Information
-
Patent Grant
-
6401470
-
Patent Number
6,401,470
-
Date Filed
Thursday, September 14, 200024 years ago
-
Date Issued
Tuesday, June 11, 200222 years ago
-
Inventors
-
Original Assignees
-
Examiners
- Walberg; Teresa
- Dahbour; Fadi H.
Agents
- Brinks Hofer Gilson & Lione
-
CPC
-
US Classifications
Field of Search
US
- 062 222
- 062 223
- 062 224
- 062 225
- 236 92 B
- 236 93 R
-
International Classifications
-
Abstract
A vapor compression system including a line for flowing heat transfer fluid, a compressor connected with the line for increasing the pressure and temperature of the heat transfer fluid, a condenser connected with the line for liquefying the heat transfer fluid, and an expansion device connected with the line for expanding the heat transfer fluid. The expansion device includes a housing defining a first orifice, and at least one blade connected with the housing, wherein the blade is movable between a first position and a second position, wherein the first orifice is larger in the first position than in the second position. The vapor compression system also includes an evaporator connected with the line for transferring heat from ambient surroundings to the heat transfer fluid.
Description
BACKGROUND
This invention relates, in general, to vapor compression systems, and more particularly, to an expansion device for a vapor compression system.
In a closed-loop vapor compression cycle, heat transfer fluid changes state from a vapor to a liquid in the condenser, giving off heat to ambient surroundings, and changes state from a liquid to a vapor in the evaporator, absorbing heat from the ambient surroundings during vaporization. A typical vapor compression system includes a compressor for pumping heat transfer fluid, such as a freon, to a condenser, where heat is given off as the heat transfer fluid condenses into a liquid. The heat transfer fluid then flows through a liquid line to an expansion device, where the heat transfer fluid undergoes a volumetric expansion. The heat transfer fluid exiting the expansion device is usually a low quality liquid vapor mixture. As used herein, the term “low quality liquid vapor mixture” refers to a low pressure heat transfer fluid in a liquid state with a small presence of flash gas that cools off the remaining heat transfer fluid as the heat transfer fluid continues on in a sub-cooled state. The expanded heat transfer fluid then flows into an evaporator. The evaporator includes a coil having an inlet and an outlet, wherein the heat transfer fluid is vaporized at a low pressure absorbing heat while it undergoes a change of state from a liquid to a vapor. The heat transfer fluid, now in the vapor state, flows through the coil outlet and exits the evaporator. The heat transfer fluid then flows through a suction line and back to the compressor. A typical vapor compression system may include more than one expansion device. Moreover, the expansion device may be placed in various locations within a vapor compression system. For example, as the heat transfer fluid flows into an evaporator it may flow through a second expansion device, where the heat transfer fluid undergoes a second volumetric expansion. Additionally, a typical vapor compression system may include a nozzle or fixed orifice.
In one aspect, the efficiency of the vapor compression cycle depends upon the precise control of the volumetric expansion of a heat transfer fluid in various locations within a vapor compression system. Heat transfer fluid is volumetrically expanded when the heat transfer fluid flows through an expansion device, such as a thermostatic expansion valve, a capillary tube, and a pressure control, or when the heat transfer fluid flows through a nozzle or fixed orifice. Often times, the rate in which a heat transfer fluid is volumetrically expanded needs to be varied depending on the conditions within the vapor compression system. Devices such as capillary tubes, pressure controls, nozzles, or fixed orifices, are fixed in size and cannot vary the rate in which a heat transfer fluid is volumetrically expanded. While many thermostatic expansion valves can vary the rate in which a heat transfer fluid is volumetrically expanded, they are complex and rather costly to manufacture.
Accordingly, further development of vapor compression systems, and more specifically, expansion devices for vapor compression systems, is necessary in order to decrease the complexity and cost of manufacturing expansion devices that can vary the rate in which a heat transfer fluid is volumetrically expanded.
SUMMARY
According to one aspect of the present invention, a vapor compression system is provided. The vapor compression system includes a line for flowing heat transfer fluid, a compressor connected with the line for increasing the pressure and temperature of the heat transfer fluid, a condenser connected with the line for liquefying the heat transfer fluid, and an expansion device connected with the line for expanding the heat transfer fluid. The expansion device includes a housing defining a first orifice, and at least one blade connected with the housing, wherein the blade is movable between a first position and a second position, wherein the first orifice is larger in the first position than in the second position. The vapor compression system also includes an evaporator connected with the line for transferring heat from ambient surroundings to the heat transfer fluid.
