EP0294693A2 - Use of a silver-iron material for electric contacts - Google Patents

Use of a silver-iron material for electric contacts Download PDF

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Publication number
EP0294693A2
EP0294693A2 EP88108735A EP88108735A EP0294693A2 EP 0294693 A2 EP0294693 A2 EP 0294693A2 EP 88108735 A EP88108735 A EP 88108735A EP 88108735 A EP88108735 A EP 88108735A EP 0294693 A2 EP0294693 A2 EP 0294693A2
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Prior art keywords
silver
iron
oxide
electrical contacts
antimony
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EP88108735A
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German (de)
French (fr)
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EP0294693A3 (en
EP0294693B1 (en
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Wolfgang Dr. Weise
Roger Wolmer
Peter Dr. Braumann
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Evonik Operations GmbH
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Degussa GmbH
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    • 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 amounts of in total 0.2 to 2 wt .-% 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 which, in addition to 3 to 20% iron 0.2 to 2%, only contain 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.

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  • 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)

Abstract

Für elektrische Kontakte wird ein Silber- Eisen- Werkstoff verwendet, der eine geringe Verschweißneigung, einen geringen Kontaktwiderstand und einen breiten Anwendungsbereich besitzt. Er enthält neben Silber 3 - 30 Gew.-% Eisen und einen oder mehrere der Zusätze Mangan, Kupfer, Zink, Antimon, Wismutoxid, Molybdänoxid, Wolframoxid und Chromnitrid in Mengen von insgesamt 0,05 bis 5 Gew.-%.A silver-iron material is used for electrical contacts, which has a low tendency to weld, a low contact resistance and a wide range of applications. In addition to silver, it contains 3 to 30% by weight of iron and one or more of the additions of manganese, copper, zinc, antimony, bismuth oxide, molybdenum oxide, tungsten oxide and chromium nitride in a total amount of 0.05 to 5% by weight.

Description

Die Erfindung betrifft die Verwendung eines Silber- ­Eisen- Werkstoffs mit weiteren Zusätzen für elektrische Kontakte.The invention relates to the use of a silver-iron material with further additives for electrical contacts.

Die wesentlichen Anforderungen an einen elektrischen Kontaktwerkstoff sind hohe Abbrandfestigkeit, geringe Verschweißkraft und niedriger Kontaktwiderstand. Je nach Belastungsart und Schaltstrom ergibt sich eine unter­schiedliche Gewichtung hinsichtlich des Anforderungs­profils. Für luftoffene Schaltgeräte der Nieder­spannungstechnik eignet sich z.B. Ag/SnO₂ aufgrund seiner hohen Abbrandfestigkeit und Sicherheit gegen Verschweißen besonders gut für Schaltströme von 100 - 3000 A. Für geringere Belastungen hat sich z.B. der Verbundwerkstöff Ag/Ni bewährt. Er besitzt gegenüber Feinsilber eine erhöhte Abbrandfestigkeit, ohne eine wesentliche Erhöhung des Kontaktwiderstandes zu bewirken.The essential requirements for an electrical contact material are high erosion resistance, low welding force and low contact resistance. Depending on the type of load and switching current, there is a different weighting with regard to the requirement profile. 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.

Ein weiterer, häufig verwendeter Verbundwerkstoff ist Ag/W, der sich durch hohe Abbrandfestigkeit auszeichnet. Beim häufigen Schalten an Luft bildet sich jedoch eine Deckschicht aus Silberwolframat, die zu einer Erhöhung des Kontaktwiderstands führt.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.

Aus der japanischen Patentanmeldung 79/148 109 sind elektrische Kontaktwerkstoffe bekannt, die neben Silber noch Eisen, Nickel, Chrom und/oder Kobalt enthalten. Besonders Werkstoffe der Zusammensetzung Ag 10 Fe zeigen einen hohen Verschweißwiderstand bei noch guter elektrischer Leitfähigkeit.From Japanese patent application 79/148 109 electrical contact materials are known which contain iron, nickel, chromium and / or cobalt in addition to silver. Especially materials with the composition Ag 10 Fe show a high welding resistance with good electrical conductivity.

