EP0659507B1 - Kobaltmetallpulver sowie daraus hergestellte Verbundsinterkörper - Google Patents
Kobaltmetallpulver sowie daraus hergestellte Verbundsinterkörper Download PDFInfo
- Publication number
- EP0659507B1 EP0659507B1 EP94119399A EP94119399A EP0659507B1 EP 0659507 B1 EP0659507 B1 EP 0659507B1 EP 94119399 A EP94119399 A EP 94119399A EP 94119399 A EP94119399 A EP 94119399A EP 0659507 B1 EP0659507 B1 EP 0659507B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal powder
- cobalt metal
- cobalt
- ppm
- atomised
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0433—Nickel- or cobalt-based alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
- Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
- Y10T428/12049—Nonmetal component
- Y10T428/12056—Entirely inorganic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12931—Co-, Fe-, or Ni-base components, alternative to each other
Definitions
- the present invention relates to cobalt metal powder as a binder metal for the Manufacture of diamond and / or hard metal tools and / or wear protection coatings and composite sintered bodies made therefrom.
- JP-A 53-093 165 discloses the manufacture and use atomize Cobalt metal.
- the cobalt metal powder is produced by grinding processes not only more expensive, but also contaminated.
- Cobalt metal powders can be produced quite cheaply by atomization from the melt are produced, but these powders are available as binder metals, e.g. for the Manufacture of diamond tools completely unsuitable because of the spheroidal grain shape and grain size at the usual sintering temperatures between 800-900 ° C no dense composite sintered parts from result in sufficient hardness.
- the main reason for the inadequate performance properties of hot-pressed composite sintered bodies made of atomized cobalt metal powder is the lack of compressibility of the pre-pressed shaped bodies due to the spheroidal grain shape, the relatively narrow grain size distribution and the coarse primary particles (FIG. 2).
- the necessary density of at least 8.5 g / cm 3 is also not achieved by hot pressing.
- Cobalt metal powder with an FSSS value of 3 to 5 ⁇ m so-called 400 mesh powder (Fig. 1) available. This designation is explained by the sieve passage this powder through a 400 mesh sieve.
- Such powders meet requirements that of the matrix metal for composite materials in terms of hardness and sintered density be put.
- the so-called 400-mesh powders are quite right high level of impurities. It is generally known that Aluminum, calcium, sodium, magnesium and silicon easily with the oxygen form stable oxides of the cobalt metal powder. These can be in diamond segments cause undesirable porosity.
- Porosity can reduce the strength of hard metals, if the above impurities as well as sulfur in too high Amounts are included. Cobalt metal powder is therefore used in both applications low levels of impurities are desirable. Depending on the cleaning effort in the metallurgical precursors, the purity of the cobalt metal powder be adapted to requirements. The effort for the production Particularly pure cobalt metal powder is naturally expensive and such Powders are therefore very expensive.
- This invention relates to a cobalt metal powder Binder metal for the production of diamond and / or hard metal tools and / or wear protection coatings, which is characterized by that it is 20 to 80 wt .-% of an atomized cobalt metal powder with optical determined grain sizes from 5 to 150 microns and the rest missing to 100 wt .-% from an optionally agglomerated cobalt metal powder optically determined primary size of less than 3 microns exists.
- the cobalt metal powder according to the invention has the price advantage of Oxides or oxygen-containing compounds by reduction of cobalt metal powder obtained on, but contains significantly smaller amounts of the above critical contaminants. It preferably contains less than 20 ppm Al, 20 ppm Ca, 30 ppm Na, 20 ppm Mg, 30 ppm S and 75 ppm Si.
- the cobalt metal powder according to the invention is a Mixing of atomized cobalt metal powder with fine cobalt powder from the Hydrogen reduction.
- the amount of atomized cobalt metal powder is preferably 30 to 70% by weight.
- the atomized cobalt metal powder is both a water atomized cobalt metal powder with predominantly spheroidal habit as well as a gas atomized Cobalt metal powder with spheroidal habit suitable.
- the cobalt metal powder with a crystalline structure preferably has BET surface areas, determined by the nitrogen 1-point method (DIN 66 131), of greater than 0.8 m 2 / g.
- the cobalt metal powder according to the invention has a bulk density of less than 1.4 kg / cm 3 .
- the cobalt metal powder according to the invention is outstandingly suitable for powder metallurgy Manufacture of diamond tools and / or hard metals, in which the cobalt - optionally together with other customary matrix metals - represents the binder phase.
- Example 1 (mixture 70/30)
- Fig. 4 clearly shows that large round cobalt particles in addition to fine primary crystals have been preserved in the polished and etched sample.