According to another aspect of the present invention, an expansion device for a vapor compression system is provided. The expansion device includes a housing defining a first orifice, and at least one blade connected with the housing, wherein the blade is movable between a first position and a second position, wherein the first orifice is larger in the first position than in the second position.
According to yet another aspect of the present invention, an expansion device for a vapor compression system is provided. The expansion device includes a first sheet defining a first orifice, and a second sheet overlapping the first sheet, the second sheet defining a second orifice, wherein the second orifice is movable between a first position and a second position, and wherein the second orifice is larger in the first position than in the second position.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1
is a schematic drawing of a vapor compression system arranged in accordance with one embodiment of the invention;
FIG. 2
is a perspective view of an expansion device connected with a line, in accordance with one embodiment of the invention;
FIG. 3
is a cross-sectional perspective view of the expansion device in
FIG. 2
, wherein the expansion device is in a partially open position;
FIG. 4
is a cross-sectional perspective view of the expansion device in
FIG. 2
, wherein the expansion device is in a fully open position;
FIG. 5
is a cross-sectional perspective view of the expansion device in
FIG. 2
, wherein the expansion device is in a fully closed position;
FIG. 6
is a cross-sectional perspective view of an expansion device, in accordance with one embodiment of the invention;
FIG. 7
is a cross-sectional perspective view of an expansion device, wherein the expansion device is in a closed position, in accordance with one embodiment of the invention;
FIG. 8
is a cross-sectional perspective view of the expansion device in
FIG. 6
, wherein the expansion device is in a partially open position;
FIG. 9
is a cross-sectional perspective view of the expansion device in
FIG. 6
, wherein the expansion device is in a fully open position;
FIG. 10
is a perspective view of an expansion device connected with a line, in accordance with one embodiment of the invention;
FIG. 11
is an exploded perspective view of the expansion device in
FIG. 9
;
FIG. 12
is a cross-sectional view of the expansion device in
FIG. 9
, wherein the expansion device is in a partially open position;
FIG. 13
is a cross-sectional view of the expansion device in
FIG. 9
, wherein the expansion device is in a fully open position;
FIG. 14
is a cross-sectional view of the expansion device in
FIG. 9
, wherein the expansion device is in a fully closed position; and
FIG. 15
is an exploded perspective view of an expansion device, in accordance with one embodiment of the invention.
For simplicity and clarity of illustration, elements shown in the Figures have not necessarily been drawn to scale. For example, dimensions of some elements are exaggerated relative to each other. Further, when considered appropriate, reference numerals have been repeated among the Figures to indicate corresponding elements.
DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED EMBODIMENTS
One embodiment of a vapor compression system
10
is illustrated in FIG.
1
. Vapor compression system
10
includes a compressor
12
for increasing the pressure and temperature of a heat transfer fluid
34
, a condenser
14
for liquefying the heat transfer fluid
34
, an evaporator
16
for transferring heat from ambient surroundings to the heat transfer fluid
34
, an expansion device
18
for expanding the heat transfer fluid
34
, and a line
19
for flowing the heat transfer fluid. Line
19
allows for the flow of a heat transfer fluid
34
from one component of vapor compression system
10
, such as compressor
12
, condenser
14
, evaporator
16
, and expansion device
18
, to another component of vapor compression system
10
. Compressor
12
, condenser
14
, evaporator
16
, and expansion device
18
are all connected with line
19
. In one embodiment, line
19
includes discharge line
20
, liquid line
22
, saturated vapor line
28
, and suction line
30
, as illustrated in FIG.
1
. In this embodiment, compressor
12
is connected with condenser
14
through discharge line
20
, condenser
14
is connected with expansion device
18
through liquid line
22
, expansion device
18
is connected with evaporator
16
through saturated vapor line
28
, and evaporator
16
is connected with compressor
12
through suction line
30
, as illustrated in FIG.
1
.
