Method of joining components using a silver-based composition

Information

  • Patent Grant
  • 6757963
  • Patent Number
    6,757,963
  • Date Filed
    Wednesday, January 23, 2002
    22 years ago
  • Date Issued
    Tuesday, July 6, 2004
    20 years ago
Abstract
A surface of a first ceramic component is joined to a surface of a second ceramic component using a silver-based composition. The silver-based composition is a mixture of silver metal and a metal oxide and the metal in the metal oxide is a metal other than silver. The silver-based composition is applied to the surface of the first ceramic component and to the surface of the second ceramic component. The silver-based composition applied to the first ceramic component is contacted to the silver-based composition applied to the second ceramic component. The surfaces of the first and second ceramic components are heated to melt the applied silver-based compositions. The surfaces of the first and second ceramic components are cooled to form a bond between the first and second ceramic components.
Description




TECHNICAL FIELD




This application relates to a method of joining materials that may be used in surge arresters and other types of electrical power distribution equipment.




BACKGROUND




Electrical transmission and distribution equipment is subject to voltages within a fairly narrow range under normal operating conditions. However, system disturbances, such as lightning strikes and switching surges, may produce momentary or extended voltage levels that greatly exceed the levels experienced by the equipment during normal operating conditions. These voltage variations often are referred to as over-voltage conditions.




If not protected from over-voltage conditions, critical and expensive equipment, such as transformers, switching devices, computer equipment, and electrical machinery, may be damaged or destroyed by over-voltage conditions and associated current surges. Accordingly, it is routine practice for system designers to use surge arresters to protect system components from dangerous over-voltage conditions.




A surge arrester is a protective device that is commonly connected in parallel with a comparatively expensive piece of electrical equipment to shunt or divert over-voltage-induced current surges safely around the equipment, thereby protecting the equipment and its internal circuitry from damage. When exposed to an over-voltage condition, the surge arrester operates in a low impedance mode that provides a current path to electrical ground having a relatively low impedance. The surge arrester otherwise operates in a high impedance mode that provides a current path to ground having a relatively high impedance. The impedance of the current path is substantially lower than the impedance of the equipment being protected by the surge arrester when the surge arrester is operating in the low-impedance mode, and is otherwise substantially higher than the impedance of the protected equipment.




When the over-voltage condition has passed, the surge arrester returns to operation in the high impedance mode. This high impedance mode prevents normal current at the system frequency from flowing through the surge arrester to ground.




Conventional surge arresters typically include an elongated outer enclosure or housing made of an electrically insulating material, a pair of electrical terminals at opposite ends of the enclosure for connecting the arrester between a line-potential conductor and electrical ground, and an array of other electrical components that form a series electrical path between the terminals. These components typically include a stack of voltage-dependent, nonlinear resistive elements, referred to as varistors. A varistor is characterized by having a relatively high impedance when exposed to a normal system frequency voltage, and a much lower resistance when exposed to a larger voltage, such as is associated with over-voltage conditions. In addition to varistors, a surge arrester also may include one or more spark gap assemblies electrically connected in series or parallel with one or more of the varistors. Some arresters also include electrically conductive spacer elements coaxially aligned with the varistors and gap assemblies.




For proper arrester operation, contact must be maintained between the components of the stack. To accomplish this, it is known to apply an axial load to the components of the stack. Good axial contact is important to ensure a relatively low contact resistance between the adjacent faces of the components, to ensure a relatively uniform current distribution through the components, and to provide good heat transfer between the components and the end terminals.




One way to apply this load is to employ springs within the housing to assure the stacked components engage with one another. Another way to apply the load is to wrap the stack of arrester components with glass fibers to axially-compress the components within the stack.




SUMMARY




In one general aspect, a surface of a first ceramic component is joined to a surface of a second ceramic component using a silver-based composition. The silver-based composition is a mixture of silver metal and a metal oxide and the metal in the metal oxide is a metal other than silver. The silver-based composition is applied to the surface of the first ceramic component and to the surface of the second ceramic component. The silver-based composition applied to the first ceramic component is contacted to the silver-based composition applied to the second ceramic component. The surfaces of the first and second ceramic components are heated to melt the applied silver-based compositions. The surfaces of the first and second ceramic components are cooled to form a bond between the first and second ceramic components.




Implementations may include one or more of the following features. The first ceramic component may include a varistor or, more particularly, a metal oxide varistor. The second ceramic component may include a varistor or, more particularly, a metal oxide varistor.




