EP0548636A1 - Utilisation d'alliage de cuivre durcissant - Google Patents
Utilisation d'alliage de cuivre durcissant Download PDFInfo
- Publication number
- EP0548636A1 EP0548636A1 EP92120775A EP92120775A EP0548636A1 EP 0548636 A1 EP0548636 A1 EP 0548636A1 EP 92120775 A EP92120775 A EP 92120775A EP 92120775 A EP92120775 A EP 92120775A EP 0548636 A1 EP0548636 A1 EP 0548636A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- casting
- nickel
- copper alloy
- beryllium
- rest
- 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.)
- Granted
Links
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000005266 casting Methods 0.000 claims abstract description 49
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 13
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 11
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 description 29
- 239000000956 alloy Substances 0.000 description 29
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 238000009749 continuous casting Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
Definitions
- the invention relates to the use of a hardenable copper alloy for the production of casting rolls and casting wheels, which are subject to changing temperature stresses during casting close to the final dimensions.
- the lower electrical conductivity of a known CuNiBe alloy with an addition of up to 1% niobium also leads to a higher surface temperature compared to a CuCrZr alloy. Since the electrical conductivity is inversely proportional to the thermal conductivity, the surface temperature of a casting roll made of CuNiBe alloy will be about 540 compared to a casting roll made of CuCrZr with a maximum temperature of 400 ° C on the surface and 30 ° C on the back Increase ° C.
- Ternary CuNiBe or CucoBe alloys generally have a Brinell hardness of over 200 HB, but the electrical conductivity of the standard semi-finished products made from these materials, such as rods for the production of resistance welding electrodes or sheets and strips for the production of springs or Lead frames, at most values in the range from 26 to about 32 m / ⁇ mm2. Under optimal conditions, these standard materials would only achieve a casting roll surface temperature of around 585 ° C.
- the object of the present invention is to provide a material for the production of casting rolls, casting roll jackets and casting wheels, which is insensitive to changing temperature loads even at casting speeds of over 3.5 m / min, or which has high fatigue resistance at the working temperature which has casting rolls.
- a hardenable copper alloy made from 1.0 to 2.6% nickel, 0.1 to 0.45% beryllium, the rest of copper including manufacturing-related impurities and usual processing additives, with a Brinell hardness of at least 200 HB and one has proven particularly suitable for this application electrical conductivity over 38 m / ⁇ mm2.
- a further improvement in the mechanical properties, in particular an increase in the tensile strength, can advantageously be achieved by adding 0.05 to 0.25% zirconium.
- Copper alloys according to the invention are preferred in which the ratio of the nickel content to the beryllium content with a nickel content of more than 1.2% in the alloy composition is at least 5: 1.
- alloys to be used according to the invention show how critical the composition is in order to achieve the desired combination of properties.
- the composition of the example alloys is given in Table 1 in% by weight. The corresponding test results are summarized in Table 2.
- Table 1 Leg. Ni Be Cu A 1.43 0.54 rest B 1.48 0.40 rest C. 1.83 0.42 rest D 2.12 0.53 rest F 1.48 0.29 rest G 1.86 0.33 rest H 1.95 0.30 rest K 2.26 0.35 rest Leg.
- Table 2 shows the hardness and conductivity values achieved for alloys with different nickel and beryllium contents - corresponding to different Ni / Be ratios. All of the alloys were melted in a vacuum furnace, hot-formed and, after solution annealing at 925 ° C. for at least one hour and then quenched in water, hardened for 4 to 32 hours at a temperature in the range from 350 to 550 ° C.
- the desired combination of properties can be achieved if the weight ratio of nickel to beryllium is at least 5: 1.
- casting rolls or casting roll shells are subjected to an additional cold deformation of about 25% after solution annealing, a further improvement in the electrical conductivity can be achieved.
- a 32-hour hardening treatment at 480 ° C achieves a conductivity of 43 m / ⁇ mm2 and a Brinell hardness of 225 HB.
- the properties can be further optimized by increasing the Ni / Be ratio.
- a copper alloy with 2.26% nickel and a Ni / Be ratio of 6.5 has a Brinell hardness of 230 HB and an electrical conductivity of 40.5 m / ⁇ mm2 after a 32-hour hardening treatment at 480 ° C.
- a Ni / Be ratio of 7.5 is possible for a nickel content of 2.3% in order to achieve the desired combination of properties.