In one embodiment, vapor compression system
10
includes a sensor
32
operably connected to expansion device
18
. Sensor
32
can be used to vary the rate in which a heat transfer fluid
34
is volumetrically expanded through expansion device
18
. Preferably, sensor
32
is mounted to a portion of line
19
, such as suction line
30
, and is operably connected to expansion device
18
. Sensor
32
can be any type of sensor known by those skilled in the art designed to detect conditions in and around vapor compression system
10
, such as the temperature, pressure, enthalpy, and moisture of heat transfer fluid
34
or any other type of conditions that may be monitored in and around vapor compression system
10
. For example, sensor
32
may be a pressure sensor that detect the pressure of heat transfer fluid
34
at a certain point within vapor compression system
10
, or sensor
32
may be a temperature sensor which detects the temperature of ambient surroundings
11
around vapor compression system
10
. Preferably, sensor
32
is operably connected to expansion device
18
through control line
33
.
Vapor compression system
10
can utilize essentially any commercially available heat transfer fluid
34
including refrigerants such as, for example, chlorofluorocarbons such as R-12 which is a dicholordifluoromethane, R-22 which is a monochlorodifluoromethane, R-500 which is an azeotropic refrigerant consisting of R-12 and R-152a, R-503 which is an azeotropic refrigerant consisting of R-23 and R-13, and R-502 which is an azeotropic refrigerant consisting of R-22 and R-115. Vapor compression system
10
can also utilize heat transfer fluids
34
including, but not limited to, refrigerants R-13, R-113, 141b, 123a, 123, R-114, and R-11. Additionally, vapor compression system
10
can utilize heat transfer fluids
34
including hydrochlorofluorocarbons such as 141b, 123a, 123, and 124; hydrofluorocarbons such as R-134a, 134, 152, 143a, 125, 32, 23; azeotropic HFCs such as AZ-20 and AZ-50 (which is commonly known as R-507); and blended refrigerants such as MP-39, HP-80, FC-14, R-717, and HP-62 (commonly known as R-404a). Accordingly, it should be appreciated that the particular heat transfer fluid
34
or combination of heat transfer fluid
34
utilized in the present invention is not deemed to be critical to the operation of the present invention since this invention is expected to operate with a greater system efficiency with virtually all heat transfer fluids
34
than is achievable by any previously known vapor compression system utilizing the same heat transfer fluid
34
.
In one embodiment, compressor
12
compresses heat transfer fluid
34
, to a relatively high pressure and temperature. The temperature and pressure to which heat transfer fluid
34
is compressed by compressor
12
will depend upon the particular size of vapor compression system
10
and the cooling load requirements of vapor compression system
10
. Compressor
12
then pumps heat transfer fluid
34
into discharge line
20
and into condenser
14
. In condenser
14
, a medium such as air, water, or a secondary refrigerant is blown past coils within condenser
14
causing the pressurized heat transfer fluid
34
to change to a liquid state. The temperature of the heat transfer fluid
34
drops as the latent heat within the heat transfer fluids
34
is expelled during the condensation process. Condenser
14
discharges the liquefied heat transfer fluid
34
to liquid line
22
.
As shown in
FIG. 1
, liquid line
22
discharges the heat transfer fluid
34
into expansion device
18
whereupon the heat transfer fluid
34
undergoes a volumetric expansion. In one embodiment, the heat transfer fluid discharged by condenser
14
enters expansion device
18
and undergoes a volumetric expansion at a rate determined by the conditions of suction line
30
, such as temperature and pressure, at sensor
32
. Sensor
32
relays information about the conditions of suction line, such a pressure and temperature, through control line
33
to expansion device
18
. Upon undergoing a volumetric expansion, expansion device
18
discharges the heat transfer fluid
34
as a saturated vapor into saturated vapor line
28
. Saturated vapor line
28
connects the expansion device
18
with the evaporator
16
. Evaporator
16
transfers heat from ambient surroundings
11
to the heat transfer fluid
34
. Ambient surroundings
11
is the atmosphere surrounding vapor compression system
10
, as illustrated in FIG.
1
. Upon exiting evaporator
16
, heat transfer fluid then travels through suction line
30
back to compressor
12
.
While in the above embodiment expansion device
18
is connected with saturated vapor line
28
and liquid line
22
, expansion device
18
may connected with any component within vapor compression system
10
and expansion device
18
may be located at any point within vapor compression system
10
. Preferably, expansion device
18
is located at a point within vapor compression system
10
in which it is desired to volumetrically expand heat transfer fluid
34
, such as between condenser
14
and evaporator
16
. More preferably, expansion device
18
is located at a point within vapor compression system
10
in which it is desired to vary the rate in which a heat transfer fluid
34
is volumetrically expanded, such as between condenser
14
and evaporator
16
, as illustrated in FIG.
