containers, medical assets, or monitoring environmental conditions in data centers all start at $50 and can go up over $100 each. BAP tags are in the $3-10 range and also have sensor capability like temperature and humidity.
In an embodiment of the present technology, the ID tag 13 is implemented by using a combination of an RFID tag and an infra-red tag. The combination of active RFID tags and infrared technology enables the system to work in data environment that have both open and closed Data Generation Devices. In this scenario, the short range of infrared signal is an advantage.
In an embodiment of the present technology, the ID tag 13 is implemented by using an ultra sound tag.
For example, the PC-Detector from Sonitor Technologies uses ultrasound indoor positioning and real time location systems (RTLS) technology to automatically track the real time location of patients and moveable hospital equipment. The RTLS solution makes the Sonitor ultrasound tag signal detectable by computers not already equipped with the hardware and sound processing capabilities that are required to pinpoint indoor positioning system tags. By leveraging existing computer hardware and LAN connectivity, mobile computing systems such as tablet PCs, computer/medication carts, and other point-of-care devices can track the tags with reliable 100 percent room-level and bed-level location accuracy. Sonitor Technologies Inc. is located in Largo, Fla.
Referring still to FIG. 1 , in an embodiment of the present technology, the ID tag 13 includes an externally readable code selected from the group consisting of: a radio code transmitted on a specific frequency, a radio code transmitted on a specific frequency periodically, a radio code transmitted on a specific frequency aperiodically, an infrared code, an infrared code transmitted on a specific frequency periodically, an infrared code transmitted on a specific frequency aperiodically, an ultrasound transmitted on a specific frequency, an ultrasound transmitted on a specific frequency periodically, and an ultrasound transmitted on a specific frequency aperiodically.
Referring to FIG. 2 , in an embodiment of the present technology, the Meta-data set collector 40 includes an ID tag reader 52 .
Referring still to FIG. 1 , in an embodiment of the present technology, the ID tag reader 52 (of FIG. 2 ) is selected from the group consisting of: an RFID tag reader, an Infrared tag reader, and an Ultra Sound tag reader.
In an embodiment of the present technology the RFID reader 52 can be implemented by using ThingMagic® Mercury 6 (M6) 4-port, multiprotocol RFID reader.
Depending on mobility, RFID readers 52 are classified into two different types: fixed RFID and mobile RFID. If the reader reads tags in a stationary position, it is called fixed RFID. These fixed readers are set up specific interrogation zones and create a “bubble” of RF energy that can be tightly controlled if the physics is well-engineered. This allows a very definitive reading area for when tags go in and out of the interrogation zone.
In an embodiment of the present technology, if ID tag 13 is implemented by using a passive RFID tag 13 (without a battery), it can be read if passed within close enough proximity to the RFID reader 52 . It is not necessary to “show” them to it, as with a bar code. In other words it does not require line of sight to “see” an RFID tag, the tag can be read inside a case, carton, box or other container, and unlike barcodes RFID tags can be read hundreds at a time. Bar codes can only read one at a time.
Some RFID tags 13 can be read from several meters away and beyond the line of sight of the reader. The application of bulk reading enables an almost simultaneous reading of tags.
In an embodiment of the present technology, the Infra-Red (IR) tag reader 52 can be implemented by using tag return signal generation using a light source to return a signal from the IR tag 13 to the tag reader 52 . A modulated light signal could be produced by turning on and off a small infrared LED using short current pulses.
In an embodiment of the present technology, the Infra-Red (IR) tag reader 52 can be implemented by using a light shutter to modulate the light striking the IR tag reader 52 . Some ferroelectric devices, which require low power and behave like liquid crystal displays, could be placed in front of a plastic corner cube type reflective surface. A corner cube reflector has the unique property that it will send light back to the source in a parallel path. Such reflectors are often used on street signs, bicycle reflectors and on reflective clothing. When the ferroelectric device is turned on, light would be allowed to pass through the device and would then bounce off the reflective material, sending the light back to the source. When the ferroelectric device is turned off, light would not reach the reflective material and would therefore be adsorbed. Some ferroelectric devices have been used for high speed video displays so they could allow high data rates. Texas Instruments also has perfected arrays of tiny mirrors that can be moved using electrostatic methods to produce a light modulator. The beauty of the optical reflective method is that the level of light reflected back to a reader would be proportional to the amount of light striking the OPID tag. The approach might allow the tag read range to be extended to hundreds of feet or perhaps even 1 miles.
In an embodiment of the present technology, the Ultra Sound tag reader 52 can be implemented by using Sonitor's ultrasound technology.
In an embodiment of the present technology, referring still to FIG. 1 , the local database of meta-data sets 18 is created by using the meta-data set collector 16 .
In an embodiment of the present technology, referring still to FIG. 1 , the local/remote storage database of meta-data sets 20 is created by using the meta-data set collector 16 . The storage database 20 is remotely located on the rented web server and is configured to keep the local database 18 records for an indefinite time period.
In an embodiment of the present technology, referring still to FIG. 1 , the Local Database of meta-data sets 18 (and/or the Remote/Local Storage Database 20 ) is periodically updated by using the Updating Engine (shown as block 66 in FIG. 3 ) and implemented by the meta-data set Collector 16 .
In an embodiment of the present technology, referring still to FIG. 1 , the meta-data set Collector 16 can be implemented by using a wireless communication device selected from the group consisting of: a laptop; a netbook; a smartphone which is equipped with a wireless local communications system; a tablet; and a general wireless communication device having a display.
In an embodiment of the present technology, referring still to FIG. 1 , the Local Database 18 can be implemented by using a device selected from the group consisting of: a laptop; a netbook; a smartphone, which is equipped with a wireless local communications system; a tablet; and a general wireless communication device having a display.
In an embodiment of the present technology, referring still to FIG. 1 , the Remote/Local Storage Database of meta-data sets 20 can be implemented by using a remote server.
In an embodiment of the present technology, referring still to FIG. 1 , the Access & Manipulation Engine 22 can be utilized to perform a number of functions related to the Local Database of meta-data sets 18 (and/or Remote/Local Storage Database of meta-data sets 20 ).
In an embodiment of the present technology, referring still to FIG. 1 , the Access & Manipulation Engine 22 can be implemented by using a device selected from the group consisting of: a laptop, a netbook, a smartphone equipped with a wireless local communication system; a tablet; and a special purpose portable devices with a display.
In an embodiment of the present technology, referring to FIG. 1 , more specifically, the Access & Manipulation Engine 22 can be utilized as a Tracking Engine 64 (of FIG. 3 ) to perform tracking of at least one object 11 in the Local Database of meta-data sets 18 and/or in the Remote/Local Storage Database of meta-data sets 20 .
In an embodiment of the present technology, referring still to FIG. 1 , more specifically, the Access & Manipulation Engine 22 can be utilized as a Reminder Service Engine 62 (of FIG. 3 ) to provide a reminder service for at least one object 11 in the Local Database of meta-data sets 18 (and/or in the Remote/Local Storage Database of meta-data sets 20 ).
In an embodiment of the present technology, the reminder service is selected from the group consisting of: expiration of warranty reminder for a selected object; service intervals reminder for a selected object; and factory call-backs reminder for a selected object.
In an embodiment of the present technology, referring still to FIG. 1 , more specifically, the Access & Manipulation Engine 22 can be utilized as the Access code & Encryption Engine 68 (of FIG. 3 ) to provide and encrypt an access code to the Local Database of meta-data sets 18 (and/or to the Remote/Local Storage Database of meta-data sets 20 .
In an embodiment of the present technology, FIG. 4 illustrates an Object Recognition Engine 80 that provides an integrated platform for the Asset Management & Visibility.
In an embodiment of the present technology, the Object Recognition Engine 80 of FIG. 4 utilizes a summarized language of Identities to automate the recognition function. Indeed, an object can have many identities including: (a) Visual identity—including brand identity etc. that can be looked up using visual recognition; (b) Electronic identity—Barcodes, RFID, tags, QR codes that needs either local or remote recognizers; (c) Engineering identity—drawings, an Application Program, Interface; a source code, accessories, data sheets, application notes etc. that can be looked up; (d) Material identity—what this object is made of.
In an embodiment of the present technology, more specifically, the Object Recognition Engine 80 of FIG. 4 uses inputs from RFID tag 82 , from QR code 84 , and from other sensors 86 to the sensor abstraction layer 100 .
In an embodiment of the present technology, the data visualization layer 96 uses a generic visualization component (for example, an enhancement to the Trimble Connected Community software) to process the data from the sensor abstraction layer 100 .
In an embodiment of the present technology, the data integration layer 98 uses the inputs from the data visualization layer 96 , the tag store 94 , from Rules Engine and Router 92 , and from Event Trigger layer 90 to create the Object data store 88 (database of meta-data sets 18 of FIG. 1 ). The outputs 102 , 104 , 106 represent the responses to the data requests from the customers.
In an embodiment of the present technology, FIG. 5 illustrates the diagram 110 that explains the functioning of the Object Recognition Engine 80 (of FIG. 4 ) in more details.
In an embodiment of the present technology, the functioning diagram 110 of FIG. 5 of the Object Recognition Engine 80 (of FIG. 4 ) takes any one of visual and electronic identities available to the mobile (or stationary, e.g. scanner station at a toll shop) terminal (not shown) and returns as many of other identities as possible, along with a probability or confidence level. It also returns the best method to tag the object with an RFID tag which might have the form shown at the block 114 of FIG. 5 .
In an embodiment of the present technology, the Trimble ID: M X 3 4 N S 9 3 http://www.trimble.com/id/MX34NS93 could provide the following information about the object: Manuals 116 , Visual Identity 118 , Electronic Identity 120 , Engineering identity 122 , Material identity 124 , Consumable reordering 124 , Sales and service information 126 , and Warranty information 120 .
In an embodiment of the present technology, for example, if only a photograph is available, the Object Recognition Engine 80 (of FIG. 4 ) looks up the name and other identities either maintained in an Object Registry or on the Internet and returns them in the form of a URL that points to a page containing all available information. This page is available to authenticated users.
In an embodiment of the present technology, FIG. 6 illustrates a flow chart 130 of the method of creating and managing a database of meta-data sets for a plurality of objects using the apparatus 10 of FIG. 1 .
At the step 132 of FIG. 6 , the meta-data set for the object 11 is identified by using the meta-data set identified 14 of FIG. 1 .
At the step 134 of FIG. 6 ; all identified items of the meta-data set and the ID tag for the object 11 are collected by using the plurality of sensors ( 42 , 44 , 46 , 42 , and 50 of FIG. 2 ) and the ID tag reader 52 (of FIG. 2 ).
At the step 136 of FIG. 6 , the Local database 18 is created by using the meta-data sets obtained in the step 134 for each object.
At the step 138 of FIG. 6 , the Local database 18 is stored in the Remote rented server 20 .
At the step 140 of FIG. 6 , the Local database 18 and/or the Remote Database 20 are accessed by using the Access & Manipulation Engine 22 by providing a valid access code to an authorized customer.
The above discussion has set forth the operation of various exemplary systems and devices, as well as various embodiments pertaining to exemplary methods of operating such systems and devices. In various embodiments, one or more steps of a method of implementation are carried out by a processor under the control of computer-readable and computer-executable instructions. Thus, in some embodiments, these methods are implemented via a computer.
In an embodiment, the computer-readable and computer-executable instructions may reside on computer useable/readable media.
Therefore, one or more operations of various embodiments may be controlled or implemented using computer-executable instructions, such as program modules, being executed by a computer. Generally, program modules include routines, programs, objects, components, data structures, etc., that perform particular tasks or implement particular abstract data types. In addition, the present technology may also be practiced in distributed computing environments where tasks are performed by remote processing devices that are linked through a communications network. In a distributed computing environment, program modules may be located in both local and remote computer-storage media including memory-storage devices.
Although specific steps of exemplary methods of implementation are disclosed herein, these steps are examples of steps that may be performed in accordance with various exemplary embodiments. That is, embodiments disclosed herein are well suited to performing various other steps or variations of the steps recited. Moreover, the steps disclosed herein may be performed in an order different than presented, and not all of the steps are necessarily performed in a particular embodiment.
Although various electronic and software based systems are discussed herein, these systems are merely examples of environments that might be utilized, and are not intended to suggest any limitation as to the scope of use or functionality of the present technology. Neither should such systems be interpreted as having any dependency or relation to any one or combination of components or functions illustrated in the disclosed examples.
Although the subject matter has been described in a language specific to structural features and/or methodological acts, the subject matter defined in the appended claims is not necessarily limited to the specific features or acts described above. Rather, the specific features and acts described above are disclosed as exemplary forms of implementing the claims.
|
A method of creating and managing a database of meta_data sets for a plurality of objects is provided. The meta-data set is configured to characterize an object. The meta_data set for a “j”-object is selected from the group consisting of: a first item; a second item; an “i”-th item; and ID-j tag; wherein “i” and “j” being integers. The method comprises: (A) identifying a meta_data set for at least one object; (B) collecting a meta_data set for at least one object; (C) creating the database of meta_data sets for the plurality of objects; (D) storing the database of meta_data sets for the plurality of objects; and (E) accessing the database of meta_data sets for the plurality of objects.
| 6
|
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation of U.S. patent application Ser. No. 13/964,135, filed Aug. 12, 2013, now U.S. Pat. No. 9,557,584, which is a continuation of U.S. patent application Ser. No. 13/689,800, filed Nov. 30, 2012, now U.S. Pat. No. 8,508,384, which is a continuation of U.S. patent application Ser. No. 13/284,197, filed Oct. 28, 2011, now U.S. Pat. No. 8,325,055, which is a continuation of U.S. patent application Ser. No. 13/035,297, filed Feb. 25, 2011, now U.S. Pat. No. 8,049,640, which is a continuation of U.S. patent application Ser. No. 11/926,882, filed Oct. 29, 2007, now U.S. Pat. No. 7,978,094, which is a continuation of U.S. patent application Ser. No. 10/556,754, filed Nov. 15, 2005, now U.S. Pat. No. 7,289,037, which is a 371 U.S. national phase application of PCT Application No. PCT/US2004/015424, filed May 18, 2004, which claims benefit of U.S. provisional applications, Ser. No. 60/556,259, filed Mar. 25, 2004; Ser. No. 60/525,537, filed Nov. 26, 2003; and Ser. No. 60/471,546, filed May 19, 2003, which are hereby incorporated herein by reference in their entireties.
FIELD OF THE INVENTION
[0002] The present invention relates generally to the field of interior rearview mirror assemblies for vehicles and, more particularly, to interior rearview mirror assemblies which incorporate an accessory or feature, particularly an electronic accessory or feature.
BACKGROUND OF THE INVENTION
[0003] The base level mirror for a vehicle is often a prismatic mirror assembly, which may provide a low cost mirror for the vehicle. The mirror assembly is often economically assembled by snapping or inserting the toggle assembly and prismatic reflective element into the casing at the front or bezel portion of the mirror casing substantially immediately after the casing (which may be formed of a hot molded polypropylene or the like) is formed and while the casing is still hot and pliable. As the casing cools, it shrinks to secure the reflective element in place in the casing. Because the reflective element is inserted into the casing while the casing is hot (such as after being freshly molded), the timing for the insertion process may be limited. Thus, it may be difficult to install or insert other accessories or components into the casing before the casing cools and shrinks.
[0004] It is often desirable to provide an electronic feature in the mirror assembly, such as a compass sensor and/or compass display, a tire pressure monitoring system and/or display and/or the like. In order to facilitate the addition of accessories or other components in the mirror assembly, the mirror assembly may typically have a casing and a separate bezel portion, which allows the accessory or accessories or the like to be installed into the casing (via its front opening) after it has cooled, and then allows the reflective element and bezel portion to be installed at the front portion of the casing. The bezel portion may be snapped to the casing or may be otherwise attached to the casing via sonic welding or the like to secure the bezel portion to the casing and to secure the components or accessories and the reflective element at or within the mirror casing. Although practical, this involves a less economical two-part, non-unitary casing and bezel design.
[0005] It is typically preferred to have the unitarily formed casing and bezel portion so that the reflective element is inserted into the casing while the casing is hot and pliable. However, it is also desirable to provide additional features or functions to the mirror assembly. Therefore, there is a need in the art for an improved mirror assembly which overcomes the shortcomings of the prior art.
SUMMARY OF THE INVENTION
[0006] The present invention provides an interior rearview mirror assembly which has one or more cap portions which attach or secure to a rear portion of a mirror holder. The mirror holder comprises part of a reflective element assembly portion comprising a mirror reflective element and a bezel portion or the like that preferably encompasses at least a perimeter portion of the reflective element, thereby at least partially securing the reflective element in the reflective element assembly portion. The cap portion or portions may include one or more electronic accessories or circuitry to provide additional features or functions to the mirror assembly. The additional features or functions may thus be back-loaded into the mirror holder after the mirror holder is formed and after the reflective element is attached at the bezel portion or front portion of the mirror holder.
[0007] According to an aspect of the present invention, an interior rearview mirror assembly for a vehicle comprises a mirror holder having a front portion and a rear portion, a reflective element positioned at the front portion of the mirror holder and received at least partially within the front portion of the mirror holder, and at least one cap portion. The rear portion of the mirror holder has at least one opening therethrough and the at least one cap portion is attachable to the rear portion of the mirror holder generally at the at least one opening. The at least one cap portion includes circuitry for at least one accessory. The at least one cap portion provides a rear cover for the mirror holder generally over the at least one opening.
[0008] According to another aspect of the present invention, a method of manufacturing an interior rearview mirror assembly portion includes forming a first molding by injection molding a first resinous material in a mold. The first resinous material has a tool shrinkage factor of at least approximately 1%. The first molding is at an elevated temperature when the first molding is removed from the mold. A reflective element is provided and positioned at the first molding before the first molding has cooled to approximately ambient temperature. The first molding at least partially encompasses a perimeter portion of the reflective element to form a reflective element assembly portion. The first molding is allowed to cool and shrink to retain the reflective element at the first molding. A cap portion comprises a second resinous material, which has a tool shrinkage factor of at less than or equal to approximately 1%. The cap portion includes at least one accessory. The cap portion is attached to the reflective element assembly portion after the first molding has cooled and shrunk. The cap portion is attached to the reflective element assembly portion such that the accessory is at least partially within the mirror assembly.
[0009] The accessory may comprise a compass sensor and/or display, a tire pressure monitoring system receiver/control circuitry and/or display, an antenna, a garage door opener, or any other accessory and/or accessory display and associated circuitry. For example, the circuitry may comprise compass display circuitry and the reflective element may have at least one port or icon or character etched or otherwise formed thereon, and preferably with an element of the circuitry aligned with/juxtaposed with the at least one port or icon or character etched or otherwise formed on the reflective element. The display circuitry may include at least one illumination source or lighting element for projecting illumination through a corresponding or appropriate port or icon or character on the mirror reflective element.
[0010] The cap portion or portions may be detachably attached to the mirror holder or first molding or bezel portion, such as via accessible detents or snaps or the like, and may be detachably removable from the mirror holder or first molding or bezel portion for service or replacement. However, the cap portion may alternatively be non-detachably attached, such as by adhesive attachment or by heat staking or by ultrasonic welding or the like.
[0011] Therefore, the present invention provides an interior rearview mirror assembly which may include one or more electronic accessories or features. The accessory or feature may be installed at the rear portion of the mirror holder or bezel portion opposite the reflective element, and may be installed after the reflective element is inserted into the freshly molded or hot mirror holder or bezel portion and after the mirror holder has cooled and shrunk to secure the reflective element. Preferably, the accessory or feature may be mounted or positioned at, within or on one or more cap portions (preferably also with any associated wiring, interconnects and/or connectors and the like) which may be secured to the rear portion of the mirror holder and which may form a rear wall or surface of the mirror holder. The cap portion may be snapped to or attached to the mirror holder (which has the reflective element already inserted/installed therein) after the mirror holder has cooled, such that the assembly may be completed at a facility or assembly line that is remote from the facility or line at which the reflective element and mirror holder are assembled together. The present invention thus facilitates the addition of an electronic accessory or feature into a low cost mirror assembly with minimal additional investment to add the accessory or feature. The present invention may thus easily accommodate various features which may be selected by a customer.
[0012] These and other objects, advantages, purposes and features of the present invention will become apparent upon review of the following specification in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a front perspective view of an interior rearview mirror assembly in accordance with the present invention;
[0014] FIG. 2 is an exploded perspective view of the interior rearview mirror assembly of FIG. 1 ;
[0015] FIG. 3 is an exploded perspective view of another interior rearview mirror assembly in accordance with the present invention;
[0016] FIG. 4 is an exploded perspective view of another interior rearview mirror assembly in accordance with the present invention;
[0017] FIG. 5 is an exploded perspective view of another interior rearview mirror assembly in accordance with the present invention;
[0018] FIG. 6 is a perspective view of a reflective element assembly portion of the mirror assembly of the present invention, with the reflective element removed to show additional details;
[0019] FIG. 7 is an opposite perspective view of the reflective element assembly portion of FIG. 6 ;
[0020] FIG. 8 is a perspective view of a cap portion of the mirror assembly of FIG. 5 ;
[0021] FIG. 9 is a perspective view of a cap portion and circuit boards of FIG. 5 , as assembled;
[0022] FIG. 10 is a rear perspective view of another interior rearview mirror assembly of the present invention;
[0023] FIG. 11 is a rear elevation of another interior rearview mirror assembly of the present invention;
[0024] FIG. 12 is a front elevation of an interior rearview mirror assembly, having directional heading or compass display in accordance with the present invention;
[0025] FIGS. 13A-D are enlarged elevations of customized compass displays in accordance with the present invention;
[0026] FIG. 14 is a front elevation of another interior rearview mirror assembly, showing another compass display in accordance with the present invention;
[0027] FIG. 15 is a front elevation of another interior rearview mirror assembly, showing another compass display in accordance with the present invention;
[0028] FIG. 16 is a front elevation of another interior rearview mirror assembly, showing another compass display in accordance with the present invention
[0029] FIG. 17 is a front elevation of another interior rearview mirror assembly having a compass and temperature display;
[0030] FIG. 18 is a front elevation of another interior rearview mirror assembly, having a garage door opening system display and user inputs in accordance with the present invention;
[0031] FIG. 19 is a front elevation of another interior rearview mirror assembly, having a compass display and a tire pressure monitoring system display in accordance with the present invention;
[0032] FIG. 20 is a front elevation of another interior rearview mirror assembly, having a tire pressure monitoring system display in accordance with the present invention;
[0033] FIG. 21 is an enlarged front elevation of another tire pressure monitoring system display in accordance with the present invention;
[0034] FIG. 22 is a front elevation of another interior rearview mirror assembly, having a telematics module and display in accordance with the present invention;
[0035] FIG. 23 is a front elevation of another interior rearview mirror assembly, having a telematics module and display in accordance with the present invention;
[0036] FIG. 24 is a perspective view of a cap portion for an interior rearview mirror assembly in accordance with the present invention;
[0037] FIG. 25 is an enlarged perspective view of a light actuator of the cap portion of FIG. 24 ;
[0038] FIG. 26 is a perspective view of another cap portion of the present invention;
[0039] FIG. 27 is an upper perspective view of an interior rearview mirror assembly of the present invention, with microphones positioned along an upper cap portion;
[0040] FIG. 28 is a sectional view of an interior rearview mirror assembly having a battery in accordance with the present invention;
[0041] FIG. 29 is an exploded perspective view of another interior rearview mirror assembly in accordance with the present invention;
[0042] FIG. 30 is a rear perspective view of the mounting assembly of the mirror assembly of FIG. 29 ;
[0043] FIG. 31 is a sectional view of the mounting arm and mount of FIG. 30 ;
[0044] FIG. 32 is a rear perspective view of another mounting assembly of the present invention;
[0045] FIG. 33A is a sectional view of an electrochromic reflective element assembly portion in accordance with the present invention;
[0046] FIG. 33B is a sectional view of another electrochromic reflective element assembly portion in accordance with the present invention;
[0047] FIG. 33C is a sectional view of a prismatic reflective element assembly portion and rear mirror casing cap portion in accordance with the present invention;
[0048] FIG. 34 is a perspective view of another interior rearview mirror assembly and a windshield accessory module in accordance with the present invention;
[0049] FIGS. 35A-D are perspective views of different accessory modules of the present invention;
[0050] FIG. 36 is a sectional view of an electro-optic reflective element assembly;
[0051] FIG. 37A is a plan view of the third surface of a rear substrate for an exterior electro-optic reflective element assembly in accordance with the present invention; and
[0052] FIG. 37B is a plan view of the second surface of a front substrate for the exterior electro-optic reflective element assembly.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0053] Referring now to the drawings and the illustrative embodiments depicted therein, an interior rearview mirror assembly or modular prismatic rearview mirror assembly 10 for a vehicle includes a reflective element assembly portion 13 including a mirror holder 12 and a reflective element 14 ( FIG. 1 ) positioned at and at least partially within the mirror holder and/or bezel portion, that preferably is molded from a polyolefin material, such as a polypropylene material or the like. Mirror assembly 10 includes a plastic molded cap or cap portion 16 , preferably molded from an ABS material, an engineering resin material, such as a filled or unfilled nylon material, or the like (and may be integrally molded with metallic or ceramic materials or inserts or the like to provide mechanical bracing and enhanced structural rigidity). Cap portion 16 is mountable or attachable to a rear portion or open portion 12 a of mirror holder 12 , and may include an accessory or feature or the like, such as a printed circuit board 18 having an electronic accessory or circuitry thereon or integrated therein or attached thereto. Cap portion 16 may be snapped or otherwise mounted to or attached to the open rear portion 12 a of mirror holder 12 to install or back-load the printed circuit board and/or accessory within the mirror holder 12 of mirror assembly 10 . Cap portion 16 may be detachably mounted or attached to the mirror holder, such as via accessible detents or snaps or the like, and may be removable or detachable from the rear portion of the mirror holder, such as for service or replacement of the cap portion or one or more accessories of the cap portion.
[0054] Various cap portions of the present invention may be provided with different options or accessories, and may be selected to mount to or attach to a universal or common mirror holder to form different mirror assemblies having different content. The present invention thus allows an automobile manufacturer to order or purchase common or standard mirror holders or reflective element assembly portions and different or custom cap portions and to assemble the mirror assembly with the desired cap portion and content at the vehicle assembly plant. The automobile manufacturer may even choose to purchase the mirror holders (which may include the reflective element) from one source and the cap portions from another source, and may complete the mirror assembly at the vehicle assembly plant or at another facility, such as a mirror assembly plant or the like. The present invention thus allows an automobile manufacturer to order or purchase the mirror holder and reflective element (and maybe the toggle assembly and mounting assembly as well, such as shown in FIGS. 6 and 7 ) from a mirror specialist, and the cap portions and accessories (such as shown in FIG. 9 ) from an electronics specialist. The cap portion may snap or otherwise attach to the mirror holder to complete the assembly of the rearview mirror assembly.
[0055] Because the cap portion or portions may be purchased separately, the present invention lends itself to aftermarket applications or to dealership or consumer customizations/personalizations, where a cap portion having the desired accessories or appearance or design may be purchased and installed to a mirror holder to alter or upgrade the mirror assembly of the vehicle. It is envisioned that such an upgrade could be made to a base mirror that does not originally include any electronic accessories, whereby the cap portion could provide electrical content to the mirror assembly. In such applications, the cap portion may connect to a power source or the like of the vehicle (such as via a wire or cable that extends between the mirror assembly and the headliner or an accessory module of the vehicle when the mirror assembly is installed in the vehicle) or the cap portion may include a battery or self-contained power source to provide power to the accessories and circuitry contained within the cap portion, such as discussed below with respect to FIG. 28 .
[0056] In an aftermarket application, cap portions may be provided as aftermarket cap portions, and a consumer may purchase a desired cap portion, which may have desired content or features and/or may have a desired color or texture or appearance or the like, and may readily remove the existing cap portion from the mirror of their vehicle and replace it with the new cap portion. For example, the cap portion and/or the mirror holder may have snaps or clasps that may retain the cap portion and the mirror holder together, but that may release or detach such that the cap portion may be detachable from the mirror holder by a user. The cap portion may be pulled or detached from the mirror holder and a new cap portion may be pressed or snapped into place on the mirror holder to provide the vehicle owner with the new cap portion having the desired content or functions or features and/or the desired appearance or the like, as discussed in detail below.
[0057] Reflective element 14 may comprise a prismatic reflective element having a wedge shaped prism with a reflective coating on its rear surface, such as described in U.S. Pat. Nos. 6,318,870; 5,327,288; 4,948,242; 4,826,289; 4,436,371 and 4,435,042; and/or U.S. patent application Ser. No. 10/709,434, filed May 5, 2004, now U.S. Pat. No. 7,420,756; and/or U.S. provisional application Ser. No. 60/525,952, filed Nov. 26, 2003, which are all hereby incorporated herein by reference. Reflective element 14 may include one or more displays which may be laser-etched or otherwise formed thereon, such as via an appliqué or the like on the surface of the reflective element or such as a display on demand type of display (discussed below). The display may include one or more display elements, such as illumination sources, such as vacuum fluorescent (VF) elements, liquid crystal displays (LCDs), light emitting diodes (LEDs), such as inorganic LEDs or organic light emitting diodes (OLEDs), electroluminescent (EL) elements or the like. Optionally, the prismatic reflective element may comprise a display on demand or transflective prismatic element (such as described in PCT Application No. PCT/US03/29776, filed Sep. 19, 2003 and published Apr. 1, 2004 as International Publication No. WO 2004/026633; and/or U.S. provisional application Ser. No. 60/525,952, filed Nov. 26, 2003, which are all hereby incorporated herein by reference) so that the displays are viewable through the reflective element, while the display area still functions to substantially reflect light, in order to provide a generally uniform prismatic reflective element even in the areas that have display elements positioned behind the reflective element.
[0058] For example, as shown in FIGS. 1-5 and 12 , prismatic reflective element 14 may include a compass display 14 a and/or other display, such as a passenger side inflatable restraint status display 14 b ( FIGS. 2-4 ) or the like, formed or etched on the reflective element. For example, the compass display 14 a may include ports 15 a , such as icons, characters or directional headings (N, S, E, W), etched or formed in the reflective coating of the reflective element (such as via removing the reflective coating of the reflective element to form a desired port or icon or character and/or such as by utilizing aspects described in U.S. Pat. No. 4,882,565, issued to Gallmeyer, which is hereby incorporated herein by reference) to allow light from corresponding illumination sources or elements 19 a (such as light emitting diodes or the like) to pass through the reflective element to illuminate or back light the appropriate port or icon or heading character for viewing by the driver or occupant of the vehicle, such as similar to the compass systems disclosed in U.S. patent application Ser. No. 10/456,599, filed Jun. 6, 2003, now U.S. Pat. No. 7,004,593, which is hereby incorporated herein by reference in its entirety, and as discussed below.
[0059] As shown in FIG. 5 , the reflective element 14 may include an anti-scatter film or sheet or tape 14 c applied over its rear surface. The tape 14 c may be adhered or otherwise attached to the rear surface of the reflective element so as to limit shattering or scattering of the mirror glass if the vehicle is involved in an accident. Also, the reflective element 14 may include a display appliqué 14 d that may be adhered or applied to the rear surface of the reflective element in the general region of the display 14 a (and/or at the region of other displays at the reflective element). The display appliqué 14 d may comprise a diffusing element or material, such as a white diffusing material with a smoked front or the like, to diffuse the light emitted by the display elements so that a person viewing the display 14 a will not readily discern the individual lighting elements or filaments, but will view substantially uniform illumination provided by the lighting elements or filaments.
[0060] Interior rearview mirror assembly 10 may include a toggle assembly 20 and a mounting portion 22 , which may be pivotally connected to toggle assembly 20 and mounted to the vehicle to provide pivotal movement of the mirror holder and reflective element relative to the vehicle. Toggle assembly 20 may include a toggle member 20 a , which may be actuated or moved by a user to adjust the mirror holder and reflective element relative to the vehicle. Optionally, toggle member 20 a may comprise a soft touch surface or portion, such as disclosed in U.S. Pat. Nos. 6,318,870 and 6,349,450, which are hereby incorporated herein by reference. Such a soft touch surface or portion preferably comprises a soft touch material (such as a thermoplastic elastomer or other similar thermoplastic materials, such as Santoprene or the like), preferably having a Shore A durometer value of less than about 110 Shore A, more preferably less than about 90 Shore A, and most preferably less than about 70 Shore A, that may be molded over a rigid or harder material or structure, such as by utilizing aspects described in U.S. Pat. No. 6,349,450, which is hereby incorporated herein by reference. The toggle assembly or the mirror holder may also include a pivot joint or pivot element 20 b , such as a socket and/or ball member, molded or formed thereon or attached or mounted thereto, in order to provide pivotal movement or adjustment of the mirror assembly relative to the mounting arm or portion. The mounting portion 22 may be mounted to the vehicle, such as to an interior surface of the vehicle windshield or to a header portion of the vehicle or the like, via any mounting arm and button or any other mounting arrangement or construction, such as the types disclosed in U.S. Pat. Nos. 6,499,850; 6,318,870; 6,315,421; 6,227,675; 5,671,996; 5,813,745; 5,673,994; 5,820,097; 5,708,410; 5,680,263; 5,582,383; 5,576,687; 5,555,136; 5,521,760; 5,330,149; 5,100,095; 5,058,851; 4,930,742; 4,936,533; 4,436,371; 4,524,941; 4,435,042 and/or 4,646,210; and/or PCT Publication No. WO 03/095269, published Nov. 20, 2003; and/or PCT Publication No. WO 03/099614, published Dec. 4, 2003, which are hereby incorporated by reference herein, without affecting the scope of the present invention. Optionally, the mirror assembly may be mounted to the vehicle portion (such as to the windshield or headliner of the vehicle) via a substantially plastic or all plastic double ball mounting arrangement, such as described in U.S. Pat. No. 6,318,870 and/or U.S. patent application Ser. No. 10/032,401, filed Dec. 20, 2001, now U.S. Pat. No. 6,877,709, which are hereby incorporated herein by reference. The mounting arrangement may be configured to provide for wiring to the mirror assembly through the mounting arrangement and to or into the mirror assembly, without affecting the scope of the present invention.
[0061] During assembly of the reflective element assembly portion, the mounting member or arm may be inserted into the socket portion at the reflective element assembly portion (such as at the reflective element or at a backing plate of the reflective element or at a toggle assembly of the mirror assembly or the like) via an automated device or machine or by a robot. The automatic device or machine may be used to attach or snap the front end of the mounting member to the socket portion at the reflective element.
[0062] Optionally, the mirror assembly may provide or include an automatic flip prismatic reflective element, such as described in U.S. Pat. Nos. 6,717,712; 6,568,414 and/or 6,382,806, which are hereby incorporated herein by reference. Because the circuit board and any display elements positioned thereon is/are generally fixedly secured to the cap portion, which in turn is generally fixedly secured to or relative to the mirror holder and reflective element, the circuit board and display elements move with the reflective element during adjustment of the mirror, such that there is substantially no change in the juxtapositioning/alignment of the lighting or display through the prismatic reflective element.
[0063] Mirror holder 12 of interior rearview mirror assembly 10 preferably comprises a unitary or one-piece mirror holder (preferably molded from a thermoplastic resin, such as a polyolefin, such as polypropylene or the like), which may be molded or otherwise formed with a bezel portion 12 b integrally formed therewith, and which receives the prismatic reflective element therein. As shown in FIGS. 6 and 7 , the toggle assembly 20 and mounting portion 22 may be attached to the mirror holder/bezel portion 12 , preferably while the mirror holder is still warm and pliable. Although not shown in FIGS. 6 and 7 , the reflective element 14 may be attached to or inserted into the mirror holder/bezel portion 12 at around the same time to form a mirror holder assembly that may be attached to the appropriate or desired cap portion, as discussed below. The reflective element and molded portion or bezel portion thus may define a reflective element assembly portion 13 of the mirror assembly 10 . The toggle assembly 20 and the prismatic reflective element 14 thus may be secured into place (such as by snapping together) at or in the mirror holder 12 while the molded mirror holder (preferably the freshly molded mirror holder) is still warm and pliable, such as disclosed in U.S. Pat. No. 4,436,371, issued to Wood et al., which is hereby incorporated herein by reference. When the molded mirror holder (preferably the freshly molded mirror holder and thus just exiting the injection molding press, or alternately, and less desirably, a heated mirror holder having been heated, such as in an oven or the like, to make the mirror holder warm and pliable) cools and shrinks, the mirror holder grips around the toggle assembly and the prismatic reflective element to retain the toggle assembly and the reflective element in the reflective element assembly portion.
[0064] The material of the mirror holder or bezel portion, and/or of the reflective element assembly portion in totality, may be selected to have a desired linear mold shrinkage or tool shrinkage factor to provide the desired amount or degree of shrinkage as the mirror holder cools and shrinks around the reflective element to secure the reflective element at the mirror holder or bezel portion. For example, at least the bezel material, and preferably the reflective element assembly portion in totality, may have a linear mold shrinkage or tool shrinkage factor of preferably at least about 0.01 cm/cm or about 1%, and more preferably at least about 0.015 cm/cm or about 1.5%. For example, a UV stabilized, general purpose black polypropylene polymeric molding resinous material, such as is commercially available from Huntsman Corp. of Houston, Tex. under the trade name REXENE 17C9A, and having a tool shrinkage factor of 0.018 cm/cm or 1.8%, may be a suitable material for the bezel portion in that it provides a desired degree of shrinkage around the reflective element as the material cools, and after formation of the mirror holder or bezel portion by molding in an injection molding operation and/or after heating an already-molded mirror holder or bezel portion to an elevated temperature (such as greater than 70 degrees Celsius or higher), in order to sufficiently retain the reflective element at the bezel portion.
[0065] The linear mold shrinkage or tool shrinkage factors, as known in the material science arts, are determinable by test standards, such as by test standards set by the American Society for Testing and Materials (ASTM), such as the ASTM D 955 (Standard Test Method of Measuring Shrinkage from Mold Dimensions of Thermoplastics), which is hereby incorporated herein by reference, or such as by ISO 294-4, which is hereby incorporated herein by reference. The test measures the shrinkage from the mold cavity to the molded dimensions of thermoplastics when molded by compression or injection molding processes with specified process conditions or parameters.
[0066] As shown in FIGS. 2 and 3 , the rear portion 12 a of mirror holder 12 may have openings or apertures 12 c formed therethrough at either or both sides of the toggle assembly to allow for insertion of the accessory or accessories supported by the corresponding cap portions, as discussed below. Optionally, and as shown in FIGS. 4-7 , the mirror holder 12 ′ may be substantially open for a unitary cap portion 16 ″ to attach at, as also discussed below.
[0067] After the mirror holder and reflective element are assembled together, and maybe after the mirror holder has cooled and shrunk (such as in applications where the reflective element/mirror holder assembly is provided or shipped from a different location than where the cap portion and electrical circuitry or electrical content are from), the cap portion 16 may be attached or secured to the rear portion 12 a of mirror holder 12 to complete the assembly of rearview mirror assembly 10 . In comparison to the bezel material, the material selected for the cap portion need not have such shrinkage properties as described above, because the cap portion may be fabricated at and supplied from separate operations, locations and/or facilities than the bezel portion. However, the cap portion may be fabricated at the same facility or location, but could be made during a different operation and/or at a different time, without affecting the scope of the present invention. For example, the cap portion preferably is formed by injection molding of a polymeric resinous material having a tool shrinkage factor of less than and preferably substantially less than about 0.01 cm/cm or about 1% (although it may also have higher tool shrinkage factors, without affecting the scope of the present invention), and preferably less than approximately 0.008 cm/cm or about 0.8%. This enables the provision in the cap portion of material properties not readily deliverable by the higher linear mold shrinkage or tool shrinkage factor materials used for the bezel portion.
[0068] For example, the cap portion material may have a higher heat stability/higher heat deflection property/higher flexural modulus compared to the reflective element assembly portion, in order to maintain any accessories or elements mechanically attached thereto or therein. Also, the cap portion material may be selected to provide a higher structural strength if desired. For example, the cap portion material may comprise a high temperature ABS material, such as available from BASF or others under the trade name TERLURAN® GRADE-HH106, which has a tool shrinkage factor of around 0.006 cm/cm or 0.6%, or other suitable materials, such as Nylon and preferably a filled Nylon material or the like. Such a material may also provide structural characteristics that are suitable for supporting accessories or the like. For example, the cap portion material may desirably have a heat deflection temperature under load of 0.45 MPa of greater than approximately 100 degrees Celsius (and more desirably, greater than approximately 110 degrees Celsius and most desirably greater than approximately 115 degrees Celsius), as determined by standard testing, such as by ASTM 648 or ISO 75-1/-2 (which are hereby incorporated herein by reference) or the like. Such testing may determine the temperature at which an arbitrary deformation occurs when a specimen of the material is subjected to an arbitrary set of testing conditions or parameters.
[0069] The tool shrinkage factor of the resinous material molded to form the cap portion thus is preferably less than the tool shrinkage factor of the resinous material molded to form the bezel portion of the reflective element assembly portion. Also, the flexural modulus of the material that forms the cap portion may preferably be greater than the flexural modulus of the material that forms the mirror holder or bezel portion. Also, the material that forms the cap portion may preferably have a higher heat deflection temperature (such as may be determined by standard testing, such as ASTM D-790, which is hereby incorporated herein by reference) than the material that forms the bezel portion or mirror holder. Such standardized testing may determine the flexural properties or flexural strength of the material via bending or breaking of specimens of the material in accordance with the appropriate test parameters. Desirably, although the polymeric resinous materials used for the bezel portion and the cap portion may be different, the portions may have similar exterior finishes and/or textures. Alternatively, however, the portions may have different finishes and/or textures or the like as discussed below, without affecting the scope of the present invention.
[0070] Optionally, and as described above, the mirror holder and reflective element assembly portion may be packaged and moved to another facility and/or the cap portion may be received from another facility to complete the mirror assembly. The appropriate or selected cap portion (with the appropriate associated electrical circuitry/accessory/content) may then be attached to the reflective element/mirror holder assembly, such as at the vehicle assembly line, to assemble the mirror assembly for installation into the appropriate vehicle having the optional content of the mirror assembly, as discussed below. The modular mirror assembly of the present invention thus facilitates assembly of the reflective element assembly portion and of the cap portion at different assembly locations, whereby the two portions may be joined or assembled together at a different location, such as at the vehicle assembly plant, to complete the mirror assembly. The cap portion may attach to the reflective element assembly portion via a snap together connection or other type of connection, and may removably or detachably attach, so that the cap portion may be removed from the reflective element assembly portion if desired. However, the cap portion may alternatively be non-detachably attached, such as by adhesive attachment or by heat staking or by ultrasonic welding or the like, without affecting the scope of the present invention. The cap portion may attach to the reflective element assembly portion via any manner, such as, for example, utilizing aspects described in U.S. Pat. No. 6,402,331, which is hereby incorporated herein by reference. Thus, the present invention encompasses customization/selection of material properties for the cap portion to be different from material properties selected for the reflective element assembly portion so that decorative finishes and/or functional properties may be customized/delivered to be the same or different for one or both of the portions.
[0071] Optionally, one or more accessory modules or blocks (such as discussed below) may be attached to or inserted or plugged into the cap portion and/or mirror assembly, such as at the vehicle assembly line, to provide a desired or selected or customized optional feature or accessory to the mirror assembly. The accessory module may insert or attach to the mirror assembly or cap portion utilizing aspects described in U.S. Pat. Nos. 6,672,744; 6,402,331; 6,386,742 and 6,124,886, and/or U.S. patent application Ser. No. 10/739,766, filed Dec. 18, 2003, now U.S. Pat. No. 6,877,888, which are hereby incorporated herein by reference. The accessory module may include circuitry and display elements and user inputs, and may plug into the cap portion or mirror assembly in a manner whereby mechanical and electrical connections are preferably simultaneously made as the module is inserted into the cap portion or mirror assembly, such as by utilizing aspects described in U.S. Pat. No. 6,669,267, and/or U.S. patent application Ser. No. 10/727,731, filed Dec. 3, 2003, now U.S. Pat. No. 6,969,101, which are hereby incorporated herein by reference. The mirror assemblies thus may be customized to particular work orders or selected options at the vehicle assembly line via insertion or attachment of the appropriate accessory module, such that the cap portion and the reflective element assembly portion may comprises common or universal components for two or more options offered for the particular mirror assembly or vehicle application.
[0072] The modular mirror assembly of the present invention thus may provide fully assembled mirror assemblies to a vehicle assembly plant and line, where the cap portion and selected content are attached to the reflective element assembly portion at a remote location, such that different mirror assemblies are provided for different options or applications. Optionally, the modular mirror assembly may provide a universal or common reflective element assembly portion to a vehicle assembly plant, and a selected cap portion (with the appropriate or desired or selected optional content) may be attached to the reflective element assembly portion at the vehicle assembly line to customize the mirror assembly for the particular selected option or application. Optionally, the modular mirror assembly of the present invention may provide a universal reflective element assembly portion and a partially or substantially universal (at least universal as to two or more selectable options) cap portion, whereby the selected accessory module may be inserted into or attached to the cap portion and/or mirror assembly at the vehicle assembly line to complete the mirror assembly and to provide the desired or selected option or feature to the mirror assembly.
[0073] As shown in FIG. 2 , cap portion 16 may comprise two separate cap portions 16 a , 16 b , or a cap portion 16 ′ ( FIG. 3 ) may have two cap portions 16 a ′, 16 b ′ joined together by a connecting portion or wire channel 16 c . One or both of the cap portions 16 a , 16 b may have an accessory or circuit board 18 a , 18 b attached thereto. The circuit board or boards may snap or otherwise affix or secure to the cap portion or portions. As shown in FIG. 2 , the cap portions may have retainers or pillars extending from an interior surface for retaining and supporting the circuit board or boards thereon. Optionally, the cap portion may comprise a unitary cap portion 16 ″ ( FIGS. 4, 5, 8-11, 24 and 26 ) substantially covering the rear portion of the mirror holder (opposite the reflective element) and receiving or supporting one or more printed circuit boards thereon. The cap portion may receive the mounting portion 22 between the side portions of the cap portion 16 ′ ( FIG. 3 ) or through an opening 25 a in the cap portion 16 ″ ( FIGS. 4, 8-11, 24 and 26 ) as the cap portion is attached to the mirror holder. For example, the mounting portion 22 may be threaded through the opening 25 a in the cap portion as the cap portion is moved toward and into engagement with the bezel portion during the mirror assembly process. The mirror assemblies 10 ′ and 10 ″ (with cap portions 16 ′ and 16 ″, respectively) may be substantially similar to and may have substantially similar components and accessories as mirror assembly 10 (with cap portions 16 a , 16 b ), such that a detailed description will not be repeated for the different mirror assemblies. The common or similar components of the mirror assemblies are referred to in FIGS. 2-11 with the same reference numbers.
[0074] The cap portion 16 or portions 16 a , 16 b may be positioned at openings 12 c of mirror holder 12 such that the accessories or circuitry supported by the cap portions are positioned generally within mirror holder 12 . The cap portions may snap onto the rear portion 12 a of mirror holder 12 and generally cover the openings 12 c in mirror holder 12 . Optionally, the unitary cap portion 16 ″ may snap onto or otherwise secure to the mirror holder and generally cover or define the rear portion of the mirror assembly when so assembled. The cap portion or portions thus support the circuit board or circuit boards and associated circuitry and/or accessories at or within the mirror assembly.
[0075] Optionally, the circuit boards or accessories may be provided at, within or on the cap portions at a cap portion manufacturing facility or electrical accessory manufacturing facility, such that the cap portion and circuitry assemblies are provided as a unit to the mirror assembly facility or plant. The cap portion and circuitry units may then be snapped or otherwise affixed to the mirror holder or reflective element assembly portion of an appropriate mirror assembly having features or components or displays corresponding to the cap portion and circuitry units, as discussed below. The assembly or back-loading of the cap portions to the mirror holder and reflective element assembly portion thus may be performed remote from the molding tool for molding the mirror holder, since the cap portions may be mounted to the mirror holder after the mirror holder has cooled and shrunk.
[0076] Each cap portion may support one or more desired accessories or circuit boards for providing the desired feature to the mirror assembly. The cap portions, and corresponding accessory or feature or electrical content, may be selected and attached to a universal or common mirror holder to provide different features to the mirror depending on the options selected for a particular application or vehicle. Optionally, the cap portions may be selected/configured to have accessories contained/supported therein to correspond to and be aligned with/juxtapositioned with one or more displays of a particular or respective reflective element secured in the common mirror holder and/or may correspond with a particular mirror holder for applications where the accessory includes buttons or controls which may extend through openings or recesses in the mirror holder for access thereto by the driver or occupant of the vehicle, as discussed in detail below.
[0077] The cap portion or cap portions may be snapped or otherwise secured to the rear portion 12 a of mirror holder 12 , such as generally at and covering corresponding openings 12 c through the rear portion 12 a of mirror holder 12 . The opening or openings 12 c may be at either or both sides of the toggle assembly and mounting portion of the mirror assembly. The cap portion may snap over or otherwise interconnect with the respective opening via a plurality of hooks or snap clasps (which may extend from the cap portion or the mirror holder) engaging a plurality of corresponding slots or the like at the other of the cap portion and the mirror holder. The cap portion may be formed to provide an exterior surface which may substantially match the exterior surface of the mirror holder to provide a finished appearance to the mirror assembly when the cap portions are attached to the mirror holder and thus form the rear or back portion of the mirror holder and/or it may provide a contrast or distinctive aesthetic or functional appearance or finish. The mirror holder and the cap portions may be formed of a polypropylene material or a talc-filled polypropylene material or the like, or preferably the mirror holder is formed of a molded polyolefin, while the cap portion is formed of a molded engineering resin, such as ABS or a Nylon or the like. Optionally, the cap portion may comprise a metallic material or may comprise a polymeric molding overcoated with a metallic layer or coating, and may have ribs or ripples to provide enhanced rigidity of the cap portion, without affecting the scope of the present invention.
[0078] Optionally, the cap portion may have a different color or texture (such as a chrome or colored or textured surface or the like) than the mirror holder or bezel portion to provide a two-tone configuration to the mirror assembly. Optionally, the cap portion and/or the mirror holder may have a decorative finish, and may be painted or plated, such as electroplated or the like, or may have a film or an in mold film or coating thereon to provide the desired surface to the cap portion and/or the mirror holder. For example, the cap portion (or the mirror holder) may provide a contrast or accent color or may be chrome plated or may be brushed aluminum or the like or may provide an angle variant color (where the perceived color may change depending on the viewing angle) or may provide various colors or patterns or textures or the like as may be desired by a consumer (for example, certain colors or patterns or textures may be provided to target different demographics, such as for targeting teenagers or other age groups or genders or the like). Optionally, the cap portion or bezel portion may have a fabric cover (such as, for example, leather or cloth or denim or other cover material or the like) at and substantially over at least a portion or the entirety of its exterior surface to provide a desired appearance or texture or the like. Optionally, the cap portion and/or the mirror holder or bezel portion may have a soft touch surface, such as a soft touch surface and material similar to that described above (preferably having a Shore A durometer value of less than about 110 Shore A, more preferably less than about 90 Shore A, and most preferably less than about 70 Shore A) with respect to the toggle tab and/or similar to the types described in U.S. Pat. Nos. 6,318,870 and/or 6,349,450, which are hereby incorporated herein by reference. For example, either the mirror holder or the cap portion may have such a soft touch surface independent of the other, or both may have such a soft touch surface or neither may have a soft touch surface. Although the cap portion may be finished with a metallized reflective finish, such as a chrome or chrome-plated finish, the bezel portion desirably may not be chrome or chrome-plated or the like, in order to reduce reflections or glare at the bezel portion around the reflective element, and thus not be specularly reflecting.
[0079] It is further envisioned that the cap portion or bezel of the interior or exterior mirror assembly may include a personalization element, such as a logo or text or pattern or other indicia, thereon as desired by the consumer to provide highly personalized and unique mirror assemblies for the particular consumers that purchase the vehicles or the mirror assemblies, such as described in U.S. provisional applications, Ser. No. 60/553,842, filed Mar. 17, 2004; and Ser. No. 60/563,342, filed Apr. 19, 2004, which are hereby incorporated herein by reference. For example, the cap portion may include a school logo and colors, such as, for example, the letters “MSU” in green and white print/background, to provide a desirable appearance to the personalized mirror assembly for a particular consumer, such as, for example, a student or graduate of Michigan State University. Optionally, the cap portion may include other text or logos or brand names or other types of identifying indicia, such as, for example, “FORD” to identify the vehicle manufacturer, or “TOMMY HILFIGER” to identify the vehicle owner's clothing preference or the like, or other text or messages or images or trademarks or colors or patterns or indicia or the like to provide a desired appearance or identification or message or statement or advertisement or logo or sponsorship identification or style or brand identification on the interior or exterior mirror assembly. The mirror assemblies may thus be assembled to have the desired or personalized cap portion with the desired or personalized logo or color or message or indicia thereon to provide the desired or personalized finish or appearance of the interior or exterior mirror assembly.
[0080] In an aftermarket application, various cap portions as described above may be provided as aftermarket interior or exterior mirror cap portions. A consumer may then purchase a desired cap portion, which may have desired content or features and/or may have a desired color or texture or appearance or the like, and may readily remove the existing cap portion from the interior or exterior mirror assembly of their vehicle and replace it with the new cap portion. For example, the cap portion and/or the mirror holder or reflective element assembly portion (such as the mirror support arm for an interior rearview mirror assembly or a mirror mount for an exterior rearview mirror assembly) may have snaps or clasps that may retain the cap portion and mirror holder/mount/bezel together, but that may release or detach such that the cap portion may be detachable from the mirror assembly by a user/consumer. The cap portion may be pulled or detached from the mirror assembly and a new cap portion (with the desired content therein and/or personalized text or indicia or colors or the like thereon) may be pressed or snapped into place on the mirror assembly to provide the vehicle owner with the new cap portion having the desired content or functions or features and/or the desired or personalized appearance or the like.
[0081] Optionally, the modular mirror assembly of the present invention may provide customizing of other visible or viewable portions of the mirror assembly as well. For example, the flip tab or toggle tab 20 a (or a rotary knob or the like depending on the type of toggle assembly of the particular mirror assembly) may be removably attached to the toggle assembly, such that the tab may be selected or replaced as desired. The tab may threadedly attach to a threaded stud or bolt or nut or the like at the toggle assembly (or may detachably attach via other means, such as snaps, twist-on connections, a bayonet connection or the like), such that a desired tab may be readily attached to the toggle assembly to provide the desired tab for the mirror assembly. The selectable or replaceable or customized toggle tabs may provide various styles, sizes, shapes, appearances, textures, touches/feels (such as a soft touch material or the like), colors, patterns, indicia (such as logos or icons or the like as described below with respect to the center port 15 c of the compass display 14 a in FIGS. 13A-D ). The customer/consumer thus may select the desired toggle tab for attachment to the mirror assembly (such as a tab that matches or is associated with the selected cap portion and/or bezel portion and/or reflective element ports (discussed below) or the like) to customize the mirror assembly. The customization and selection or replacement of the toggle tab may occur at the reflective element assembly portion assembly plant or at the mirror assembly plant or at the vehicle assembly plant or at the vehicle dealership or at any other aftermarket facility or the like, without affecting the scope of the present invention. The custom tab may thus be selected and attached or replaced at the mirror assembly to provide a custom appearance without having to retool or mold a different toggle assembly.
[0082] Optionally, the bezel portion 12 may be molded of a universal or standard color, finish and/or material, such as a black plastic material or black polypropylene or the like, and an outer rim portion or perimeter trim portion element may attach to a forward edge of the bezel portion (at the viewable side of the reflective element) to provide a desired appearance and/or functionality of the bezel portion of the mirror assembly to the driver and passenger of the vehicle. The bezel portion 12 may be formed to have a recess or trough or lip or the like around its perimeter portion (such as at 12 b in FIG. 2 ), and the desired trim portion element may be selected and snapped to or pressed into or otherwise received in/attached to the perimeter portion of the bezel portion to provide the desired appearance/functionality to the mirror assembly. The attachable trim portion element may provide various styles, appearances, textures, touches/feels (such as a rubber or elastomeric material or soft touch material or the like), colors, patterns, indicia (such as logos, icons or the like as described below with respect to the center port 15 c of the compass display 14 a in FIGS. 13A-D ). The customer thus may select the desired trim portion element for attachment to the bezel portion of the mirror assembly (such as a trim portion element that matches or is associated with the selected cap portion and/or toggle tab and/or reflective element ports (discussed below) or the like) to customize the mirror assembly. The trim portion element may be selected to provide a soft material or an impact absorbing material, and may have a Shore A durometer hardness that is less than that of the bezel portion or mirror holder. The customization and selection or replacement of the trim portion element may occur at the reflective element assembly portion assembly plant or at the mirror assembly plant or at the vehicle assembly plant or at the vehicle dealership or at any other aftermarket facility or the like, without affecting the scope of the present invention. The bezel portion thus may be formed as a universal or common bezel portion, and the viewable rim of the bezel portion (such as around the perimeter of the reflective element and viewable by a driver of the vehicle when the mirror is installed in the vehicle) may be selected or replaced to provide the desired or customized appearance and/or feel of the mirror assembly.
[0083] Optionally, the cap portion, or one of the cap portions, such as the cap portion 16 b on the side of the mirror assembly, such as the side which will be toward the passenger side of the vehicle when the mirror assembly is installed in the vehicle, may include an electrical connector for connecting the accessory or circuit board or boards 18 a , 18 b to a vehicle wiring harness or power source of the vehicle. Optionally, the circuit board 18 b at the cap portion may include a multi-pin connector 24 for connecting to a corresponding multi-pin connector of the vehicle wire harness. In such applications, an opening (such as opening 25 b of cap portion 16 ″ in FIGS. 4, 5 and 8-11 ) of sufficient size may be provided in the cap portion (or optionally in the mirror holder) to allow the connector on the wire harness to insert therethrough for connection to the connector on the circuit board 18 b . The circuit board 18 b or connector 24 may be substantially supported at the cap portion to provide sufficient support of the connector when a corresponding connector of the wire harness is pushed into engagement with connector 24 .
[0084] For example, the cap portion or mirror holder may have a connector formed therein, whereby the wire harness may then connect to or plug into the connector at the rear of the mirror assembly. The connector may be formed as a selected or appropriate connector (such as a six pin or eight pin connector or the like) depending on the accessories of the cap portions. Optionally, the connector may be formed with an insert in the mold or tool for forming the cap portion, such that an appropriate insert may be placed in the mold or tool to form the desired or appropriate connector on that particular cap portion. In the illustrated embodiment of FIGS. 4, 5 and 8-11 , the connector 24 of the circuit board includes a plurality of pins 24 a for connecting to a connector or plug, and the cap portion 16 ″ has an opening 25 b formed therethrough so that the connector or plug may readily connect to the circuit board, and may snap or otherwise be fastened or secured thereto, such as via clasps or the like at the plug and/or at the cap portion 16 ″.
[0085] In applications where both cap portions 16 a , 16 b support an accessory or circuit board, the circuit board 18 a on the cap portion 16 a (or the circuit board on one side of the unitary cap portion) opposite the connector 24 may be connected to the other circuit board 18 b and/or connector 24 via one or more connecting wires 26 , in order to provide power and/or control to the accessory on cap portion 16 a . The connecting wire or wires 26 may extend between the cap portions 16 a , 16 b within the mirror holder 12 or may extend along the rear surface of the mirror holder 12 , without affecting the scope of the present invention. As shown in FIG. 3 , cap portion 16 ′ of an interior rearview mirror assembly 10 ′ may comprise a single cap portion having a wire channel or connector 16 c extending between opposite end caps or end portions 16 a ′, 16 b ′. The connecting wire (not shown in FIG. 3 ) may extend between the circuit boards 18 a , 18 b or accessories supported on the end portions 16 a ′, 16 b ′ and may be routed within the wire channel 16 c or between the channel 16 c and the rear portion 12 a of the mirror holder 12 . Optionally, and as shown in FIGS. 4, 5, 8-11, 24 and 26 , a mirror assembly 10 ″ may have the single or unitary cap portion 16 ″ in accordance with the present invention, and a connecting wire between two circuit boards or accessories may extend along the cap portion to electrically connect the circuit boards or accessories together.
[0086] As shown in FIG. 2 , printed circuit board 18 b may include circuitry 19 for a compass display 14 a and/or other accessory display, such as a passenger side inflatable restraint display 14 b or the like, at reflective element 12 . More particularly, circuit board 18 b may include compass display circuitry 19 having a plurality of illumination sources 19 a which are individually illuminated or illuminated in combination to project illumination through respective openings in circuit board 18 b to illuminate one or more of the ports or direction characters 15 a etched or formed in reflective element 14 , such as in the manner disclosed in U.S. patent application Ser. No. 10/456,599, filed Jun. 6, 2003, now U.S. Pat. No. 7,004,593, which is hereby incorporated herein by reference in its entirety. The compass display thus may be controlled or actuated by a microcontroller or microprocessor of the cap portion of the mirror assembly. The controller may drive or energize the illumination sources (such as light emitting diodes or the like) directly, without the need for additional display drivers. The direct energization of the illumination sources of the display thus avoids the need for other controllers or drivers within the cap portion or the mirror assembly or the vehicle.
[0087] When the cap portion 16 b (or cap portion 16 ″ or the like) and circuit board 18 b are attached to or juxtaposed with the mirror holder 12 , circuit board 18 b may be pressed or urged toward the rear surface of reflective element 14 such that the illumination sources 19 a (such as light emitting diodes or the like) at the circuit board may generally align with the appropriate ports or characters or icons formed in the reflective element 14 , as discussed below. For example, and as best shown in FIGS. 8 and 9 , the cap portion may include guide members or posts 25 c for engaging corresponding guide members or tabs or holes or notches or recesses 18 c of the circuit board for guiding the circuit board into the appropriate position and orientation on the cap portion as the circuit board is attached or snapped to the cap portion. The cap portion may then attach to the mirror holder/bezel portion via engagement and guiding of corresponding tabs and holes and the like, which function to position the cap portion in the desired location relative to the bezel portion, such that the circuit board (and any illumination devices or the like positioned thereon) is/are properly aligned with any associated display ports or switches or the like at the mirror holder/bezel portion/reflective element.
[0088] As shown in FIGS. 4 and 5 , a seal or sealing member or layer 17 or the like may be applied to the rear surface of reflective element 14 or to the forward face 18 d of circuit board 18 b to substantially seal the interface between the circuit board 18 b and the reflective element 14 , in order to limit or substantially preclude light from one of the illumination sources from illuminating a port or character or icon at the reflective element other than the respective port or character or icon aligned with that illumination source and opening. The seal 17 may comprise an opaque material, and may comprise a white (or other color) silicone gasket or the like, to diffuse and/or reflect light. The seal 17 may be at least partially and preferably substantially flexible or resilient to compress and seal against the reflective element and the circuit board to limit or substantially preclude light leakage from one illumination source to one of the other ports or characters of the display.
[0089] The circuit board may also include a connecting wire 28 which may connect to a compass pod or module 30 or other accessory or accessory module or the like for communication of compass heading or control information to the compass display circuitry 19 at the circuit board or for communication of other control information between the accessory module and the circuit board of the cap portion. For example, the connecting wire 28 may extend from the cap portion and the rear of the mirror assembly to the compass module 30 , which may be attached to the mounting arm or mounting button of the mirror assembly or otherwise positioned or mounted at or near the mirror assembly. Compass module 30 may include the compass circuitry (which may include calibration circuitry, a microprocessor and the like) and magnetoresponsive compass sensors (such as magnetoresistive sensors, magneto-capacitive sensors, magnetoinductive sensors or the like or a flux gate sensor or the like), such as described in U.S. Pat. Nos. 6,513,252 and 5,802,727, and/or U.S. patent application Ser. No. 10/456,599, filed Jun. 6, 2003, now U.S. Pat. No. 7,004,593, which are hereby incorporated herein by reference in their entireties. The compass pod may also include an ambient light sensor, whereby the intensity of the compass display (and other displays of the mirror assembly) may be adjusted in response to the detected ambient light levels. Optionally, the compass system may utilize principles disclosed in U.S. Pat. Nos. 5,924,212; 4,862,594; 4,937,945; 5,131,154; 5,255,442 and/or 5,632,092, which are hereby incorporated herein by reference.
[0090] Although shown and described as having a separate compass pod that may mount to the mirror mounting portion of the mirror assembly that in turn mounts to the likes of a mirror mounting button on the windshield (such as described in U.S. Pat. Nos. 6,648,478; 5,708,410 and/or 5,576,687, which are hereby incorporated herein by reference) to remain generally stationary, it is envisioned that a compass pod or module or compass circuitry and sensors may be positioned in a post or arm of a single ball mounting arrangement such that the sensors and circuitry are generally fixedly positioned relative to the mounting button and the vehicle. A wire may be routed along the generally fixed mounting arm (via and through the single ball joint) and to the display elements or illumination sources, such as in a manner similar to that shown in FIG. 34 , or a wire may be routed along the mounting arm and through the single ball and into the mirror casing or a wire or conductor may be routed or positioned along the arm and ball in any other manner to communicate electrical signals and the like to the circuitry and/or illumination sources of the cap portion, without affecting the scope of the present invention. The wire may provide slack to allow for the adjustment and movement of the mirror holder/cap portion about the single arm to avoid pulling at the wire during adjustment of the mirror.
[0091] The compass circuitry 19 on circuit board 18 b may also include a button or switch or control or may be in communication with a button or control 23 ( FIGS. 8, 10 and 11 ), such as at the rear of the cap portion 16 ″ or at the rear of the mirror holder, for actuating a calibration or zone function of the compass circuitry. In the illustrated embodiment, the button 23 may include an inward protrusion 23 a ( FIGS. 8 and 24 ) that extends forwardly from the cap portion 16 ″ or inwardly toward the button or switch or control on the circuit board when the cap portion 16 ″ is attached to the circuit board. The button 23 may comprise a flexible tab 23 b integrally formed with and extending partially along the cap portion 16 ″. When a user presses at the button 23 , the tab 23 b flexes and the protrusion 23 a is moved toward and urged against the button or switch on the circuit board 18 b to actuate the switch to control or activate/deactivate the associated function of the compass circuitry (or other circuitry or accessory or the like that may be associated with the switch on the circuit board). Although shown and described as being integrally formed with the single cap portion 16 ″ in FIGS. 8, 10, 11 and 24 , the button/flexible tab or flip actuation tab member may be integrally formed on one of the side cap portions 16 a , 16 b or end portions 16 a ′, 16 b ′ of cap portion 16 ′ or the like, or on other types of casings or housings or the like, without affecting the scope of the present invention.
[0092] Optionally, an additional illumination source or lighting element may be provided on the circuit board 18 b for projecting illumination through a corresponding port or icon or character 15 b formed on the reflective element 14 to indicate that the compass system is in the calibration mode or zone setting mode. Optionally, the calibration mode may be indicated by a light emitting diode (LED) at the center port 15 c of the display. For example, a dual-color LED may be provided at the center port, where illumination in one color (such as, for example, red) indicates that the compass system is in the calibration mode. Once the compass system is calibrated, however, illumination may be provided in the other color (such as, for example, blue). Thus, when the compass system is not in the calibration mode, the other color (such as blue) indication color may be provided. Optionally, the calibration mode could be indicated without a dedicated illumination source or light emitting diode or the like (because such an indicator would be used very rarely in the life of the part). For example, the center illumination source or LED (which may be activated to provide an anchor point or focal point for the display, as discussed below) may be flashed or otherwise modulated or adjusted when the system is in the calibration mode, or other similar types of indication may be provided to convey to the driver that the compass is in its calibration mode.
[0093] The circuit board 18 b may also have an ambient light sensor or photocell (not shown) for detecting the ambient light level at the mirror assembly, whereby the circuitry may adjust the intensity of the display in response to the detected ambient light levels. A corresponding opening in the mirror holder 12 or at the rear of the cap portion 16 (such as opening 25 d in cap portion 16 ″ of FIGS. 8, 10 and 11 ) may allow the ambient light sensor to detect the ambient light levels through the opening. The light sensor may alternately be positioned at the compass pod or module 30 , without affecting the scope of the present invention.
