Green compact electrode for discharge surface treatment and method of manufacturing green compact electrode for discharge surface treatment

Information

  • Patent Grant
  • 6441333
  • Patent Number
    6,441,333
  • Date Filed
    Tuesday, August 15, 2000
    24 years ago
  • Date Issued
    Tuesday, August 27, 2002
    22 years ago
Abstract
A green compact electrode for discharge surface treatment used for discharge surface treatment for generating discharge between a work and a green compact electrode obtained by pressuring and compacting a metal powder or a powder of a compound metal, and using the discharge energy forming a coating of an electrode material or a substance obtained through a reaction of the electrode material with the discharge energy on the work surface; the electrode is obtained by mixing a soft metal powder as a bonding agent with the metal powder or the compound metal powder, and pressuring and compacting the mixed powder.
Description




1. Technological Field




The present invention relates to a green compact electrode for discharge surface treatment and a method of manufacturing the green compact electrode for discharge surface treatment and more particularly, to a green compact electrode (discharge electrode) used for discharge surface treatment to form hard anodic oxidation coatings on a work surface as well as to a method of manufacturing the green compact electrode.




2. Background Technology




Disclosed in Japanese Patent Laid-Open Publication No. HEI 9-19829 is a method of discharge surface treatment that uses a green compact electrode in the presence of a treatment liquid such as discharge treatment oil, and uses a pulse discharge between a green compact electrode and a work to form a hard anodic coating of the material of the electrode or of a substance such as metal carbide of TiC or so yielded through reaction of the electrode material on the work surface by the discharge energy.




Generally, the green compact electrode is prepared by making use of a property of the metal powder that the powder hardens when a powder of metal such as Ti is filled in a die and the metal powder in the die is pressured and compacted by a pressure punch.




The green compact electrode does not undergo sintering even when the metal powder is used, which is different from the electrode for discharge processing disclosed in Japanese Patent Laid-Open Publication No. SHO 56-126535 and Japanese Patent Laid-Open Publication No. SHO 62-127448, therefore, the electrode strength and the electric resistance finally achieved are decided depending on a state when its pressure and compacting are completed.




Therefore, in order to obtain a required final electrode strength and electric resistance, the green compact electrode requires the pressure of about 5 tonf/cm


2


as the compacting pressure. If the compacting pressure is lower than this, the strength of the compacted electrode may not be sufficient or the electric resistance of the electrode may become extremely large, so that the electrode can not appropriately be used as a green compact electrode for discharge surface treatment.




On the other hand, however, when an electrode is compacted with such the large compacting pressure, the pressure to the metallic die is also larger, and for this reason the green compact electrode may be chipped or broken when the green compact electrode is being taken out of the metallic die after being compacted, so that manufacture yields of the green compact electrode are resultantly low.




As described above, the requirement of a large compacting pressure for pressuring and compacting a green compact electrode for discharge surface treatment is largely caused by the facts that a linkage structure of particles can be loose only with particles of metal carbide such as TiC, and that powder can not uniformly be filled in a metallic die. The technology using a submerged discharge phenomenon has been disclosed in Japanese Patent Laid-Open Publication No. Hei. 7-197275. There has been disclosed in Japanese Patent Laid-Open Publication No. Hei. 7-197275 compression and compaction as a method of manufacturing a green compact electrode. However, with only the compression and compaction pressure distribution easily becomes non-uniform, and especially, when the size of the electrode is large it is difficult to maintain a high-quality.




The present invention has been made for solving the problems described above, and it is an object of the present invention to provide a green compact electrode for discharge surface treatment which has required electrode strength and electric resistance value as a green compact electrode for discharge surface treatment through compacting with a comparatively smaller compacting pressure and which can obtain high manufacture yields, and a method of manufacturing the green compact electrode for discharge surface treatment.




DISCLOSURE OF THE INVENTION




The present invention can provide a green compact electrode for discharge surface treatment used for discharge surface treatment for generating discharge between a work and a green compact electrode obtained by pressuring and compacting a metal powder or a powder of a compound metal, and by using the discharge energy forming a coating consisting of an electrode material or a substance obtained through reaction of the electrode material with the discharge energy on the work surface; the electrode is obtained by mixing soft metal powder with a metal powder or a powder of a compound metal, and pressuring and compacting the mixed powder.