1
. Expansion device
18
may be used in place of or in combination with metering devices such as, but not limited to, a thermostatic expansion valve, a capillary tube, a pressure control, a nozzle, and a fixed orifice. Preferably, heat transfer fluid
34
is volumetrically expanded when the heat transfer fluid
34
flows through expansion device
18
.
Shown in
FIG. 2
is a perspective view of expansion device
18
connected with line
19
, in accordance with one embodiment. Expansion device
18
includes a housing
40
and at least one blade
48
, as illustrated in
FIGS. 3-8
. Housing
40
defines a first orifice
44
. Preferably, housing
40
is manufactured from and includes a rigid, steel material, however housing
40
can be manufactured from any material known by those skilled in the art, such as ceramics, carbon fiber, any metal or metallic alloy, any plastic, or any other material. As defined herein, an orifice, such as first orifice
44
, is any opening in which fluid, such as heat transfer fluid
34
, can pass through. Orifice may have one of many shapes, such as a circular shape (as illustrated in FIGS.
7
-
9
), a tear dropped shape, an eye shape (as illustrated in FIGS.
3
-
6
), a square or rectangular shape, or any irregular shape. Blade
48
is connected with housing
40
. Preferably, blade
48
is connected to housing
40
, as illustrated in
FIGS. 3-8
. In one embodiment, blade
48
is connected to at least one track
56
within housing
40
, wherein track
56
defines a path upon which blade
48
travels. Blade
48
may have one of many shapes, such as a circular shape or disc shape, a V shape (as illustrated in FIGS.
3
-
5
), a curved shape (as illustrated in FIGS.
7
-
9
), a square or rectangular shape (as illustrated in FIG.
6
), or any irregular shape. Blade
48
includes and is manufactured from any material known by those skilled in the art, such as ceramics, carbon fiber, any metal or metallic alloy, any plastic, or any other material. Preferably, blade
48
includes and is manufactured from spring steel.
Blade
48
is movable between a first position, as illustrated in
FIG. 4
, and a second position, as illustrated in
FIGS. 3 and 5
, wherein the first orifice
44
is larger in the first position than in the second position. Blade
48
can be either manually moved from a first position to a second position or automatically moved, by means of a motor or other means, from a first position to a second position. As defined herein, an orifice, such as orifice
44
, is made larger when the cross-sectional area of the orifice is effectively increased and an orifice is made smaller when the cross-sectional area of the orifice is effectively decreased, as illustrated in
FIGS. 3-5
. By increasing or decreasing the cross-sectional areas of an orifice, such as orifice
44
, the rate of volumetric expansion within a heat transfer fluid
34
can be controlled and varied. Preferably, blade
48
overlaps a at least a portion of the first orifice when blade
48
is in the second position, thereby making the first orifice smaller.
In one embodiment, expansion device
18
includes a first blade
50
and a second blade
52
, as illustrated in
FIGS. 3-5
. Preferably, first and second blades
50
,
52
are connected to housing
40
, as illustrated in
FIGS. 3-8
. In one embodiment, first and second blades
50
,
52
are connected to at least one track
56
within housing
40
, wherein track
56
defines a path upon which first and second blades
50
,
52
travel. First blade
50
and second blade
52
are movable between a first position and a second position, wherein the first orifice
44
is larger in the first position than in the second position, as illustrated in
FIGS. 3-5
.
In one embodiment, expansion device includes a single blade
48
, wherein single blade
48
defines a second orifice
46
, as illustrated in FIG.
6
. Preferably, second orifice
46
is adjacent first orifice
44
. Blade
48
is movable between a first position and a second position, wherein the first orifice is larger in the first position than in the second position. By moving blade
48
between a first and second position, second orifice
46
overlaps with portions of first orifice
44
, and first orifice
44
can be made larger or smaller.