[0094] The compass display 14 a ( FIGS. 1-5 and 12 ) thus may include a plurality of direction indicating ports 15 a (such as four such ports formed to represent the cardinal directional points or “N”, “E”, “S” and “W” or the like) and may include an additional port 15 b for a calibration indicator or light source, such as described in U.S. patent application Ser. No. 10/456,599, filed Jun. 6, 2003, now U.S. Pat. No. 7,004,593, which is hereby incorporated herein by reference in its entirety. Compass display 14 a may further include a center port 15 c etched or otherwise formed at a central region of the display 14 a . Center port 15 c may provide an opening or port for a rearward facing photosensor positioned at the circuit board to receive light therethrough to determine the ambient light at or in the vehicle cabin (or a glare sensor for determining glare at the mirror assembly for controlling an exterior electrochromic mirror assembly or cell or the like as discussed below) when the mirror assembly is assembled and positioned in the vehicle, such as discussed below.
[0095] Optionally, center port 15 c may align with an illumination source or light emitting diode at the circuit board to provide a visible center indicator or central anchor or focal point at the central region of the display 14 a such that a person may readily identify the center of the compass display. For example, when one of the directional heading indicators at ports 15 a are illuminated or energized, the indicator or light source at center port 15 c may also be energized to provide a visible central anchor point for a person to recognize as the central region of the display. The provision of an extra illumination source or port that is central to the rosette N-E-S-W indicia thus helps to serve as a reference point for the driver, in order to aid the driver's cognitive association of the cardinal direction point that is intended to be communicated when any one (or combination of two) of the N, E, S, W icons or ports are illuminated.
[0096] Optionally, the light emitting diodes aligned with the directional indicating ports 15 a may be one color, while the light emitting diodes at the central port 15 c and/or at the calibration indicating port 15 b may be another color or colors. For example, the directional indicating ports 15 a may be illuminated or back lit via blue indicators or light emitting diodes or the like, while the central port 15 c may be illuminated or back lit via a red or amber indicator or light emitting diode or the like, so that a person viewing the compass display in darkened conditions may readily discern which indicator is indicative of the central region of the display and thus where the center of the display is, such that the person may readily recognize which directional indicating port is illuminated, without having to look to see whether it is an “N” or an “E” or the like.
[0097] Optionally, the center port may be illuminated whenever the vehicle is on or powered, in order to provide substantially continuous illumination of the center port. Preferably, the center port is illuminated at a lower light output intensity than that of the respective cardinal N, E, S, W ports, so as to serve as a subtle eye point, but not to be confused with an actual directional indication. For this reason, a color contrast as well as an intensity contrast may be desirable.
[0098] In such applications where the center port is illuminated or back lit, an ambient sensor may be positioned elsewhere in the mirror assembly, such as elsewhere in the cap portion, and may be a forwardly facing sensor (i.e. toward the windshield when the interior rearview mirror assembly is normally mounted in the interior cabin of a vehicle) and may receive light through a port or opening 25 d in the cap portion. Alternatively, the ambient sensor may be facing downwardly or upwardly when installed in the vehicle, without affecting the scope of the present invention. The ambient sensor may be generally aligned with or juxtaposed at the port or opening or may receive the ambient light via a light pipe or the like, without affecting the scope of the present invention.
[0099] Optionally, and with reference to FIGS. 13A-D , the center port 15 c of the compass display 14 a (or other port or display area of the reflective element) may provide a graphic depiction of a desired image, such as a logo of the vehicle manufacturer or other desired image. For example, the center port 15 c may be etched (such as by laser etching or ablation or by sandblasting or the like) or otherwise formed to provide the letters “FORD” or may be etched or otherwise formed in a pattern similar to the design or designs indicative of the manufacturer, such as the Chevrolet “bowtie” or the like. Optionally, other designs or patterns or text or logos or indicia or the like may be provided at the center port 15 c (or elsewhere on the reflective element) to provide a desired image or logo. In the illustrated embodiments of FIGS. 13A-D , the central port is formed to be indicative of the vehicle manufacturer, such as for Dodge ( FIG. 13A ), Honda ( FIG. 13B ) or Jeep ( FIG. 13C ), or Subaru ( FIG. 13D ). However, the central port may be formed to be indicative of other vehicle manufacturers or entities or sponsors or indicia or trademarks or emblems or signature items, or representations of a certain political views, religious beliefs, tribal affiliations, community ties, collegiate affiliations, allegiances and/or advocacy (such as, for example, a “peace” sign or other symbol or text or the like) or other views, affiliations, beliefs, etc., or other custom ports or icons may be formed elsewhere on the reflective element to convey other information or logos or the like, without affecting the scope of the present invention.
[0100] The desired image or logo may be indicative of the vehicle manufacturer, or may be selected by the user or vehicle owner to provide a customized interior rearview mirror assembly, such as described above with respect to the different logos or colors or textures or appearances or touch/feel provided on the cap portion or bezel portion of the mirror assembly, without affecting the scope of the present invention. For example, a person may select the logo or mascot of their alma mater to be etched at the center of the compass display (or elsewhere on the reflective element) to customize the mirror assembly for that particular person or owner. The customized or selected port may be at the central port of the compass display or may at or incorporated into another display at the reflective element or may be elsewhere at the reflective element and separate from any other information display, without affecting the scope of the present invention. Optionally, the light source or indicator positioned at the circuit board behind the custom port may be selected to match the color that may be typically associated with the selected logo, such as a green or red or blue indicator or light emitting diode or the like for the school color or the like. Other forms of customized logos or indicia or the like may be etched or otherwise formed at the reflective element, without affecting the scope of the present invention.
[0101] Optionally, and with reference to FIGS. 14-16 , an interior rearview mirror assembly 10 ′″ may include an intuitive heading instructional icon element or display 14 a ′ at the reflective element 14 ′, such as the types described in U.S. provisional application Ser. No. 60/553,517, filed Mar. 16, 2004, which is hereby incorporated herein by reference. The compass display 14 a ′ may be associated with or controlled or adjusted by a compass system and/or a navigational system, such as a compass and/or navigational system of the types described in U.S. Pat. Nos. 6,678,614; 6,477,464; 5,924,212; 4,862,594; 4,937,945; 5,131,154; 5,255,442 and/or 5,632,092, and/or U.S. patent application Ser. No. 10/456,599, filed Jun. 6, 2003, now U.S. Pat. No. 7,004,593; Ser. No. 10/645,762, filed Aug. 20, 2003, now U.S. Pat. No. 7,167,796; and Ser. No. 10/422,378, filed Apr. 24, 2003, now U.S. Pat. No. 6,946,978; and/or PCT Application No. PCT/US03/40611, filed Dec. 19, 2003 and published Jul. 15, 2004 as International Publication No. WO 2004/058540, which are all hereby incorporated herein by reference.
[0102] Display 14 a ′ includes a plurality of characters or icons or letters 15 a (such as N, E, S, W as shown in FIGS. 14-16 ) formed or etched in the reflective coating or layer of the reflective element 14 ′ and includes an arrow or direction pointer 15 d at each of the characters 15 a . The display 14 a ′ may also include a central port 15 c through the reflective coating or layer reflective element 14 ′ behind which may be positioned an illumination source as described above or a glare sensor, such as a photo sensor or the like, such as a glare sensor and/or an ambient light sensor and electrochromic automatic dimming circuitry described in U.S. Pat. Nos. 4,793,690 and 5,193,029, and U.S. patent application Ser. No. 10/456,599, filed Jun. 6, 2003, now U.S. Pat. No. 7,004,593, which are all hereby incorporated herein by reference. The arrows of direction pointers may point generally upward when the mirror assembly is mounted in the vehicle with the reflective element facing generally rearward and opposite to the direction of forward travel of the vehicle. The arrows or pointers thus may be representative of the direction of forward travel of the vehicle. As shown in FIGS. 14-16 , the direction pointers of display 14 a ′ may comprise generally triangular shaped icons or pointers 15 d positioned outward from the characters 15 a and opposite the characters from the center or port 15 c of the display (such as shown in FIG. 14 ), or the direction pointers of the display may comprise arrows 15 d ′ positioned next to the characters 15 a (such as shown in FIG. 15 ), or the direction pointers of the display may comprise arrows 15 d ″ positioned inward of the characters 15 a and between the respective characters and the center or port 15 c (such as shown in FIG. 16 ).
[0103] The compass/navigation system may be operable to energize one or more illumination sources positioned at and rearward of a respective one of the characters 15 a and corresponding direction pointer 15 d to illuminate or back light the respective character and direction pointer. For example, the compass/navigation system may be operable to illuminate or back light a particular character and adjacent direction pointer to indicate to an occupant of the vehicle the direction that the vehicle is currently heading. For example, if the character “W” and the arrow or direction pointer next to the “W” are illuminated, then the display indicates that the vehicle is heading west. The intuitive heading instructional icon element or display thus may provide reinforcement to a viewer that when the character (such as “W” or other character) is illuminated, it is done so to indicate that the vehicle is traveling in the direction (such as west or other direction) indicated by the character. This is reinforced by the illumination of the corresponding arrow or direction pointer that points upward so as to be representative of pointing in the direction of forward travel of the vehicle. A person viewing the display thus will not misinterpret the illumination of the characters to be indicative of a driving or turning instruction (such as an instruction to turn the vehicle right or east to follow a programmed route) in connection with the navigation system.
[0104] Optionally, the display may function as a display for providing both an indication of the directional heading of the vehicle and an indication of which direction the vehicle should be turned in order to follow a programmed route or path. For example, only a particular direction pointer may be illuminated or back lit to indicate that the vehicle is heading in the direction indicated by the non-lit character next to the illuminated pointer, while a different character (separate from the illuminated pointer) may be illuminated or back lit to indicate that the vehicle is to be turned in that direction to follow a programmed route to a desired destination. The compass/navigation system and display thus may clearly display to a driver of the vehicle which direction the vehicle is heading at that time via the directional arrows, while the compass/navigation system and display may also be operable to provide driving or turning instructions to a driver of the vehicle to instruct the driver as to which direction the driver is to turn to follow a particular route to a desired destination. For example, the compass/navigation system may be associated with a global positioning system and/or telematics system of the vehicle, and may generate and display driving instructions to the driver of the vehicle as the vehicle is driven along a generated route, such as by utilizing aspects described in U.S. Pat. Nos. 6,678,614 and 6,477,464, and/or U.S. patent application Ser. No. 10/456,599, filed Jun. 6, 2003, now U.S. Pat. No. 7,004,593; Ser. No. 10/645,762, filed Aug. 20, 2003, now U.S. Pat. No. 7,167,796; and Ser. No. 10/422,378, filed Apr. 24, 2003, now U.S. Pat. No. 6,946,978; and/or PCT Application No. PCT/US03/40611, filed Dec. 19, 2003 and published Jul. 15, 2004 as International Publication No. WO 2004/058540, which are all hereby incorporated herein by reference.
[0105] During operation, the compass/navigation system thus may be operable to energize an illumination source positioned at and rearward of/behind a respective one of the characters to provide a driving instruction to the driver of the vehicle that is separate from the directional heading indication also provided by illumination or back lighting of the arrows or pointers of the display. For example, if the vehicle is heading generally west, the compass/navigation system may illuminate or back light the arrow next to the “W” to indicate to the driver of the vehicle that the vehicle is traveling generally in that direction. If the programmed route for the vehicle involves an upcoming right turn onto a generally northbound road, the compass/navigation system may then illuminate or back light the letter “N” to indicate to the driver of the vehicle that the driver should turn the vehicle to head north.
[0106] It is further envisioned that the illuminated character may be altered or adjusted as the vehicle gets closer to the turning point or intersection, such as by flashing the illumination source or intensifying the illumination source or changing the color of the illumination as the vehicle approaches the desired or appropriate turning point or intersection. It is also further envisioned that arrows pointing sideways may be provided at one or more of the characters of the display (or elsewhere at the display), and the appropriate arrow may be illuminated or back lit to indicate that the driver is to turn right or left to stay on the desired course or route. In such an embodiment, illumination or back lighting of the character may be indicative of the directional heading of the vehicle, while illumination or back lighting of the arrows may be indicative of the driving instructions to the driver of the vehicle.
[0107] The intuitive display elements thus provide a clear indication as to which direction the vehicle is presently traveling by providing a directional heading arrow or pointer at each of the compass heading characters. The driver of the vehicle thus will not likely become confused as to the meaning of the illuminated characters or letters. The compass/navigation system and display of the present invention also may provide point-to-point driving instructions and the present directional heading of the vehicle with the same display or display icons/characters.
[0108] Optionally, the compass display may include a temperature display or another type of information display with an LED array at or near the compass display ports or icons. One or more control buttons or inputs (such as at the rear side of the mirror assembly) may be provided to allow the driver or occupant of the vehicle to select or actuate the calibration or zone or temperature display functions. The circuit board may be in communication with a temperature sensor or system, such as via a connecting wire or the like, to receive an electronic signal indicative of the temperature to be displayed. Optionally, the cap portions and circuit boards may support or provide a compass and/or temperature display utilizing vacuum fluorescent displays and filters to display the compass heading and/or temperature via two or more characters or letters or numbers. For example, and as shown in FIG. 17 , a compass heading display 32 a and a temperature display 32 b may be provided or formed at a display region 32 c of a reflective element 14 ″ of a mirror assembly. The displays may comprise alphanumeric characters or the like to convey the directional heading information and temperature information to the driver of the vehicle.
[0109] Optionally, the circuit board may also or otherwise include circuitry for another accessory and/or display at the reflective element. The other display circuitry may illuminate or project information via illuminating ports or icons or characters or the like which are etched or otherwise formed on the reflective element, such as in a similar manner as described above. The display circuitry and associated control circuitry may be positioned at the circuit board. Optionally, some of the circuitry may be positioned outside of the mirror assembly, such as at an accessory pod or module, and may be in communication with the circuitry of the circuit board via a connecting wire or the like, such as described above with respect to the compass circuitry.
[0110] Optionally, the illumination sources utilized to back light or illuminate the display icons or characters may emit a desired color of light, such as a blue colored or tinted light or other color as may be desired. In many mirror applications, a blue light is typically preferred because it provides high visibility of the display during high lighting or daytime conditions, but may not be as favorable during low light or nighttime conditions. Optionally, a control or multiplexer may be operable to change the color of the display in response to an ambient light sensor or the like. For example, the control may deactivate a blue illumination source and activate an amber or red illumination source (or other color) when the ambient light level drops to a threshold level. The nighttime color may be selected to provide enhanced viewing of the displays and may be selected to generally match the lighting color scheme or signature color of the particular vehicle in which the display is implemented. Optionally, the colors may be ramped on and off, such that in intermediate lighting conditions, both colors may be provided and mixed, in order to provide a gradual change from one color to the next as the ambient light levels increase or decrease. Optionally, the control may activate a second illumination source (a nighttime illumination source that may be directed toward and through the same port as a daytime illumination source) in parallel with the daytime illumination source (such as a blue illumination source), which may remain activated so that the colors of the illumination sources are mixed during nighttime or darkened conditions.
[0111] As also shown in FIGS. 2-5 , one of the circuit boards, such as circuit board 18 a supported by cap portion 16 a ( FIG. 2 ) or circuit board 18 a supported by cap portion 16 ″ ( FIGS. 4 and 5 ) or the like, may include an accessory or circuitry 21 and associated manual inputs or controls or buttons 21 a for providing manual control of the circuitry or accessory 21 . For example, circuitry 21 may comprise circuitry for a garage door opening device or system, such as a universal garage door opener or the like. With reference to FIG. 2 , one or more buttons 21 a (and/or one or more lights or illuminated buttons or controls) may extend or project from circuitry 21 and may extend at least partially through or may be accessible through corresponding openings or holes 21 b in mirror holder 12 . Optionally, and as shown in FIGS. 4 and 5 , one or more buttons 21 a ′ may be provided at a circuit board 18 a , and may be positioned or received in a recessed area 21 b ′ along the bezel portion or mirror holder 12 and/or in a recessed area 25 e along the cap portion 16 ″, such that the buttons may be secured in place between the mirror holder and cap portion when the cap portion is attached to or secured to the mirror holder. The buttons 21 a , 21 a ′ may be readily accessible by the driver or occupant of the vehicle to actuate or control the circuitry 21 , such as to actuate a transmitting device to open or close a garage door, such as utilizing the principles disclosed in U.S. Pat. Nos. 6,396,408; 6,362,771; 5,798,688 and 5,479,155; and/or U.S. patent application Ser. No. 10/770,736, filed Feb. 3, 2004, now U.S. Pat. No. 7,023,322, which are hereby incorporated herein by reference.
[0112] Optionally, and as shown in FIG. 18 , a garage door opener display 34 may be provided at the reflective element of the mirror assembly for displaying a Homelink® icon (or other icon or indicia indicative of such a system) at the buttons or inputs 21 a , 21 a ′ for the garage door opener system, such as might be useful as an indicator to assist a user when training or operating in a learning mode of a trainable garage door opener (such as by intermittently illuminating or modulating/flashing/blinking an LED or the like behind a Homelink® icon or the like when in the learning mode) and/or as an indicator for company brand promotion/feature illustration promotion, such as by constantly illuminating the LED or the like, such as when a trainable garage door opener is not in the training or learning mode. The garage door opener display 34 may have an illumination source (such as a light emitting diode or the like) that may be activated or energized to back light or otherwise illuminate the display as desired. The display elements and circuitry and user inputs may be added to or attached to the cap portion as a module so that the desired feature or content may be readily added to a corresponding cap portion to provide the desired feature or content to the appropriate mirror assembly.
[0113] Because it is desirable that the mirror holder be a universal mirror holder for mirror assemblies having various accessories or no accessories, it is envisioned that the openings 21 b in mirror holder 12 for the input controls 21 a of accessory 21 (and/or other openings for other user inputs or buttons or switches or the like for other accessories or the like) may be formed in the mirror holder via inserts positioned in the mirror holder mold or tool for mirror holders which require such openings. The inserts may be removed from the tool to provide molding of a mirror holder without such openings for applications where no such accessory and associated controls or buttons is selected. Similarly, the recessed regions 21 b ′ in the mirror holder and/or the cap portion may be formed via inserts placed in the molds during the forming of the mirror holder or cap portion. The different mirror holders may thus be molded or formed using the same tool, yet may receive different cap portions having or supporting different accessories or features.
[0114] In the illustrated embodiment, the buttons 21 a are positioned at the mirror assembly so that user actuation of the buttons requires a generally vertical upward force (when the mirror assembly is installed in the vehicle) to move the button or input upwardly to actuate the electronic switch. Optionally, however, the buttons or inputs may be positioned at the mirror assembly so that actuation of the button or switch or input may be accomplished by a generally horizontal force or movement, such as a generally horizontal force toward the mirror assembly or in the direction of travel of the vehicle. For example, the user inputs may be positioned in a gondola or pod or attachment or extension of the cap portion that extends outwardly (such as downwardly or upwardly or sidewardly) from the cap portion so as to be viewable and readily accessible by the driver of the vehicle. The user inputs may be positioned within the gondola or pod so that pressing the user inputs generally horizontally actuates the switch (such as an electronic switch at the printed circuit board within the cap portion of the mirror assembly). The cap portion or attachment may include mechanical elements or structure for mechanically translating the generally horizontal movement of the input to a generally vertical actuation of an electronic switch, or the electronic switch may be oriented at the circuit board to be responsive to the generally horizontal actuation movement, without affecting the scope of the present invention. Preferably, such gondola or pod may extend upward or toward the passenger side of the mirror assembly (when the mirror assembly is installed in the vehicle) to limit or reduce any interference with the forward field of view of the driver of the vehicle.
[0115] Although shown and described as having buttons such as shown in FIGS. 2-5 and 10 , it is envisioned that the mirror assembly may include buttons or inputs of the types described in U.S. provisional applications, Ser. No. 60/553,517, filed Mar. 16, 2004; and Ser. No. 60/535,559, filed Jan. 9, 2004, which are hereby incorporated herein by reference. For example, the buttons may be integrally molded in the cap portion or bezel, or the buttons may extend downward through openings in the cap portion or bezel or between the cap portion and bezel when the cap portion is attached to the bezel, without affecting the scope of the present invention.
[0116] Optionally, the cap portions and circuit boards may support one or more other accessories and/or corresponding displays at or within the mirror holder, such as a tire pressure monitoring system and display 36 , 36 ′ ( FIGS. 19-21 ), whereby the display may indicate when a tire pressure has dropped below a set or preselected tire pressure. For example, a particular light source may be energized or activated to back light or illuminate an icon 36 a indicative of one of the tires of the vehicle when the pressure in that tire drops below the threshold tire pressure. The individual light sources may be individually energized, such as in a similar manner as the directional heading indicators discussed above and/or described in U.S. patent application Ser. No. 10/456,599, filed Jun. 6, 2003, now U.S. Pat. No. 7,004,593, which is hereby incorporated herein by reference. The display may include an iconistic display that may be laser etched or otherwise formed on the reflective element (such as described above), and may provide for illumination (via one or more illumination sources at the circuit board of one of the cap portions) of one or more icons 36 a representative of a particular tire of the vehicle. Optionally, and as shown in FIG. 21 , the tire pressure display 36 ′ may be printed on a screen and placed at and generally aligned with a window formed in the reflective layer of the prismatic reflective element, without affecting the scope of the present invention. The display may further provide for illumination of an additional icon or character 36 b or may provide a different color illumination when a puncture is detected at one of the tires of the vehicle. Optionally, the tire pressure monitoring display 36 ′ may include a digital display 36 c (or other type of character or alphanumeric display) for indicating the tire pressure of one of the tires. The tire pressure monitoring system may utilize principles disclosed in U.S. Pat. Nos. 6,124,647; 6,294,989; 6,445,287; 6,472,979 and/or 6,731,205, which are hereby incorporated herein by reference.
[0117] The tire pressure display thus may be controlled or actuated by a microcontroller or microprocessor of the cap portion of the mirror assembly. The controller may drive or energize the illumination sources (such as light emitting diodes or the like) directly, without the need for additional display drivers. The direct energization of the illumination sources of the display thus avoids the need for other controllers or drivers within the mirror assembly or the vehicle. The tire pressure monitoring system display 36 , 36 ′ may utilize aspects of the compass display disclosed in U.S. patent application Ser. No. 10/456,599, filed Jun. 6, 2003, now U.S. Pat. No. 7,004,593, which is hereby incorporated herein by reference in its entirety.
[0118] Optionally, the cap portion may include circuitry and user inputs associated with a telematics system, such as ONSTAR® or the like. For example, a circuit board may include circuitry for the telematics system and may be attached to or mounted to a cap portion, such as a circuit board similar to circuit board 18 a described above. The cap portion and/or mirror holder may include a recess or opening for one or more user inputs to be positioned when the mirror assembly is assembled, so that the user inputs may be readily accessible by a driver of the vehicle when the mirror assembly is installed in the vehicle. As shown in FIG. 22 , the user inputs or buttons 38 may extend along a lower portion of the mirror assembly and may be readily viewable and accessible at the lower portion of the mirror assembly by a driver of the vehicle. The user inputs 38 may comprise a keypad or the like that is positioned within corresponding notches or recesses along the opposed or mating edges of the mirror holder and the cap portion, such as described above with respect to user inputs 21 a ′ of FIGS. 4 and 5 . A telematics display 40 may be etched or otherwise formed in the reflective element 14 to indicate to a user the function of the user inputs 38 . The display 40 may include one or more icons or images or characters 40 a or the like that may be etched or formed in the reflective element and backlit by respective illumination sources. The illumination source or sources may be activated during low ambient lighting conditions (such as dusk or night, such as when ambient lighting is less than, for example, about 200 lux) to illuminate the display 40 so a user can see the function of the user inputs (which may also be illuminated or backlit or the like) during low lighting conditions, such as at nighttime. Optionally, individual illumination sources may be provided at each icon or port 40 a to independently illuminate or back light the respective icon, such as in response to actuation of a respective one of the user inputs (such as in a manner as described above with respect to the individual directional icons of the compass display). Optionally, and with reference to FIG. 23 , the display 40 ′ may be positioned at a window 42 of the reflective element 14 and may be viewable through the reflective element window.
[0119] The cap portions of the present invention thus may provide a desired content, such as a garage door opening system and respective user inputs or a telematics feature and respective user inputs, to a particular mirror assembly. The desired system may be provided to the cap portion as a module, such as a garage door opening system module (which may include the transmitter and circuitry and user inputs) or a telematics module (which may include the circuitry and user inputs and display elements), and the module may be attached to or snapped to or mounted to the cap portion, such as at a cap portion assembly facility or at the vehicle assembly facility. Although shown as a garage door opening system module or a telematics module, clearly, the cap portion may include or incorporate other modules or displays or the like, such as, for example, a passenger side air bag status display (typically on the lower passenger side corner or area of the reflective element) or other displays, or a rear-facing sensor (which may align with an opening or port or window formed in the reflective element when the cap portion is attached to the mirror holder), or other types of displays or systems or modules, without affecting the scope of the present invention. Optionally, the user inputs or buttons or switches or the like may be positioned in the cap portion or in the bezel portion (or between the cap portion and bezel portion), or the cap portion may include an eyebrow portion or gondola portion or underbrow portion or chin portion or attachment (that may extend or protrude partially outward and/or partially around the bezel portion, and that may extend upwardly or downwardly or sidewardly therefrom) in which the inputs may be positioned, such that the inputs are contained at or in the cap portion and readily viewable and/or accessible at a desired location around the bezel portion.
[0120] The desired cap portion (with the desired features or content) may be readily attached to a common or universal mirror holder (which may include the reflective element and toggle and mounting assembly, which may be assembled at a mirror holder assembly facility) to assemble the mirror assembly, such as at a mirror assembly facility. The mirror holder may be adapted to partially receive the user inputs therein, and/or the reflective element contained in the mirror holder may have a particular display or displays formed thereon. The display icons or ports or windows formed in the reflective layer of the reflective element may generally align with the respective display elements or illumination sources of the circuitry within the cap portion when the cap portion is attached to the mirror assembly, such as described above with respect to the compass display. In applications where different modules may be provided that provide different display information at the reflective element, the reflective element may be selected to have the appropriate ports or icons or the like that correspond with the particular module, or the reflective element may have a window or windows formed in the desired or appropriate locations or may comprise a transflective prismatic reflective element (such as described in PCT Application No. PCT/US03/29776, filed Sep. 19, 2003 and published Apr. 1, 2004 as International Publication No. WO 2004/026633; and/or U.S. provisional application Ser. No. 60/525,952, filed Nov. 26, 2003, which are hereby incorporated herein by reference), such that the display elements (which may be illuminated alphanumeric characters or icons or indicia or the like) of the modules may be viewable through the reflective element to view the information being displayed by the display elements. The present invention thus provides for various mirror assemblies having different features or electronic content, while providing common or universal mirror holders and cap portions, where different circuitry or circuit boards or modules may be attached to the cap portion to provide the desired content to the mirror assembly.
[0121] Optionally, the cap portion or portions and circuit board or boards may support one or more other accessories or features at or within the mirror holder, such as one or more electrical or electronic devices or accessories. For example, and as can be seen in FIGS. 24-26 , illumination sources or lights, such as map reading lights 46 or one or more other lights or illumination sources (which may be positioned at or aligned with openings formed in the bottom of the mirror holder to direct illumination generally downward to illuminate the console of the vehicle), such as illumination sources of the types disclosed in U.S. Pat. Nos. 6,690,268; 5,938,321; 5,813,745; 5,820,245; 5,673,994; 5,649,756; 5,178,448; 5,671,996; 4,646,210; 4,733,336; 4,807,096; 6,042,253 and/or 5,669,698, and/or U.S. patent application Ser. No. 10/054,633, filed Jan. 22, 2002, now U.S. Pat. No. 7,195,381; and/or Ser. No. 10/745,056, filed Dec. 22, 2003, now U.S. Pat. No. 6,971,775; and/or U.S. provisional application Ser. No. 60/500,858, filed Sep. 5, 2003, which are hereby incorporated herein by reference, may be included with the cap portion 16 ″. The illumination source or sources 46 may be attachable to or positionable at or molded into the cap portion and may connect to a circuit board 47 of the cap portion 16 ″. The illumination sources and/or the circuit board may be connected to one or more buttons or inputs 48 for activating and deactivating the illumination sources.
[0122] Optionally, and with reference to FIG. 26 , the circuitry 47 a may comprise a stamped circuit that is molded into and/or along the cap portion, with the electrical connections between the lights and buttons and power source being made via stamped connectors or terminals molded into the cap portion (such as terminals of the type described in U.S. Pat. No. 6,227,689, which is hereby incorporated herein by reference) and extending between the lights 46 and/or inputs/buttons (not shown in FIG. 26 ) and/or the power source/circuit board 47 . The illumination sources 46 and inputs 48 may be positioned at recesses in and along a forward edge or portion of cap portion 16 ″ and may be partially received in corresponding recesses along the rearward edge of the corresponding mirror holder to secure the illumination sources and buttons at the mirror assembly.
[0123] As best shown in FIGS. 24 and 25 , the light actuators or buttons 48 may comprise a push button actuator having a user actuating portion 48 a at a lower end of a body portion 48 b . The actuator 48 may comprise any known switch or button assembly, or may be of the type described in U.S. patent application Ser. No. 10/447,641, filed May 29, 2003, now U.S. Pat. No. 6,953,905, which is hereby incorporated herein by reference. Body portion 48 b may be slidably mounted to or positioned in or at the cap portion 16 ″ and may slide between an activated position, where the switch closes the circuit to activate the light source, and a deactivated position, where the switch opens the circuit to deactivate the light source. The actuator 48 includes a torsional spring 49 wrapped around a shaft 48 c protruding from body portion 48 b . One end 49 a of the spring 49 engages a stop 50 a extending from the cap portion 16 ″, while the other end 49 b is movable around a detent 50 b as the switch body 48 b is moved between the activated and deactivated positions. For example, when the switch is in the lowered or deactivated position, the spring may bias the switch downward (which may open the circuit) via engagement with the stop 50 a . When the switch is pressed upward, the end 49 b may move upward around the detent 50 b and may rest within a recess 50 c of the detent 50 b when the switch is released to retain the switch in the raised or activated position (which may close the circuit). When the switch is again pressed upward by a user, the end 49 b may move upward and out from the recess 50 c and may move downward around the detent 50 b as the switch is urged or moved downward in response to the biasing forces of the spring 49 . The actuator 48 thus provides a low cost actuating device that only has a few components and, thus, is less costly and less complicated and more durable than many multiple component switches in use today.
[0124] Optionally, the cap portion may provide circuitry or power for a light or illumination source, such as a map reading light or the like, and a desired or appropriate lighting capsule or module (including the light source and user input or button or switch) may be plugged into the mirror assembly (such as described in U.S. patent application Ser. No. 10/054,633, filed Jan. 22, 2002, now U.S. Pat. No. 7,195,381; and Ser. No. 10/745,056, filed Dec. 22, 2003, now U.S. Pat. No. 6,971,775, which are hereby incorporated herein by reference). The circuit board of the cap portion may include prongs or connectors or the like at a lower portion of the circuit board, and the lighting capsule may be inserted through an opening in the cap portion and/or mirror holder and may engage and connect to the prongs or connectors to electrically connect the light to the circuit board. The lights thus may be readily inserted into or connected to the circuit board of the cap portion if desired or appropriate to provide the desired feature or content to the cap portion and the mirror assembly.
[0125] Optionally, the mirror assembly may include a white light emitting diode, or a cluster of LEDs may be provided, as a map/reading light or light module. Optionally, the cap portion or bezel portion may include illumination sources, such as light emitting diodes or the like, that may be embedded in the rim of the bezel portion or the lower portion of the cap portion to emit or project illumination toward the desired area of the vehicle cabin. The illumination sources may be switched on locally, such as via user inputs or switches or buttons as described above, or may be activated/deactivated/controlled by a control or system remote from the mirror assembly, such as via a vehicle electronic or communication system, and may be connected via a hard wire or via various protocols or nodes, such as Bluetooth, SCP, UBP, J1850, CAN J2284, Fire Wire 1394, MOST, LIN and/or the like, depending on the particular application.
[0126] Optionally, the illumination sources may comprise modular light sources, and may comprise one or more incandescent light sources or light emitting diodes or the like, such as described in U.S. patent application Ser. No. 10/054,633, filed Jan. 22, 2002, now U.S. Pat. No. 7,195,381; and Ser. No. 10/745,056, filed Dec. 22, 2003, now U.S. Pat. No. 6,971,775, which are hereby incorporated herein by reference. Optionally, the light emitting diodes may be operable to individually emit illumination in different colors as desired, so as to provide mood lighting or the like. The illumination sources may be controlled via a user input at the lights or a separate or remote control device, such as a vehicle electronic or communication system, and may be connected via a hard wire or via various protocols or nodes, such as Bluetooth, SCP, UBP, J1850, CAN J2284, Fire Wire 1394, MOST, LIN and/or the like (which may also control the exterior mirror or mirrors of the vehicle), and may provide ramped activation and/or deactivation to provide theater like lighting or the like if desired.
[0127] Optionally, the cap portion may include or incorporate or receive other modules as selected or desired to customize the mirror assembly. For example, the cap portion and/or reflective element assembly portion may receive a microphone array module, a garage door opening system module, a telematics user access button/input module, and/or the like. The modules may be provided at the vehicle assembly plant or at the mirror assembly plant, and may be inserted or plugged into the cap portion or mirror assembly to provide the desired content to the mirror assembly. The modules and the cap portion may include connectors that provide both electrical and mechanical connection so that the modules are electrically connected to the appropriate circuitry as they are inserted or received into or snapped to or attached to the cap portion. An operator at the vehicle assembly plant thus may readily connect the appropriate module to the cap portion or to the mirror assembly to provide the desired content for that particular mirror assembly. For a base mirror that may not include such content, a blank module or plug may be inserted into or attached to the cap portion or mirror assembly, so as to fill or conceal any opening in the mirror assembly that otherwise may receive an electronic module or accessory. The modules may also be readily removed and replaced to ease repair and replacement of the accessory or circuitry, and to ease replacement or changeover to a different accessory or module, if a different option is desired, such as an aftermarket module or the like.
[0128] Optionally, the cap portion or portions and the circuit board or boards of the present invention may also or otherwise include other accessories, such as microphones 51 (such as shown in FIGS. 5 and/or 27 ). The microphones may comprise analog microphones or digital microphones or the like, and may be positioned at or aligned with one or more openings formed in the top and/or bottom of the cap portion or the mirror holder. The microphones, such as microphones of the types disclosed in U.S. Pat. Nos. 6,243,003; 6,278,377 and/or 6,420,975, and/or in PCT Application No. PCT/US03/308877, filed Oct. 1, 2003 and published Apr. 15, 2004 as International Publication No. WO 2004/032568, may be provided for interfacing with a vehicle telematics system or the like. Optionally, the cap portion or portions and the circuit board or boards may also or otherwise include other accessories, such as a telematics system, speakers, antennas, including global positioning system (GPS) or cellular phone antennas, such as disclosed in U.S. Pat. No. 5,971,552, a communication module, such as disclosed in U.S. Pat. No. 5,798,688, a voice recorder, a blind spot detection system, such as disclosed in U.S. Pat. Nos. 5,929,786 and/or 5,786,772, and/or U.S. patent application Ser. No. 10/427,051, filed Apr. 30, 2003, now U.S. Pat. No. 7,038,577; and Ser. No. 10/209,173, filed Jul. 31, 2002, now U.S. Pat. No. 6,882,287, transmitters and/or receivers, such as for a garage door opener or a vehicle door unlocking system or the like (such as a remote keyless entry system), a digital network, such as described in U.S. Pat. No. 5,798,575, a high/low headlamp controller, such as a camera-based headlamp control, such as disclosed in U.S. Pat. Nos. 5,796,094 and/or 5,715,093, a memory mirror system, such as disclosed in U.S. Pat. No. 5,796,176, a hands-free phone attachment, a video device for internal cabin surveillance (such as for sleep detection or driver drowsiness detection or the like) and/or video telephone function, such as disclosed in U.S. Pat. Nos. 5,760,962 and/or 5,877,897, a remote keyless entry receiver, a seat occupancy detector, a remote starter control, a yaw sensor, a clock, a carbon monoxide detector, status displays, such as displays that display a status of a door of the vehicle, a transmission selection (4wd/2wd or traction control (TCS) or the like), an antilock braking system, a road condition (that may warn the driver of icy road conditions) and/or the like, a trip computer, a tire pressure monitoring system (TPMS) receiver (such as described in U.S. Pat. Nos. 6,124,647; 6,294,989; 6,445,287; 6,472,979 and/or 6,731,205), an ONSTAR® system and/or the like (with all of the above-referenced patents and PCT and U.S. patent applications being commonly assigned, and with the disclosures of the referenced patents and patent applications being hereby incorporated herein by reference in their entireties). The accessory or accessories may be positioned at or on the cap portions and thus positioned at or within the mirror holder and may be included on or integrated in a printed circuit board positioned within the mirror holder.
[0129] Optionally, the cap portion or portions of the present invention may include one or more attachments, such as attachments of the types described in U.S. Pat. Nos. 6,690,268 and/or 6,428,172, which are hereby incorporated herein by reference. The attachment or attachments, such as a pen holder or display screen or the like, may be incorporated into the cap portion or may be removably attached to the cap portion and, thus, may be removable if not desired for the particular mirror application, without affecting the scope of the present invention. The desired attachment may be selected for the particular application of the cap portion and mirror assembly, and may provide additional features to the cap portion and mirror assembly as may be desired or selected for the particular mirror application.
[0130] Optionally, the cap portion or portions may include a conversation mirror that may flip up or out from the cap portion to allow the driver of the vehicle to view a person in the rear seat (such as a child in the rear seat) to see and talk to the person in the rear seat without having to adjust the reflective element of the mirror assembly. The conversation mirror may be pulled out when desired or may be spring loaded to pop up or out when actuated or depressed, or may be electronically controlled to extend out from the cap portion when an input is actuated, without affecting the scope of the present invention.
[0131] Optionally, a blind spot detection or side object detection system or circuitry and corresponding display or indicator may be provided on one of the cap portions and on the reflective element for indicating to the driver or occupant of the vehicle that another vehicle may be in a lane adjacent to the subject vehicle. The indicator may comprise any iconistic type of display which may indicate that another vehicle has been detected and/or that the subject vehicle is changing lanes toward the detected object or vehicle. The side object detection and warning system may utilize the principles disclosed in U.S. patent application Ser. No. 10/427,051, filed Apr. 30, 2003, now U.S. Pat. No. 7,038,577; and Ser. No. 10/209,173, filed Jul. 31, 2002, now U.S. Pat. No. 6,882,287, which are hereby incorporated herein by reference.
[0132] Optionally, the side object detection system may be operable to detect objects or other vehicles at one or both sides of the subject vehicle and to detect and identify a lane marker or lane markers at one or both sides of the vehicle, such as disclosed in U.S. patent application Ser. No. 10/427,051, filed Apr. 30, 2003, incorporated above. The side object detection system may be further operable to provide a visible and/or audible warning to the driver of the subject vehicle in response to the detection of another object or vehicle at a side of the subject vehicle and in response to the position or movement of the subject vehicle relative to the lane markers. The use of lane marker detection integrated with such side object detection systems can be used to reduce false positives (where the system detects a vehicle in the adjacent lane when there is no vehicle in the adjacent lane) significantly and enable longer distances of detection, which in turn improves response time for system warnings from high speed target vehicles. In known or conventional side object detection systems, the systems do not track lane markings. Known radar systems are incapable of lane tracking due to the nature of the technology, and conventional vision systems do not currently include this functionality. This forces the detection zone of such known side object detection systems to be static or non-changing regardless of any curvature in the road, and does not allow for higher warning functionality based on the lane position of the subject vehicle.
[0133] It is envisioned that the side object detection system (which may have components and/or circuitry on a cap portion or portions of the interior rearview mirror assembly, or on or at or in the mirror assembly or on or at or in an accessory module or pod mounted to or positioned at or near the mirror assembly or positioned elsewhere in the vehicle) may utilize lane marking detection and recognition to allow the side object detection system to determine or adjust a detection zone or target zone or area based on the lane markings of the adjacent lane. Such lane marking detection may accommodate a non-linear detection zone when the subject vehicle is turning or on a curve. This may provide a longer detection distance because non-linear lanes may cause false positives in a static detection zone, whereas a dynamic zone may facilitate a better area of interest at greater distances, since it may avoid tracking trailing vehicles (such as in the same lane as the subject vehicle) on sharp curves. Such a side object detection system may also allow higher human/machine interface (HMI) processing.
[0134] Known side object detection systems may be specified to warn when a vehicle is in the blind spot or will be in a short amount of time. This may force the system to warn the driver of a detected object even when a driver is not intending to make a lane change toward the detected object. This can be a source of annoyance to the driver, and it emphasizes the effect of false positives from detection of infrastructure, shadows, miscellaneous road clutter and the like. However, if the side object detection system requires the above condition or detection and also requires a close proximity to or movement toward the lane markers or adjacent lane (i.e. the subject vehicle is moving toward the lane markers and thus toward the adjacent lane) prior to providing a warning, then the system may only provide such a warning when actual danger is present (i.e. the subject vehicle is changing lanes toward an adjacent lane which is occupied by a detected vehicle or object).
[0135] Such a side object detection system may provide a large reduction of false positives over current side object detection systems, and the warning may thus represent a heightened level of risk for the current maneuver, instead of a heightened level of risk for a potential maneuver. The side object detection system thus may reduce annoyance, improve perceived reliability, and improve overall detection distances, which in turn may improve the predictive nature of the system to reduce latencies based on human response. The side object detection system, or circuitry and/or display of the side object detection system, may be incorporated into one or more cap portions mounted at the interior rearview mirror assembly, or may be incorporated into the rearview mirror assembly or an accessory module or pod positioned at or near the rearview mirror assembly. The display may be at the reflective element of the mirror assembly and may be an iconistic display of the subject vehicle and a detected object adjacent to the subject vehicle, or any other type of display, and may provide an audible signal to the driver of the vehicle, without affecting the scope of the present invention.
[0136] Optionally, the cap portion or portions may include a display element, such as a video display element or the like, that may slide out or flip up or down from the cap portion to provide a video screen that is viewable by the driver of the vehicle, such as a video display screen of the type described in PCT Application No. PCT/US03/40611, filed Dec. 19, 2003 and published Jul. 15, 2004 as International Publication No. WO 2004/058540, which is hereby incorporated herein by reference. The video display screen may be operable to display information to the driver of the vehicle, and may be incorporated into or may be in communication with a vision system or imaging system of the vehicle, such as a rearwardly directed vehicle vision system utilizing principles disclosed in U.S. Pat. Nos. 5,550,677; 5,760,962; 5,670,935; 6,201,642 and/or 6,717,610, and/or in U.S. patent application Ser. No. 10/010,862, filed Dec. 6, 2001, now U.S. Pat. No. 6,757,109, which are hereby incorporated herein by reference, a trailer hitching aid or tow check system, such as the type disclosed in U.S. patent application Ser. No. 10/418,486, filed Apr. 18, 2003, now U.S. Pat. No. 7,005,974, which is hereby incorporated herein by reference, a cabin viewing device or system, such as a baby viewing or rear seat viewing camera or device or system or the like, such as disclosed in U.S. Pat. Nos. 5,877,897 and 6,690,268, which are hereby incorporated herein by reference, a video communication device or system, such as disclosed in U.S. Pat. No. 6,690,268, which is hereby incorporated herein by reference, and/or the like. Optionally, the video display screen may also or otherwise serve as a screen for a navigation system of the vehicle or the like, such as a GPS-based navigation system, such as is known in the automotive art.
[0137] Optionally, the mirror assembly may include a heating device or element for heating the display element or the area around the display element. At low temperatures, it may be desirable to heat the display element, such as a liquid crystal display (LCD) element or the like (or such as a video screen display or illuminated display or the like), in order to enhance the performance and response of the display element in such low temperatures or cold conditions or environments. The display element may comprise any type of display element or light emitting element, such as a vacuum fluorescent (VF) display element, a light emitting diode (LED) display element (such as an inorganic LED display element or an organic light emitting diode (OLED) display element or a high intensity, high efficiency LED display element, such as disclosed in U.S. Pat. Nos. 6,690,268 and 6,428,172 and in U.S. patent application Ser. No. 10/054,633, filed Jan. 22, 2002, now U.S. Pat. No. 7,195,381, which are hereby incorporated herein by reference), a multi-pixel, dot-matrix liquid crystal display element, an electroluminescent display element, a backlit display element, such as a back lit iconistic display (such as disclosed in U.S. Pat. Nos. 6,642,851; 6,501,387 and 6,329,925, which are hereby incorporated herein by reference), a display element backlit by an incandescent light source, or a backlit liquid crystal display (LCD), a video display screen (such as the type described in PCT Application No. PCT/US03/40611, filed Dec. 19, 2003 and published Jul. 15, 2004 as International Publication No. WO 2004/058540, which is hereby incorporated herein by reference) or the like, without affecting the scope of the present invention.
[0138] The heating device may be operable to heat the reflective element at the area of the display element or may heat the display element itself. For example, the rear surface of the reflective element may have a transparent conductive coating or layer, such as an indium tin oxide (ITO), a tin oxide (TO) or the like (such as transparent conductive layers of the types suitable for use in electrochromic cells and such as described in U.S. Pat. Nos. 6,690,268; 5,668,663; 5,724,187; 5,140,455; 5,151,816; 6,178,034; 6,154,306; 6,002,544; 5,567,360; 5,525,264; 5,610,756; 5,406,414; 5,253,109; 5,076,673; 5,073,012; 5,117,346; 5,910,854; 5,142,407 and 4,712,879, and/or in U.S. patent application Ser. No. 10/054,633, filed Jan. 22, 2002, now U.S. Pat. No. 7,195,381, and/or in PCT Application No. PCT/US03/29776, filed Sep. 19, 2003 and published Apr. 1, 2004 as International Publication No. WO 2004/026633; PCT Application No. PCT/US03/35381, filed Nov. 5, 2003 and published May 21, 2004 as International Publication No. WO 2004/042457; and/or in PCT Application No. PCT/US03/036177, filed Nov. 14, 2003 and published Jun. 3, 2004 as International Publication No. WO 2004/047421; and/or U.S. provisional applications, Ser. No. 60/531,838, filed Dec. 23, 2003; Ser. No. 60/553,842, filed Mar. 17, 2004; and Ser. No. 60/563,342, filed Apr. 19, 2004, which are hereby incorporated herein by reference), applied thereto or deposited thereon in at least the area at which the display element may be positioned. An electrical current may then be applied to the transparent conductive layer (such as via a pair of terminals contacting opposite portions of the transparent conductive layer or the like) to energize the conductive layer and to heat the conductive layer. For example, the transparent conductive coating or layer may generate heat as electrons or electricity flow from a contact of a power terminal across the surface or coating or layer to a contact of a ground terminal. The contacts may be spaced apart at generally opposite sides of the transparent conductive layer and may provide for generally uniform and thorough heating of the transparent conductive layer when electricity is applied to the heating or power terminal.
[0139] The display element may be positioned behind the reflective element and transparent conductive coating and may be next to or urged against or optically coupled to the transparent conductive coating on the rear surface of the reflective element. When the electrical current is applied across the transparent conductive layer, the resistivity in the conductive layer causes the conductive layer to be heated, which functions to heat the display element to enhance the performance of the display element during low temperature conditions. Optionally, other types of heating devices may be implemented at or against the display element and/or the reflective element, or may be positioned at the printed circuit board upon which the display element may be mounted, without affecting the scope of the present invention.
[0140] Optionally, for example, a heating device may be implemented at or near a display (such as a video display screen displaying, for example, driver information such as navigational information or a view of an interior or exterior scene, such as a curb side view such as is now being required for certain vehicles in Japan, or a parking/reversing view or the like) to heat the display or display area at least initially upon startup of the vehicle in extremely cold conditions. When the vehicle is in a cold climate (such as, for example, in northern Minn. in the winter time where the temperature may drop to around thirty degrees below zero), the heater may be activated on the first ignition cycle of the vehicle or when the vehicle is first turned on or the like and when the temperature is below a threshold temperature. The heating device may include a thermometer or thermistor or the like to determine the ambient temperature at the vehicle or at or near the display, and the heater may be activatable in response to an output of the thermometer. Optionally, if the temperature is below a threshold temperature, the heater may be operable in a “quick heat mode” to rapidly heat the display so that it works properly very quickly after startup of the vehicle. The heater may be operable at a higher than normal power dissipation during the quick heat mode to provide rapid heating or thawing or defrosting of the display when the vehicle ignition is first turned on during winter or cold conditions, but after the initial rapid heating phase is completed, the heater may operate at a lower power dissipation level more suited for ongoing heating during the driving event. This is particularly useful when the display is associated with a backup aid or reverse vision system or the like (such as those described in U.S. Pat. Nos. 5,550,677; 5,760,962; 5,670,935; 6,201,642; 6,717,610; 5,877,897 and 6,690,268, and/or in U.S. patent application Ser. No. 10/010,862, filed Dec. 6, 2001, now U.S. Pat. No. 6,757,109, and Ser. No. 10/418,486, filed Apr. 18, 2003, now U.S. Pat. No. 7,005,974, and/or in PCT Application No. PCT/US03/40611, filed Dec. 19, 2003 and published Jul. 15, 2004 as International Publication No. WO 2004/058540, which are hereby incorporated herein by reference), where it is important for the display to be fully operational at the startup of the vehicle so it provides a proper or desired display of the rearward field of view of the camera as the vehicle is initially backed out of its parking space or driveway or the like.
[0141] The heating device and the construction of the mirror assembly thus may provide heating of a display or display element (such as, for example, heating of a slide out display screen such as the type described in PCT Application No. PCT/US03/40611, filed Dec. 19, 2003 and published Jul. 15, 2004 as International Publication No. WO 2004/058540, which is hereby incorporated herein by reference), such as for a backup aid or rear vision system or the like, during cold temperatures to enhance the performance of the display during such cold temperatures. The heating device may provide intimate heating of the display medium, such as for a liquid crystal display element or the like, to enhance the performance of the display element. The heating device may provide such intimate heating of the display medium while not interfering with or heating other components or circuitry of the mirror assembly. The heating device may be included in the construction of the mirror assembly itself, such as a transparent conductive layer across the display screen or element or reflective element or such as a wire grid or other heating element or the like at or near the display area, to intimately heat the display element or display medium without substantially heating other components and circuitry in the vicinity of the display element. Optionally, the heating device may be activated/deactivated/controlled in conjunction with the heating elements for the exterior rearview mirrors of the vehicle (in such applications where the exterior rearview mirrors may be heated or defrosted, such as when a rear window defroster/defogger is actuated or the like). The heating device may utilize or incorporate aspects of heating devices used to heat and defrost exterior rearview mirror reflective elements, such as the heating means described in U.S. Pat. No. 5,446,576, issued to Lynam et al., which is hereby incorporated herein by reference, such as a positive thermal coefficient (PTC) heater element that is continuously connected to voltage ignition, but that principally only operates at low temperatures, such as less than about 10 degrees Celsius or lower. Optionally, a separate temperature controller, such as a thermistor, may be provided at or near the display in the interior rearview mirror assembly that powers the heater element at low temperatures.
[0142] Optionally, it is envisioned that the cap portion or portions may include a shielding element or sleeve or the like to provide shielding from external fields and unwanted radiation fields. The shielding may comprise a thin metal or foil member or sleeve or sheet or the like that is placed over and along an interior surface or portion of the cap portion (such that the shielding is within the mirror assembly and thus not readily visible when the mirror assembly is assembled). The shielding may be attached to the cap portion or portions so as to be retained thereto during the mirror assembly process. The shielding material/sheet preferably has a magnetic and/or electromagnetic permeability appropriate for shielding the accessories and the like within the cap portion and mirror assembly from external fields and unwanted radiation fields and the like.
[0143] Optionally, the cap portion or portions may include a hands free phone attachment to allow a driver of the vehicle to use a cellular or mobile telephone via circuitry and microphones and speakers of the mirror assembly and/or vehicle. The cap portion or portions may include a connector, such as a plug or socket type of connector or telephone docking device or the like, for a user to plug their mobile telephone into, which would connect the mobile telephone to a communication system or the like of the mirror assembly or vehicle.
[0144] Optionally, and as shown in FIG. 28 , the cap portion or portions 16 may house or include a battery 52 for providing power to one or more electronic accessories or to a circuit board 58 of the cap portion or mirror assembly (such as, for example, described in U.S. Pat. No. 6,690,298, which is hereby incorporated herein by reference). The accessory or accessories of the mirror assembly thus may be powered by the battery such that the mirror assembly or circuitry of the cap portion may not have to connect to the power source of the vehicle. The battery may be contained within the cap portion and at or near an exterior or outer portion of the cap portion and may be readily accessible by a user to facilitate changing of the battery when desired or necessary. For example, the battery 52 may be within a recess 54 of cap portion 16 and may be contained therein via a trap door or panel or door 56 that may cover battery 52 and recess 54 when closed. Panel 56 may be opened and may be removable or may be hingedly attached or otherwise movably attached to cap portion 16 to facilitate access to recess 54 and battery 52 . For example, panel 56 may be molded with cap portion 16 and may be hingedly attached to cap portion 16 via a living hinge 56 a along an edge of panel 56 . Other means for storing a battery and selectively accessing the battery may be implemented, without affecting the scope of the present invention. The various accessories and electronic content and directly driven or energized displays may function via power from the battery or internal power source of the cap portion.
[0145] Optionally, and with reference to FIGS. 29-32 , an interior rearview mirror assembly 60 may include a bezel portion 62 of a mirror casing, a reflective element 64 and a cap portion or rear portion 66 of the mirror casing. The mirror assembly 60 may include a mounting arrangement or mounting assembly 68 for pivotally or adjustably mounting or attaching the mirror assembly to the vehicle, such as to a windshield of the vehicle or the like. The mounting assembly 68 may include a mounting arm 70 having a ball member 70 a at one end and an attachment end or mounting end 70 b opposite to the ball member 70 a . Ball member 70 a may be pivotally received within a socket 72 that may be positioned at or formed with or established at or attached to an attachment plate 74 at the reflective element 64 . When so positioned, attachment end 70 b may extend from attachment plate 74 and may insert through an opening 66 a in rear casing portion 66 . The attachment end 70 b may then attach or mount to a mounting portion or base portion or mounting base 76 , which in turn may be attached or mounted to the vehicle or to a mounting button or the like (not shown) at the windshield or headliner or overhead console of the vehicle.
[0146] In the illustrated embodiment, attachment end 70 b is a threaded stud or end, and is secured to or mounted to the mounting or base portion 76 via insertion of the threaded end 70 b through an opening 76 a ( FIG. 31 ) in mounting portion 76 and tightening a female fastener or nut 78 onto threaded end 70 b . The mounting arm 70 thus may have a narrow end for insertion through the opening 66 a in rear casing portion 66 , such that the opening in the rear casing portion may be smaller than is typically required (because typically the ball end of the mounting arm is inserted through the opening in the rear casing and snapped into the socket at the attachment plate). The mounting arm may be inserted into the socket of the attachment plate, which may be attached to the reflective element at the bezel portion, and then may be inserted through the opening in the rear casing portion or cap portion as the rear casing portion or cap portion is moved toward and into engagement with the bezel portion, such that the attachment end of the mounting arm extends or protrudes from the rear casing portion or cap portion after the mirror is assembled. The attachment end may then be attached or secured to the mounting portion or base portion via the nut or other type of fastener. As shown in FIG. 29 , the mirror assembly may also include a circuit board 80 (with circuitry and/or accessories such as those described above), which may be attached to the attachment plate 74 or which may be attached to the cap portion for mirror assemblies of the types described above.
[0147] Although shown as having a threaded attachment end for securing the mounting arm to a mounting base via a nut or the like, it is envisioned that the mounting arm may have other forms of attachment ends for fixedly or pivotally or adjustably mounting the mounting arm to a mounting base or the like, without affecting the scope of the present invention. For example, the attachment end may provide a female fastener which may threadedly receive a male fastener or screw or bolt or stud, or the attachment end may provide a bayonet type fastener, or the attachment end and mounting base may cooperate to provide a snap together attachment or the like, or the attachment end and mounting base may otherwise attach or secure together, such as via adhesive or welding, such as ultrasonic welding or the like. Optionally, the attachment end may attach to or receive another ball member, which may be received within a socket at the mounting base, in order to provide a double ball mounting arrangement. The mounting arm, socket and/or mounting base may comprise plastic or polymeric materials, or may be die cast or otherwise formed, without affecting the scope of the present invention.
[0148] Optionally, and as shown in FIG. 32 , the ball member 70 a of mounting arm 70 may be received in a socket 72 ′ attached to or positioned at or formed with or established at a toggle assembly 82 , such as for a prismatic reflective element. The toggle assembly may be any type of toggle assembly, such as described above, and may be attached to or mounted to the mirror holder or the mirror casing, whereby the attachment end of the mounting arm may extend or protrude from the mirror casing when the toggle assembly and mounting arm are mounted therein or attached thereto. The attachment end may then connect or attach to the appropriate connector or attachment (such as to the mounting base 76 via a fastener or nut 78 as shown in FIG. 32 ) as described above to adapt the mirror assembly for the particular application.
[0149] The mounting arrangement of the present invention thus may provide a pre-established pivot element or member, such as a ball joint, at the attachment plate of the reflective element or at the toggle assembly or the like, whereby other attachments or mounting elements may be attached to the other end of the mounting arm to provide the desired attachment or mounting arrangement for the particular application of the mirror assembly. The mounting arm and ball member may be inserted within the socket and then the backing plate or toggle assembly (at which the socket may be formed) may be attached or secured to the reflective element with the pre-established pivot joint or element. The ball member of the mounting arm may already be inserted or snapped into the socket when the backing plate or toggle assembly is attached to or juxtaposed with the reflective element, such that the ball member need not be rammed into the socket when the socket is positioned at or juxtaposed with the reflective element, which avoids the impact or shock to the reflective element that typically occurs when a ball member is rammed into a socket that is at or attached to or juxtaposed with a reflective element.
[0150] The other end of the mounting arm may then be attached, such as via a snap together arrangement or a threaded fastener or the like, to another mounting portion or base portion or the like at the vehicle. Optionally, the other portion may have a second pivot element or member, such as a ball member, already received within a socket at a mounting base, and the end of the mounting arm may readily attach to the end of the other ball member to mount the mirror assembly in the vehicle. For example, the attachment end of the mounting arm extending from the reflective element assembly may threadedly attach to a corresponding attachment end of another ball member extending from a socket at a base portion at the vehicle. The mounting arrangement thus may provide a single or double ball mounting arrangement without the need to press or ram the ball member or ball members into the respective socket after the socket is attached to or positioned at the reflective element. The mounting arrangement also avoids the impact or shock of ramming the opposite ball member into the respective socket at the mounting base or button.
[0151] Because the pivot element or member, such as a ball member or ball members, is/are already inserted into their respective sockets so that the pivot joints are pre-established at the reflective element and mounting base, the ball member(s) do not have to be rammed or snapped into place in their respective sockets during installation of the mirror assembly, which substantially reduces the stresses at the reflective element to substantially limit or reduce cracking of the reflective element during installation of the mirror assembly. The mounting arrangement thus may substantially reduce the stresses at the reflective element during the installation processes.
[0152] Also, because the mounting arm may have an attachment end opposite a ball member, the ball member may be received or pre-established in any suitable or corresponding socket of a substantially universal bezel portion or reflective element assembly portion, whereby the attachment end of the mounting arm may be attached to any corresponding connector or attachment at the vehicle to complete the installation process for the respective mirror assembly. The present invention thus may provide a substantially universal and pre-established ball joint or pivot joint at the reflective element (and thus lends itself to provision of a universal reflective element assembly portion) that does not require attachment or insertion of the ball member at a later time (after the socket portion is positioned at or established at or juxtaposed with the reflective element), and may provide the capability of adapting or configuring the mounting arm to fixedly or pivotally or adjustably attach to a particular mounting base or vehicle portion or console or the like for the particular mirror application. The mounting arrangement may be suitable for applications with the cap portion and mirror holder assemblies as described above, or may be suitable for applications with other types of mirror assemblies, such as a mirror assembly of the type shown in FIG. 29 , without affecting the scope of the present invention.
[0153] Optionally, and as shown in FIG. 31 , the mounting arm 70 may comprise a hollow mounting arm that provides a wiring channel or passageway 70 c therethrough. One or more wires or cables or the like thus may be routed through the mounting arm to provide power and/or control to the circuitry and accessories within the mirror assembly. As can be seen in FIGS. 30 and 31 , the wires may route along and within the mounting base 76 and through the mounting arm and into the mirror casing or housing. Optionally, the attachment end of the mounting arm may include a connector and may plug into or connect to a corresponding connector at the mounting base or the like to establish mechanical and electrical connections (such as via utilizing aspects described in U.S. Pat. Nos. 6,672,744; 6,669,267; 6,402,331; 6,386,742 and 6,124,886, and/or U.S. patent application Ser. No. 10/739,766, filed Dec. 18, 2003, now U.S. Pat. No. 6,877,888, and Ser. No. 10/355,454, filed Jan. 31, 2003, now U.S. Pat. No. 6,824,281, which are hereby incorporated herein by reference) as the mirror assembly is mounted within the vehicle. The mounting arm may include wiring therethrough to electrically connect the connector or attachment end to the circuitry within the mirror assembly.
[0154] As shown in FIGS. 29 and 30 , the mounting base 76 may have a hollow body portion 76 b that may extend along the interior surface of the windshield and that may extend generally downwardly from an attaching portion 76 c of mounting base 76 . The attaching portion 76 c may attach to the mounting button or other attachment element (not shown) positioned at or attached to the interior surface of the windshield or the headliner or an overhead console of the vehicle to position the mounting base at the desired or appropriate location at the vehicle. As shown in FIG. 29 , the mounting base 76 may include a cover plate 76 d that may encase or enclose the body portion 76 b to provide a finished appearance to the mounting base 76 along the windshield. Optionally, the body portion 76 b may include or receive one or more electronic elements or accessories, such as a rain sensor or the like (such as a rain sensor of the types described in commonly assigned U.S. Pat. Nos. 6,516,664; 6,320,176; 6,353,392; 6,313,454; 6,341,523 and 6,250,148; and/or in U.S. patent application Ser. No. 10/355,454, filed Jan. 31, 2003, now U.S. Pat. No. 6,824,281; and Ser. No. 10/348,514, filed Jan. 21, 2003, now U.S. Pat. No. 6,968,736, which are all hereby incorporated herein by reference), that may be positioned at the windshield and that may be optically coupled to the windshield, depending on the particular application. In such embodiments, the cover plate 76 d may include one or more openings or apertures at which the rain sensor camera or sensing device may be positioned.
[0155] Although the mirror assembly may include a prismatic reflective element, it is envisioned that the cap portion or portions may include controls or circuitry for controlling electro-optic or electrochromic reflective elements, such as electrochromic reflective elements of one or more exterior rearview mirror assemblies of the vehicle. The circuitry or controls may control the dimming of the exterior mirrors, such as in a known manner, such as described in commonly assigned U.S. Pat. Nos. 5,140,455; 5,151,816; 6,178,034; 6,154,306; 6,002,544; 5,567,360; 5,525,264; 5,610,756; 5,406,414; 5,253,109; 5,076,673; 5,073,012; 5,117,346; 5,724,187; 5,668,663; 5,910,854; 5,142,407 and/or 4,712,879, which are hereby incorporated herein by reference. Optionally, the cap portion or portions may include one or more photo-sensors, such as an ambient light photo-sensor and a glare sensor, and the controls or circuitry may control the exterior electro-optic or electrochromic reflective elements in response to such photo-sensors.
[0156] Optionally, the exterior rearview mirror assemblies of the vehicle may comprise electrochromic mirror reflective element assemblies, while the sensors and electronic circuitry for glare detection and ambient light detection may be positioned inside the vehicle, such as at an interior electrochromic rearview mirror assembly. In applications where the exterior mirror assemblies comprise passenger and/or driver side electrochromic exterior rearview mirror assemblies, such as may be implemented in large vehicles, such as SUVs and the like, the electrochromic controls and circuitry may be contained within the exterior rearview mirror assemblies or the exterior electrochromic reflective element assemblies may be slaved off of the controls and circuitry of an associated electrochromic interior rearview mirror assembly of the vehicle. Optionally, it is envisioned that such sensors and electronic circuitry may be positioned at or near or incorporated into an interior prismatic rearview mirror assembly having a prismatic reflective element. The circuitry and the glare sensor and/or ambient light sensor (such as a photo sensor or the like, such as a glare sensor and/or an ambient light sensor and electrochromic automatic dimming circuitry of the types described in U.S. Pat. Nos. 4,793,690 and 5,193,029, and U.S. patent application Ser. No. 10/456,599, filed Jun. 6, 2003, now U.S. Pat. No. 7,004,593, which are all hereby incorporated herein by reference) thus may be positioned at or in or near or incorporated into the added feature prismatic interior rearview mirror assembly. The sensors may be positioned at or within the prismatic interior rearview mirror assembly such that the glare sensor is directed generally rearwardly (in the direction opposite to the forward direction of travel of the vehicle), such as through a bezel portion of the prismatic interior rearview mirror assembly, while the ambient sensor may be directed generally forwardly (in the direction of travel of the vehicle) or downwardly toward the floor of the vehicle when the mirror assembly is installed in the vehicle.
[0157] It is further envisioned that the sensors and/or control circuitry may be provided at, on or within a cap portion of the interior rearview mirror assembly and, thus, may be provided as an option for vehicles that offer the electrochromic exterior rearview mirror assemblies with a base or prismatic interior rearview mirror assembly. The appropriate cap portion (with electrochromic control circuitry and sensors and the like incorporated therein) may be selected and attached to the interior rearview mirror reflective element assembly portion to provide glare and light sensing capability and electrochromic reflective element assembly control capability to the interior rearview mirror assembly. Optionally, the cap portion may include the glare sensor in a location therein that may extend downward or outward from the cap portion so that the glare sensor may be directed generally rearward toward the rear of the vehicle when the mirror assembly is installed in the vehicle. For example, the cap portion may include a gondola or pod extending therefrom for housing the sensor or sensors and/or control circuitry. Alternately, the cap portion may include the glare sensor at a location therein that may align with a view port or the like through the reflective element, such as for applications where, for example, the mirror assembly includes a compass/display system or other display system, such as the types described herein and/or the types disclosed in U.S. patent application Ser. No. 10/456,599, filed Jun. 6, 2003, now U.S. Pat. No. 7,004,593, which is hereby incorporated herein by reference. In such applications, the ambient sensor may provide a dual function of providing an input to the control circuitry for controlling the exterior electrochromic reflective element assemblies and providing an input to the control circuitry for the display element of the interior rearview mirror assembly. The cap portion may include the ambient light sensor in a location and orientation whereby the ambient light sensor is directed generally forwardly in the direction of travel of the vehicle when the mirror assembly is installed in the vehicle.
[0158] Optionally, the electrochromic controls and glare/ambient light sensors thus may be provided in a cap portion (such as in a protrusion therefrom, such as a gondola or the like) and, thus, may be provided as an option for use with a common bezel and prismatic reflective element assembly. The present invention thus provides for optional controls and circuitry and sensors for optional accessories, such as electrochromic exterior rearview mirror assemblies, while providing a common bezel and prismatic reflective element and mounting attachment. The desired or appropriate cap portion (with the desired or appropriate controls/sensors/circuitry) may be selected for a particular application and may be snapped onto or otherwise attached to the common bezel and prismatic reflective element assembly. The assembled mirror assembly may then be installed in the appropriate vehicle with the exterior electrochromic mirror assemblies. The present invention thus may provide added feature prismatic interior rearview mirror assemblies, where the desired content of the mirror assemblies may be selected and provided on a respective optional cap portion while the rest of the mirror assemblies comprise common components.