Accordingly, when a green compact electrode is pressured and compacted, the soft metal powder enters in the inter-particle space of the metal powder or compound metal powder as a bonding agent and plastically forms in the inter-particle space to harden the electrode with powder, which makes the electric resistance of the electrode lower. With this feature, the electrode strength and electric resistance required as a green compact electrode for discharge surface treatment can be obtained even though the electrode is compacted at a low compacting pressure.




The present invention can provide a green compact electrode for discharge surface treatment in which the compound metal powder is a powder of TiH


2


and the soft metal powder is a powder of Ag.




Accordingly, when a green compact electrode is pressured and compacted, the Ag powder which is comparatively soft and has low electric resistance enters the inter TiH


2


-particle space, plastically deforms in the inter-particle space and harden the electrode with powder, which makes the electric resistance of the electrode lower. With this feature, the electrode strength and electric resistance required as a green compact electrode for discharge surface treatment can be obtained even though the electrode is compacted at a low compacting pressure. In this green compact electrode, hard anodic oxidation coating of TiC is obtained in the discharge surface treatment due to a reaction of TiH


2


with the carbon in the treatment liquid.




The present invention can provide a green compact electrode for discharge surface treatment used for discharge surface treatment for generating discharge between a work and a green compact electrode obtained by pressuring and compacting a metal powder or a powder of a compound metal, and using the discharge energy forming a coating consisting of an electrode material or a substance obtained through a reaction of the electrode material with the discharge energy on the work surface; the electrode is obtained by mixing a bonding agent with the metal powder or the compound metal powder, and pressuring and compacting the mixed powder with a die.




Accordingly, particles of the metal powder or the compound metal powder are bonded to each other by a bonding agent to harden an electrode with powder, which make electric resistance of the electrode lower. With this feature, the electrode strength and electric resistance required as a green compact electrode for discharge surface treatment can be obtained even though the electrode is compacted at a low compacting pressure.




The present invention can provide a green compact electrode for discharge surface treatment in which the bonding agent is a carbon-contained polymer-base bonding agent such as epoxy resin or phenol resin.




Accordingly, in the discharge surface treatment, in addition to reaction of the metal powder or the compound metal powder with the carbon in treatment liquid, the metal powder or the compound metal powder reacts with the carbon in the bonding agent, so that hard carbide metal coating can be obtained.




The present invention can provide a method of manufacturing the green compact electrode for discharge surface treatment used for discharge surface treatment for generating discharge between a work and a green compact electrode obtained by pressuring and compacting the metal powder or a powder of a compound metal, and using the discharge energy forming a coating consisting of an electrode material or a substance obtained through a reaction of the electrode material with the discharge energy on the work surface; the method comprising the steps of mixing a soft metal powder with the metal powder or the compound metal powder, and pressuring and compacting the mixed powder with a die.




Accordingly, when a green compact electrode is pressured and compacted, the soft metal powder enters the inter-particle space of the metal powder or the compound metal powder as a bonding agent and plastically deforms along the inter-particle space to harden the electrode with powder, which makes the electric resistance of the electrode lower. With this feature, the electrode strength and electric resistance required as a green compact electrode for discharge surface treatment can be obtained even though the electrode is compacted at a low compacting pressure.




The present invention can provide a method of manufacturing the green compact electrode for discharge surface treatment in which the compound metal powder is a powder of TiH


2


, and the soft metal powder is a powder of Ag.




Accordingly, when a green compact electrode is pressured and compacted, the Ag powder which is comparatively soft and has low electric resistance enters the inter-TiH


2


-particle space and plastically deforms in the inter-particle space to harden the electrode with powder, which makes the electric resistance of the electrode lower. With this feature, the electrode strength and electric resistance required as a green compact electrode for discharge surface treatment can be obtained even though the electrode is compacted at a low compacting pressure. In this green compact electrode, hard anodic oxidation coating of TiC is obtained in the discharge surface treatment due to a reaction of TiH


2


with the carbon in the treatment liquid.