In one embodiment expansion device
18
includes a series of blades
48
, wherein the series of blades
48
define a second orifice
46
, as illustrated in
FIGS. 7-9
. Second orifice
46
overlaps first orifice
44
. Preferably, second orifice
46
is adjacent first orifice
44
. Blades
48
are movable between a first position and a second position, wherein the second orifice
46
is larger in the first position than in the second position. By moving blades
48
between a first and second position, second orifice
46
can be made larger or smaller. Since second orifice
46
overlaps first orifice
44
, first orifice
44
can be made larger or smaller as second orifice
46
is made larger or smaller. In one embodiment, the series of blades
48
define a second orifice
46
that is generally circular, as illustrated in
FIGS. 7-9
. In this embodiment, the series blades
48
are arranged in a formation that resembles the aperture of a camera lens.
In one embodiment, sensor
32
controls the movement of at least one blade
48
between a first position a second position. Preferably, sensor is connected with a moving device (not shown), such as an electric motor or an electromagnet, wherein the moving device can be used to automatically move blade
48
from a first position to a second position upon receiving a signal from sensor
32
.
In one embodiment, expansion device
18
includes a first sheet
60
defining a first orifice
62
, and a second sheet
62
overlapping the first sheet
60
, as illustrated in
FIGS. 10-15
. First sheet
60
and second sheet
64
can be manufactured from and include any material known by those skilled in the art, such as ceramics, carbon fiber, any metal or metallic alloy, any plastic, or any other material. Preferably, first sheet
60
and second sheet
64
are manufactured from and include ceramic material. First sheet
60
and second sheet
64
may have one of many shapes, such as a circular shape or disc shape (as illustrated in FIGS.
3
-
5
), a V shape, a curved shape, a square or rectangular shape, or any irregular shape. Second sheet
64
defines a second orifice
66
, wherein the second orifice
66
is movable between a first position and a second position, and wherein the second orifice is larger in the first position than in the second position. In one embodiment, at least one of first sheet
60
and second sheet
64
rotate about a common axis
68
, as illustrated in FIG.
11
. Preferably, the common axis
68
is generally centered on first sheet
60
and second sheet
64
. In one embodiment, first sheet
60
is fixed with respect to a housing
70
, and second sheet
64
rotates about a common axis
68
, wherein axis
68
is located at the center of bother first sheet
60
and second sheet
64
, as illustrated in FIG.
10
. Preferably, expansion device
18
includes a tab
58
protruding from housing
70
and connected with second sheet
64
, wherein tab
58
allows for one to manually move second sheet
64
from a first position to a second position.
Preferably, heat transfer fluid
34
is used to lubricate either blades
48
or first and second sheets
60
,
64
, so that blades
48
and/or first and second sheets
60
,
64
may move more freely about.
In one embodiment, second sheet
64
defines multiple orifices
66
and first sheet
60
defines a single orifice
62
, wherein the size and shape of orifice
62
allows orifice
62
to overlap multiple orifices
66
, as illustrated in FIG.
15
. Multiple orifices
66
are movable between a first position and a second position, wherein the single orifice overlaps the multiple orifices in the second position, and wherein the single orifice
62
is made larger as the multiple orifices move to the second position, as illustrated in FIG.
15
.
Expansion device
18
may be combined with a traditional expansion device, wherein the traditional expansion device volumetrically expands heat transfer fluid
34
at a fixed rate. By combining expansion device
18
with a traditional expansion device, heat transfer fluid
34
can be volumetrically expanded at a varied rate, and thus simulate the effect of a thermostatic expansion valve, at a reduced cost.
Those skilled in the art will appreciate that numerous modifications can be made to enable vapor compression system
10
to address a variety of applications. For example, vapor compression system
10
operating in a retail food outlet may include a number of evaporators
16
that can be serviced by a common compressor
12
. Also, in applications requiring refrigeration operations with high thermal loads, multiple compressors
12
can be used to increase the cooling capacity of the vapor compression system
10
.
Those skilled in the art will recognize that vapor compression system
10
can be implemented in a variety of configurations. For example, the compressor
12
, condenser
14
, expansion device
18
, and the evaporator
16
can all be housed in a single housing and placed in a walk-in cooler. In this application, the condenser
14
protrudes through the wall of the walk-in cooler and ambient air outside the cooler is used to condense the heat transfer fluid
34
. In another application, vapor compression system
10
can be configured for air-conditioning a home or business. In yet another application, vapor compression system
10
can be used to chill water. In this application, the evaporator
16
is immersed in water to be chilled. Alternatively, water can be pumped through tubes that are meshed with the evaporator coil
44
. In a further application, vapor compression system
10
can be cascaded together with another system for achieving extremely low refrigeration temperatures. For example, two vapor compression systems using different heat transfer fluids
34
can be coupled together such that the evaporator of a first system provides a low temperature ambient. A condenser of the second system is placed in the low temperature ambient and is used to condense the heat transfer fluid in the second system.