The silver-based composition is applied to the surface of the first ceramic component by preparing a powder of the metal oxide and then mixing the prepared metal oxide powder to form a metal oxide paste. A foil of silver metal is applied to the surface of the first ceramic component and the metal oxide paste is spread onto the applied silver foil to obtain the silver-based composition.




The silver-based composition may melt at a temperature less than melting points of the first and second ceramic components. In particular, the silver-based composition may melt between around 900° Celsius and 1000° Celsius.




The silver-based composition may be a mixture of silver metal and vanadium oxide. In this case, the mixture may include between around 0.1 to around 10% vanadium oxide by weight.




The first and second ceramic components may be compressed together before heating the surfaces of the ceramic components.




Application of the silver-based composition to the surface of the first ceramic component may include preparing the metal oxide and the silver metal, mixing the prepared metal oxide and the prepared silver metal to form a silver-based composition paste, and then spreading the silver-based composition paste on the first ceramic component to obtain the silver-based composition.




In another general aspect, a surface of a first ceramic component is joined to a surface of a second ceramic component using a silver-based composition. The silver-based composition is a mixture of silver metal and a metal oxide and the metal in the metal oxide is a metal other than silver. The silver-based composition is applied to the surface of the first ceramic component. The silver-based composition applied to the first ceramic component is contacted to the surface of the second ceramic component. The surfaces of the first and second ceramic components are heated to melt the applied silver-based composition. The surfaces of the first and second ceramic components are cooled to form a bond between the first and second ceramic components.




In another general aspect, a bonded component stack for use in surge arrester includes a first ceramic component having a surface, a second ceramic component having a surface, and a silver-based composition. The silver-based composition is a mixture of silver metal and a metal oxide and the metal in the metal oxide is a metal other than silver. The silver-based composition is brazed to the surfaces of the first and second ceramic components to bond the surface of the first ceramic component to the surface of the second ceramic component.




Implementations may include one or more of the following features. The first ceramic component may include a varistor or, more particularly, a metal oxide varistor. The second ceramic component may include a varistor or, more particularly, a metal oxide varistor.




The silver-based composition may be brazed between the surfaces of the first and second ceramic components by applying the silver-based composition to the surface of the first ceramic component; contacting the silver-based composition applied to the first ceramic component to the surface of the second ceramic component; heating the surfaces of the first and second ceramic components to melt the applied silver-based composition; and cooling the surfaces of the first and second ceramic components to form a bond between the first and second ceramic components.




The silver-based composition may be brazed between the surfaces of the first and second ceramic components by compressing the first and second ceramic components together before heating the surfaces of the ceramic components.




The silver-based composition may be brazed between the surfaces of the first and second ceramic components by applying the silver-based composition to the surface of the first ceramic component and to the surface of the second ceramic component; contacting the silver-based composition applied to the first ceramic component to the silver-based composition applied to the second ceramic component; heating the surfaces of the first and second ceramic components to melt the applied silver-based compositions; and cooling the surfaces of the first and second ceramic components to form a bond between the first and second ceramic components.




The silver-based composition may melt at a temperature less than melting points of the first and second ceramic components. The silver-based composition may melt between around 900° Celsius and 1000° Celsius.




The silver-based composition may be a mixture of silver metal and vanadium oxide. In that case, the mixture may include between around 0.1 to around 10% vanadium oxide by weight.




The bonded component stack and the method of making the bonded component stack provides the following advantages. The surfaces may be joined in an air atmosphere, which reduces production and manufacturing costs. The surfaces joined without the use of aggressive fluxes or a secondary heat treatment. The resulting bonded component stack has a relatively low contact resistance between the adjacent faces of the components, a relatively uniform current distribution through the components, and good heat transfer between the components. For these reasons, the need for additional mechanical reinforcement, such as axially-loaded springs, is eliminated.




Additionally, the method of joining eliminates the need for a metallized layer on the surface of the ceramic components because the silver-based composition is bonded directly to the surface. The method of joining also may be used without the need for additional heat treatment steps to recover varistor properties, which otherwise may be lost during the joining process.




Other features and advantages will be apparent from the description, the drawings, and the claims.











DESCRIPTION OF THE DRAWINGS





FIG. 1

is a cross-sectional view of an electrical component module.