The present invention can provide a method of manufacturing the green compact electrode for discharge surface treatment used for discharge surface treatment for generating discharge between a work and a green compact electrode obtained by pressuring and compacting a metal powder or a powder of a compound metal, and using the discharge energy forming a coatings consisting of an electrode material or a substance obtained through a reaction of the electrode material with the discharge energy on the work surface; the method comprises the steps of filling the metal powder or the compound metal powder into a die while vibrating the die, and pressuring and compacting the powder in the die. The case of the vibration filling as described above assumes conditions as follows: several grams to hundreds of grams as a filled amount; tens of seconds as a time for vibration filling; 1-50 μm as a particle diameter; 5 μm or more as an amplitude; and 10 Hz or more as a vibration frequency.




Because of the vibration filling, the metal powder or the compound metal powder is densely filled in the die, and the metal powder or the compound metal powder can uniformly be filled in the die. With this feature, the electrode strength and electric resistance required as a green compact electrode for discharge surface treatment can be obtained even through the electrode is compacted at a low compacting pressure.




The present invention can provide a method of manufacturing the green compact electrode for discharge surface treatment in which ultrasonic vibration is applied to the die.




Because of the ultrasonic vibration filling, the metal powder or the compound metal powder is effectively densely filled in the die, and the metal powder or the compound metal powder can uniformly be filled in the die. With this feature, the electrode strength and electric resistance required as a green compact electrode for discharge surface treatment can be obtained even though the electrode is compacted at a low compacting pressure.




The present invention can provide a method of manufacturing the green compact electrode for discharge surface treatment used for discharge surface treatment for generating discharge between a work and a green compact electrode obtained by pressuring and compacting metal powder or compound metal powder, and by using the discharge energy forming a coating consisting of an electrode material or a substance obtained through reaction of the electrode material with the discharge energy on the work surface; the method comprises the steps of mixing a bonding agent with a metal powder or a compound metal powder, and pressuring and compacting the mixed powder with a die.




Accordingly, the metal powder or compound metal powder is bonded by a bonding agent to harden an electrode with powder, which make electric resistance of the electrode lower. With this feature, the electrode strength and electric resistance required as a green compact electrode for discharge surface treatment can be obtained even though the electrode is compacted at a low-compacting pressure.




The presents invention can provide a method of manufacturing the green compact electrode for discharge surface treatment in which the bonding agent is a carbon-contained polymer-base bonding agent such as epoxy resin and phenol resin.




Accordingly, in the discharge surface treatment, in addition to a reaction of the metal powder or the compound metal powder with the carbon in the treatment liquid, the metal powder or the compound metal powder reacts with the carbon in the bonding agent, so that a hard carbide metal coating can be obtained.











BRIEF DESCRIPTION OF THE DRAWINGS





FIG. 1

is a view schematically showing an example of a microstructure of the green compact electrode for discharge surface treatment according to the present invention,





FIG. 2

is a cross-sectional view showing an example of a manufacturing device used for executing the method of manufacturing the green compact electrode for discharge surface treatment according to the present invention,





FIG. 3

is a cross-sectional view showing another example of the manufacturing device used for executing the method of manufacturing the green compact electrode for discharge surface treatment according to the present invention, and





FIG. 4

is a view schematically showing another example of the microstructure of the green compact electrode for discharge surface treatment according to the present invention.











BEST MODE FOR CARRYING OUT THE INVENTION




Description is made for preferred embodiments of the present invention with reference to the accompanying drawings.




Embodiment 1





FIG. 1

schematically shows a microstructure of the green compact electrode for discharge surface treatment according to the present invention. The green compact electrode for discharge surface treatment


10


according to the present invention is obtained by pressuring and compacting the mixed powder


13


which is a mixture of a metal powder or a compound metal powder (described as metal powder hereinafter)


11


such as metal carbide as a main component of hard anodic oxidation coating yielded by discharge surface treatment and the soft metal powder


12


to a form of an electrode with a die.




The metal powder


11


is a powder of TiH


2


(Titanium hydride), and the soft metal powder


12


is a powder of Ag.




A particle diameter of the metal powder


11


of about 1 to 40 μm may be sufficient and a particle diameter of the soft metal powder


12


of about 1 to 100 μm may be sufficient in this case, and the ratio of the metal powder


11


and soft metal powder


13


may be about 10:1 by weight percent.