- a fine cobalt metal powder obtained from the reduction of cobalt hydroxide with an average grain size of 0.9 ⁇ m, a BET value of 1.85 m 2 / g, sieved through a 100 ⁇ m sieve (bulk density 0.8 g / cm 3 ), was sieved with 0.5 kg of a water-atomized cobalt metal powder (11.7 ⁇ m FSSS) with a BET value of 0.73 m 2 / g, through a 38 ⁇ m sieve (bulk density 3.3 g / cm 3 ), mixed in a "Turbula mixer" for 15 minutes.
- the resulting mixture had an FSSS value of 1.5 ⁇ m FSSS, a BET value of 1.06 m 2 / g with a bulk density of 0.8 g / cm 3 .
- a hardness of HR B 100.4 and a density of 8.5 g / cm 3 were measured from a hot-pressed sample plate according to Example 1.
- Comparative Example 1 (100% water-atomized cobalt metal powder ⁇ 63 ⁇ m):
- the atomized cobalt metal powder achieve the required minimum density of 8.5 g / cm 3 and the minimum hardness of 98 HRB.
- Example 5 (100% water-atomized cobalt metal powder ⁇ 38 ⁇ m):
- Table 1 summarizes the data from Examples 1 to 3 and the comparative data for the 400-mesh cobalt powder and the atomized powder (according to the prior art).
- Example 5 Mixture from example 1 (70/30) Mixture from example 2 (60/40) Mixture from example 3 (50/50) Co 400 mesh St.dT 830 8.1 g / cm 3 8.54 g / cm 3 8.54 g / cm 3 8.5 g / cm 3 8.45 80 HR B 101.6 HR B 101.2 HR B 100 HR B 97.7 HR B
- Impurities 400-mesh cobalt 400-mesh cobalt metal powder ("Cobalt Powder 400-mesh” from Hoboken Overpelt, Belgium)) and mixtures according to Examples 1, 2 and 3 according to the invention: Impurities 400 mesh-Co (100/0) Mixture example 1 (70/30) Mixture example 2 (60/40) Mixture example 3 (50/50) Al (ppm) 180 6 7 6 Ca (ppm) 320 12th 12th 13 Na (ppm) 55 25th 22 9 Mg (ppm) 150 8th 8th 3rd S (ppm) 140 13 14 15 Si (ppm) 310 34 36 41
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Description
- Aufheizgradient:
- 180 K/min
- Sintertemperatur:
- 830°C (in der Graphitform gemessen)
- Sinterdruck:
- 350 N/mm2
- Haltzeit:
- 3 min
- Aufheizgradient:
- 180 K/min
- Sinterdruck:
- 350 N/mm2
- Haltezeit:
- 3 min
Sintertemperatur | Härtewerte (HRB) | Dichte |
800°C | Preßkörper zerfällt, Härte nicht bestimmbar | n.b. |
850°C | 25 | 7,0 |
900°C | 40 | 7,5 |
950°C | 47 | 7,8 |
(Versuchsergebnisse aus dem Härtetest): | |||||
Heißpreßtemperatur | Sinterdichten/Rockwell-Härten (HRB) | ||||
(°C) | Verdüstes Co-Pulver Beispiel 5 | Mischung aus Beispiel 1 (70/30) | Mischung aus Beispiel 2 (60/40) | Mischung aus Beispiel 3 (50/50) | Co 400 mesh St.d.T. |
830 | 8,1 g/cm3 | 8,54 g/cm3 | 8,54 g/cm3 | 8,5 g/cm3 | 8,45 |
80 HRB | 101,6 HRB | 101,2 HRB | 100 HRB | 97,7 HRB |
Verunreinigungen | 400 mesh-Co (100/0) | Mischung Beispiel 1 (70/30) | Mischung Beispiel 2 (60/40) | Mischung Beispiel 3 (50/50) |
Al (ppm) | 180 | 6 | 7 | 6 |
Ca (ppm) | 320 | 12 | 12 | 13 |
Na (ppm) | 55 | 25 | 22 | 9 |
Mg (ppm) | 150 | 8 | 8 | 3 |
S (ppm) | 140 | 13 | 14 | 15 |
Si (ppm) | 310 | 34 | 36 | 41 |
Claims (9)
- Kobaltmetallpulver als Bindermetall für die Herstellung von Diamant- und/oder Hartmetallwerkzeugen und/oder Verschleißschutzbeschichtungen, dadurch gekennzeichnet, daß es zu 20 bis 80 Gew.-% aus einem verdüsten Kobaltmetallpulver mit optisch ermittelten Korngrößen von 5 bis 150 µm und dem zu 100 Gew.-% fehlenden Rest aus einem, gegebenenfalls agglomeriert vorliegenden, Kobaltmetallpulver einer optisch ermittelten Primärgröße von kleiner als 3 µm besteht.
