EP0294693B1 - Verwendung eines Silber-Eisen-Werkstoffs für elektrische Kontakte - Google Patents
Verwendung eines Silber-Eisen-Werkstoffs für elektrische Kontakte Download PDFInfo
- Publication number
- EP0294693B1 EP0294693B1 EP88108735A EP88108735A EP0294693B1 EP 0294693 B1 EP0294693 B1 EP 0294693B1 EP 88108735 A EP88108735 A EP 88108735A EP 88108735 A EP88108735 A EP 88108735A EP 0294693 B1 EP0294693 B1 EP 0294693B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver
- iron
- oxide
- electrical contacts
- remainder
- 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
- 239000000463 material Substances 0.000 title claims description 23
- OVMJVEMNBCGDGM-UHFFFAOYSA-N iron silver Chemical compound [Fe].[Ag] OVMJVEMNBCGDGM-UHFFFAOYSA-N 0.000 title claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 7
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 5
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 5
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 5
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010944 silver (metal) Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 230000003628 erosive effect Effects 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 1
- QEKREONBSFPWTQ-UHFFFAOYSA-N disilver dioxido(dioxo)tungsten Chemical group [Ag+].[Ag+].[O-][W]([O-])(=O)=O QEKREONBSFPWTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution 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
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
-
- 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
- C22C1/0466—Alloys based on noble metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
- H01H1/023—Composite material having a noble metal as the basic material
Definitions
- the invention relates to the use of a silver-iron material with further additives for electrical contacts.
- the essential requirements for an electrical contact material are high erosion resistance, low welding force and low contact resistance.
- For air-tight switching devices in low-voltage technology e.g. Ag / SnO2 is particularly good for switching currents of 100 - 3000 A due to its high erosion resistance and protection against welding.
- For lower loads e.g. the composite material Ag / Ni has proven itself. Compared to fine silver, it has an increased erosion resistance without causing a significant increase in contact resistance.
- Another frequently used composite material is Ag / W, which is characterized by its high resistance to erosion. With frequent switching in air, however, a cover layer of silver tungstate forms, which leads to an increase in the contact resistance.
- the object is achieved according to the invention by using a silver-iron material with 3 to 30% by weight of iron and one or more of the following additives: manganese, copper, zinc, antimony, bismuth oxide, molybdenum oxide, tungsten oxide, chromium nitride in a total amount of 0. 05 to 5 wt .-% dissolved.
- These materials surprisingly achieve a reduction in the contact resistance and thus the contact heating, without the inherently good security against welding being impaired.
- the improvement in contact heating is up to 43% compared to Ag / Fe-90/10.
- the improvement is achieved by favorably influencing the formation of the Fe oxide layers that form. While the material Ag / Fe-90/10 has a continuous oxide layer without additives, this oxide layer is influenced by the additives mentioned in such a way that there is a low contact resistance combined with good security against welding.
- a material with 3 - 20% Fe and one or more of the additives Mn, Cu, Zn, Bi, Bi2O3, MoO3, WO3 and / or CrN in a total amount of 0.2 to 2% by weight is particularly suitable. It has also proven useful to add to the silver, in addition to 3 to 20% by weight of iron, either 0.2 to 2% only of metallic additives or 0.2 to 2% of only non-metallic additives.
- materials that, in addition to 3 to 20% iron, 0.2 to 2%, contain only one of the additives manganese, copper, zinc, antimony, bismuth oxide, molybdenum oxide or tungsten oxide, the rest silver.