FIG. 2

is a partial cross-sectional view of a surge arrester employing the module of FIG.


1


.





FIG. 3

is a perspective view of a ceramic component of the module of FIG.


1


.





FIGS. 4

,


6


A,


6


B,


8


A, and


8


B are flow charts of procedures for use in bonding components of an electrical component module.





FIGS. 5A and 5B

are perspective views of steps in preparing the ceramic components to be bonded according to the procedure of FIG.


4


.





FIG. 5C

is a perspective view of a bonded component stack formed according to the procedure of FIG.


4


.





FIGS. 7A-7C

are perspective views of steps in preparing the ceramic components to be bonded according to the procedure of FIG.


4


.





FIG. 7D

is a perspective view of a bonded component stack formed according to the procedure of FIG.


4


.











Like reference symbols in the various drawings indicate like elements.




DETAILED DESCRIPTION




Referring to

FIGS. 1 and 2

, an electrical component module includes a bonded component stack


100


that serves as both the electrically-active component and the mechanical support component of a surge arrester


110


. The stack


100


also exhibits high surge durability, in that it can withstand high current, short duration conditions, or other required impulse duties. For example, an implementation of the stack for use in heavy duty distribution arresters has proven capable of withstanding 100 kA pulses having durations of 4/10 microseconds, where 4/10 indicates that a pulse takes


4


microseconds to reach 90% of its peak value and 10 microseconds more to get back down to 50% of its peak value.




Components of the bonded component stack


100


are stacked in an end-to-end relationship and bonded together at their end surfaces. Since the components of the stack


100


are affirmatively bound together, the arrester


110


does not need to include a mechanism or structure for applying an axial load to the components.




The surge arrester


110


may be implemented as a distribution class surge arrester, such as a 10 kA heavy duty 10 kV (8.4 kV Maximum Continuous Operating Voltage) arrester. It should be understood, however, that the stack


100


may be used in other types of surge arresters, and in other electrical protective equipment.




The bonded component stack


100


may include different numbers of components, and components of different sizes or types. Examples of components include varistors, capacitors, thyristors, thermistors, resistors, terminals, spacers, and gap assemblies. For purposes of explanation, the stack is shown as including three metal oxide varistors (MOVs)


115


and a pair of terminals


120


.




Referring also to

FIG. 3

, a ceramic component such as a MOV


115


is made of a metal oxide ceramic formed into a short cylindrical disk having a first surface


125


, a second surface


130


opposite the first surface, and an outer cylindrical portion


135


. The MOV


115


has a longitudinal axis


140


. The metal oxide used in the MOV


115


maybe of the same material used for any high energy, high voltage MOV, such as a formulation of zinc oxide.




The MOV may be sized according to the desired application. For example, in one set of implementations, the MOV may have a diameter between approximately 1 to 3 inches, such that the surfaces


125


,


130


each have areas of between about 0.785 and 7.070 square inches.




Given a particular metal oxide formulation and a uniform or consistent microstructure throughout the MOV, the thickness of the MOV determines the operating voltage level of the MOV. In one implementation, each MOV is about 0.75 inches thick. In some implementations, this thickness may be increased substantially (for example, tripled).




It is desirable to minimize the cross-sectional areas of the MOVs to minimize the size, weight, and cost of the arrester. However, the durability and recoverability of the MOVs tend to be directly related to the sizes of the MOVs. In view of these competing considerations, MOVs having diameters of approximately 1.6 inches have been used.




A terminal


120


is disposed at each end of the stack


100


. Each terminal


120


is a relatively short, cylindrical block formed from a conductive material, such as, for example, aluminum. Each terminal


120


has a diameter substantially equal to that of an MOV


115


. In some implementations, each terminal may also include a threaded bore


150


in which may be positioned a threaded conductive stud


155


.




In general, the terminals


120


may be thinner than terminals associated with modules that, for example, are wrapped with a structural layer to provide an axial load on the components of the module. This reduced thickness may result from changes in the geometry of the device, or simply because thicker metal is not needed for bonding with the structural layer.