Trotzdem fand dieser Werkstoff bislang keine breitere Anwendung, was auf die sich während des Schaltens bildenden Deckschichten und damit zu hohen Kontakterwärmungen zurückzuführen ist. Das gleiche gilt für die übrigen bekannten Zusätze Nickel, Chrom und/oder Kobalt.Nevertheless, this material has so far not been used more widely, which can be attributed to the cover layers that form during switching and thus excessive contact heating. The same applies to the other known additives nickel, chromium and / or cobalt.

Es war daher Aufgabe der vorliegenden Erfindung, einen Silber- Eisen- Werkstoff für elektrische Kontakte zu finden, der eine geringe Verschweißneigung, einen möglichst geringen Kontaktwiderstand und damit Kontakterwärmung zeigt und eine hohe Lebensdauer und breiten Anwendungsbereich in bezug auf die Schaltstromstärke besitzt.It was therefore an object of the present invention to find a silver-iron material for electrical contacts which has a low tendency to weld, the lowest possible contact resistance and thus contact heating and has a long service life and a wide range of applications with regard to the switching current.

Die Aufgabe wird erfindungsgemäß durch die Verwendung eines Silber- Eisen- Werkstoffs mit 3 bis 30 Gew.-% Eisen und einem oder mehreren der folgenden Zusätze Mangan, Kupfer, Zink, Antimon, Wismutoxid, Molybdänoxid, Wolframoxid, Chromnitrid in Mengen von insgesamt 0,05 bis 5 Gew.-% gelöst.
Mit diesen Werkstoffen wird überraschenderweise eine Verringerung des Kontaktwiderstandes und damit der Kontakterwärmung erreicht, ohne daß die an sich gute Sicherheit gegen Verschweißen beeinträchtigt wird. Die Verbesserung in der Kontakterwärmung beträgt im Vergleich zu Ag/Fe-90/10 bis zu 43 %. Die Verbesserung wird durch eine günstige Beeinflussung der Ausbildung der sich bildenden Fe-Oxidschichten erreicht. Während der Werkstoff Ag/Fe-90/10 ohne Zusätze eine durchgehende Oxidschicht aufweist, wird durch die genannten Zusätze diese Oxidschicht derart beeinflußt, so daß sich ein niedriger Kontaktwiderstand in Verbindung mit einer guten Sicherheit gegen das Verschweißen ergibt.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.

Besonders gut geeignet ist ein Werkstoff mit 3 - 20 % Fe und einem oder mehreren der Zusätze Mn, Cu, Zn, Bi, Bi₂O₃, MoO₃, WO₃ und/oder CrN in Mengen von insgesamt 0,2 bis 2 Gew.-%. Außerdem hat es sich bewährt, dem Silber neben 3 bis 20 Gew.-% Eisen entweder 0,2 bis 2 % nur metallische Zusätze oder 0,2 bis 2 % nur nichtmetallische Zusätze zuzugeben.A material with 3 - 20% Fe and one or more of the additives Mn, Cu, Zn, Bi, Bi₂O₃, MoO₃, WO₃ and / or CrN in amounts of in total 0.2 to 2 wt .-% 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.

Günstige Eingenschaften haben Werkstoffe gezeigt, die neben 3 bis 20 % Eisen 0,2 bis 2 % nur einen der Zusätze Mangan, Kupfer, Zink, Antimon, Wismutoxid, Molybdänoxid oder Wolframoxid, Rest Silber enthalten. Vorzugsweise enthalten sie neben 3 bis 20 % Eisen 0,2 bis 2 % Zink und gegebenenfalls 0 bis 2 % Kupfer,Tantal und/­oder Antimon, Rest Silber oder 0,2 bis 2 % Molybdänoxid, Rest Silber.Favorable properties have shown materials which, in addition to 3 to 20% iron 0.2 to 2%, only contain one of the additives manganese, copper, zinc, antimony, bismuth oxide, molybdenum oxide or tungsten oxide, the rest silver. In addition to 3 to 20% iron, 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.