[0159] Although shown and described as having a prismatic reflective element, the interior rearview mirror assembly of the present invention may optionally have an electro-optic or electrochromic mirror assembly. The electrochromic mirror element of the electrochromic mirror assembly may utilize the principles disclosed in commonly assigned U.S. Pat. Nos. 6,690,298; 5,140,455; 5,151,816; 6,178,034; 6,154,306; 6,002,544; 5,567,360; 5,525,264; 5,610,756; 5,406,414; 5,253,109; 5,076,673; 5,073,012; 5,117,346; 5,724,187; 5,668,663; 5,910,854; 5,142,407 and/or 4,712,879, which are hereby incorporated herein by reference, and/or as disclosed in the following publications: N. R. Lynam, “Electrochromic Automotive Day/Night Mirrors”, SAE Technical Paper Series 870636 (1987); N. R. Lynam, “Smart Windows for Automobiles”, SAE Technical Paper Series 900419 (1990); N. R. Lynam and A. Agrawal, “Automotive Applications of Chromogenic Materials”, Large Area Chromogenics: Materials and Devices for Transmittance Control, C. M. Lampert and C. G. Granquist, EDS., Optical Engineering Press, Wash. (1990), which are hereby incorporated by reference herein; and/or as described in U.S. patent application Ser. No. 10/054,633, filed Jan. 22, 2002, now U.S. Pat. No. 7,195,381, which is hereby incorporated herein by reference. Optionally, the electrochromic circuitry and/or a glare sensor and circuitry and/or an ambient light sensor and circuitry may be provided on one or more circuit boards at the cap portion or portions of the mirror assembly.
[0160] Optionally, the electrochromic reflective element may include one or more displays, such as for the accessories or circuitry described above. The displays may be similar to those described above, or may be of types disclosed in U.S. Pat. Nos. 5,530,240 and/or 6,329,925, which are hereby incorporated herein by reference, and/or may be display-on-demand or transflective type displays, such as the types disclosed in U.S. Pat. Nos. 6,690,298; 5,668,663 and/or 5,724,187, and/or in U.S. patent application Ser. No. 10/054,633, filed Jan. 22, 2002, now U.S. Pat. No. 7,195,381; and/or in U.S. provisional application Ser. No. 60/525,952, filed Nov. 26, 2003, and/or in PCT Application No. PCT/US03/29776, filed Sep. 19, 2003 and published Apr. 1, 2004 as International Publication No. WO 2004/026633, which are all hereby incorporated herein by reference.
[0161] Optionally, and with reference to FIG. 33A , a reflective element assembly portion 84 may hold or receive or comprise an electrochromic reflective element assembly or cell 86 , which includes a front substrate 88 and a rear substrate 90 and an electrochromic medium 92 sandwiched therebetween. In the illustrated embodiment, the reflective element assembly or cell 86 comprises a front substrate 88 that is larger than the rear substrate 90 so as to create a relief region or overhang region or ledge 93 around the perimeter of the reflective element assembly, such as described in PCT Application No. PCT/US03/35381, filed Nov. 5, 2003 and published May 21, 2004 as International Publication No. WO 2004/042457; and/or in U.S. provisional applications, Ser. No. 60/553,842, filed Mar. 17, 2004; and Ser. No. 60/563,342, filed Apr. 19, 2004, which are hereby incorporated herein by reference.
[0162] The larger front substrate 88 allows the bezel portion or molding 94 to be molded around the electrochromic reflective element assembly and allows the bezel portion to shrink and directly stress the front substrate 88 without placing the interpane seal 96 under the hoop stresses and shear stresses that typically occur with conventional electrochromic cells or reflective element assemblies (where the front and rear substrates are offset one to another such that any bezel shrinkage typically places the front substrate in shear stress relative to the rear substrate, potentially leading to failure of the seal therebetween that protects the electrochromic medium from the outside environment) when the bezel portion cools and contracts around the cell. The bezel portion or molding 94 thus may be formed around the reflective element assembly or cell, and the cap portion (not shown in FIG. 33A ) may be provided at a later step after the bezel portion has cooled around the reflective element assembly (such as described above) to provide a modular electrochromic mirror assembly in accordance with the present invention. Optionally, the bezel portion may be formed of a soft polymer or impact absorbing material (such as a soft touch material as described above, and/or preferably having a Shore A durometer value of less than about 110 Shore A, more preferably less than about 90 Shore A, and most preferably less than about 70 Shore A) at or around the perimeter of the front substrate 88 or of the front or first surface 88 b of the front substrate 88 , or a soft or impact absorbing trim portion or element may be provided at or around the perimeter of the front substrate 88 , without affecting the scope of the present invention.
[0163] The front substrate 88 includes a transparent conductive coating or layer 89 (such as an indium tin oxide (ITO), a tin oxide (TO) or the like) on its rear surface 88 a (the second surface of the cell), while the rear substrate 90 includes a metallic conductive coating or layer or layers or stack of coatings or layers 91 on its front surface 90 a (the third surface of the cell), such as is generally done with electrochromic reflective element assemblies, and such as by utilizing aspects described in U.S. Pat. Nos. 6,690,268; 5,668,663; 5,724,187; 5,140,455; 5,151,816; 6,178,034; 6,154,306; 6,002,544; 5,567,360; 5,525,264; 5,610,756; 5,406,414; 5,253,109; 5,076,673; 5,073,012; 5,117,346; 5,910,854; 5,142,407 and 4,712,879, and/or in U.S. patent application Ser. No. 10/054,633, filed Jan. 22, 2002, now U.S. Pat. No. 7,195,381, and/or in PCT Application No. PCT/US03/29776, filed Sep. 19, 2003 and published Apr. 1, 2004 as International Publication No. WO 2004/026633; PCT Application No. PCT/US03/35381, filed Nov. 5, 2003 and published May 21, 2004 as International Publication No. WO 2004/042457; and/or in PCT Application No. PCT/US03/036177, filed Nov. 14, 2003 and published Jun. 3, 2004 as International Publication No. WO 2004/047421; and/or U.S. provisional applications, Ser. No. 60/531,838, filed Dec. 23, 2003; Ser. No. 60/553,842, filed Mar. 17, 2004; and Ser. No. 60/563,342, filed Apr. 19, 2004, which are hereby incorporated herein by reference.
[0164] As shown in FIG. 33A , the metallic conductive coating or layer or layers 91 may be removed from (or not disposed at) a perimeter region 90 b of the front surface 90 a of rear substrate 90 , and the interpane seal 96 may be disposed around the masked or uncoated perimeter region, in order to electrically isolate the conductive coatings 91 from the perimeter edge of the rear substrate 90 , such as described in U.S. provisional applications, Ser. No. 60/553,842, filed Mar. 17, 2004; and Ser. No. 60/563,342, filed Apr. 19, 2004, which are hereby incorporated herein by reference. The conductive coatings or layers 91 may provide a tab out region (not shown in FIG. 33A ) along the front surface of the rear substrate to provide for electrical connection between the third surface coating 91 and the perimeter edge of the substrate (such as described in U.S. provisional applications, Ser. No. 60/553,842, filed Mar. 17, 2004; and Ser. No. 60/563,342, filed Apr. 19, 2004, which are hereby incorporated herein by reference. A conductor or electrical connector 100 may connect to the conductive coating 89 via a solder or conductive strip 101 around the overhang region, while a second conductor or electrical connector (not shown in FIG. 33A ) may connect to the conductive coating 91 via connection to the tab out region. The reflective element assembly may include a reflective perimeter region around the perimeter of the reflective element assembly or may have an opaque or blackened or darkened perimeter region, such as by utilizing the principles described in U.S. Pat. No. 5,066,112, which is hereby incorporated herein by reference, in order to at least partially conceal the seal 96 from being readily viewable by the driver of the vehicle.
[0165] Optionally, and with reference to FIG. 33B , a reflective element assembly portion 84 ′ may hold an electro-optic reflective element assembly 86 , such as an electrochromic reflective element assembly or cell, and may include a mounting or attachment plate 98 positioned at the rear surface of the reflective element assembly 86 (the fourth surface of the cell). The bezel portion or molding 94 ′ may be molded or formed around the reflective element assembly 86 and around or at the attachment plate 98 to retain the attachment plate 98 and the reflective element assembly 86 within the bezel portion or molding 94 ′. As can be seen in FIG. 33B , the mounting plate 98 may include protrusions or recesses or the like 98 a at least partially around its perimeter edge to facilitate mechanical connection and securement of the bezel portion 94 ′ (such as by snap on or snap in) to the mounting plate 98 when the bezel portion 94 ′ is molded around the mounting plate 98 . The attachment plate 98 may include a pivot joint or element 102 established or formed thereon. The reflective element assembly portion 84 ′ may be otherwise substantially similar to reflective element assembly portion 84 , discussed above, such that a detailed description of the reflective element assembly will not be repeated herein. The components that are common with the reflective element assemblies 84 and 84 ′ are shown with the same reference numbers in FIGS. 33A and 33B .
[0166] Therefore, the reflective element assembly portion may be formed or molded with the molding or bezel portion molded or formed around the larger front substrate to contain the reflective element assembly or cell within or at the bezel portion. The pivot element or joint 102 may be formed or established at the rear of the reflective element assembly, such as in the manners described above, and the mounting arm 104 may extend generally rearwardly from the pivot joint. The cap portion (such as cap portion 166 shown in FIG. 33C ) may then receive the mounting arm 102 through an opening or the like in the cap portion such that the mounting arm extends from the cap portion after the cap portion is attached to or snapped to the reflective element assembly portion (such as at structure 95 shown in FIG. 33C ). The electrical connectors of the reflective element assembly portion may connect to the appropriate electrical connectors or terminals or circuitry of the cap portion as the cap portion is assembled to or attached to the reflective element assembly portion, such as in the manners described above, in order to provide electrical power and/or control to the electrochromic cell.
[0167] The electrochromic reflective element assembly portion of the present invention thus may comprise a standard or universal or common reflective element assembly or cell and mirror holder or bezel portion, which may then be attached to a customized or selected or desired cap portion, as described above. Optionally, the reflective element assembly portion may be customized as well. For example, a selected bezel material may be molded around a common reflective element assembly or cell. The reflective element assembly portion may be formed by placing an electrochromic cell into a mold cavity (such as face down into the mold cavity with the rear surface of the rear substrate facing upward), and the plastic piece or mounting plate (preferably with a pivot element or member already established therein or thereon) may be inserted into the mold or placed generally at or on the rear surface of the rear substrate of the reflective element assembly or cell (i.e. the fourth surface of the cell). The mounting plate may be generally smaller than the profile of the rear substrate and may include the pivot element or socket formed thereon (or such pivot components may be added or attached or molded later). Optionally, the mounting plate may include electronic circuitry and the like, such as for making the electrical connection to the electrical connectors of the cell and/or for providing other electronic content or features or functions as may be desired (such as display elements for displaying information through the cell to a driver of the vehicle or the like, or such as ports or aperture for aligning with display elements of the cap portion so that information may be displayed or projected through the apertures in the mounting plate and through the cell to a driver of the vehicle). The bezel portion or molding may then be molded (such as via injection molding or reaction injection molding of a desired or selected or appropriate material into the mold cavity) to form the bezel portion around the perimeter of the front substrate (such as described above).
[0168] Optionally, the electrochromic reflective element assembly portion may be readily customized by injection molding a selected material into the mold to form the bezel portion of a selected or customized material. For example, the material may be selected to be a desired color, or may be selected to have desired properties, such as, for example, a soft touch or desired feel or appearance or finish or the like. The present invention thus may provide a common cell and attachment or mounting plate (and pivot element or joint), but may readily customize the appearance and/or feel of the bezel portion or molding to provide a particular, selected and customized reflective element assembly portion, while utilizing the same molding tool or mold to form the customized molding or bezel portion. Optionally, the reflective element assembly or cell and attachment or backing plate may comprise standard or common components for multiple mirror assemblies, and may be placed in desired or appropriate molds for molding the appropriate bezel portion for a particular mirror application. The customized reflective element assembly portion may then be attached to the desired or selected or customized cap portion as described above, and the electrical connections of the electronic circuitry and the like at the plate of the reflective element assembly portion may be made to the corresponding or appropriate connectors or circuitry of the cap portion as the cap portion is attached to the reflective element assembly portion. Although shown and described as molding a bezel portion around the perimeter region of a larger front substrate (which is larger than the rear substrate) of an electrochromic reflective element assembly or cell, it is envisioned that the bezel portion or molding may be molded or formed around other types of electrochromic reflective element assemblies or cells (such as flush cells or offset or staggered cells or the like), and/or may be molded or formed around prismatic reflective elements and the like (such as the bezel portion or molding 94 ″ at the prismatic reflective element 86 ′ shown in FIG. 33C ), without affecting the scope of the present invention.
[0169] Optionally, and such as described in PCT Publication No. WO 03/095269, published Nov. 20, 2003, which is hereby incorporated by reference herein, an electro-optic rearview mirror assembly portion may comprise an electro-optic reflective element assembly or unit or cell, such as an electrochromic reflective unit or cell (whose reflectivity is variable in response to an electrical voltage applied thereto), and an electrical circuit for controlling operation of the mirror cell in response to one or more one light sensors. The interior mirror assembly portion may also comprise at least one pivot element or member, such as a ball and socket member, which allows angular adjustment of the mirror reflective element when the mirror assembly is mounted in the vehicle. Optionally, the ball member may include a plurality of electrical contacts on an exposed surface thereof for sliding engagement by respective counter-contacts over a range of angular movement of the mirror unit for supplying power to the electrical circuit from a vehicle electrical system external to the mirror assembly. Optionally, other means for providing electrical power and/or control to the circuitry/accessories of the mirror assembly may be provided (such as a wire or cable along an exterior surface or portion of the mounting arm or member or the like), without affecting the scope of the present invention.
[0170] Optionally, a prismatic mirror assembly portion and cap portion of the present invention may include electrochromic drive circuitry for controlling the exterior electrochromic reflective elements of the exterior rearview mirror assemblies of the vehicle, such as described above. The cap portion may include a glare sensor and an ambient sensor to determine the glare levels and ambient light levels and the control circuitry may adjust the dimming of the exterior mirrors accordingly. The glare sensor may receive the light through an aligned port in the reflective element or may receive light via a light pipe or the like, without affecting the scope of the present invention. The cap portion thus may provide electrochromic control circuitry for applications where the vehicle may have exterior electrochromic mirror assemblies, while the interior rearview mirror assembly may comprise a base or prismatic mirror that may otherwise not include such control circuitry. The cap portion of the present invention thus may provide a low cost conversion of an interior rearview mirror to provide electrochromic mirror control for the exterior rearview mirrors of the vehicle.
[0171] Optionally, and with reference to FIGS. 34 and 35A -D, an interior rearview mirror assembly 110 may be attachable or mountable to a windshield accessory module 112 , which may be attachable or mountable to an interior surface of the windshield of a vehicle, such as at a mounting button or the like. Windshield accessory module 112 may include a body portion 114 that extends generally along the windshield and may include a head portion 116 at the upper end of the body portion 114 generally above the mirror assembly 110 and viewable by a driver of the vehicle when the windshield accessory module 112 and mirror assembly 110 are mounted in a vehicle, such as in a similar manner as described in U.S. patent application Ser. No. 10/355,454, filed Jan. 31, 2003, now U.S. Pat. No. 6,824,281, which is hereby incorporated herein by reference. Windshield accessory module 112 may include one or more accessories or circuitry therein, and may include one or more user interface controls or inputs and/or a display or indicator or indicators or the like at the head portion that are readily viewable and/or accessible above the mirror assembly, such as discussed below and as shown in FIGS. 35A-D and/or as described in U.S. patent application Ser. No. 10/355,454, filed Jan. 31, 2003, now U.S. Pat. No. 6,824,281, which is hereby incorporated herein by reference. As shown in FIGS. 34 and 35A , a wiring or cabling conduit 118 may extend upward from the body portion 114 and along the windshield 111 to conceal and route the wiring harness between the headliner of the vehicle and the windshield accessory module 112 .
[0172] Preferably, the windshield accessory module may be configured to attach to a typical mounting button or the like for an interior rearview mirror assembly, and may include a replica of the mounting button or the like for the mirror assembly to mount thereto. The accessory module thus may attach to the existing button on the windshield and the mirror assembly may be attached to the button on the accessory module in the same manner. The mirror assembly may comprise a modular mirror assembly as described above, or may comprise other types of prismatic or electro-optic or electrochromic mirror assembly, without affecting the scope of the present invention. As shown in FIG. 34 , a wiring harness 119 and connector or plug 119 a may extend from accessory module 112 and plug into the back of the mirror casing or cap portion, such as in a similar manner as described above. The accessory module thus may provide an aftermarket addition to add additional electronic content or accessories, without having to replace the mirror assembly. The accessory module of the present invention thus may provide the desired accessories or options, while providing the vehicle manufacturer and/or the customer the freedom to select any mirror assembly. Optionally, for aftermarket applications, the windshield accessory module may be battery-operated and may include a battery compartment for receiving and connecting to a battery or power source or the like.
[0173] As shown in FIG. 35A , windshield accessory module 112 may include or may be associated with a garage door opening system, and head portion 116 may include one or more user actuatable inputs 120 a - c for controlling or actuating the garage door opening system. Head portion 116 may also include an icon or indicia 122 or the like, which may be illuminated or back lit via a light source in head portion 116 to indicate to the user of the garage door opening system that the system is activated or that the button or input was successfully actuated. The garage door opening system may comprise a trainable garage door opening system and/or may utilize principles disclosed in U.S. Pat. Nos. 6,396,408; 6,362,771; 5,798,688 and 5,479,155; and/or U.S. patent application Ser. No. 10/770,736, filed Feb. 3, 2004, now U.S. Pat. No. 7,023,322, which are hereby incorporated herein by reference.
[0174] Optionally, and with reference to FIG. 35B , the windshield accessory module 112 ′ may also or otherwise include or be associated with a telematics system or cellular telephone system or the like. The head portion 116 ′ thus may provide user inputs 124 a , 124 b , 124 c for actuating the system, placing a telephone call and ending a telephone call, respectively. The head portion 116 ′ may also include a microphone 126 for receiving voice or audio signals from within the cabin of the vehicle, such as via a microphone system of the types described in U.S. Pat. Nos. 6,243,003; 6,278,377 and/or 6,420,975, and/or in PCT Application No. PCT/US03/308877, filed Oct. 1, 2003 and published Apr. 15, 2004 as International Publication No. WO 2004/032568, which are hereby incorporated herein by reference. In the illustrated embodiment of FIG. 35B , the head portion 116 ′ includes user inputs and/or indicators 120 a ′, 120 b ′, 120 c ′ for controlling and actuating the garage door opening system and/or for indicating successful operation of the garage door opening system, such as described above.
[0175] Optionally, and with reference to FIG. 35C , the windshield accessory module 112 ″ may also or otherwise include or be associated with a tire pressure monitoring system. The head portion 116 ″ may include a display 128 that includes a pressure display 128 a for displaying the tire pressure of a particular tire of the vehicle and indicators or light sources 128 b for indicating which tire the display 128 a is showing the pressure for. Head portion 116 ″ may also include a reset button or input 128 c for resetting the tire pressure monitoring system. The tire pressure monitoring system may comprise any tire pressure monitoring system, and may utilize the principles described in U.S. Pat. Nos. 6,124,647; 6,294,989; 6,445,287; 6,472,979 and/or 6,731,205, which are hereby incorporated herein by reference. The head portion 116 ″ may also include one or more user inputs and/or indicators 120 a ″, 120 b ″, 120 c ″ for controlling and actuating the garage door opening system and/or for indicating successful operation of the garage door opening system, such as described above.
[0176] Optionally, and with reference to FIG. 35D , the windshield accessory module 112 ″ may also or otherwise include or be associated with a navigational system for providing instructions to the driver to follow to arrive at a desired or input destination. The head portion 116 ″ may include a display screen or display device 130 for providing directional heading or driving instructions to the driver. For example, the display device 130 may display the next step to follow and may indicate how far the vehicle has to travel until it arrives at the next turn or intersection. The head portion 116 ′″ may also include one or more user inputs or buttons 132 for controlling the navigational display and/or for scrolling through the instructions being displayed by the display device 130 . The navigational system may be associated with or controlled or adjusted by a global positioning system of the vehicle and/or a telematics system of the vehicle and/or a compass system of the vehicle, and may utilize principles such as used in the compass and/or navigational systems of the types described in U.S. Pat. Nos. 6,678,614; 6,477,464; 5,924,212; 4,862,594; 4,937,945; 5,131,154; 5,255,442 and/or 5,632,092, and/or U.S. patent application Ser. No. 10/456,599, filed Jun. 6, 2003, now U.S. Pat. No. 7,004,593; Ser. No. 10/645,762, filed Aug. 20, 2003, now U.S. Pat. No. 7,167,796; and Ser. No. 10/422,378, filed Apr. 24, 2003, now U.S. Pat. No. 6,946,978; and/or PCT Application No. PCT/US03/40611, filed Dec. 19, 2003 and published Jul. 15, 2004 as International Publication No. WO 2004/058540, which are all hereby incorporated herein by reference. As shown in FIG. 35D , head portion 116 ″ may also include one or more user inputs and/or indicators 120 for controlling and actuating the garage door opening system and/or for indicating successful operation of the garage door opening system, such as described above.
[0177] The desired accessory module or content may be used with any mirror assembly and, for aftermarket applications, may be used with an existing mirror assembly in the vehicle. The existing mirror assembly may be removed from the mounting button and the windshield module may be attached to the windshield button and the mirror assembly may be attached to the button of the module. Optionally, and particularly for aftermarket applications, the accessory module may include a power source or battery for providing power to the electronic accessories contained within the module and/or within an associated mirror assembly.
[0178] Although certain examples of the controls and/or displays that may be provided at the head portion of the windshield accessory module are shown in FIGS. 35A-D and described above, clearly other displays and/or user inputs and/or accessories or functions or features may be provided within or at the windshield accessory module, without affecting the scope of the present invention. The desired features or content may be provided on a circuit board and may include display elements and/or display screens or panels or the like. The circuit board and associated display elements and circuitry and inputs (or appropriate or selected or desired display elements and the like) may be mounted to or attached to or snapped into a common or universal body or base portion to convert or form the desired windshield electronics module for the particular application. If the screen or circuitry is larger than the standard head size of the module, a larger cap portion (such as shown in FIGS. 35B and 35D ) may be implemented to contain and conceal the circuitry and the like within the head portion. The windshield electronics module or accessory module of the present invention thus provides various modules with the desired features or content, while utilizing common or universal components.
[0179] The windshield electronics module of the present invention thus eases assembly of various modules having varied content, and eases disassembly and repair of the modules. Optionally, however, the module may be sealed to contain the circuit board and display elements therewithin, without affecting the scope of the present invention. The components of the module, such as the telematics controls and the like, may be associated with other components and/or circuitry and/or systems of vehicle, such as a vehicle electronic or communication system, and may be connected via a hard wire or via various protocols or nodes, such as Bluetooth, SCP, UBP, J1850, CAN J2284, Fire Wire 1394, MOST, LIN and/or the like, depending on the particular application.
[0180] Therefore, the present invention provides a modular prismatic interior rearview mirror assembly which may have features, such as electronic accessories and/or displays or the like. The accessories or circuitry may be attached to one or more cap portions which may snap or otherwise affix or secure or mount to the rear portion of the mirror holder or bezel portion or reflective element assembly portion. The mirror holder may receive the reflective element, which may be a prismatic reflective element or an electro-optic or electrochromic reflective element, soon after the mirror holder is formed or heated, such that the reflective element may be installed to the mirror holder without a separate bezel portion. The cap portions and associated accessories and/or circuitry may be mounted to the mirror holder after the reflective element is installed and after the mirror holder has cooled and shrunk. The cap portion of the present invention thus avoids the increased costs associated with a two piece mirror holder having a separate bezel portion which is secured to the mirror holder to secure the reflective element at the mirror holder. The cap portions may be selected to have accessories and/or circuitry corresponding to openings in the mirror holder and/or to displays or display icons or the like at the reflective element. The cap portion may be selected to be formed of a different material than the bezel portion or molding, so as to provide the desired material properties and characteristics to both the bezel portion and the cap portion.
[0181] As described in PCT Application No. PCT/US03/35381, incorporated above, and as can also be seen with reference to FIG. 36 , an electro-optic or electrochromic cell or reflective element assembly 210 , such as for an interior or exterior rearview mirror assembly of a vehicle, includes a front substrate 212 and a rear substrate 214 , with an electro-optic or electrochromic medium 216 disposed or sandwiched therebetween. Front substrate 212 includes an opaquifying or darkening or hiding conductive coating or layer 219 (such as, for example, an opaque or black conductive epoxy or dark colored conductive frit or chrome oxide/metallic chrome bilayer or the like, or other materials) applied or deposited around the border or perimeter of the front substrate 212 . The opaquifying layer 219 may at least partially wrap around the perimeter edges of the substrate so that an edge portion 219 c of opaquifying layer 219 extends at least partially along the perimeter edge 212 c of substrate 212 . The front substrate 212 also includes a semi-conductive, transparent coating or layer 218 (such as an ITO layer or doped ITO layer or the like) applied to or deposited on the rear surface 212 a of front substrate 212 and overlapping the opaquifying or hiding conductive border layer or coating 219 . Alternately, the semi-conductive layer 518 may be applied to or deposited on the rear surface of front substrate first, and then the opaquifying or black conductive layer may be applied to or deposited on the perimeter region of the semi-conductive layer.
[0182] The rear substrate 214 includes a metallic or conductive layer or coating 220 applied to or deposited on and substantially over the third surface 214 a of rear substrate 214 . The outer perimeter edge area or border region of the third surface 214 a of the rear substrate 214 may be masked while the metallic reflector 220 is applied, such that the border region of the front surface 214 a of substrate 214 provides a non-conductive surface or path or raceway 214 e (such as a glass surface or the like) at least partially around the metallic reflector 220 and proximate to the edge of substrate 214 .
[0183] As shown in FIG. 36 , the front substrate has a height dimension that is greater than a corresponding height dimension of the rear substrate, such that the upper perimeter region or edge portion 212 f and lower perimeter region or edge portion 212 g of front substrate 212 extend beyond the corresponding perimeter regions or edge portions 214 f , 214 g of rear substrate 214 and define upper and lower overhang regions 212 h , 212 i . The connector or connectors may connect to the conductive layer at the rear surface of the front substrate at the overhang region or regions 212 h , 212 i and thus may not interfere or overlap the perimeter edge of the front substrate. The overhang regions of the front substrate relative to the rear substrate thus may allow for the electrical connectors to connect to the respective conductive layers substantially or entirely within the viewable profile of the front substrate by extending along the respective perimeter edges of the rear substrate, such that the connectors do not overlap the perimeter regions of the front substrate and, thus, are not viewable at the front surface of the front substrate. The front substrate may include a hiding layer or concealing layer at the perimeter regions or overhang regions, such as at the rear surface of the front substrate, to substantially hide or conceal the connectors and the seal of the reflective element assembly. The reflective element assembly thus may be suitable for a bezelless or minimal bezel mirror assembly.
[0184] As also described in PCT Application No. PCT/US03/35381, incorporated above, and as can also be seen with reference to FIG. 36 , reflective element assembly 210 may provide an electrically conductive opaque or hiding or concealing layer 219 at least substantially around the perimeter edges of the front substrate, with the transparent semi-conductive layer 218 overlapping the opaque conducting layer 219 in the area at which the seal 217 is positioned around the electrochromic medium 216 . The opaque conducting layer 219 thus provides a contacting region around the perimeter of the substrate for contacting the transparent semi-conductive layers or coatings 218 . The seal 217 is positioned along the opaque conductive layer 219 and is thus masked or hidden by the opaque conductive layer to enhance the appearance of the reflective element assembly, particularly when the electro-optic or electrochromic medium is darkened or colored. The opaque conductive layer may thus allow for a smaller or no bezel overhang around the perimeter of the reflective element assembly. As can be seen in FIG. 36 , the seal 217 may be positioned around the masked or border region of the rear substrate 214 . The non-conductive perimeter seal 217 at least partially fills or covers or encompasses the non-conductive glass surface or masked region 214 e to electrically isolate or insulate the conductive coating 220 from the conductive adhesive 226 , such that the conductive coating 220 of rear substrate 214 is electrically isolated from the connector that connects to the conductive surface 218 of front substrate 212 .
[0185] Optionally, and as also described in PCT Application No. PCT/US03/35381, incorporated above, and with reference to FIGS. 37A and 37B , an exterior rearview mirror cell or reflective element assembly for an exterior rearview mirror assembly of a vehicle includes a first or front substrate 312 ( FIG. 37A ) and a second or rear substrate 314 ( FIG. 37B ) and an electro-optic or electrochromic medium and seal 317 sandwiched therebetween, such as described above. As also described above, the front substrate 312 may have a transparent semi-conductive layer or coating 318 (such as ITO or the like) applied to the second or rear surface 312 a of the substrate, and may include an opaquifying conductive border/perimeter coating or layer 319 (such as, for example, a black conductive epoxy or dark colored conductive frit or black chrome/metallic chrome layer or the like) applied around the perimeter edges of the front substrate 312 . As shown in FIG. 37A , the perimeter coating or layer 319 may be along the perimeter edges of the front substrate 312 except in an electrical connection area or region 325 of substrate 312 , where the perimeter coating 319 is inward of the outer edges of substrate 312 . The electrical connection region 325 is coated by the semi-conductive layer 318 and/or a conductive layer or the like. A deletion line 321 , such as a non-conductive area in the region 325 where the busbar layer and semi-conductive layer is etched off or otherwise removed from or not applied to the surface of the substrate, is formed at the electrical connection area 325 to separate and define and electrically isolate a rear substrate electrical connection area 325 a or raceway portion of the semi-conductive layer from a front substrate electrical connection area 325 b or surface portion of the semi-conductive layer.
[0186] An electrical connection or contact 322 is connected to or applied to the front substrate electrical connection area 325 b to provide electrical power or connection to the semi-conductive layer 318 on the rear surface of the front substrate 312 . Likewise, an electrical connection or contact 324 is connected to or applied to the electrically isolated rear substrate electrical connection area 325 a and is in electrical communication with the conductive layer of the third surface 314 a of rear substrate 314 via a conductive material or bridge 323 , as discussed below.
[0187] With reference to FIG. 37B , rear substrate 314 includes a metallic reflector layer 320 (such as a layer or layers comprising, for example, chromium, chromium/rhodium, aluminum, silver, aluminum alloy, silver alloy, an ITO/silver/ITO stack, an ITO/aluminum/ITO stack or the like, such as ITO-silver-ITO stacks or layers, or display on demand stacks or layers or infrared transmitting stacks or layers of the types described in PCT application No. PCT/US03/29776, filed Sep. 19, 2003 and published Apr. 1, 2004 as International Publication No. WO 2004/026633) on its front or third surface 314 a , and a perimeter black seal 317 generally around the perimeter edges of the substrate. As can be seen in FIG. 37B , an electrical connection area 327 may be defined at a region of the rear substrate 314 , such as at a corner of the substrate, where the perimeter seal 317 is positioned inward of the outer edge of the substrate. The rear substrate 314 is formed to be substantially identical in shape to the front substrate 312 , except at the electrical connection area 327 , where the rear substrate may be cut back or reduced along a cut-away or cut back edge 314 c . The conductive bridge 323 is positioned at a portion of the electrical connection area 327 to provide electrical connection to the metallic reflective coating or layer 320 via electrical connector 324 at front substrate 312 .
[0188] When the substrates 312 , 314 are placed together to form the electro-optic or electrochromic mirror cell or reflective element assembly (with the electro-optic or electrochromic medium disposed or sandwiched therebetween), the electrical connection area 327 of rear substrate 314 generally aligns with a portion of the electrical connection area 325 of front substrate 312 . The conductive bridge 323 bridges or spans the gap or spacing between the electrical connection areas 325 a and 327 to connect the electrical contact or connector 324 and electrical connection area 325 a to the metallic conductive reflective layer 320 of rear substrate 314 .
[0189] The cut-away edge 314 c of rear substrate 314 provides for exposure of the electrical connectors or contacts 322 , 324 along the outer edge 312 c of the electrical connection area 325 of front substrate 312 . The electrical contacts for providing electrical power to the conductive or semi-conductive layers at both substrates are made at only one of the substrates. The other edges of the substrates 312 , 314 are generally flush or aligned to form a flush reflective element assembly for an exterior rearview mirror assembly. The reflective element assembly may thus be implemented in a mirror assembly having a minimal bezel or a bezelless mirror assembly to enhance the appearance of the mirror assembly.
[0190] As disclosed in U.S. patent application Ser. No. 10/427,051, filed Apr. 30, 2003, now U.S. Pat. No. 7,038,577, incorporated above, a camera or imaging sensor of an object detection system or lane change assist system is operable to capture an image of the exterior scene within the field of view of the camera. The captured image comprises an image data set, which is representative of the exterior scene, and which is received by the control. The control is operable to process image data within a reduced data set or subset of the image data set more than other image data of the image data set to reduce the processing requirements of the control. The reduced data set or subset or subsets is/are representative of a target zone or area or areas in the exterior scene where a vehicle or other object of interest may realistically be expected to be present within the exterior scene. The control is thus operable to primarily process the significant or relevant area or areas of the scene more than less relevant areas, and may limit or reduce processing of or substantially ignore the image data representative of some areas of the exterior scene where it is not likely that a vehicle or other object of interest would be present or where a vehicle cannot be present.
[0191] The camera or imaging sensor may comprise an imaging array sensor, such as a CMOS sensor or a CCD sensor or the like, such as disclosed in commonly assigned U.S. Pat. Nos. 5,550,677; 5,670,935; 5,796,094 and 6,097,023, and U.S. patent application Ser. No. 09/441,341, filed Nov. 16, 1999, now U.S. Pat. No. 7,339,149, or an extended dynamic range camera, such as the types disclosed in U.S. provisional application Ser. No. 60/426,239, filed Nov. 14, 2002. The imaging sensor may be implemented and operated in connection with other vehicular systems as well, or may be operable utilizing the principles of such other vehicular systems, such as a vehicle headlamp control system, such as the type disclosed in U.S. Pat. No. 5,796,094, a rain sensor, such as the types disclosed in commonly assigned U.S. Pat. Nos. 6,353,392; 6,313,454 and/or 6,320,176, a vehicle vision system, such as a forwardly or sidewardly or rearwardly directed vehicle vision system utilizing the principles disclosed in U.S. Pat. Nos. 5,550,677; 5,670,935 and 6,201,642, and/or in U.S. patent application Ser. No. 09/199,907, filed Nov. 25, 1998, now U.S. Pat. No. 6,717,610, a traffic sign recognition system, a system for determining a distance to a leading vehicle or object, such as utilizing the principles disclosed in U.S. Pat. No. 6,396,397.
[0192] The camera preferably comprises a pixelated imaging array sensor which has a plurality of photon accumulating light sensors or pixels. The camera includes circuitry which is operable to individually access each photosensor pixel or element of the array of photosensor pixels and to provide an output or image data set associated with the individual signals to the control, such as via an analog to digital converter (not shown). As the camera receives light from objects and/or light sources in the target scene, the control may then be operable to process the signal from at least some of the pixels to analyze the image data of the captured image, as discussed below.
[0193] The camera may be positioned along one or both sides of the vehicle, such as at or within the exterior rearview mirror at either or both sides of the vehicle. However, the camera may be positioned elsewhere along either or both sides and/or at the rear of the vehicle and directed sidewardly and rearwardly from the vehicle to capture an image at either side of the vehicle, without affecting the scope of the present invention. The camera may be positioned at the vehicle and oriented or angled downwardly so as to capture an image which has an upper edge or region generally at the horizon. Positioning or orienting the camera in such a manner provides for an increased horizontal pixel count across the captured image at the important areas along the side of the vehicle, since any vehicle or significant object positioned at or along a side of the subject vehicle will be substantially below the horizon and thus substantially within the captured image. The lane change assist system of the present invention thus may provide an increased portion of the captured image or increased pixel count at important or significant or relevant areas of the exterior scene, since the area well above the road or horizon is not as significant to the detection of a vehicle at or along a side of the subject vehicle. Additionally, positioning the camera to be angled generally downwardly also reduces the adverse effects that the sun and/or headlamps of other vehicles may have on the captured images. The camera thus may be operable to capture substantially an entire image of the sideward scene below the horizon.
[0194] Changes and modification in the specifically described embodiments may be carried out without departing from the principles of the present invention, which is intended to be limited only by the scope of the appended claims as interpreted according to the principles of patent law.
|
An interior rearview mirror assembly includes a mirror reflective element having a glass substrate with planar front and rear surfaces. A plastic molding is circumferentially disposed about a circumferential edge of the glass substrate without overlapping onto the front surface of the glass substrate. The plane of the front surface of the glass substrate is generally flush with an outermost part of the plastic molding, which provides a curved rounded transition from the front surface of the mirror reflective element to a side surface of the plastic molding. The plastic molding includes at least a portion of a mirror housing of the interior rearview mirror assembly. The plastic molding includes structure for attaching a rear mirror casing cap portion thereat. With the rear mirror casing cap portion attached at the structure, the rear mirror casing cap portion at least partially encases a rear portion of the plastic molding.
| 1
|
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority of U.S. Provisional Application No. 60/508,540, filed Oct. 3, 2003.
FIELD OF THE INVENTION
[0002] The present invention relates to certain flame resistant polyamide resin molding compositions employing a non-halogenated flame retardant. More particularly, the present invention relates to such polyamide resin molding compositions comprising selected phosphinates (and optionally also selected melamine products) as flame retardant, novolac, and inorganic reinforcing agents.
BACKGROUND OF THE INVENTION
[0003] Polyamide resins possess excellent mechanical properties, moldability, and chemical resistance and have therefore been used in automotive parts, electric/electronic components, mechanical components, and many other applications. Articles made from polyamide resins possess extremely desirable physical properties. However, in certain applications, it is desirable that polyamide resin compositions be flame retardant and meet the UL-94 standard for a high degree of flame retardance. This requirement has promoted research into a variety of methods for imparting flame retardance to polyamide resins. A common method of imparting flame retardance to thermoplastic resin compositions involves incorporating a halogenated organic compound such as brominated polystyrene as a flame retardant along with an antimony compound that acts as a synergist for the flame retardant. However, the use of halogenated flame retardants has certain drawbacks in that these materials tend to decompose or degrade at the temperatures used to mold polyamide compositions. The degradation products can corrode the barrels of compounding extruders, the surfaces of molding machines, and other equipment halogenated flame retardants come in contact with at elevated temperatures. The degradation products of halogenated flame retardants can also result in molded articles that have poor surface appearance.
[0004] The use of non-halogenated flame retardants such as phosphate or phosphinate compounds with triazine derivatives has been proposed in WO 96/09344 but these flame retardants are unstable at high temperatures and can decompose or degrade during molding, leading to detrimental effects on the electrical properties of a compounded polyamide resin composition containing these flame retardants, especially under conditions of high humidity.
[0005] Thus, effective non-halogenated flame retardants that have good heat stability and that do not have a detrimental effect upon a resin's properties, in particular electrical properties, are desirable. For example, U.S. Pat. No. 6,255,371 discloses a flame retardant combination comprising polymers such as polyamide or polyester, phosphinate or diphosphinate, and condensation products of melamine and/or reaction products of melamine with phosphoric acid and/or reaction products of condensation products of melamine with phosphoric acid and/or a mixture of these. U.S. Pat. No. 5,773,556 discloses compositions comprising polyamide and phosphinic acid salt or a disphosphinic acid salt.
[0006] Based on the foregoing discussion, an object of the present invention is to provide a flame resistant polyamide resin composition capable of yielding articles that possess excellent flame retardance and good physical properties and good electrical insulation properties even under conditions of high humidity. A further object of the present invention is to provide shaped structures and parts that meet UL-94 standards for flame retardancy for use in electrical and electronic parts that require good electrical insulation properties. A feature of the present flame resistant polyamide resin compositions is their good heat stability in molding and attendant excellent moldability. An advantage of the present compositions is their notable mechanical properties. These and other objects, features and advantages of the present invention will become better understood upon having reference to the following description of the invention.
SUMMARY OF THE INVENTION
[0007] The present invention, which allows the stated objective to be attained, concerns a flame retardant polyamide resin composition, comprising:
(a) about 20 to about 90 weight percent of (A) polyamide and (B) phenolic resin, wherein the ratio of (A) to (B) is between about 99:1 and about 40:60 by weight; (b) about 5 to about 50 weight percent of (C) flame retardant comprising a phosphinate of the formula (I) and and/or a disphosphinate of the formula (II) and/or polymers of these
wherein R 1 and R 2 are identical or different and are C 1 -C 6 alkyl, linear or branched, and/or aryl; R 3 is C 1 -C 10 -alkylene, linear or branched, C 6 -C 10 -arylene, -alkylarylene or -arylalkylene; M is calcium ions, magnesium ions, aluminum ions and/or zinc ions, m is 2 to 3; n is 1 or 3; x is 1 or 2; and (c) 0 to about 50 weight percent of (D) inorganic reinforcing agent and/or filler,
the above stated percentages being based on the total weight of the composition.
[0012] Further provided are articles made from the composition of the invention and more particularly such articles and compositions for use in electrical and electronic applications.
DETAILED DESCRIPTION OF THE INVENTION
[0000] Polyamide
[0013] The polyamide used in the present invention may be a homopolymer, copolymer, terpolymer, or higher polymer. It may also be a blend of two or more polyamides. The polyamide may be aromatic or aliphatic. Aromatic polyamides are derived from monomers containing aromatic groups. Examples of monomers containing aromatic groups are terephthalic acid and its derivatives, isophthalic acid and its derivatives, and m-xylylenediamine.
[0014] The polyamide may be derived from adipic acid, sebacic acid, azelaic acid, dodecandoic acid, terephthalic acid, isophthalic acid or their derivatives and other aliphatic and aromatic dicarboxylic acids and aliphatic alkylenediamines, aromatic diamines, and/or alicyclic diamines. Preferred diamines include hexamethylenediamine, 2-methylpentamethylenediamine, 1,9-diaminononane, 1,10-diaminodecane, and 1,12-diaminododecane. It may also be derived from lactams or aminoacids.
[0015] Examples of suitable aliphatic polyamides are polyamides 6, 66, 46, 610, 69, 612, 10, 10, 11, 12. Preferred aromatic polyamides include poly(m-xylylene adipamide) (polyamide MXD,6); poly(docemethylene terephthalamide) (polyamide 12,T); poly(decaamethylene terephthalamide) (polyamide 10,T); poly(nonamethylene terephthalamide) (polyamide 9,T); the polyamide of hexamethylene terephthalamide and hexamethylene adipamide (polyamide 6,T/6,6); the polyamide of hexamethyleneterephthalamide and 2-methylpentamethyleneterephthalamide (polyamide 6,T/D,T); the polyamide of hexamethylene terephthalamide and hexamethylene isophthalamide (polyamide 6,T/6,I) and copolymers and mixtures of these polymers. Aromatic monomers will preferably comprise at least 10 mole percent of the dicarboxylic acid monomers used to make preferred aromatic polyamides used in the present invention. Preferred aromatic monomers are terephthalic acid and its derivatives and isophthalic acid and its derivatives.
[0016] Examples of aliphatic polyamide copolymers or aliphatic polyamide terpolymers include polyamide 66/6 copolymers, polyamide 66/68 copolymers, polyamide 66/610 copolymers, polyamide 66/612 copolymers, polyamide 66/10 copolymers, polyamide 66/12 copolymers, polyamide 6/68 copolymers, polyamide 6/610 copolymers, polyamide 6/612 copolymers, polyamide 6/10 copolymers, polyamide 6/12 copolymers, polyamide Jun. 66, 19610 terpolymers, polyamide Jun. 66, 1969 terpolymers, polyamide 6/66/11 terpolymers, polyamide 6/66/12 terpolymers, polyamide 6/610/11 terpolymers, polyamide 6/610/12 terpolymers, and polyamide 6/66/PACM [where PACM refers to bis-p-(aminocyclohexyl)methane)] terpolymers.
[0017] Of these, polyamide 66/6 copolymers, polyamide Jun. 66, 19610 terpolymers, polyamide Jun. 66, 19612 terpolymers, and mixtures of two or more of these polymers are preferred. Especially preferred are polyamide 66/6 copolymers in which the molar ratio of polyamide 66 units to polyamide 6 units ranges from 98:2 to 2:98; polyamide Jun. 66, 19610 terpolymers in which the ratio of the moles of polyamide 6 units and polyamide 66 units combined to the moles of polyamide 610 units is from 98:2 to 25:75, and the molar ratio of polyamide 6 units to polyamide 66 units is from 2:98 to 98:2; and polyamide Jun. 66, 19612 terpolymers in which the ratio of the moles of polyamide 6 units and polyamide 66 units combined to the moles of polyamide 612 units is from 98:2 to 25:75, and the molar ratio of polyamide 6 units to polyamide 66 units is from 2:98 to 98:2.
[0018] Polyamides 66, 11, 12, 6/10, 6/12, and 10/10 are especially advantageous for use in molding articles for uses in applications that require good barrier properties to the permeation of fluid (both liquid and gaseous) fuel materials as well as good mechanical properties, moldability, and chemical resistance properties.
[0019] The polyamides used in the present invention may also be blended with other thermoplastic polymers such as ABS (acrylonitrile/butadiene/styrene terpolymers), polypropylene, poly(ethylene oxide), polyether ester amides, ionomers, polystyrene, polycarbonate, styrene maleimide copolymer, and AES.
[0000] Phenolic Resin
[0020] The phenolic resin used in the present invention is not restricted in so far as it can be used in a resin for conventional plastic moldings and may be either a thermoplastic novolac or resol or a blend of two or more novolacs, two or more resols, or at least one novolac and at least one resol. Preferred are novolacs, also known as thermoplastic phenol-formaldehyde resins, that are prepared by reacting at least one aldehyde with at least one phenol or substituted phenol in the presence of an acid or other catalyst such that there is a molar excess of the phenol or substituted phenol. Suitable phenols and substituted phenols include phenol, o-cresol, m-cresol, p-cresol, thymol, p-butyl phenol, tert-butyl catechol, resorcinol, bisphenol A, isoeugenol, o-methoxy phenol, 4,4′-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2,6-di-tert-butyl-p-cresol, and the like. Suitable aldehydes and aldehyde precusors include formaldehyde, paraformaldehyde, polyoxymethylene, trioxane, and the like. More than one aldehyde and/or phenol may be used in the preparation of the novolac. A blend of two more different novolacs may also be used. Any novolac that can be used for conventional plastic molding is suitable, although a number average molecular weight of between 500 and 1500 will provide minimal warpage and optimal mechanical properties.
[0021] The phenolic resin can act as a char former when the compositions of the present invention are burned and reduces the amount of moisture that is absorbed by the compositions.
[0022] The total amount of polyamide and phenolic resin used in the composition of the present invention is about 20 to about 90 weight percent, based on the total weight of the composition. The ratio of polyamide to novolac by weight is between about 99:1 and about 40:60, or preferably between about 98:2 and about 50:50, or more preferably between about 97:3 and about 60:40.
[0000] Flame Retardant
[0023] The flame retardants in the polyamide resin composition in this invention are flame retardant combinations (such as those disclosed in U.S. Pat. No. 6,255,371) comprising (a), a phosphinate of the formula (I) and/or a diphosphinate of the formula (II) and/or polymers of these,
wherein R 1 and R 2 are identical or different and are C 1 -C 6 alkyl, linear, or branched, and/or aryl; R 3 is C 1 -C 10 -alkylene, linear, or branched, C 6 -C 10 -arylene, -alkylarylene or -arylalkylene; M is calcium ions, magnesium ions, aluminum ions and/or zinc ions; m is 2 to 3; n is 1 or 3; and x is 1 or 2; and optionally comprising, condensation products of melamine and/or reaction products of melamine with phosphoric acid and/or reaction products of condensation products of melamine with phosphoric acid and/or comprising a mixture of these.
[0024] R 1 and R 2 may be identical or different and are preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and/or phenyl. R 3 is preferably methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene, or phenylene or naphthylene, or methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene or tert-butylnaphthylene, or phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene. M is preferably aluminum ions or zinc ions.
[0025] Preferred phosphinates are aluminum diethylphosphinate and aluminum methylethylphosphinate.
[0026] The flame retardant may optionally further comprise condensation products of melamine and/or reaction products of melamine with phosphoric acid and/or reaction products of condensation products of melamine with phosphoric acid and/or a mixture of these (where the foregoing are collectively referred to as “melamine derivatives”). Examples of condensation products of melamine are preferably melem, melam, melon and/or more highly condensed compounds thereof. Preferred reaction products of melamine with phosphoric acid and/or reaction products of condensation products of melamine with phosphoric acid are melamine pyrophosphate, dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate and/or mixed polysalts of this type.
[0027] Particularly preferred reaction products of melamine with phosphoric acid are melamine polyphosphates having chain lengths >2, and in particular >10.
[0028] The composition of the present invention contains about 5 to about 50 weight percent, or preferably about 10 to about 40 weight percent of the above flame retardants, each of the above percentages being based on the total of the composition. When melamine derivatives are present, the ratio by weight of phosphinate and/or diphosphinate to melamine derivatives will be preferably between about 95:5 and 30:70, or more preferably between about 90:10 and 40:60, or yet more preferably between about 80:20 and 50:50.
[0029] Other flame retardant synergists may also be optionally included in the composition in conventional amounts and as understood by those having skill in the field. Examples include silicone, metal oxides such as silica, aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide and tungsten oxide, metal powder such as aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, copper and tungsten, and metal salts such as zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, and barium carbonate,
[0000] Inorganic Reinforcing Agent and/or Filler
[0030] The inorganic reinforcing agent and/or filler of the present invention are those customarily used in the reinforcement and filling of engineering polymers. Mixtures of two or more inorganic fillers and/or reinforcing agents may be used. Examples of inorganic reinforcing agents and/or fillers include one or more of glass fibers, glass flakes, kaolin, clay, talc, wollastonite, calcium carbonate, silica, carbon fibers, potassium titanate, etc. Glass fibers are preferred. The inorganic reinforcing agent and/or filler used in the present invention is present in up to about 60 weight percent, or, preferably, in about 5 to about 50 weight percent, based on the total weight of the composition.
[0031] The polyamide resin compositions of the present invention may further contain other polymers, impact modifiers, organic fillers, heat stabilizers, plasticizers, antioxidants, nucleating agents, dyes, pigments, mold-release agents, lubricants, flame retardants, impact modifiers, and other additives in addition to the components mentioned previously. Examples of antioxidants include phenolic antioxidants, thioether antioxidants, and phosphite antioxidants.
[0032] The polyamide resin compositions of the present invention are melt-blended and can be manufactured by any known manufacturing methods. The component materials may be mixed to homogeneity using a melt-mixer such as a single or twin-screw extruder, blender, kneader, Banbury mixer, etc. to give a resin composition. Or, part of the materials may be mixed in a melt-mixer, and the rest of the materials may then be added and further melt-mixed until homogeneous.
[0033] The articles of the present invention may be formed from the composition of the invention by any known means such as injection molding, blow molding, extrusion, or thermoforming. Examples of articles that may be formed from the compositions of the present invention are housings, electrical connectors and connector housings and cases, breaker housings, and contactor housings.
[0034] The invention is illustrated by the following Examples.
EXAMPLES
Example 1 and Comparative Example 1
[0035] The components were dry blended and then compounded at a temperature of 295° C. and a screw speed of 200 rpm using a ZSK40 twin-screw extruder manufactured by W&P. Upon exiting the extruder, the molten polymer was quenched in a water bath and palletized.
[0036] The resultant resin compositions were used to mold 13 mm×130 mm×3.2 mm test pieces according to ASTM D638. The following test procedures were used:
Surface Surface resistivity of test specimens after conditioning at resistivity: 60 □ and 100% relative humidity for 240 hours was measured by a Mitsubishii Yuka Hiresta resistivity meter. Mold deposit: The mold surface was visually checked after 30 0.8 mm thickness UL bars were molded in a Toshiba IS170F3 molding machine with a melt temperature of 290° C. and a mold temperature of 80° C. If mold deposit was seen on the surface of the mold, this is indicated in Tables 1 and 2. Flex strain at Measured strain at break of 0.8 mm thickness test break: specimens using ASTM D790. Swelling in 127×76×3.2 mm plates were conditioned at 60° C. and TD/MD: 100% relative humidity for 220 hours. The percentage change in the dimensions of the plate in the machine direction (MD) and transverse direction (TD) after conditioning were determined. TE: Tensile elongation at break of specimens measured dry-as-molded following ISO 527-1/2. TE after 500 h at Tensile elongation at break of specimens conditioned 130° C.: at '130° C. for 500 hours and measuring following ISO 527-1/2.
Flame resistance testing was done according to UL-94 (20 mm Vertical Burning Test) using {fraction (1/32)}nd inch (referred to in the table as 0.8 mm) thick test pieces which are then conditioned for either 48 hours at 23° C. and 50% relative humidity or 168 hours at 70° C.
[0046] The components shown in Table 1 were as follows:
TABLE 1 Example 1 Comp. Exp. 1 Polyamide 66 47 56 Flame retardant 20 24 Novolac resin 10 — Glass fiber 23 20 Total 100 100 Mold deposit No No Surface resistivity 3.E+07 3.E+05 (ohm) Swelling in TD/MD (%) 0.75/0.30 0.99/0.39 UL94 (0.8 mm) V-0 V-0 Flex strain at break (%) 1.9 3.4 TE initial (%) 2.1 2.5 TE after 500 h at 130° C. 1.6 1.6 (%) Polyamide 66: Polyamide 66 (Zytel ® FE1111, manufactured by DuPont) Flame retardant: Exolit OP1312 available from Clariant. Novolac resin: Phenolite ® TD2091 (available from Dainippon Ink & Chemicals) Glass fibers FT756X (Asahi Fiber Glass)
Ingredient amounts are given in weight percent relative to the total weight of the composition.
[0047] It can thus be seen that the polyamide resin composition of the present invention is a resin composition which possesses excellent flame retardance and good mechanical properties and exhibits superb electrical insulation properties even when under high humidity conditions. In addition, the compositions can be molded without generating significant mold deposit.
|
The present invention relates to a flame resistant polyamide resin compositions for moulded articles and articles formed therefrom, comprising polyamide, phenolic resin, and a flame retardant comprising phosphinate and/or diphosphinate and, optionally, melamine derivatives. Further provided are articles for use in a variety of applications including electrical and electronic parts requiring electrical insulation.
| 2
|
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates generally to flooring installation tools and procedures, and in particular to a tongue-and-groove flooring installation tool and method.
[0003] 2. Description of the Related Art
[0004] In construction, floorings are made from various materials and assembled using different techniques and tools. Engineered flooring is attractive for both the customer and the installer. Customers are attracted to engineered flooring because it is a high quality, durable product that has versatile applications, and can come in a variety of colors, finishes, surface textures, and materials, such as plastic, laminate, wood, or tile. Floor installers appreciate engineered flooring because of the consistency of the manufactured product and ease by which the material can be installed.
[0005] Many engineered flooring products come in planks of varying dimensions that need to be fitted together to create the overall flooring application. Depending on the type of engineered flooring, the material is installed and secured in a variety of ways, such as nailing, stapling, gluing or floating. A floating floor is a fast and easy method of installing engineered flooring because the individual planks snap or slide together utilizing a tongue-and-groove engineering, and a limited number of tools are needed.
[0006] When assembling a floating floor, the installer mates opposing tongue-and-groove edges of the flooring material together by applying a force in the direction of the joint the installer is trying to close. The most common way of applying force to join engineered flooring is using a tapping block or pulling iron to abut the edge of flooring opposite the joint, and manually striking the object with a separate striking device such as a hammer or mallet to drive the planks together. A tapping block or pulling iron is used to prevent damaging the tongue-and-groove edge of the plank. A tapping block is abutted to the edge of the plank opposite the joint the installer is trying to close, and the back of the block is struck with a striking device, driving the planks together. Tapping blocks can be made from a variety of materials, such as wood, nylon, thermoplastic, or any other material that would not damage the edge of the plank. When there is not enough room to use a tapping block and swing a striking device, a pulling iron is substituted for the tapping block to join the planks. A pulling iron has a lip which abuts the edge of the plank and a striking surface that permits room for swinging the striking device.
[0007] A problem with using a tapping block, pulling iron, and striking device for installation of an engineered floor is that all of the tools are necessary for proper installation. Depending on the type of engineered flooring, the tongue-and-groove configuration can create the need for different sized tapping blocks with varying edges to prevent damage to the finished edge of the plank. Further, a pulling iron traverses the finished flooring requiring measures to be taken to prevent damage of the engineered flooring surface such as by placing a towel or cloth underneath the tool when it is in use. In addition, the striking device is often out of reach of the installer when he or she is preparing to join planks together, and when not in use, the striking device could damage the surface of the installed planks. The result is numerous tools are required to properly install engineered flooring without causing damage to the surfaces and edges of the planks, and time is wasted gathering the tools and using them properly.
[0008] Heretofore there has not been available a floor installation tool and method with the advantages and features of the present invention.
BRIEF DESCRIPTION OF THE INVENTION
[0009] In the practice of the present invention, a flooring installation tool is provided which includes a cylinder slidably mounted on a guide shaft for striking movement between a block mounted on one end of the guide shaft and a foot mounted on the other end. The block includes a cleat, which hooks and engages the edges of floor planks being installed. The planks can be installed in various floor conditions, which can be accommodated by the installation tool.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The drawings constitute a part of this specification and include exemplary aspects of the present invention and illustrate various objects and features thereof.
[0011] FIG. 1 is an upper, front, side perspective view of a floor installation tool comprising an aspect of the present invention;
[0012] FIG. 2 is a side view thereof, showing flooring being installed;
[0013] FIG. 3 is a side view thereof, showing another flooring installation condition;
[0014] FIG. 4 is a side view thereof, showing yet another flooring installation condition;
[0015] FIG. 5 is a fragmentary, vertical cross-sectional view of a tongue-and-groove joint between first and second flooring planks; and
[0016] FIG. 6 is another fragmentary, vertical cross-sectional view of the tongue-and-groove joint, shown in an engaged configuration.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
I. Introduction and Environment
[0017] As required, detailed aspects of the present invention are disclosed herein; however, it is to be understood that the disclosed aspects 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 how to variously employ the present invention in virtually any appropriately detailed structure.
[0018] Certain terminology will be used in the following description for convenience in reference only and will not be limiting. For example, up, down, front, back, right and left refer to the invention as orientated in the view being referred to. The words, “inwardly” and “outwardly” refer to directions toward and away from, respectively, the geometric center of the aspect being described and designated parts thereof. Forwardly and rearwardly are generally in reference to the direction of travel, if appropriate. Said terminology will include the words specifically mentioned, derivatives thereof and words of similar meaning.
II. Preferred Aspect Flooring Installation Tool 2
[0019] Referring to the drawings in more detail, the reference numeral 2 generally designates a flooring installation tool, as shown in FIGS. 1-4 . Without limitation on the generality of useful applications of the present invention, the flooring installation tool 2 can be utilized for assembling an engineered flooring system 80 on a floor 72 by joining flooring planks, e.g., 75 , 76 and 78 .
[0020] The engineered flooring system 80 is comprised of a plurality of first flooring planks 75 , second flooring planks 76 and third flooring planks 78 secured together by interlocking the groove profile 82 of a second flooring planks 76 with the tongue profile 82 of a third flooring planks 78 . The first flooring plank 75 , second flooring plank 76 , and third flooring plank 78 can comprise a variety of materials, such as plastic laminate, wood, etc.
[0021] FIG. 1 shows the flooring installation tool 2 , embodying the invention. The flooring installation tool 2 generally comprises a first impact member, such as a block 4 , longitudinally connected to a second impact member, such as a collar 52 and a foot 60 by a guide shaft 44 . An impactor, such as a cylinder 46 , freely moves between the block 4 and collar 52 along the guide shaft 44 . The block 4 has a sole 20 fixedly attached to the bottom block surface 12 by sole set screws 33 within the sole 20 and the block 4 .
[0022] The block 4 is composed of a durable metal (e.g., hardened aluminum) and generally includes a front block surface 6 , a back block surface 8 , top block surface 10 , bottom block surface 12 , side block surfaces 14 and a cleat 34 . The cleat 34 consists of a portion of the front block surface 6 that protrudes below the bottom sole surface 28 , creating a bottom cleat surface 38 and a back cleat surface 36 . The block 4 is fixedly secured to the front end of the guide shaft 44 by suitable mechanical fasteners, such as block set screws or pins 18 within the block 4 .
[0023] The sole 20 is comprised of a suitable material that will not mar the surface of the engineered flooring system 80 (e.g. high molecular weight (HMW) plastic), and fits snugly against the bottom block surface 12 and the upper portion of the back cleat surface 36 along the top sole surface 26 , and the front sole surface 22 respectively, thereby creating the back cleat surface 36 . The sole 20 is fixedly secured to the bottom block surface 12 by sole set screws 33 within the sole 20 and the block 4 . The side sole surface 30 is flush with the side block surface 14 , and the back block surface 8 is flush with the back sole surface 24 .
[0024] The cylinder 46 is comprised of a durable metal (e.g., steel) with a front cylinder surface 48 , back cylinder surface 50 , and center cylinder bore 51 . The cylinder 46 has a length of, for example, approximately 2.5″ between the front cylinder surface 48 and back cylinder surface 50 , and a diameter of, for example, approximately 2″. The center cylinder bore 51 is a diameter of, for example, approximately ⅜″ throughout extending the longitudinal length of the cylinder 46 from the center of the front cylinder surface 48 to the center of the back cylinder surface 50 .
[0025] The guide shaft 44 consists of a first end 3 and second end 5 , and is comprised of a durable metal (e.g., steel) with a length of, for example, approximately 15″, and a diameter of, for example, approximately ⅜″, and extends longitudinally from the interior of the block 4 at the first end 3 through the back block surface 8 , through the center cylinder bore 51 , through the front collar surface 54 , terminating at the second end 5 within the collar 52 . The guide shaft has a cross-sectional diameter less than the diameter of the center cylinder bore 51 allowing the cylinder 46 to freely move along the guide shaft 44 .
[0026] The collar 52 is located at the second end 5 of the flooring installation tool 2 , and is comprised of a durable metal (e.g., steel) with a length of, for example, approximately 2.5″, a cross-sectional diameter of, for example, approximately ¾″, and a center collar bore 53 greater than the diameter of the guide shaft 44 . The collar 52 extends longitudinally through the foot 60 . The collar 52 is fixedly secured to the second end 5 of the guide shaft 44 by suitable mechanical fasteners, such as collar set screws or pins 58 within the collar 52 .
[0027] The foot 60 is located at the second end 5 of the flooring installation tool 2 , and is comprised of a suitable material that will not mar the surface of the engineered flooring system 80 (e.g. plastic), with a thickness of, for example, approximately ¾″ thick. The foot 60 fits snug around the back end of the collar 52 , fixedly secured to the second ends of the guide shaft 44 , and the collar 52 by a foot set screw 70 within the foot 60 , collar 52 , and guide shaft 44 .
[0028] FIG. 2 shows an aspect of the flooring installation tool 2 as it is used to install a first flooring plank 75 when said plank abuts an obstacle such as a wall 74 . The flooring installation tool 2 is positioned relative to the first flooring plank 75 whereby the bottom cleat surface 38 is placed on the top portion of a tongue profile 82 with the lower portion of the front block surface 6 in snug contact with the remaining edge of the first flooring plank 75 . The bottom foot surface 68 rests upon the floor 72 . The first flooring plank 75 is driven into place by sliding the cylinder 46 longitudinally along the guide shaft 44 from the second end 5 toward the first end 3 thereby bringing the front cylinder surface 48 in contact with the back block surface 8 with sufficient force to move the first flooring plank 75 into the desired alignment.
[0029] FIG. 3 shows an aspect of the flooring installation tool 2 as it is used to install a third flooring plank 78 into alignment with a second flooring plank 76 when there is no obstacle preventing positioning the foot 60 of the flooring installation tool on the installed portion of the engineered flooring system 80 . The flooring installation tool 2 is positioned relative to the third flooring plank 78 whereby the back edge of the bottom sole surface 28 is placed on the top portion of a tongue profile 82 with the back sole surface 24 in snug contact with the remaining edge of the third flooring plank 78 . The bottom foot surface 68 rests upon the installed portion of the engineered flooring system 80 . The groove profile 84 of the third flooring plank 78 is driven into the tongue profile 82 of the second flooring plank 76 by sliding the cylinder 46 longitudinally along the guide shaft 44 from the first end 3 toward the second end 5 thereby bringing the back cylinder surface 50 in contact with the front collar surface 54 with sufficient force to move the third flooring plank 78 into the desired alignment with the second flooring plank 76 .
[0030] FIG. 4 shows an aspect of the flooring installation tool 2 as it is used to install a third flooring plank 78 when said plank abuts an obstacle such as a wall 74 . The flooring installation tool 2 is positioned relative to the third flooring plank 78 whereby the bottom cleat surface 38 is placed on the top portion of a tongue profile 82 with the back cleat surface 36 in snug contact with the remaining edge of the third flooring plank 78 . The bottom foot surface 68 rests upon the installed portion of the engineered flooring system 80 . The groove profile 84 of the third flooring plank 78 is driven into the tongue profile 82 of the second flooring plank 76 by sliding the cylinder 46 longitudinally along the guide shaft 44 from the first end 3 toward the second end 5 thereby bringing the back cylinder surface 50 in contact with the front collar surface 54 with sufficient force to move the third flooring plank 78 into the desired alignment with the second flooring plank 76 .
[0031] It will be appreciated that the components of the flooring installation tool 2 can be used for various other applications. Moreover, the flooring installation tool 2 can be fabricated in various sizes and from a wide range of suitable materials, using various manufacturing and fabrication techniques.
[0032] It is to be understood that while certain aspects of the invention have been shown and described, the invention is not limited thereto and encompasses various other embodiments and aspects.
|
A tool is provided for installing flooring with snap together edges. Specifically, the tool has a longitudinally-extending guide rod having a first impact member having a first impact face at a first end, and a second impact member having a second impact face at a second end. The first impact member has cleat extending below its lower surface adapted for engaging flooring edges. A sole is secured to the lower edge of the first impact member to protect the underlying flooring surface. The second impact member comprises a foot with an impact face. An impactor with first and second impact faces is slidably movable between the first impact member and second impact member for impacting the first and second impact faces respectively.
| 4
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to devices providing compensation of lumber to remove lateral warping and similar defects during the installation process and more particularly pertains to the straightening of individual planks employed as a deck surface wherein the straightening is performed while a plank is being affixed to underlying joists.
2. Description of the Prior Art
The use of lumber compensation devices is known in the prior art. More specifically, lumber compensation devices heretofore devised and utilized for the purpose of recovering lumber to a particular straightness are known to consist basically of familiar, expected and obvious structural configurations, notwithstanding the myriad of designs encompassed by the crowded prior art which have been developed for the fulfillment of countless objectives and requirements.
The present invention is directed to improving devices for lumber compensation in a manner which is safe, secure, economical and aesthetically pleasing.
For example, U.S. Pat. No. 4,821,784 to Cone discloses a tool for removing lateral deflection in a wood plank comprising a lever having a fulcrum member affixed to an underlying joist, an elongated arm portion to which restoring force is applied by a human, and a short length force application portion engaging the deflected plank. The Cone invention employs the mechanical advantage of a fixed radius lever to force the plank into an acceptable degree of straightness and requires a substantially elongated lever arm to which force is applied. And in most cases the applied force must be maintained by continued human interaction with the lever throughout the nailing process. The present invention comprises a continuous cam manually driven by an attached lever wherein the cam rotational axis is affixed to an underlying joist. The cam of the present invention is designed to reposition the deflected plank in varying proportion to the rotational position of the attached lever and thereby providing more controlled application of straightening force. And furthermore, the present invention enables the plank installer to apply straightening force and leave the device unattendedly maintaining the force during nailing.
In U.S. Pat. No. 5,181,703 to Gilstad et al. an apparatus for installing wooden decking is disclosed. The Gilstad et al. apparatus comprises a pneumatically energized actuator having a series of clamps and spacers which provide for alignment and relative spacing of one plank with respect to another for the purpose of nailing. The Gilstad et al. invention is a complicated machine requiring a significant monetary investment and an incidental air compressor for operation, and therefore is generally limited to the professional construction marketplace. And furthermore, the Gilstead et al. apparatus, being more or less designed for plank positioning, may be unable to apply adequate force to restore a warped plank. The present invention is of inexpensive construction not requiring a supply of compressed air for operation and therefore is well suited for a range of construction levels of involvement including the fundamentally equipped novice and the professional builder. The present invention is capable of applying a substantial force to the plank thereby enabling correction of warpage in lumber pieces which may be discarded in use of the Gilstad et al. invention.