- Kobaltmetallpulver gemaß Anspruch 1, dadurch gekennzeichnet, daß die Menge des verdüsten Kobaltmetallpulvers 30 bis 70 Gew.-% beträgt.
- Kobaltmetallpulver gemäß einem der Ansprüche 1 oder 2, dadurch gekennzeichnet daß das Kobaltmetallpulver mit kristalliner Struktur BET-Oberflächen, gemessen nach der Stickstoff-1-Punkt-Methode (DIN 66131), von größer als 0,8 m2/g aufweist.
- Kobaltmetallpulver gemäß einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das verdüste Kobaltmetallpulver ein wasserverdüstes Kobaltmetallpulver mit überwiegend sphäroidischem Habitus ist.
- Kobaltmetallpulver gemäß einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das verdüste Kobaltmetallpulver ein gasverdüstes Kobaltmetallpulver mit sphäroidischem Habitus ist.
- Kobaltmetallpulver gemäß einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es ein Schüttgewicht von kleiner als 1,4 g/cm3 aufweist.
- Kobaltmetallpulver gemäß einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es weniger als 20 ppm Aluminium, 20 ppm Kalzium, 30 ppm Natrium, 20 ppm Magnesium, 30 ppm Schwefel und 75 ppm Silizium enthält.
- Kobaltmetallpulver gemäß einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es eine Rockwell-Härte, gemessen an heißgepreßten Prüfplättchen, von mindestens 98 HRB aufweist.
- Verbundsinterkörper, hergestellt aus Hartstoffpulvern und/oder Diamantpulver und Bindermetallen, wobei als Bindermetall, gegebenenfalls neben anderen Metallpulvern, das Kobaltmetallpulver gemäß einem oder mehreren der Ansprüche 1 bis 6 verwendet wird.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4343594A DE4343594C1 (de) | 1993-12-21 | 1993-12-21 | Kobaltmetallpulver sowie daraus hergestellte Verbundsinterkörper |
DE4343594 | 1993-12-21 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0659507A1 EP0659507A1 (de) | 1995-06-28 |
EP0659507B1 true EP0659507B1 (de) | 1998-07-08 |
Family
ID=6505607
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94119399A Expired - Lifetime EP0659507B1 (de) | 1993-12-21 | 1994-12-08 | Kobaltmetallpulver sowie daraus hergestellte Verbundsinterkörper |
Country Status (10)
Country | Link |
---|---|
US (1) | US5482530A (de) |
EP (1) | EP0659507B1 (de) |
JP (1) | JP3435660B2 (de) |
KR (1) | KR100340161B1 (de) |
CN (1) | CN1070094C (de) |
AT (1) | ATE168054T1 (de) |
DE (2) | DE4343594C1 (de) |
ES (1) | ES2118304T3 (de) |
GR (1) | GR3027693T3 (de) |
RU (1) | RU2126310C1 (de) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19519329C1 (de) * | 1995-05-26 | 1996-11-28 | Starck H C Gmbh Co Kg | Kobaltmetallagglomerate, Verfahren zu ihrer Herstellung sowie deren Verwendung |
DE19519331C1 (de) * | 1995-05-26 | 1996-11-28 | Starck H C Gmbh Co Kg | Kobaltmetallagglomerate, Verfahren zu ihrer Herstellung sowie deren Verwendung |
DE19540076C1 (de) * | 1995-10-27 | 1997-05-22 | Starck H C Gmbh Co Kg | Ultrafeines Kobaltmetallpulver, Verfahren zu seiner Herstellung sowie Verwendung des Kobaltmetallpulvers und des Kobaltcarbonates |
DE19544107C1 (de) * | 1995-11-27 | 1997-04-30 | Starck H C Gmbh Co Kg | Metallpulver-Granulat, Verfahren zu seiner Herstellung sowie dessen Verwendung |
SE9703204L (sv) * | 1997-09-05 | 1999-03-06 | Sandvik Ab | Verktyg för borrning/fräsning av kretskortsmaterial |
US7344557B2 (en) * | 2003-11-12 | 2008-03-18 | Advanced Stent Technologies, Inc. | Catheter balloon systems and methods |
US7360991B2 (en) * | 2004-06-09 | 2008-04-22 | General Electric Company | Methods and apparatus for fabricating gas turbine engines |
US7470307B2 (en) * | 2005-03-29 | 2008-12-30 | Climax Engineered Materials, Llc | Metal powders and methods for producing the same |