As shown in

FIG. 2

, the surge arrester


110


includes the bonded component stack


100


, a polymeric housing


165


, and an arrester hanger


170


. The stack


100


is disposed within the polymeric housing


165


. An insulating or dielectric compound (not shown), such as room temperature vulcanized silicone, may be used to fill any voids between the stack


100


and the inner surface of the housing


165


. A threaded conductive stud (not shown) is disposed in the bore


150


of each terminal


120


. The upper stud extends through the housing


165


and includes threads for engaging a terminal assembly (not shown). The lower stud extends through an aperture (not shown) in hanger


170


for connection to a ground lead disconnector


175


. A threaded stud


180


extends from the disconnector


175


to engage a ground lead terminal assembly (not shown). The housing


165


is sealed about the upper and lower ends of the stack


100


.




Components of the bonded component stack


100


are bonded together at their end surfaces, such that the stack


100


serves as both the electrically-active structure and the mechanical support structure of an electrical protective device such as the surge arrester


110


. Components such as MOVs, thyristors, or capacitors are ceramic components. Components such as terminals and spacers are non-ceramic components. Bonding between components must provide bonds that are both mechanically stable and electrically conductive.




Referring to

FIG. 4

, bonding between a surface on a first ceramic component (for example, an MOV


115


) and the surface of second ceramic component (for example, a thyristor or another MOV) may be achieved according to a procedure


400


. The procedure


400


may be performed in an air atmosphere.




Initially, a silver-based composition is placed between the first component and the second component (step


405


). The silver-based composition is a mixture of silver metal and a metal oxide, in which the metal in the metal oxide is any suitable metal other than silver and the metal oxide is a low-melting-point oxide. A low-melting-point oxide is any oxide that has a melting point lower than the melting point of the first and second components between which it is placed. The general formula for the silver-based composition is Ag—M


x


O


y


, where Ag is silver metal, M


x


O


y


is a low-melting-point metal oxide, and M is a metal selected from the group consisting of: vanadium, copper, zinc, indium, germanium, tin, lead, and magnesium. The ratio of the metal to oxygen (given by the ratio of x to y) depends upon the oxidation state of the metal in the metal oxide. In general, x and y are integers greater than zero. Particular examples of metal oxides include vanadium oxide (V


2


O


5


), magnesium oxide (MgO), and zinc oxide (ZnO).




In one implementation, the metal oxide is vanadium oxide (V


2


O


5


). Thus, the silver-based composition is a mixture of silver metal and vanadium oxide (V


2


O


5


), or silver-vanadium oxide (Ag—V


2


O


5


). Preferably, the silver-vanadium oxide has between approximately 0.1 to approximately 10% vanadium oxide by weight. Vanadium oxide is selected because the melting temperature of vanadium oxide is less than 1000° C., which is the melting temperature of zinc oxide, a common material used in metal oxide varistors.




The amount of silver-based composition placed between the first and second components will depend on the requirements for the type and/or strength of the resulting bond. At a minimum, the silver-based composition, once applied, should cover the entire surfaces of the first and second components. The amount of silver-based composition placed between the first and second components will be limited by, for example, the manufacturing cost and the mechanical integrity of the resulting bond. Thus, any suitable thickness may be contemplated, as long as the silver-based composition covers the entire surfaces of the first and second components, the manufacturing cost is reasonable, and the amount of silver-based composition does not adversely affect the mechanical integrity.




After the silver-based composition is placed between the first and second components (step


405


), the first and second components are joined together (step


410


). To join the first and second components together, pressure may be applied to the components along the longitudinal axis. For example, the applied pressure may range from approximately 25 to approximately 100 pounds per square inch.




Once the first component is joined with the second component (step


410


), the joined components are heated to a temperature sufficient to melt the silver-based composition, a process that may be referred to as brazing (step


415


). In one implementation, the brazing process may be performed in an air atmosphere or a near-air atmosphere.




The temperature to which the joined components are heated must be less than the melting point of the joined components. Additionally, the temperature to which the joined components are heated must be less than a temperature that results in a degradation of electrical and mechanical properties of the joined components. In one implementation, if the components to be joined are zinc oxide varistors, then the joined components may be heated to a temperature ranging from approximately 960° C. to approximately 1000° C., above which the electrical and mechanical properties of the zinc oxide begin to degrade. The heat may be applied to the joined components (step


415


) for any suitable hold time. Because the mechanical properties of the bond may depend upon the hold time, it is appropriate to select a hold time depending on the requirements for the type and/or strength of the bond. In one implementation, the hold time may vary within the range of approximately zero to approximately ten minutes. In other implementations, longer hold times might be suitable.




After the hold time has elapsed, the first and second components are cooled to bond the first and second components together into a bonded component stack (step


420


).