In U.S. Pat. No. 4,850,114 to Vockins a decking spacer is described. The Vockins spacer has only a provision for providing a correct spacing of adjacent deck planks but omits a means for forcing warped planks into conformance prior to nailing. The present invention provides a means for correcting warpage and may be used in conjunction with the Vockins device.
In U.S. Pat. No. 3,779,515 to Larios et al. an adjustable decking and framing tool is disclosed for performing a variety of functions one of pertinence being to move deck boards into position on their supporting joists. A disadvantage in this prior art lies in a lack of a provision for leaving the tool unattended and having the deck plank under adjustment remain positioned for nailing. The present invention maintains the plank in corrected position for nailing without attention to the device.
U.S. Pat. No. 4,046,362 to Spillers discloses a board holding device. The disclosure teaches an apparatus for clamping a plurality of boards for subsequent breaking in the martial arts such as karate. The disclosure makes no provision for applying corrective force to planks during installation and is ill suited for such application in having an ability to apply force to boards solely at their respective ends. The present invention employs a single force application device and is directly suitable for rendering warped decking planks straight as required for nailing.
In this respect, the lumber compensation device according to the present invention substantially departs from the conventional concepts and designs of the prior art, and in so doing provides an apparatus primarily developed for the purpose of correcting curvature in planks during installation.
Therefore, it can be appreciated that there exists a continuing need for new and improved lumber compensation device which can be employed by the novice and expert alike to rapidly and with minimal effort compensate the curvature of planking thereby providing for the desired linear installation. In this regard, the present invention substantially fulfills this need.
As illustrated by the background art, efforts are continuously being made in an attempt to improve lumber compensation devices. No prior effort, however, provides the benefits attendant with the present invention. Additionally, the prior patents and commercial techniques do not suggest the present inventive combination of component elements arranged and configured as disclosed and claimed herein.
The present invention achieves its intended purposes, objects, and advantages through a new, useful and unobvious combination of method steps and component elements, with the use of a minimum number of functioning parts, at a reasonable cost to manufacture, and by employing only readily available materials.
SUMMARY OF THE INVENTION
In view of the foregoing disadvantages inherent in the known types of lumber compensation devices now present in the prior art, the present invention provides an improved lumber compensation device construction wherein the same can be utilized for maintaining straightness of planking during installation As such, the general purpose of the present invention, which will be described subsequently in greater detail, is to provide a new and improved lumber compensation device apparatus and method which has all the advantages of the prior art lumber compensation devices and none of the disadvantages.
The invention is defined by the appended claims with the specific embodiment shown in the attached drawings. For the purpose of summarizing the invention, the invention may be incorporated into a hand operated device comprising a cam having an attachment which affixes the cam rotational axis to an underlying joist, and a hand operated lever affixed to the cam rotationally disposes the cam against a plank requiring correction and, being further rotated, applies corrective forces wherein the plank is nailed in place.
There has thus been outlined, rather broadly, the more important features of the invention in order that the detailed description thereof that follows may be better understood, and in order that the present contribution to the art may be better appreciated. There are, of course, additional features of the invention that will be described hereinafter and which will form the subject matter of the claims appended hereto. In as much as the foregoing has outlined rather broadly the more pertinent and important features of the present invention in order that the detailed description of the invention that follows may be better understood so that the present contribution to the art can be more fully appreciated. Additional features of the invention will be described hereinafter which form the subject of the claims of the invention. It should be appreciated by those skilled in the art that the conception and the disclosed specific methods and structures may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present invention. It should be realized by those skilled in the art that such equivalent methods and structures do not depart from the spirit and scope of the invention as set forth in the appended claims.
In this respect, before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purpose of description and should not be regarded as limiting.
As such, those skilled in the art will appreciate that the conception, upon which this disclosure is based, may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention.
Further, the purpose of the foregoing abstract is to enable the U.S. Patent and Trademark Office and the public generally, and especially the scientists, engineers and practitioners in the art who are not familiar with patent or legal terms or phraseology, to determine quickly from a cursory inspection the nature and essence of the technical disclosure of the application. The abstract is neither intended to define the invention of the application, which is measured by the claims, nor is it intended to be limiting as to the scope of the invention in any way.
Therefore, it is an object of the present invention to provide an improved lumber compensation device.
It is therefore an additional object of the present invention to provide a new and improved lumber compensation device which has all the advantages of the prior art lumber compensation devices and none of the disadvantages.
It is another object of the present invention to provide a new and improved lumber compensation device which may be easily and efficiently manufactured and marketed.
It is a further object of the present invention to provide a new and improved lumber compensation device which is of a durable and reliable construction.
An even further object of the present invention is to provide a new and improved lumber compensation device which is susceptible of a low cost of manufacture with regard to both materials and labor, and which accordingly is then susceptible of low prices of sale to the consuming public, thereby making such lumber compensation devices economically available to the buying public.
Still yet another object of the present invention is to provide a new and improved lumber compensation device which provides in the apparatuses and methods of the prior art some of the advantages thereof, while simultaneously overcoming some of the disadvantages normally associated therewith.
Still another object of the present invention is to provide a new and improved device which permits manual correction of an inappropriatiately curved plank and subsequent nailing by a single worker.
Yet another object of the present invention is to provide a new and improved lumber compensation device which has a diminishing lateral displacement of a lumber member under correction with rotation of an operating lever.
Even still another object of the present invention is to provide a new and improved lumber compensation device requiring only manually applied forces to correct substantial lateral warpage in decking lumber during the installation process.
These together with other objects of the invention, along with the various features of novelty which characterize the invention, are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and the specific objects attained by its uses, reference should be had to the accompanying drawings and descriptive matter in which there is illustrated preferred embodiments of the invention. The foregoing has outlined some of the more pertinent objects of this invention. These objects should be construed to be merely illustrative of some of the more prominent features and applications of the present invention. Many other beneficial results can be attained by applying the disclosed invention in a different manner or by modifying the invention within the scope of the disclosure. Accordingly, other objects and a fuller understanding of the invention may be had by referring to the summary of the invention and the detailed description of the preferred embodiment in addition to the scope of the invention defined by the claims taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein:
FIG. 1 is a right perspective view of the lumber compensation device showing the operational disposition of the device.
FIG. 2 is a left perspective view of the lumber compensation device in a pre-installation position.
FIG. 3 is a fragmentary side sectional view of the lumber compensation device taken substantially upon the plane indicated by the section line 3--3 of FIG. 2.
FIG. 4 is an exploded left perspective view of the lumber compensation device.
FIG. 5 is a fragmentary perspective view of a lumber compensation device showing a means for engaging underlying joists.
FIG. 6 is a fragmentary perspective view of a lumber compensation device showing a lever means for operation of the device.
DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference now to the drawings, and in particular to FIG. 1 thereof, a new and improved lumber compensation device embodying the principles and concepts of the present invention and generally designated by the reference numeral 10 will be described.
From an overview standpoint, the lumber compensation device 10 is adapted for use by humans to engage and effectively correct objectionable lateral curvature of decking lumber during the installation process. See FIG. 1. Lumber compensation device 10 comprises a lever operated cam 12 rotatable affixed to a joist engagement member 14. Cam 12 engages lumber member 16 by manually induced rotation of lever 18. Joist engagement member 14 maintains the position of cam 12 by engaging joist 20.
More specifically, it will be noted that the lumber compensation device 10 comprises a cam 12 rotationally disposed about an axis affixed to joist engagement member 14 by application of human force to lever 18. Cam 12 is a substantially planar ellipsoid rotating about an axis which may or may not be centrally located. See FIG. 2. And furthermore, cam 12 may depart from an ellipsoidal shape in having a substantially greater radial dimension on portion 40 than on portion 42 thereby providing more corrective displacement for a given rotation of lever 18, wherein the displacement is dependent upon which portion engages lumber member 16.
Cam 12 may also be effectively configured as a circular plate having an eccentric rotation axis. Lever 18 is perforated in two places in lever first portion 52 is affixed to cam 12 by bolt 50 which threadedly engages cam 12 and shoulder bolt 54, said shoulder bolt 54 in simultaneity being an axle member about which cam 12 is free to rotate. See FIGS. 3 and 4. Cam 12 and lever 18 are held in position by nut 56 threadedly engaging shoulder bolt 54. Flat washer 60 acts as a thrust bearing being interdisposed between cam 12 and joist engagement member 14.
Lockwasher 58 is interdisposed between nut 56 and lever first portion 52 thereby affixing shoulder bolt 54 to lever first portion 52 by frictional engagement of the shoulder portion 62 of shoulder bolt 54 and lever first portion 52. Shoulder bolt 54 must therefore be free to rotate in joist engagement member 14. Shoulder bolt 54 has head portion 55 recessed within joist engagement member 14 thereby producing a substantially planar joist engagement surface. Head portion 55 may employ an internal hex or Allen spline, or a Bristol spline, or a number of alternate means for engaging a tool for performance of a tightening operation upon shoulder bolt 54. FIG. 5 shows the joist engagement member 14 comprising an elongated toothed engagement portion 70 and a lateral spring clamp 72.
Lever second portion 53 comprises an extension of lever first portion 52 being disposed at a slight angle thereto. Telescoping handle member 64 comprises an elongated extension of lever second portion 53 and is slidably engaged thereon. A stopping means is provided to preclude disengagement of the telescoping handle member 64 from lever second portion 53. And furthermore, one or more detents may be provided to releasably stop telescoping handle member 64 at various position of extension. Telescoping handle member 64 is most useful when cam member 12 comprises a discoid having two differing curved cam portions 40 and 42.
Elongated toothed portion 70 and lateral spring clamp 72 are co-joined at shoulder bolt through hole 74 by using single piece or welded construction, or by casting a single part. Elongated toothed engagement portion 70 comprises a flattened elongate central portion 76 terminating at the two most separate ends in orthogonal teeth 78 disposed toward the lateral spring clamp 72. Shoulder bolt through hole 74 perforates elongate central portion 76 at a site nearer to one set of orthogonal teeth 78 than complimentary orthogonal teeth 78.
The actual nearer linear distance is established as being no greater than the most minor radius of the cam 12. Lateral spring clamp 72 comprises a U shaped member having a flattened portion 80, being perforated by shoulder bolt through hole 74, and two equal length opposing legs 82 being substantially perpendicularly disposed with respect to flattened portion 80. Legs 82 are parallel or directed slightly toward one another over a substantial portion of their length beginning at a junction with flattened portion 80.
Near the free end of legs 82 there is some widening of the interleg spacing to facilitate attachment of the lumber compensation device 10 to joist member 20. When operationally disposed lateral spring clamp member 72 frictionally engages the sides of joist member 20 preventing twisting or lateral movement of the lumber compensation device 10 and elongated toothed engagement member 70 engages the deck attachment portion of joist 20 by digging into the joist 20 material.
A simplified embodiment of lever 18 comprises a previously described lever first portion 52, a lever second portion 90, and a sheath 94. See FIG. 6. Lever second portion 90 comprises a flattened elongated extension of lever first portion 52 being disposed at a slight angle to the lever first portion 52 and terminating in a smoothly rounded free end 92. Free end 92 and a portion of lever second portion 53 are covered by a polymeric sheath 94 providing the advantage of protection of human hands, aesthetic appeal, and provision of a superior grip surface. Sheath 94 may be applied by a dipping technique, as an adhering tape, or as a frictionally engaging slip on cap. Telescoping handle member 64 may also be covered by a substantially similar sheath.
As to the manner of usage and operation of the present invention, the same should be apparent from the above description. Accordingly, no further discussion relating to the manner of usage and operation will be provided.
With respect to the above description then, it is to be realized that the optimum dimensional relationships for the parts of the invention, to include variations in size, materials, shape, form, function and manner of operation, assembly and use, are deemed readily apparent and obvious to one skilled in the art, and all equivalent relationships to those illustrated in the drawings and described in the specification are intended to be encompassed by the present invention.
Therefore, the foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention. In as much as the present disclosure includes that contained in the appended claims as well as that of the foregoing description. Although this invention has been described in its preferred forms with a certain degree of particularity, it is understood that the present disclosure of the preferred form has been made only by way of example and numerous changes in the details of construction and combination and arrangement of parts may be resorted to without departing from the spirit and scope of the invention.
|
A lumber compensation device including a lever operated pivoting cam engaging the lumber wherein the cam is affixed to an underlying joist. The cam is affixed to the joist by an elongated toothed member and a U shaped clamp which preclude translational motion of the device. Rotational motion applied to the lever engages the cam with the lumber and further lever rotation forces the lumber into desired conformance after which the lumber is nailed in place. The lumber compensation device is operated by a single individual who is enabled in the performance of nailing the lumber while the device hold the lumber in place.
| 4
|
[0001] This application claims the benefit of U.S. Provisional Patent Application 60/791,324 filed on Apr. 12, 2006, the entirety of which is incorporated herein by reference. This application includes material which is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the patent disclosure, as it appears in the Patent and Trademark Office files or records, bat otherwise reserves all copyright rights whatsoever.
FIELD OF THE INVENTION
[0002] The present invention relates to the field of fuel vapor emissions systems for engines and more particularly to a fuel tank assembly for controlling evaporative emissions.
BACKGROUND OF THE INVENTION
[0003] Evaporative emissions systems and the use of carbon or charcoal canisters have been used in combination with automotive engines and fuel tanks. However, new regulations have propelled the need for evaporative emissions control systems for small utility engines. Typically, these small utility engines and their associated gas tank have confined locations and dimensions forcing most of the components and lines of an evaporative emissions system to be exposed. Such exposure is both unsightly and problematic as such valves, components and lines are subject to damage.
[0004] A typical emission control system 100 , as seen in FIG. 1A , for a small utility engine consists of a fuel tank 102 which stores a fuel 104 , such as gasoline, and mates with a sealed cap 108 . The fuel tank 102 contains fuel which during operation of the engine is fed through hue 118 to a carburetor 120 . The flow of fuel along line 118 may be controlled by a feel shutoff valve (not shown). Attached to the tank 102 is a valve 105 , such as a slant valve, which allows emission vapors to escape the tank 102 , as pressure in the tank 102 increases, to a charcoal canister 125 through line 107 . The charcoal, canister 125 receives and treats the evaporative emissions. Upon starting the utility engine, suction is created drawing outside air in through vent 122 and thus purging the charcoal of the accumulated hydrocarbons and pulling the evaporative emissions within the charcoal canister 125 through line 124 into carburetor 120 where the evaporative emissions and hydrocarbons can be burned. After the engine is shut off the charcoal canister 125 continues to receive and treat the evaporative emissions from tank 102 until the engine is started again and the evaporative emissions and hydrocarbons are purged from the canister 125 , drawn into and burned by carburetor 120 .
[0005] As seen in FIG. 1B , a generator 101 is depicted which incorporates a known evaporative emissions system which exposes the valve 105 and the evaporative emissions line 107 leading to charcoal canister 125 . On or near the top surface of the fuel tank 102 is an opening 110 for receiving a sealed cap. Additionally, valve 105 mates with fuel tank 102 at a position on a top surface of the fuel tank 102 . The valve 105 is exposed creating an unsightly appearance for industrial design as well as exposing the valve 1 . 05 to possible damage. Further, the evaporative emissions line 107 runs along the top, down the side and along the end of fuel tank 102 before traveling down, the frame 103 of she generator 101 before finally connecting to canister 125 . Both the valve 105 and line 107 are susceptible to damage and create an unsightly appearance.
[0006] Therefore, what is needed is an evaporative emissions system which provides a compact, cost effective and easy to manufacture design while reducing the unsightly appearance and exposure of the evaporative emissions valve and lines.
SUMMARY OF INVENTION
[0007] The present invention provides an evaporative emissions fuel system for a general-purpose engine which overcomes the obstacles described above by providing a system with a fuel tank, a canister which absorbs fuel vapor from the fuel tank, a carburetor communicating with the fuel vapor from the canister and communicating with the fuel from the fuel tank; a valve assembly located within the fuel tank for receiving the fuel vapor from within the fuel tank and communicating the fuel vapor to the canister; and the valve assembly comprising a valve opening for receiving fuel vapor and a float responsive to the fuel within the tank for sealing the valve opening when the fuel within the tank is at a fuel level capable of entering the valve opening. The valve opening may be located above a max fuel level of the fuel tank and below a top interior surface of the fuel tank. The Post may be attached to a sealing element which seals the valve opening. The evaporative emissions fuel system may also comprise a valve assembly brace attached to an interior surface of the tank and to the valve assembly.
[0008] Another aspect of the present invention provides a fuel tank assembly for a general-purpose engine comprising; a closed fuel tank having an inlet to the interior of the tank, a fuel outlet, and a fuel vapor outlet; an unvented fuel cap receivable on the inlet for sealing the closed fuel tank; a valve assembly located within the fuel tank for receiving fuel vapor from inside the fuel tank and communicating the fuel vapor through the fuel vapor outlet to a canister which absorbs and treats fuel vapor; a carburetor communicating with the fuel vapor from the canister and communicating with the fuel from the fuel tank through the fuel outlet; and the valve assembly comprising a valve opening for receiving fuel vapor and a float responsive to the fuel within the tank for sealing the valve opening when the fuel within the tank is at a fuel level, capable of entering the valve opening. Further, the valve opening may be located above a max fuel level of the fuel tank and below a top interior surface of the fuel tank. The float may be attached to a sealing element which seals the valve opening. Additionally, a valve assembly brace may be attached to an interior surface of the tank and to the valve assembly.
BRIEF DESCRIPTION OF DRAWINGS
[0009] FIG. 1A is a schematic view of a known fuel tank and exposed evaporative emissions system;
[0010] FIG. 1B is a side elevation view of a generator incorporating a known and exposed evaporative emissions system;
[0011] FIG. 2 is a schematic view of a fuel tank and evaporative emissions system of the present invention;
[0012] FIG. 3 is a sectional side view of an evaporative emissions valve of the evaporative emissions system of the present invention;
[0013] FIG. 4A is a front view of an alternative evaporative emissions valve which could be incorporated in the evaporative emissions system of the present invention;
[0014] FIG. 4B is a side view of the alternative evaporative emissions valve depicted in FIG. 4A ; and
[0015] FIG. 5 is a front view of an alternative evaporative emissions valve which could be incorporated in the evaporative emissions system of the present invention.
DETAILED DESCRIPTION
[0016] The system of the present invention will now be described in conjunction with FIGS. 2-5 . The present invention provides an evaporative emissions system which overcomes the obstacles described above by providing an evaporative emissions system which integrates the evaporative emissions valve and all or portions of the emissions flow line within the internal chamber of the fuel tank.
[0017] As seen in FIG. 2 , the evaporative emissions system 200 of the present invention includes a gas tank 202 which is used to house or contain a fuel 204 such as gasoline. The fuel tank 202 mates with a fill cap 208 which seals the emissions vapors and fuel within the fuel tank 202 . The cap 208 mates with a cap mating structure 210 which is also used to support a fuel filter or screen 209 . Fuel exits the tank 202 from an exit location 214 such as a welded pipe fitting or threaded sealed fitting. A threaded sealed fitting 214 is depicted in FIG. 2 which also includes a brass fitting 216 which connects the exit 214 to a fuel shutoff valve 212 . A fluid passage line 218 connects the fuel shutoff valve 212 to carburetor 220 , During engine (not shown) operation, fuel is drawn from tank 202 through the fuel shutoff valve 212 and line 218 to carburetor 220 .
[0018] When the engine is not in operation, external temperatures on the fuel, tank 202 can cause an increase of the fuel 204 temperature within the tank 202 causing an increase in vapor pressure within the tank 202 . Historically, this increased vapor pressure was simply released through vent holes in the cap. However, new emissions regulations do not allow untreated vapor pressure to be released into the atmosphere. Therefore, the vapor emissions system of the present invention cheers the vapor pressure in the fuel, tank 202 through a charcoal treatment section or canister 225 . In the present invention, the vapor pressure is directed to a charcoal treatment canister or chamber 225 through a fuel tank valve assembly 230 . The canister 225 typically uses activated carbon to treat the fuel vapor by removing the hydrocarbons. Once the engine is started the hydrocarbons from within the canister 225 are pulled into the carburetor 220 and burned.
[0019] The fuel tank emissions valve assembly 230 is located inside the tank and includes a top portion 232 and an emissions line 233 . The emissions vapor exits the tank 202 from an exit location 236 such as a welded pipe fitting or threaded sealed fitting, A threaded sealed lining 234 is depleted hi FIG. 2 which also includes a brass fitting 236 which connects the exit 234 to an emissions line 238 through connection 237 . The emissions vapors are drawn into the top portion 232 of the valve assembly 230 and are then passed through lines 233 and 238 into canister 225 where the vapors are treated.
[0020] The top portion 232 of the emissions valve assembly 230 may be secured to the inside top or side surface of tank 202 , Additionally, or as an alternative, the emissions line 233 may be secured to a bracket 235 , such as through welding or placement in a grommet, where the bracket is secured to die inside of the tank 202 . Securing the top 232 of the valve assembly 230 or securing the emissions line 233 prevents the emissions valve assembly 230 from significant movement thereby preventing or minimizing the emissions valve assembly 230 from becoming damaged. Still further, line or tube 233 may be a metal piping or some form of tubing which may be sealed or secured to the bottom of tank 202 through use of welding, a grommet or some other fitting.
[0021] When the engine is not running, pressure in the tank 202 will be released as the emissions vapor flows from the top portion 232 of the valve assembly 230 down the emissions line 233 , exits the tank 202 at the emissions exit 234 and flows into the canister 225 though line 238 . Once in the chamber 225 , the evaporate emissions vapor is treated. Upon starting the utility engine, suction is created drawing outside air through vent 222 and pulling the evaporative emissions within the charcoal canister 225 through line 224 into carburetor 220 where the evaporative emissions and hydrocarbons can be burned. During operation of the engine, emissions vapor can also be drawn into the emission valve assembly 230 , through treatment canister 225 , and into carburetor 220 where the emissions will be burned. Once the engine is shut off the suction pulling air through dm charcoal canister 225 is removed and the canister 225 is set to receive and treat the evaporative emissions within tank 202 until the engine is started again and the evaporative emissions can be drawn into and burned by carburetor 220 .
[0022] As fuel 204 is added to tank 202 the fuel 204 will reach or obtain a max fuel level 206 . Exceeding the max fuel level 206 would cause fuel 204 to overflow from tank 202 . The present invention incorporates a design to prevent fuel 204 from entering the vapor emissions valve assembly 230 by sizing the valve assembly 230 so that the top portion 232 of the valve assembly 230 is above the max fuel level 206 . Specifically, the valve assembly 230 is sized so that a valve opening for receiving emissions vapor is located above the max fuel level 206 but below the top interior surface 207 of the tank 202 . The valve opening is located within the top portion 232 of the valve assembly 230 . By having the valve opening above the max fuel level 206 the opening is positioned in area 205 where vapor pressure resides but above the max fuel level 306 so that fuel does not easily flow into the emissions vapor valve assembly 230 or line 233 . Proper sizing of the valve assembly 230 may require sizing of both the valve assembly 230 and fuel tank 202 .
[0023] As shown in FIG. 2 , the tank 202 provides at least one high section or vapor area 205 which allows the top portion 232 of valve assembly 230 to reside between the max fuel level 206 and the top interior surface 207 of the fuel tank 202 . The distance between the top interior surface 207 and the max fuel level 200 has some height “h” as shown in FIG. 2 . Understandably, Par shipping, storage, and material costs there is a benefit to minimizing the height “h” while still allowing enough space to properly place the valve opening within the top portion 232 of valve assembly 230 within area 205 . In a preferred embodiment, the height “h” is about 10 millimeters but could be as small as 1-2 millimeters and as largo as the industrial design of the tank will allow. However, it is unlikely that most tanks 202 would have an area 205 height “h” above several hundred millimeters.
[0024] FIG. 3 provides a more detailed view of the top portion 332 of the emissions valve assembly 330 for an exemplary embodiment. The top portion 232 of valve assembly 330 may be connected to, in contact with or in close proximity to a top interior surface 307 of the fuel tank 202 . The emissions valve assembly 330 may be a roll over or snorkel type valve which is comprised of a ball 340 or other float like device which is responsive to the fuel level 306 . Fuel is allowed to enter the valve chamber 346 through the chamber holes 342 . As the fluid level rises, such as might happen when the unit is being moved or tilted, the bid level in chamber 346 will rise causing the float ball 340 to rise until it contacts tapered surface 348 . A seal is created when the float ball 340 contacts the tapered surface 348 preventing the fuel from entering line 333 .
[0025] Under normal conditions, the float bad 340 rest on the top of the fluid surface level 306 within chamber 346 at some distance from the tapered surface 348 . The evaporative emissions are able to enter the chamber 346 from the top chamber holes 342 and flow through line 333 to the charcoal canister. The top portion 332 of the valve assembly 330 should be sized such that height “h” provides enough space to allow the evaporative emissions to escape when the float ball 340 is resting on the surface of the max fuel level 306 .
[0026] As seen in FIGS. 2 and 3 , another aspect of the top portion 332 of the valve assembly 330 may be the width “w” of the top portion 332 . In one exemplary embodiment, the tank 202 will have already been constructed with an opening located on the bottom, of tank 202 for receiving the valve assembly 230 . The opening is sized to properly receive an appropriately sized grommet or threaded fitting 234 to properly fasten and seal the valve assembly 230 to the tank 202 . After the tank 202 is assembled, the entire valve assembly 330 would be inserted into the opening. Therefore, the width “w” of the valve assembly 330 must be smaller then the width or diameter of the cutout or opening on the bottom of fuel tank 202 . One advantage of a valve assembly 330 properly sized for insertion, into an opening would be ease of removal of the valve assembly 230 for service or replacement. The valve assembly 330 or the top portion 332 could include bends or sections enabling the total, width “w” of the valve assembly 230 to be wider than the opening but no one point could be larger than the opening. Further, the opening need not be on the bottom or underside of tank 202 and could be located in various other locations on tank 202 .
[0027] Additionally, all or a portion of valve assembly 230 could be placed in the tank 202 prior to complete assembly of the tank 202 . In one exemplary embodiment, the top portion 232 of the valve assembly 230 is fastened to the top surface 202 of the fuel tank 202 . The line 233 might also be fastened to a bracket 235 to support the valve assembly 330 , Finally the two halves of the tank 202 would be mated and sealed together to from the tank 202 with all or a portion of the valve assembly 230 already in tank 202 . The valve assembly or vapor exit 234 could be a welded fitting, grommet or threaded fitting to properly seal the vapor exit 234 from tank 202 , In addition to metal, the tank 202 could also be constructed using a conventional blow molded plastic technique, or other known techniques, enabling proper sizing and fitting of the tank 202 for interaction with the valve assembly 230 .
[0028] Tank 202 would likely have a generally flat bottom, a generally flat top with a recessed opening 210 for cap 208 . The opening 210 for cap 208 would be lower than the highest point on the top surface of tank 202 . The integral design of the fuel vapor valve assembly 230 located within the tank 202 allows for the top surface of the tank to be clean and free from valves and lines. The tank 202 would also have four sidewalk any or all of which may be inclined or configured with a unique shape as required for a particular application.
[0029] In addition to the snorkel or hall float valve depicted in FIG. 3 , the evaporative emissions system of the present invention could use alternative valve assembly designs. As seen in FIGS. 4A and 4B , a simple angled and open tube 433 could be used where the opening 431 resides above the max fuel level 406 . FIG. 4B is a side elevation view of the hoe or tube 433 depicted in FIG. 4A . FIG. 5 provides an additional evaporative emissions system with an inverse “J” or ISO degree bend at the top of tube 533 such that the opening 531 is below die maximum height of tube 533 . The designs depicted in FIGS. 4A , 4 B, and 5 do not create a seal preventing fuel from entering the line 433 , 533 when the unit with the fuel tank 202 is tilted, slanted or moved. However, experimentation has shown that even with openings 431 , 531 of a small diameter that very little fuel is allowed to pass through tubes 433 , 533 even with vigorous sloshing. Still further, the evaporative emissions system 200 and the charcoal filter canister 225 can handle some fuel entering the canister 225 as it will eventually evaporate, be treated, and burned by the carburetor 220 .
[0030] Still further, the evaporative emissions system of the present invention could use a valve assembly which comprises a much larger float device not within a defined valve assembly chamber. The large float would be connected or attached to the valve assembly and could have a sealing element connected or incorporated into the float design to provide a seal against the opening in the valve assembly leading to the vapor passage path or line.
[0031] The present invention provides an internal evaporative emissions valve assembly which is responsive to the fuel level with the fuel tank. Further, the top portion of the fuel valve assembly, and specifically the opening in the valve assembly for receiving the fuel vapor, is positioned such that the valve assembly opening is above the max fuel level of the tank but below the interior top surface of the fuel tank.
[0032] Although a preferred embodiment and exemplary embodiments of dm present invention has been described in detail the present invention is not limited to the embodiments described herein and can be modified in a variety of ways without departing from the spirit and scope of the present invention.
|
An evaporative emissions fuel system for a general-purpose engine includes a fuel tank with a valve assembly located within the fuel tank for guiding fuel vapor to a canister. The canister contains activated charcoal to treat the fuel vapor and guide the vapor to a carburetor which burns the fuel vapor and hydrocarbons. The valve assembly has a valve opening for receiving the fuel vapor and a float responsive to the fuel within the tank for sealing the valve opening when the fuel within the tank is at a feel level capable of entering the valve opening.
| 5
|
BACKGROUND OF THE INVENTION
Exhaust gases which provide the propulsion force for a propulsion system generally contain water molecules in substantial amounts. The propulsion gases may also contain particulate matter. The transmission of signals and the reception of signals by a propulsion vehicle can be greatly effected by the presence of the water molecule or particulate matter in the gases.
This invention is concerned with the problem caused by the presence of water molecules in exhaust gases from propulsion systems. The problem involves infrared radiance bands and radiance intensity of the water molecule which will seriously degrade the on-board detector's performance of certain advanced terminal interceptors.
In particular, water is recognized as being a highly undesirable constitutent insofar as its adverse effects on the long-wave infrared sensor performance is concerned. Experience has demonstrated that if the exhaust products contain more than 25% water, it would completely mask out the signal from the sensor. The masking out of the signal is very prevalent for a non-aluminized propellant of the difluoroamino type which contains 26% water in their exhaust products and of the smokeless composite propellants which contain about 37% water in their exhaust products.
An object of this invention is to provide means for the removal of water molecules from the exhaust gases of the main rocket motor and from reaction control devices of propulsion systems which employ on-board detectors whose performance is seriously degraded from the infrared bands and radiance intensity of the water molecule.
Another object of this invention is to provide a means which can serve as a propellant constituent which is reactive with the water molecule and which also acts to provide propulsion gases having high nitrogenous content and lower flame temperature.
SUMMARY OF THE INVENTION
High nitrogen-containing compounds selected from tetrazole and bitetrazole provide means for obtaining substantially water-free exhaust gases. The reaction of these compounds with water can be depicted as follows: ##EQU1##
A selected specified compound may be either incorporated into the propellant as an ingredient, affixed in the shape of a doughnut forward of the nozzle throat of a propulsion system, or affixed as a toroidal ring to the aft end of the nozzle exit cone of a propulsion system.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view in section of a propulsion system utilizing an insert of a high nitrogen-containing compound, doughnut shaped, affixed forward of the nozzle throat.
FIG. 2 is a view in section of a propulsion system utilizing a toroidal ring of a high nitrogen-containing compound, affixed to the aft end of the nozzle exit cone.
FIG. 3 is a view in section of a test rocket motor configuration for determining the influence of a high nitrogen-containing donut on the spectral scan data of propellant combustion products.
FIG. 4 is a short wave infrared spectral scan (scale of about 2-6 microns) of solid propellant exhaust products, with and without a water scavenger.
FIG. 5 is a spectral scan (scale of about 6-12 microns) of solid propellant exhaust products, with and without a water scavenger.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The means for obtaining substantially water-free solid propellant exhaust gases comprise high nitrogen-containing compounds selected from tetrazole and bitetrazole. The specified high nitrogen-containing compounds may be either incorporated into the propellant as an ingredient, affixed in the shape of a doughnut forward of the nozzle throat of a propulsion system, or affixed as a toroidal ring to the aft end of the nozzle exit cone of a propulsion system.
Reference to the accompanying drawings are made wherein FIG. 1 depicts a T-configured propulsion system 10 which employs donut shaped structures of bitetrazole 16 forward of the nozzle throat. FIG. 1 illustrates the associated parts of the propulsion system wherein the propellant case 12 contains the solid propellant charge 14 within the case. Attached to the case is an exhaust nozzle 20. The nozzle throat 18 has in communication therewith a pair of doughnut shaped structures of bitetrazole 16 through which the propulsion system exhaust gases exit. Water molecules of the exhaust gases are involved in reactions with the bitetrazole to form gaseous products which include nitrogen, hydrogen, and carbon monoxide. The reactions result in obtaining substantially water-free exhaust gases.
FIG. 2 illustrates a second embodiment wherein a toroidal ring of bitetrazole 22 is affixed to the aft end of the nozzle exit cone 24 of the propulsion system 10. Similarly, as in the embodiment of FIG. 1 the gases which exit from the exhaust nozzle undergo reactions with bitetrazole to yield substantially water-free exhaust gases.
FIG. 3 depicts a test motor configuration for determining the influence of a bitetrazole donut on the spectral scan data of exhaust products of propellant. The test motor 30 comprises a rocket motor combustion chamber 32 which contains propellant web inserts 34. A bitetrazole donut 36 is shown positioned forward of the nozzle throat area 38 of the exhaust nozzle 40 which is detachably secured to the rocket combustion chamber or rocket motor case. The exhaust plume envelope is designated as 42 and a spectrometer's field of view (2-12 μm scan) is illustrated as 44. During a test procedure the spectrometer instruments are positioned in a radiometer mode in which fixed wavelength bandpass data are acquired. The instruments are positioned diametrically across the test chamber so that each act as a cold, trapped background for the other, line-of-sight variations through the plume is obtained by moving the rocket motor relative to the fields-of-view.
FIG. 4, curve A, depicts spectral scan data for a typical non-metallized solid propellant without a water scavenger. Curve B depicts spectral scan data for a non-metallized solid propellant using bitetrazole as water scavenger. The scan curves depict radiance × 10 - 1 against wavelength (microns), for range from about 2-6 microns. Radiance × 10 - 1 equals W-cm 2 - sr - 1 -μ m - 1 . Whether the curves relate to millivolt output or radiance to wavelength, the relationship of lower radiance values or lower millivolt output when the water scavenger is used is plainly illustrated. The reduction of the water molecules in the exhaust plume and the corresponding reduction in radiance provide a much needed improvement in reducing adverse effects on sensors and reducing the reactive effect on the graphite constituents of rocket nozzle.
FIG. 5, curve C, depicts spectral scan data for a typical non-metallized solid propellant without a water scavenger. Curve D depicts spectral scan data for a non-metallized solid propellant using bitetrazole as water scavenger. The scan curves depict millivolt output (arbitrary scale) against wavelength (microns), for the range from about 6-12 microns.
Alternately, the high nitrogen-containing compounds may be employed in the propellant as an ingredient. The high nitrogen-containing compounds are energetic monopropellants which have a high positive heat of formation. Therefore, tetrazole and bitetrazole also act to provide propulsion gases with a lower flame temperature because of their high nitrogenous content.
Compression molding of the high nitrogen-containing compounds to the desired shape or molding in place to the nozzle exit cone or molding in place forward of the nozzle throat can be accomplished using standard procedures and pressures of generally in the range of from 10,000 to 20,000 psi. A compatible binder material such as a curable rubbery binder composition (e.g. polybutadiene with curatives) can be used in combination with the described molding procedure as an assist for affixing the donut or toroidal ring shaped material in place.
Representative non-metallized propellants, of the composite-modified double base, nitrogen-fluorine or polybutadiene types yield exhaust products which contain 1.0-1.5 moles of water vapor per 100 g of gaseous exit species. Thus, to tie up the water in these propellant would require ##EQU2## 0.69 g bitetrazole to tie up the water vapor calculated to be in 1 gram of the gaseous exit species. About 70 grams of bitetrazole reacts with 1 mole of water. The weight of the bitetrazole required for a particular use is readily calculated by using the above formula. By a similar formula the amount of tetrazole is likewise readily calculated. Similarly, bitetrazole or tetrazole can be employed as a propellant ingredient in the calculated amount. The amount of the water scavenger required for each propellant grain or an assembly of a multitude of grains would constitute only a fractional part of the total weight of the grain since the amount required is based on the water vapor to be reacted with. As noted earlier, additional contributions are realized from using the high nitrogen compounds in addition to the water scavenger function which they preform since the products of reactions are propulsion gases with a high nitrogenous content which means lower flame temperatures.
Because several factors influence the reduction of the signal-to-noise ratio, the amount of bitetrazole that needs to be used for a particular application does not have to be such that it reacts fully with all of the water, but it is only necessary to reduce the water content in the exhaust plume to acceptable levels.
The removal of water by scavenging it from the exhaust gases of a solid propelled rocket motor provides an additional benefit. This is so because the most reactive ingredient present in the combustion products of a propellant towards the graphite constituents of the rocket nozzle is water vapor. The reaction of steam and carbon is thermodynamically highly favored at temperatures about 3300°K (6000°F). Water is present in reasonably high concentrations in all contemporary solid propellants, namely, about 15% in aluminized, ammonium perchlorate-oxidized composite propellants, about 37% in non-aluminized, ammonium perchlorate-oxidized, smokeless composite propellants, and about 26% in TVOPA-plasticized, ammonium perchlorate-oxidized, non-aluminized difluoroamino propellants. As a consequence, removal of water from the exhaust would be highly beneficial from the standpoint of nozzle erosion and plume-sensor interactions. The plume-sensor interaction is not limited to the long wave infrared but also occurs in the short range infrared. A further discussion of the possible mechanisms of sensor interaction is given below after Table I.
The exhaust gas compositions of various types of typical propellants, both solid and liquid, are presented in Table I.
TABLE I__________________________________________________________________________EXHAUST GAS COMPOSITIONS OF REPRESENTATIVEPROPELLANT TYPESSOLID PROPELLANT EXHAUST CONSTITUENTS (%) H.sub.2 O HCl CO CO.sub.2 H.sub.2 HF Al.sub.2 O.sub.3 NH.sub.3 N.sub.2__________________________________________________________________________Difluoroamino* 26 14 9 15 21Smokeless Composite** 37 16 17 9 10Aluminized Composite*** 15 14 21 3 26 8LIQUID PROPELLANTHydrazine 1 43 28 28Hydrogen Peroxide 70-80Hydrazine-Nitrogen Tetroxide 50 3Monomethylhydrazine-Nitrogen Tetroxide 29 18 8 42__________________________________________________________________________ *5.21 wt % Polyethyl acrylate-acrylic acid prepolymer, 29.5% 1,2,3-tris[α,β-bis(difluoramino)ethoxy]propane (TVOPA), 1.33% 4,5-epoxycyclohexylmethyl 4',5'-epoxycyclohexylcarboxylate (Unox 221), 1.0% Carbon, 63% ammonium perchlorate **50.0% Nitrocellulose, 34.9% Nitroglycerin, 10.5% Diethyl phthalate/2.0 2-Nitrodiphenylamine, 1.2% 2-Nitrodiphenylamine, 1.2% lead salicylate, 1.2% lead 2-ethyl hexoate, 0.2% Candelilla wax ***10.5% Carboxyl-Terminated polybutadiene polymer plus curatives, 2.5% n-Butylferrocene, 16.0% aluminum, 71.0% ammonium perchlorate
SENSOR SIGNAL-TO-NOISE INTERACTIONS
Two possible mechanisms by which a plume can reduce the sensor signal-to-noise ratio can be identified as: (1) impingement of exhaust constituents (gas or particles) from the attitude control systems, vernier engines, and main motors on the cold surfaces of the sensor and (2) through radiation from the particles and gases of the plume which have been excited by several different mechanisms to radiate within the sensor's wavelength region and field-of-view.
The magnitude of the reduction of the signal-to-noise ratio is dependent upon many variables, including: the composition of the propellant, the nozzle configuration, the altitude and velocity of the missile, the angle between the plume axis and the velocity vector of the missile, the optical sensor's field-of-view, and the location and orientation of the sensor relative to the nozzle. Other factors which influence the radiation from the plume include: the size of the particles produced by the solid propellant and the size of the liquid droplets from liquid propellants.
The evaluation of this invention included making measurements of the radiance from the exhaust plume of a test rocket motor as described below under the headings: "Description of the Solid Propellant Test Motor", "General Description of the Long-Wave Infrared Diagnostic Optical System", and "General Description of Motor Testing Procedures".
DESCRIPTION OF THE SOLID PROPELLANT TEST MOTOR
The test motor consists of a combustion chamber, propellant web inserts, bolt-on nozzle, nozzle closure diaphragm and ignition system. The propellant is loaded into the combustion chamber on reusable metal propellant holder inserts. Almost any grain geometry (wedges, star, cruciform, concentric cylinders, etc.) can be provided by this technique. The propellant is cut into thin strips which are approximately 35 mils thick, and bonded onto the interior surface of a cylindrical propellant holder which is then inserted into the motor combustion chamber.
GENERAL DESCRIPTION OF THE LONG-WAVE INFRARED DIAGNOSTIC OPTICAL SYSTEM
The principal radiance data is obtained with two cooled-optics long-wave infrared instruments which cover the general ranges between 6-12 and 12-24 micrometers. For these tests, these instruments are used in a radiometer mode in which fixed wavelength bandpass data are acquired. The instruments are located diametrically across the test chamber so that each acted as a cold, trapped background for the other. Line-of-sight variations through the plume are obtained by moving the rocket motor relative to the fields-of-view. Ge:Hg and Si:As detectors are used, with fixed or circular variable filters to cover the 6-12 and 12-24 micrometer wavelength ranges. The circular filters are spun at high speeds, thereby providing complete spectral scans during the 10-40 milliseconds of steady-state test-time duration in the rocket motor test chamber.
The instruments are situated on opposite sides of the diameter of the test chamber so that each served as a cold background for the other. In this manner, any performance degradation from the ideal 70°K liquid nitrogen optics and background resulted only from stray light from the room temperature tank walls. The detectors are focused onto the plume axis, and a rotating circular variable filter (CVF) is used to achieve the spectral scan. Each circular variable filter is a one-piece substrate disc which scans from 6 to 12 to 6 micrometers and from 12 to 24 to 12 micrometers in one revolution. Appropriate Ge:Hg and Si:As detectors are used. The circular variable filters are spun at 3600 rpm and, as a result, a spectrum is recorded every 8 msec. This rate is consistent with the facility test time intervals of 10-40 msec.
GENERAL DESCRIPTION OF MOTOR TESTING PROCEDURES
The testing to acquire spectral scan data on solid propellants is carried out in a simulated-altitude facility which is capable to producing the conditions existing in the exoatmosphere. The propellant is bonded onto and around the motor wall to provide a surface area of 192 in 2 . Propellant ignition is accomplished by means of a hydrogen/oxygen mixture (O/F = 20) and a spark system. A series of test firings is first carried out to obtain the propellant burn surface required to produce a particular motor pressure (Pc ˜ 450 psi) and to properly size the thickness of the mylar diaphragm needed to insure rapid ignition.
The test motor configuration for determining the spectral scan for the comparison of the various solid propellant is depicted in FIG. 3 as further described hereinabove.
|
This invention disclosure relates to the incorporation of a high nitrogenntaining compound selected from tetrazole and bitetrazole in the form of a doughnut forward of the nozzle throat or in the form of a toroidal ring attached to the aft end of the nozzle exit cone. Both have been demonstrated as an effective means of reducing the quantity of water in the exhaust plume to an acceptable level which does not impart adverse effects on sensors or cause a reactive effect on the graphite constituents of the rocket nozzle. The compound, bitetrazole or tetrazole, can also be incorporated into the solid propellant where it will function similarly as a means or mechanism for water removal from the exhaust plume. Because of its contribution to the propellant's performance through the generation of near-incompressible gases, N 2 , H 2 and CO, it is a desirable propellant ingredient.
| 2
|
FIELD OF THE INVENTION
The present invention relates generally to docked applications and application toolbars. More specifically, it relates to continuously maintaining visibility of and accessability to docked applications, including conveying information to a user while docked applications are presented as a minimal pixel representation.
BACKGROUND OF THE INVENTION
Increases in processing capability and decreases in the cost of personal computers has led to the proliferation of personal computers in all aspects of society. Personal computers are utilized in schools, homes and business. Furthermore, with the decreased cost of personal computers, it has become more feasible from a cost perspective to use computers for tasks and functions which were previously done without the use of computers.
With the proliferation of computers throughout numerous aspects of life, a tendency towards graphical user interfaces has evolved which makes the use of the computer more intuitive and therefore requires less expertise of the users. Examples of such graphical user interfaces include IBM® OS/2®, Apple® System 7®, and Microsoft® Windows®. These operating systems all rely on a "window-like" work space for applications, operating system information such as directory information, and program groupings.
As users become more comfortable with many benefits of a computer they are using additional functions and features of the computer. Since most applications are now associated with their own window or windows and there are more applications that people are using concurrently, the desktops are becoming extremely cluttered. When the application tool bars (or appbars) and the windows they are docked to (i.e. attached along as a common edge) are also taken into account, the confusion of the desktop becomes even more apparent. This is very obvious in a mobile environment where a typical user may have a host emulator session, an e-mail application, multiple browser sessions, an application such as a word processor and still needs to monitor his signal strength and battery strength. In an effort to organize their desktops, many people are moving parts of windows off to the sides so that much of these windows is outside of the view of the user. This allows the user to be aware of the window and the application that is running in it without the application consuming a considerable amount of screen space, but this methodology also causes a problem in that important information may be scrolled or positioned outside of the user's view. Many users also choose to move their appbars out of view by putting them into a mode called hide mode. This causes the appbar to be readily accessible by indicating or activating it using the cursor, which makes it unhidden (i.e., fully visible), but only displays an edge of the appbar, referred to hereinafter as a `visible strip`. The preferred embodiment implements this visible strip as a two-pixel strip although any indication of or subset of the appbar could be used. A mode called auto-hide also allows the appbar to automatically enlarge itself when the cursor is positioned over the visible strip.
The problem of appbar or status bar hiding becomes more intense as appbars, docked to applications, get moved off the edge of the screen and out of the view of the user.
OBJECTS OF THE INVENTION
It is an object of the present invention to notify a user in a windowed computer environment of changes in the status or state of applications.
If is a further object of the present invention to inhibit the user from inadvertently making important status information nonobvious or not readily accessible.
It is yet another object of the present invention to minimize the use of screen space while conveying information to the user in a windowed environment.
SUMMARY OF THE INVENTION
The present invention presents unique methods of allowing a user in a windowed environment to be made aware of changes to applications by way of the appbar while still enabling the user to place the appbar in hide mode or move the application window to which the appbar is docked partially off the presentation space. This is done by symbolically coding the minimal pixel representation of the hidden appbar and/or prohibiting the appbar from being located outside the viewable presentation space. The present invention will be described in further detail with respect to the figures.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1a is a block representation of a computer in which the present invention may be embodied.
FIG. 1b shows a typical display presentation space.
FIG. 1c represents a typical display device and keyboard.
FIG. 2 is an example of a typical appbar docked to an edge of an application window.
FIG. 3a is an example of a typical docked appbar in hide mode.
FIG. 3b is a close-up view of an appbar in hide mode.
FIG. 4a depicts the movement of the appbar to the adjacent edge when the user attempts to position the appbar off the screen.
FIG. 4b depicts the appbar remaining in place as the window to which it is attached is positioned beneath it and off the screen.
FIGS. 5a & 5b depict a progress indicator in the visible edge of a hidden appbar.
FIG. 6a depicts the automatic displaying of a hidden appbar when a threshold is reached or a status changes.
FIG. 6b deptict an appbar that is attached to the edge of the presentation space and has become unhidden.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The preferred embodiment of the present invention is presented in an information processing system having a presentation space upon which one or more presentation windows reside. Methods are presented which maintain the information conveyance to the user through an application bar either in visible mode or in hidden mode. The methods include the movement of the application bar from an edge to which it is docked to a more visible adjacent or opposite edge when the user attempts to position the window which is edge attached to the application bar off the screen, preventing further movement of a window when the user attempts to move the portion of the window containing the application bar off the screen, or presenting status information in the application bar in a minimized form using the minimized pixel representation of an application bar in hidden mode. The current art provides this minimized pixel representation as two pixels, but one skilled in the art could easily modify this representation to any subset or representation of pixels smaller than the entire presentation of the application bar. The currently used terms of `auto hide mode` and `hidden mode` are slightly confusing because in the current art this mode does present a minimal pixel indication of the underlying application, making the appbar not completely hidden. The use of such a narrow strip of pixels in the current art is to provide a surface to activate with the pointer so that the hidden window can easily be made visible and to indicate to the user that the hidden bar exists, but it conveys no other information with the minimal pixel representation itself. The present invention takes advantage of using this minimal pixel representation to present additional status information.
FIG. 1a is a symbolic representation of a computer in which the present invention may be embodied. The computer has associated with it at least a processor 107, memory 101 and a presentation space memory 109. The presentation space is an area of memory which is associated with what is displayed on an output device 121 as shown in FIG. 1c.
FIG. 1c provides a pictorial example of a display device 121 which contains a presentation space 123 upon which one or more windows may be displayed. FIG. 1c also depicts an input device 125 which can be any of a multitude of input devices well known in the art. The display device 121 and input device 125 are both connected to a processor presented in FIG. 1a.
FIG. 1b is exemplary of the content 150 of a presentation space 123 residing on a display device 121 as presented in FIG. 1c. The presentation space 123 contains several icons 152, each icon representing an application.
FIG. 2 demonstrates an application window being opened 201 which may be done by double clicking on the icon 152 associated with the application or by any other means as will be obvious to one skilled in the art. In the present example of the preferred embodiment the user has opened an emulator session on a mobile computer. In a mobile or wireless computing environment, it is very important to be aware of the quality of the connection at all times, therefore when the window is opened for the emulator session, an appbar 203 is attached to an edge of the application window to display the status of the connectivity with the server 210 and signal strength 212 as well as other important information. When the window is presented as in FIG. 2, the users are constantly reminded of the status of their critical connection information, but this occupies what can become critical presentation space, especially when there are multiple application windows opened or the presentation space is rather small as it is on some notebook or hand held computers. When screen space becomes a premium concern, many users choose to run with their appbars in hidden mode as shown in FIGS. 3a and 3b.
FIG. 3a shows the emulator application of FIG. 2 with the appbar hidden 207. In hidden mode, as implemented in the preferred embodiment, the user is only presented a two-pixel line 207 indicating that there is something attached to the application that can be opened or expanded. When the user moves the pointer over the narrow visible edge of the hidden appbar, or alternatively clicks on the narrow visible edge, the appbar will expand to its full size. As is obvious to one skilled in the art, any subset or portion of the actual appbar could be used to place the appbar in hide mode and the current two pixel implementation is small enough to be unobtrusive yet still be accessible. FIG. 3b is a close-up view of the left side of the appbar in hide mode.
In the scenario of FIG. 3a, if the user is working on the computer with the appbar hidden and using the emulator session and the quality of the connection with the server is degraded, the user is not notified until there is a failure in the system. This failure could cause unnecessary loss of data. An object of the present invention is to ensure that this information is presented to the user prior to the actual failure, while not consuming valuable presentation space on a continuous basis. A first method of accomplishing this is to allow the user to create a profile (or to provide a default profile) for the appbar that indicates thresholds for each of the status indicators in the appbar. If any of the status indicators exceeds its predetermined threshold and the appbar is in hide mode, the appbar automatically becomes unhidden to notify the user of the problem. In this example, if the user were running the emulator session of FIG. 3a and the server response time decreased below the threshold set in the profile, the appbar would return to its full size as in FIG. 6a with the indicator highlighted 601. FIG. 6b displays this same concept with the appbar docked to the edge of the presentation space rather than the edge of a window.
An alternative method of notifying the user without returning the appbar to it's original size would be to provide some other visual indication using the minimal pixel representation of the appbar. One method of accomplishing this is shown in FIGS. 5a and 5b. FIGS. 5a and 5b show a fluctuation in the appearance of the hidden appbar. This could be a change in color or a change in shade or intensity and could present itself in many embodiments such as flashing, a gradual intensity modification more like a wave, or by having subsets of the minimal pixel line change color or intensity in sequence as is represented in FIGS. 5a and 5b, where the darker subset of the pixels 505 move across the bottom of the narrow presentation space 201.
Another problem with the use of appbars in conveying application critical status to the user is that users sometimes move the application windows partially or wholly off the space 123. When the user moves the appbar off the presentation space, the same problem occurs as it does for hidden appbars. A first solution to this problem would be to programmatically prevent the user from moving the appbar off the presentation space. While this is effective, it can be rather bothersome to the user. FIG. 4a demonstrates a method of maintaining the conveyance of information to the user as they move the application window across the presentation space. As the user moves the window 201 of FIG. 2 down the presentation space 123, the appbar is automatically moved to an edge where it is more visible. FIG. 4a shows the appbar 203 now attached to the top of the application window 201. When the movement of the docked appbar is to the opposite edge, the movement of the appbar is rather simple. It is just detached from one edge and attached to the other. When the furthest edge of the application window from the presentation space is an adjacent edge to that which the appbar is presently docked, normal programming skill must be used to rotate the appbar 90 degrees.
Another solution to the problem of the user moving appbars edge docked to windows off the presentation space is addressed in FIG. 4b. In FIG. 4b the appbar 203 stops moving when it reaches the edge of the presentation space and the application window 201 to which it is attached continues to move off the presentation space underneath the appbar until the point where the appbar is the only portion of the application window left visible.
|
A method and system is presented which enables the user to maintain the receipt of information from an application bar while the application bar is minimized. In addition, the conveyance of information and availability of controls to the user is maintained while the user moves the window which the application bar is docked to off or around the presentation space.
| 6
|
BACKGROUND OF THE INVENTION
This invention relates to a chain and cord safety device for use with horizontal or vertical panel blinds, whereby the hanging looped ends of the blind control chain and blind control cord used to open or close the blind panels and to open or close the blind itself are enclosed as a safety measure.
In conventional horizontal or vertical blinds, two control cords and/or chains are used to control the operation of the blind. The cords or chains hang down from the housing for the blind, which extends transversely across or in a window or doorway opening. One cord or chain is used to control the rotational movement of the blind panels relative to the opening to open or close the blind. The other is used to physically displace the panels either horizontally or vertically with respect to the opening, to selectively place the blind panels in their operating position with respect to the opening, or to remove the blind panels from the opening. The cords or chains hang down from the housing in the form of loops, a selected side of which is manually pulled to produce the function associated with that cord or chain. Preferably, both loops are formed at the same side of the housing, for ease of operation.
It has been found that the use of unprotected loops presents a safety hazard to small children, as the loops conventionally are located near the floor. The loop may be placed about the child's neck, resulting in choking, or, in extreme cases, strangulation, or the loop may be placed in the child's mouth, which, in addition to the obvious lack of sanitation, may also result in choking if attempted to be swallowed. Consequently, there is a need for devices which provide for ease of use of the blind controls while avoiding the danger presented by the use of unprotected cord and chain loops. In addition, while a chain normally does not stretch in use over time, even when under tension, a cord will stretch over time, thus becoming loose after a period of use in many of the prior art control devices which use combined chain and cord control systems.
BRIEF SUMMARY OF THE INVENTION
According to the present invention, a chain and cord safety device for use in controlling an adjustable blind having a looped control cord and a looped control chain utilizes a housing which is generally rectangular in lateral cross-section with sides and a bottom which are normally closed and a top, within which a wheel adapted to engage the chain loop is rotatably disposed and within which a cord loop receiver having a semi-circular lower portion adapted to receive the cord loop is mounted so as to permit limited longitudinal but not lateral movement of the receiver within the housing so as to normally be urged away from the housing top, the top providing for access to the interior of the housing so as to permit the chain loop to engage the wheel and the cord loop to engage the lower portion of the cord receiver.
BRIEF DESCRIPTION OF THE DRAWING
The invention may be more readily understood by reference to the accompanying drawing, in which:
FIG. 1 is a partial view, in perspective, of a the chain and cord safety device of the present invention installed for use with a vertical blind, the utilization of a vertical blind being for purposes of illustration only, as the present invention is equally applicable to horizontal blinds;
FIG. 2 is a view, in perspective, of the chain and cord safety device of FIG. 1 shown in its disassembled form;
FIG. 3 is a front elevation, in section, of the chain and cord safety device of FIG. 2;
FIG.4 is a view, in section, of the chain and cord safety device of FIG. 2, taken along line 4--4 of FIG. 3; and
FIG. 5 is a view, in section similar to that of FIG. 4, of an alternate embodiment of a chain and cord safety device according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1, there is shown a partial view of a vertical blind 10, which has a slide track casing 12, from which a plurality of vertical panels 14 depend in conventional fashion. A looped chain 16 and a looped cord 18 depend from one end 20 of the casing 12 in conventional fashion. The chain 16 is utilized to control the longitudinal rotational adjustment of the panels and the cord 18 is utilized to draw the panels laterally toward or extend the panels laterally out from the end 20 in conventional fashion.
A cord and chain safety device housing 22 according to the present invention encloses the looped ends (not shown) of the chain 16 and cord 18. In the preferred embodiment, the housing 22 is attached to a wall or other building structural member (not shown) by an attaching member 24 so as to maintain a greater tension on the cord 18 than would otherwise occur if the weight of the housing 22 is solely relied upon for providing the tension, as will be explained hereinafter.
Referring now to FIGS. 2, 3 and 4, the housing 22 illustrated in FIG. 1 is shown in its disassembled form. As seen in FIG. 2, the housing 22 includes a first housing element 26, a second housing element 28, a chain engaging wheel 30, and a cord engaging receiver 32, together with a spring 34 and a mounting pin 36. The attaching plate 24 has a pair of vertical walls 24A, 24B, connected together by a horizontal base plate 24C. The vertical walls 24A, 24B each have a pin receiving aperture 38, axially aligned with one another through which the pin 36 extends so as to provide a rotatable mounting for the wheel 30, as is best shown in FIGS. 3 and 4. The attaching plate wall 24A also has a pair of mounting apertures 40 formed therein to permit the attachment of the attaching member 24 to a wall by conventional fasteners, and the horizontal base plate 24C has a pair of mounting slots 42 formed therein to facilitate the attachment of the attaching member 24 to a floor or sill, if desired rather than the wall attachment.
The first housing member 26 and the second housing member 28 have various complementary structural features to assist in the alignment of the two housing members, when assembled, to provide the unitary housing 22 illustrated in FIG. 1. Thus, the second housing element 28 has an upper pin 44 and a lower pin 46 which fit into complementary recesses 48, 50 formed in the first housing element 26. In addition, the first housing element 26 has a pair of blades 52 which fit into complementary slots 54 formed in the second housing element 28.
The first housing element 26 has a pin receiving aperture 56 centrally disposed in the lower portion thereof, and the second housing member 28 has a similar aperture 58 formed therein so as to be axially aligned with the first housing element aperture 56 when the two housing elements 26, 28 are assembled together by the engagement of the complementary elements 44 and 48, 46 and 50, 52, and 54. In this disposition the pin 26 extends through an axially disposed mounting aperture 60 in the wheel 30, so that the wheel 30 is rotatably mounted within the housing 22.
The wheel 30 has a plurality of chain engaging spokes 62 extending radially outwardly from adjacent the aperture 60. Each of the spokes has a notch 64 formed therein so as to accept links 66 which connect together balls 68 forming the chain 16, while holding the balls 68 between adjacent spokes 62, so that the wheel 30 rotates as the chain 16 is pulled to adjust the panels 14.
The cord engaging receiver 32 is U-shaped with a generally semi-circular lower portion 70, with a peripheral cord receiving groove 72 formed therein so as to extend upwardly away from the lower portion 70. A pair of shoulders 74 are formed on the receiver 32 so as to extend outwardly transversely of the groove 72. The shoulders 74 engage a pair of complementary recesses 76 formed in the first and second housing members 28, 28, so as to permit longitudinal movement of the receiver 32 in the housing 22, while preventing lateral movement of the receiver 32 there within.
The receiver has a boss 78 formed on its upper surface. The boss engages the spring 34 at one end thereof. A stop pin 80 is formed on the interior of the second housing element 28 (see FIG. 3) so as to engage the other end of the spring 34 to hold the spring 34 within the housing 22 and urge the receiver 32 downwardly away from the top of the housing 22. A stop plate 82 formed on the first housing element 26 so as to be located between the wheel 30 and the receiver 32 limits the downward motion of the receiver 32 under the influence of the spring 34. Extending upwardly from each end of the stop plate 82 is a separator plate 84, which serves to separate the loop of the chain 16 within the housing 22 from contact with the loop of the cord 18 within the housing, as is best shown in FIG. 3. The top of the second housing element 28 has openings 86 on both sides the upper pin 44 to provide for ingress and egress of the chain 16 and cord 18. The first housing element 26 has complementary openings (not shown in FIG. 3).
In use, the housing 22 is opened as shown in FIG. 2 by the removal of the pin 36. The chain 16 and cord 18 are installed about the wheel 30 and receiver 32, respectively, as shown in FIG. 3 after the respective lengths of the chain and cord loops have been adjusted to provide for the desired tension on the cord 18. The device is then reassembled by the insertion of the pin through the housing elements 26, 28 and the wheel 30. The housing 22 is then attached to the attaching plate 24 by the pin 36 and the entire assembly fixed to the desired surface by use of the attaching plate 24 and appropriate fasteners (not shown). Failure to use the attaching plate 24 may result in insufficient tension being applied to the cord 18 by the receiver 32 and spring 34 after a period of use because the cord was not initially under maximum tension, thereby degrading the performance of the device of the present invention.
In FIGS. 2, 3, and 4, the housing 22 is configured so that the wheel 30 and receiver 32 are disposed one over the other in vertical alignment, with the receiver 32 on top. While this is the presently preferred configuration of this embodiment of the invention, it is, of course, within the scope of the invention to reverse these relative dispositions, so that the wheel 30 is above the receiver 32, by an appropriate change in the relative dimensions thereof.
FIG. 5 illustrates, in cross section, an alternate embodiment of the invention, in which the wheel and receiver are in horizontal alignment, rather than in vertical alignment. In the embodiment of FIG. 5, a housing 22' has a first housing element 26' and a second housing element 28'. An attaching plate 24' has a pin 36' extending therethrough so as to attach the housing 22' to the attaching plate. The pin 36' passes through the wheel 30, which may be identical to the wheel 30 of FIG. 2. A receiver 32' differs from the receiver 32 of FIG. 2 in that there is a longitudinal slot 100 formed in the body of the receiver 32' so as to permit the pin 26' to pass through the receiver, thereby permitting the receiver 32' to move longitudinally with respect to the housing in order to apply the appropriate tension to the cord 18. A stop plate 102 extends inwardly from the interior face of the first housing element 26' so as to retain the spring 34 in place against the receiver 32' at a boss 78'. The remaining details of the structure and operation of the alternate embodiment of FIG. 5 will be apparent from the foregoing description of the structure and operation of the embodiment of FIGS. 2, 3, and 4.
The present invention has been described as to the details of its presently preferred embodiments. It will be obvious to those skilled in the art that various changes can be made in the specific structures disclosed herein, which do not depart from the scope of the invention as defined in the claims hereof and the equivalents of the various claim elements.
|
A blind cord safety device for use in controlling an adjustable blind having a looped control cord and a looped control chain by enclosing the loops has housing within which are disposed a rotatable wheel adapted to engage the chain loop thereabout and a U-shaped cord loop receiver adapted to receive the cord loop in a peripheral groove formed thereon. The receiver is mounted within the housing so as to permit limited longitudinal but not lateral movement of the receiver within the housing. A spring is disposed within the housing between the receiver and the housing top so as to normally urge the receiver away from the housing top so as to avoid slack in the cord as a result of the cord stretching over time as a result of use.
| 4
|
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of and priority to U.S. Provisional Patent Application No. 62/352,683 filed Jun. 21, 2016, the entire disclosure of which is incorporated by reference herein.
BACKGROUND
1. Technical Description
[0002] The present disclosure is directed to an anvil assembly for use with a surgical stapling device. More particularly, the present disclosure is directed to an anvil assembly for a circular surgical stapling device including a stabilizing collet positioned to prevent damage to the anvil assembly.
2. Background of Related Art
[0003] Circular staplers are commonly used to perform a variety of surgical procedures including anastomosis procedures for joining ends of tubular tissue sections and hemorrhoidectomy procedures for treating hemorrhoids. Typically, circular staplers include a stapling device and an anvil assembly. The stapling device includes a handle assembly, a body portion extending from the handle assembly, a shell assembly including a staple cartridge, and a trocar extending from the shell assembly. The anvil assembly is releasably secured to the trocar of the stapling device and includes an anvil assembly having an anvil shaft and an anvil head assembly. The shell assembly includes a circular knife. When the circular stapler is fired, the circular knife is advanced from the shell assembly and cuts tissue as staples are ejected from the staple cartridge and formed against the anvil head assembly. In use, the stapling device and the anvil assembly are delivered to a surgical site within a patient separately and coupled to each other prior to use.
[0004] Typically, the stapling device and the anvil assembly are coupled together at the surgical site by a clinician using a grasper. More particularly, the clinician grasps the anvil shaft of the anvil assembly with the grasper and positions the anvil shaft about the trocar of the stapling device to couple the trocar to the anvil shaft. This coupling procedure takes place within a body lumen or orifice where visibility is limited.
[0005] When a clinician applies too much pressure on the anvil shaft, the anvil shaft can be damaged, e.g., crushed or deformed, such that the anvil shaft cannot be properly coupled to the stapling device. This problem is exacerbated because due to the poor visibility at the surgical site, the clinician may be unaware that the anvil shaft has been damaged and is not properly coupled to the stapling device. As such, when circular stapler is fired, the anvil assembly may become disengaged from the stapling device such that the staples are not formed in cut tissue.
[0006] Accordingly, a need exists in the surgical arts for an anvil assembly that is less susceptible to damage during attachment of the anvil assembly to the stapling device to facilitate reliable attachment of the anvil assembly to a stapling device.
SUMMARY
[0007] In one aspect of the disclosure, an anvil assembly includes an anvil shaft defining a first longitudinal bore and an anvil head assembly. The anvil shaft has a proximal portion and a distal portion. The proximal portion includes a plurality of flexible legs that define the first longitudinal bore. The anvil head assembly is secured to the distal portion of the anvil shaft and supports an anvil plate that defines a plurality of staple deforming pockets. A stabilizing collet defines a second longitudinal bore. The collet is supported within the first longitudinal bore and is positioned to prevent damage to the plurality of flexible legs.
[0008] In another aspect of the disclosure, a surgical stapler includes a stapling device and an anvil assembly. The stapling device includes a handle assembly, a body portion that extends distally from the handle assembly, a shell assembly including a staple cartridge having a plurality of staples, and a trocar extending from the shell assembly. The anvil assembly includes an anvil shaft and an anvil head assembly. The anvil shaft has a proximal portion and a distal portion and defines a first longitudinal bore configured to receive the trocar of the stapling device. The proximal portion includes a plurality of flexible legs that defines the first longitudinal bore. The anvil head assembly is secured to the distal portion of the anvil shaft and supports an anvil plate that defines a plurality of staple deforming pockets. A stabilizing collet defines a second longitudinal bore configured to receive the trocar. The collet is supported within the first longitudinal bore and is positioned to prevent damage to the plurality of flexible legs.
[0009] In embodiments, the collet is cylindrical.
[0010] In certain embodiments, the collet is substantially rigid.
[0011] In some embodiments, the collet has a distal end including a plurality of cantilevered fingers, wherein each of the plurality of cantilevered fingers has a protrusion configured to secure the collet within the first longitudinal bore of the anvil shaft.
[0012] In certain embodiments, each of the plurality of flexible legs defines a longitudinal channel with an adjacent one of the plurality of flexible legs.