Aufgrund der Unlöslichkeit von Eisen in Silber können diese Werkstoffe nicht auf schmelzmetallurgischem Weg hergestellt werden. Die Herstellung der Werkstoffe erfolgt nach bekannten pulvermetallurgischen Verfahren. Dabei hat es sich als günstig erwiesen, wenn das verwendete Eisenpulver nicht größer als 32 µm ist. Dadurch erzielt man eine sehr gleichmäßige Verteilung der Eisenpartikel im Gemisch und im Zusammenwirken mit den weiteren Zusätzen eine sehr geringe Deckschichtausbildung beim Schalten.Due to the insolubility of iron in silver, these materials cannot be produced using the melt metallurgical method. The materials are manufactured using known powder metallurgical processes. It has proven to be advantageous if the iron powder used is not larger than 32 µm. This results in a very uniform distribution of the iron particles in the mixture and, in conjunction with the other additives, a very low formation of the top layer when switching.

Mit den so gefertigten Werkstoffen wurden elektrische Schaltversuche durchgeführt. Neben der Prüfung des Kontaktwiderstandes in einem Modellprüfstand wurde auch ein serienmäßiger Schutz zur Prüfung der Kontakterwärmung herangezogen.Electrical switching tests were carried out with the materials manufactured in this way. In addition to testing contact resistance in a model test bench, standard protection was also used to test contact heating.

Die Ergebnisse dieser Versuche sind in folgender Tabelle enthalten und zeigen die Verbesserung der erfindungsgemäßen Werkstoffe hinsichtlich Kontaktwiderstand und Kontakt­erwärmung gegenüber dem bekannten Werkstoff Ag/Fe-90/10.

Figure imgb0001
The results of these tests are contained in the following table and show the improvement of the materials according to the invention in terms of contact resistance and contact heating compared to the known material Ag / Fe-90/10.
Figure imgb0001

Claims (6)

1. Verwendung eines Silber- Eisen-Werkstoffs mit 3 bis 30 Gew.-% Eisen und einem oder mehreren der Zusätze Mangan, Kupfer, Zink, Antimon, Wismutoxid, Molybdänoxid, Wolframoxid, Chromnitrid in Mengen von insgesamt 0,05 bis 5 Gew.-%, Rest Silber, für elektrische Kontakte.1. Use of a silver-iron material with 3 to 30 wt .-% iron and one or more of the additions of manganese, copper, zinc, antimony, bismuth oxide, molybdenum oxide, tungsten oxide, chromium nitride in a total amount of 0.05 to 5 wt. -%, balance silver, for electrical contacts. 2. Verwendung eines Silber- Eisenwerkstoffs gemäß Anspruch 1, mit 3 bis 20 % Eisen und einem oder mehreren der Zusätze Mangan, Kupfer, Zink, Antimon, Wismutoxid, Molybdänoxid, Wolframoxid, Chromnitrid in Mengen von insgesamt 0,2 bis 2 Gew.-%, Rest Silber, für elektrische Kontakte.2. Use of a silver iron material according to claim 1, with 3 to 20% iron and one or more of the additions of manganese, copper, zinc, antimony, bismuth oxide, molybdenum oxide, tungsten oxide, chromium nitride in a total amount of 0.2 to 2% by weight. %, Balance silver, for electrical contacts. 3. Verwendung eines Werkstoffs gemäß Anspruch 1 und 2, aus 3 bis 20 % Eisen und insgesamt 0,2 bis 2 % Mangan, Kupfer, Zink, und/oder Antimon, Rest Silber, für elektrische Kontakte.3. Use of a material according to claim 1 and 2, from 3 to 20% iron and a total of 0.2 to 2% manganese, copper, zinc, and / or antimony, the rest silver, for electrical contacts. 4. Verwendung eines Werkstoffs gemäß Anspruch 1 und 2, aus 3 bis 20 % Eisen und insgesamt 0,2 bis 2 % Wismutoxid, Molybdänoxid und/oder Wolframoxid, Rest Silber, für elektrische Kontakte.4. Use of a material according to claim 1 and 2, from 3 to 20% iron and a total of 0.2 to 2% bismuth oxide, molybdenum oxide and / or tungsten oxide, the rest silver, for electrical contacts. 5. Verwendung eines Werkstoffs gemäß einem der vorhergehenden Ansprüche, aus 3 bis 20 % Eisen, 0,2 bis 2 % Zink und 0 bis 2 % Kupfer, Antimon und/oder Tantal, Rest Silber, für elektrische Kontakte.5. Use of a material according to any one of the preceding claims, from 3 to 20% iron, 0.2 to 2% zinc and 0 to 2% copper, antimony and / or tantalum, the rest silver, for electrical contacts. 6. Verwendung eines Werkstoffs gemäß einem der vorhergehenden Ansprüche, aus 3 bis 20 % Eisen und 0,2 bis 2 % Molybdänoxid, Rest Silber, für elektrische Kontakte.6. Use of a material according to one of the preceding claims, from 3 to 20% iron and 0.2 to 2% molybdenum oxide, the rest silver, for electrical contacts.
EP88108735A 1987-06-06 1988-06-01 Use of a silver-iron material for electric contacts Expired - Lifetime EP0294693B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88108735T ATE81734T1 (en) 1987-06-06 1988-06-01 USE OF A SILVER-IRON MATERIAL FOR ELECTRICAL CONTACTS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3719052 1987-06-06
DE3719052 1987-06-06