- the sample alloy N was selected for the additional investigation of the fatigue behavior, since it has a relatively low electrical conductivity. With alloy N, a maximum surface temperature for a casting roll of around 490 ° C can be achieved. Under the previously known stress of a casting roll when casting steel, the service life of the alloy N to be used according to the invention is then increased by 2 to 3 times compared to a CuCrZr alloy. Due to the high Brinell hardness, there is also no danger that the surface of the casting roll will be damaged by the injection of melt spatter.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Continuous Casting (AREA)
- Laminated Bodies (AREA)
- Electrolytic Production Of Metals (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Dental Preparations (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Chemically Coating (AREA)
- Rolls And Other Rotary Bodies (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Conductive Materials (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Materials For Medical Uses (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4142941A DE4142941A1 (de) | 1991-12-24 | 1991-12-24 | Verwendung einer aushaertbaren kupferlegierung |
| DE4142941 | 1991-12-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0548636A1 true EP0548636A1 (fr) | 1993-06-30 |
| EP0548636B1 EP0548636B1 (fr) | 1997-10-01 |
Family
ID=6448112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92120775A Expired - Lifetime EP0548636B1 (fr) | 1991-12-24 | 1992-12-05 | Utilisation d'alliage de cuivre durcissant |
Country Status (21)
| Country | Link |
|---|---|
| US (1) | US6083328A (fr) |
| EP (1) | EP0548636B1 (fr) |
| JP (1) | JP3504284B2 (fr) |
| KR (1) | KR100260058B1 (fr) |
| CN (1) | CN1031762C (fr) |
| AT (1) | ATE158822T1 (fr) |
| AU (1) | AU661529B2 (fr) |
| BR (1) | BR9205131A (fr) |
| CA (1) | CA2086063C (fr) |
| CZ (1) | CZ282842B6 (fr) |
| DE (2) | DE4142941A1 (fr) |
| DK (1) | DK0548636T3 (fr) |
| ES (1) | ES2109302T3 (fr) |
| FI (1) | FI97108C (fr) |
| GR (1) | GR3025195T3 (fr) |
| MX (1) | MX9206426A (fr) |
| PL (1) | PL170470B1 (fr) |
| RU (1) | RU2102515C1 (fr) |
| SK (1) | SK369692A3 (fr) |
| TR (1) | TR27606A (fr) |
| ZA (1) | ZA929480B (fr) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0702094A1 (fr) * | 1994-08-06 | 1996-03-20 | KM Europa Metal Aktiengesellschaft | Utilisation d'un alliage de cuivre durcissable |
| US5651844A (en) * | 1995-02-01 | 1997-07-29 | Brush Wellman Inc. | Metamorphic processing of alloys and products thereof |
| WO2001079574A1 (fr) * | 2000-04-14 | 2001-10-25 | Sms Demag Aktiengesellschaft | Utilisation d'un cupro-alliage durcissable par vieillissement pour coquilles |
| FR2813159A1 (fr) | 2000-08-31 | 2002-03-01 | Const Agricoles Etmetallurgiqu | Dispositif selecteur pour semoir de precision |
| EP1314789A1 (fr) * | 2001-11-21 | 2003-05-28 | KM Europa Metal Aktiengesellschaft | Alliage de cuivre durcissable par précipitation pour la fabrication de moules |
| EP1314495A2 (fr) * | 2001-11-21 | 2003-05-28 | KM Europa Metal Aktiengesellschaft | Manchon pour cylindre de coulée d'une installation de coulée continue entre cylindres |
| EP1340564A2 (fr) * | 2002-02-15 | 2003-09-03 | KM Europa Metal Aktiengesellschaft | Alliage de cuivre durcissable |
| EP1762630A1 (fr) * | 2005-09-09 | 2007-03-14 | Ngk Insulators, Ltd. | Alliage de cuivre avec nickel et beryllium et procédé de sa fabication |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10045251A1 (de) * | 2000-09-13 | 2002-03-21 | Sms Demag Ag | Wasserkühlbare Ofenrolle zum Fördern von bspw. Stranggußmaterial-Werkstücken durch einen Rollenherdofen |