[0013] In embodiments, the anvil shaft defines a hole positioned adjacent the distal end of each of the longitudinal channels. Each of the holes is configured to receive a respective one of the protrusions.
[0014] In some embodiments, each of the holes is circular.
[0015] In certain embodiments, the anvil head assembly is pivotally secured to the anvil shaft.
[0016] In embodiments, the anvil plate is annular.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Various embodiments of the presently disclosed crush resistant anvil assembly are described herein below with reference to the drawings, wherein:
[0018] FIG. 1 is a side perspective view of a surgical stapler including an exemplary embodiment of the presently disclosed crush resistant anvil assembly;
[0019] FIG. 2 is an enlarged view of the indicted area of detail shown in FIG. 1 ;
[0020] FIG. 3 is a cross-sectional view taken along section line 3 - 3 of FIG. 2 ;
[0021] FIG. 4 is a side perspective view of the anvil assembly shown in FIG. 2 ;
[0022] FIG. 5 is an enlarged view of the indicated area of detail shown in FIG. 4 ;
[0023] FIG. 6 is a side perspective view of a collet of the anvil assembly shown in FIG. 4 ;
[0024] FIG. 7 is a side cross-sectional view of the collet shown in FIG. 6 and the anvil shaft of the anvil assembly shown in FIG. 4 with parts separated;
[0025] FIG. 8 is a side cross-sectional view of the collet and anvil shaft shown in FIG. 7 as the collet is slid into the anvil shaft;
[0026] FIG. 9 is a side cross-sectional view of the collet and anvil shaft shown in FIG. 8 with the collet secured within the anvil shaft; and
[0027] FIG. 10 is a side cross-sectional view of the collet and anvil shaft shown in FIG. 9 as a trocar of the stapling device is positioned within the anvil shaft.
DETAILED DESCRIPTION OF EMBODIMENTS
[0028] Exemplary embodiments of the presently disclosed damage resistant anvil assembly will now be described in detail with reference to the drawings in which like reference numerals designate identical or corresponding elements in each of the several views. In this description, the term “proximal” is used generally to refer to that portion of the stapler that is closer to a clinician, while the term “distal” is used generally to refer to that portion of the stapler that is farther from the clinician. In addition, the term “endoscopic” is used generally to refer to procedures performed through a small incision or a cannula inserted into a patient's body including endoscopic, laparoscopic, and arthroscopic procedures. Finally, the term clinician is used generally to refer to medical personnel including doctors, nurses, and support personnel.
[0029] The presently disclosed anvil assembly includes an anvil head assembly, an anvil shaft, and a stabilizing collet. In embodiments, the stabilizing collet may be formed of a substantially rigid material. Alternately, other materials of construction that provide support to the anvil shaft are envisioned. The anvil shaft includes a plurality of flexible legs that flex outwardly in response to insertion of a trocar of a surgical stapling device into the anvil shaft to releasably couple the anvil shaft to the trocar. The collet is received within a longitudinal bore defined by the flexible legs of the anvil shaft at a location to support the flexible legs and minimize the likelihood of damage to the anvil shaft caused by engagement of the anvil shaft with a grasper. The collet is also positioned in a location not to interfere with flexing of the legs during coupling of the anvil shaft to the trocar of the stapling device.
[0030] FIG. 1 illustrates a manually powered surgical stapler 10 including a stapling device 12 supporting an exemplary embodiment of anvil assembly 100 . The stapling device 12 includes a handle assembly 14 , a body portion 16 that extends distally from the handle portion 14 , and a shell assembly 18 that supports a staple cartridge 20 . The staple cartridge 20 supports a plurality of staples (not shown) that are arranged in an annular configuration within the shell assembly 18 . The stapling device 12 also includes a trocar 22 that extends from the distal end of the body portion 16 through the shell assembly 18 . The trocar 22 is configured to releasably engage the anvil assembly 100 as described in further detail below. For a more detailed description of a suitable stapling device, see U.S. Pat. Nos. 7,234,624, 7,364,060 and 7,857,187 (“the incorporated patents”) which are incorporated herein by reference in their entirety.
[0031] Referring also to FIGS. 2-4 , the anvil assembly 100 includes an anvil head assembly 102 and an anvil shaft 104 . Although not specifically described in this application, the anvil head assembly 102 can be pivotally or fixedly attached to the anvil shaft 104 . Examples of pivotally attached anvil head assemblies are described in the incorporated patents.
[0032] The anvil head assembly 102 includes a housing 106 that supports an anvil plate 108 ( FIG. 2 ) and a cut ring assembly 110 . The housing 106 has a smoothly curved distal surface 112 that facilitates atraumatic entry of the anvil assembly 100 into and through a body orifice or lumen. A proximal side of the housing 106 defines a cavity (not shown) that is configured to receive the anvil plate 108 and the cut ring assembly 110 . For a more detailed description of the components of the anvil head assembly 102 , see the incorporated patents.
[0033] The anvil shaft 104 includes a longitudinal body portion 116 that includes a tubular portion 118 and a plurality of flexible legs 120 that extend proximally from the tubular portion 118 . Each of the flexible legs 120 has a semi-cylindrical configuration such that the legs 120 cooperate to define a longitudinal bore 122 ( FIG. 3 ) that is dimensioned to receive the trocar 22 of the stapling device 12 ( FIG. 1 ) when the anvil assembly 100 is secured to the stapling device 12 . The bore 122 extends from the proximal end of the flexible legs 120 at least partially into the tubular portion 118 of the anvil shaft 104 .
[0034] In embodiments, the anvil shaft 104 may include a plurality of splines 126 positioned about the anvil shaft 104 . As is known in the art, the splines 126 mate with recesses (not shown) defined within the shell assembly 16 FIG. 2 ) of the surgical stapling device 12 to properly orient the staple cartridge 20 in relation to the anvil plate 108 of the anvil assembly 100 when the anvil assembly 100 and the shell assembly 18 are approximated. The anvil shaft 104 may also include one or more stabilization rings 130 (only one is shown) positioned about the anvil shaft 104 at a position to engage the shell assembly 16 when the anvil assembly 100 and the shell assembly 18 are approximated to provide added stability to the anvil assembly 100 . For a more detailed description of an anvil assembly including a stabilization ring, see U.S. Pat. No. 8,424,535 which is incorporated herein by reference in its entirety. Although the splines 126 and the stabilization ring 130 are shown to be formed integrally with the anvil shaft 104 , it is contemplated the either or both could be formed separately from the anvil shaft 104 and secured to the anvil shaft 104 using any known fastening technique including welding, crimping gluing or the like.
[0035] Referring to FIGS. 4 and 5 , each of the flexible legs 120 of the anvil shaft 104 defines a longitudinal channel 134 with an adjacent leg 120 . Each longitudinal channel 134 includes an enlarged cutout or hole 136 formed at the distal end of the longitudinal channel 134 . The holes 136 are configured to secure a collet 150 within the longitudinal bore 122 of the anvil shaft 104 . In embodiments, the hole 136 is substantially circular although other configurations are envisioned. One or more of the flexible legs 120 may also include a bore 140 which is configured to receive a suture or the like (not shown). The suture can be used to allow a clinician to retrieve or position the anvil assembly 100 from or within a surgical site. The proximal end of each of the flexible legs 120 has an inner surface that defines a recess 160 ( FIG. 7 ) such that the recesses 160 collectively define an annular recess 160 a ( FIG. 9 ). The annular recess 160 a facilitates releasable engagement of the anvil assembly 100 to the stapling device 12 .
[0036] Referring also to FIG. 6 , the collet 150 may be substantially rigid and is positioned within the longitudinal bore 122 defined by the anvil shaft 104 . The collet 150 is substantially cylindrical and defines a longitudinal bore 152 ( FIG. 7 ) that is dimensioned to receive the trocar 22 ( FIG. 10 ). A distal portion 154 of the collet 150 includes a plurality of cantilevered fingers 156 . Each of the fingers 156 includes a protrusion 158 that is dimensioned and configured to be received in a respective one of the holes 136 ( FIG. 5 ) formed in the anvil shaft 104 as described in further detail below.
[0037] Referring to FIGS. 7-9 , in order to assemble the collet 150 within the anvil shaft 104 , the distal end of the collet 150 is inserted into the proximal end of the longitudinal bore 122 of the anvil shaft 104 and slid distally in the direction indicated by arrow “A” in FIGS. 7 and 8 . The collet 150 is positioned to align the protrusions 158 with the longitudinal channels 134 positioned between the flexible legs 120 . When the protrusions 158 engage an inner wall of the flexible legs 120 , the fingers 156 are deflected inwardly in the direction indicated by arrow “B” in FIG. 8 to facilitate passage of the collet 150 through the longitudinal bore 122 . When the protrusions 158 are moved into alignment with the holes 136 , the fingers 156 spring outwardly in the direction indicated by arrow “C” in FIG. 9 to move the protrusions 158 into the holes 136 to secure the collet 150 within the longitudinal bore 122 .
[0038] Referring to FIG. 10 , the trocar 22 includes a pointed distal end 30 and an enlarged proximal portion 32 that defines a shoulder 32 a . As known in the art, the proximal end of the trocar 22 is secured to an approximation mechanism (not shown) of the stapling device 12 ( FIG. 1 ) to facilitate movement of the trocar 22 between retracted and advanced positions. When the trocar 22 is inserted into the longitudinal bore 122 of the anvil shaft 104 and the longitudinal bore 152 of the collet 150 in the direction indicated by arrow “D” in FIG. 10 , the enlarged proximal portion 32 of the trocar 22 engages a proximal end of the flexible legs 120 of the anvil shaft 104 to urge the flexible legs 120 outwardly in the direction indicated by arrows “E”. When the enlarged proximal portion 32 of the trocar 22 is moved distally in the direction indicated by arrow “D” into alignment with the recess 160 defined at the proximal end of the flexible legs 120 , the flexible legs 120 return to their undeformed configuration to receive the enlarged proximal portion 32 of the trocar 22 . When the enlarged proximal portion 32 is received within the recess 160 , the shoulder 32 a on the enlarged proximal portion 32 of the trocar 32 engages a proximal wall 161 defining the recess 160 to secure the anvil shaft 104 to the trocar 22 .
[0039] During an endoscopic surgical procedure, the anvil assembly 100 is grasped with a grasper (not shown) that is inserted through a small incision in the skin to position the trocar 22 within the longitudinal bore 122 of the anvil shaft 104 and secure the anvil assembly 100 to the trocar 22 of the surgical stapling device 12 . The collet 150 is positioned within the longitudinal bore 122 of the anvil shaft 104 and extends from a distal end of the flexible legs 120 towards the proximal end of the flexible legs 120 to support the flexible legs 120 and inhibit radial compression or other deformation of the flexible legs 120 that may result from pressure applied to the flexible legs 120 by a manipulating instrument (not shown). Collet 150 may be formed from any suitable, medical grade material having a stiffness to perform the functions described herein. Suitable materials include, for example, stainless steel or nylon. The collet 150 is secured within the longitudinal bore 122 of the anvil shaft 104 in a position that does not interfere with outward flexing of the flexible legs 120 and, thus, allows the anvil assembly 100 to be readily connected to the trocar 22 .
[0040] Persons skilled in the art will understand that the devices and methods specifically described herein and illustrated in the accompanying drawings are non-limiting exemplary embodiments. It is envisioned that the elements and features illustrated or described in connection with one exemplary embodiment may be combined with the elements and features of another without departing from the scope of the present disclosure. As well, one skilled in the art will appreciate further features and advantages of the disclosure based on the above-described embodiments. Accordingly, the disclosure is not to be limited by what has been particularly shown and described, except as indicated by the appended claims.
|
An anvil assembly is disclosed that includes an anvil shaft including a proximal portion and a distal portion and defining a first longitudinal bore. The proximal portion includes a plurality of flexible legs that define the first longitudinal bore dimensioned to receive a trocar of a stapling device. An anvil head assembly is secured to the distal portion of the anvil shaft and supports an annular anvil plate that a plurality of staple deforming pockets. The anvil assembly also includes a rigid collet defining a second longitudinal bore that is configured to receive the trocar of the stapling device. The rigid collet is supported within the first longitudinal bore and is positioned to prevent crushing of the plurality of flexible legs when the anvil assembly is manipulated with a grasper.
| 0
|
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a continuation of U.S. patent application Ser. No. 15/165,136, filed 26 May 2016, which is a continuation of U.S. patent application Ser. No. 15/008,473, filed 28 Jan. 2016, (now issued as U.S. Pat. No. 9,394,471), which is a continuation of U.S. patent application Ser. No. 14/829,253, filed 18 Aug. 2015, (now issued as U.S. Pat. No. 9,267,071), which is a continuation of U.S. patent application Ser. No. 14/495,454, filed 24 Sep. 2014, (now U.S. Pat. No. 9,175,209), which is a continuation of U.S. patent application Ser. No. 13/717,636, filed 17 Dec. 2012, (now issued as U.S. Pat. No. 9,359,546), which is a continuation of U.S. patent application Ser. No. 13/629,018, filed 27 Sep. 2012, (now issued as U.S. Pat. No. 8,466,093), which is a continuation of U.S. patent application Ser. No. 13/353,542, filed 19 Jan. 2012, (now issued as U.S. Pat. No. 8,278,373), which in turn is a continuation of prior U.S. application Ser. No. 13/340,080, filed 29 Dec. 2011, (now issued as U.S. Pat. No. 8,455,403), which in turn is a continuation of prior U.S. application Ser. No. 12/980,510, filed 29 Dec. 2010, (now issued as U.S. Pat. No. 8,088,718), which in turn is a continuation of prior U.S. application Ser. No. 12/870,076, filed 27 Aug. 2010 (now issued as U.S. Pat. No. 7,902,125), which in turn is a divisional of prior U.S. application Ser. No. 11/323,031, filed 30 Dec. 2005, (now issued as U.S. Pat. No. 7,803,740), which in turn claims priority from U.S. Provisional Application Ser. No. 60/640,965, filed 30 Dec. 2004, all of which are hereby incorporated by reference herein in their entireties.
FIELD OF THE INVENTION
The present invention relates to lightweight thermoset polymer nanocomposite particles, to processes for the manufacture of such particles, and to applications of such particles. The particles of the invention contain one or optionally more than one type of nanofiller that is intimately embedded in the polymer matrix. It is possible to use a wide range of thermoset polymers and nanofillers as the main constituents of the particles of the invention, and to produce said particles by means of a wide range of fabrication techniques. Without reducing the generality of the invention, in its currently preferred embodiments, the thermoset matrix consists of a terpolymer of styrene, ethyvinylbenzene and divinylbenzene; particulate carbon black of nanoscale dimensions is used as the nanofiller, suspension polymerization is performed in the presence of the nanofiller, and optionally post-polymerization heat treatment is performed with the particles still in the reactor fluid that remains after the suspension polymerization to further advance the curing of the matrix polymer. When executed in the manner taught by this patent, many properties of both the individual particles and packings of said particles can be improved by the practice of the invention. The particles exhibit enhanced stiffness, strength, heat resistance, and resistance to aggressive environments; as well as the improved retention of high conductivity of liquids and gases through packings of said particles in aggressive environments under high compressive loads at elevated temperatures. The thermoset polymer nanocomposite particles of the invention can be used in many applications. These applications include, but are not limited to, the construction, drilling, completion and/or fracture stimulation of oil and natural gas wells; for example, as a proppant partial monolayer, a proppant pack, an integral component of a gravel pack completion, a ball bearing, a solid lubricant, a drilling mud constituent, and/or a cement additive.
BACKGROUND
The background of the invention can be described most clearly, and hence the invention can be taught most effectively, by subdividing this section in three subsections. The first subsection will provide some general background regarding the role of crosslinked (and especially stiff and strong thermoset) particles in the field of the invention. The second subsection will describe the prior art that has been taught in the patent literature. The third subsection will provide additional relevant background information selected from the vast scientific literature on polymer and composite materials science and chemistry, to further facilitate the teaching of the invention.
A. General Background
Crosslinked polymer (and especially stiff and strong thermoset) particles are used in many applications requiring high stiffness, high mechanical strength, high temperature resistance, and/or high resistance to aggressive environments. Crosslinked polymer particles can be prepared by reacting monomers or oligomers possessing three or more reactive chemical functionalities, as well as by reacting mixtures of monomers and/or oligomers at least one ingredient of which possesses three or more reactive chemical functionalities.
The intrinsic advantages of crosslinked polymer particles over polymer particles lacking a network consisting of covalent chemical bonds in such applications become especially obvious if an acceptable level of performance must be maintained for a prolonged period (such as many years, or in some applications even several decades) under the combined effects of mechanical deformation, heat, and/or severe environmental insults. For example, many high-performance thermoplastic polymers, which have excellent mechanical properties and which are hence used successfully under a variety of conditions, are unsuitable for applications where they must maintain their good mechanical properties for many years in the presence of heat and/or chemicals, because they consist of assemblies of individual polymer chains. Over time, the deformation of such assemblies of individual polymer chains at an elevated temperature can cause unacceptable amounts of creep, and furthermore solvents and/or aggressive chemicals present in the environment can gradually diffuse into them and degrade their performance severely (and in some cases even dissolve them). By contrast, the presence of a well-formed continuous network of covalent bonds restrains the molecules, thus helping retain an acceptable level of performance under severe use conditions over a much longer time period.
Oil and natural gas well construction activities, including drilling, completion and stimulation applications (such as proppants, gravel pack components, ball bearings, solid lubricants, drilling mud constituents, and/or cement additives), require the use of particulate materials, in most instances preferably of as nearly spherical a shape as possible. These (preferably substantially spherical) particles must generally be made from materials that have excellent mechanical properties. The mechanical properties of greatest interest in most such applications are stiffness (resistance to deformation) and strength under compressive loads, combined with sufficient “toughness” to avoid the brittle fracture of the particles into small pieces commonly known as “fines”. In addition, the particles must have excellent heat resistance in order to be able to withstand the combination of high compressive load and high temperature that normally becomes increasingly more severe as one drills deeper. In other words, particles that are intended for use deeper in a well must be able to withstand not only the higher overburden load resulting from the greater depth, but also the higher temperature that accompanies that higher overburden load as a result of the nature of geothermal gradients. Finally, these materials must be able to withstand the effects of the severe environmental insults (resulting from the presence of a variety of hydrocarbon and possibly solvent molecules as well as water, at simultaneously elevated temperatures and compressive loads) that the particles will encounter deep in an oil or natural gas well. The need for relatively lightweight high performance materials for use in these particulate components in applications related to the construction, drilling, completion and/or fracture stimulation of oil and natural gas wells thus becomes obvious. Consequently, while such uses constitute only a small fraction of the applications of stiff and strong materials, they provide fertile territory for the development of new or improved materials and manufacturing processes for the fabrication of such materials.
We will focus much of the remaining discussion of the background of the invention on the use of particulate materials as proppants. One key measure of end use performance of proppants is the retention of high conductivity of liquids and gases through packings of the particles in aggressive environments under high compressive loads at elevated temperatures.
The use of stiff and strong solid proppants has a long history in the oil and natural gas industry. Throughout most of this history, particles made from polymeric materials (including crosslinked polymers) have been considered to be unsuitable for use by themselves as proppants. The reason for this prejudice is the perception that polymers are too deformable, as well as lacking in the ability to withstand the combination of elevated compressive loads, temperatures and aggressive environments that are commonly encountered in oil and natural gas wells. Consequently, work on proppant material development has focused mainly on sands, on ceramics, and on sands and ceramics coated by crosslinked polymers to improve some aspects of their performance. This situation has prevailed despite the fact that most polymers have densities that are much closer to that of water so that in particulate form they can be transported much more readily into a fracture by low-density fracturing or carrier fluids such as unviscosified water.
Nonetheless, the obvious practical advantages [see a review by Edgeman (2004)] of developing the ability to use lightweight particles that possess almost neutral buoyancy relative to water have stimulated a considerable amount of work over the years. However, as will be seen from the review of the prior art provided below, progress in this field of invention has been very slow as a result of the many technical challenges that exist to the successful development of cost-effective lightweight particles that possess sufficient stiffness, strength and heat resistance.
B. Prior Art
The prior art can be described most clearly, and hence the invention can be placed in the proper context most effectively, by subdividing this section into four subsections. The first subsection will describe prior art related to the development of “as-polymerized” thermoset polymer particles. The second subsection will describe prior art related to the development of thermoset polymer particles that are subjected to post-polymerization heat treatment. The third subsection will describe prior art related to the development of thermoset polymer composite particles where the particles are reinforced by conventional fillers. The fourth subsection will describe prior art related to the development of ceramic nanocomposite particles where a ceramic matrix is reinforced by nanofillers.
1. “as-Polymerized” Thermoset Polymer Particles
As discussed above, particles made from polymeric materials have historically been considered to be unsuitable for use by themselves as proppants. Consequently, their past uses in proppant materials have focused mainly on their placement as coatings on sands and ceramics, in order to improve some aspects of the performance of the sand and ceramic proppants.
Significant progress was made in the use of crosslinked polymeric particles themselves as constituents of proppant formulations in prior art taught by Rickards, et al. (U.S. Pat. No. 6,059,034; U.S. Pat. No. 6,330,916). However, these inventors still did not consider or describe the polymeric particles as proppants. Their invention only related to the use of the polymer particles in blends with particles of more conventional proppants such as sands or ceramics. They taught that the sand or ceramic particles are the proppant particles, and that the “deformable particulate material” consisting of polymer particles mainly serves to improve the fracture conductivity, reduce the generation of fines and/or reduce proppant flowback relative to the unblended sand or ceramic proppants. Thus while their invention differs significantly from the prior art in the sense that the polymer is used in particulate form rather than being used as a coating, it shares with the prior art the limitation that the polymer still serves merely as a modifier improving the performance of a sand or ceramic proppant rather than being considered for use as a proppant in its own right.
Bienvenu (U.S. Pat. No. 5,531,274) disclosed progress towards the development of lightweight proppants consisting of high-strength crosslinked polymeric particles for use in hydraulic fracturing applications. However, embodiments of this prior art, based on the use of styrene-divinylbenzene (S-DVB) copolymer beads manufactured by using conventional fabrication technology and purchased from a commercial supplier, failed to provide an acceptable balance of performance and price. They cost far more than the test standard (Jordan sand) while being outperformed by Jordan sand in terms of the liquid conductivity and liquid permeability characteristics of their packings measured according to the industry-standard API RP 61 testing procedure. [This procedure is described by the American Petroleum Institute in its publication titled “Recommended Practices for Evaluating Short Term Proppant Pack Conductivity” (first edition, Oct. 1, 1989).] The need to use a very large amount of an expensive crosslinker (50 to 80% by weight of DVB) in order to obtain reasonable performance (not too inferior to that of Jordan Sand) was a key factor in the higher cost that accompanied the lower performance.
The most advanced prior art in stiff and strong crosslinked polymer particle technologies for use in applications in oil and natural gas drilling was developed by Albright (U.S. Pat. No. 6,248,838) who taught the concept of a “rigid chain entanglement crosslinked polymer”. In summary, the reactive formulation and the processing conditions were modified to achieve “rapid rate polymerization”. While not improving the extent of covalent crosslinking relative to conventional isothermal polymerization, rapid rate polymerization results in the “trapping” of an unusually large number of physical entanglements in the polymer. These additional entanglements can result in a major improvement of many properties. For example, the liquid conductivities of packings of S-DVB copolymer beads with w DVB =0.2 synthesized via rapid rate polymerization are comparable to those that were found by Bienvenu (U.S. Pat. No. 5,531,274) for packings of conventionally produced S-DVB beads at the much higher DVB level of w DVB =0.5. Albright (U.S. Pat. No. 6,248,838) thus provided the key technical breakthrough that enabled the development of the first generation of crosslinked polymer beads possessing sufficiently attractive combinations of performance and price characteristics to result in their commercial use in their own right as solid polymeric proppants.
2. Heat-Treated Thermoset Polymer Particles
There is no prior art that relates to the development of heat-treated thermoset polymer particles for use in oil and natural gas well construction applications. One needs to look into another field of technology to find prior art of some relevance. Nishimori, et. al. (JP1992-22230) focused on the development of particles for use in liquid crystal display panels. They taught the use of post-polymerization heat treatment to increase the compressive elastic modulus of S-DVB particles at room temperature. They only claimed compositions polymerized from reactive monomer mixtures containing 20% or more by weight of DVB or other crosslinkable monomer(s) prior to the heat treatment. They stated explicitly that improvements obtained with lower weight fractions of the crosslinkable monomer(s) were insufficient and that hence such compositions were excluded from the scope of their patent.
3. Thermoset Polymer Composite Particles
This subsection will be easier to understand if it is further subdivided into two subsections. As was discussed above, the prior art on the use of polymers as components of proppant particles has focused mainly on the development of thermoset polymer coatings for rigid inorganic materials such as sand or ceramic particles. These types of heterogeneous (composite) particles will be discussed in the first subsection. Composite particles where the thermoset polymer plays a role that goes beyond that of a coating will be discused in the second subsection.
a. Thermoset Polymers as Coatings
The prior art discussed in this subsection is mainly of interest for historical reasons, as examples of the evolution of the use of thermoset polymers as components in composite proppant particles.
Underdown, et al. (U.S. Pat. No. 4,443,347) and of Glaze, et al. (U.S. Pat. No. 4,664,819) taught the coating of particles such as silica sand or glass beads with a thermoset polymer (such as a phenol-formaldehyde resin) that is cured fully (in their terminology, “pre-cured”) prior to the injection of a proppant charge consisting of such particles into a well.
An interesting alternative coating technology was taught by Graham, et al. (U.S. Pat. No. 4,585,064) who developed resin-coated particles comprising a particulate substrate, a substantially cured inner resin coating, and a heat-curable outer resin coating. According to their teaching, the outer resin coating should cure, and should thus enable the particles to form a coherent mass possessing the desired level of liquid conductivity, under the temperatures and compressive loads found in subterranean formations. However, it is not difficult to anticipate the many technical difficulties that can arise in attempting to reduce such an approach reliably and consistently to practice.
b. Thermoset Polymers as Matrix Phase Containing Dispersed Finely Divided Filler Material
McDaniel, et al. (U.S. Pat. No. 6,632,527) describes composite particles made of a binder and filler; for use in subterranean formations (for example, as proppants and as gravel pack components), in water filtration, and in artificial turf for sports fields. The filler consists of finely divided mineral particles that can be of any available composition. Fibers are also used in some embodiments as optional fillers. The sizes of the filler particles are required to fall within the range of 0.5 microns to 60 microns. The proportion of filler in the composite particle is very large (60% to 90% by volume). The binder formulation is required to include at least one member of the group consisting of inorganic binder, epoxy resin, novolac resin, resole resin, polyurethane resin, alkaline phenolic resole curable with ester, melamine resin, urea-aldehyde resin, urea-phenol-aldehyde resin, furans, synthetic rubber, and/or polyester resin. The final thermoset polymer composite particles of the required size and shape are obtained by a succession of process steps such as the mixing of a binder stream with a filler particle stream, agglomerative granulation, and the curing of granulated material streams.
4. Ceramic Nanocomposite Particles
Nguyen, et al. (U.S. 20050016726) taught the development of ceramic nanocomposite particles comprising a base material (present at roughly 50% to 90% by weight) and at least one nanoparticle material (present at roughly 0.1% to 30% by weight). Optionally, a polymeric binder, an organosilane coupling agent, and/or hollow microspheres, can also be included. The base material comprises clay, bauxite, alumina, silica, or mixtures thereof. It is stated that a suitable method for forming the composite particulates from the dry ingredients is to sinter by heating at a temperature of between roughly 1000° C. and 2000° C., which is a ceramic fabrication process. Given the types of formulation ingredients used as base materials by Nguyen, et al. (U.S. 20050016726), and furthermore the fact that even if they were to incorporate a polymeric binder in an embodiment of their invention said polymeric binder would not retain its normal chemical composition and polymer chain structure when a particulate is sintered by heating it at a temperature of between 1000° C. and about 2000° C., their composite particulates consist of the nanofiller(s) dispersed in a ceramic matrix.
C. Scientific Literature
The development of thermoset polymer nanocomposites requires the consideration of a vast and multidisciplinary range of polymer and composite materials science and chemistry challenges. It is essential to convey these challenges in the context of the fundamental scientific literature.
Bicerano (2002) provides a broad overview of polymer and composite materials science that can be used as a general reference for most aspects of the following discussion. Many additional references will also be provided below, to other publications which treat specific issues in greater detail than what could be accommodated in Bicerano (2002).
1. Selected Fundamental Aspects of the Curing of Crosslinked Polymers
It is essential, first, to review some fundamental aspects of the curing of crosslinked polymers, which are applicable to such polymers regardless of their form (particulate, coating, or bulk).
The properties of crosslinked polymers prepared by standard manufacturing processes are often limited by the fact that such processes typically result in incomplete curing. For example, in an isothermal polymerization process, as the glass transition temperature (T g ) of the growing polymer network increases, it may reach the polymerization temperature while the reaction is still in progress. If this happens, then the molecular motions slow down significantly so that further curing also slows down significantly. Incomplete curing yields a polymer network that is less densely crosslinked than the theoretical limit expected from the functionalities and relative amounts of the starting reactants. For example, a mixture of monomers might contain 80% DVB by weight as a crosslinker but the final extent of crosslinking that is attained may not be much greater than what was attained with a much smaller percentage of DVB. This situation results in lower stiffness, lower strength, lower heat resistance, and lower environmental resistance than the thermoset is capable of manifesting when it is fully cured and thus maximally crosslinked.
When the results of the first scan and the second scan of S-DVB beads containing various weight fractions of DVB (w DVB ), obtained by Differential Scanning calorimetry (DSC), as reported by Bicerano, et al. (1996) (see FIG. 1 ) are compared, it becomes clear that the low performance and high cost of the “as purchased” S-DVB beads utilized by Bienvenu (U.S. Pat. No. 5,531,274) are related to incomplete curing. This incomplete curing results in the ineffective utilization of DVB as a crosslinker and thus in the incomplete development of the crosslinked network. In summary, Bicerano, et al. (1996), showed that the T g of typical “as-polymerized” S-DVB copolymers, as measured by the first DSC scan, increased only slowly with increasing w DVB , and furthermore that the rate of further increase of T g slowed down drastically for w DVB >0.08. By contrast, in the second DSC scan (performed on S-DVB specimens whose curing had been driven much closer to completion as a result of the temperature ramp that had been applied during the first scan), T g grew much more rapidly with w DVB over the entire range of up to w DVB =0.2458 that was studied. The more extensively cured samples resulting from the thermal history imposed by the first DSC scan can, thus, be considered to provide much closer approximations to the ideal theoretical limit of a “fully cured” polymer network.
2. Effects of Heat Treatment on Key Properties of Thermoset Polymers
a. Maximum Possible Use Temperature
As was illustrated by Bicerano, et al. (1996) for S-DVB copolymers with w DVB of up to 0.2458, enhancing the state of cure of a thermoset polymer network can increase T g very significantly relative to the T g of the “as-polymerized” material. In practice, the heat distortion temperature (HDT) is used most often as a practical indicator of the softening temperature of a polymer under load. As was shown by Takemori (1979), a systematic understanding of the HDT is possible through its direct correlation with the temperature dependences of the tensile (or equivalently, compressive) and shear elastic moduli. For amorphous polymers, the precipitous decrease of these elastic moduli as T g is approached from below renders the HDT well-defined, reproducible, and predictable. HDT is thus closely related to (and usually slightly lower than) T g for amorphous polymers, so that it can be increased significantly by increasing T g significantly.
The HDT decreases gradually with increasing magnitude of the load used in its measurement. For example, for general-purpose polystyrene (which has T g =100° C.), HDT=95° C. under a load of 0.46 MPa and HDT=85° C. under a load of 1.82 MPa are typical values. However, the compressive loads deep in an oil well or natural gas well are normally far higher than the standard loads (0.46 MPa and 1.82 MPa) used in measuring the HDT. Consequently, amorphous thermoset polymer particles can be expected to begin to deform significantly at a lower temperature than the HDT of the polymer measured under the standard high load of 1.82 MPa. This deformation will cause a decrease in the conductivities of liquids and gases through the propped fracture, and hence in the loss of effectiveness as a proppant, at a somewhat lower temperature than the HDT value of the polymer measured under the standard load of 1.82 MPa.
b. Mechanical Properties
As was discussed earlier, Nishimori, et. al. (JP1992-22230) used heat treatment to increase the compressive elastic modulus of their S-DVB particles (intended for use in liquid crystal display panels) significantly at room temperature (and hence far below T g ). Deformability under a compressive load is inversely proportional to the compressive elastic modulus. It is, therefore, important to consider whether one may also anticipate major benefits from heat treatment in terms of the reduction of the deformability of thermoset polymer particles intended for oil and natural gas drilling applications, when these particles are used in subterranean environments where the temperature is far below the T g of the particles. As explained below, the enhancement of curing via post-polymerization heat treatment is generally expected to have a smaller effect on the compressive elastic modulus (and hence on the proppant performance) of thermoset polymer particles when used in oil and natural gas drilling applications at temperatures far below their T g .
Nishimori, et. al. (JP1992-22230) used very large amounts of DVB (w DVB >>0.2). By contrast, much smaller amounts of DVB (w DVD ≦0.2) must be used for economic reasons in the “lower value” oil and natural gas drilling applications. The elastic moduli of a polymer at temperatures far below T g are determined primarily by deformations that are of a rather local nature and hence on a short length scale. Some enhancement of the crosslink density via further curing (when the network junctions created by the crosslinks are far away from each other to begin with) will hence not normally have nearly as large an effect on the elastic moduli as when the network junctions are very close to each other to begin with and then are brought even closer by the enhancement of curing via heat treatment. Consequently, while the compressive elastic modulus can be expected to increase significantly upon heat treatment when w DVB is very large, any such effect will normally be less pronounced at low values of w DVB . In summary, it can thus generally be expected that the enhancement of the compressive elastic modulus at temperatures far below T g will probably be small for the types of formulations that are most likely to be used in the synthesis of thermoset polymer particles for oil and natural gas drilling applications.
3. Effects of Nanoparticle Incorporation on Key Properties of Thermoset Polymers
a. Maximum Possible Use Temperature
As was pointed out by Takemori (1979), the addition of rigid fillers has a negligible effect on the HDT of amorphous polymers. However, nanocomposite materials and technologies had not yet been developed in 1979. It is, hence, important to consider, based on the data that have been gathered and the insights that have been obtained more recently, whether nanofillers may be expected to behave in a qualitatively different manner because of their geometric characteristics.
A review article by Aharoni (1998) considered this question and showed that three criteria must be considered. Here are the most relevant excerpts from his article: “When a combination of the following three conditions is fulfilled, then the glass transition temperature . . . may be increased relative to that of the same polymer in the absence of these three conditions . . . . First, very large surface area of a rigid heterogeneous material in close contact with the amorphous phase of the polymer. Such large surface areas may be obtained by having a rigid additive material extremely finely ground, preferably to nanometer length scale. Second, strong attractive interactions should exist between the heterogeneous surfaces and the polymer. In the absence of strong attractive interactions with the heterogeneous rigid surfaces, the chain segments in the boundary layer are capable of relaxing to a state approximating the bulk polymer and the T g will be identical or very slightly higher than that of the pure bulk polymer. Third, measure of motional cooperation must exist between interchain and intrachain fragments. Unlike the effects of high modulus heterogeneous additives on the averaged modulus of the system in which they are present, the elevation of T g of the polymer matrix was repeatedly shown to require not only that the polymer itself will be a high molecular weight substance, but that the additive will be finely comminuted to generate very large polymer-heterophase interfacial surface area, and, especially important, that strong attractive interactions will exist between the polymer and the foreign additive. These interactions are generally of an ionic, hydrogen bonding, or dipolar nature and, as a rule, require that the foreign additive will have surface energy higher than or at least equal to, but never lower than, that of the amorphous polymer in which it is being incorporated.”
Almost by definition, Aharoni's first condition will be satisfied for any nanofiller that has been dispersed well in the polymer matrix. Furthermore, since a thermoset polymer contains a covalently bonded three-dimensional network structure, his third condition will also be satisfied if any thermoset polymer is used as the matrix material. However, in most systems, there will not be strong attractive interactions “generally of an ionic, hydrogen bonding, or dipolar nature” between the polymer and the nanofiller, so that the second criterion will not be satisfied. It can, therefore, be concluded that, for most combinations of polymer and nanofiller, T g will not increase significantly upon incorporation of the nanofiller so that the maximum possible use temperature will not increase significantly either. There will, however, be exceptions to this general rule. Combinations of polymer and nanofiller that manifest strong attractive interactions can be found, and for such combinations both T g and the maximum possible use temperature can increase significantly upon nanofiller incorporation.
b. Mechanical Properties
It is well-established that the incorporation of rigid fillers into a polymer matrix can produce a composite material which has significantly greater stiffness (elastic modulus) and strength (stress required to induce failure) than the base polymer. It is also well-established that rigid nanofillers can generally stiffen and strengthen a polymer matrix more effectively than conventional rigid fillers of similar composition since their geometries allow them to span (or “percolate through”) a polymer specimen at much lower volume fractions than conventional fillers. This particular advantage of nanofillers over conventional fillers is well-established and a major driving force for the vast research and development effort worldwide to develop new nanocomposite products.
FIG. 2 provides an idealized schematic illustration of the effectiveness of nanofillers in terms of their ability to “percolate through” a polymer specimen even when they are present at a low volume fraction. It is important to emphasize that FIG. 2 is of a completely generic nature. It is presented merely to facilitate the understanding of nanofiller percolation, without implying that it provides an accurate depiction of the expected behavior of any particular nanofiller in any particular polymer matrix. In practice, the techniques of electron microscopy are generally used to observe the morphologies of actual embodiments of the nanocomposite concept. Specific examples of the ability of nanofillers such as carbon black and fumed silica to “percolate” at extremely low volume fractions when dispersed in polymers are provided by Zhang, et al (2001). The vast literature and trends on the dependences of percolation thresholds and packing fractions on particle shape, aggregation, and other factors, are reviewed by Bicerano, et al. (1999).
As has also been studied extensively [for example, see Okamoto, et al. (1999)] but is less widely recognized by workers in the field, the incorporation of rigid fillers of appropriate types and dimensions in the right amount (often just a very small volume fraction) can toughen a polymer in addition to stiffening it and strengthening it. “Toughening” implies a reduction in the tendency to undergo brittle fracture. If and when it is realized for proppant particles, it is an important additional benefit since it reduces the risk of the generation of “fines” during use.
4. Technical Challenges to Nanoparticle Incorporation in Thermoset Polymers
It is important to also review the many serious technical challenges that exist to the successful incorporation of nanoparticles in thermoset polymers. Appreciation of these obstacles can help workers in the field of the invention gain a better understanding of the invention. There are three major types of potential obstacles. In general, each potential obstacle will tend to become more serious with increasing nanofiller volume fraction, so that it is usually easier to incorporate a small volume fraction of a nanofiller into a polymer than it is to incorporate a larger volume fraction. This subsection is subdivided further into the following three subsections where each type of major potential obstacle will be discussed in turn.
a. Difficulty of Dispersing Nanofiller
The most common difficulty that is encountered in preparing polymer nanocomposites involves the need to disperse the nanofiller. The specific details of the source and severity of the difficulty, and of the methods that may help overcome the difficulty, differ between types of nanofillers, polymers, and fabrication processes (for example, the “in situ” synthesis of the polymer in an aqueous or organic medium containing the nanofiller, versus the addition of the nanofiller into a molten polymer). However, some important common aspects can be identified.
Most importantly, nanofiller particles of the same kind often have strong attractive interactions with each other. As a result, they tend to “clump together”; for example, preferably into agglomerates (if the nanofiller is particulate), bundles (if the nanofiller is fibrous), or stacks (if the nanofiller is discoidal). In most systems, their attractive interactions with each other are stronger than their interactions with the molecules constituting the dispersing medium, so that their dispersion is thermodynamically disfavored and hence extremely difficult.
Even in systems where the dispersion of the nanofillers is thermodynamically favored, it is often still very difficult to achieve because of the large kinetic barriers (activation energies) that must be surmounted. Consequently, nanofillers are very rarely easy to disperse in a polymer.
b. High Dispersion Viscosity
Another difficulty with the fabrication of nanocomposites is the fact that, once the nanofiller is dispersed in the appropriate medium (for example, an aqueous or organic medium containing the nanofiller for the “in situ” synthesis of the polymer, or a molten polymer into which nanofiller is added), the viscosity of the resulting dispersion may (and often does) become very high. When this happens, it can impede the successful execution of the fabrication process steps that must follow the dispersion of the nanofiller to complete the preparation of the nanocomposite.
Dispersion rheology is a vast area of both fundamental and applied research. It dates back to the 19 th century, so that there is a vast collection of data and a good fundamental understanding of the factors controlling the viscosities of dispersions. Nonetheless, it is still at the frontiers of materials science, so that major new experimental and theoretical progress is continuing to be made. In fact, the advent of nanotechnology, and the frequent emergence of high dispersion viscosity as an obstacle to the fabrication of polymer nanocomposites, have been instrumental in advancing the state of the art in this field. Bicerano, et al. (1999) have provided a comprehensive overview which can serve as a resource for workers interested in learning more about this topic.
c. Interference with Polymerization and Network Formation
An additional potential difficulty may be encountered in systems where chemical reactions are taking place in a medium containing a nanofiller. This is the possibility that the nanofiller may have an adverse effect on the chemical reactions. As can reasonably be expected, any such adverse effects can be far more severe in systems where polymerization and network formation take place simultaneously in the presence of a nanofiller than they can in systems where preformed polymer chains are crosslinked in the presence of a nanofiller. The preparation of an S-DVB nanocomposite via suspension polymerization in a medium containing a nanofiller is an example of a process where polymerization and network formation both take place in the presence of a nanofiller. On the other hand, the vulcanization of a nanofilled rubber is a process where preformed polymer chains are crosslinked in the presence of a nanofiller.
The combined consideration of the work of Lipatov, et al. (1966, 1968), Popov, et al. (1982), and Bryk, et al. (1985, 1986, 1988) helps in providing a broad perspective into the nature of the difficulties that may arise. To summarize, the presence of a filler with a high specific surface area can disrupt both polymerization and network formation in a process such as the suspension polymerization of an S-DVB copolymer nanocomposite. These outcomes can arise from the combined effects of the adsorption of initiators on the surfaces of the nanofiller particles and the interactions of the growing polymer chains with the nanofiller surfaces. Adsorption on the nanofiller surface can affect the rate of thermal decomposition of the initiator. Interactions of the growing polymer chains with the nanofiller surfaces can result both in the reduction of the mobility of growing polymer chains and in their breakage. Very strong attractions between the initiator and the nanofiller surfaces (for example, the grafting of the initiators on the nanofiller surfaces) can potentially augment all of these detrimental effects.
Taguchi, et al. (1999) provided a fascinating example of how drastically the formulation can affect the particle morphology. They described the results obtained by adding hydrophilic fine powders [nickel (Ni) of mean particle size 0.3 microns, indium oxide (In 2 O 3 ) of mean particle size 0.03 microns, and magnetite (Fe 3 O 4 ) of mean particle size 0.1, 0.3 or 0.9 microns] to the aqueous phase during the suspension polymerization of S-DVB. These particles had such a strong affinity to the aqueous phase that they did not even go inside the S-DVB beads. Instead, they remained entirely outside the beads. Consequently, the composite particles consisted of S-DVB beads whose surfaces were uniformly covered by a coating of inorganic powder. Furthermore, these S-DVB beads rapidly became smaller with increasing amount of powder at a fixed powder particle diameter, as well as with decreasing powder particle diameter (and hence increasing number concentration of powder particles) at a given powder weight fraction.
SUMMARY OF THE INVENTION
The present invention involves a novel approach towards the practical development of stiff, strong, tough, heat resistant, and environmentally resistant ultralightweight particles, for use in the construction, drilling, completion and/or fracture stimulation of oil and natural gas wells.
The disclosure is summarized below in three key aspects: (A) Compositions of Matter (thermoset nanocomposite particles that exhibit improved properties compared with prior art), (B) Processes (methods for manufacture of said compositions of matter), and (C) Applications (utilization of said compositions of matter in the construction, drilling, completion and/or fracture stimulation of oil and natural gas wells).
The disclosure describes lightweight thermoset nanocomposite particles whose properties are improved relative to prior art. The particles targeted for development include, but are not limited to, terpolymers of styrene, ethyvinylbenzene and divinylbenzene; reinforced by particulate carbon black of nanoscale dimensions. The particles exhibit any one or any combination of the following properties: enhanced stiffness, strength, heat resistance, and/or resistance to aggressive environments; and/or improved retention of high conductivity of liquids and/or gases through packings of said particles when said packings are placed in potentially aggressive environments under high compressive loads at elevated temperatures.
The disclosure also describes processes that can be used to manufacture said particles. The fabrication processes targeted for development include, but are not limited to, suspension polymerization in the presence of nanofiller, and optionally post-polymerization heat treatment with said particles still in the reactor fluid that remains after the suspension polymerization to further advance the curing of the matrix polymer.
The disclosure finally describes the use of said particles in practical applications. The targeted applications include, but are not limited to, the construction, drilling, completion and/or fracture stimulation of oil and natural gas wells; for example, as a proppant partial monolayer, a proppant pack, an integral component of a gravel pack completion, a ball bearing, a solid lubricant, a drilling mud constituent, and/or a cement additive.
A. Compositions of Matter
The compositions of matter of the present invention are thermoset polymer nanocomposite particles where one or optionally more than one type of nanofiller is intimately embedded in a polymer matrix. Any additional formulation component(s) familiar to those skilled in the art can also be used during the preparation of said particles; such as initiators, catalysts, inhibitors, dispersants, stabilizers, rheology modifiers, buffers, antioxidants, defoamers, impact modifiers, plasticizers, pigments, flame retardants, smoke retardants, or mixtures thereof. Some of the said additional component(s) may also become either partially or completely incorporated into said particles in some embodiments of the invention. However, the two required major components of said particles are a thermoset polymer matrix and at least one nanofiller. Hence this subsection will be further subdivided into three subsections. Its first subsection will teach the volume fraction of nanofiller(s) that may be used in the particles of the invention. Its second subsection will teach the types of thermoset polymers that may be used as matrix materials. Its third subsection will teach the types of nanofillers that may be incorporated.
1. Nanofiller Volume Fraction
By definition, a nanofiller possesses at least one principal axis dimension whose length is less than 0.5 microns (500 nanometers). This geometric attribute is what differentiates a nanofiller from a finely divided conventional filler, such as the fillers taught by McDaniel, et al. (U.S. Pat. No. 6,632,527) whose characteristic lengths ranged from 0.5 microns to 60 microns.
The dispersion of a nanofiller in a polymer is generally more difficult than the dispersion of a conventional filler of similar chemical composition in the same polymer. However, if dispersed properly during composite particle fabrication, nanofillers can reinforce the matrix polymer far more efficiently than conventional fillers. Consequently, while 60% to 90% by volume of filler is claimed by McDaniel, et al. (U.S. Pat. No. 6,632,527), only 0.001% to 60% by volume of nanofiller is claimed in the present invention.
Without reducing the generality of the present invention, a nanofiller volume fraction of 0.1% to 15% is used in its currently preferred embodiments.
2. Matrix Polymers
Any rigid thermoset polymer may be used as the matrix polymer of the present invention. Rigid thermoset polymers are, in general, amorphous polymers where covalent crosslinks provide a three-dimensional network. However, unlike thermoset elastomers (often referred to as “rubbers”) which also possess a three-dimensional network of covalent crosslinks, the rigid thermosets are, by definition, “stiff”. In other words, they have high elastic moduli at “room temperature” (25° C.), and often up to much higher temperatures, because their combinations of chain segment stiffness and crosslink density result in a high glass transition temperature.
Some examples of rigid thermoset polymers that can be used as matrix materials of the invention will be provided below. It is to be understood that these examples are being provided without reducing the generality of the invention, merely to facilitate the teaching of the invention.
Rigid thermoset polymers that are often used as matrix (often referred to as “binder”) materials in composites include, but are not limited to, crosslinked epoxies, epoxy vinyl esters, polyesters, phenolics, polyurethanes, and polyureas. Rigid thermoset polymers that are used less often because of their high cost despite their exceptional performance include, but are not limited to, crosslinked polyimides. These various types of polymers can, in different embodiments of the invention, be prepared by starting either from their monomers, or from oligomers that are often referred to as “prepolymers”, or from suitable mixtures of monomers and oligomers.
Many additional types of rigid thermoset polymers can also be used as matrix materials in composites, and are all within the scope of the invention. Such polymers include, but are not limited to, various families of crosslinked copolymers prepared most often by the polymerization of vinylic monomers, of vinylidene monomers, or of mixtures thereof.
The “vinyl fragment” is commonly defined as the CH 2 ═CH— fragment. So a “vinylic monomer” is a monomer of the general structure CH 2 ═CHR where R can be any one of a vast variety of molecular fragments or atoms (other than hydrogen). When a vinylic monomer CH 2 ═CHR reacts, it is incorporated into the polymer as the —CH 2 —CHR— repeat unit. Among rigid thermosets built from vinylic monomers, the crosslinked styrenics and crosslinked acrylics are especially familiar to workers in the field. Some other familiar types of vinylic monomers (among others) include the olefins, vinyl alcohols, vinyl esters, and vinyl halides.
The “vinylidene fragment” is commonly defined as the CH 2 ═CR″— fragment. So a “vinylidene monomer” is a monomer of the general structure CH 2 ═CR′R″ where R′ and R″ can each be any one of a vast variety of molecular fragments or atoms (other than hydrogen). When a vinylidene monomer CH 2 ═CR′R″ reacts, it is incorporated into a polymer as the —CH 2 —CR′R″— repeat unit. Among rigid thermosets built from vinylidene polymers, the crosslinked alkyl acrylics [such as crosslinked poly(methyl methacrylate)] are especially familiar to workers in the field. However, vinylidene monomers similar to each type of vinyl monomer (such as the styrenics, acrylates, olefins, vinyl alcohols, vinyl esters and vinyl halides, among others) can be prepared. One example of particular interest in the context of styrenic monomers is α-methyl styrene, a vinylidene-type monomer that differs from styrene (a vinyl-type monomer) by having a methyl (—CH 3 ) group serving as the R″ fragment replacing the hydrogen atom attached to the α-carbon.
Thermosets based on vinylic monomers, on vinylidene monomers, or on mixtures thereof, are typically prepared by the reaction of a mixture containing one or more non-crosslinking (difunctional) monomer and one or more crosslinking (three or higher functional) monomers. All variations in the choices of the non-crosslinking monomer(s), the crosslinking monomers(s), and their relative amounts [subject solely to the limitation that the quantity of the crosslinking monomer(s) must not be less than 1% by weight], are within the scope of the invention.
Without reducing the generality of the invention, in its currently preferred embodiments, the thermoset matrix consists of a terpolymer of styrene (non-crosslinking), ethyvinylbenzene (also non-crosslinking), and divinylbenzene (crosslinking), with the weight fraction of divinylbenzene ranging from 3% to 35% by weight of the starting monomer mixture.
3. Nanofillers
By definition, a nanofiller possesses at least one principal axis dimension whose length is less than 0.5 microns (500 nanometers). Some nanofillers possess only one principal axis dimension whose length is less than 0.5 microns. Other nanofillers possess two principal axis dimensions whose lengths are less than 0.5 microns. Yet other nanofillers possess all three principal axis dimensions whose lengths are less than 0.5 microns. Any reinforcing material possessing one nanoscale dimension, two nanoscale dimensions, or three nanoscale dimensions, can be used as the nanofiller in embodiments of the invention. Any mixture of two or more different types of such reinforcing materials can also be used as the nanofiller in embodiments of the invention.
Some examples of nanofillers that can be incorporated into the nanocomposites of the invention will be provided below. It is to be understood that these examples are being provided without reducing the generality of the invention, merely to facilitate the teaching of the invention.
Nanoscale carbon black, fumed silica and fumed alumina, such as products of these types that are currently being manufactured by the Cabot Corporation, consist of aggregates of small primary particles. See FIG. 3 for a schematic illustration of such an aggregate, and of a larger agglomerate. The aggregates may contain many very small primary particles, often arranged in a “fractal” pattern, resulting in aggregate principal axis dimensions that are also shorter than 0.5 microns. These aggregates (and not the individual primary particles that constitute them) are, in general, the smallest units of these nanofillers that are dispersed in a polymer matrix under normal fabrication conditions. The available grades of such nanofillers include variations in specific surface area, extent of branching (structure) in the aggregates, and chemical modifications intended to facilitate dispersion in different types of media (such as aqueous or organic mixtures). Some product types of such nanofillers are also provided in “fluffy” grades of lower bulk density that are easier to disperse than the base grade but less convenient to transport and store since the same weight of material occupies more volume when it is in its fluffy form. Some products grades of such nanofillers are also provided pre-dispersed in an aqueous medium.
Carbon nanotubes, carbon nanofibers, and cellulosic nanofibers constitute three other classes of nanofillers. When separated from each other by breaking up the bundles in which they are often found and then dispersed well in a polymer, they serve as fibrous reinforcing agents. In different products grades, they may have two principal axis dimensions in the nanoscale range (below 500 nanometers), or they may have all three principal axis dimensions in the nanoscale range (if they have been prepared by a process that leads to the formation of shorter nanotubes or nanofibers). Currently, carbon nanotubes constitute the most expensive nanofillers of fibrous shape. Carbon nanotubes are available in single-wall and multi-wall versions. The single-wall versions offer the highest performance, but currently do so at a much higher cost than the multi-wall versions. Nanotubes prepared from inorganic materials (such as boron nitride) are also available.
Natural and synthetic nanoclays constitute another major class of nanofiller. Nanocor and Southern Clay Products are the two leading suppliers of nanoclays at this time. When “exfoliated” (separated from each other by breaking up the stacks in which they are normally found) and dispersed well in a polymer, the nanoclays serve as discoidal (platelet-shaped) reinforcing agents. The thickness of an individual platelet is around one nanometer (0.001 microns). The lengths in the other two principal axis dimensions are much larger. They range between 100 and 500 nanometers in many product grades, thus resulting in a platelet-shaped nanofiller that has three nanoscale dimensions. They exceed 500 nanometers, and thus result in a nanofiller that has only one nanoscale dimension, in some other grades.
Many additional types of nanofillers are also available; including, but not limited to, very finely divided grades of fly ash, the polyhedral oligomeric silsesquioxanes, and clusters of different types of metals, metal alloys, and metal oxides. Since the development of nanofillers is an area that is at the frontiers of materials research and development, the future emergence of yet additional types of nanofillers that are not currently known may also be readily anticipated.
Without reducing the generality of the invention, in its currently preferred embodiments, nanoscale carbon black grades supplied by Cabot Corporation are being used as the nanofiller.
B. Processes
In most cases, the incorporation of a nanofiller into the thermoset polymer matrix will increase the compressive elastic modulus uniformly throughout the entire use temperature range (albeit usually not by exactly the same factor at each temperature), while not increasing T g significantly. The resulting nanocomposite particles will then perform better as proppants over their entire use temperature range, but without an increase in the maximum possible use temperature itself. On the other hand, if a suitable post-polymerization process step is applied to the nanocomposite particles, in many cases the curing reaction will be driven further towards completion so that T g (and hence also the maximum possible use temperature) will increase along with the increase induced by the nanofiller in the compressive elastic modulus.
Processes that may be used to enhance the degree of curing of a thermoset polymer include, but are not limited to, heat treatment (which may be combined with stirring and/or sonication to enhance its effectiveness), electron beam irradiation, and ultraviolet irradiation. We focused mainly on the use of heat treatment in order to increase the T g of the thermoset matrix polymer, to make it possible to use nanofiller incorporation and post-polymerization heat treatment as complementary methods, to improve the performance characteristics of the particles even further by combining the anticipated main benefits of each method. FIG. 4 provides an idealized schematic illustration of the benefits of implementing these methods and concepts.
The processes that may be used for the fabrication of the thermoset nanocomposite particles of the invention have at least one, and optionally two, major step(s). The required step is the formation of said particles by means of a process that allows the intimate embedment of the nanofiller in the polymer matrix. The optional step is the use of an appropriate postcuring method to advance the curing reaction of the thermoset matrix and to thus obtain a polymer network that approaches the “fully cured” limit. Consequently, this subsection will be further subdivided into two subsections, dealing with polymerization and with postcure respectively.
1. Polymerization and Network Formation in Presence of Nanofiller
Any method for the fabrication of thermoset composite particles known to those skilled in the art may be used to prepare embodiments of the thermoset nanocomposite particles of the invention. Without reducing the generality of the invention, some such methods will be discussed below to facilitate the teaching of the invention.
The most practical methods for the formation of composites containing rigid thermoset matrix polymers involve the dispersion of the filler in a liquid (aqueous or organic) medium followed by the “in situ” formation of the crosslinked polymer network around the filler. This is in contrast with the formation of thermoplastic composites where melt blending can instead also be used to mix a filler with a fully formed molten polymer. It is also in contrast with the vulcanization of a filled rubber, where preformed polymer chains are crosslinked in the presence of a filler.
The implementation of such methods in the preparation of thermoset nanocomposite particles is usually more difficult to accomplish in practice than their implementation in the preparation of composite particles containing conventional fillers. As discussed earlier, common challenges involve difficulties in dispersing the nanofiller, high nanofiller dispersion viscosity, and possible interferences of the nanofiller with polymerization and network formation. Nonetheless, these challenges can all be surmounted by making judicious choices of the formulation ingredients and their proportions, and then also determining and using the optimum processing conditions.
McDaniel, et al. (U.S. Pat. No. 6,632,527) prepared polymer composite particles with thermoset matrix formulations. Their formulations were based on at least one member of the group consisting of inorganic binder, epoxy resin, novolac resin, resole resin, polyurethane resin, alkaline phenolic resole curable with ester, melamine resin, urea-aldehyde resin, urea-phenol-aldehyde resin, furans, synthetic rubber, and/or polyester resin. They taught the incorporation of conventional filler particles, whose sizes ranged from 0.5 microns to 60 microns, at 60% to 90% by volume. Their fabrication processes differed in details depending on the specific formulation, but in general included steps involving the mixing of a binder stream with a filler particle stream, agglomerative granulation, and the curing of a granulated material stream to obtain thermoset composite particles of the required size and shape. These processes can also be used to prepare the thermoset nanocomposite particles of the present invention, where nanofillers possessing at least one principal axis dimension shorter than 0.5 microns are used at a volume fraction that does not exceed 60% and that is far smaller than 60% in the currently preferred embodiments. The processes of McDaniel, et al. (U.S. Pat. No. 6,632,527) are, hence, incorporated herein by reference.
As was discussed earlier, many additional types of thermoset polymers can also be used as the matrix materials in composites. Examples include crosslinked polymers prepared from various styrenic, acrylic or olefinic monomers (or mixtures thereof). It is more convenient to prepare particles of such thermoset polymers (as well as of their composites and nanocomposites) by using methods that can produce said particles directly in the desired (usually substantially spherical) shape during polymerization from the starting monomers. (While it is a goal of this invention to create spherical particles, it is understood that it is exceedingly difficult as well as unnecessary to obtain perfectly spherical particles. Therefore, particles with minor deviations from a perfectly spherical shape are considered perfectly spherical for the purposes of this disclosure.) Suspension (droplet) polymerization is the most powerful method available for accomplishing this objective. Two main approaches exist to suspension polymerization. The first approach is isothermal polymerization which is the conventional approach that has been practiced for many decades. The second approach is “rapid rate polymerization” as taught by Albright (U.S. Pat. No. 6,248,838) which is incorporated herein by reference. Without reducing the generality of the invention, suspension polymerization as performed via the rapid rate polymerization approach taught by Albright (U.S. Pat. No. 6,248,838) is used in the current preferred embodiments of the invention.
2. Optional Post-Polymerization Advancement of Curing and Network Formation
As was discussed earlier and illustrated in FIG. 1 with the data of Bicerano, et al. (1996), typical processes for the synthesis of thermoset polymers may result in the formation of incompletely cured networks, and may hence produce thermosets with lower glass transition temperatures and lower maximum use temperatures than is achievable with the chosen formulation of reactants. Furthermore, difficulties related to incomplete cure may sometimes be exacerbated in thermoset nanocomposites because of the possibility of interference by the nanofiller in polymerization and network formation. Consequently, the use of an optional post-polymerization process step (or a sequence of such process steps) to advance the curing of the thermoset matrix of a particle of the invention is an aspect of the invention. Suitable methods include, but are not limited to, heat treatment (also known as “annealing”), electron beam irradiation, and ultraviolet irradiation.
Post-polymerization heat treatment is a very powerful method for improving the properties and performance of S-DVB copolymers (as well as of many other types of thermoset polymers) by helping the polymer network approach its “full cure” limit. It is, in fact, the most easily implementable method for advancing the state of cure of S-DVB copolymer particles. However, it is important to recognize that another post-polymerization method (such as electron beam irradiation or ultraviolet irradiation) may be the most readily implementable one for advancing the state of cure of some other type of thermoset polymer. The use of any suitable method for advancing the curing of the thermoset polymer that is being used as the matrix of a nanocomposite of the present invention after polymerization is within the scope of the invention.
Without reducing the generality of the invention, among the suitable methods, heat treatment is used as the optional post-polymerization method to enhance the curing of the thermoset polymer matrix in the preferred embodiments of the invention. Any desired thermal history can be optionally imposed; such as, but not limited to, isothermal annealing at a fixed temperature; nonisothermal heat exposure with either a continuous or a step function temperature ramp; or any combination of continuous temperature ramps, step function temperature ramps, and/or periods of isothermal annealing at fixed temperatures. In practice, while there is great flexibility in the choice of a thermal history, it must be selected carefully to drive the curing reaction to the maximum final extent possible without inducing unacceptable levels of thermal degradation.
Any significant increase in T g by means of improved curing will translate directly into an increase of comparable magnitude in the practical softening temperature of the polymer particles under the compressive load imposed by the subterranean environment. Consequently, a significant increase of the maximum possible use temperature of the thermoset polymer particles is the most common benefit of advancing the extent of curing by heat treatment.
A practical concern during the imposition of optional heat treatment is related to the amount of material that is being subjected to heat treatment simultaneously. For example, very small amounts of material can be heat treated uniformly and effectively in vacuum; or in any inert (non-oxidizing) gaseous medium, such as, but not limited to, a helium or nitrogen “blanket”. However, heat transfer in a gaseous medium is not nearly as effective as heat transfer in an appropriately selected liquid medium. Consequently, during the optional heat treatment of large quantities of the particles of the invention (such as, but not limited to, the output of a run of a commercial-scale batch production reactor), it is usually necessary to use a liquid medium, and furthermore also to stir the particles vigorously to ensure that the heat treatment is applied as uniformly as possible. Serious quality problems may arise if heat treatment is not applied uniformly; for example, as a result of the particles that were initially near the heat source being overexposed to heat and thus damaged, while the particles that were initially far away from the heat source are not exposed to sufficient heat and are thus not sufficiently postcured.
If a gaseous or a liquid heat treatment medium is used, said medium may contain, without limitation, one or a mixture of any number of types of constituents of different molecular structure. However, in practice, said medium must be selected carefully to ensure that its molecules will not react with the crosslinked polymer particles to a sufficient extent to cause significant oxidative and/or other types of chemical degradation. In this context, it must also be kept in mind that many types of molecules which do not react with a polymer at ambient temperature may react strongly with said polymer at elevated temperatures. The most relevant example in the present context is that oxygen itself does not react with S-DVB copolymers at room temperature, while it causes severe oxidative degradation of S-DVB copolymers at elevated temperatures where there would not be much thermal degradation in its absence.
Furthermore, in considering the choice of medium for heat treatment, it is also important to keep in mind that organic molecules can swell organic polymers, potentially causing “plasticization” and thus resulting in undesirable reductions of T g and of the maximum possible use temperature. The magnitude of any such detrimental effect increases with increasing similarity between the chemical structures of the molecules in the heat treatment medium and of the polymer chains. For example, a heat transfer fluid consisting of aromatic molecules will tend to swell a styrene-divinylbenzene copolymer particle, as well as tending to swell a nanocomposite particle containing such a copolymer as its matrix. The magnitude of this detrimental effect will increase with decreasing relative amount of the crosslinking monomer (divinylbenzene) used in the formulation. For example, a styrene-divinylbenzene copolymer prepared from a formulation containing only 3% by weight of divinylbenzene will be far more susceptible to swelling in an aromatic liquid than a copolymer prepared from a formulation containing 35% divinylbenzene.
Various means known to those skilled in the art, including but not limited to the stirring and/or the sonication of an assembly of particles being subjected to heat treatment, may also be optionally used to enhance further the effectiveness of the optional heat treatment. The rate of thermal equilibration under a given thermal gradient, possibly combined with the application of any such additional means, depends on many factors. These factors include, but are not limited to, the amount of polymer particles being heat treated simultaneously, the shapes and certain key physical and transport properties of these particles, the shape of the vessel being used for heat treatment, the medium being used for heat treatment, whether external disturbances (such as stirring and/or sonication) are being used to accelerate equilibration, and the details of the heat exposure schedule. Simulations based on the solution of the heat transfer equations may hence be used optionally to optimize the heat treatment equipment and/or the heat exposure schedule.
Without reducing the generality of the invention, in its currently preferred embodiments, the thermoset nanocomposite particles are left in the reactor fluid that remains after suspension polymerization if optional heat treatment is to be used. Said reactor fluid thus serves as the heat treatment medium; and simulations based on the solution of the heat transfer equations are used to optimize the heat exposure schedule. This embodiment of the optional heat treatment works especially well (without adverse effects such as degradation and/or swelling) in enhancing the curing of the thermoset matrix polymer in the currently preferred compositions of matter of the invention. Said preferred compositions of matter consist of terpolymers of styrene, ethylvinylbenzene and divinylbenzene. Since the reactor fluid that remains after the completion of suspension polymerization is aqueous while these terpolymers are very hydrophobic, the reactor fluid serves as an excellent heat transfer medium which does not swell the particles. The use of the reactor fluid as the medium for the optional heat treatment also has the advantage of simplicity since the particles would have needed to be removed from the reactor fluid and placed in another fluid as an extra step before heat treatment if an alternative fluid had been required.
It is, however, important to reemphasize the much broader scope of the invention and the fact that the particular currently preferred embodiments summarized above constitute just a few among the vast variety of possible qualitatively different classes of embodiments. For example, if a hydrophilic thermoset polymer particle were to be developed as an alternative preferred embodiment of the invention in future work, it would obviously not be possible to subject such an embodiment to heat treatment in an aqueous slurry, and a hydrophobic heat transfer fluid would work better for its optional heat treatment.
C. Applications
The obvious practical advantages [see a review by Edgeman (2004)] of developing the ability to use lightweight particles that possess almost neutral buoyancy relative to water have stimulated a considerable amount of work over the years. However, progress in this field of invention has been very slow as a result of the many technical challenges that exist to the successful development of cost-effective lightweight particles that possess sufficient stiffness, strength and heat resistance. The present invention has resulted in the development of such stiff, strong, tough, heat resistant, and environmentally resistant ultralightweight particles; and also of cost-effective processes for the fabrication of said particles. As a result, a broad range of potential applications can be envisioned and are being pursued for the use of the thermoset polymer nanocomposite particles of the invention in the construction, drilling, completion and/or fracture stimulation of oil and natural gas wells. Without reducing the generality of the invention, in its currently preferred embodiments, the specific applications that are already being evaluated are as a proppant partial monolayer, a proppant pack, an integral component of a gravel pack completion, a ball bearing, a solid lubricant, a drilling mud constituent, and/or a cement additive.