- they preferably contain 0.2 to 2% zinc and optionally 0 to 2% copper, tantalum and / or antimony, the rest silver or 0.2 to 2% molybdenum oxide, the rest silver.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Contacts (AREA)
- Conductive Materials (AREA)
- Powder Metallurgy (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT88108735T ATE81734T1 (de) | 1987-06-06 | 1988-06-01 | Verwendung eines silber-eisen-werkstoffs fuer elektrische kontakte. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3719052 | 1987-06-06 | ||
| DE3719052 | 1987-06-06 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0294693A2 EP0294693A2 (de) | 1988-12-14 |
| EP0294693A3 EP0294693A3 (en) | 1989-03-15 |
| EP0294693B1 true EP0294693B1 (de) | 1992-10-21 |
Family
ID=6329234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88108735A Expired - Lifetime EP0294693B1 (de) | 1987-06-06 | 1988-06-01 | Verwendung eines Silber-Eisen-Werkstoffs für elektrische Kontakte |
Country Status (23)
| Country | Link |
|---|---|
| US (1) | US4859238A (da) |
| EP (1) | EP0294693B1 (da) |
| JP (1) | JP2680038B2 (da) |
| CN (1) | CN1011421B (da) |
| AR (1) | AR241971A1 (da) |
| AT (1) | ATE81734T1 (da) |
| AU (1) | AU1730388A (da) |
| BR (1) | BR8802712A (da) |
| CA (1) | CA1309278C (da) |
| CS (1) | CS275704B6 (da) |
| DE (1) | DE3875385D1 (da) |
| DK (1) | DK303088A (da) |
| ES (1) | ES2035154T3 (da) |
| GR (1) | GR3006495T3 (da) |
| HU (1) | HUT50262A (da) |
| IN (1) | IN167229B (da) |
| MX (1) | MX170300B (da) |
| NO (1) | NO882389L (da) |
| PL (1) | PL156711B1 (da) |
| PT (1) | PT87662B (da) |
| RU (1) | RU1785579C (da) |
| YU (1) | YU46258B (da) |
| ZA (1) | ZA883891B (da) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10012250A1 (de) * | 2000-03-14 | 2001-09-27 | Dmc2 Degussa Metals Catalysts | Kontaktwerkstoffe auf Basis Silber-Eisen-Kupfer |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE58909449D1 (de) * | 1988-04-16 | 1995-11-02 | Duerrwaechter E Dr Doduco | Pulvermetallurgisches Verfahren zum Herstellen eines Halbzeugs für elektrische Kontakte aus einem Verbundwerkstoff auf Silberbasis mit Eisen. |
| WO1989010417A1 (en) * | 1988-04-20 | 1989-11-02 | Siemens Aktiengesellschaft | Sintered contact material based on silver for use in power engineering switchgear, in particular for contact pieces in low-voltage switches |
| US5286441A (en) * | 1989-12-26 | 1994-02-15 | Akira Shibata | Silver-metal oxide composite material and process for producing the same |
| DE4117312A1 (de) * | 1991-05-27 | 1992-12-03 | Siemens Ag | Kontaktwerkstoff auf silberbasis zur verwendung in schaltgeraeten der energietechnik sowie verfahren zur herstellung von kontaktstuecken aus diesem werkstoff |
| DE4117311A1 (de) * | 1991-05-27 | 1992-12-03 | Siemens Ag | Kontaktwerkstoff auf silberbasis zur verwendung in schaltgeraeten der energietechnik |
| DE4201940A1 (de) * | 1992-01-24 | 1993-07-29 | Siemens Ag | Sinterverbundwerkstoff fuer elektrische kontakte in schaltgeraeten der energietechnik |
| DE4343550A1 (de) * | 1993-12-20 | 1995-06-22 | Siemens Ag | Kontaktwerkstoff auf Silberbasis zur Verwendung in Schaltgeräten der Energietechnik |
| JPH0892708A (ja) * | 1994-07-28 | 1996-04-09 | Kawasaki Steel Corp | 粉末冶金用混合鉄粉および切削性に優れた焼結鋼の製造方法 |