Referring also to

FIGS. 5A

,


5


B, and


6


A, in one implementation, the procedure


405


for placing a silver-based composition


510


between first and second components


500


and


505


includes applying the silver-based composition


510


to a second surface of the first component


500


using any suitable techniques (step


600


). Then, the first and second components


500


and


505


are joined together (step


410


) as shown in

FIGS. 5B and 5C

.




Referring also to

FIGS. 7A-7C

and


6


B, in another implementation, the procedure


405


for placing a silver-based composition


710


between first and second components


700


and


705


includes applying the silver-based composition


510


to a second surface of the first component


700


(step


650


) as shown in FIG.


7


A. Additionally, the silver-based composition


510


is applied to a first surface of the second component


705


(step


655


) as shown in FIG.


7


B. The application of the silver-based composition


510


may be performed using any suitable technique. Then, the first and second components


700


and


705


are joined together (step


410


) as shown in

FIGS. 7C and 7D

.




In a further implementation, the silver-based composition may be sandwiched between the first and second components using any suitable procedure.




Referring to

FIG. 8A

, the silver-based composition may be applied (for example, as in step


600


, step


650


, or step


655


) to a surface of a ceramic component according to a procedure


800


. Initially, a metal oxide powder is prepared (step


805


). The metal oxide powder is mixed to form a paste (step


810


). In one implementation, mixing includes grinding the metal oxide powder in a blender. Then, a silver metal foil is applied to the surface of the ceramic component using any suitable technique (step


815


). For example, the silver metal foil may be applied to the ceramic component by gluing the silver metal foil to the surface of the ceramic component using a suitable glue. The metal oxide paste then is spread on the applied silver metal foil to obtain the silver-based composition (step


820


).




The amount of metal oxide paste spread on the silver metal foil and the thickness of the silver metal foil are interdependent parameters that may be varied. These parameters also may be varied depending on the target weight percentage of the metal oxide in the silver-based composition, the type of metal used in the metal oxide, and the surface area and/or size of the ceramic component to which the silver-based composition is applied. In any case, the parameters are varied to produce a stack having suitable mechanical and electrical properties.




Referring to

FIG. 8B

, in another implementation, the silver-based composition maybe applied (for example, as in step


600


, step


650


, or step


655


) to a surface of a ceramic component according to a procedure


850


. Initially, the silver metal and the metal oxide are prepared as a powder (step


855


). Then, the powder is mixed to form a paste of the silver-based composition (step


860


), which is spread directly onto the surface of the ceramic to form the silver-based composition (step


865


).




Other implementations are within the scope of the following claims. For example, in some implementations, an insulative coating may be bonded to the bonded component stack to form a component module, thus preventing the undesired entry of moisture or other contaminants to the surge arrester. The coating also may provide increased tensile and mechanical strength to the bonded component stack, as well as controlled venting of gases during a surge arrester failure. The insulative coating may cover the circumferential sides of the stack


100


and may be made thin enough to permit the stack to vent gas that may evolve during arrester component failure. In particular, when an MOV


115


or other internal component of the stack fails, pressure within the insulative coating would build as the internal arc burns adjacent materials. The pressure would increase until it reaches a magnitude that causes the insulative coating to burst, thus relieving the internal pressure and venting the evolved gas. An outer cylindrical surface of a terminal in the stack may be knurled, ribbed, or otherwise textured to improve adherence to the insulative coating.




Details regarding formulation of an insulative coating are described in U.S. Pat. No. 6,225,567, titled “Polymeric Weathershed Surge Arrester and Method” and issued May 1, 2001; and U.S. application Ser. No. 09/432,147, titled “Surge Arrester Module with Bonded Component Stack” and filed Nov. 2, 1999, which are incorporated by reference.




As noted above, the brazing technique using a silver-based composition may be applied between various ceramic components, including other types of varistors and thyristors.