| CN102191405B (zh) * | 2011-05-27 | 2013-03-27 | 马鞍山钢铁股份有限公司 | 一种带钢焊接设备夹持和加载工具用铜合金及其生产方法 |
| RU2569286C1 (ru) * | 2014-07-01 | 2015-11-20 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") | Бериллиевая бронза и изделие, выполненное из нее |
| JP2021155837A (ja) * | 2020-03-30 | 2021-10-07 | 日本碍子株式会社 | ベリリウム銅合金リング及びその製造方法 |
| CN115233032B (zh) * | 2022-08-01 | 2023-06-27 | 河南云锦空天特导新材料有限公司 | 一种铜合金线材及其制备方法和应用 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3196006A (en) * | 1963-05-10 | 1965-07-20 | Westinghouse Electric Corp | Copper base alloys containing cobalt, beryllium, and zirconium |
| US4179314A (en) * | 1978-12-11 | 1979-12-18 | Kawecki Berylco Industries, Inc. | Treatment of beryllium-copper alloy and articles made therefrom |
| US4377424A (en) * | 1980-05-26 | 1983-03-22 | Chuetsu Metal Works Co., Ltd. | Mold of precipitation hardenable copper alloy for continuous casting mold |
| US4657601A (en) * | 1983-11-10 | 1987-04-14 | Brush Wellman Inc. | Thermomechanical processing of beryllium-copper alloys |
| EP0271991B1 (fr) * | 1986-11-13 | 1991-10-02 | Ngk Insulators, Ltd. | Fabrication d'alliages cuivre-béryllium |
| JPH01165736A (ja) * | 1987-12-21 | 1989-06-29 | Dowa Mining Co Ltd | ワイヤーハーネスのターミナル用銅合金およびその製造法 |
| JPH02111835A (ja) * | 1988-10-20 | 1990-04-24 | Chuetsu Gokin Chuko Kk | 電磁攪拌用鋳型材料 |
| JPH083141B2 (ja) * | 1989-10-27 | 1996-01-17 | 日本碍子株式会社 | ベリリウム銅合金部材の製造法 |
-
1991
- 1991-12-24 DE DE4142941A patent/DE4142941A1/de not_active Withdrawn
-
1992
- 1992-10-14 CN CN92113077A patent/CN1031762C/zh not_active Expired - Lifetime
- 1992-11-09 MX MX9206426A patent/MX9206426A/es unknown
- 1992-12-05 EP EP92120775A patent/EP0548636B1/fr not_active Expired - Lifetime
- 1992-12-05 ES ES92120775T patent/ES2109302T3/es not_active Expired - Lifetime
- 1992-12-05 DE DE59208945T patent/DE59208945D1/de not_active Expired - Lifetime
- 1992-12-05 AT AT92120775T patent/ATE158822T1/de active
- 1992-12-05 DK DK92120775.9T patent/DK0548636T3/da active
- 1992-12-07 ZA ZA929480A patent/ZA929480B/xx unknown
- 1992-12-09 FI FI925597A patent/FI97108C/fi not_active IP Right Cessation
- 1992-12-16 CZ CS923696A patent/CZ282842B6/cs not_active IP Right Cessation
- 1992-12-16 SK SK3696-92A patent/SK369692A3/sk not_active IP Right Cessation
- 1992-12-16 PL PL92297032A patent/PL170470B1/pl unknown
- 1992-12-18 TR TR01213/92A patent/TR27606A/xx unknown
- 1992-12-22 BR BR9205131A patent/BR9205131A/pt not_active IP Right Cessation
- 1992-12-22 CA CA002086063A patent/CA2086063C/fr not_active Expired - Lifetime
- 1992-12-22 JP JP34279492A patent/JP3504284B2/ja not_active Expired - Fee Related
- 1992-12-23 AU AU30372/92A patent/AU661529B2/en not_active Expired
- 1992-12-23 KR KR1019920025225A patent/KR100260058B1/ko not_active IP Right Cessation
- 1992-12-24 RU RU92016273A patent/RU2102515C1/ru active
-
1994
- 1994-05-06 US US08/239,439 patent/US6083328A/en not_active Expired - Lifetime
-
1997
- 1997-10-29 GR GR970402830T patent/GR3025195T3/el unknown
Non-Patent Citations (3)
| Title |
|---|
| CHEMICAL ABSTRACTS, Band 107, 02. November 1987 Columbus, Ohio, USA K. KISHIDA et al. "Corrosion- -resistant copper alloys for high-strength castings", Seite 349, Spalte 1, Zusammenfassung-Nr. 159 751v & Jpn. Kokai Tokkyo Koho JP 62 37 333 (87 37 333) * |
| CHEMICAL ABSTRACTS, Band 108, 11. JÛnner 1988 Columbus, Ohio, USA S. ISHIKAWA et al. "High- -strength copper alloys and their processing", Seite 251, Spalte 1, Zusammenfassung-Nr. 10 096y & Jpn. Kokai Tokkyo Koho JP 62 199 743 (87 199 743) * |