| DE19543223C1 (de) * | 1995-11-20 | 1997-02-20 | Degussa | Silber-Eisen-Werkstoff für elektrische Schaltkontakte (III) |
| DE19543208C1 (de) * | 1995-11-20 | 1997-02-20 | Degussa | Silber-Eisen-Werkstoff für elektrische Schaltkontakte (II) |
| DE19543222C1 (de) * | 1995-11-20 | 1997-02-20 | Degussa | Silber-Eisen-Werkstoff für elektrische Schaltkontakte (I) |
| DE19607183C1 (de) * | 1996-02-27 | 1997-04-10 | Degussa | Gesinterter Silber-Eisen-Werkstoff für elektrische Kontakte und Verfahren zu seiner Herstellung |
| JP2001052930A (ja) * | 1999-08-06 | 2001-02-23 | Tdk Corp | 積層インダクタとその製造方法 |
| WO2005124804A1 (ja) * | 2004-06-18 | 2005-12-29 | Tanaka Kikinzoku Kogyo K.K. | 密閉形交流負荷用リレー及びそれに用いるＡｇ系接点素子材料 |
| JP5342931B2 (ja) * | 2009-06-05 | 2013-11-13 | マブチモーター株式会社 | 摺動接点材料及びクラッド複合材並びにモーター |
| WO2013142765A1 (en) * | 2012-03-23 | 2013-09-26 | Technic, Inc. | Silver antimony coatings and connectors |
| CN106238721B (zh) * | 2016-08-03 | 2018-06-19 | 施海峰 | 一种复合触点材料及其制备方法 |
| CN107299244B (zh) * | 2017-06-09 | 2019-07-16 | 佛山通宝精密合金股份有限公司 | 一种制备高性能AgFeRe材料的方法 |
| CN109777991A (zh) * | 2019-03-25 | 2019-05-21 | 杭州辰卓科技有限公司 | 一种电子引线键合用耐腐蚀高阻尼银合金及其工艺 |
| JP7327476B2 (ja) * | 2019-05-31 | 2023-08-16 | オムロン株式会社 | Ａｇ合金を主成分とする接点用材料、該接点用材料を用いた接点、及び電気機器 |
| CN114457253B (zh) * | 2021-12-30 | 2022-12-09 | 无锡日月合金材料有限公司 | 一种用于微动开关的银镍-氧化铋材料及其制造方法 |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2394501A (en) * | 1942-09-12 | 1946-02-05 | Square D Co | Electrical contact |
| US2664618A (en) * | 1944-04-22 | 1954-01-05 | Fansteel Metallurgical Corp | Electrical contact |
| US3401024A (en) * | 1965-10-04 | 1968-09-10 | Mallory & Co Inc P R | Electrical contact material |
| DE2240493C3 (de) * | 1972-08-17 | 1978-04-27 | Siemens Ag, 1000 Berlin Und 8000 Muenchen | Durchdringungsverbundmetall als Kontaktwerkstoff für Vakuumschalter und Verfahren zu seiner Herstellung |
| CH588152A5 (da) * | 1972-12-11 | 1977-05-31 | Siemens Ag | |
| US3992199A (en) * | 1973-12-03 | 1976-11-16 | P. R. Mallory & Co., Inc. | Method of making electrical contact materials |
| US3951872A (en) * | 1973-12-03 | 1976-04-20 | P. R. Mallory & Co., Inc. | Electrical contact material |
| US3933486A (en) * | 1974-02-12 | 1976-01-20 | Chugai Denki Kogyo Kabushiki-Kaisha | Silver-metal oxide composite and method of manufacturing the same |
| US4141727A (en) * | 1976-12-03 | 1979-02-27 | Matsushita Electric Industrial Co., Ltd. | Electrical contact material and method of making the same |
| DE2659012C3 (de) * | 1976-12-27 | 1980-01-24 | Siemens Ag, 1000 Berlin Und 8000 Muenchen | Verfahren zum Herstellen eines Sinterkontaktwerkstoffes aus Silber und eingelagerten Metalloxiden |
| JPS5913578B2 (ja) * | 1977-01-25 | 1984-03-30 | 日本科学冶金株式会社 | 電気接点材料 |
| US4330331A (en) * | 1978-06-16 | 1982-05-18 | Nippon Telegraph And Telephone Public Corporation | Electric contact material and method of producing the same |
| US4294616A (en) * | 1979-01-02 | 1981-10-13 | Gte Products Corporation | Electrical contacts |
| JPS56133438A (en) * | 1980-03-24 | 1981-10-19 | Tanaka Kikinzoku Kogyo Kk | Composite electrical contact material |
| JPS57108232A (en) * | 1980-12-25 | 1982-07-06 | Tanaka Kikinzoku Kogyo Kk | Electrical contact material and its manufacture |