US9764448B2 (en) * | 2005-11-14 | 2017-09-19 | National University of Science and Technology “MISIS” | Binder for the fabrication of diamond tools |
WO2009068154A2 (en) * | 2007-11-26 | 2009-06-04 | Umicore | Thermally stable co powder |
US8197885B2 (en) * | 2008-01-11 | 2012-06-12 | Climax Engineered Materials, Llc | Methods for producing sodium/molybdenum power compacts |
CN102728832B (zh) * | 2012-07-30 | 2016-12-21 | 河北航华金刚石制品有限公司 | 钴粉包覆金刚石颗粒的工艺 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1279332B (de) * | 1962-08-18 | 1968-10-03 | Krebsoege Gmbh Sintermetall | Verfahren zum pulvermetallurgischen Herstellen von Genauteilen aus Stelliten oder stellitaehnlichen Legierungen |
US3746518A (en) * | 1965-02-26 | 1973-07-17 | Crucible Inc | Alloy composition and process |
SE378260B (de) * | 1973-11-29 | 1975-08-25 | Hoeganaes Ab | |
JPS5274508A (en) * | 1975-12-18 | 1977-06-22 | Mitsubishi Metal Corp | Co-base sintered alloy |
JPS5393165A (en) * | 1977-01-27 | 1978-08-15 | Sumitomo Electric Industries | Cobalt powder adapted for wet type ball mill mixing and manufacturing process |
US4724000A (en) * | 1986-10-29 | 1988-02-09 | Eaton Corporation | Powdered metal valve seat insert |
EP0298593A3 (de) * | 1987-05-19 | 1990-01-10 | Kabushiki Kaisha Toshiba | Bindemasse zum Verbinden von abrasivem Material sowie Verfahren ihrer Herstellung |
US4927456A (en) * | 1987-05-27 | 1990-05-22 | Gte Products Corporation | Hydrometallurgical process for producing finely divided iron based powders |
US4818482A (en) * | 1987-07-09 | 1989-04-04 | Inco Alloys International, Inc. | Method for surface activation of water atomized powders |
US5114471A (en) * | 1988-01-04 | 1992-05-19 | Gte Products Corporation | Hydrometallurgical process for producing finely divided spherical maraging steel powders |
US5338508A (en) * | 1988-07-13 | 1994-08-16 | Kawasaki Steel Corporation | Alloy steel powders for injection molding use, their compounds and a method for making sintered parts from the same |
EP0504391A4 (en) * | 1990-10-09 | 1993-05-26 | Iowa State University Research Foundation, Inc. | Environmentally stable reactive alloy powders and method of making same |
US5250101A (en) * | 1991-04-08 | 1993-10-05 | Mitsubishi Gas Chemical Company, Inc. | Process for the production of fine powder |
-
1993
- 1993-12-21 DE DE4343594A patent/DE4343594C1/de not_active Expired - Fee Related
-
1994
- 1994-12-02 US US08/348,610 patent/US5482530A/en not_active Expired - Fee Related
- 1994-12-08 EP EP94119399A patent/EP0659507B1/de not_active Expired - Lifetime
- 1994-12-08 ES ES94119399T patent/ES2118304T3/es not_active Expired - Lifetime
- 1994-12-08 AT AT94119399T patent/ATE168054T1/de not_active IP Right Cessation
- 1994-12-08 DE DE59406412T patent/DE59406412D1/de not_active Expired - Fee Related
- 1994-12-19 JP JP33446694A patent/JP3435660B2/ja not_active Expired - Fee Related
- 1994-12-20 KR KR1019940035311A patent/KR100340161B1/ko not_active IP Right Cessation
- 1994-12-21 CN CN94112792A patent/CN1070094C/zh not_active Expired - Fee Related
- 1994-12-21 RU RU94045279A patent/RU2126310C1/ru active
-
1998
- 1998-08-20 GR GR980401870T patent/GR3027693T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
JP3435660B2 (ja) | 2003-08-11 |
DE4343594C1 (de) | 1995-02-02 |
KR950017006A (ko) | 1995-07-20 |
CN1112466A (zh) | 1995-11-29 |
CN1070094C (zh) | 2001-08-29 |
GR3027693T3 (en) | 1998-11-30 |
RU2126310C1 (ru) | 1999-02-20 |
RU94045279A (ru) | 1997-04-20 |
JPH07207301A (ja) | 1995-08-08 |
ES2118304T3 (es) | 1998-09-16 |
DE59406412D1 (de) | 1998-08-13 |
US5482530A (en) | 1996-01-09 |
KR100340161B1 (ko) | 2002-10-31 |
ATE168054T1 (de) | 1998-07-15 |
EP0659507A1 (de) | 1995-06-28 |
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