This green compact electrode for discharge surface treatment


10


is pressured and compacted by using a press punch


50


and a die


52


fixed on a die plate


51


as shown in

FIG. 2

, filling the mixed powder


13


of the metal powder


11


with soft metal powder


12


in the die


52


, and pressuring the powder by the punch


50


. The green compact electrode for discharge surface treatment


10


is pressured and compacted in a state where the soft metal powder


12


such as Ag is mixed in the metal powder


11


such as TiH


2


, so that the green compact electrode


10


can firmly harden even when the compacting pressure for the electrode is lowered as far as around 2 tonf/cm


2


, with which the electrode strength and electric resistance required as a green compact electrode for discharge surface treatment can be obtained.




When the green compact electrode


10


is pressured and compacted, the soft metal powder


12


enters the inter-particle space of the metal powder


11


as a bonding agent and plastically deforms in the inter-particle space, which is effective in hardening the electrode with powder as well as in making the electric resistance of the electrode lower. The electric resistance of the green compact electrode


10


can be maintained to a sufficiently low value especially by mixing thereinto Ag powder having low electric resistance.




With this, the green compact electrode for discharge surface treatment


10


having the electrode strength and electric resistance required as a green compact electrode for discharge surface treatment can be pressured and compacted with a low compacting pressure, so that the pressure to the metallic die is reduced, and therefor, the probability of chipping or breaking a green compact electrode


10


when the green compact electrode


10


is being taken out of the metallic die after being compacted is drastically reduced, and manufacture yields of the green compact electrode


10


are improved.




If the compacting pressure for an electrode is lower, the force pressed to the metallic die is smaller, which makes it possible to compact a thick green compact electrode or a slim and long green compact electrode.




With the green compact electrode


10


obtained by mixing Ag powder with TiH


2


powder, high-quality hard anodic oxidation coatings with TiC yielded through a reaction thereof with the carbon in the treatment liquid by the discharge energy can be obtained.




Discharge surface treatment is performed under the same conditions using the green compact electrode according to the present invention obtained by mixing Ag powder with TiH


2


powder, and pressuring and compacting at about 2 tonf/cm


2


and also the conventional type of green compact electrode obtained by pressuring and compacting at 5 tonf/cm


2


without mixing Ag thereinto, as a result, the properties of the coating in both of the electrodes were obtained as follows: Vickers hardness of about 2500 HV; adhesive force was strong; and the coating thickness was about 5 μm, and no difference was found in the two.




The metal powder


11


for the green compact electrode


10


could be a powder of a metal carbide or the like such as WC other than TiH


2


, and the soft metal powder


12


to be mixed with the metal powder


11


could be a powder of a soft metal such as Au, Ag, Pb, Sn, In, and Ni other than Ag, and further a ceramics powder can also be mixed with the metal powder.




Embodiment 2





FIG. 3

shows an embodiment of the manufacturing device used for executing the method of manufacturing the green compact electrode for discharge surface treatment according to the present invention. In this embodiment, a die plate


51


is located on an exciting device


53


. When metal powder


11


such as TiH


2


is filled in the die


52


, the die


52


is vibrated using the exciting device


53


, and the metal powder


11


is filled in the die


52


while the vibrations are being applied thereto.




With this processing, the density of the metal powder


11


filled in the die becomes high, so that the metal powder


11


is uniformly filled in the die


52


.




The exciting device


53


may employ a device for applying ultrasonic vibrations to a die or a device for applying vibrations with a longer cycle. However, application of ultrasonic vibration thereto has the better effect when filling the metal powder densely. A vibration system which tapson a metallic die with a hammer may be employed in place of the exciting device


53


.




Powder weight was compared when the metal powder


11


is completely filled in a metallic die by using the exciting device


53


and by not using the exciting device


53


, and as a result, when the exciting device


53


is used, 1.3 times of powder could be filled as compared to the case when the exciting device is not used.




With this feature, it was possible to ascertain that a required green compact electrode can sufficiently be compacted even when the compacting pressure is lowered a little. Generally, when a green compact electrode is pressured and compacted without using the exciting device


53


, the pressure of about 5 tonf/cm


2


is required for compacting, but when the exciting device


53


was used, a green compact electrode was compacted without any trouble even when the compacting pressure was lowered as far as 4 tonf/cm


2


.




Thus, the probability of chipping or breaking of a green compact electrode when it is being taken out of the metallic die after being compacted is reduced, and manufacture yields of the green compact electrode are also improved.