-
1988
- 1988-05-27 YU YU103288A patent/YU46258B/sh unknown
- 1988-05-30 IN IN440/CAL/88A patent/IN167229B/en unknown
- 1988-05-31 NO NO882389A patent/NO882389L/no unknown
- 1988-06-01 ZA ZA883891A patent/ZA883891B/xx unknown
- 1988-06-01 DE DE8888108735T patent/DE3875385D1/de not_active Expired - Lifetime
- 1988-06-01 AT AT88108735T patent/ATE81734T1/de not_active IP Right Cessation
- 1988-06-01 EP EP88108735A patent/EP0294693B1/de not_active Expired - Lifetime
- 1988-06-01 ES ES198888108735T patent/ES2035154T3/es not_active Expired - Lifetime
- 1988-06-02 MX MX011746A patent/MX170300B/es unknown
- 1988-06-02 AU AU17303/88A patent/AU1730388A/en not_active Abandoned
- 1988-06-03 AR AR88311030A patent/AR241971A1/es active
- 1988-06-03 CS CS883853A patent/CS275704B6/cs not_active IP Right Cessation
- 1988-06-03 RU SU884355886A patent/RU1785579C/ru active
- 1988-06-03 DK DK303088A patent/DK303088A/da not_active Application Discontinuation
- 1988-06-03 CA CA000568602A patent/CA1309278C/en not_active Expired - Lifetime
- 1988-06-03 US US07/201,726 patent/US4859238A/en not_active Expired - Lifetime
- 1988-06-03 HU HU882908A patent/HUT50262A/hu unknown
- 1988-06-03 BR BR8802712A patent/BR8802712A/pt not_active IP Right Cessation
- 1988-06-06 PL PL1988272879A patent/PL156711B1/pl unknown
- 1988-06-06 CN CN88103378A patent/CN1011421B/zh not_active Expired
- 1988-06-06 JP JP63137628A patent/JP2680038B2/ja not_active Expired - Lifetime
- 1988-06-06 PT PT87662A patent/PT87662B/pt not_active IP Right Cessation
-
1992
- 1992-12-09 GR GR920402851T patent/GR3006495T3/el unknown
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN, Band nr. 6, Nr. 11 (C-88)(889), 22 January 1982; & JP-A-56133438 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10012250A1 (de) * | 2000-03-14 | 2001-09-27 | Dmc2 Degussa Metals Catalysts | Kontaktwerkstoffe auf Basis Silber-Eisen-Kupfer |
| DE10012250B4 (de) * | 2000-03-14 | 2006-06-01 | Umicore Ag & Co. Kg | Kontaktwerkstoffe auf Basis Silber-Eisen-Kupfer |
Also Published As
| Publication number | Publication date |
|---|---|
| RU1785579C (ru) | 1992-12-30 |
| PL156711B1 (pl) | 1992-04-30 |
| EP0294693A2 (de) | 1988-12-14 |
| NO882389D0 (no) | 1988-05-31 |
| ZA883891B (en) | 1989-02-22 |
| CA1309278C (en) | 1992-10-27 |
| IN167229B (da) | 1990-09-22 |
| DK303088A (da) | 1988-12-07 |
| GR3006495T3 (da) | 1993-06-21 |
| MX170300B (es) | 1993-08-16 |
| DE3875385D1 (de) | 1992-11-26 |
| PT87662B (pt) | 1992-10-30 |
| ATE81734T1 (de) | 1992-11-15 |
| CN1030098A (zh) | 1989-01-04 |
| NO882389L (no) | 1988-12-07 |
| YU103288A (en) | 1990-04-30 |
| YU46258B (sh) | 1993-05-28 |
| CS8803853A2 (en) | 1991-04-11 |
| JPS6452346A (en) | 1989-02-28 |
| CS275704B6 (en) | 1992-03-18 |
| AR241971A1 (es) | 1993-01-29 |
| JP2680038B2 (ja) | 1997-11-19 |
| US4859238A (en) | 1989-08-22 |
| BR8802712A (pt) | 1988-12-27 |
| CN1011421B (zh) | 1991-01-30 |
| PT87662A (pt) | 1988-07-01 |
| AU1730388A (en) | 1988-12-08 |
| ES2035154T3 (es) | 1993-04-16 |
| DK303088D0 (da) | 1988-06-03 |
| PL272879A1 (en) | 1989-03-06 |
| EP0294693A3 (en) | 1989-03-15 |
| HUT50262A (en) | 1989-12-28 |
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