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EP0294693A2 true EP0294693A2 (en) 1988-12-14
EP0294693A3 EP0294693A3 (en) 1989-03-15
EP0294693B1 EP0294693B1 (en) 1992-10-21

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Country Status (23)

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US (1) US4859238A (en)
EP (1) EP0294693B1 (en)
JP (1) JP2680038B2 (en)
CN (1) CN1011421B (en)
AR (1) AR241971A1 (en)
AT (1) ATE81734T1 (en)
AU (1) AU1730388A (en)
BR (1) BR8802712A (en)
CA (1) CA1309278C (en)
CS (1) CS275704B6 (en)
DE (1) DE3875385D1 (en)
DK (1) DK303088A (en)
ES (1) ES2035154T3 (en)
GR (1) GR3006495T3 (en)
HU (1) HUT50262A (en)
IN (1) IN167229B (en)
MX (1) MX170300B (en)
NO (1) NO882389L (en)
PL (1) PL156711B1 (en)
PT (1) PT87662B (en)
RU (1) RU1785579C (en)
YU (1) YU46258B (en)
ZA (1) ZA883891B (en)

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EP0338401B1 (en) * 1988-04-16 1995-09-27 DODUCO GMBH + Co Dr. Eugen DÀ¼rrwächter Powder-metallurgical process for the production of a semi-finished product for electrical contacts made from a composite material based on silver and iron