It is also important to note that the current selection of preferred embodiments of the invention has resulted from our focus on application opportunities in the construction, drilling, completion and/or fracture stimulation of oil and natural gas wells. Many other applications can also be envisioned for the compositions of matter that fall within the scope of thermoset nanocomposite particles of the invention. For example, one such application is described by Nishimori, et. al. (JP1992-22230), who developed heat-treated S-DVB copolymer (but not composite) particles prepared from formulations containing very high DVB weight fractions for use in liquid crystal display panels. Alternative embodiments of the thermoset copolymer nanocomposite particles of the present invention, tailored towards the performance needs of that application and benefiting from its less restrictive cost limitations, could potentially also be used in liquid crystal display panels. Considered from this perspective, it can be seen readily that the potential applications of the particles of the invention extend far beyond their uses by the oil and natural gas industry.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are included to provide further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
FIG. 1 shows the effects of advancing the curing reaction in a series of isothermally polymerized styrene-divinylbenzene (S-DVB) copolymers containing different DVB weight fractions via heat treatment. The results of scans of S-DVB beads containing various weight fractions of DVB (w DVB ), obtained by Differential Scanning calorimetry (DSC), and reported by Bicerano, et al. (1996), are compared. It is seen that the T g of typical “as-polymerized” S-DVB copolymers, as measured by the first DSC scan, increased only slowly with increasing w DVB , and furthermore that the rate of further increase of T g slowed down drastically for w DVB >0.08. By contrast, in the second DSC scan (performed on S-DVB specimens whose curing had been driven much closer to completion as a result of the temperature ramp that had been applied during the first scan), T g grew much more rapidly with w DVB over the entire range of up to w DVB =0.2458 that was studied.
FIG. 2 provides an idealized, generic and schematic two-dimensional illustration of how a very small volume fraction of a nanofiller may be able to “span” and thus “bridge through” a vast amount of space, thus potentially enhancing the load bearing ability of the matrix polymer significantly at much smaller volume fractions than possible with conventional fillers.
FIG. 3 illustrates the “aggregates” in which the “primary particles” of nanofillers such as nanoscale carbon black, fumed silica and fumed alumina commonly occur. Such aggregates may contain many very small primary particles, often arranged in a “fractal” pattern, resulting in aggregate principal axis dimensions that are also shorter than 0.5 microns. These aggregates (and not the individual primary particles that constitute them) are, usually, the smallest units of such nanofillers that are dispersed in a polymer matrix under normal fabrication conditions, when the forces holding the aggregates together in the much larger “agglomerates” are overcome successfully. This illustration was reproduced from the product literature of Cabot Corporation.
FIG. 4 provides an idealized schematic illustration, in the context of the resistance of thermoset polymer particles to compression as a function of the temperature, of the most common benefits of using the methods of the present invention. In most cases, the densification of the crosslinked polymer network via post-polymerization heat treatment will have the main benefit of increasing the softening (and hence also the maximum possible use) temperature, along with improving the environmental resistance. On the other hand, in most cases, nanofiller incorporation will have the main benefits of increasing the stiffness and strength. The use of nanofiller incorporation and post-polymerization heat treatment together, as complementary methods, will thus often be able to provide all (or at least most) of these benefits simultaneously.
FIG. 5 provides a process flow diagram depicting the preparation of the example. It contains four major blocks; depicting the preparation of the aqueous phase (Block A), the preparation of the organic phase (Block B), the mixing of these two phases followed by suspension polymerization (Block C), and the further process steps used after polymerization to obtain the “as-polymerized” and “heat-treated” samples of particles (Block D).
FIG. 6 shows the variation of the temperature with time during polymerization.
FIG. 7 shows the results of the measurement of the glass transition temperatures (T g ) of the three heat-treated thermoset nanocomposite samples via differential scanning calorimetry (DSC). The samples have identical compositions. They differ only as a result of the use of different heat treatment conditions after polymerization. T g was defined as the temperature at which the curve showing the heat flow as a function of the temperature goes through its inflection point.
FIG. 8 provides a schematic illustration of the configuration of the conductivity cell.
FIG. 9 shows the measured liquid conductivity of a packing of particles of 14/16 U.S. mesh size (diameters ranging from 1.19 mm to 1.41 mm) from Sample 40m200C, at a coverage of 0.02 lb/ft 2 , under a closure stress of 4000 psi at a temperature of 190° F., as a function of time.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Because the invention will be understood better after further discussion of its currently preferred embodiments, further discussion of said embodiments will now be provided. It is understood that said discussion is being provided without reducing the generality of the invention, since persons skilled in the art can readily imagine many additional embodiments that fall within the full scope of the invention as taught in the SUMMARY OF THE INVENTION section.
A. Nature, Attributes and Applications of Currently Preferred Embodiments
The currently preferred embodiments of the invention are lightweight thermoset nanocomposite particles possessing high stiffness, strength, temperature resistance, and resistance to aggressive environments. These attributes, occurring in combination, make said particles especially suitable for use in many challenging applications in the construction, drilling, completion and/or fracture stimulation of oil and natural gas wells. Said applications include the use of said particles as a proppant partial monolayer, a proppant pack, an integral component of a gravel pack completion, a ball bearing, a solid lubricant, a drilling mud constituent, and/or a cement additive.
B. Thermoset Polymer Matrix
1. Constituents
The thermoset matrix in said particles consists of a terpolymer of styrene (S, non-crosslinking), ethyvinylbenzene (EVB, also non-crosslinking), and divinylbenzene (DVB, crosslinking). The preference for such a terpolymer instead of a copolymer of S and DVB is a result of economic considerations. To summarize, DVB comes mixed with EVB in the standard product grades of DVB, and the cost of DVB increases rapidly with increasing purity in special grades of DVB. EVB is a non-crosslinking (difunctional) styrenic monomer. Its incorporation into the thermoset matrix does not result in any significant changes in the properties of the thermoset matrix or of nanocomposites containing said matrix, compared with the use of S as the sole non-crosslinking monomer. Consequently, it is far more cost-effective to use a standard (rather than purified) grade of DVB, thus resulting in a terpolymer where some of the repeat units originate from EVB.
2. Proportions
The amount of DVB in said terpolymer ranges from 3% to 35% by weight of the starting mixture of the three reactive monomers (S, EVB and DVB) because different applications require different maximum possible use temperatures. Even when purchased in standard product grades where it is mixed with a large weight fraction of EVB, DVB is more expensive than S. It is, hence, useful to develop different product grades where the maximum possible use temperature increases with increasing weight fraction of DVB. Customers can then purchase the grades of said particles that meet their specific application needs as cost-effectively as possible.
C. Nanofiller
1. Constituents
The Monarch™ 280 product grade of nanoscale carbon black supplied by Cabot Corporation is being used as the nanofiller in said particles. The reason is that it has a relatively low specific surface area, high structure, and a “fluffy” product form; rendering it especially easy to disperse.
2. Proportions
The use of too low a volume fraction of carbon black results in ineffective reinforcement. The use of too high a volume fraction of carbon black may result in difficulties in dispersing the nanofiller, dispersion viscosities that are too high to allow further processing with available equipment, and detrimental interference in polymerization and network formation. The amount of carbon black ranges from 0.1% to 15% by volume of said particles because different applications require different levels of reinforcement. Carbon black is more expensive than the monomers (S, EVB and DVB) currently being used in the synthesis of the thermoset matrix. It is, therefore, useful to develop different product grades where the extent of reinforcement increases with increasing volume fraction of carbon black. Customers can then purchase the grades of said particles that meet their specific application needs as cost-effectively as possible.
D. Polymerization
Suspension polymerization is performed via rapid rate polymerization, as taught by Albright (U.S. Pat. No. 6,248,838) which is incorporated herein by reference, for the fabrication of said particles. Rapid rate polymerization has the advantage, relative to conventional isothermal polymerization, of producing more physical entanglements in thermoset polymers (in addition to the covalent crosslinks). Suspension polymerization involves the preparation of an the aqueous phase and an organic phase prior to the commencement of the polymerization process. The Monarch™ 280 carbon black particles are dispersed in the organic phase prior to polymerization. The most important additional formulation component (besides the reactive monomers and the nanofiller particles) that is used during polymerization is the initiator. The initiator may consist of one type molecule or a mixture of two or more types of molecules that have the ability to function as initiators. Additional formulation components, such as catalysts, inhibitors, dispersants, stabilizers, rheology modifiers, buffers, antioxidants, defoamers, impact modifiers, plasticizers, pigments, flame retardants, smoke retardants, or mixtures thereof, may also be used when needed. Some of the additional formulation component(s) may become either partially or completely incorporated into the particles in some embodiments of the invention.
E. Attainable Particle Sizes
Suspension polymerization produces substantially spherical polymer particles. (While it is a goal of this invention to create spherical particles, it is understood that it is exceedingly difficult as well as unnecessary to obtain perfectly spherical particles. Therefore, particles with minor deviations from a perfectly spherical shape are considered perfectly spherical for the purposes of this disclosure.) Said particles can be varied in size by means of a number of mechanical and/or chemical methods that are well-known and well-practiced in the art of suspension polymerization. Particle diameters attainable by such means range from submicron values up to several millimeters. Hence said particles may be selectively manufactured over the entire range of sizes that are of present interest and/or that may be of future interest for applications in the oil and natural gas industry.
F. Optional Further Selection of Particles by Size
Optionally, after the completion of suspension polymerization, said particles can be separated into fractions having narrower diameter ranges by means of methods (such as, but not limited to, sieving techniques) that are well-known and well-practiced in the art of particle separations. Said narrower diameter ranges include, but are not limited to, nearly monodisperse distributions. Optionally, assemblies of particles possessing bimodal or other types of special distributions, as well as assemblies of particles whose diameter distributions follow statistical distributions such as gaussian or log-normal, can also be prepared.
The optional preparation of assemblies of particles having diameter distributions of interest from any given “as polymerized” assembly of particles can be performed before or after any optional heat treatment of said particles. Without reducing the generality of the invention, in the currently most preferred embodiments of the invention, any optional preparation of assemblies of particles having diameter distributions of interest from the product of a run of the pilot plant or production plant reactor is performed after the completion of any optional heat treatment of said particles.
The particle diameters of current practical interest for various uses in the construction, drilling, completion and/or fracture stimulation of oil and natural gas wells range from 0.1 to 4 millimeters. The specific diameter distribution that would be most effective under given circumstances depends on the details of the subterranean environment in addition to depending on the type of application. The diameter distribution that would be most effective under given circumstances may be narrow or broad, monomodal or bimodal, and may also have other special features (such as following a certain statistical distribution function) depending on both the details of the subterranean environment and the type of application.
G. Optional Heat Treatment
Said particles are left in the reactor fluid that remains after suspension polymerization if optional heat treatment is to be used. Said reactor fluid thus serves as the heat treatment medium. This approach works especially well (without adverse effects such as degradation and/or swelling) in enhancing the curing of said particles where the polymer matrix consists of a terpolymer of S, EVB and DVB. Since the reactor fluid that remains after the completion of suspension polymerization is aqueous while these terpolymers are very hydrophobic, the reactor fluid serves as an excellent heat transfer medium which does not swell the particles. The use of the reactor fluid as the medium for the optional heat treatment also has the advantage of simplicity since the particles would have needed to be removed from the reactor fluid and placed in another fluid as an extra step before heat treatment if an alternative fluid had been required.
Detailed and realistic simulations based on the solution of the heat transfer equations are often used optionally to optimize the heat exposure schedule if optional heat treatment is to be used. It has been found that such simulations become increasingly useful with increasing quantity of particles that will be heat treated simultaneously. The reason is the finite rate of heat transfer. Said finite rate results in slower and more difficult equilibration with increasing quantity of particles and hence makes it especially important to be able to predict how to cure most of the particles further uniformly and sufficiently without overexposing many of the particles to heat.
EXAMPLE
The currently preferred embodiments of the invention will be understood better in the context of a specific example. It is to be understood that said example is being provided without reducing the generality of the invention. Persons skilled in the art can readily imagine many additional examples that fall within the scope of the currently preferred embodiments as taught in the DETAILED DESCRIPTION OF THE INVENTION section. Persons skilled in the art can, furthermore, also readily imagine many alternative embodiments that fall within the full scope of the invention as taught in the SUMMARY OF THE INVENTION section.
A. Summary
The thermoset matrix was prepared from a formulation containing 10% DVB by weight of the starting monomer mixture. The DVB had been purchased as a mixture where only 63% by weight consisted of DVB. The actual polymerizable monomer mixture used in preparing the thermoset matrix consisted of roughly 84.365% S, 5.635% EVB and 10% DVB by weight.
Carbon black (Monarch 280) was incorporated into the particles, at 0.5% by weight, via dispersion in the organic phase of the formulation prior to polymerization. Since the specific gravity of carbon black is roughly 1.8 while the specific gravity of the polymer is roughly 1.04, the amount of carbon black incorporated into the particles was roughly 0.29% by volume.
Suspension polymerization was performed in a pilot plant reactor, via rapid rate polymerization as taught by Albright (U.S. Pat. No. 6,248,838) which is incorporated herein by reference. In applying this method, the “dual initiator” approach, wherein two initiators with different thermal stabilities are used to help drive the reaction of DVB further towards completion, was utilized.
The required tests only require a small quantity of particles. The use of a liquid medium (such as the reactor fluid) is unnecessary for the heat treatment of a small sample. Roughly 500 grams of particles were hence removed from the slurry, washed, spread very thin on a tray, heat-treated for ten minutes at 200° C. in an oven in an inert gas environment, and submitted for testing.
The glass transition temperature of these “heat-treated” particles, and the liquid conductivity of packings thereof, were then measured by independent testing laboratories (Impact Analytical in Midland, Mich., and FracTech Laboratories in Surrey, United Kingdom, respectively).
FIG. 5 provides a process flow diagram depicting the preparation of the example. It contains four major blocks; depicting the preparation of the aqueous phase (Block A), the preparation of the organic phase (Block B), the mixing of these two phases followed by suspension polymerization (Block C), and the further process steps used after polymerization to obtain the “as-polymerized” and “heat-treated” samples of particles (Block D).
The following subsections will provide further details on the formulation, preparation and testing of this working example, to enable persons who are skilled in the art to reproduce the example.
B. Formulation
An aqueous phase and an organic phase must be prepared prior to suspension polymerization. The aqueous phase and the organic phase, which were prepared in separate beakers and then used in the suspension polymerization of the particles of this example, are described below.
1. Aqueous Phase
The aqueous phase used in the suspension polymerization of the particles of this example, as well as the procedure used to prepare said aqueous phase, are summarized in TABLE 1. TABLE 1. The aqueous phase was prepared by adding Natrosol Plus 330 and gelatin (Bloom strength 250) to water, heating to 65° C. to disperse the Natrosol Plus 330 and the gelatin in the water, and then adding sodium nitrite and sodium carbonate. Its composition is listed below.
INGREDIENT
WEIGHT (g)
%
Water
1493.04
98.55
Natrosol Plus 330 (hydroxyethylcellulose)
7.03
0.46
Gelatin (Bloom strength 250)
3.51
0.23
Sodium Nitrite (NaNO 2 )
4.39
0.29
Sodium Carbonate (Na 2 CO 3 )
7.03
0.46
Total Weight in Grams
1515.00
100.00
2. Organic Phase
The organic phase used in the suspension polymerization of the particles of this example, as well as the procedure used to prepare said organic phase, are summarized in TABLE 2. Note that the nanofiller (carbon black) was added to the organic phase in this particular example. TABLE 2. The organic phase was prepared by placing the monomers, benzoyl peroxide (an initiator), t-amyl peroxy(2-ethylhexyl)monocarbonate (TAEC, also an initiator), Disperbyk-161 and carbon black together and agitating the resulting mixture for at least 15 minutes to disperse carbon black in the mixture. Its composition is listed below. After taking the other components of the 63% DVB mixture into account, the polymerizable monomer mixture actually consisted of roughly 84.365% S, 5.635% EVB and 10% DVB by weight. The total polymerizable monomer weight of was 1356.7 grams. The resulting thermoset nanocomposite particles thus contained [100×6.8/(1356.7+6.8)]=0.5% by weight of carbon black.
INGREDIENT WEIGHT (g) % Styrene (pure) 1144.58 82.67 Divinylbenzene (63% DVB, 98.5% 215.35 15.56 polymerizable monomers) Carbon black (Monarch 280) 6.8 0.49 Benzoyl peroxide 13.567 0.98 t-Amyl peroxy(2- 4.07 0.29 ethylhexyl)monocarbonate (TAEC) Disperbyk-161 0.068 0.0049 Total Weight in Grams 1384.435 100
C. Preparation of Particles from Formulation
Once the formulation is prepared, its aqueous and organic phases are mixed, polymerization is performed, and “as-polymerized” and “heat-treated” particles are obtained, as described below.
1. Mixing
The aqueous phase was added to the reactor at 65° C. The organic phase was then introduced over roughly 5 minutes with agitation at the rate of 90 rpm. The mixture was held at 65° C. with stirring at the rate of 90 rpm for at least 15 minutes or until proper dispersion had taken place as manifested by the equilibration of the droplet size distribution.
2. Polymerization
The temperature was ramped from 65° C. to 78° C. in 10 minutes. It was then further ramped from 78° C. to 90° C. at the rate of 0.1° C. per minute in 120 minutes. It was then held at 90° C. for 90 minutes to provide most of the conversion of monomer to polymer, with benzoyl peroxide (half life of one hour at 92° C.) as the effective initiator. It was then further ramped to 115° C. in 30 minutes and held at 115° C. for 180 minutes to advance the curing with TAEC (half life of one hour at 117° C.) as the effective initiator. The particles were thus obtained in an aqueous slurry. FIG. 6 shows the variation of the temperature with time during polymerization.
3. “As-Polymerized” Particles
The aqueous slurry was cooled to 40° C. It was then poured onto a 60 mesh (250 micron) sieve to remove the aqueous reactor fluid as well as any undesirable small particles that may have formed during polymerization. The “as-polymerized” beads of larger than 250 micron diameter obtained in this manner were then washed three times with warm (40° C. to 50° C.) water
4. “Heat-Treated” Particles
Three sets of “heat-treated” particles, which were imposed to different thermal histories during the post-polymerization heat treatment, were prepared from the “as-polymerized” particles. In preparing each of these heat-treated samples, washed beads were removed from the 60 mesh sieve, spread very thin on a tray, placed in an oven under an inert gas (nitrogen) blanket, and subjected to the desired heat exposure. Sample 10m200C was prepared with isothermal annealing for 10 minutes at 200° C. Sample 40m200C was prepared with isothermal annealing for 40 minutes at 200° C. to explore the effects of extending the duration of isothermal annealing at 200° C. Sample 10m220C was prepared with isothermal annealing for 10 minutes at 220° C. to explore the effects of increasing the temperature at which isothermal annealing is performed for a duration of 10 minutes. In each case, the oven was heated to 100° C., the sample was placed in the oven and covered with a nitrogen blanket; and the temperature was then increased to its target value at a rate of 2° C. per minute, held at the target temperature for the desired length of time, and finally allowed to cool to room temperature by turning off the heat in the oven. Some particles from each sample were sent to Impact Analytical for the measurement of T g via DSC.
Particles of 14/16 U.S. mesh size were isolated from Sample 40m200C by some additional sieving. This is a very narrow size distribution, with the particle diameters ranging from 1.19 mm to 1.41 mm. This nearly monodisperse assembly of particles was sent to FracTech Laboratories for the measurement of the liquid conductivity of its packings.
D. Reference Sample
A Reference Sample was also prepared, to provide a baseline against which the data obtained for the particles of the invention can be compared.
The formulation and the fabrication process conditions used in the preparation of the Reference Sample differed from those used in the preparation of the examples of the particles of the invention in two key aspects. Firstly, carbon black was not used in the preparation of the Reference Sample. Secondly, post-polymerization heat treatment was not performed in the preparation of the Reference Sample. Consequently, while the examples of the particles of the invention consisted of a heat-treated and carbon black reinforced thermoset nanocomposite, the particles of the Reference Sample consisted of an unfilled and as-polymerized thermoset polymer that has the same composition as the thermoset matrix of the particles of the invention.
Some particles from the Reference Sample were sent to Impact Analytical for the measurement of T g via DSC. In addition, particles of 14/16 U.S. mesh size were isolated from the Reference Sample by sieving and sent to FracTech Laboratories for the measurement of the liquid conductivity of their packings.
E. Differential Scanning Calorimetry
DSC experiments (ASTM E1356-03) were carried out by using a TA Instruments Q100 DSC with nitrogen flow of 50 mL/min through the sample compartment. Roughly nine milligrams of each sample were weighed into an aluminum sample pan, the lid was crimped onto the pan, and the sample was then placed in the DSC instrument. The sample was then scanned from 5° C. to 225° C. at a rate of 10° C. per minute. The instrument calibration was checked with NIST SRM 2232 indium. Data analysis was performed by using the TA Universal Analysis V4.1 software.
DSC data for the heat-treated samples are shown in FIG. 7 . T g was defined as the temperature at which the curve for the heat flow as a function of the temperature went through its inflection point. The results are summarized in TABLE 3. It is seen that the extent of polymer curing in Sample 10m220C is comparable to that in Sample 40m200C, and that the extent of polymer curing in both of these samples has advanced significantly further than that in Sample 10m200C whose T g was only slightly higher than that of the Reference Sample. TABLE 3. Glass transitions temperatures (T g ) of the three heat-treated samples and of the Reference Sample, in ° C. In addition to being an “as-polymerized” (rather than a heat-treated) sample, the Reference Sample also differs from the other three samples since it is an unfilled sample while the other three samples each contain 0.5% by weight carbon black.
ISOTHERMAL HEAT SAMPLE TREATMENT IN NITROGEN T g (° C.) Reference Sample None 117.17 10m200C For 10 minutes at a temperature of 200° C. 122.18 10m220C For 10 minutes at a temperature of 220° C. 131.13 40m200C For 40 minutes at a temperature of 200° C. 131.41
F. Liquid Conductivity Measurement
A fracture conductivity cell allows a particle packing to be subjected to desired combinations of compressive stress (simulating the closure stress on a fracture in a downhole environment) and elevated temperature over extended durations, while the flow of a fluid through the packing is measured. The flow capacity can be determined from differential pressure measurements. The experimental setup is illustrated in FIG. 8 .
Ohio sandstone, which has roughly a compressive elastic modulus of 4 Mpsi and a permeability of 0.1 mD, was used as a representative type of outcrop rock. Wafers of thickness 9.5 mm were machined to 0.05 mm precision and one rock was placed in the cell. The sample was split to ensure that a representative sample is achieved in terms of its particle size distribution and then weighed. The particles were placed in the cell and leveled. The top rock was then inserted. Heated steel platens were used to provide the correct temperature simulation for the test. A thermocouple inserted in the middle port of the cell wall recorded the temperature of the pack. A servo-controlled loading ram provided the closure stress. The conductivity of deoxygenated silica-saturated 2% potassium chloride (KCl) brine of pH 7 through the pack was measured.
The conductivity measurements were performed by using the following procedure:
1. A 70 mbar full range differential pressure transducer was activated by closing the bypass valve and opening the low pressure line valve. 2. When the differential pressure appeared to be stable, a tared volumetric cylinder was placed at the outlet and a stopwatch was started. 3. The output of the differential pressure transducer was fed to a data logger 5-digit resolution multimeter which logs the output every second during the measurement. 4. Fluid was collected for 5 to 10 minutes, after which time the flow rate was determined by weighing the collected effluent. The mean value of the differential pressure was retrieved from the multimeter together with the peak high and low values. If the difference between the high and low values was greater than the 5% of the mean, the data point was disregarded. 5. The temperature was recorded from the inline thermocouple at the start and at the end of the flow test period. If the temperature variation was greater than 0.5° C., the test was disregarded. The viscosity of the fluid was obtained from the measured temperature by using viscosity tables. No pressure correction is made for brine at 100 psi. The density of brine at elevated temperature was obtained from these tables. 6. At least three permeability determinations were made at each stage. The standard deviation of the determined permeabilities was required to be less than 1% of the mean value for the test sequence to be considered acceptable. 7. At the end of the permeability testing, the widths of each of the four corners of the cell were determined to 0.01 mm resolution by using vernier calipers.
The test results are summarized in TABLE 4.
TABLE 4. Measurements on packings of 14/16 U.S. mesh size of Sample 40m200C and of the Reference Sample at a coverage of 0.02 lb/ft 2 . The conductivity (mDft) of deoxygenated silica-saturated 2% potassium chloride (KCl) brine of pH 7 through each sample was measured at a temperature of 190° F. (87.8° C.) under a compressive stress of 4000 psi (27.579 MPa).
Reference Sample
Sample 40m200C
Time (hours)
Conductivity (mDft)
Time (hours)
Conductivity (mDft)
27
1179
45
1329
49
1040
85
1259
72
977
109
1219
97
903
133
1199
120
820
157
1172
145
772
181
1151
168
736
205
1126
192
728
233
1110
218
715
260
720
These results are shown in FIG. 9 . They demonstrate clearly the advantage of the particles of the invention in terms of the enhanced retention of liquid conductivity under a compressive stress of 4000 psi at a temperature of 190° F.
|
Use of two different methods, either each by itself or in combination, to enhance the stiffness, strength, maximum possible use temperature, and environmental resistance of thermoset polymer particles is disclosed. One method is the application of post-polymerization process steps (and especially heat treatment) to advance the curing reaction and to thus obtain a more densely crosslinked polymer network. The other method is the incorporation of nanofillers, resulting in a heterogeneous “nanocomposite” morphology. Nanofiller incorporation and post-polymerization heat treatment can also be combined to obtain the benefits of both methods simultaneously. The present invention relates to the development of thermoset nanocomposite particles. Optional further improvement of the heat resistance and environmental resistance of said particles via post-polymerization heat treatment; processes for the manufacture of said particles; and use of said particles in the construction, drilling, completion and/or fracture stimulation of oil and natural gas wells are described.
| 2
|
BACKGROUND
1. Technical Field
The present disclosure relates to curved slideable doors and, in particular, to adjustable curved shower doors.
2. Description of the Related Art
Bathing enclosures are used to retain water from, e.g., a showerhead within an enclosed area. Recently, bathing enclosures utilize curved outer walls in order to create additional space within the enclosure. The outer walls may be a shower curtain on a curved rod, for example, or a curved door on a correspondingly curved slider track.
A favored material for curved doors used in bathroom enclosures is glass, which admits light to the enclosure, is waterproof and can be easily cleaned. In order to support the weight of the glass doors, the curved tracks along which the doors slide may be made from a robust, bulky material. In some cases, curved tracks may deflect when the weight of the glass door assembly is placed on a track, resulting in a “dip” or depression at the middle of the track together with rotation of the track due to the moment created by the curve. Misalignment of the tracks may also cause or exacerbate such a “dip.” This deflection and/or rotation may urge the door or doors toward the middle of the enclosure, causing the door or doors to open unintentionally.
Curved-door designs may have a moveable door panel which slides between open and closed positions, and a stationary door panel which is rigidly fixed to the surrounding support structures and may itself be used as a support for mounting the sliding door.
SUMMARY
The present disclosure provides a door assembly which compensates for any deflection of the track which may occur with a heavy door material and/or a curved door support track. In particular, the present disclosure provides track mounting assemblies which can be tilted in order to “fine tune” the orientation of the door with respect to the surrounding support structure, e.g., the bathtub or shower base threshold. If the curved track deflects from the weight of one or more sliding doors, the track can be tilted to ensure that the door remains level and functions as intended.
In one form thereof, the present disclosure provides a sliding door assembly comprising: a door; a support track slideably supporting the door, the support track having axial ends with a longitudinal extent therebetween, and a cross-sectional shape perpendicular to the longitudinal extent, the cross-sectional shape defining a first pivot area and an adjuster engagement area spaced from the first pivot area; and a track mounting assembly fixable to an adjacent support surface, the track mounting assembly comprising: a support body including a track slot sized to receive the support track, the track slot defining a second pivot area adapted to pivotably engage with the first pivot area; and a tilt adjuster engaging the adjuster engagement area of the support track to selectively adjust a tilt of the support track within the track slot.
In another form thereof, the present disclosure a sliding door adjustment mechanism comprising: a support body having a tapered track slot including a narrow portion defining a pivot area and a wide portion defining an adjuster area, the tapered track slot sized to pivotably receive a support track of a sliding door; and a support anchor coupled to the support body and adapted to be fixed to an adjacent support surface.
In yet another form thereof, the present disclosure provides a method for adjusting a tilt angle of a sliding door, the method comprising: affixing axial ends of a support track to a pair of mutually opposed support surfaces; slideably attaching a door to the support track such that the support track supports the weight of the door, and the support track experiences a downward deflection; tilting at least one of the axial ends of the support track to correct the downward deflection.
BRIEF DESCRIPTION OF THE DRAWINGS
The above-mentioned and other features of the disclosure, and the manner of attaining them, will become more apparent and will be better understood by reference to the following description of embodiments of the disclosure taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is a perspective view of a curved door assembly made in accordance with the present disclosure;
FIG. 2 is an enlarged, partial perspective view of the door assembly shown in FIG. 1 , illustrating a support track mounting assembly;
FIG. 3 is an exploded, perspective view of the support track mounting assembly shown in FIG. 2 ;
FIG. 4 is a cross-section view of the support track mounting assembly shown in FIG. 2 , taken along the line 4 - 4 , in which the support rod is in a centered vertical orientation;
FIG. 5 is another cross-section view of the support track mounting assembly shown in FIG. 2 , taken along the line 4 - 4 , in which the support track is in a deflection-correction orientation; and
FIG. 6 is a perspective view of an alternative support track mounting assembly in accordance with the present disclosure, in which the support track is vertically adjustable with respect to the track mounting assembly.
Corresponding reference characters indicate corresponding parts throughout the several views. The exemplifications set out herein illustrate embodiments of the disclosure and such exemplifications are not to be construed as limiting the scope of the invention in any manner.
DETAILED DESCRIPTION
The present disclosure provides a curved and sliding door assembly 10 ( FIG. 1 ) for bathing enclosures. Assembly 10 includes support tracks 16 which slidably support first and second curved doors 12 , 14 and can be tilted away from a centered, vertical position to a deflection-correction orientation in order to provide for onsite adjustment of the tilt angle of support tracks 16 . This adjustable tilt can be used to selectively correct for a downward deflection of support tracks 16 due to the weight of doors 12 and/or 14 . The tilting of tracks 16 is effected by adjustment of track mounting assemblies 30 disposed at one or both ends of support tracks 16 . In an exemplary embodiment and as further described below, mounting assemblies 30 provide for user-manipulable fine adjustment of the tilt angle of support tracks 16 , such that an appropriate corrective tilt angle can be selected as needed for each individual installation of sliding door assembly 10 .
Turning to FIG. 1 , sliding door assembly 10 includes a first curved sliding door 12 supported by an upper support track 16 and a second curved sliding door 14 supported by a lower support track 16 . In the illustrated embodiment, first and second doors 12 , 14 are laterally offset with respect to one another such that each of the doors 12 , 14 is slidable from a closed configuration, as shown in FIG. 1 , to an open configuration by pushing a respective handle 20 away from the adjacent wall of the bathing enclosure (not shown).
In particular, each of doors 12 , 14 is slideably supported by a pair of roller assemblies 18 affixed to the respective door panel. Roller assemblies 18 each engage a respective support track 16 as illustrated, and provide a secure and low-friction interface between doors 12 , 14 and their respective support tracks 16 . In an exemplary embodiment shown in FIG. 2 , roller assembly 18 includes weight bearing roller 36 rotatably mounted to an axle, which is in turn fixed to the panel of door 14 . Weight bearing roller 36 is rollingly received on the upper surface of the adjacent support track 16 . Roller assembly 18 also includes retainer roller 38 which is rollingly received on a lower surface of support track 16 , and operates to “capture” or slideably fix door 14 upon support track 16 . Roller arm 40 couples weight bearing roller 36 to retainer roller 38 .
In the illustrative embodiment of FIG. 1 , doors 12 , 14 have a convex outer surface and a correspondingly concave inner surface. Support tracks 16 may be similarly curved and disposed along the concave inner surfaces of doors 12 , 14 , such that the outer surfaces (visible from the room in which the bathing enclosure is located) present a clean and uncluttered appearance.
Doors 12 , 14 include side gaskets 22 and bottom gaskets 24 which provide a waterproof seal between the outside and lower edges, respectively, of doors 12 , 14 and the adjacent support surfaces of the bathing enclosure. For example, side gasket 22 may interface with a vertical wall of the bathing enclosure to provide a fluid-tight seal between the interior and exterior of the bathing enclosure along the vertical wall, while bottom gaskets 24 similarly provide a fluid tight seal between the lower edges of doors 12 , 14 and the adjacent floor, threshold or tub wall of the bathing enclosure. Door guide 26 may be provided along the lower door surfaces to restrain lateral movement of doors 12 , 14 as they are moved between the open and closed positions as described above.
Door stops 28 may be mounted on each of support tracks 16 in order to limit the slidable motion range of each door 12 , 14 along the longitudinal extent of the support track 16 to which the door is mounted. Referring to FIG. 2 , each door stop 28 includes retainer 34 sized to mount to a respective support track 16 , and a bumper 32 extending upwardly from retainer 34 and positioned to engage one of rollers 36 when the respective door 12 or 14 reaches a fully open configuration. As shown in FIG. 1 , door stops 28 are positioned to allow each of doors 12 , 14 to be slidably opened a substantial distance such that roller assemblies 18 are allowed to traverse most of the longitudinal extent of the support track 16 . The distance from the axial end of support track 16 to the door stop 28 may be set by an installer according to the particular spatial arrangement of the bathing enclosure to which sliding door assembly 10 is applied.
Support tracks 16 mount to the walls of the bathing enclosure via track mounting assemblies 30 , as shown in FIG. 1 . FIG. 2 provides a detailed illustration of the connection between support tracks 16 and tracking mounting assembly 30 at an axial end of each support track 16 . In the illustrated embodiment of FIG. 1 , the opposite axial ends of support tracks 16 are coupled to a track mounting assembly 30 in the same manner as illustrated in FIG. 2 . Track mounting assembly 30 includes upper support body 42 which receives the upper support track 16 , and lower support body 44 which receives the lower support track 16 , and support anchor 46 . As illustrated in FIG. 3 , support anchor 46 is a generally elongate component defining a generally vertical longitudinal axis A. Support anchor 46 has support bodies 42 , 44 coupled to its opposite ends as shown in FIG. 2 , such that longitudinal axis A is also the pivot axis about which upper and lower support bodies 42 , 44 rotate ( FIG. 3 ).
Support anchor 46 is coupled to each of the upper and lower support bodies 42 , 44 , and provides a fixed mounting point for affixing support bodies 42 , 44 , and therefore support tracks 16 the other associated structures of sliding door assembly 10 , relative to the adjacent support surfaces. In particular, as shown in FIG. 3 , support anchor 46 includes fastener apertures 64 sized to receive fasteners 48 therethrough. Upon assembly, support anchor 46 may be affixed to the adjacent support surface by driving fasteners 48 into the support surface, followed by assembly of the remaining components of track mounting assembly 30 .
Upper support body 42 is rotatably coupled to anchor 46 by lowering boss 68 into support mounting aperture 66 . Pivot pin 50 may then be passed through pivot pin aperture 74 and threadably engaged with support mounting aperture 66 to affix upper support body 42 with respect to support anchor 46 . When pivot pin 50 is loose, upper support body 42 may pivot with respect to anchor 46 , such that the curved support track 16 may approach the support surface at a non-perpendicular orientation. This configuration facilitates the use of the curved support tracks 16 (and the correspondingly curved first and second doors 12 , 14 ) between parallel walls commonly found in bathing enclosures. Moreover, the pivotability of upper support body 42 with respect to anchor 46 ensures that an installer of sliding door assembly 10 can align support tracks 16 with track slot 60 (as further described below), regardless of whether slot 60 is perpendicular with the adjacent support surface. When support body 42 is pivoted to its desired orientation (e.g., when slot 60 received and is aligned with an axial end of support track 16 ), pivot pin 50 may be tightened to secure support body 42 to anchor 46 and, therefore, to the adjacent support surface.
Lower support body 44 is also pivotably mounted to support anchor 46 by pivot pin 50 ( FIG. 3 ), in the same manner as upper support body 42 . However, the spatial arrangement of the track slots 60 relative to axis A varies between upper and lower support bodies 42 and 44 , in order to laterally offset the two slots 60 are with respect to one another. That is, the plane defined by slot 60 in lower body 44 is not coplanar with the plane defined by slot 60 in upper body, even if upper and lower bodies 42 , 44 are pivoted parallel to one another as shown in FIG. 3 . This lateral offset accommodates the corresponding lateral offset between the upper and lower support tracks 16 , as described above, which in turn accommodates the lateral offset of first and second doors 12 and 14 .
In addition to the pivotable adjustment of upper and lower support bodies 42 and 44 , support tracks 16 have an adjustable “tilt” when received within track slots 60 , as noted above and shown in FIG. 3 . In the illustrated embodiment, support bodies 42 , 44 each include adjuster aperture 56 , which is a slotted aperture allowing for passage of flange bolt 52 therethrough at a variety of positions along the longitudinal extent of slot 60 . When an axial end of support track 16 is received within track slot 60 , threaded aperture 58 formed in track 16 aligns with adjuster aperture 56 , such that a threaded portion of flange bolt 52 may be threadably engaged with aperture 58 , as shown in FIG. 4 . At this point, support track 16 is affixed with respect to the adjacent support surface via one of support bodies 42 , 44 and support anchor 46 . Further adjustment of flange bolt 52 operates to change the tilt of support track 16 , as further described below.
FIG. 4 illustrates the cross-sectional shape and configuration of support track 16 and support body 42 , as taken in a cross-section perpendicular to the longitudinal axes of support track 16 and track slot 60 , it being understood that these two longitudinal axes are substantially aligned when track 16 is received in slot 60 . For purposes of clarity, upper support body 42 only is shown in FIG. 4 , though the same cross-sectional configuration may be used for lower support body 44 and the lower support track 16 .
Track slot 60 defines a tapered cross-sectional profile, including a substantially vertical first inner wall 70 and an angled second inner wall 72 defining taper angle Θ, which is equal to the overall taper angle of slot 60 . Slot 60 is narrower at its bottom portion and becomes wider with progression toward the top portion, i.e., toward flange bolt 52 . In the configuration of FIG. 4 , support track 16 is in a centered vertical orientation within slot 60 , such that the vertical walls of support track 16 are substantially parallel to the vertical first inner wall 70 and define angle Θ with respect to angled wall 72 . In this configuration, the longitudinal axis of flange bolt 52 is substantially horizontal and gap G is formed between a lower portion of the flange of bolt 52 and the adjacent surface of upper support body 42 as illustrated. The configuration of FIG. 4 will typically result in a generally level curved support track 16 , provided the axial ends of track 16 are at equal heights and track 16 is not deflected downwardly. On the other hand, downward deflection of track 16 may cause a “dip” in the center portion of track 16 which can be corrected by tilting track 16 at track mounting assembly 30 , as discussed further below.
When first door 12 is installed upon the upper support track 16 , weight bearing rollers 36 are rollingly received upon an upper surface of support track 16 , as illustrated in FIG. 1 and described above. At this point, all or nearly all of the weight of door 12 is supported by support track 16 . Particularly in the case of curved door 12 and the associated curved support track 16 , this weight may create a moment which urges downward deflection and rotation of support track 16 to create the aforementioned “dip” near the center of support track 16 . For purposes of the present disclosure, references to “deflection” in the context of curved tracks 16 may encompass both downward deflection and rotation, it being understood that both can be expected to occur under the weight of doors 12 and/or 14 . This dip may in turn urge doors 12 to roll “downhill” toward the middle of the longitudinal extent of track 16 , such that door 12 is urged toward an open position. Moreover, depending on the size, material, and configuration of door 12 , the amount of such deflection and the corresponding depth of the central dip in track 16 may vary among various individual installations of sliding door assembly 10 .
In order to selectively correct for such deflection of track 16 , track mounting assembly 30 may be used to “tilt” support track 16 through a continuously adjustable range of potential tilt angles. The chosen level of tilt is that which corrects for the particular deflection encountered in an installation of sliding door assembly 10 , such that an installer may selectively tilt support track 16 into a desired orientation which eliminates any central “dip” and facilitates the desired operation during the opening and closing of door 12 . The same correction may be applied to the lower track 16 and door 14 , as appropriate. Moreover, although the moment created by the use of curved support tracks and curved doors 12 , 14 inherently contributes to the creation of this central dip, it is contemplated that the present system of tilt adjustment may also be applied to non-curved enclosures, e.g., those including substantially planar doors and substantially linear support tracks, in order to correct for any deflection which may occur in that context.
FIG. 5 illustrates a cross-section of track mounting assembly 30 similar to that of FIG. 4 , except that support track 16 is in a fully tilted orientation. Support track 16 includes an upper portion which forms an adjuster engagement area which is allowed to move within the wide upper portion of tapered slot 60 , and a lower portion which forms a pivot area which is captured in the narrow lower portion of slot 60 . The upper portion includes the threaded engagement between flange bolt 52 and threaded aperture 58 ( FIG. 3 ), which can be used to selectively tilt the upper portion within slot 60 , while the lower portion defines pivot area P about which support track 16 pivots as it tilts.
To achieve the tilted orientation of FIG. 5 , the tilt adjuster (i.e., by rotating flange bolt 52 ) is tightened to draws only the upper portion of support track 16 toward the flange head of bolt 52 . As a result, the upper portion of support track 16 laterally displaces in the wide portion of the tapered slot 60 while the lower portion of support track 16 pivots about pivot area P in the narrow lower portion of support track 16 of slot 60 . When reconfigured to the fully tilted configuration as shown in FIG. 5 , the formerly vertical walls of support track 16 become substantially parallel to the angled second inner wall 72 , such that walls of support track 16 form angle Θ with respect to the vertical inner wall 70 of slot 60 . Meanwhile, gap G ( FIG. 4 ) substantially closes as the longitudinal axis of flange bolt 52 tilts along with support track 16 .
Thus, the axial end of support track 16 is tilted within slot 60 such that the outer surface of track 16 faces upwardly as shown in FIG. 5 . This upward tilt also tilts the rest of the longitudinal extent of track 16 , including its center portion. If the center portion had a central dip or low point as noted above, this upward tilting may render the center portion substantially level.
Moreover, the amount of tilt imparted to support track 16 may be finally adjusted by rotating flange bolt 52 to achieve any desired tilt within the tilt range allowed by the taper of slot 60 . In an exemplary embodiment, the maximum tilt angle Θ is about 2 degrees, though it is appreciated that other tilt angle ranges may be provided as required or desired for a particular application. In some applications, the maximum available tilt angle Θ may be varied by increasing or decreasing the amount of taper within slot 60 , and may be set as low as 0.5 degrees, 1 degree, or 1.5 degrees, and may be as large as 2.5 degrees, 3 degrees, or 3.5 degrees, or may be any tilt angle within any range defined by any of the range of the foregoing values. In one exemplary embodiment using tracks 16 with an outward curvature defining a radius of 106 inches, for example, a tilt angle Θ of 2 degrees may result in a ⅛-inch corrective elevation change at the middle of the longitudinal extent of support track 16 . That is, if the lower portion of track 16 is ⅛-inch lower than the axial ends of track 16 due to weight-induced deflection, a 2-degree upward tilt of track 16 will result in the center portion becoming level with the axial ends. Similar correlations may be inferred for other tilt angles, though it is appreciated that such correlations will vary for varying materials, geometries and sizes used in sliding door assembly 10 . For example, the “dip” to be corrected can be expected to increase as the curve radius of curved tracks 16 decreases (i.e., as the tracks become “more curved”), and can be expected to decrease as the curve radius of curved tracks 16 increases. For an completely straight support track (i.e., one having an infinite radius), the dip is essentially zero.
When a desired tilt of support track 16 has been achieved, one or more set screws 54 (e.g., two set screws 54 as illustrated in FIGS. 2 and 3 ) may be used to affix support track 16 at the desired tilt angle. In the illustrated embodiment, set screws 54 are received in limiter apertures 62 ( FIG. 3 ) and can be rotated to axially advance set screws 54 into and out of track slot 60 . Limiter apertures 62 are formed in the top surfaces of upper support body 42 and lower support body 44 , respectively, such that set screws 54 engage the tiltable upper portion of support track 16 within the wide upper portion of tapered slot 60 . When it is desired to affix support track 16 at its present tilt angle, set screws 54 are rotated to axially protrude into track slot 60 until their distal ends engage the upper surface of support track 16 , at which point set screws 54 act as to limit any further adjustment of the tilt of track 16 .
Although flange bolt 52 and threaded aperture 58 are used for tilt adjustment in the illustrated embodiment, it is contemplated that other mechanisms may be used in alternative embodiments to achieve a similar tilt adjustment functionality. Examples of such alternative mechanisms include worm gears, wedges received between support track 16 and one of inner slot walls 70 , 72 , and the like. Yet another alternative is a ball joint or U-joint connection between tracks 16 and the adjacent support surface (e.g., via modified support bodies 42 , 44 ) which is lockable in a desired configuration.
Turning now to FIG. 6 , an alternative support track mounting assembly 130 is illustrated in conjunction with support track 16 . The structures shown in FIG. 6 are similar to the structures of sliding door assembly 10 described in detail above, and the structures shown in FIG. 6 have corresponding reference numbers to the structures of FIGS. 1-5 , except with 100 added thereto. Moreover, the support track mounting assembly 130 shown in FIG. 6 may be used interchangeably with the other structures of sliding door assembly 10 , and the same functions and features of assembly 30 may be present in assembly 130 .
However, support track assembly 130 allows for vertical adjustment of the axial end of support track 16 , such that the elevation of one or both of the ends of support track 16 can be adjusted to ensure that the overall track 16 is level upon installation. In the illustrated embodiment, slot 160 has been vertically expanded relative to slot 60 , such that track 16 is vertically moveable within slot 160 through a limited range while still remaining captured by support body 142 . Vertical adjustment of track 16 is effected by adjustment of adjuster screw 176 , which is threadably engaged in threaded aperture 178 formed in the lower surface of body 142 . Rotation of screw 176 causes screw 176 to protrude upwardly into slot 160 , engaging a lower surface of track 16 and raising track 16 within slot 160 .
In order to accommodate the tilt adjustment functionality of flange bolt 52 while maintaining alignment between bolt 52 and threaded aperture 58 , adjuster aperture 156 is vertically enlarged as compared to adjuster aperture 56 , as illustrated by a comparison of FIGS. 3 and 6 . Set screws 154 may also be made longer to accommodate the extra vertical extent to which screws 154 may need to protrude into slot 160 . To adjust the height of the axial end of track 16 within slot 160 , vertical adjuster screw 176 is advanced into or out of slot 160 until track 16 is at a desired position within slot 160 . Next, the tilt of track 16 is adjusted by manipulation of flange bolt 52 , as described in detail above with respect to support body 42 . Finally, set screws 154 may be tightened into engagement with the top surface of track 16 to fix the height and tilt of track 16 .
Height-adjustable support track assembly 130 may be provided at one or both axial ends of tracks 16 , as required or desired for a particular application. Lower support body 144 may also be provided with vertical adjustment in a similar fashion to upper support body 142 , as shown in FIG. 6 , though it is contemplated that support bodies 42 , 142 and 44 , 144 are interchangeable such that only one of the upper and lower support bodies in assemblies 30 or 130 may be vertically adjustable as required or desired for a particular application.
While this invention has been described as having an exemplary design, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.
|
A door assembly compensates for any deflection of the track which may occur with a heavy door material and/or a curved door support track. In particular, the present disclosure provides track mounting assemblies which can be tilted in order to “fine tune” the orientation of the door with respect to the surrounding support structure, e.g., the bathtub or shower base threshold. If the curved track deflects from the weight of one or more sliding doors, the track can be tilted to ensure that the door remains level and functions as intended.
| 4
|
REFERENCE TO RELATED APPLICATIONS
[0001] This patent application claims priority to U.S. Provisional Patent Application No. 60/379,491 filed on May 9, 2002.
TECHNICAL FIELD
[0002] This invention relates generally to an energy absorber for a motor vehicle steering column.
BACKGROUND OF THE INVENTION
[0003] Various vehicle components are known to transmit energy from collisions to vehicle occupants. A typical component is a steering column of a steering wheel that includes a housing or mask jacket that collapses during a vehicle collision. The mask jacket translates the collision energy through an energy absorber to convert the crash energy to a fraction of the kinetic energy transferred to the vehicle operator.
[0004] A common energy absorber transmits force created by a plastic deformation of a metal element or strap disposed in the energy absorber. An example is disclosed in U.S. Pat. No. 6,322,103 where deformation of a flat metal strap over an anvil as disclosed to absorb crash energy. It has been discovered that a benefit is derived by adjusting the amount of energy absorbed relative to the amount of energy that may be translated to the vehicle operator based on such variables as vehicle speed, vehicle weight, and operator weight. Also, U.S. Pat. No. 6,189,929 discloses an anvil having various diameters where the anvil is adjusted to position a desired diameter in contact with the metal strap to adjust the amount of energy absorption produced by the energy absorber.
[0005] While these devices are capable of producing various amounts of energy absorption, they have not provided a desirable degree of variable energy absorption. Further, these devices are known to provide an imprecise amount of energy absorption relative to the desired amount of energy absorption due to mechanical failures such as, for example “bounce back” where the anvil is initially moved to a desirable position but rebounds back to an initial position. Therefore, it would be desirable to provide an energy absorber having both an increased degree of variable energy absorption along with a more accurate degree of energy absorption.
SUMMARY OF THE INVENTION
[0006] The present invention relates to an improved energy absorbing device that provides variable energy absorption transmitted from an energy transmitting component of a motor vehicle. A mounting bracket mounts the energy absorbing device to the energy transmitting component. An elongated strap is secured at at least one end for absorbing energy received from the energy transmitting component. Cooperating anvils are slidably received by the mounting bracket and are oriented so that the elongated strap is interwoven between the anvils. The anvils include a generally parallel axis along which each anvil defines stepped diameters. Each anvil is slideable along its axis in response to a predetermined force to provide variable energy absorption relative to the stepped diameters of each anvil.
[0007] Further, a catch is included to secure each anvil in a desired position to prevent the anvil from moving once the desired amount of energy absorption is determined and the anvil has been positioned to produce the desired amount of energy absorption.
[0008] By including cooperating anvils each slideable relative to the other, a more precise variation in the amount of energy absorption is provided. Further, by providing a catch to secure the anvil in its desired position once the anvil has been moved to provide a desired amount of energy absorption, mechanical failures known to prior art assemblies have been eliminated.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] Other advantages of the present invention will be readily appreciated as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings wherein:
[0010] [0010]FIG. 1 is a perspective view of a steering column having the inventive energy absorbing assembly attached thereto;
[0011] [0011]FIG. 2 is a sectional view of the energy absorbing assembly showing a single anvil configuration cooperable with an elongated strap;
[0012] [0012]FIG. 3 shows a perspective view of an assembly having a single anvil;
[0013] [0013]FIGS. 3A and 3B show a sectional view of the anvil of FIG. 3 prior to firing and subsequent to firing;
[0014] [0014]FIG. 4 shows a side sectional view of a cooperable anvil embodiment having the strap interwoven therebetween;
[0015] FIGS. 5 A- 5 D cooperable anvils having stepped diameters in various stages of orientation.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0016] Referring to FIG. 1, an energy transmitting component in the form of a steering column is generally shown at 10 . The column includes a steering shaft 12 that is disposed within a steering housing 14 . A mounting brackets ( 16 ) is fixedly attached to the steering housing 14 providing attachment locations 18 disposed upon opposing sides of the steering column 10 . An energy absorbing assembly 20 is secured at each attachment location 18 to absorb energy received from the steering column 14 upon a collision of the motor vehicle.
[0017] In a collision of the motor vehicle (not shown), the vehicle body decelerates more rapidly than the operator so that the operator can be thrust against the steering wheel (not shown) generating an impact force relative to the speed of the vehicle, mass of the vehicle and mass of the vehicle operator amongst other variables. When the operator impacts the steering wheel, the corresponding force on the steering column housing 14 causes the housing 14 to collapse relative to the vehicle body. In order to reduce the amount of impact force transmitted to the vehicle operator, the energy absorbing assemblies 20 absorb energy generated from the vehicle operator impacting the steering column 10 .
[0018] A flat metal strap 22 includes a first end 24 fixedly attached to the mounting bracket ( 16 ). A second end 26 is unattached, or floats freely relative to the assembly 20 .
[0019] Referring to FIG. 2, the strap 22 is shown interwoven through the assembly 20 forming a generally S-shaped configuration between a protuberance 28 in the assembly 20 and an anvil 30 . The anvil 30 is displaceable as will be explained further below to alter the amount of energy absorption produced by the strap 22 as is shown in phantom in FIG. 2.
[0020] Referring now to FIGS. 3, 3A and 3 B, the anvil 30 is shown slidably disposed within an elongated chamber 32 defined by the assembly 20 . An actuation device 34 is disposed at a first end 36 of the elongated chamber 32 . Preferably, the actuation device 34 is an explosive charge. However, other equivalent methods of propelling the anvil 30 through the elongated chamber 32 may be used. The actuation device 34 includes electrical connectors 38 that receive an electrical charge signalled from a controller (not shown) to activate the actuation device 34 .
[0021] A retaining pin 40 releasably secures the anvil 30 in a first position 42 (FIG. 3A). Upon discharging, the anvil 30 is moved from the first position 42 to a second anvil position 44 (FIG. 3B). A catch 46 secures the anvil 30 in the second position 44 to prevent the anvil 30 from rebounding back to the first position 42 . An opening 48 disposed in a second chamber end 50 allows air to vent from the chamber 32 enabling the anvil 30 to move from the first position 42 to the second position 44 . When the anvil 30 is located in the first position 42 , a greater level of energy absorption is provided than when the anvil 30 has been moved to the second position 44 and out of engagement with the strap 22 .
[0022] Referring to FIGS. 4 , and 5 A through 5 D, an alternate embodiment is shown having cooperating anvils 30 A, 30 B. Each anvil 30 A, 30 B includes stepped diameters along an anvil axis a so that each anvil 30 A, 30 B includes at least two sections having different diameters as is best represented in FIG. 5A through D as A, B, C, D. Preferably, the anvils 30 A, 30 B include generally parallel axes a and are slidably disposed in generally parallel elongated chambers 32 A, 32 B. Referring now to FIG. 4, a sectional view shows the cooperating anvils 30 A, 30 B having generally parallel axes. The strip 22 is interwoven between the cooperating anvils 30 A, 30 B taking a generally S-shaped configuration.
[0023] Referring again to FIG. 5A, each anvil 30 A, 30 B is disposed in first position 42 . Therefore, a first diameter A of the first anvil 30 A cooperable with a first diameter B of the second anvil 30 B. As should be understood, if the controller determines the appropriate amount of energy absorption is provided from the strap 22 interacting with diameters A and B of the anvils 30 A, 30 B the actuation devices 34 A, 34 B are not discharged. Therefore, the energy absorption is derived from the anvils 30 A, 30 B as provided by diameters A and B. Referring now to FIG. 5B, the second actuation device 34 B is discharged by the controller to provide a second level of energy absorption different from the first level. In this case, diameter A of the first anvil 30 A is cooperable with the diameter D of the second anvil 30 B. A receptor 52 comprising a compressible material such as, for example, a honeycomb material, optionally receives the first anvil 30 A when propelled by the actuation device 34 A through the elongated chamber 32 A. A catch 46 A secures the anvil 30 A in the discharged position to prevent the anvil 30 A from rebounding once the actuation device 34 A has fired.
[0024] Referring now to FIG. 5C, actuation device 34 A is shown discharged moving anvil 30 A to a discharged position. Now, diameter C of anvil 30 B- is cooperable with diameter D of anvil 30 B providing yet an additional level of energy absorption. As previously described, anvil 30 B is received by a receptor 52 B and secured in the discharged position by catch 46 B.
[0025] Referring now to FIG. 5D, actuation devices 34 A and 34 B are shown discharged so that diameter C of anvil 30 A and diameter D of anvil 30 B are cooperable. This provides still another level of energy absorption. In this case, both anvils 30 A and 30 B are received by the receptor 52 and secured in the discharged position by catches 46 A and 46 B. It should be understood that while two cooperating anvils 30 A, 30 B are shown, more than two anvils may be used to achieve even a further level of energy absorption. Further, providing anvils 30 A, 30 B with more than two stepped diameters such as, for example, three stepped diameters achieves still further levels of energy absorption.
[0026] The invention has been described in an illustrative manner, and it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation.
[0027] Obviously, many modifications and variations of the present invention are possible in light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims, wherein reference numerals are merely for convenience and are not to be in any way limiting, the invention may be practiced otherwise than as specifically described.
|
An energy absorbing assembly providing variable energy absorption from an energy transmitting component is mounted upon a mounting bracket for mounting the energy absorbing assembly to the energy transmitting component. An elongated strap immovably secured at a first end absorbs energy received from the energy transmitting component during a collision. Cooperating anvils are slidably received by the mounting bracket and the elongated strap is interwoven between the anvils. The anvils include generally parallel axis along which each anvil defines stepped diameters, and are slidable along the axis in response to a predetermined force to provide variable energy absorption relative to the stepped diameters.
| 5
|
FIELD OF THE INVENTION
The invention relates to a process for removing the drillings from the drilling site of a drill, to an apparatus for operating this process, and to a drilling machine, a drill and an adapter, modified for use in said apparatus for operating said process.
It is the purpose of the present invention to provide a process for removing the drillings from the drilling site of a drill whereby clogging of the removal duct by the drillings that are to be removed, is obviated.
SUMMARY
The preferred embodiment of the present invention solves the problem of possible clogging of the removal ducts or conduits for customary drilling machines by providing a process for removing the drillings from the drilling site of the drill through a conduit extending along the axis of said drill, comprising the steps of (a) producing a vacuum in said conduit by a compressed air stream traversing said conduit (b) sucking the drillings into said conduit by said vacuum, and (c) blowing the sucked in drillings out of said conduit by said traversing compressed air stream.
Since the compressed air stream crosses the suction conduit extending in longitudinal direction of the drill axis with great speed, a vacuum is produced in the suction conduit which sucks the drillings from the drilling site through the straight suction conduit into the compressed air stream. The drillings thus sucked in are carried along by the compressed air stream. Since removal occurs only through the straight axial suction conduit which has no corners, already a comparatively small vacuum suffices to ensure that the drillings are sucked into the compressed air stream without having to anticipate possible obstructions. However, as soon as the drillings are absorbed by the compressed air stream, they are blown "around the corner", whereby it is possible to use compressed air of the high pressure necessary for a flawless conveyance "around the corner" to blow the drillings out of the suction conduit with certainty.
The process of the present invention is particularly advantageous for its purpose, because the cooling air of an electromotor driving the drill can be used as the compressed air stream, a fan wheel of the motor possibly providing the compressed air source.
This process can be operated with an apparatus in connection with a drilling machine having a housing and a motor for driving a drill inserted into the cavity of a chuck, such apparatus comprising:
A. a cylindrical wall surrounding a closed end part of a suction conduit extending from its open end at the drilling site in the direction of the axis of said drill, said conduit for sucking in the drillings from the drilling site to said closed end part,
b. first and second cross or transverse holes in said wall, said holes traversing said end part of said suction conduit and merging to continue each as the other on different sides of said suction conduit to convey said compressed air stream tranversely to said suction conduit,
c. a connecting ring surrounding said cylindrical wall and forming an inner supply air annulus closed by said cylindrical wall,
d. a connecting piece on said connecting ring for connecting said annulus to a source of said compressed air stream, and
e. said connecting ring adapted for non-rotating connection to said housing in such a position, that said first cross hole connects said inner supply air annulus with said suction conduit and said second cross hole connects said suction conduit with a location outside of said supply air annulus to remove the drillings from said end part of said suction conduit by said compressed air stream.
The invention is also directed to an apparatus for operating the process of the present invention, such apparatus provided with a connecting ring non-rotatably attachable to the housing of the apparatus and, together with a cylindrical outer wall rotatable during drilling of a suction conduit extending in the direction of the spindle axis, enclosing an inner supply air annulus open toward the inside of said ring, such annulus connectable to a compressed-air feed line by means of a connecting piece. This connecting piece can be non-rotatably attached to the housing of the apparatus, merely by a line provided for feeding the compressed air, which line, for example, connects the connecting piece for removing the cooling air of the electromotor driving the drilling machine with the connecting piece of the connecting ring. This connecting ring can be placed onto a drill or onto an adapter which is introduced into the chuck of a drilling machine, if such drill or adapter is provided with a removal conduit and has at least one pair of cross or transverse holes of which the first cross hole connects the supply air annulus of the connecting ring with the suction conduit and the second cross hole of the same pair connects the suction conduit with a location outside of the supply air annulus for the purpose of removing the drillings.
One of the advantageous embodiments of the apparatus pursuant to the present invention provides for positioning the suction conduit in the spindle of the drilling machine such that the connecting ring surrounds the cylindrical outer surface of the spindle, that the spindle has, for the purpose of conveying the compressed-air stream traversing the suction conduit, at least one pair of cross or transverse holes which merge to essentially continue each as the other on different sides of the suction conduit, whereby the first cross hole of one pair connects the supply air annulus of the connecting ring with the suction conduit and the second cross hole of the same pair connects the suction conduit for the purpose of removing the drillings with a location outside the supply air annulus, preferably with the exhaust air annulus. Thereby it is possible to use commercially available drills with the process of the present invention, provided such drills have an axially extending passage for forming a suction conduit.
A further advantageous embodiment of the present invention provides that both cross or transverse holes of one pair of holes on the one hand and the suction conduit on the other hand define two longitudinal axes forming an acute angle, so that the first cross hole is closer to the drilling site than the second cross hole. This has the effect that the drillings are diverted from the axial suction conduit into the second cross hole around a bend greater than 90°, whereby one component of the speed vector of the compressed air drops in the direction of suction of the suction conduit, which promotes drawing off the drillings through the suction conduit and blowing the drillings away, out of the suction conduit.
In order to achieve as strong a suction effect in the suction conduit as possible at a specific pressure of the compressed air, the two cross or transverse holes of one pair may together form a Venturi-tube with a constricted middle section which is crossed by the suction conduit.
The process of the present invention can be used with drilling machines of different types; this always guarantees that removal occurs only through the suction conduit extending in longitudinal direction of the drill axis, and the drillings are then blown out at the end of this suction conduit by the compressed air stream crossing the same.
The invention also pertains to a drill for operating the process of the present invention, said drill having a suction conduit extending along its axis. This particular drill has at least one pair of cross or transverse holes which merge to continue each as the other at different sides of the suction conduit, whereby the first cross hole of the one pair is intended for connecting the supply air annulus of the connecting ring with the suction conduit, and the second cross hole of the same pair for connecting the suction conduit with a location outside of the supply air annulus, optionally with the exhaust air annulus. The connecting ring for feeding the compressed air may thereby be connected to the drilling machine. In order to be able to use drills of different diameters with one and the same drilling machine, one advantageous embodiment of the drill according to the present invention has a collar at the drill spindle for accepting transverse holes, the outer diameter of said collar being always of the same size and the inner diameter adapted to the connecting ring of the drilling machine.
In a further embodiment of the drill, the connecting ring is rotatably supported on the drill spindle, optionally on the collar of the spindle, but it cannot be axially displaced. This embodiment of the drill has the advantage that the drill can be used with any kind of drilling machine, whereby it is merely necessary to provide for the compressed air feed to the connecting ring, which can be accomplished simply by connecting the connecting piece of the supply air annulus of the connecting ring with the exhaust connection for the cooling air of the driving motor of the drilling machine.
The invention is also directed to an adapter for insertion into the tool chuck of the drilling machine, for accepting a drill having an axial suction conduit to operate the process of the invention. The adapter of this embodiment is provided with an axial suction conduit which continues the axial conduit of the drill, with at least one pair of traverse or cross holes merging to continue each as the other on different sides of a suction conduit, whereby the first cross hole of one pair is provided for connecting the fresh air annulus of the connecting ring with the suction conduit, and the second cross hole of the same pair for connecting the suction conduit with a location outside of the supply air annulus, optionally with the exhaust air annulus. This permits operating the process of the present invention with a commercially available drill, if the same is provided with an axially extended through suction conduit. Particular advantages result if the connecting ring is rotatably, but not axially displaceably supported on a cylindrical part of the adapter body. In such case, a commercially available drilling machine can be used. It is then merely necessary to provide for a supply of compressed air to the connecting piece of the supply air annulus, e.g., by attaching this connecting piece to the exhaust connection piece of the cooling system of the driving motor.
Still further embodiments and advantages of the present invention will readily occur to one skilled in the art to which the invention pertains, upon reference to the following detailed description.
DESCRIPTION OF THE DRAWINGS
The description refers to the accompanying drawings in which like reference characters refer to like parts throughout the several views and in which:
FIG. 1 is a partial cross section of a side view of an embodiment of a drilling machine;
FIG. 2 is a cross section of an embodiment of a drill;
FIG. 3 is a cross section of an embodiment of an adapter.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, the invention is described with reference to a drill press as illustrated in FIG. 1 having a housing 11 and a spindle 12. At its free end, the spindle 12 is provided with a threaded female chuck 13 for accepting tools, such as a drill 14 with an axial suction conduit 15 extending the entire length of the drill. The chuck 13 of the spindle 12 continues in a suction conduit 16 which is in alignment with the suction conduit 15 of the drill 14 inserted into the spindle. Furthermore, the spindle 12 is provided with a pair of cross or traverse holes 17 and 18, each of which continues as the other on different sides of the suction conduit 16, each of said cross holes tapering off toward the suction conduit 16 and together forming a cross conduit 17, 18 traversing the suction conduit 16, similar to a Venturi-tube having its smallest diameter at the spot where it traverses the suction conduit 16. The axis of the cross conduit 17, 18 forms an acute angle with the spindle axis 19 so that the second cross hole 18 is closer to the drill press housing 11 than the first cross hole 17.
A connecting ring 21 is attached to the housing 11 of the drill press, and surrounds the cylindrical outer surface of the spindle 12. Together with the cylindrical outer surface of the spindle 12, said connecting ring encloses a supply air annulus 22 and an exhaust air annulus 23, separated from each other by an annular rib 24. Seals 25 and 26 serve to seal any slot or gap between the ring 21 and the spindle 12 connecting the supply air annulus 22 and the exhaust air annulus 23 with the atmosphere, respectively. In addition, rib 24 is equipped with a further seal 27 to provide an tight seal between the two annuli 22 and 23. The connecting ring 21 is provided with a connecting piece 28 by means of which a compressed-air line 29 can be connected to the supply air annulus 22. The other end of the compressed-air line 29 is attached to a connecting piece 31 serving to remove the cooling air of the electromotor 20 driving the drill press, which then is fed into the supply air chamber 22 through the line 29 as compressed air.
Operation of the embodiment of the drill press as represented in FIG. 1 consists in feeding the cooling air leaving the connecting piece 31 during rotation of the electromotor of the drill press, through the line 29 into the supply air annulus 22 as compressed air, from where it is conducted through cross conduit 17, 18 into the exhaust air annulus 23 and conveyed from there by means of a line 32 into a collecting bin for the drillings. As a result of the compressed air stream passing through the cross conduit, a vacuum is produced in the suction conduit 16, causing air to be drawn in through both suction conduits 15 and 16, from the free end of drill 14. By means of this air stream, the drillings formed at the free end of the drill during drilling operations, are drawn into the suction conduits 15 and 16, until they reach the cross conduit 17, 18 and are caught up in the compressed air stream and are blown out through the line 32 by way of the exhaust air annulus 23. Although the suction produced in the suction conduits 15 and 16 as a result of the compressed air stream is less than 1 Atm in any case, the drillings are readily drawn away from the drilling site, because the suction conduits merge rectilinearly, thus obviating suction of the drillings "around the corner". The drillings are picked up by the compressed air upon entry into the cross conduit 17, 18 and only then are propelled away "around the corner" through the cross hole 18. This avoids clogging of the suction and removal lines.
Those parts of the embodiment illustrated in FIG. 2 corresponding to similar parts contained in the embodiment of FIG. 1 were assigned the same reference characters to which the number 100 has been added, so that a reference to the previous section of the specification is thereby provided.
The embodiment of a drill pursuant to the invention as illustrated in FIG. 2, differs from the previous example in that the connecting ring 121 is arranged rotatable but not axially displaceable on the collar 133 of the drill 114. In order to secure the connecting ring 121 against axial displacement, spring washers 134 are provided for both ends of said connecting ring, inset in annular grooves of the collar 133. The suction conduit 115 of this drill does not extend all the way through, but ends inside of the collar 133 where, similar to the previous example, it is traversed at an angle by the cross conduit 117, 118 formed by the two cross holes 117 and 118. In this case, connecting ring 121 again forms a lower supply air annulus 122 and a top exhaust air annulus 123, into which the cross holes 117 and 118 discharge, respectively.