It should be noted that this manufacturing method is applicable to the case where mixed powder


13


of metal powder


11


with soft metal powder


12


is used, and the same effect can be obtained. Embodiment 3





FIG. 4

schematically shows the microstructure of the green compact electrode for discharge surface treatment according to the present invention. The green compact electrode for discharge surface treatment


20


according to the present invention is obtained by mixing a bonding agent


22


into a metal powder or a compound metal powder such as metal carbide as a main component of hard anodic oxidation coatings yielded by discharge surface treatment, and further into either of the powder with ceramics powder mixed thereinto (described metal powder hereinafter)


21


, and pressuring and compacting the powder to a form of an electrode with a die.




Carbon-contained polymer-base bonding agent such as epoxy resin and phenol resin may be used as a bonding agent


22


.




This green compact electrode for discharge surface treatment


20


is also pressured and compacted by using the press punch


50


and the die


52


fixed on the die plate


51


as shown in

FIG. 2

, filling powder with the bonding agent


22


mixed into metal powder


21


, and pressuring the powder by the punch


50


.




The bonding agent


22


bonds the particles of the metal powder


21


to each other and acts so that a required electrode strength can be obtained. In a case of the metal powder


21


with TiH


2


, the green compact electrode


20


can firmly harden with the bonding agent


22


even when the compacting pressure for the electrode is lowered as far as around 2 tonf/cm


2


or less, therefore, the electrode strength and electric resistance required as a green compact electrode for discharge surface treatment can be obtained.




With those features, the green compact electrode for discharge surface treatment


20


having the electrode strength and electric resistance required as a green compact electrode for discharge surface treatment can be pressured and compacted with a low compacting pressure, so that the pressure applied on the metallic die is reduced, therefore, the probability of chipping or breaking of a green compact electrode


20


when the green compact electrode


20


is being taken out of the metallic die after being compacted is reduced, and manufacture yields of the green compact electrode


20


are also improved.




When the bonding agent


22


is mixed in the metal powder, in addition to the action of harden the electrode, the effect of making the hardness of coatings formed through discharge surface treatment higher can also be obtained.




For example, when a green compact electrode with metal powder of TiH


2


is used, the main component of the coatings is TiC, that is because TiC is yielded through a reaction between Ti in the electrode with the carbon C as a component in treatment liquid. In this case, when the supply of carbon is larger than what is consumed by the green compact electrode, unreacted Ti which is not converted into TiC remains in the coating, which causes the hardness of the coatings to be lowered.




A bonding agent is decomposed by thermal energy due to discharge because it is a substance comprising carbon C, hydrogen H, and oxygen O, and hydrogen is decomposed mainly into water H


2


O or hydrogen gas H


2


, oxygen into water H


2


O and carbon dioxide CO


2


, and carbon into carbon dioxide CO


2


and carbon C. The carbon yielded herein is used when Ti in the green compact electrode reacts with TiC, which helps to form hard anodic oxidation coatings.




Namely, hard carbide metal coatings can be obtained through reaction of metal powder


21


with carbon in the bonding agent


22


in addition to reaction of metal powder


21


with carbon in treatment liquid.




INDUSTRIAL APPLICABILITY




The green compact electrode according to the present invention is applicable to a discharge electrode used for discharge surface treatment for forming hard anodic oxidation coatings thereon.