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DE58904983D1 (en) * 1988-04-20 1993-08-26 Siemens Ag SILVER-BASED SINTER CONTACT MATERIAL FOR USE IN SWITCHGEAR DEVICES IN ENERGY TECHNOLOGY, ESPECIALLY FOR CONTACT PIECES IN LOW VOLTAGE SWITCHES.
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DE4201940A1 (en) * 1992-01-24 1993-07-29 Siemens Ag SINTER COMPOSITE FOR ELECTRICAL CONTACTS IN SWITCHGEAR OF ENERGY TECHNOLOGY
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DE19543223C1 (en) * 1995-11-20 1997-02-20 Degussa Silver@-iron@ material contg. oxide additives
DE19543208C1 (en) * 1995-11-20 1997-02-20 Degussa Silver@-iron@ material contg. oxide additives
DE19543222C1 (en) * 1995-11-20 1997-02-20 Degussa Silver@-iron material contg. oxide additives
DE19607183C1 (en) * 1996-02-27 1997-04-10 Degussa Sintered silver@-iron@ alloy for making electrical contacts
JP2001052930A (en) * 1999-08-06 2001-02-23 Tdk Corp Laminated inductor and manufacture thereof
DE10012250B4 (en) * 2000-03-14 2006-06-01 Umicore Ag & Co. Kg Contact materials based on silver-iron-copper
JP4427058B2 (en) * 2004-06-18 2010-03-03 Ｔａｎａｋａホールディングス株式会社 Sealed AC load relay and Ag contact element material used therefor
JP5342931B2 (en) * 2009-06-05 2013-11-13 マブチモーター株式会社 Sliding contact material, clad composite material and motor
WO2013142765A1 (en) * 2012-03-23 2013-09-26 Technic, Inc. Silver antimony coatings and connectors
CN106238721B (en) * 2016-08-03 2018-06-19 施海峰 A kind of composite contact material and preparation method thereof
CN107299244B (en) * 2017-06-09 2019-07-16 佛山通宝精密合金股份有限公司 A method of preparing high-performance AgFeRe material
CN109777991A (en) * 2019-03-25 2019-05-21 杭州辰卓科技有限公司 A kind of electric leads bonding corrosion-resistant high-damping silver alloy and its technique
WO2020241854A1 (en) * 2019-05-31 2020-12-03 オムロン株式会社 Material for contact and containing ag alloy as main component, contact using said material for contact, and electrical device
CN114457253B (en) * 2021-12-30 2022-12-09 无锡日月合金材料有限公司 Silver nickel-bismuth oxide material for microswitch and manufacturing method thereof

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Publication number Priority date Publication date Assignee Title
EP0338401B1 (en) * 1988-04-16 1995-09-27 DODUCO GMBH + Co Dr. Eugen DÀ¼rrwächter Powder-metallurgical process for the production of a semi-finished product for electrical contacts made from a composite material based on silver and iron
DE4117312A1 (en) * 1991-05-27 1992-12-03 Siemens Ag SILVER-BASED CONTACT MATERIAL FOR USE IN SWITCHGEAR DEVICES OF ENERGY TECHNOLOGY AND METHOD FOR THE PRODUCTION OF CONTACT PIECES FROM THIS MATERIAL
WO1992022079A1 (en) * 1991-05-27 1992-12-10 Siemens Aktiengesellschaft Silver-based contact material for use in power-engineering switchgear, and a method of manufacturing contacts made of this material

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Publication number Publication date
DK303088A (en) 1988-12-07
PL156711B1 (en) 1992-04-30
MX170300B (en) 1993-08-16
JPS6452346A (en) 1989-02-28
CS8803853A2 (en) 1991-04-11
CN1011421B (en) 1991-01-30
RU1785579C (en) 1992-12-30
ZA883891B (en) 1989-02-22
IN167229B (en) 1990-09-22
DE3875385D1 (en) 1992-11-26
NO882389L (en) 1988-12-07
PL272879A1 (en) 1989-03-06
NO882389D0 (en) 1988-05-31
PT87662B (en) 1992-10-30
GR3006495T3 (en) 1993-06-21
JP2680038B2 (en) 1997-11-19
PT87662A (en) 1988-07-01
DK303088D0 (en) 1988-06-03
ES2035154T3 (en) 1993-04-16
EP0294693A3 (en) 1989-03-15
EP0294693B1 (en) 1992-10-21
AR241971A1 (en) 1993-01-29
US4859238A (en) 1989-08-22
CN1030098A (en) 1989-01-04
YU46258B (en) 1993-05-28
BR8802712A (en) 1988-12-27
YU103288A (en) 1990-04-30
CS275704B6 (en) 1992-03-18
ATE81734T1 (en) 1992-11-15
HUT50262A (en) 1989-12-28
CA1309278C (en) 1992-10-27
AU1730388A (en) 1988-12-08

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