The drill represented in FIG. 2 can be employed with any commercially available drill press having a suitable tool carrier or chuck. In this case, the connecting piece 128 must merely be connected to a compressed air source, e.g., by means of the connecting piece 31 of the driving motor 20 of the drill press, through which the cooling air of the motor is discharged. Also in the case of this example, the supply air annulus 122 and exhaust air annulus 123 are sealed by means of seals 125, 126, and 127.
The inventive features of the drill of FIG. 2 have the same effect as the inventive features of the drill press shown in FIG. 1.
Those parts of FIG. 3 which correspond to similar parts already shown in the examples of the invention illustrated in FIGS. 1 and 2, were assigned like reference characters to which either 200 or 100 were added, respectively, so that a reference to the previous section of the specification is thereby provided.
The adapter 235 represented in FIG. 3 serves to accept drills 214 having one axial suction conduit 215 extending all the way through, as illustrated in the example shown in FIG. 1. Correspondingly, the adapter 235 is provided with a tool chuck for a drill 214 corresponding to that of the spindle 12 of the first embodiment. The other end of the adapter 235, not represented in this drawing is constructed in a manner familiar from the prior art to fit tool chucks in drill presses, so that the adapter can be inserted into the tool chuck of a drill press in a manner similar to that of a drill.
Similar to spindle 12, adapter 235 is provided with a suction conduit 216, and also with cross or transverse holes 217 and 218 inclined in a similar fashion and shaped like the cross holes of the previous illustrating examples. A connecting ring 221 sits on the adapter 235 in a manner similar to that of the connecting ring 121 on the collar 133 of the drill 114. Said ring encloses a supply air annulus 222 and an exhaust air annulus 223 that are sealed off from each other and with respect to the atmosphere, just as in the case of the connecting rings of the previous illustrating examples. Thereby, the connecting ring 221 is movably positioned on the adapter 235 and secured against axial displacement by the spring washers 234.
The performance of the inventive embodiment of this adapter is the same as in the case of the examples just described. This particular embodiment has the additional advantage that commercially available drill presses as well as commercially available drills 214 with axial suction conduits 215 extending the length of the drill, can be employed with the adapter 235. This, just as in the case of the example illustrated in FIG. 2, one must only take care that compressed air is fed to the connecting piece 228.
In a further illustrating example, the connecting ring 121 of the drill according to FIG. 2 can be left off. Such drill may be employed with a drill press of the present invention as illustrated for example in FIG. 1, if the spindle with the chuck 13 extends into the housing 11 such that the interior of the connecting ring 21 is free for receiving the collar 133 of the drill, and if connecting ring 21 has been constructed to fit on collar 133 of the drill.
The connecting ring 21 of the drill press shown in FIG. 1 furthermore can only be connected to the housing 11 by means of the compressed-air line 29. In such a case, the drill press can take the drill shown in FIG. 2, for example, without the connecting ring 121. In this case, the connecting ring 121 merely must be positioned on the drill at the time the drill is inserted, and must then be secured against axial displacement, e.g., by the spring washers 134. In this arrangment, drills of different sizes may be used for the same drill press, provided they have the same collar 133.
Furthermore, an adapter 235 pursuant to the present invention may also be constructed corresponding to FIG. 3, but without the connecting ring 221. What has just been said concerning the corresponding construction of the drill of FIG. 2, would then apply here as well.
The exhaust air annulus 23, 123, 223 is not absolutely necessary. It merely serves to prevent that the drillings that are discharged are blown out into space. For the purpose of collecting the drillings, the spindle 12 or the end of the drill press closest to the tool chuck may be surrounded by a collecting bin of arbitrary construction, which merely prevents the drilling from being blown out into space.
Although my invention has been illustrated and described with reference to the preferred embodiments thereof, I wish to have it understood that it is in no way limited to the details of such embodiments, but is capable of numerous modifications within the scope of the appended claims.
|
In the process and apparatus for removing the drillings from the drilling te of a drill described, removal is effected through a conduit, extending along the axis of a drill and possibly an adapter for a drilling machine, by a vacuum provided by a compressed-air stream traversing the removal conduit, said compressed air also serving to blow the drillings sucked into the conduit out of the conduit and away from the drilling site.
| 8
|
REFERENCES CITED
U.S. PATENT DOCUMENTS
[0001] U.S. No. Pat. 4,353,713 10/1982 Cheng . . . 48/202
[0002] U.S. No. Pat. 4,448,588 5/1984 Cheng . . . 48/99
[0003] U.S. No. Pat. 4,597,771 7/1986 Cheng . . . 48/77
[0004] U.S. No. Pat. 4,594,140 6/1986 Cheng . . . 208/414
STATEMENT REGARDING FEDERALLY SPONSORED AND DEVELOPMENT
[0005] Not applicable.
REFERENCE TO A “MICROFICHE APPENDIX”
[0006] Not applicable.
FIELD OF INVENTION
[0007] This present invention relates to processes and equipment for the integrated gasification of coal, municipal solid wastes, sewage sludge and hazardous wastes. It also relates to the generation of clear energy from various wastes and coal.
BACKGROUND OF THE INVENTION
[0008] With the declining of cheap energy sources and increasing concern for environmental contamination by various wastes, I made a number of proposals in form of U.S. patents. These include: 1. a process which can gasify municipal solid wastes, coal, sewage sludge and hazardous wastes at the same time (U.S. Pat. No. 4,353,713), 2. an apparatus to accommodate the said process (U.S. Pat No. 4,448, 588), 3. a fluidized reactor system for the integrated gasification of coal and various wastes (U.S. Pat. No. 4,597,771), and 4. an integrated gasification system for carrying out coal liquefaction and electricity generation simultaneously. (U.S. Pat. No. 4,594,140). All of these processes or apparatus have three common features: 1. All of them have an integrated gasifier, which is operated at temperatures above 800° C. At such high temperatures, the reactor life may be shortened, 2. in all of them, the reaction heat for the C—H 2 reaction comes from CO 2 —CaO reaction only. It is designed to use the latter reaction to supply all the heat required by the gasification, the feed to the gasifier will be too bulky and the gasifying reactor will be oversized, 3. for economical as well as environmental reasons, all the prior arts prefer to use sewage sludge as source of steam to support the integrated gasification. However, even sewage sludge contain only 3 to 4% of solids, the colloid nature of the suspension renders the conventional separation methods ineffective. Therefore, without improvement in the separation of the solid contents from the sludge before it is converted into steam, pipe lines in the steam generation system tend to be plugged by solid deposits. Due to these mentioned technical difficulties, the mentioned prior art processes or apparatus must be improved to make them more effective and less troublesome.
BRIEF SUMMARY OF THE INVENTION
[0009] It is therefore an object of the present invention to provide a catalytic reaction lowering the gasification temperature by about 100° C., prolonging the gasifier's life and improving the quality of product fuel gas. It is another object of this invention to provide a flexible method of supplying the heat required for gasification and a smoother operation. The third object of this invention is to provide the system of zero-pollution wastes disposal and clean energy generation with a process of producing clean steam from raw sewage sludge.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0010] The above mentioned objects, features and advantages of the present invention will become more readily apparent from the attached drawing. There is only one view for the drawing. However, this drawing serves as a flow sheet for the preferred embodiment of an apparatus complex for implementing the method of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0011] Reference will now be made in detail to the present preferred embodiment of the method of the invention.
Mixing the Feeds Into The Pyrolyzer
[0012] As can be seen from the attached drawing, coal is fed into co storage 2 via line 101 . From the storage, the coal is sent into a crusher 3 via line 102 . The coal may be ground to a finer size if necessary. The catalyst comes from feed line 113 . The ground municipal solid wastes (WSW) pass through MSW feed line 115 , then the MSW grinder 10 , via the MSW feed line, 114 , into pyrolyzer 5 . Finally, the solid contents from sludge solids removers, 17 and 18 , together with the solids from the filter 19 via line 119 are also fed into pyrolyzer 5 through line 120 .
Pyrolysis of Coal, MSW and Solid Contents of Municipal Sewage Sludge (MSS)
[0013] Coal, ground MSW, sludge solid contents and the catalyst are all pyrolyzed in 5 . Alternatively, the catalyst can be fed into the integrated gasifier 9 directly instead of feeding into the pyrolyzer 5 indirectly. The heat required by pyrolysis is supplied by burning pyrolyzed gases from the storage 1 via line 152 , or by burning a part of the product gas coming from gas storage 6 through lines 107 and 104 . The pyrolyzer is a part of a kiln or a furnace (not shown).
The Integrated Gasification
[0014] The pyrolyzed residues are continuously or intermittently flow into the feed mixture bin 4 . From which, the pyrolyzed residues are fed into the integrated gasifier 9 via lines 106 and 111 by means of a screw conveyor 4 a. Compressed CO 2 from line 155 which leads from the CO 2 compressor 23 is fed into the gasifier. The carbon dioxide reacts with lime (or calcined dolomite) which is recycled into the gasifier via stream 154 from the air preheater 8 . From time to time the system is replenished with fresh lime (or calcined dolomite) through line 110 . The required steam comes from the waste heat boiler 15 via lines 129 and 130 . And the pressure of the steam is bolstered by the compressor 14 . To decrease the gasification temperature by about 100° C. and improve the quality of the product gas, a catalyst is added directly into the gasifier or indirectly into the system through the pyrolyzer. Without the catalyst, the carbon-steam reaction carries out at temperatures around 850 to 900° C. These high temperatures would shorten the life of the gasifier. Since these temperature are above the decomposition temperatures of limestone and dolomite, in order to drive the recombination of carbon dioxide and lime or calcined dolomite, a high pressure in the gasifier is necessary for carrying out the exothermic reaction to provide the reaction-heat for carbon-steam reaction. The use-of catalyst can lower the optimum temperature of carbon-steam reaction down to around 777° C. The catalysts employed are various combinations of alkaline metal salts-and salts of iron and chromium. Alkaline metal salts consist of NaCl, KCl, Na 2 CO 3 , K 2 CO 3 , LiCl, Li 2 CO 3 and sulfates of sodium, potassium and lithium. The second part of the catalyst consists of chlorides, sulfates and carbonates of iron and chromium. The atomic ratio between alkaline metal and iron or chromium varies between 5 to 95 to 95 to 5. The quantity of catalyst used is in the range from 0.01 to 5%. If the gasification-heat is solely coming from the recombination of carbon dioxide and lime (or calcined dolomite), the feed mixture to the gasifier will be too bulky. Therefore, a part of the heat required for the gasification should come from indirect-heat-transfer from burning a part of the pyrolyzed gas generated. The ratio between these two heat sources(heat from indirect-heat-transfer to the chemical reaction heat) varies from 1:4 to 4:1. To lower the cost of carbon dioxide, the supply of carbon dioxide to the gasifier should adopt a counter-current principle to keep the partial pressure of carbon dioxide in the product stream leaving the gasifier as low as possible.
Generation of Clean Steam From Municipal Sewage Sludge (MSS)
[0015] Municipal sewage sludge is pumped from the MSS storage 13 , via line 151 , and mixed with 0.05 to 4.0% of electrolytes choosing from soluble salts of sodium, potassium and iron, into a series of sludge solids removers 17 and 18 . They are screw-conveyor type heat-exchangers. The water content of the sludge flows into a filter 19 . The solid contents of the MSS are removed from the liquid phase by a combined influence of mechanical shears, heat, electrolytes and filtration. The soluble contents and the hardness of the MSS are removed by chromatograph and ion exchangers (not shown in the drawing). The purified water is pumping to waste-heat-boiler 15 via line 131 . The heat supplied to the boiler is coming from the flue gas leaving the combustor 7 via line 128 . The steam from boiler 15 is fed into steam compressor 14 . High pressure steam from 14 is fed into the integrated gasifier to support the carbon-steam reaction.
Combustion of Gasification Residues
[0016] The gasification residues leave the gasifier via lines 118 , 125 and move into combustor 7 . They are burnt with the preheated air from air preheater 8 . Air comes into preheater 8 via line 109 . The air is preheated by the outgoing calcined lime (or dolomite) and the ashes from the burning of gasification residues. The air should be preheated to 700-800° C. or above before entering combustor 7 . The preheater and the combustor can be two zones of one piece of equipment. In the combustor, the preheated air meets with the hot (around 777° C.) gasification residues from the gasifier counter-currently. A combustion temperature above 1600° C. can be achieved. Under such condition, the limestone (or dolomite) formed in the gasifier decomposes to carbon dioxide and calcined lime (or calcined dolomite). A part of the heat from the combustion is stored endothermically in the mixture of carbon At dioxide and calcined lime (calcined dolomite) as chemical energy. This energy will later release exothermically when carbon dioxide and lime (or calcined dolomite) recombine in the gasifier to support the carbon-steam reaction (which is endothermic). Hazardous materials present originally in the feed stocks or in the raw hazardous wastes introduced into the combustor, or formed in the pyrolysis or gasification, such as PCBS, dioxins, pesticides, etc. are destroyed at such high temperatures. Hydrochloric acid and chlorine formed are neutralized by the lime or calcined dolomite present. In both the preheater and the combustor, high turbulence is produced in the air and solids streams by rotary stirrers in case of small scale operation and by means of rotary type kiln in case of large scale operation. Extremely efficient heat-transfer is maintained between the media, the lime (or dolomite) mixed with ashes and the air. The lime (or calcined dolomite) and ashes, after serving as heat transfer agents, are returned to the gasifier to recombine with carbon dioxide to generate heat required for carbon-steam reaction. The flue gas which contains considerable quantity of carbon dioxide is first sent to a waste heat boiler 15 vis line 128 , then into a carbon dioxide recovery system through lines 132 and 141 . The walls of the combustor and the preheater are subjected to high temperatures, they should be made of tantalum or its alloys. The combustor and preheater pair is optimally designed to achieve a combustion with a highly preheated air, thermal field averaging, highly efficient heat transfer, maximum heat recovery and minimum NOX formation. Additional heat transfer agent such as ceramic balls may be introduced into the system to increase the temperature of the preheated air. In a extreme case, pure oxygen may be admitted to enrich the oxygen content of the incoming air.
The Treatment of Lime (or Calcined Dolomite)-Ash Mixture
[0017] After recycling many times between the gasifier and the combustor, the lime (or calcined dolomite) will lose its ability to recombine with carbon dioxide. Therefore, part of the lime (or calcined dolomite)-ash mixture must be purged, and fresh lime (or limestone) or dolomite must be added into the system through line 110 . The purged stream is leached with water. The heavy metals content of the leachate is recovered fractionally with hydrogen sulfide or other agents. The remaining solution is evaporated to recover its soluble salt contents which is recycled back to the system to served as catalyst.
[0018] Purification, Disposal and Utilization of Carbon Dioxide There are three reasons for the recovery of carbon dioxide from both the product gas and the flue gas: 1. The removal of carbon dioxide from the product gas will increase its heating value of combustion, which will in turn increase the efficient of power generation when the product gas is used as the energy source. 2. The removal of carbon dioxide from the flue gases will prevent the releasing of this global warming gas into the atmosphere. 3. This process requires that a part of recovered carbon dioxide be recycled to the gasifier to promote the recombination of carbon dioxide and lime (or calcined dolomite) to supply the heat required by the carbon-steam reaction. In this system, there are two absorber-stripper pairs. One for the product gas, another for flue gases. The raw product gas comes from cyclone 12 attaching to gasifier 9 . Then it passes through line 127 into waste-heat-boiler 16 , then via line 140 into the CO 2 absorber 24 . In 24 , carbon dioxide is absorbed by one of the solutions of alkali, methyl and ethyl amine or other absorbing agents. In stripper 25 , carbon dioxide is stripped from the absorbing agent by a low pressure steam. The absorbing liquid is recycled between the two towers via line 142 . A part of the recovered carbon dioxide is compressed as a gas by compressor 23 and it is recycled into the gasifier via line 155 . And the rest carbon dioxide is further liquefied, and discharged through lines 146 and 148 , to beneficial disposal, such as ocean dumping, replacing methane from methane-hydrate, tertiary oil recovery or-other industrial utilization. Equipment E 1 is another similar carbon dioxide recovery system for the flue gases. Flue gases come from waste-heat-boilers 16 and 20 and via lines 132 and 140 . The clean flue gas is discharged into atmosphere through line 153 .
Dual Cycle Power Generation
[0019] A part of the carbon-dioxide-free product gas from the absorber 24 , passing through lines 138 and 135 , is burned in a gas turbine 22 . Electricity is delivered via line 144 . The combustion exhaust from 22 is sent to a steam turbine to generate additional electricity, which is delivered via line 143 . The exhaust steam from the steam turbine, passing through line 145 and entering tower 25 , is used as process steam, mainly to recover pure carbon dioxide in the carbon dioxide stripping tower 25 . The balance of the product gas is sent to the product gas storage 6 via line 123 for the propose of process heating.
|
A zero-pollution wastes disposal and clean-energy generation system is improved by introducing to it a catalyst to lower down the gasification temperature and to prolong the life of the gasification reactor, a simultaneous direct and indirect heat transfer to supply the heat required for carbon-steam reaction and a means for extracting clean water from raw sewage sludge to supply the steam required by carbon-steam reaction. These improvements increase the efficiency and economy of the system and promote the smoothness of its operation.
| 2
|
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims priority under 35 U.S.C. §119 to German Application No. DE 103 61 695.0, filed on Dec. 30, 2003, and titled “Transistor Structure with a Curved Channel Memory Cell and Memory Cell Array for DRAMs, and Methods for Fabricating a DRAM,” the entire contents of which are hereby incorporated by reference.
FIELD OF THE INVENTION
The invention relates to a transistor structure having two source/drain regions, which are formed in a semiconductor substrate, are arranged in a horizontal plane along an x axis with respect to a substrate surface of the semiconductor substrate and are spaced apart from one another by a recess structure, a surface contour of an active zone being predefined by a contour of an auxiliary area composed of the cross sections of the source/drain regions and also the recess structure in the horizontal plane and a sidewall of the active zone being predefined by vertical projection lines of the surface contour into the semiconductor substrate, and the formation of a conductive channel between the two source/drain regions being controllable by a potential at a gate electrode.
BACKGROUND
Memory cells of dynamic random access memories (DRAMs) are usually provided with a respective storage capacitor for storing electrical charge and a selection transistor for addressing the storage capacitor. In this case, a lower limit results for a channel length of the selection transistor, below which lower limit the insulation properties of the selection transistor are inadequate in the turned-off, non-addressed state of the memory cell. The lower limit for an effective channel length L eff limits the scalability of conventional planar transistor cells (PTCs) with a selection transistor oriented horizontally with respect to a substrate surface of a semiconductor substrate.
The functionality of a memory cell is furthermore determined by the resistance of the selection transistor in the turned-on state given addressing of the memory cell. With advancing miniaturization of the structures, an effective channel width W eff of the selection transistor is being increasingly reduced and the charging/discharging current I on of the memory cell is disadvantageously limited.
Therefore, fin field-effect transistors (FinFETs) are known, as are described for example in “Fabrication of Body-Tied FinFETs (omega MOSFETs) using Bulk Si Wafers,” Park et al.; in “2003 Symposium on VLSI Technology Digest of Technical Papers.” Between two source/drain regions of a transistor cell that are arranged in planar fashion, a semiconductor substrate is etched back by a recess step and a fin formed by the semiconductor substrate is shaped between the two source/drain regions in the process. A gate electrode structure envelops the fin from at least two sides. The effective channel length L eff is determined by the length of the fin in accordance with a minimum feature size F governed by the production technology. The effective channel width W eff is determined from the height of the fin, or the depth to which the recess step is carried out.
The effective channel length L eff is linked to the minimum feature size F and limits the scaling potential of the finFET with regard to the leakage current or the insulator properties in the off state. The switching threshold of the finFET depends greatly on production parameters. The fabrication of a fin field-effect transistor as selection transistor of a memory cell with a hole trench capacitor proves to be complex.
Arrangements with vertical transistor cells (VTCs) are known for memory cells with a hole trench capacitor. The source/drain regions of the selection transistor are essentially arranged vertically one above the other in the semiconductor substrate. A channel controlled by a gate electrode of the selection transistor is formed perpendicular to the cell array plane or substrate surface of the semiconductor substrate. The minimum channel width W eff results in accordance with the minimum feature size F. The channel length L eff is dependent on the depth at which the lower source/drain region or a lower edge of the gate electrode is formed.
Disadvantages of the vertical transistor cell are the difficult integration in memory cells having stacked capacitors, the increase in the aspect ratio of a hole trench for forming the memory cell in the case of integration in memory cells having hole trench capacitors, the restricted switch-on/switch-off current I on and also the parasitic action of the gate electrode of a selection transistor on adjacent memory cells.
A vertical memory cell with a vertical transistor structure in which the gate electrode completely encloses a body region arranged between the two source/drain regions is described in “Fully Depleted Surrounding Gate Transistor (SGT) for 70 nm DRAM and Beyond”; Goebel et al. A fin is formed by etching back a semiconductor substrate. A first source/drain region is formed by outdiffusion from an adjacent structure in the base region of the fin. A second source/drain region is provided at the upper edge of the fin. The gate electrode is arranged along the four sidewalls of the fin. The effective channel length L eff results from the depth of etching back for the fin. The effective channel width W eff corresponds to the contour of the fin, at least one side length resulting in a manner dependent on the minimum feature size F. The total effective channel width correspondingly amounts to 2F to 3F. Like the vertical transistor cell, the transistor cell with a surrounding gate electrode, too, can only be integrated in a complex manner in memory cells having stacked capacitors. The high aspect ratios established in the course of processing and the resultant restrictions in the processing and with regard to the storage capacitor are furthermore disadvantageous.
A field-effect transistor with a curved channel is described in “The Breakthrough in Data Retention time of DRAM using Recess-Channel-Array Transistor (RCAT) for 88 nm Feature Size and Beyond”; Kim et al.; in “2003 Symposium on VLSI Technology Digest of Technical Papers.” The two source/drain regions of the field-effect transistor are arranged in a horizontal plane. The gate electrode is arranged in a recess trench introduced into the semiconductor substrate between the two source/drain regions of the transistor. The effective channel length L eff results from the distance between the two source/drain regions and also the depth to which the recess trench provided between the two source/drain regions is introduced into the semiconductor substrate. The effective channel width W eff corresponds to the minimum feature size F.
The continuing restriction of the effective channel width disadvantageously limits the switch-on/switch-off current.
In the case of integration of recess channel FETs in memory cells with a high packing density, the alignment of the gate electrodes with respect to the recess trenches proves to be complex, for instance if both are respectively patterned in the course of a photolithographic method. In contrast to finFET or SGT transistor cells, the active zone is not shielded from the adjacent memory cells by the gate electrode. A parasitic punchthrough of the potential of a gate electrode to the adjacent transistor cells occurs.
An arrangement for memory cells having hole trench capacitors and selection transistors having a gate electrode grooved into the semiconductor substrate (grooved gate) is described in U.S. Pat. No. 5,945,707 (Bronner et al.) and is explained below with reference to FIG. 1 .
In accordance with FIG. 1 , storage capacitors 6 are formed as hole trench capacitors 8 in a semiconductor substrate 1 below a substrate surface 10 . A hole trench capacitor 8 comprises a storage electrode 61 arranged in the interior of a hole trench and a counterelectrode 63 formed as a doped zone in a section of the semiconductor substrate 1 that surrounds a lower section of the storage electrode 61 . A capacitor dielectric 62 is provided between the storage electrode 61 and the counterelectrode 63 . In an upper section of the hole trench capacitor 6 , the storage electrode 61 is insulated from the semiconductor substrate 1 by a collar insulator structure 81 .
An active zone 11 with two selection transistors 9 , 9 ′ is formed by the semiconductor substrate 1 between in each case two adjacent capacitor structures 6 . The source/drain regions 12 , 13 of the selection transistors 9 , 9 ′ are in each case doped sections of the active zone 11 . A respective first source/drain region 12 adjoins the storage electrode 61 of a storage capacitor 6 in the region of a contact window 82 . The second source/drain region 13 is connected via a bit contact 31 to a-data line 33 arranged above the substrate surface 10 . The gate electrode 2 comprises a highly conductive section 2 a . The gate electrodes of selection transistors that are adjacent in the direction perpendicular to the cross-sectional plane are connected to one another and form addressing lines. The addressing lines are enclosed by a gate stack insulator structure 95 and insulated from the data line 33 formed thereabove by an interlayer dielectric 41 .
Between the two source/drain regions 12 , 13 of the selection transistors 9 , 9 ′, a recess trench 18 is introduced in each case from the substrate surface 10 . The recess trench 18 is filled with the material of the gate electrode 2 . A channel region 15 of the selection transistor 9 , 9 ′ extends in the semiconductor substrate 1 along the sidewalls and the bottom of the recess trench 18 . A gate dielectric 16 is provided between the gate electrode 2 and the semiconductor substrate 1 . The recess trench 18 lengthens the effective channel length L eff with regard to a cell current 96 compared with a conventional planar transistor structure.
The patterning of the addressing lines is carried out in a manner aligned with the recess trenches 18 introduced beforehand and the patterning of the recess trenches 18 is carried out in a manner aligned with the hole trenches of the hole trench capacitors 8 . The effective channel width W eff is disadvantageously predefined, in the direction perpendicular to the cross-sectional plane, by the distance with respect to the memory cells that are adjacent in this direction.
SUMMARY
The invention provides a transistor structure which has an improved switch-on and switch-off behavior given the same area requirement in relation to a comparable conventional transistor structure. The invention further encompasses a memory cell with an improved switch-on and switch-off behavior and also a memory cell array and methods for fabricating a DRAM.
A transistor structure with a curved channel has two source/drain regions, which are formed in a semiconductor substrate, are arranged in a horizontal plane with respect to a substrate surface of the semiconductor substrate along an x axis, and are spaced apart from one another by a recess structure. A surface contour of an active zone of the transistor structure is predefined by the outer contours of the source/drain regions and also the recess structure in the horizontal plane. Vertical projection lines of the surface contour into the semiconductor substrate define an active zone of the transistor structure that is delimited by the vertical projection lines. A sidewall of the active zone is predefined by the vertical projection lines of the surface contour.
According to the invention, the gate electrode is provided along the sidewall of the active zone. The gate electrode has at least one section that extends in the x axis between the two source/drain regions and in the vertical direction from the lower edges of the source/drain regions to beyond a lower edge of the recess structure.
In contrast to conventional transistor structures with a curved channel, in the case of the transistor structure according to the invention, the effective channel width is determined largely independently of the known feature size F and results from the depth to which the gate electrodes are formed at the sidewalls of the active zone of the transistor structure.
The gate electrode advantageously has a second section situated symmetrically opposite to the first section at the recess structure. The active zone is protected against interfering influences (cross-gating effects) and the effective channel width is doubled.
In a particularly preferred manner, the active zone of the transistor structure, along the sidewall, is completely surrounded by the gate electrode. The active zone is largely shielded against influences of adjacent transistor structures and a maximum effective channel width is obtained.
A high packing density of transistor structures according to the invention can advantageously be obtained by providing the active zone with two sidewall sections parallel to the x axis. The active zones of a plurality of transistor structures can then be arranged next to one another in rows in a simple manner.
The active zone is preferably formed in a fin of the semiconductor substrate that is provided between two parallel gate electrode trenches. A gate dielectric is provided between the active zone and the gate electrode. The gate electrode is arranged in the gate electrode trenches in a manner spaced apart from the active zone by the gate dielectric.
The invention's transistor structure with a curved channel (curved double gate/surrounded gate FET, CFET) leads to a memory cell according to the invention having a storage capacitor for storing electrical charge and a selection transistor connected in series with the storage capacitor by a source/drain path and having a curved channel. The selection transistor has a first source/drain region connected to a storage electrode of the storage capacitor. A second source/drain region of the selection transistor is connected to a data line for transferring electrical charge to be stored or stored electrically charge. A gate electrode of the selection transistor is connected to an addressing line for the control of the memory cell. An effective channel length L eff of the selection transistor is determined by the depth of a recess structure introduced between the two source/drain regions.
The gate electrode of the selection transistor is formed in accordance with the above-described transistor structure according to the invention and an effective channel width W eff of the selection transistor is thereby increased. The increased effective channel width W eff improves the switching behavior of the memory cell. As a result of the lower resistance in the turned-on state of the selection transistor, a faster access to the memory cell is possible with a reduced power loss. The punchthrough from the gate electrode arranged at least on two sides to the active zone or substrate situated in between is improved. The shielding effect against cross-gating effects is increased.
The memory cells according to the invention can advantageously be ordered to form a novel memory cell array. The memory cell array then has a plurality of memory cells arranged in cell rows and cell columns. Each memory cell comprises a storage capacitor for storing electrical charge and a selection transistor with a curved channel that is connected in series with the storage capacitor by a source/drain path. A first source/drain region of the selection transistor is connected to a storage electrode of the storage capacitor. A second source/drain region of the selection transistor is connected to a data line for transferring electrical charge to be stored and also electrical charge that has formerly been installed. A gate electrode of the selection transistor is connected to an addressing line for the control of the memory cell. An effective channel length L eff of the selection transistor is determined by the depth of a recess structure fitted between the two source/drain regions.
The gate electrodes of the selection transistors are in each case formed in accordance with the gate electrode of the transistor structure according to the invention, so that an effective channel width W eff of the selection transistors is in each case increased. The gate electrodes of selection transistors of memory cells that are respectively arranged in a cell row are connected to one another and form the addressing lines for the control of the memory cells.
Compared with conventional memory cell arrays having selection transistors with a curved channel, for instance that in U.S. Pat. No. 5,945,707, cited in the background, the introduction of recess trenches for the recess structures, on the one hand, and the formation of the gate electrodes, on the other hand, are advantageously decoupled from one another. A difficulty that results from the fact that, by way of example, a first mask for introducing the recess trenches and a second mask for patterning the gate electrodes have to be aligned relative to one another is obviated.
The storage capacitors and the selection transistors of the memory cell array are advantageously arranged in the manner of a chessboard pattern, the selection transistors being assigned to first arrays that are in each case diagonally adjacent to one another and the storage capacitors being assigned in each case to second arrays that are situated in between. In a first preferred embodiment of the memory cell array according to the invention, the storage capacitors are formed as stacked capacitors above a substrate surface of the semiconductor substrate and, in a second preferred embodiment of the memory cell array according to the invention, the storage capacitors are formed as hole trench capacitors, the hole trench capacitors in each case being formed in a manner oriented to a hole trench introduced into the semiconductor substrate.
If the storage capacitors are provided as stacked capacitors, then the active zones are preferably formed with a rectangular surface contour and in each case separated from one another within a cell row by narrow cell insulator trenches. Adjacent cell rows are in each case isolated from one another by wide word line trenches. The recess structures are provided parallel to the cell insulator trenches and approximately equidistantly from in each case two adjacent cell insulator trenches. The addressing lines are arranged in the word line trenches the data lines are led above the substrate surface in each case essentially over the recess structures and also over the cell insulator trenches. This advantageously results in a small area requirement of the memory cells, comparatively minor requirements being made of the alignment of required masks relative to one another.
The cell insulator trenches and the word line trenches preferably emerge from the same etching step and have the same depth.
Preferably, the width of the cell insulator trenches is less than and the width of the word line trenches is greater than twice the layer thickness of the gate electrodes. If the gate electrodes emerge from a spacer etching with a conformal disposition of a gate electrode material and subsequent anisotropic etching-back of the deposited gate electrode material, then the gate electrodes of selection transistors of memory cells that are adjacent in a cell row adjoin one another and form the addressing lines, while gate electrode sections that are separated from one another are produced at the sidewalls of the word line trenches.
The recess structures are preferably made of silicon oxide.
If the storage capacitors of the memory cells are formed as hole trench capacitors, then the active zones and the hole trench capacitors assigned to the active zones are in each case arranged within a cell row, in each case two active zones being separated from one another by a hole trench capacitor situated in between. The cell rows are isolated from one another by word line trenches, and the recess trenches are formed perpendicular to the word line trenches and also arranged approximately equidistantly from the two respectively adjacent hole trench capacitors. The addressing lines are provided in the word line trenches and the data lines are led above the substrate surface perpendicular to the word line trenches. The recess structures provided in the recess trenches are arranged offset to the data lines or respectively equidistantly from two adjacent data lines, thus resulting in a small area requirement of the memory cells of approximately 8×F 2 .
For memory cells with hole trench capacitors, the recess trenches are preferably filled with silicon nitride. If the recess trenches are introduced with the aid of a silicon oxide mask, then it is possible, when using silicon nitride as filling material, for the filling material to be caused to recede selectively as far as the upper edge of the silicon oxide layer.
In accordance with the method according to the invention for fabricating a DRAM having a memory cell array formed from memory cells having stacked capacitors, and a logic region having logic transistor structures for control, addressing and evaluation of the information stored in the memory cell array, firstly a protective layer is provided on a semiconductor substrate. The protective layer comprises a comparatively thick silicon nitride layer (pad nitride) and a stress compensating layer between the semiconductor substrate and the silicon nitride layer. The stress compensating layer reduces thermomechanical stresses between the silicon nitride layer and the semiconductor substrate that are attributable to different coefficients of thermal expansion of the materials.
Afterward, in a photolithographic process, word line trenches and, perpendicular to the word line trenches, cell insulator trenches are introduced through the protective layer into the semiconductor substrate. In this case, the cell insulator trenches are provided such that they are narrower than the word line trenches. A gate dielectric is provided at sidewalls both of the word line trenches and of the cell insulator trenches.
By conformal deposition and anisotropic etching-back, gate electrodes in the form of sidewall spacers are arranged at the sidewalls of the word line trenches and the cell insulator trenches. In the wide word line trenches, the sections of the sidewall spacers that are opposite one another in a respective one of the word line trenches remain insulated from one another, while the gate electrodes in the narrow cell insulator trenches adjoin one another and are connected to one another.
The word line trenches and the cell insulator trenches are filled with a dielectric from which a word line insulator structure emerges. The protective layer is removed in the memory cell array and the uncovered sections of the semiconductor substrate are doped in order to prepare for the formation of the source/drain regions of the selection transistors in a section adjoining the substrate surface.
An auxiliary layer made of a conductive semiconductor material is applied in the region of the memory cell array and caused to recede as far as the upper edge of the word line insulator structures. Through the auxiliary layer, recess trenches are introduced into the semiconductor substrate between the cell insulator trenches, source/drain regions of the selection transistors that are separated from one another by the recess trenches emerging from the doped sections of the semiconductor substrate.
The recess trenches are either covered or partly or completely filled with a dielectric material. Logic transistor structures are produced in the logic region by processing the logic region. The source/drain regions in the memory cell array are in each case connected to a storage electrode of a stacked capacitor or to a data line.
The method according to the invention makes it possible to fabricate DRAMs having the above-described transistor structures as selection transistors in the memory cell array. It is necessary merely to align an exposure mask for forming the recess trenches relative to a mask for forming the cell insulator trenches. Since none of the effective channel length nor the effective channel width W eff is significantly influenced by a misalignment of the mask for the recess trenches, the method according to the invention advantageously has no critical mask processes or alignment processes for lithographic masks.
A further simplification of the processing results by virtue of the word line trenches, the cell array insulator trenches and also shallow insulator trenches in each case being formed simultaneously in the logic region and being filled with a dielectric material. Afterward, the logic region including the shallow insulator structure is covered with a blocking mask and the dielectric material is etched back in the memory cell array to an extent such that it only fills a lower section of the word line trenches and of the cell insulator trenches and forms bottom insulator structures.
The recess trenches are preferably introduced by a hard mask made of silicon oxide being provided on the auxiliary layer and being patterned photolithographically. The recess trenches are introduced into the semiconductor substrate in the region of the openings of the hard mask by an etching process that acts selectively with respect to silicon oxide.
The processing of the logic region preferably comprises the following steps: firstly, the protective layer is removed in the logic region and a silicon nitride protective coating is applied. After the removal of the silicon nitride protective coating in the logic region, logic transistor structures are formed in the logic region. In this case, the region of the memory cell array remains protected against the processing in the logic region by virtue of the overlying silicon nitride protective coating.
The method according to the invention for fabricating a DRAM having a memory cell array having memory cells with hole trench capacitors as storage capacitors firstly comprises the provision of a protective layer on a semiconductor substrate, in which case the protective layer may have a plurality of partial layers, as described above. Hole trench capacitors are formed in the semiconductor substrate, the hole trench capacitors in each case having a contact window (buried strap window) in the upper section. In the region of the contact window, a storage electrode of the hole trench capacitor that is arranged in the interior of a hole trench electrically conductively adjoins the adjoining semiconductor substrate. Outside the contact window, the hole trench capacitor is electrically insulated from the surrounding semiconductor substrate.
The hole trench capacitors are arranged to form cell rows in the memory cell array. Through the protective layer, word line trenches running parallel to the cell rows are introduced between the cell rows.
A gate dielectric is provided on sidewalls of the word line trenches and gate electrodes are arranged in the manner of sidewall spacers on the gate dielectric. The gate electrodes of selection transistors of memory cells that are adjacent in a cell row adjoin one another and form addressing lines. The word line trenches are filled with a dielectric material that forms word line insulator structures beneath the upper edge of the protective layer. The storage electrodes of the hole trench capacitors are caused to recede to below the upper edge of a substrate surface of the semiconductor substrate, thereby uncovering vertical sidewalls of the protective layer that are oriented toward the hole trench capacitors.
The protective layer or the silicon nitride layer as a constituent part of the protective layer is caused to recede in an etching process having a high isotropic component. Since the vertical sidewalls of the protective layer that are oriented toward the hole trenches are uncovered, a section of the protective layer resting between two hole trench capacitors is in each case caused to recede from the sides oriented toward the hole trench capacitors. After the receding step, residual sections of the protective layer remain only over those regions of the semiconductor substrate which are provided for forming the recess trenches. Since no vertical sidewalls of the protective layer are uncovered in the logic region, the protective layer is caused to recede there only in terms of the layer thickness.
An auxiliary oxide layer is applied and caused to recede as far as the upper edge of the residual sections of the protective layer. The residual sections of the protective layer are removed selectively with respect to the auxiliary oxide layer.
A mask for forming the recess trenches has thus emerged from the protective layer in an advantageous and self-aligned manner and without a photolithographic process.
Before the introduction of the recess trenches, the logic region is covered by a blocking mask. The recess trenches are introduced into the semiconductor substrate with the auxiliary oxide layer as a mask in the region of the memory cell array. The blocking mask over the logic region is removed. The recess trenches are covered or at least partly filled with a dielectric.
The logic region is processed, logic transistor structures being formed in the logic region.
The source/drain regions of the selection transistors that are not connected to a storage electrode via a contact window are in each case connected to a data line.
An essential advantage of the method according to the invention resides in the self-aligned formation of a non-photolithographic mask for forming the recess trenches.
In accordance with a preferred embodiment of the method according to the invention, the word line trenches and shallow insulator trenches are filled with a dielectric material in the logic region, the logic region including the shallow insulator structures is covered with a temporary blocking mask and the dielectric material is then caused to recede in the memory cell array. As a result of the dielectric material that has been caused to recede, bottom insulator structures are formed in lower sections of the word line trenches. The insulator structures are advantageously formed simultaneously in the logic region and in the memory cell array.
In accordance with a preferred embodiment of the method according to the invention, source/drain regions of the selection transistors are formed by an implantation, the residual sections of the protective layer that have been caused to recede being used as an implantation mask.
According to a preferred embodiment of the method according to the invention, the filling of the recess trenches firstly comprises an oxidation of the sidewalls of the recess trenches. A conformal nitride liner is deposited and caused to recede essentially anisotropically to below the upper edge of the auxiliary oxide layer.
Parts of the method described can advantageously also be used for fabricating known recess channel transistor structures for memory cells. For this purpose, a protective layer is provided on a semiconductor substrate. Hole trench capacitors arranged to form cell rows are formed in the semiconductor substrate, a storage electrode of the hole trench capacitor being formed in each case by filling a hole trench with a conductive material. The storage electrodes of the hole trench capacitors are caused to recede to below the lower edge of the protective layer. The protective layer is etched back in an etching process having a high isotropically acting component, with the result that residual sections of the protective layer in each case remain in a self-aligned manner approximately centrally between in each case two hole trench capacitors that are adjacent in a cell row. The residual sections of the protective layer that have been caused to recede form a mask for implantation of source/drain regions of the selection transistors that are to be provided in the semiconductor substrate and/or a precursor mask for forming recess trenches.
In order to form the recess trenches, after the protective layer has been caused to recede isotropically, an auxiliary oxide layer is applied, which is subsequently caused to recede as far as the upper edge of the residual sections of the protective layer. After the removal of the residual sections of the protective layer, a self-aligned mask for the introduction of recess trenches is produced by the auxiliary oxide layer.
In contrast to the previously mentioned methods, in this case a section of a gate electrode of the respective selection transistor is provided in the recess trenches. In contrast to customary methods for fabricating conventional recess channel transistors, the critical overlay of the lithographic mask for forming the hole trenches with the mask for forming the recess trenches is obviated. According to the invention, the lithographic mask for forming the recess trenches is unnecessary; it is instead produced in a self-aligned manner with respect to the hole trenches.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention and its advantages are explained in more detail below with reference to figures, mutually corresponding components in each case being designated by the same reference symbols, in each case in a simplified schematic illustration that is not true to scale:
FIG. 1 shows a schematic cross section through a known memory cell arrangement having selection transistors having gate electrodes grooved into the semiconductor substrate (grooved gate);
FIG. 2 shows two cross sections through a transistor structure according to the invention according to a first exemplary embodiment of the invention;
FIGS. 3A-3K show a plan view of and cross sections through a memory cell array according to the invention having stacked capacitors according to a second exemplary embodiment of the invention in different phases of the method according to the invention according to a third exemplary embodiment; and
FIGS. 4A-4I show a plan view of and cross sections through a memory cell array according to the invention having hole trench capacitors according to a fourth exemplary embodiment of the invention in different phases of the method according to the invention according to a further exemplary embodiment.
DETAILED DESCRIPTION
FIG. 2 shows on the left a cross section through a transistor structure 98 according to the invention, and a cross section perpendicular thereto in the right-hand illustration.
In a semiconductor substrate 1 , a first source/drain region 12 and a second source/drain region 13 are formed along a substrate surface 10 along an x axis. The two source/drain regions 12 , 13 are spaced apart from one another by a recess trench 18 . The recess trench 18 is introduced from the substrate surface 10 to below a lower edge of the source/drain regions 12 , 13 . Beneath the source/drain regions 12 , 13 , a body region 14 of the transistor structure 98 is formed by the semiconductor substrate 1 . The body region 14 is surrounded by a gate electrode 2 and is in this case spaced apart from the gate electrode 2 by a gate dielectric 16 . The gate electrode 2 extends essentially from the lower edge of the source/drain regions 12 , 13 to beneath a lower edge of the recess trench 18 . The recess trench 18 is filled with a dielectric material or remains unfilled. The filled or only covered recess trench 18 forms a recess structure. The gate electrode 2 is provided in two partial sections in two gate electrode trenches 20 a running parallel to the x axis.
During operation of the transistor structure 98 , by a suitable potential at the gate electrode 2 , in a section of the body region that adjoins the gate dielectric 16 , a conductive channel 15 is formed between the two source/drain regions 12 , 13 . A cell current 96 flows through the channel 15 . The length of the channel 15 is essentially determined by the depth of the recess structure 18 . The effective channel width is determined by the extent of the gate electrode 2 in the vertical direction with respect to the substrate surface 10 . The source/drain regions 12 , 13 and also the body region 14 form an active zone 11 , which is formed in a fin 17 of the semiconductor substrate 1 , the fin 17 being bounded by the gate electrode 2 on at least two mutually opposite sides.
FIG. 3A shows a plan view of a detail from a memory cell array. In this case, the storage capacitors of the memory cells are formed as stacked capacitors. The memory cells are arranged in mutually orthogonal cell rows and cell columns and the storage capacitors are arranged within the cell rows and cell columns in each case in a manner alternating with selection transistors in a chessboard-like manner.
The active zones 11 of the selection transistors are illustrated as rectangular and separated from one another within a row by narrow cell insulator trenches 64 . Word line trenches 20 are introduced between the cell rows formed by the active zones 11 and the cell insulator trenches 64 , the word line trenches having a larger width than the cell insulator trenches 64 . The source/drain regions 12 , 13 of the active zones 11 are in each case arranged along the row axis corresponding to the x axis of FIG. 2 . The two source/drain regions 12 , 13 of a respective active zone 11 are separated from one another by a recess trench 18 , which has a smaller depth than the word line trenches 20 and the cell insulator trenches 64 . Respectively adjacent source/drain regions 12 , 13 of active zones 11 arranged in a cell column are in each case assigned alternately to a data line 33 or a stacked capacitor. The position of the stacked capacitors results from the position of the respective storage electrodes 61 , which in each case rests on a node pad 36 as upper termination of a capacitor connection structure.
The first source/drain regions 12 are connected to the storage electrode 61 of the respectively assigned stacked capacitor via the capacitor connection structures. The second source/drain regions 13 are connected via bit line contacts 32 to data lines 33 routed between the bit line contacts 32 and an upper edge of the capacitor connection structures or node pads 36 .
FIG. 3C to FIG. 3K illustrate cross sections along the line A-B-C-D in FIG. 3A in various phases of an exemplary embodiment of the method according to the invention.
A semiconductor substrate 1 is provided and a stress equalizing layer, for instance made of silicon dioxide (pad oxide), is applied on a substrate surface 10 of the semiconductor substrate 1 . Well implantations are optionally embodied in the memory cell array at this point in time. A silicon nitride layer (pad nitride) is applied as protective layer 51 to the stress equalizing layer. Active zones 11 of selection transistors are patterned in a photolithographic process. The requisite exposure is performed twice with a head-to-head distance of less than F.
The semiconductor substrate 1 is patterned in the region of a memory cell array 91 by wide word line trenches 20 and narrow cell insulator trenches 64 running perpendicular to the word line trenches 20 , fins with the active zones 11 being shaped between the word line trenches 20 and the cell insulator trenches 64 in the semiconductor substrate 1 . The sidewalls of the active zones 11 are oxidized by an oxidation process. Shallow insulator trenches are formed at the same time as the word line trenches 20 and the cell insulator trenches 64 in a logic region 92 supplementing the memory cell array 91 .
The cell insulator trenches 64 , the word line trenches 20 and also the shallow insulator trenches are filled with silicon oxide. The silicon oxide is planarized and in the process caused to recede as far as the upper edge of the protective layer 51 . The logic region 92 including the shallow insulator trenches is covered by a blocking mask and the silicon oxide is etched back into the trenches 20 , 64 in the memory cell array 91 .
FIG. 3C reveals the state of a semiconductor substrate 1 processed in the manner described after the silicon oxide has been caused to recede. The protective layer 51 rests on a substrate surface 10 of the semiconductor substrate 1 . In the logic region 92 , shallow insulator structures 23 ′ have emerged from the shallow insulator trenches.
In the memory cell array 91 , word line trenches 20 and cell insulator trenches 64 having the same depth are introduced into the semiconductor substrate 1 through the protective layer 51 . Bottom insulator structures 23 formed by the silicon oxide are in each case arranged in the lower section of the word line trenches 20 and of the cell insulator trenches 64 .
A gate dielectric 16 is formed on the sidewalls of the active zones 11 by oxidation of the material of the semiconductor substrate 1 . By conformal deposition of titanium nitride or doped polysilicon, sidewall spacer structures 21 are formed as sections of gate electrodes on the sidewalls of the word line trenches 20 and of the cell insulator trenches 64 .
As illustrated in FIG. 3D , in this case the sidewall spacer structures 21 are separated from one another in the wide word line trenches 20 , whereas in the narrow cell insulator trenches 64 they adjoin one another and form conductive structures or addressing lines that are contiguous along the cell row.
After the formation of the sidewall spacer structures 21 , the word line trenches 20 and also the cell insulator trenches 64 are filled with a dielectric material. The dielectric material is caused to recede as far as the upper edge of the protective layer 51 by a planarization step. The dielectric material that has been caused to recede forms word line insulator structures 24 in the word line trenches 20 and the cell insulator trenches 64 .
In the memory cell array 91 , the protective layer 51 is removed and the formation of source/drain regions 12 , 13 is prepared by doping of sections of the semiconductor substrate 1 which is uncovered in the region of the memory cell array 91 , said sections adjoining the substrate surface 10 . An auxiliary layer 71 made of n-doped polysilicon is applied and caused to recede by a planarization step as far as the upper edge of the word line insulator structures 24 in a manner corresponding to the upper edge of the protective layer 51 in the logic region 92 .
In accordance with FIG. 3E , the protective layer 51 is replaced by the auxiliary layer 71 in the memory cell array 91 . A section of the semiconductor substrate 1 that adjoins the substrate surface 10 is doped in preparation for the formation of the source/drain regions 12 , 13 .
A hard mask 72 is applied to the auxiliary layer 71 in the region of the memory cell array 91 and also to the section of the protective layer 51 that remains in the logic region 92 , and is patterned by a photolithographic method for forming the recess trenches 18 .
In accordance with FIG. 3F , the hard mask 72 is opened at the locations provided for forming the recess trenches 18 .
The recess trenches 18 are introduced into the semiconductor substrate 1 through the openings of the hard mask 72 and through the auxiliary layer 71 by an etching process that acts selectively with respect to silicon oxide. The mask for forming the recess trenches 18 is striplike.
The sidewalls of the recess trenches 18 are oxidized. The recess trenches 18 are filled with silicon oxide, which is subsequently caused to recede as far as the upper edge of the auxiliary layer 71 by a planarization step. The protective layer 51 is removed in the logic region 92 . A silicon nitride protective coating 73 is applied over the whole area and subsequently removed again in the logic region 92 .
FIG. 3G shows the recess trenches 181 filled with silicon oxide and also the silicon nitride protective coating 73 covering the memory cell array 91 .
The silicon nitride layer protective coating 73 protects the structures formed in the region of the memory cell array 91 against processing in the logic region 92 . In the course of the processing of the logic region 92 , logic transistor structures 93 having logic gate structures 53 and logic source/drain regions 54 are formed in the logic region 92 for instance in the course of a dual work function process. An interlayer dielectric 41 is applied and planarized. In a photolithographic process, openings corresponding to second source/drain regions 13 that are to be connected to a data line 33 are introduced into the interlayer dielectric 41 .
FIG. 3H shows logic transistor structures 93 having logic gate structures 53 and logic source/drain regions 54 in the logic region 92 . In the memory cell array 91 , the interlayer dielectric 41 together with the underlying silicon nitride protective coating 73 is opened above the second source/drain regions 13 .
The openings in the interlayer dielectric 41 are filled with a conductive material, for instance tungsten. After a planarization step, the conductive material caused to recede into the openings forms bit contacts 32 , which adjoin the sections of the auxiliary layer 71 which are assigned to the second source/drain regions 13 .
Once again a conductive material, for instance tungsten, and also silicon nitride are deposited successively. In a photolithographic method, the silicon nitride layer and the underlying layer made of the conductive material are patterned jointly, data lines 33 emerging from the layer made of the conductive material and a data line dielectric 42 covering the data lines 33 emerging from the silicon nitride layer. Vertical sidewalls of the data lines 33 are covered with silicon nitride spacer structures by conformal deposition and anisotropic etching-back. A further filling dielectric 43 (BL interdielectric fill) is provided between the data lines 33 by deposition and subsequent receding as far as the upper edge of the data line dielectric 42 .
In accordance with FIG. 3I , the second source/drain regions are in each case connected via bit line contacts 32 to data lines 33 routed above the substrate surface 10 . The data lines 33 are covered by a data line dielectric 42 . Between the data lines 33 , an intermediate data line dielectric 43 supplements the interlayer dielectric 41 . Equivalently to this, a wiring plane 32 ′ is shaped in the logic region 92 .
A further silicon dioxide layer is deposited and capacitor connection structures 35 are patterned, via which the first source/drain regions 12 are to be connected to storage electrodes 61 of stacked capacitors 7 that are subsequently to be processed. In this case, sections of the conductive auxiliary layer 71 are uncovered in the region of the first source/drain regions 12 by an etching through the further silicon dioxide layer and between two data lines 33 that are in each case encapsulated by silicon nitride spacer structures. The contact holes produced in this way are filled with a conductive material, for instance tungsten. The conductive material is planarized, capacitor connection structures 35 being formed in the contact holes. Aerially extended node pads 36 rest on the capacitor connection structures 35 .
FIG. 3J shows capacitor connection structures 35 that are led as far as the upper edge of the sections of the auxiliary layer 71 that correspond to the first source/drain regions 12 .
Stacked capacitors 7 are subsequently formed, the storage electrodes 61 of which in each case rest on the node pads 36 and adjoin them.
FIG. 3K illustrates storage capacitors 6 formed as stacked capacitors 7 . The stacked capacitors 7 in each case comprise a storage electrode 61 , a counterelectrode 63 and a capacitor dielectric 62 that spaces apart the two electrodes 61 , 63 from one another. The storage electrode 61 in each case electrically conductively adjoin the respectively assigned node pad 36 .
The structure and also the functioning of the memory cell are explained with reference to the two cross sections illustrated in FIG. 3B .
The left-hand illustration of FIG. 3B shows a cross section through a memory cell according to the invention along a row direction which is predetermined by the arrangement of the two source/drain regions 12 , 13 and defines an x axis. The right-hand illustration shows two memory cells arranged in two adjacent cell rows perpendicular to the x axis, the two source/drain regions 12 , 13 of two adjacent selection transistors in each case being arranged offset relative to one another.
As can further be gathered from the left-hand illustration of FIG. 3B , the active zones 11 of selection transistors that are in each case adjacent in a cell row are separated from one another by cell insulator trenches 64 . A first source/drain region 12 is in each case formed within the active zone 11 , and is connected to a storage electrode 61 of a stacked capacitor via a section of an auxiliary structure 71 and a capacitor connection structure 36 . A second source/drain region 13 is connected to a data line 33 via a further section of the auxiliary structure 71 and via an adjoining bit line contact 32 . The lower section of the cell insulator trenches 64 is filled with a bottom insulator structure 23 . Between the two source/drain regions 12 , 13 , the semiconductor substrate 1 forms a body region 14 into which a recess trench 18 is introduced.
The right-hand illustration of FIG. 3B reveals that the active zones 11 are enclosed along the x axis by gate electrodes in the form of sidewall spacer structures 21 which are spaced apart from the semiconductor substrate 1 and the active zones 11 by a gate dielectric 16 .
If a suitable potential is applied to the gate electrode or the sidewall spacer structure 21 , then a conductive channel 15 forms in the sections of the body zone 14 that are opposite to the sidewall spacer structures 21 at the gate dielectric 16 , the conductive channel connecting the two source/drain regions 12 , 13 to one another. The effective channel length L eff of the channel 15 results from the depth of the filled recess trench 18 . The effective channel width W eff of the channel 15 results from the distance between the lower edge of the recess structure in the recess trench 18 and the lower edge of the sidewall spacer structures 21 .
The drawings of FIGS. 4A-4I illustrate an exemplary embodiment of a method for forming a memory cell array having hole trench capacitors as storage capacitors.
FIG. 4A shows the structure to be processed in plan view. In this case, the selection transistors are represented by active zones 11 assigned to them. The active zones 11 are arranged with the respectively assigned hole trench capacitors 8 in cell rows which are arranged offset relative to one another, thus resulting in a chessboard-like arrangement of active zones 11 and hole trench capacitors 8 . The active zone 11 of a memory cell is delimited by in each case two hole trench capacitors 8 within a cell row, one of the two hole trench capacitors 8 that delimit the active zone 11 having a contact window in the region of which a first source/drain region 12 of the active zone 11 adjoins a storage electrode 61 in the interior of the hole trench capacitor 8 . The active zone 11 is insulated from the storage electrode of the other hole trench capacitor 8 ′ by a collar insulator structure provided in the interior of the hole trench capacitor 8 .
Word line trenches 20 are introduced between the cell rows formed by the hole trench capacitors 8 and the active zones 11 , said word line trenches intersecting an upper section of the hole trench capacitors 8 . Data lines 33 are routed orthogonally with respect to the word line trenches 20 , and are connected via bit line contacts 32 to in each case a second source/drain region 13 of the selection transistors or the active zones 11 . Recess trenches 18 are introduced into the active zones 11 in each case between the bit lines 33 , which recess trenches in each case separate the first source/drain regions 12 from the second source/drain regions 13 and the depth of which recess trenches predefines an effective channel length L eff of the selection transistors.
An illustration is given below of an exemplary embodiment of the method according to the invention for fabricating a DRAM having such a memory cell array along the cross section A-B-C-D of FIG. 4A .
A protective layer 51 made of silicon nitride, under which is situated a stress equalizing layer, is applied to a semiconductor substrate 1 . Hole trenches are introduced into the semiconductor substrate 1 by a photolithographic process. Hole trench capacitors 8 are formed in a manner oriented in or at the hole trenches. In an upper section, the hole trench capacitors 8 are in each case lined by a collar insulator structure 81 , which insulates a storage electrode 61 provided in the interior of the hole trench from the active zones 11 formed in the adjoining semiconductor substrate 1 . Opposite a respective active zone 11 that is adjacent in the cell row, the collar insulator structure 81 has an opening that forms a contact window 82 . The formation of the hole trench capacitor 8 is concluded by the formation of the storage electrode 61 , for which the hole trench is finally filled with doped polysilicon that is subsequently caused to recede as far as the upper edge of the protective layer 51 .
By a photolithographic process, word line trenches 20 are introduced in striplike fashion parallel to the cell rows. The cell rows are separated from one another by the word line trenches 20 . Uncovered vertical sidewalls of the active zones 11 are oxidized. The word line trenches 20 in the memory cell array 91 and shallow insulator trenches in the logic region 92 , which have emerged for instance from the same lithographic process, are filled with silicon oxide that is subsequently caused to recede as far as the upper edge of the protective layer 51 . The silicon oxide is caused to recede into the word line trenches 20 by an etching-back step that acts only in the memory cell array 91 .
FIG. 4B illustrates the silicon oxide that has been caused to recede and forms bottom insulator structures 23 in lower sections of the word line trenches 20 . In the logic region 92 , the silicon oxide is not caused to recede and forms shallow insulator structures 23 ′.
In the memory cell array 91 , the active zone 11 of a selection transistor assigned to a hole trench capacitor 8 ′ is delimited by two hole trench capacitors 8 , 8 ′. The storage electrode 61 of the hole trench capacitor 8 ′ adjoins the active zone 11 in the region of a contact window 82 . The storage electrode 61 of the second hole trench capacitor 8 that delimits the active zone 11 in the cell row is insulated from the active zone 11 of the memory cell by the collar insulator structure 81 .
A gate dielectric 16 is formed on the uncovered vertical sidewalls of the active zones 11 by an oxidation process. By conformal deposition and anisotropic etching-back of a conductive material such as titanium nitride or doped polysilicon, gate electrodes are formed in the manner of sidewall spacer structures 21 on the sidewalls of the word line trenches 20 . The word line trenches 20 are subsequently filled with a dielectric material that is caused to recede as far as the upper edge of the protective layer 51 by a planarization step and forms word line insulator structures 24 in the word line trenches 20 . The upper edge of the storage electrode 61 is caused to recede to below the lower edge of the protective layer 51 by an etching step that acts selectively on polysilicon.
FIG. 4C illustrates the sidewall spacer structures 21 in the word line trenches 20 , which in each case enclose an active zone 11 on both sides. The sidewall spacer structures 21 arranged within a word line trench 20 are insulated from one another by the word line insulator structure 24 . The sidewall spacers structures 21 respectively forming the gate electrode of active zones 11 that are respectively adjacent in a cell row adjoin one another via the intervening hole trench capacitors 8 , 8 ′ and form addressing lines.
The protective layer 51 or a silicon nitride layer portion thereof is caused to recede by an etching process having an isotropically acting component. Since the vertical sidewalls of the residual sections of the protective layer 51 that are oriented toward the hole trench capacitors 8 , 8 ′ are uncovered, the protective layer 51 is also caused to recede from the side areas oriented toward the hole trench capacitors 8 , 8 ′. The receding process is terminated as soon as residual sections 511 of the protective layer that has been caused to recede in each case cover that section of the active zone 11 which is provided for forming the recess trenches 18 .
FIG. 4D illustrates the sections of the protective layer 511 that has been caused to recede in this way. The sections of the protective layer 511 that has been caused to recede have a smaller layer thickness than the original protective layer 51 . No etching attack has taken place via the side areas of the protective layer 51 that are covered by the word line insulator structures 24 . By contrast, the protective layer 51 has been caused to recede from the side areas oriented toward the hole trench capacitors 8 and completely covers only a central section of the active zone 11 between the two adjacent word line insulator structures 24 . The protective layer 51 has not been caused to recede from the side areas facing the word line insulator structures 24 .
A section of the semiconductor substrate 1 that adjoins the substrate surface 10 is doped by implantation, thus preparing for the formation of source/drain regions 12 , 13 . An auxiliary oxide layer 84 is applied and is caused to recede by a planarization step as far as the upper edge of the protective layer 511 that has been caused to recede. The residual sections 511 of the protective layer that have been caused to recede are removed and, for the subsequent etching step, the logic region 93 is covered by a blocking mask 52 made of a photoresist material.
The structure illustrated in FIG. 4E is produced. The protective layer 51 or 511 has been completely removed. Instead, a patterned auxiliary oxide layer 84 rests in the region of the memory cell array 91 . The openings of the auxiliary oxide layer 84 corresponds to the residual sections 511 of the protective layer 51 that have been caused to recede. The auxiliary layer 84 forms a mask for the subsequent etching process for forming the recess trenches 18 . The mask is self-aligned with respect to the hole trench capacitors 8 . The logic region 92 is covered by a blocking mask 52 .
Recess trenches 18 are introduced into the semiconductor substrate 1 through the openings of the auxiliary oxide layer 84 .
The etching process for forming the recess trenches 18 is effected selectively with respect to the silicon oxide of the auxiliary oxide layer 84 and furthermore selectively with respect to the photoresist material of the blocking mask 52 .
FIG. 4F illustrates the recess trenches 18 introduced into the semiconductor substrate 1 in the region of the active zones 11 . Within the active zone 11 , a first source/drain region 12 connected to the storage electrode 61 of the assigned hole trench capacitor 8 is separated from a second source/drain region 13 by the recess trench 18 .
The blocking mask 52 is removed and the sections of the active zones 11 that are freed by the recess trenches 18 are oxidized. A conformal silicon nitride layer is deposited and the recess trenches 18 are filled in the process. The conformally deposited silicon nitride layer is caused to recede as far as the upper edge of the auxiliary oxide layer 84 .
In accordance with FIG. 4G , the recess trenches 18 are filled with a silicon nitride filling structure 182 . The deposition of the silicon nitride layer and also the process of causing it to recede are controlled such that the silicon nitride layer is completely removed in the logic region 92 .
The logic region 92 is processed, logic transistor structures having logic gate structures 53 and logic source/drain regions 54 being formed. After the formation of the logic gate structures 53 , a dielectric material is applied, which insulates the logic gate structures 53 from one another and is provided as an interlayer dielectric 41 in the region of the memory cell array 91 .
The structures covered by the interlayer dielectric 41 in the memory cell array 91 and also in the logic region 92 are illustrated in FIG. 4H .
By a photolithographic method, openings are provided in the interlayer dielectric 41 as far as the substrate surface 10 in the region of the second source/drain regions 13 . The openings are filled with a conductive material, for instance tungsten. After the filling material has been caused to recede as far as the upper edge of the interlayer dielectric 41 , the conductive material forms bit line contacts 32 that adjoin the semiconductor substrate 1 in the region of the second source/drain regions 13 . A layer made of a conductive material is applied and data lines 33 are patterned from the layer made of the conductive material by a photolithographic method. An intermediate data line dielectric 43 is provided between the data lines 33 .
In accordance with FIG. 4I , the method yields a DRAM having a memory cell array 91 and a logic region 92 . The memory cell array 91 comprises memory cells having in each case a selection transistor 9 and a hole trench capacitor 8 . The active zone 11 of the selection transistor 9 is formed in a fin 17 of the semiconductor substrate 1 .
Within a cell row, the fin 17 is delimited by in each case two adjacent hole trench capacitors 8 . Toward adjacent cell rows, the fin 17 is delimited by word line trenches 20 running parallel. A gate dielectric 16 is formed along the sidewalls of the fins 17 oriented toward the word line trenches 20 .
Furthermore, provision is made of gate electrodes that are arranged along the fins 17 in the word line trenches 20 , said gate electrodes being formed in the manner of sidewall spacer structures 21 . The sidewall spacer structures 21 are seated on bottom insulator structures 23 in the word line trenches 20 . In the upper section, the hole trench capacitors 8 are lined by a collar insulator structure 81 , which insulates a storage electrode 61 arranged in the interior of a hole trench from the semiconductor substrate 1 adjoining the upper section of the hole trench and from the structures formed there. The collar insulator structure 81 is caused to recede on the side facing the active zone 11 of the assigned selection transistor, with the result that the storage electrode 61 electrically conductively adjoins the first source/drain region 12 of the assigned selection transistor in the region of a contact window 82 .
A second source/drain region 13 of the selection transistor adjoins the collar insulator structure 81 of the hole trench capacitor 8 of the adjacent memory cell. A recess trench 18 is introduced between the two source/drain regions 12 , 13 and is filled with a silicon nitride filling 182 . The second source/drain region 13 adjoins a bit line contact 32 which rests on the substrate surface 10 and via which the second source/drain region 13 is connected to a data line 33 provided above the bit line contacts.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. Accordingly, it is intended that the present invention covers the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
LIST OF REFERENCE SYMBOLS
1 Semiconductor substrate
10 Substrate surface
11 Active zone
12 First source/drain region
13 Second source/drain region
14 Body region
15 Channel
16 Gate dielectric
17 Fin
18 Recess trench
181 Filling of recess trench
182 Filling of recess trench
2 Gate electrode
2 a Highly conductive section
20 Word line trench
20 a Gate electrode trench
21 Sidewall spacer structure
23 Bottom insulator structure
23 ′ Shallow insulator structure
24 Word line insulator structure
31 Bit contact
32 Bit line contact
33 Data line
33 ′ Date line
35 Capacitor connection structure
36 Node pad
41 Interlayer dielectric
42 Data line dielectric
43 Intermediate data line dielectric
44 Intermediate capacitor dielectric
51 Protective layer
511 Protective layer caused to recede
52 Blocking mask
53 Logic gate structure
54 Logic source/drain region
6 Storage capacitor
61 Storage electrode
62 Capacitor dielectric
63 Counterelectrode
64 Cell insulator trench
7 Stacked capacitor
71 Auxiliary layer
72 Hard mask
73 Silicon nitride protective coating
8 Hole trench capacitor
80 Hole trench recess
81 Collar insulator structure
82 Contact window
84 Auxiliary oxide layer
9 Selection transistor
91 Cell array
92 Logic region
93 Logic transistor structure
94 Intergate dielectric fill
95 Gate stack insulator structure
96 Cell current
97 Memory cell
98 Transistor structure
|
A transistor structure having source/drain regions arranged in a horizontal plane along an x axis has a recess structure, which separates the two source/drain regions from one another and increases the effective channel length L eff of the transistor structure. A vertical gate electrode with respect to the horizontal plane extends along the x axis and in this case encloses an active zone of the transistor structure from two sides or completely. The effective channel width W eff is dependent on the depth to which the gate electrode is formed. A memory cell having a selection transistor in accordance with the transistor structure has both a low leakage current and a good switching behavior. By a suitable integration concept, the transistor structure is integrated into a memory cell array of a DRAM having hole trench capacitors or stacked capacitors.
| 7
|
BACKGROUND
1. Technical Field
The present invention relates to a horizontal multi-joint robot and a robot.