| CHEMICAL ABSTRACTS, Band 96, 31. Mai 1982 Columbus, Ohio, USA NGK INSULATORS LTD "Beryllium-copper alloy sheet", Seite 320, Spalte 2, Zusammenfassung-Nr. 185 965s * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0702094A1 (fr) * | 1994-08-06 | 1996-03-20 | KM Europa Metal Aktiengesellschaft | Utilisation d'un alliage de cuivre durcissable |
| US6565681B1 (en) | 1994-08-06 | 2003-05-20 | Km-Kabelmetal Aktiengesellschaft | Age-hardenable copper alloy casting molds |
| US5651844A (en) * | 1995-02-01 | 1997-07-29 | Brush Wellman Inc. | Metamorphic processing of alloys and products thereof |
| WO2001079574A1 (fr) * | 2000-04-14 | 2001-10-25 | Sms Demag Aktiengesellschaft | Utilisation d'un cupro-alliage durcissable par vieillissement pour coquilles |
| FR2813159A1 (fr) | 2000-08-31 | 2002-03-01 | Const Agricoles Etmetallurgiqu | Dispositif selecteur pour semoir de precision |
| EP1314495A3 (fr) * | 2001-11-21 | 2003-12-10 | KM Europa Metal Aktiengesellschaft | Manchon pour cylindre de coulée d'une installation de coulée continue entre cylindres |
| EP1314495A2 (fr) * | 2001-11-21 | 2003-05-28 | KM Europa Metal Aktiengesellschaft | Manchon pour cylindre de coulée d'une installation de coulée continue entre cylindres |
| EP1314789A1 (fr) * | 2001-11-21 | 2003-05-28 | KM Europa Metal Aktiengesellschaft | Alliage de cuivre durcissable par précipitation pour la fabrication de moules |
| AU2002302077B2 (en) * | 2001-11-21 | 2008-10-02 | Kme Germany Gmbh & Co. Kg | Temperable Copper Alloy as Material for Producing Casting Moulds |
| NO337790B1 (no) * | 2001-11-21 | 2016-06-20 | Kme Germany Gmbh & Co Kg | Støpeform produsert fra en utherdbar kobberlegering |
| NO340437B1 (no) * | 2001-11-21 | 2017-04-24 | Kme Germany Gmbh & Co Kg | Støpevalse for et to-valsestøpeanlegg |
| EP1340564A2 (fr) * | 2002-02-15 | 2003-09-03 | KM Europa Metal Aktiengesellschaft | Alliage de cuivre durcissable |
| EP1340564A3 (fr) * | 2002-02-15 | 2005-04-27 | KM Europa Metal Aktiengesellschaft | Alliage de cuivre durcissable |
| KR100967864B1 (ko) * | 2002-02-15 | 2010-07-05 | 카엠이 저머니 아게 | 시효 경화성 구리 합금 |
| EP1762630A1 (fr) * | 2005-09-09 | 2007-03-14 | Ngk Insulators, Ltd. | Alliage de cuivre avec nickel et beryllium et procédé de sa fabication |
| US7628873B2 (en) | 2005-09-09 | 2009-12-08 | Ngk Insulators, Ltd. | Beryllium copper alloy and method of manufacturing beryllium copper alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| FI925597A (fi) | 1993-06-25 |
| EP0548636B1 (fr) | 1997-10-01 |
| RU2102515C1 (ru) | 1998-01-20 |
| ES2109302T3 (es) | 1998-01-16 |
| KR930013179A (ko) | 1993-07-21 |
| FI97108B (fi) | 1996-07-15 |
| CN1031762C (zh) | 1996-05-08 |
| DE4142941A1 (de) | 1993-07-01 |
| ATE158822T1 (de) | 1997-10-15 |
| US6083328A (en) | 2000-07-04 |
| JP3504284B2 (ja) | 2004-03-08 |
| MX9206426A (es) | 1993-06-01 |
| ZA929480B (en) | 1993-06-10 |
| SK280704B6 (sk) | 2000-06-12 |
| AU661529B2 (en) | 1995-07-27 |
| PL170470B1 (pl) | 1996-12-31 |
| CA2086063A1 (fr) | 1993-06-25 |
| DK0548636T3 (da) | 1998-05-18 |
| BR9205131A (pt) | 1993-06-29 |
| FI925597A0 (fi) | 1992-12-09 |
| FI97108C (fi) | 1996-10-25 |
| CZ282842B6 (cs) | 1997-10-15 |
| SK369692A3 (en) | 2000-06-12 |
| PL297032A1 (en) | 1993-11-02 |
| CZ369692A3 (en) | 1993-07-14 |
| TR27606A (tr) | 1995-06-13 |
| JPH05247565A (ja) | 1993-09-24 |
| DE59208945D1 (de) | 1997-11-06 |
| CN1075755A (zh) | 1993-09-01 |
| KR100260058B1 (ko) | 2000-07-01 |
| CA2086063C (fr) | 1999-12-14 |
| GR3025195T3 (en) | 1998-02-27 |
| AU3037292A (en) | 1993-07-01 |
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