As known by one of ordinary skill in the art, every element of vapor compression system
10
described above, such as evaporator
16
, liquid line
22
, and suction line
30
, can be scaled and sized to meet a variety of load requirements. In addition, the refrigerant charge of the heat transfer fluid in vapor compression system
10
, may be equal to or greater than the refrigerant charge of a conventional system.
Thus, it is apparent that there has been provided, in accordance with the invention, a vapor compression system that fully provides the advantages set forth above. Although the invention has been described and illustrated with reference to specific illustrative embodiments thereof, it is not intended that the invention be limited to those illustrative embodiments. Those skilled in the art will recognize that variations and modifications can be made without departing from the spirit of the invention. For example, non-halogenated refrigerants can be used, such as ammonia, and the like can also be used. It is therefore intended to include within the invention all such variations and modifications that fall within the scope of the appended claims and equivalents thereof.
Claims
- 1. A vapor compression system comprising:a line for flowing heat transfer fluid; a compressor connected with the line for increasing the pressure and temperature of the heat transfer fluid; a condenser connected with the line for liquefying the heat transfer fluid; an expansion device connected with the line for expanding the heat transfer fluid, comprising: a housing defining a first orifice; at least one blade connected with the housing, wherein the blade is movable between a first position and a second position, wherein the first orifice is larger in the first position than in the second position; and an evaporator connected with the line for transferring heat from ambient surroundings to the heat transfer fluid.
- 2. The vapor compression system of claim 1, further comprising a first blade and a second blade, wherein the first blade and second blade are movable between a first position and a second position, wherein the first orifice is larger in the first position than in the second position.
- 3. The vapor compression system of claim 1, wherein the blade defines a second orifice.
- 4. The vapor compression system of claim 1, further comprising a series of blades, wherein the series of blades define a second orifice adjacent the first orifice, and wherein the blades are movable between a first position and a second position, wherein the second orifice is larger in the first position than in the second position.
- 5. The vapor compression system of claim 3, wherein the second orifice is generally circular.
- 6. The vapor compression system of claim 1, wherein the blade is generally disc-shaped.
- 7. The vapor compression system of claim 1, wherein the blade comprises ceramic material.
- 8. The vapor compression system of claim 1, further comprising a sensor connected with the expansion device.
- 9. The vapor compression system of claim 8, wherein the sensor controls the movement of the blade between the first position and the second position.
- 10. An expansion device for a vapor compression system, comprising:a housing defining a first orifice; at least one blade connected with the housing, wherein the blade is movable between a first position and a second position, wherein the first orifice is larger in the first position than in the second position.
- 11. The expansion device of claim 10, wherein the blade overlaps at least a portion of the first orifice when the blade is the second position.
- 12. The expansion device of claim 10, further comprising a first blade and a second blade, wherein the first blade and second blade are movable between a first position and a second position, wherein the first orifice is larger in the first position than in the second position.
- 13. The expansion device of claim 10, further comprising a series of blades, wherein the blades define a second orifice adjacent the first orifice, and wherein the blades are movable between a first position and a second position, wherein the second orifice is larger in the first position than in the second position.
- 14. The expansion device of claim 13, wherein the second orifice is generally circular.
- 15. The expansion device of claim 10, wherein the blade defines a second orifice.
US Referenced Citations (180)
Foreign Referenced Citations (12)
Number |
Date |
Country |
197 52 259 |
Jun 1998 |
DE |
197 43 734 |
Apr 1999 |
DE |
0 355 180 |
Feb 1990 |
EP |
0355180 |
Feb 1990 |
EP |
58146778 |
Sep 1983 |
JP |
03020577 |
Jan 1991 |
JP |
10325630 |
Aug 1998 |
JP |
10306958 |
Nov 1998 |
JP |
WO 9306422 |
Apr 1993 |
WO |
WO 9503515 |
Feb 1995 |
WO |
WO 9803827 |
Jan 1998 |
WO |
WO 9857104 |
Dec 1998 |
WO |