Claims
  • 1. A green compact electrode structure for electrical discharge surface treatment of a work, comprising; a green compact electrode body formed of a pressurized compact of at least a metal powder or powder of a compound metal and a soft metal powder.
  • 2. A green compact electrode structure according to claim 1; wherein the compound metal powder is a powder of TiH2, and the soft metal powder is a powder of Ag.
  • 3. A green compact electrode structure for electrical discharge surface treatment of a work, comprising; a green compact electrode body formed of a pressurized compact of at least a metal powder or a powder of a compound metal and a bonding agent.
  • 4. A green compact electrode structure according to claim 3; wherein the bonding agent is a carbon-contained polymer-base bonding agent.
  • 5. A method of manufacturing a green compact electrode structure for electrical discharge surface treatment of a work said method comprising the steps of mixing a soft metal powder a the metal powder or a compound metal powder, and pressuring and compacting the mixed powder with a die.
  • 6. A method of manufacturing the green compact electrode structure according to claim 5; wherein the compound metal powder is powder of TiH2 and the soft metal powder is a powder of Ag.
  • 7. A method of manufacturing a green compact electrode structure for electrical discharge surface treatment of a work said method comprising the steps of filling a metal powder or a compound metal powder into a die while vibrating the die, and pressuring and compacting the powder within the die.
  • 8. A method of manufacturing the green compact electrode structure according to claim 7; wherein ultrasonic vibration is applied to said die.
  • 9. A method of manufacturing the green compact electrode structure for electrical discharge surface treatment of a work said method comprising the steps of mixing a bonding agent with a metal powder or a compound metal powder, and pressuring and compacting the mixed powder within a die.
  • 10. A method of manufacturing the green compact electrode structure according to claim 9; wherein the bonding agent is a carbon-contained polymer base bonding agent.
  • 11. A green compact electrode structure according to claim 4; wherein the bonding agent is an epoxy resin or a phenol resin.
  • 12. A green compact electrode structure according to claim 10; wherein the bonding agent is an epoxy resin or a phenol resin.
  • 13. A green compact electrode structure for discharge surface treatment of a work, comprising; a main body comprised of pressured and compacted powder containing a soft metal powder and a metal powder or a compound metal powder.
  • 14. A green compact electrode structure according to claim 13, wherein the compound metal powder is a powder of TiH2 and the soft metal powder is a powder of Ag.
  • 15. A green compact electrode structure for discharge surface treatment for a work, comprising; a mixture of a pressed and compacted powder containing a bonding agent and a metal powder or a compound metal powder.
  • 16. A green compact electrode structure according to claim 15, wherein the bonding agent is a carbon-contained polymer base bonding agent.
  • 17. A green compact electrode structure according to claim 16, wherein the bonding agent is an epoxy resin or a phenol resin.
  • 18. A process for producing and using a green compact electrode, comprising; mixing a soft metal powder with a metal powder or a powder of a metal compound, pressuring and compacting the mixed powder in a die, and performing electrical discharge surface treatment of a work using said green compact electrode to form a coating on said work.
  • 19. A process for producing and using a green compact electrode according to claim 18, wherein the coating is comprised of at least one material from said electrode.
  • 20. A process for producing and using a green compact electrode according to claim 18, wherein the coating is obtained from reacting electrode material with at least one of a work material and a dielectric.
  • 21. A process according to claim 18, wherein the. compound metal powder is powder of TiH2 and the soft metal powder is a powder of Ag.
  • 22. A process for producing and using a green compact electrode, comprising; filling a die with a metal powder or a powder of a metal compound while vibrating the die, pressuring and compacting the powder in said die, and performing electrical discharge surface treatment of a work using said green compact electrode to form a coating on said work.
  • 23. A process for producing and using a green compact electrode according to claim 22, wherein the coating is comprised of at least one material from said electrode.
  • 24. A process for producing and using a green compact electrode according to claim 22, wherein the coating is obtained from reacting electrode material with at least one of a work material and a dielectric.
  • 25. A process according to claim 20, wherein ultrasonic vibration is applied to said die.
  • 26. A process for producing and using a green compact electrode, comprising; mixing a bonding agent with a metal powder or a powder of a metal compound in a die, pressing and compacting the mixed powder in the die, and performing electrical discharge surface treatment of a work using said green compact electrode to form a coating on said work.
  • 27. A process for producing and using a green compact electrode according to claim 26, wherein the coating is comprised of at least one material from said electrode if formed on the work.
  • 28. A process for producing and using a green compact electrode according to claim 26, wherein the coating is obtained from reacting electrode material with at least one of a work material and a dielectric.
  • 29. A process according to claim 22, wherein the bonding agent is a carbon-contained polymer-base bonding agent.
  • 30. A process according to claim 23, wherein the bonding agent is an epoxy resin or a phenol resin.
Parent Case Info

This application is a continuation of PCT/JP98/01006, filed Mar. 11, 1998.

US Referenced Citations (2)
Number Name Date Kind
4373127 Haskett et al. Feb 1983 A
5804789 Saito et al. Sep 1998 A
Foreign Referenced Citations (5)
Number Date Country
SHO56-126535 Oct 1981 JP
SHO62-127448 Jun 1987 JP
A 7-197275 Aug 1995 JP
HEI9-19829 Jan 1997 JP
A 9-192937 Jul 1997 JP
Continuations (1)
Number Date Country
Parent PCT/JP98/01006 Mar 1998 US
Child 09/639767 US