2. Related Art
JP-A-2009-226567 describes a horizontal multi-joint robot (SCARA robot) according to the related art. The horizontal multi-joint robot described in JP-A-2009-226567 has a pedestal, a first arm mounted on the pedestal so that the first arm can swivel (i.e., turn, rotate or pivot), a second arm mounted on the first arm so that the second arm can swivel, a work head mounted on the second arm, and a harness (duct) with one side thereof mounted on the pedestal and the other side thereof mounted on the second arm. Wires and pipes connected to a second arm drive motor and a work head drive motor are housed inside the harness. Such a horizontal multi-joint robot of JP-A-2009-226567 has, for example, the following two problems.
The first problem is that driving of the horizontal multi-joint robot causes the harness to shake and thus generates unwanted vibration. Specifically, in the horizontal multi-joint robot of JP-A-2009-226567, the root of the harness on the pedestal side is shifted from the axis of the first arm and the root of the harness on the second arm side is shifted from the axis of the second arm. Therefore, when the first and second arms swivel, the distance between both roots of the harness changes and this change causes the harness to deform and vibrate unnecessarily. Also, the swiveling of the first and second arms causes the harness to twist and vibrate unnecessarily. Such unnecessary vibration of the harness causes deterioration in the vibration damping of the horizontal multi-joint robot (increases the time required for the vibration to subside to a predetermined magnitude).
The second problem is that the horizontal multi-joint robot is increased in size. Specifically, the harness has a large height since both ends of the harness extend directly upward so as to coincide with the axes of the first and second arms. Therefore, a large space is required to place the harness which increases the size of the horizontal multi-joint robot.
SUMMARY
An advantage of some aspects of the invention is that a horizontal multi-joint robot and a robot in which vibration of the duct at the time of driving can be restrained and the installation space of the duct can be reduced.
An aspect of the disclosure is directed to a horizontal multi-joint robot including: a first joint capable of swiveling around a first axis; a second joint capable of swiveling around a second axis that is parallel to the first axis and spaced apart from the first axis; and a duct connected to the first joint and the second joint. The first joint is provided with a first connecting portion forming a predetermined angle relative to the first axis. The second joint is provided with a second connecting portion forming a predetermined angle relative to the second axis. The duct has a first end and a second end. The first end is connected to the first connecting portion. The second end is connected to the second connecting portion.
With this configuration, a horizontal multi-joint robot is provided in which vibration of the duct at the time of driving can be restrained and the installation space of the duct can be reduced.
In the horizontal multi-joint robot of the aspect of the disclosure, it is preferable that the first connecting portion is inclined toward the second axis and that the second connecting portion is inclined toward the first axis.
With this configuration, the total length of the duct can be reduced and the curvature of the duct can be restrained to a small value. Therefore, vibration of the duct at the time when the first and second arms are driven or when the driving is stopped can be prevented or restrained.
In the horizontal multi-joint robot of the aspect of the disclosure, it is preferable that a duct connecting portion of the first joint and a duct connecting portion of the second joint are provided within the same plane as the normals of the first axis and the second axis.
With this configuration, the curvature of the duct can be made substantially constant along the axial direction. That is, the concentration of a bending stress on a predetermined part of the duct can be prevented or restrained.
In the horizontal multi-joint robot of the aspect of the disclosure, it is preferable that, if a center axis of the first connecting portion is a third axis, a center axis of the second connecting portion is a fourth axis, an angle formed by the third axis and the first axis is θ1, and an angle formed by the fourth axis and the second axis is θ2, a relation of θ1=θ2 is satisfied.
With this configuration, the curvature of the duct can be made substantially constant along the axial direction. That is, the concentration of a bending stress on a predetermined part of the duct can be prevented or restrained.
In the horizontal multi-joint robot of the aspect of the disclosure, it is preferable that, if a center axis of the first connecting portion is a third axis, a center axis of the second connecting portion is a fourth axis, an angle formed by the third axis and the first axis is θ1, and an angle formed by the fourth axis and the second axis is θ2, each of the angles θ1 and θ2 is 10° or greater and 60° or smaller.
With this configuration, the maximum height of the duct can be restrained and flexure of the first and second joints can also be restrained. Therefore, the curvature of wires within the first and second joints can be reduced and a bending stress applied to the wires can be reduced.
In the horizontal multi-joint robot of the aspect of the disclosure, it is preferable that the first joint and the second joint have the same shape and size.
Thus, the device design is simplified.
In the horizontal multi-joint robot of the aspect of the disclosure, it is preferable that, if a center axis of the first connecting portion is a third axis, and the center axis of the second connecting portion is a fourth axis, the duct extends along a circle having both the third axis and the fourth axis as tangents.
With this configuration, since an equal bending stress is applied to substantially the entire area of the duct, local concentration of stress on a predetermined part of the duct can be securely prevented.
In the horizontal multi-joint robot of the aspect of the disclosure, it is preferable that, if a distance between the first axis and the second axis is L, an average radius of curvature R of the duct satisfies a relation of 0.6L≦R≦L.
With this configuration, excessive flexure of the duct is restrained. Therefore, the bending strength required of the duct can be lowered and, for example, a reduction in the weight of the duct due to a reduced thickness or the like can be realized.
In the horizontal multi-joint robot of the aspect of the disclosure, it is preferable that, if a distance between the first axis and the second axis is L, a relation of 100 mm≦L≦2000 mm is satisfied.
With this configuration, the total length of the duct can be restrained and the curvature of the duct can also be reduced. Moreover, the duct can be effectively reduced in weight.
Another aspect of the disclosure is directed to a robot including: a pedestal; a first arm connected to the pedestal and capable of swiveling around a first axis in relation to the pedestal; a second arm connected to the first arm and capable of swiveling around a second axis that is parallel to the first axis and spaced apart from the first axis, in relation to the first arm; and a wiring section which accommodates a wire therein and conveys the wire from the second arm to the pedestal. The wiring section includes: a duct supporting portion provided to protrude from the pedestal and intersect with the first axis; a first joint connected to the duct supporting portion and capable of swiveling around the first axis in relation to the duct supporting portion; a second joint connected to the second arm and capable of swiveling around the second axis in relation to the second arm; and a duct connected to the first joint and the second joint. The first joint is provided with a first connecting portion forming a predetermined angle relative to the first axis. The second joint is provided with a second connecting portion forming a predetermined angle relative to the second axis. The duct has a first end and a second end. The first end is connected to the first connecting portion. The second end is connected to the second connecting portion.
With this configuration, a robot is provided in which vibration of the duct at the time of driving can be restrained and the installation space of the duct can be reduced.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the invention will be described with reference to the accompanying drawings, wherein like numbers reference like elements.
FIG. 1 is a view showing a preferred embodiment of a horizontal multi-joint robot.
FIG. 2 is an enlarged sectional view of a wiring section provided in the horizontal multi-joint robot shown in FIG. 1 .
FIG. 3 is a perspective view showing a preferred embodiment of a robot.
FIG. 4 is a view showing a first wiring section provided in the robot shown in FIG. 3 .
FIG. 5 is a view showing a second wiring section provided in the robot shown in FIG. 3 .
DESCRIPTION OF EXEMPLARY EMBODIMENTS
Hereinafter, a preferred embodiment of a horizontal multi-joint robot and a robot will be described in detail with reference to the drawings.
Horizontal Multi-Joint Robot
First, a horizontal multi-joint robot will be described.
FIG. 1 is a view showing a preferred embodiment of a horizontal multi-joint robot. FIG. 2 is an enlarged sectional view of a wiring section provided in the horizontal multi-joint robot shown in FIG. 1 .
As shown in FIG. 1 , a horizontal multi-joint robot (SCARA robot: horizontal multi-joint robot) 100 has a pedestal 110 , a first arm 120 , a second arm 130 , a work head 140 , an end effector 150 , and a wiring section 160 . The horizontal multi-joint robot 100 is a representative example of a horizontal multi-joint robot and also a robot.
The pedestal 110 is fixed, for example, to a floor surface, not shown, with bolts or the like. The first arm 120 is connected to an upper end of the pedestal 110 . The first arm 120 is capable of swiveling around a first axis J1 that extends along a vertical direction, in relation to the pedestal 110 .
Inside the pedestal 110 , a first motor 111 which causes the first arm 120 to swivel, and a first decelerator 112 are installed. An input axis of the first decelerator 112 is connected to a rotation axis of the first motor 111 . An output axis of the first decelerator 112 is connected to the first arm 120 . Therefore, when the first motor 111 is driven and a driving force thereof is transmitted to the first arm 120 via the first decelerator 112 , the first arm 120 swivels within a horizontal plane around the first axis J1 in relation to the pedestal 110 . The first motor 111 is provided with a first encoder 113 which outputs a pulse signal corresponding to the amount of rotation of the first motor 111 . Based on the pulse signal from the first encoder 113 , driving (amount of swiveling) of the first arm 120 in relation to the pedestal 110 can be detected.
The second arm 130 is connected to a distal end of the first arm 120 . The second arm 130 is capable of swiveling around a second axis J2 that extends along a vertical direction, in relation to the first arm 120 .
Inside the second arm 130 , a second motor 131 which causes the second arm 130 to swivel, and a second decelerator 132 are installed. An input axis of the second decelerator 132 is connected to a rotation axis of the second motor 131 . An output axis of the second decelerator 132 is connected and fixed to the first arm 120 . Therefore, when the second motor 131 is driven the a driving force thereof is transmitted to the first arm 120 via the second decelerator 132 , the second arm 130 swivels within a horizontal plane around the second axis J2 in relation to the first arm 120 . The second motor 131 is provided with a second encoder 133 which outputs a pulse signal corresponding to the amount of rotation of the second motor 131 . Based on the pulse signal from the second encoder 133 , driving (amount of swiveling) of the second arm 130 in relation to the first arm 120 can be detected.
The work head 140 is arranged at a distal end of the second arm 130 . The work head 140 has a spline nut 141 and a ball screw nut 142 that are coaxially arranged at the distal end of the second arm 130 , and a spline shaft 143 inserted in the spline nut 141 and the ball screw nut 142 . The spline shaft 143 is rotatable around its axis in relation to the second arm 130 and also capable of moving up and down (ascent and descent).
Inside the second arm 130 , a rotation motor 144 and a lift motor 145 are arranged. A driving force of the rotation motor 144 is transmitted to the spline nut 141 by a driving force transmission mechanism, not shown. As the spline nut 141 rotates forward and backward, the spline shaft 143 rotates forward and backward around an axis J5 that extends along a vertical direction. The rotation motor 144 is provided with a third encoder 146 which outputs a pulse signal corresponding to the amount of rotation of the rotation motor 144 . Based on the pulse signal from the third encoder 146 , the amount of rotation of the spline shaft 143 in relation to the second arm 130 can be detected.
A driving force of the lift motor 145 is transmitted to the ball screw nut 142 by a driving force transmission mechanism, not shown. As the ball screw nut 142 rotates forward and backward, the spline shaft 143 moves up and down. The lift motor 145 is provided with a fourth encoder 147 which outputs a pulse signal corresponding to the amount of rotation of the lift motor 145 . Based on the pulse signal from the fourth encoder 147 , the amount of movement of the spline shaft 143 in relation to the second arm 130 can be detected.
The end effector 150 is connected to a distal end (lower end) of the spline shaft 143 . The end effector 150 is not particularly limited and may include, for example, a unit which holds an object to be carried, a unit which processes an object to be processed, or the like.
Plural wires 170 connected to individual electronic components (for example, the second motor 131 , the rotation motor 144 , the lift motor 145 , the second, third and fourth encoders 133 , 146 , 147 and the like) arranged inside the second arm 130 pass through the pipe-like wiring section 160 connecting the second arm 130 and the pedestal 110 to each other and are drawn into the pedestal 110 . Moreover, the plural wires 170 are bundled inside the pedestal 110 and thus drawn up to a control device, not shown, which is installed outside the pedestal 110 and generally controls the horizontal multi-joint robot 100 , along with the wires connected to the first motor 111 and the first encoder 113 .
Since the wires 170 of the individual electronic components inside the second arm 130 are thus drawn into the pedestal 110 via the wiring section 160 , no space for drawing the wires 170 needs to be secured within the pedestal 110 , the first arm 120 and the second arm 130 . Also, for example, the second motor 131 and the second decelerator 132 need not be hollow in order to draw the wires 170 from the second arm 130 to the first arm 120 , and an increase in the size of the second motor 131 and the second decelerator 132 is restrained. Similarly, for example, the first motor 111 and the first decelerator 112 need not be hollow in order to draw the wires 170 from the first arm 120 to the pedestal 110 , and an increase in the size of the first motor 111 and the first decelerator 112 is restrained. Therefore, the pedestal 110 , the first arm 120 , and the second arm 130 can be reduced in size. Also, the total weight of the pedestal 110 , the first arm 120 , and the second arm 130 (the weight including each internal device) can be restrained. Therefore, a reduction in the size and weight of the horizontal multi-joint robot 100 can be realized.
As shown in FIG. 1 and FIG. 2 , the wiring section 160 has a duct supporting portion 161 , a first joint 162 , a second joint 163 , and a duct 164 . These components are connected in the order of the duct supporting portion 161 , the first joint 162 , the duct 164 , and the second joint 163 , from the side of the pedestal 110 . A wire insertion hole which connects the insides of the pedestal 110 and the second arm 130 to each other is formed within the wiring section 160 . That is, the duct supporting portion 161 , the first joint 162 , the second joint 163 , and the duct 164 are all pipe-shaped and have open inner spaces thereof connected in series.
The duct supporting portion 161 protrudes from a rear part on a lateral side of the pedestal 110 and extends with a gentle curve up above the pedestal 110 . Also, the duct supporting portion 161 is arranged so that an upper edge of a distal end of the duct supporting portion 161 is substantially at the same height as an upper end of the second arm 130 . The duct supporting portion 161 is rigid and does not substantially flex or deform.
The first joint 162 is connected to and received by a bearing at the distal end of the duct supporting portion 161 and is capable of swiveling around the first axis J1 in relation to the duct supporting portion 161 . Meanwhile, the second joint 163 is connected to and received by a bearing at a proximal end and upper end of the second arm 130 and is capable of swiveling around the second axis J2 in relation to the second arm 130 .
In this manner, in the horizontal multi-joint robot 100 , the axis of the first joint 162 coincides with the axis of the first arm 120 , and the axis of the second joint 163 coincides with the axis of the second arm 130 . Therefore, no matter how each of the first and second arms 120 , 130 is driven, an inter-axis distance between the axes of the first and second joints 162 , 163 is kept constant. Therefore, deformation (expansion or contraction) of the duct 164 connected to the first and second joints 162 , 163 is prevented or restrained. Consequently, vibration of the duct 164 at the time when the first and second arms 120 , 130 are driven or when the driving is stopped can be prevented or restrained, and vibration of the second arm 130 can be reduced accordingly.
The first joint 162 is bent or curved in the middle in the extending direction. Therefore, it can be said that the first joint 162 has a duct supporting portion connecting portion 162 a connected to the duct supporting portion 161 , a duct connecting portion (first connecting portion) 162 b connected to the duct 164 , and a curved portion 162 c which is situated between the duct supporting portion connecting portion 162 a and the duct connecting portion 162 b and connects these portions at a predetermined angle. The duct supporting portion connecting portion 162 a is provided along a vertical direction, and a center axis thereof coincides with the first axis J1. Meanwhile, the duct connecting portion 162 b is provided so that a portion of a center axis thereof (third axis) J3 overlapping the duct 164 is inclined toward the second joint 163 in relation to the first axis J1.
The second joint 163 has the same shape and size as the first joint 162 . That is, the second joint 163 is bent or curved in the middle in the extending direction and has an arm connecting portion 163 a connected to the second arm 130 , a duct connecting portion (second connecting portion) 163 b connected to the duct 164 , and a curved portion 163 c which is situated between the arm connecting portion 163 a and the duct connecting portion 163 b and connects these portions at a predetermined angle. The arm connecting portion 163 a is provided along a vertical direction, and a center axis thereof coincides with the second axis J2. Meanwhile, the duct connecting portion 163 b is provided so that a portion of a center axis thereof (fourth axis) J4 overlapping the duct 164 is inclined toward the first joint 162 in relation to the second axis J2.
As described above, since the second joint 163 has the same shape and size as the first joint 162 , the first and second joints 162 , 163 can be used interchangeably, making it easy to design the horizontal multi-joint robot 100 . Specifically, angles θ1, θ2, described later, can be easily made equal, and the first and second joints 162 , 163 can be arranged easily at the same height, as described below.
Also, as described above, since the duct connecting portion 162 b is inclined toward the second axis J2 and the duct connecting portion 163 b is inclined toward the first axis J1, the total length of the duct 164 can be restrained and the curvature of the duct can be restrained to a small value. Therefore, vibration of the duct 164 at the time when the first and second arms 120 , 130 are driven or when the driving is stopped can be prevented or restrained.
The duct 164 is flexible and has two ends, that is, a first end 164 a and a second end 164 b . The first end 164 a is connected to the duct connecting portion 162 b of the first joint 162 . The second end 164 b is connected to the duct connecting portion 163 b of the second joint 163 .
The duct 164 is straight in its natural state and is connected to the first and second joints 162 , 163 in a bent and deformed state. Since the duct connecting portions 162 b , 163 b of the first and second joints 162 , 163 are inclined in relation to the first and second axes J1, J2, as described above, upward protrusion of the duct 164 can be restrained (the maximum height T in FIG. 1 can be restrained to a low value). Therefore, a small and vertically short installation space for the duct 164 suffices and the horizontal multi-joint robot 100 can be reduced in size. Also, since the upward protrusion can be restrained, the total length of the duct 164 can be restrained accordingly. Therefore, vibration of the duct 164 at the time when the first and second arms 120 , 130 are driven or when the driving is stopped can be prevented or restrained.
The maximum height T may be preferably as short as possible and, for example, preferably shorter than a maximum reach height at the upper end of the spline shaft 143 (the height of the upper end in the state where the spline shaft 143 is situated the uppermost position). By employing such a height, the horizontal multi-joint robot 100 can be securely reduced in size.
An average radius of curvature R of the center axis of the duct 164 is not particularly limited. However, it is preferable that the average radius of curvature R satisfies the relation of 0.6L≦R≦L, where the distance between the first axis J1 and the second axis J2 is L. By employing such an average radius of curvature R, excessive curving of the duct 164 is restrained. Therefore, the bending strength required of the duct 164 can be lowered and, for example, a reduction in weight of the duct 164 due to reduced thickness or the like can be realized.
Also, the distance L between the first and second axes J1, J2 is not particularly limited. However, it is preferable that the distance L satisfies the relation of 100 mm≦L≦2000 mm. By employing such a distance L, the total length of the duct 164 can be restrained and the curvature of the duct 164 can also be reduced. Moreover, the duct 164 can be effectively reduced in weight, and vibration of the duct 164 at the time when the first and second arms 120 , 130 are driven or when the driving is stopped can be prevented or restrained more effectively.
Here, it is preferable that an angle θ1 formed by the center axis (third axis) J3 of the duct connecting portion 162 b and the first axis J1, and an angle θ2 (=θ1) formed by the center axis (fourth axis) J4 of the duct connecting portion 163 b and the second axis J2 satisfies the relation of 10°≦θ1, θ2≦60°, more preferably 20°≦θ1, θ2≦40°. By employing such a range of θ1, θ2, the maximum height T of the duct 164 can be restrained and excessive curving of the first and second joints 162 , 163 can be restrained. Therefore, the curvature of the wires 170 in the curved portions 162 c , 163 c of the first and second joints 162 , 163 can be reduced and bending stress applied to the wires 170 can be reduced. Also, since the applied bending stress is reduced, the strength required of the wires 170 is lowered accordingly. Thus, a reduction in diameter of the wires 170 and a reduction in weight due to the reduction in diameter can be realized.
Moreover, since the curvature of the duct 164 can be reduced, the bending stress applied to the duct 164 can be reduced. Also, since the applied bending stress is reduced, the strength required of the duct 164 is lowered accordingly. Thus, a reduction in thickness of the duct 164 and a reduction in weight due to the reduction in thickness can be realized.
If θ1, θ2 are below the above lower limit value and the distance L between the first and second axes J1, J2 is short, the duct 164 has a large curvature and processing to increase the strength of the duct 164 , for example, increasing the thickness of the duct 164 or the like may be necessary. On the contrary, if θ1, θ2 exceed the above upper limit value, the wires 170 in the curved portions 162 c , 163 c of the first and second joints 162 , 163 have a small curvature and processing to increase the strength of the wires 170 , for example, increasing the thickness of a coating layer or the like may be necessary.
In this embodiment, the duct connecting portions 162 b , 163 b of the first and second joints 162 , 163 are arranged at the same height. In other words, the duct connecting portions 162 b , 163 b are provided within the same plane as the normals of the first and second axes J1, J2. Moreover, the duct connecting portions 162 b , 163 b have the same slope (θ1, θ2), as described above. Therefore, the curvature of the duct 164 can be made substantially constant along the axial direction and the concentration of bending stress on a predetermined part of the duct 164 can be prevented or restrained. Since the part where stress concentrates tends to be the starting point of vibration, by preventing or restraining the concentration of stress, vibration of the duct 164 at the time when the first and second arms 120 , 130 are driven or stopped can be prevented or restrained more effectively. Also, since the strength required of the duct 164 is lowered, a reduction in thickness of the duct 164 and a reduction weight due to the reduction in thickness can be realized.
It is preferable that the duct 164 (portions excluding the parts overlapping with the first and second joints 162 , 163 ) extends so that the center axis thereof is along a circle (circumference) having the center axis J3 of the duct connecting portion 162 b and the center axis J4 of the duct connecting portion 163 b as tangents. In such a curved state, an equal bending stress is applied to substantially the entire area of the duct 164 and therefore local concentration of stress on a predetermined part of the duct 164 can be prevented more securely. Therefore, vibration of the duct 164 at the time when the first and second arms 120 , 130 are driven or stopped can be prevented or restrained more securely.
Particularly, in this embodiment, since the first and second joints 162 , 163 have the same shape and size, the duct connecting portions 162 b , 163 b can be easily arranged at the same height, for example, by equalizing the installation height of the first and second joints 162 , 163 . Since the first and second joints 162 , 163 thus have the same shape and size, components can be made interchangeable. Thus, the manufacturing cost of the horizontal multi-joint robot 100 can be restrained and the horizontal multi-joint robot 100 can be designed easily.
The above is the description of the horizontal multi-joint robot 100 .
While the duct 164 is flexible in this embodiment, the duct 164 may be rigid. As described above, the duct 164 does not substantially deform no matter how the first and second arms 120 , 130 are driven. Therefore, even if the duct 164 is rigid, this does not affect the driving of the horizontal multi-joint robot 100 . If the duct 164 is made of a rigid material, it is preferable that the duct 164 is made of, for example, a metallic material with environmental resistance. Thus, the horizontal multi-joint robot 100 suitable for use in a special environment is provided.
Robot
Next, a robot will be described.
FIG. 3 is a perspective view showing a preferred embodiment of a robot. FIG. 4 is a view showing a first wiring section provided in the robot shown in FIG. 3 . FIG. 5 is a view showing a second wiring section provided in the robot shown in FIG. 3 .
A robot 300 shown in FIG. 3 is a vertical multi-joint (six-axis) robot having a pedestal 310 , four arms 320 , 330 , 340 , 350 , and a wrist 360 that are connected in order.
The pedestal 310 is fixed, for example, to a floor surface which is not shown in the drawing with bolts or the like. The arm 320 with an attitude inclined in relation to horizontal direction is connected to an upper end of such a pedestal 310 . The arm 320 is capable of swiveling around an axis J6 that extends along a vertical direction in relation to the pedestal 310 .
Inside the pedestal 310 , a first motor 311 which causes the arm 320 to swivel, and a first decelerator 312 are installed. Although not shown, an input axis of the first decelerator 312 is connected to a rotation axis of the first motor 311 , and an output axis of the first decelerator 312 is connected to the arm 320 . Therefore, when the first motor 311 is driven and a driving force thereof is transmitted to the arm 320 via the first decelerator 312 , the arm 320 swivels within a horizontal plane around the axis J6 in relation to the pedestal 310 . The first motor 311 is provided with a first encoder 313 which outputs a pulse signal corresponding to the amount of rotation of the first motor 311 . Based on the pulse signal from the first encoder 313 , the amount of swiveling of the arm 320 in relation to the pedestal 310 can be detected.
The arm 330 is connected to a distal end of the arm 320 . The arm 330 is capable of swiveling around an axis J7 that extends along a horizontal direction in relation to the arm 320 .
Inside the arm 330 , a second motor 331 which causes the arm 330 to swivel in relation to the arm 320 , and a second decelerator 332 are installed. Although not shown, an input axis of the second decelerator 332 is connected to a rotation axis of the second motor 331 , and an output axis of the second decelerator 332 is connected and fixed to the arm 320 . Therefore, when the second motor 331 is driven and a driving force thereof is transmitted to the arm 320 via the second decelerator 332 , the arm 330 swivels within a horizontal plane around the axis J7 in relation to the arm 320 . The second motor 331 is provided with a second encoder 333 which outputs a pulse signal corresponding to the amount of rotation of the second motor 331 . Based on the pulse signal from the second encoder 333 , the driving (amount of swiveling) of the arm 330 in relation to the arm 320 can be detected.
The arm 340 is connected to a distal end of the arm 330 . The arm 340 is capable of swiveling around an axis J8 that extends along a horizontal direction in relation to the arm 330 .
Inside the arm 340 , a third motor 341 which causes the arm 340 to swivel in relation to the arm 330 , and a third decelerator 342 are installed. Although not shown, an input axis of the third decelerator 342 is connected to a rotation axis of the third motor 341 , and an output axis of the third decelerator 342 is connected and fixed to the arm 330 . Therefore, when the third motor 341 is driven and a driving force thereof is transmitted to the arm 330 via the third decelerator 342 , the arm. 340 swivels within a horizontal plane around the axis J8 in relation to the arm. 330 . The third motor 341 is provided with a third encoder 343 which outputs a pulse signal corresponding to the amount of rotation of the third motor 341 . Based on the pulse signal from the third encoder 343 , the driving (amount of swiveling) of the arm 340 in relation to the arm 330 can be detected.
The arm 350 is connected to a distal end of the arm 340 . The arm 350 is capable of swiveling around an axis J9 that extends along a center axis of the arm 340 in relation to the arm 340 .
Inside the arm 350 , a fourth motor 351 which causes the arm 350 to swivel in relation to the arm 340 , and a fourth decelerator 352 are installed. An input axis of the fourth decelerator 352 is connected to a rotation axis of the fourth motor 351 , and an output axis of the fourth decelerator 352 is connected and fixed to the arm 340 . Therefore, when the fourth motor 351 is driven and a driving force thereof is transmitted to the arm 340 via the fourth decelerator 352 , the arm 350 swivels within a horizontal plane around the axis J9 in relation to the arm 340 . The fourth motor 351 is provided with a fourth encoder 353 which outputs a pulse signal corresponding to the amount of rotation of the fourth motor 351 . Based on the pulse signal from the fourth encoder 353 , the driving (amount of swiveling) of the arm 350 in relation to the arm 340 can be detected.
The wrist 360 is connected to a distal end of the arm 350 . The wrist 360 has a ring-shaped support ring connected to the arm 350 , and a cylindrical wrist main body supported on a distal end of the support ring. A distal end surface of the wrist main body is a flat surface and serves, for example, as a mounting surface where a manipulator holding a precision device such as a wristwatch is mounted.
The support ring is capable of swiveling around an axis J10 that extends along a horizontal direction in relation to the arm 350 . The wrist main body is capable of swiveling around an axis J11 that extends along a center axis of the wrist main body in relation to the support ring.
Inside the arm 350 , a fifth motor 354 which causes the support ring to swivel in relation to the arm 350 , and a sixth motor 355 which causes the wrist main body to swivel in relation to the support ring are arranged. Driving forces of the fifth and sixth motors 354 , 355 are transmitted to the support ring and the wrist main body, respectively, by a driving force transmission mechanism, not shown. The fifth motor 354 is provided with a fifth encoder 356 which outputs a pulse signal corresponding to the amount of rotation of the fifth motor 354 . Based on the pulse signal from the fifth encoder 356 , the amount of swiveling of the support ring in relation to the arm 350 can be detected. Also, the sixth motor 355 is provided with a sixth encoder 357 which outputs a pulse signal corresponding to the amount of rotation of the sixth motor 355 . Based on the pulse signal from the sixth encoder 357 , the amount of swiveling of the wrist main body in relation to the support ring can be detected.
Plural wires 370 connected to individual electronic components (for example, third, fourth, fifth and sixth motors 341 , 351 , 354 , 355 , third, fourth, fifth and sixth encoders 343 , 353 , 356 , 357 and the like) arranged insides the arms 340 , 350 pass through a pipe-like first wiring section 380 connecting the arm 340 and the arm 330 to each other and are drawn into the arm 340 . Also, the plural wires 370 pass through a pipe-like second wiring section 390 connecting the arm 330 and the arm 320 to each other and are drawn into the arm 320 . Moreover, the plural wires 370 are bundled inside the arm 320 and thus drawn to the pedestal 310 together with wires connected to the second motor 331 and the second encoder 333 . The wires are then bundled inside the pedestal 310 and thus drawn up to a control device, not shown, which is installed outside the pedestal 310 and generally controls the robot 300 , along with the wires connected to the first motor 311 and the first encoder 313 .
Since the wires 370 of the individual electronic components inside the arms 340 , 350 are thus drawn into the pedestal 310 via the first and second wiring sections 380 , 390 , a large space for drawing the wires 370 need not be secured within the arms 320 , 330 . Therefore, as in the foregoing horizontal multi-joint robot 100 , a reduction in the size and weight of the robot 300 can be realized.
As shown in FIG. 4 , the first wiring section 380 has a first joint 382 , a second joint 383 , and a duct 384 . These components are connected in order of the first joint 382 , the duct 384 , and the second joint 383 , from the side of the arm 330 . A wire insertion hole (not shown) which connects the insides of the arm 330 and the arm 340 to each other is formed within the first wiring section 380 . That is, the first joint 382 , the second joint 383 , and the duct 384 are all pipe-shaped and have open inner spaces thereof connected in series.
The first joint 382 is received by a bearing on the arm 330 and is capable of swiveling around an axis J12 in relation to the arm 330 . Meanwhile, the second joint 383 is received by a bearing on the arm 340 and is capable of swiveling around the axis J8 in relation to the arm 340 . The axis J12 is parallel to the axis J8. Therefore, no matter how the arm 340 is driven in relation to the arm 330 , a distance between the axes of the first and second joints 382 , 383 is kept constant. Therefore, deformation (expansion or contraction) of the duct 384 connected at both ends to the first and second joints 382 , 383 is prevented or restrained. Consequently, vibration of the duct 384 at the time when the arm 340 is driven or when the driving is stopped can be prevented or restrained.
The first joint 382 , the second joint 383 and the duct 384 have similar configurations to the first joint 162 , the second joint 163 and the duct 164 of the foregoing horizontal multi-joint robot 100 , respectively, and therefore will not be described further in detail. Also, with respect to the first wiring section 380 , the arm 330 , the arm 340 , the axis J12 and the axis J8 are equivalent to the first arm, the second arm, the first axis and the second axis described in the appended claims, respectively.
As shown in FIG. 5 , the second wiring section 390 has a first joint 392 , a second joint 393 , and a duct 394 . These components are connected in order of the first joint 392 , the duct 394 , and the second joint 393 , from the side of the arm 320 . A wire insertion hole (not shown) which connects the insides of the arm 320 and the arm 330 to each other is formed within the second wiring section 390 . That is, the first joint 392 , the second joint 393 , and the duct 394 are all pipe-shaped and have open inner spaces thereof connected in series.
The first joint 392 is received by a bearing on the arm 320 and is capable of swiveling around an axis J13 in relation to the arm 320 . Meanwhile, the second joint 393 is received by a bearing on the arm 330 and is capable of swiveling around the axis J7 in relation to the arm 330 . The axis J13 is parallel to the axis J7. Therefore, no matter how the arm 330 is driven in relation to the arm 320 , a distance between the axes of the first and second joints 392 , 393 is kept constant. Therefore, deformation (expansion or contraction) of the duct 394 connected at both ends to the first and second joints 392 , 393 is prevented or restrained. Consequently, vibration of the duct 394 at the time when the arm 330 is driven or when the driving is stopped can be prevented or restrained.
The first joint 392 , the second joint 393 and the duct 394 have similar configurations to the first joint 382 , the second joint 383 and the duct 384 , respectively, and therefore will not be described further in detail. Also, with respect to the second wiring section 390 , the arm 320 , the arm 320 , the axis J13 and the axis J7 are equivalent to the first arm, the second arm, the first axis and the second axis described in the appended claims, respectively.
The above is the description of the robot 300 .
A horizontal multi-joint robot and a robot are described above, based on the illustrated embodiments. However, the invention is not limited to these embodiments and the configuration of each part can be replaced by an arbitrary configuration having similar functions. Also, other arbitrary components may be added within the scope of the invention.
The entire disclosure of Japanese Patent Application No. 2012-233499 filed Oct. 23, 2012 is hereby expressly incorporated by reference herein.
|
A horizontal multi-joint robot includes: a first joint capable of swiveling around a first axis; a second joint capable of swiveling around a second axis that is parallel to and spaced apart from the first axis; and a duct connected between the first joint and the second joint. The first joint has a first connecting portion forming a predetermined angle relative to the first axis. The second joint has a second connecting portion forming a predetermined angle relative to the second axis. The duct has a first end and a second end. The first end is connected to the first connecting portion. The second end is connected to the second connecting portion.
| 1
|
BACKGROUND OF THE INVENTION AND PRIOR ART STATEMENT
The invention relates to a process for the manufacture of substituted 3-sulfopropyl ammonium betaines.
Examples of this class of compounds are used as components of laundry and cleaning agents since they exhibit excellent cleaning power at low temperatures in a suitable formulation; they are further employed as thermostable antistatic agents for molded masses of artificial material as well as coating material for textiles and woven fabrics. Sulfobetaines are also used as emulsifiers and as flotation agents. Good biological degrading ability is of special interest in the mentioned fields of application.
It has also been known to obtain sulfobetaines derived from 2-hydroxy-propane sulfonic acid through alkylation of tert. amines with 3-chloro-2-hydroxy-propane-1-sulfonic acid (DE-OS No. 24 31 031). The synthesis requires application of temperatures from 100° to 135° C., pressure, as well as the use of a considerable excess quantity of alkylation agent, wherein, however, yields of 75% average are obtained. The products are adulterated and difficult to crystallize. A further disadvantage of this synthesis process may be observed in the multi-stage synthesis of the required alkylation agent: glycerine-1.3-dichlorhydrin is obtained starting from allyl chloride, through the addition of HOCl, the epichlorhydrin from that and, ultimately, 3-chloro-2-hydroxy-propane-1-sulfonic acid through conversion with sodium sulfite. Therefore, this synthesis of sulfobetaine is not economical. Further, it has been known to produce sulfobetaines from tert. amines through alkylation with propane sultone (DE-AS No. 24 09 412). The propane sultone is obtained starting with allyl chloride by way of allylalcohol and 3-hydroxypropane-1-sulfonic acid as intermediates. Propane sultone is considered one of the most serious carcinogenic substances and its use, especially in synthesizing processes on a technical sale, requires special preventive measures (H. Druckrey, R. Preussman and collab., Z. Krebsforschung 75 (1970); 69; Registry of Toxic Effects of Chemical Substances, National Institute for Occupational Safety and Health, Maryland, U.S. (1975), 826).
In addition, it has been proposed (W. M. Linfield and colleag., J. Amer. Oil Chem. Soc. 53 (1976), 60; 55 (1978), 87) to add hydrogen sulfite to trialkylallylammonium salts for the synthesis of sulfobetaines of formula II. The conversion requires the simultaneous action of organic peroxide and hydrogen sulfite on allylammonium salts, wherein temperatures from 90° to 100° C. and reaction times of seven hours are required: ##STR1##
Care should be taken to exclude the oxygen from the air when rinsing the reaction mixture with nitrogen. Other disadvantages of this sulfobetaine synthesis are the use of organic solvents, the long reaction times, as well as the mode of operation under pressure in autoclaves. The products obtained are not chemically uniform but comprise isomeric sulfobetaine III, besides the principal product II.
Moreover, additions of hydrogen sulfite radicals to unsubstituted olefins in the presence of peroxides have already been known from Houben-Weyl, vol. 9, page 380, This leads to yields of about 60%. In Houben-Weyl loc. cit. p. 382, chapter B, the statement is made in the example of the addition of hydrogen sulfite radicals to allyl alcohol that the use of catalytically acting heavy metallic ions in the presence of oxygen as opposed to the use of peroxides as catalysts results in an increase in yield by 50% besides other advantages. DE-OS No. 23 31 515 covers a corresponding process for the addition of hydrogen sulfite radicals to unsubstituted olefins, in which transition metals of the 1st, 7th and 8th secondary groups of the Periodic Table of the Elements are employed as catalysts in lieu of peroxides.
The olefins employed in this process, however, are not comparable with the trialkylammonium salts (positively substituted in the allyl position) of this invention since they are unsubstituted, i.e. contain double bonds (DE-OS No. 23 31 515) or are negatively substituted (Houben-Weyl, vol. 9, p. 382) and thus considerably differ from the allylammonium salts of the present invention concerning their electron configuration and reactivity.
SUMMARY OF THE INVENTION
It is the task of the present invention to avert the disadvantages of the known technical solutions and to develop a process for the manufacture of sulfobetaines in which the use of carcinogenic substances can be avoided, and which results in conceivably high yield by using mild reaction conditions, short reaction times and high selectivity.
The amount of organic waste products should be kept herein at a minimum.
This goal is achieved by a process for the production of the sulfobetaines of formula I, ##STR2## in which R 1 represents hydrogen, straight chained or branched alkyl groups with 1-22 C atoms, hydroxyalkyl or aralkyl, R 2 is alkyl groups as cited for R 1 ; R 1 and R 2 may be equivalent or different or form a closed ring; and R 3 represents alkyl groups of the formula CH 3 --(CH 2 ) n- , where n=0 to 25, or branched alkyl groups or hydroxyalkyl groups or substituted alkyl groups, through conversion of trialkylallylammonium salts with hydrogen sulfite radicals, in which an allylammonium compound of the general formula IV according to the present invention ##STR3## where R 1 , R 2 and R 3 have the recognized definition and X represents a fluoride, a chloride, a bromide, a methosulfate or equivalent sulfate, sulfite or phosphate, is reacted with salts of sulfurous acid under thorough mixing, in solution at a pH value of 2-9 and at temperatures from 0° to 100° C., in the presence of initiators, and of ions of the transition metals of the first, fifth, seventh or eighth secondary group of the Periodic Table. It was found that in contrast to the relatively drastic reaction conditions (reaction operating under pressure, high temperatures, long reaction times) required in Linfield (J. Amer. Oil Chem. Soc. 53 (1976) 60; l. c. 55 (1978) 87) for the conversion of allylammonium compounds with hydrogen sulfite radicals, hydrogen sulfite radical addition to allylammonium salts, in the presence of oxygen of air, occurs surprisingly easily by the process of the present invention and under mild conditions quantitatively, when traces of heavy metals are present, the pH range is from 2-9, preferably from 5-8. Only 1-sulfonate is selectively obtained herein, as can be established by 13 C-nucleus-resonance-spectroscopy.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The reaction is subject to a homogeneous catalysis by ions of transition metals of the 1st, 5th, 7th or 8th secondary group of the Periodic Table (for instance, Cu ++ , V 5+ , Mn 4+ , Fe +++ , Co ++ , Ni ++ ), following the same principles herein as understood from the oxidation of SO 3 2- into SO 4 2- in aqueous solution (A. Huss, J. Amer. Chem. Soc. 100 (1978), 19, 6252). The homogeneous catalysis requires extraordinarily low catalyst quantities; 10 -4 gram atoms of any transition metal per liter are entirely sufficient since sulfite oxidation is still demonstrably catalyzed by 10 -8 gram atom/liter. Under practical conditions--namely when workinng with technical chemicals and tap water in technical, metallic containers and arrangements--there are almost always sufficient quantities of Fe +++ , Cu ++ or Ni ++ disposed to trigger the catalysis effect. However, homogeneous catalysis may be excluded by blocking off the heavy metals (as sulfide, mercaptide) or through strong complex formation (ethylene-diamine-tetraacetic acid).
The metals to be catalyzed may be added as salts or oxides. Oxides are sufficiently dissolved in the HSO 3 - -containing reaction medium for homogeneous catalysis to be used. In this way it is possible to also use distinctly technical oxide compounds (as, for instance, lignite ashes) as catalysts. Even when the reaction medium is in contact with metallic Cu, Fe or Ni or in contact with alloys, it will pick up sufficient quantities of metallic ions to trigger the catalysis effect.
In a temperature range from 20°-40° C., a pH range of 5-8 is considered optimum. Then the reaction speed towards sulfobetaine is the greatest, while the secondary reaction of mere sulfite oxidation towards sulfate is minimal. The pH-range may be maintained through buffering or introducing SO 2 . According to the invention, it is desirable to arrange for buffering by a mixture of alkali or ammonium hydrogen sulfite with alkali or ammonium sulfite. Besides maintaining the pH at an optimum level, the use of additional sulfite also compensates for the loss caused while simultaneous sulfate formation is being prepared.
In view of the consumption of the HSO 3 - , the formation of sulfobetaine results in an increase of the pH value; in contrast, the oxidation towards hydrogen sulfate radical results in a pH decrease so that the buffering strength of the reactive mixture need not be great. The addition of the hydrogen sulfite radical to the allylammonium group is made exclusively as anti-Markovnikov addition to 1-sulfonate over a sulfite anion radical as an intermediate step, which is formed after equation 1 (in a homogeneous catalysis by Cu ++ ): ##STR4## In Equation 2, the sulfite anion radical is added to the allylammonium group, forming a sulfobetaine radical which reacts with the hydrogen sulfite anion of Equation 3--present in large quantities in the buffering range--to a sulfobetaine. The resultant sulfite anion radical continues the reaction according to Equation 2 so that the formation of sulfobetaine proceeds in the sense of a radical chain reaction. Oxygen from air regenerates the homogeneous catalyst Cu ++ according to Equation 4. Therefore, oxygen is also needed only in catalytic quantities so that slow air introduction is sufficient to continue sulfobetaine formation; absence of oxygen will, however, interrupt the reaction. Instead of oxygen, the reaction may also be initiated with traditional radical initiators, for instance ammonium persulfate, hydrogen peroxide, by organic peroxides or hydroperoxides or through nitrates or nitrites. This operating procedure as a rule, does not result in advantages because of the greater expenditures involved; however, the use of initiators may be of advantage when operating with foaming reaction mixtures. Also the simultaneous introduction of radical initiators and limited oxygen quantities may be of advantage when foaming substrates without anti-foam additives are to be prepared. Also, initiation by UV or gamma rays is possible.
According to the invention, aqueous solutions may be used. It will be desirable to proceed in a manner so that the solution of allyl ammonium compound and the hydrogen sulfite buffer solution too are gradually added at the same time.
Water-alcohol mixtures may be used when the solubility qualities of allylammonium salts so require, wherein tert butanol or 2-propanol are especially suitable. In long-chained compounds with high surface tension, foam formation may be counteracted by using alcohol-containing solutions. For example, the 2-propanol:water ratio may be 70:30, without the sulfite and hydrogen sulfite becoming insoluble. In the synthesis of strongly foaming sulfobetaines, it may, moreover, be advantageous in individual cases to lower the stirring speed and aeration and to introduce oxygen in low amounts instead of in an air stream.
One may also operate at higher temperatures if the solubility characteristics of the allyl ammonium salts so require; in these cases the optimal pH range is expanded downwardly.
The allyl ammonium salts required for a sulfobetaine synthesis, ##STR5## are obtained by incremental alkylations, wherein, as a rule, the much larger R 3 group or the allyl group is introduced in the last reaction step.
The alkyl group R 3 in formulas I and IV may be substituted. The substituent in R 3 herein may be an aminoalkyl, a carbonic acid amide, a fluorocarbonic acid amide, a carbonic acid ester or a sulfonic amide group. The carbonic acid amide groups or fluorocarbonamide groups may have the following structure:
R.sub.4 --CH.sub.2 --CO--NR.sub.5 --(CH.sub.2).sub.r --,
where r=0 to 3, or
C.sub.m F.sub.2m+1 --CO--NR.sub.5 --(CH.sub.2).sub.r --,
where m=1 to 12 or r=0 to 3, or
CH.sub.2 ═CH--(CH.sub.2).sub.p --CO--NR.sub.5 --CH.sub.2 --CH.sub.2 --,
where p=0 to 13, wherein R 4 and R 5 may have the same definition as R 1 in formula I or formula IV.
Carbonic acid ester groups of the following structures are possible:
R.sub.4 --CH.sub.2 --COO--(CH.sub.2).sub.2 --
or
CH.sub.2 ═CH--(CH.sub.2).sub.q --COO--(CH.sub.2).sub.2 --,
where q=0 to 13, and wherein R 4 has the definition as R 1 .
If a sulfonic amide group is available as a substituent in R 3 , structures such as
R.sub.4 --CH.sub.2 --SO.sub.2 --NR.sub.5 --(CH.sub.2).sub.r --,
where r=0 to 3, or
R.sub.4 --C.sub.6 H.sub.4 --SO.sub.2 --NR.sub.5 --(CH.sub.2).sub.r --,
where r=0 to 3, are possible. R 4 and R 5 then have the definition of R 1 . Aminoalkyl groups of the structure
R.sub.4 --CH.sub.2 --NH--(CH.sub.2).sub.r --,
where r=0-3, are possible.
When R 1 and R 2 form a closed ring, the ring may have the structure or piperidinium or of morpholinium. The advantages of the process of this invention consist in that
the reaction can be processed under mild conditions and, for this reason, power consumption is minimal;
it is possible to use technically pure starting substances;
it is possible to avoid the use of carcinogenous alkylates;
the conversion can be made by using relatively simple equipment;
the reaction times are short, and
selectivity in the reaction is very good and, thus, the yield is very high.
EXAMPLES
EXAMPLE 1
3-sulfopropyltrimethylammonium-betaine R 1 =R 2 =R 3 =CH 3 in the general formula I
1.26 g (0.01 mol) sodium sulfite (Na 2 SO 3 ) are dissolved in 60 ml tap water in a sulfonation flask with a stirrer, thermometer and gas inlet tube. Then, two aqueous solutions of 45 ml each are prepared; one is derived from 13.55 g (0.1 mol) trimethylallylammonium chloride dissolved in tap water; the other one from 9.5 g (0.05 mol) Na 2 S 2 O 5 and 6.3 g (0.05 mol) Na 2 SO 3 dissolved in tap water. The prepared solutions are simultaneously dripped with stirring and simultaneously passing air therethrough during a period of one hour, wherein the temperature of the reaction mixture increases by 8.5° C. During conversion, the pH-value remains in the 7 range. Lowering of the temperature indicates the end of the reaction after a post-reaction time of 15 minutes. Conversion at this time is quantitative, as can be established by 1 H-NMR-spectroscopy with the vanishing of the allyl protons signals.
After the reaction solution is dried in the drier, sulfobetaine is obtained as a colorless, crystalline substance in mixture with sodium sulfite, sodium sulfate and sodium chloride from which betaine cannot be extracted. The product is obtained salt-free by ion exchange. Melting point: 325° C. (decomposition). The tap water used for preparing the reaction solutions contains 2·10 -6 gram atom Fe/1. Distillated water may be employed instead of tap water, if one adds homogeneous catalysts as transitional metallic ions.
The product exhibits the following 13 C-NMR spectrum (D 2 O, external standard TMS); the figures provided with the atomic symbols correspond to the chemical displacements in ppm: ##STR6##
1 H-NMR-spectrum in D 2 O; internal standard sodium trimethylsilylpropane sulfonate (TMSPS). Chemical displacements, τ values in ppm: s: 6.82; N--CH 3 ; m: 6.3-8.1 sulfopropyl group.
The NMR spectra are completely identical with the spectra of a comparable product obtained from trimethylamine and propane sultone.
EXAMPLE 2
3-sulfopropyltriethylammoniumbetaine
R 1 =R 2 =R 3 =C 2 H 5 in the general formula I
One proceeds as described in Example I, using 17.75 g (0.1 mol) triethylallylammonium chloride as a trialkylallylammonium compound.
Quantitative conversion.
Melting point: 287°-290° C.
The product exhibits the following 13 C-NMR-spectrum (D 2 O, external standard TMS); the figures provided with the atomic symbols correspond to the chemical displacements in ppm:
______________________________________ ##STR7## .sup.x Signal splitting through the .sup.14 N quadrupole moment.
1 H-NMR spectrum (data information as in example 1): t: 8.7; J=7 Hz (CH 3 ); q: 6.67; J=7 Hz--CH 2 --; m: 6.3-8.2 sulfopropyl group.
The NMR spectra are completely identical with the spectra of a comparable product obtained from triethylamine and propane sultone.
EXAMPLE 3
3-sulfopropyldimethylammoniumbetaine R 1 =R 2 =CH 3 ; R 3 =H in the general formula I
One proceeds as described in Example 1, using as alkylallylammonium compound 12.16 g (0.1 mol) dimethylallylamine hydrochloride.
Quantitative conversion.
Melting point: 210° C.
The product exhibits the following 13 C-NMR spectrum (data as above): ##STR8##
1 H-NMR spectrum (details as before): s: 7.08; N--CH 3 ; m: 7.5-8.2 --CH 2 --; m: 6.4-7.3 N--CH 2 --, - O 3 S--CH 2 --.
The NMR spectra are identical with the spectra of a comparable product prepared from dimethyl amine and propane sultone.
EXAMPLE 4
3-sulfopropyl-dimethyl-n-dodecylammonium betaine
R 1 =R 2 =CH 3 R 3 =n--C 12 H 25 in the general formula I
Dimethyl-n-dodecyl-allylammonium chloride was produced by the alkylation of dimethyldodecylamine with allyl chloride with heating in the presence of water.
The water used in this experiment had 10 -5 gram atom Cu ++ /1. The following three solutions are prepared with this water:
1. 1160 g of a 25% solution of dimethyl-dodecylallylammonium chloride (1 mol);
2.95 g (0.5 mol) sodium metabisulfite and 63 g sodium sulfite are dissolved to make a solution of 1160 g; and
3. 12.6 g sodium sulfite (0.1 mol) are dissolved in 200 ml water.
The solution as per 3 above is put inside a sulfonation flask provided with a stirrer, dripping funnel, gas-inlet tube and thermometer. Solution 1 and solution 2 are then dripped out simultaneously from two dripping funnels during a time span of 90 minutes, starting with an initial temperature of 24° C. Air is permitted inside the flask during the dripping and a white, milky emulsion of air bubbles is produced through heavy stirring, in order to achieve a conceivably fine distribution of the oxygen. Since the reaction mixture herein foams heavily, foam formation is curbed through the addition of isopropanol. Temperature increases during dripping by approximately 10° C.; the pH-value remains around 7 during the conversion. After the temperature decreases, stirring is continued for about 30 minutes. The conversion is now quantitative ( 1 H-NMR spectroscopically ascertained). After evaporation of the solvent, sulfobetaine is obtained in a mixture with sodium salts of the remaining sulfite, sulfate and chloride. Through extraction with ethanol, the sulfobetaine can be quantitatively separated from the salts.
Melting point: 209° C.
The product obtained is identical with a comparable substance obtained from dimethyl dodecylamine with propane sultone.
EXAMPLE 5
3-sulfopropyl-dimethyl-iso-tetradecylammonium betaine
(technical mixture with C 10 -C 18 group as the longest substituents)
In formula I: R 1 =R 2 =CH 3 , R 3 =average chain length i-C 14 H 29 .
Iso-C 14 H 29 N (CH 3 ) 2 was obtained through chlorination of the hydrocarbons C 10 -C 18 (from the Parex process) and transformation of the branched alkylchloride mixture with dimethylamine; subsequent quarternization with allyl chloride resulted in a 42% aqueous iso-alkyl-dimethylallylammonium chloride solution; the experiment was conducted in tap water.
The following three solutions are prepared:
1. 755 g (1 mol) 42% iso-tetradecyldimethylallylammonium chloride solution;
2. 95 g (0.5 mol) sodium metabisulfite and 63 g (0.5 mol) sodium sulfite are dissolved in tap water to make a 755 g solution; and
3. 12.6 g sodium sulfite (0.1 mol) are dissolved in 200 ml tap water.
One proceeds as described in Example 4 and drips solution 1 and solution 2 in the course of one hour into solution 3. It is not necessary to add an anti-foaming agent. Conversion is quantitative. A non-crystallizing sulfobetaine mixture is obtained after evaporation of the solvent, which is separated by extraction with ethanol.
EXAMPLE 6
3-sulfopropyl-dimethyl-n-tetradecylammonium betaine
R 1 =R 2 =CH 3 , R 3 =n--C 14 H 29 in the general formula I
Dimethyl-n-tetradecyl-allylammonium bromide was obtained by reacting dimethylallylamine with n-tetradecyl bromide, which, as in the previous examples, was converted into sulfobetaine. Here, Mn ++ was used as a homogeneous catalyst (10 -4 gram atom Mn ++ /1).
The conversion was quantitative.
Melting point: from 125° on decomposition.
The product exhibits the following 13 C-NMR spectrum (indications as above): ##STR9##
EXAMPLE 7
3-sulfopropyl-dimethyl-n-hexadecylammonium betaine
R 1 =R 2 =CH 3 R 3 =C 16 H 33 -- in the general formula I
Dimethyl-n-hexadecyl-allyl-ammonium chloride was converted into sulfobetaine in the same manner as in the previous examples, however the ratio of the reacting components was allylammonium salts:hydrogen sulfite:sulfite=1:1:0.1. The dosage of the components was made dependent on the pH-value for each, measured electrically, to maintain the pH value of the reaction mixture around 7. In this way, the sulfite excess may be decreased. 10 -4 gram atom Fe ++ /1 (added as sulfate) was used as a catalyst.
Melting point: 108° C.
The product is identical with a comparable product obtained from dimethylhexadecylamine and propane sultone.
EXAMPLE 8
Sulfobetaine mixture C 16 -C 18
3-sulfopropyl-dimethyl-n-hexadecyl-ammoniumbetaine and 3-sulfopropyl-dimethyl-n-octadecyl-ammoniumbetaine
R 1 =R 2 =CH 3 , R 3 =C 16 H 33 and C 18 H 37 in the general formula I
The mixture of alkyldimethylallylammonium salts was obtained from alkyldimethylamines through conversion with allylchloride in water. The ratio C 16 /C 18 was 1:1.
The mixture of 0.5 mol of each of the above alkyl-ammonium salts, in the form of a 10% aqueous solution, was converted into the corresponding sulfobetaine mixture as described in the preceding examples. Isopropyl alcohol was employed to the extent necessary as an anti-foaming agent. The sulfobetaine mixture is slightly water-soluble and precipitates from the reaction mixture during conversion.
As in above examples, conversion is quantitative.
Melting point: 102°-106° C.
EXAMPLE 9
3-sulfopropyl-dimethyl-2-acetamidoethyl-ammonium betaine
R 1 =R 2 =CH 3 ; R 3 =CH 3 CO--NH--CH 2 CH 2 --in the general formula I
The starting allyl compound is formed by initially converting ethyl acetate with N,N-dimethylethylene diamine into amide and then quarternizing with allyl halide. One proceeds as described in Example 1, using the above amide as an allylammonium compound.
Conversion is quantitative.
Melting point: starting from 190° C. (decomposition).
EXAMPLE 10
3-sulfopropyl-dimethyl-2-tetradecanoylamidoethyl-ammonium betaine
R 1 =R 2 =CH 3 ; R 3 =C 13 H 27 --CO--NH--CH 2 --CH 2 --in the general formula I
The starting allyl compound is formed by initially reacting myristic acid methyl ester with N,N-dimethylethylenediamine to form an amide, and subsequently quarternizing with an allyl halide. One proceeds as described in Example 4, however using tap water instead of copper ions to produce the reaction mixture. A quantitative yield of sulfobetaine is obtained (melting point: 58° C.) from the concentrated reaction mixture extracted by alcohol.
The product exhibits the following 13 C-NMR spectrum (data as above): ##STR10## non-attributable signals: 44.8 and 33.3 ppm.
The NMR spectrum is identical with that of a product produced from propane sultone.
EXAMPLE 11
3-sulfopropyl-dimethyl-hexadecanoylamidoethyl-ammonium betaine
The starting compound is produced by reacting a palmitic acid methylester with N,N-dimethylenediamine to form an amide which is converted into an allyl.
One proceeds in the manner described in Example 4, however using 0.9 mg MnO 2 /liter reaction mixture (10 -5 gram atom Mnll) as a catalyst instead of Cu ++ . Quantitative conversion.
Melting point: 85° C.
OTHER EXAMPLES
By the same methods described in the preceding examples, the allylized amides of the N,N-dimethylethylenediamine of oleic acid, of perfluorine octane acid, of the 4-alkylbenzenesulfonic acids, of the alkylsulfonic acids and of the undecylenic acids may be converted into the corresponding sulfobetaines.
|
The invention relates to a process for the manufacture of N-substituted 3-sulfopropylammonium betaines.
N-substituted allylammonium compounds are reacted in the presence of initiators, such as oxygen, and catalytic acting transition metallic ions of the first, fifth, seventh or eighth secondary groups of the Periodic Table, with salts of sulfurous acid under mild reaction conditions.
The process can be executed with simple equipment and requires only small energy expenditures, the compounds of the present invention being produced selectively in an almost quantitative yield.
Further advantages of the process: the use of carcinogenic alkylates can be avoided, chemicals of technical purity and tap water can be employed and hardly any by-products result.
The substances have surface tension qualities and can be employed in many technical fields, especially in laundry agent formulations for energy-saving laundering processes.
| 8
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a combination compressor support and drain pan for use in an air conditioning unit. More specifically, the present invention relates to an air conditioning unit having a vertical partition and a peripherally encasing heat exchanger having.a central opening such that the compressor is mounted a selected distance from the bottom of the unit by a combination compressor support and condensate collection pan located within the heat exchanger central opening.
2. Prior Art
Wound fin heat exchangers are well known in the refrigeration and air conditioning fields. A wound fin heat exchanger consists of a tube having a fin material wrapped about the tube in heat exchange relation therewith to promote heat transfer between fluid flowing through the tube and a separate fluid flowing over the tube. The utilization of this type of heat exchanger has been found to be both cost effective and to provide an appropriate heat transfer surface with a minimum of tube length. A type of wound fin tubing includes slit fin tubing wherein a sheet of fin material is slit laterally and then rolled to a generally U-shaped arrangement such that the non-slit portion is wound against the tube and the slit portions extend outwardly therefrom.
To make advantageous use of wound fin heat exchangers it is necessary that the heat exchanger be configured to optimize heat transfer. Additionally, since the heat exchanger is made from several lengths of wound fin tubing, the heat exchanger is typically formed in a peripherally encasing configuration such as an annular or other configuration having an opening in the middle. As disclosed herein, the peripherally encasing heat exchanger will be generally rectangular in cross section defining an opening in the center.
When utilizing a peripherally encasing heat exchanger having a central opening in combination with a vertically mounted packaged unit, if the heat exchanger is sufficiently large to encase the entire outdoor portion of the packaged unit, then it is not possible to mount a compressor to the bottom of the unit. Hence, a combination support and drain pan for securing the compressor to the partition at some distance spaced from the bottom of the unit was developed.
Additionally, by mounting the compressor within the interior opening of the peripherally encasing heat exchanger, when the heat exchanger is serving in the appropriate mode, condensate drips therefrom onto the compressor and the support. It is desirable to funnel this condensate away from the bottom portion of the heat exchanger such that cold condensate as may collect in the heating mode of operation of a heat pump when the outdoor heat exchanger is serving as an evaporator, does not drip from one portion of the heat exchanger to another. The combination compressor support and drain pan not only serves to support the compressor but acts to divert the condensate from the upper portion of the heat exchanger and connecting tubing such that it is routed to bypass the lower portion of the heat exchanger because water could refreeze and prematurely block lower coil portions and because the presence of copper ions in the condensate could hasten corrosion of the lower coil portions. A second condensate pan is then placed below the entire heat exchanger such that the condensate diverted by the combination compressor support and drain pan is directed thereto. Additionally, by mounting the compressor within the interior opening of the heat exchanger, the wound fin tubing of the heat exchanger may serve to reduce the level of the noise emitted by the compressor. This arrangement also makes for easier serviceability.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide apparatus for supporting a compressor of a heat exchange unit.
It is another object of the present invention to provide apparatus suitable for mounting on a vertical partition for securing a compressor or other component of a heat exchange unit.
It is another object of the present invention to provide a condensate collection pan to be mounted within an opening defined by a peripherally encasing heat exchanger for collecting condensate dripping from the upper portions of the heat exchanger.
It is a yet further object of the present invention to direct the collected condensate around the bottom portion of the heat exchanger to a separate drain pan.
It is a still further object of the present invention to provide a combination apparatus for serving as a compressor support, as a drain condensate pan and as condensate diversion means.
It is a further object of the present invention to provide a safe, economical, reliable and easy to install and manufacture combination compressor support and drain pan for use with a heat exchange unit.
Other objects will be apparent from the description to follow and the appended claims.
The above objects are achieved according to the preferred embodiment of the invention by the provision of a heat exchange unit including a refrigeration circuit having a compressor and an outdoor heat exchanger. The unit is divided by a vertical partition into an indoor section and an outdoor section wherein the compressor and outdoor heat exchanger are located. A horizontally extending support means secured to the partition a selected distance from the bottom of the unit includes a bottom surface for supporting a compressor and for collecting condensate. A drain bracket is secured to the partition and is positioned to buttress the support means, said drain bracket additionally acting to divert the condensate collected by the support means.
A combination compressor support and condensate collection assembly for use in a heat exchange unit having a vertically extending partition is further disclosed. The combination includes an inclined bottom member extending from the partition and inclined upwardly therefrom, inclined wedge portions extending outwardly from the sides of the bottom member, side lip portions extending upwardly from the edge of the inclined edge portions mounted adjacent the bottom member, a front lip portion extending upwardly from the inclined bottom member at the end distant from the partition and being connected to the side lip portions. The inclined bottom member defines at least one drain opening and a drain bracket affixed to the partition end to support the bottom member and said drain bracket being adapted to receive condensate from the drain opening.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partially cutaway side view of an outdoor section of a vertically mounted packaged air conditioning unit.
FIG. 2 is a partially cutaway end view of the same packaged unit as shown in FIG. 1.
FIG. 3 is an isometric view of the compressor support drain bracket and drain pan shown mounted to the partition.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The embodiment as described herein is adapted for use in a vertically mounted packaged heat pump as may be used to provide conditioned air to an apartment, condominium or similar structure. The unit is designed to be mounted having an outdoor section in communication with outdoor ambient air and an indoor section for delivering conditioned air to the enclosure.
The arrangement of a combination compressor support and drain pan as set forth herein is particularly suitable for use in a unit having a vertically extending partition and a peripherally encasing heat exchanger defining a central opening. It is apparent, however, that such a device would have like applicability in heat exchange units having heat exchangers of various configurations and not necessarily being peripherally encasing heat exchangers defining central openings. It is further to be understood that although a particular packaged type heat pump is described herein this invention would have like applicability to other air conditioning units that are neither heat pumps nor packaged units. Additionally, such units as packaged terminal air conditioning units and room air or window units might be suitable application for this apparatus.
Referring to FIG. 1 there may be seen the outdoor portion of a vertically mounted packaged air conditioning unit. Partition 10 is a vertically extending support member which defines the boundary between outdoor section 6 of unit 2 and the indoor section (not shown). Heat exchanger 20 is shown mounted within the outdoor section and has compressor 60 and outdoor fan 70 mounted therewithin. Fan support legs 76 are shown secured to fan motor 72 to maintain the fan motor in position relative to partition 10. Fan orifice support 78 further connects fan orifice 74 to fan motor support legs 76 to maintain the fan orifice in position. Tube support 40 is shown at the top of the unit having loops 22 of heat exchanger 20 located between tube support 40 and rod 50. Additionally, it can be seen that nut 52 engaged to rod 50 acts to secure the tube support to the partition.
Compressor 60 of the refrigeration circuit is mounted on a compressor support 62 which additionally serves to collect condensate dripping from the upper portions of the heat exchanger. Drain bracket 64 serves to provide structural support to the compressor support 62 and to direct condensate collected therewithin to drain pan 66 through opening 68. Mounted about the exterior of the outdoor section may be seen front guard 80 which prevents air flow into that portion of the central opening defined by the heat exchanger which is not encompassed by the fan orifice. It can additionally be seen that screws 48 act to secure both fan orifice 74 and front guard 80 to the appropriate tube supports.
Additionally, it may be seen in FIG. 1 that heat exchanger 20 is made from loops 22 of wound fin heat exchange tubing wrapped to define a peripherally encasing heat exchanger having a central opening. As shown in FIG. 1, this heat exchanger is generally tapered from the partition outwardly and as may be seen in FIG. 2 is generally rectangular in configuration.
Referring now to FIG. 2 it may be seen that compressor support 62 includes numerous segments. The compressor support includes an inclined bottom member 95, front lip 91, side lips 93 and inclined wedge portions 94. The inclined bottom surface extends from the partition and is angled upwardly and outwardly until it terminates at front lip 91. Wedge portions 94 angle outwardly and upwardly from the sides of the inclined bottom member. Side lips 93 extend upwardly from the exterior edges of the inclined wedge portions. The combination of side lips and the front lip together with the inclination of the bottom surface and wedge portions act to define a condensate collection pan. Another embodiment might eliminate the front lip and have the side lips inclined to meet the bottom member at the edge where front lip 91 was mounted.
It can additionally be seen in FIG. 2 that drain bracket 64 is formed in a V-shape and has flanges 65 for securing the drain bracket to partition 10.
In FIG. 2 it may be additionally seen that fan 70 powered by fan motor 72 is mounted within fan orifice 74 secured to tube supports including rods 50. Additionally, front guard 80 is shown partially cutaway to prevent air flow into the heat exchanger other than through the runs of tubing defining the heat exchanger. Bottom casing 8 and drain pan 66 are shown located toward the bottom of the unit. Heat exchanger 20 is shown being a peripherally encasing heat exchanger defining a center cavity wherein the compressor 60 and fan 70 are mounted.
FIG. 3 is a perspective view of the partition showing just compressor bracket support 62, drain bracket 64 and drain pan 66 extending therefrom. Compressor support 62 is shown having inclined bottom 95, two wedge portions 94, side lips 93 and front lip 91 all defining a condensate collection apparatus as well as the compressor support. Mounting holes 101 are located in the bottom of the compressor support to coact with bolts extending from the compressor to secure the compressor thereto. Gromets or similar sealing devices are used such that condensate collected in the compressor support does not drip through these holes. It can be additionally seen that condensate opening 103 is provided to extend through inclined bottom 95 such that condensate collected may drip downwardly into drain bracket 64. The drain bracket then diverts the condensate backwardly such that it leaves the drain bracket at opening 68 (See FIG. 1) adjacent the partition and drops directly into drain pan 66. Screws 105 are shown for securing the compressor support to the partition.
Drain bracket 64 is shown having flanges 65 for securing the bracket to the partition. Drain bracket 64 has two angled side members as may be seen in FIG. 2 for directing the condensate to the drain pan. The drain bracket further serves to structurally support and buttress the compressor support. Drain pan 66 is shown having an inclined top surface which allows the water to drain into trough 67 from which the water is directed out of the unit through an appropriate collection means.
As described herein a combination compressor support and drain pan has been provided for mounting to a vertical member. The compressor of the refrigeration circuit is mounted to the support all within a central opening defined by a peripherally encasing heat exchanger. A drain bracket diverts the collected condensate around the bottom portion of the heat exchanger to drain pan 66.
The invention has been described with reference to a particular embodiment. It is to be understood by those skilled in the art that variations and modifications can be effected within the spirit and scope of the invention.
|
A combination compressor support and drain pan for use in a heat exchange unit is disclosed. A compressor support is mounted to a vertically extending partition and spaced a selected distance from the bottom of the unit such that a compressor may be mounted thereon. A drain bracket is secured between the partition and the compressor support to provide both structural integrity for the support and to divert condensate collected by the support to a separate drain pan.
| 5
|
Subsets and Splits
No community queries yet
The top public SQL queries from the community will appear here once available.