Claims
  • 1. A method of joining a surface of a first ceramic component to a surface of a second ceramic component, the method comprising:applying a silver-based composition to the surface of the first ceramic component, the silver-based composition being a mixture of silver metal and a metal oxide, in which the metal in the metal oxide is a metal other than silver; contacting the silver-based composition applied to the first ceramic component to the surface of the second ceramic component; heating the surfaces of the first and second ceramic components to melt the applied silver-based composition; and cooling the surfaces of the first and second ceramic components to form a bond between the first and second ceramic components.
  • 2. The method of claim 1 in which the first ceramic component comprises a varistor.
  • 3. The method of claim 2 in which the second ceramic component comprises a varistor.
  • 4. The method of claim 1 in which the first ceramic component comprises a metal oxide varistor.
  • 5. The method of claim 4 in which the second ceramic component comprises a metal oxide varistor.
  • 6. The method of claim 1 in which applying the silver-based composition to the surface of the first ceramic component includes:preparing a powder of the metal oxide; mixing the prepared metal oxide powder to form a metal oxide paste; applying a foil of silver metal to the surface of the first ceramic component; and spreading the metal oxide paste onto the applied silver foil to obtain the silver-based composition.
  • 7. The method of claim 1 in which the silver-based composition melts at a temperature less than melting points of the first and second ceramic components.
  • 8. The method of claim 7 in which the silver-based composition melts between around 900° Celsius and 1000° Celsius.
  • 9. The method of claim 1 in which the silver-based composition is a mixture of silver metal and vanadium oxide.
  • 10. The method of claim 9 in which the mixture comprises between approximately 0.1 to approximately 10% vanadium oxide by weight.
  • 11. The method of claim 1 further comprising compressing the first and second ceramic components together before heating the surfaces of the ceramic components.
  • 12. The method of claim 1 in which applying the silver-based composition to the surface of the first ceramic component includes:preparing the metal oxide and the silver metal; mixing the prepared metal oxide and the prepared silver metal to form a silver-based composition paste; and spreading the silver-based composition paste on the first ceramic component to obtain the silver-based composition.
  • 13. The method of claim 1 in which heating the surfaces of the first and second ceramic components comprises heating while in an air atmosphere or in a near air atmosphere.
  • 14. The method of claim 1 in which contacting includes contacting the silver-based composition applied to the first ceramic component to a bare surface of the second component.
  • 15. A method of joining a first ceramic component to a second ceramic component, the method comprising:placing a silver-based composition between the first ceramic component and the second ceramic component, the silver-based composition being a mixture of silver metal and a metal oxide, in which the metal in the metal oxide is a metal other than silver; joining the first ceramic component to the second ceramic component; heating the first and second ceramic components to melt the silver-based composition; and cooling the first and second ceramic components to form a bond between the first and second ceramic components.
US Referenced Citations (31)
Number Name Date Kind
3440182 Hoffman Apr 1969 A
3740830 Campbell, Jr. et al. Jun 1973 A
4272754 Lou Jun 1981 A
4369063 McGowan, Jr. Jan 1983 A
4447392 Mizuhara May 1984 A
4573265 Conaway et al. Mar 1986 A
4606980 Mizuhara Aug 1986 A
4643875 Mizuhara Feb 1987 A
4667871 Mizuhara May 1987 A
4749594 Malikowski et al. Jun 1988 A
4835593 Arnold et al. May 1989 A
4851955 Doone et al. Jul 1989 A
4992906 Doone et al. Feb 1991 A
5003689 Doone et al. Apr 1991 A
5009357 Baker et al. Apr 1991 A
5159748 Doone et al. Nov 1992 A
5176762 Berczik Jan 1993 A
5218508 Doone Jun 1993 A
5273832 Mizuhara et al. Dec 1993 A
5288351 Hoang et al. Feb 1994 A
5301861 Mizuhara et al. Apr 1994 A
5429656 Hauner et al. Jul 1995 A
5523159 Kapoor et al. Jun 1996 A
5547121 Kapoor et al. Aug 1996 A
5567525 Kapoor et al. Oct 1996 A
5680289 Robinson et al. Oct 1997 A
5720859 Czubarow et al. Feb 1998 A
5896264 Bijlenga et al. Apr 1999 A
6008977 Thatcher Dec 1999 A
6037068 de Rochemont et al. Mar 2000 A
6396676 Doone et al. May 2002 B1
Foreign Referenced Citations (9)
Number Date Country
0005312 Mar 1979 EP
0245697 Apr 1987 EP
0945414 Sep 1999 EP
0945414 Oct 1999 EP
5163075 Jun 1993 JP
7133167 May 1995 JP
2000178078 Jun 2000 JP
2000178079 Jun 2000 JP
WO9403305 Feb 1994 WO
Non-Patent Literature Citations (1)
Entry
International Search Report dated Apr. 25, 2003.