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EP0660964B2 - Material for electric contacts based on silver-tin oxide or silver-zinc oxide and process for its production - Google Patents

Material for electric contacts based on silver-tin oxide or silver-zinc oxide and process for its production Download PDF

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Publication number
EP0660964B2
EP0660964B2 EP93920746A EP93920746A EP0660964B2 EP 0660964 B2 EP0660964 B2 EP 0660964B2 EP 93920746 A EP93920746 A EP 93920746A EP 93920746 A EP93920746 A EP 93920746A EP 0660964 B2 EP0660964 B2 EP 0660964B2
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Prior art keywords
tin oxide
silver
powder
mixture
weight
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German (de)
French (fr)
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EP0660964A1 (en
EP0660964B1 (en
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Volker Behrens
Thomas Honig
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Doduco Contacts and Refining GmbH
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AMI Doduco GmbH
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Classifications

    • 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
    • H01H1/0237—Composite material having a noble metal as the basic material and containing oxides
    • H01H1/02372—Composite material having a noble metal as the basic material and containing oxides containing as major components one or more oxides of the following elements only: Cd, Sn, Zn, In, Bi, Sb or Te
    • 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
    • C22C1/059—Making alloys comprising less than 5% by weight of dispersed reinforcing phases
    • 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
    • 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
    • H01H1/0237—Composite material having a noble metal as the basic material and containing oxides
    • H01H1/02372—Composite material having a noble metal as the basic material and containing oxides containing as major components one or more oxides of the following elements only: Cd, Sn, Zn, In, Bi, Sb or Te
    • H01H1/02376—Composite material having a noble metal as the basic material and containing oxides containing as major components one or more oxides of the following elements only: Cd, Sn, Zn, In, Bi, Sb or Te containing as major component SnO2
    • 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
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/12097—Nonparticulate component encloses 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.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/12104—Particles discontinuous
    • 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.]
    • Y10T428/12146—Nonmetal particles in a component

Definitions

  • the invention is based on a material for electrical contacts based on silver-tin oxide with those specified in the preamble of claim 1 Features.
  • a material is from WO 80/01434 known; the material is obtained by mixing a powder of silver or one mainly Silver containing alloy with tin oxide powder, compacting of mixing and sintering.
  • Bismuth and germanium oxide are also additives have been mentioned (DE-A-31 02 067 and DE-A-32 32 627). These additives help to wet tin oxide particles, so that if the contact piece surface under the Effect of a switching arc melts locally, the Tin oxide remains in fine suspension. Besides this positive effect in terms of heating behavior under continuous current, however, these additives have also undesirable side effects.
  • Another disadvantage in particular of tungsten and molybdenum compounds in that they are particularly in switching mode AC1 load (DIN 57660 part 102) a material transfer favor the accelerated burnup and thus leads to a reduction in the service life.
  • a contact material with little tendency to weld and if possible low contact temperature under continuous current load be obtained by targeting one Fabricates in which areas where no or contains very little metal oxide with areas where all or the far predominant part of the metal oxide component in fine Distribution is included.
  • a composite powder which the predominant Part of the tin oxide and other oxides and / or carbides and part of the silver.
  • This composite powder is mixed with the rest of the silver powder and possibly with the smaller rest of the metal oxides mixed, compacted, sintered and formed. To this Way you get a usable material, however, after a relatively complex Method.
  • the oxides of tungsten are as metal oxides, Molybdenum, bismuth, vanadium and copper called.
  • the doped tin oxide powder is one Composite powder, which can be obtained by Mix the tin oxide powder with the powder Dopant, annealing the mixture so that the Dopant and the tin oxide powder particles diffuse, and separating the excess dopant of tin oxide powder.
  • To obtain doped tin oxide powder is in P 42 19 333.8 discloses a solution of a salt of tin and a salt of the metal or metals from which Oxides or carbides are the dopant in a hot, oxidizing atmosphere spray in which the salts are decomposed so that a fine-particle composite powder precipitates, its particles contains the tin oxide and the dopants.
  • the present invention is based on the object a material of the type mentioned at the beginning create the addition of an equally favorable heating behavior shows how the known contact materials, however, is more ductile and one in the AC1 switching case has a longer lifespan.
  • This task is solved by a material with the specified in claim 1 Features.
  • a particularly suitable process for the manufacture of such a material is the subject of claim 8.
  • Advantageous further developments the invention are the subject of the dependent claims.
  • the invention additionally uses a powder which contains one or more chemical compounds of silver, oxygen and a metal from subgroups II to VI and / or antimony, bismuth, germanium, gallium and indium, in particular silver-tungsten-oxygen compounds, silver-molybdenum-oxygen compounds, silver-antimony-oxygen compounds, silver-bismuth-oxygen compounds and silver-germanium-oxygen compounds.
  • this class of compounds also includes silver antimonate and silver molybdate, of which Christine Bourda (see above) is known to be in a silver-tin oxide-molybdenum oxide material or silver-tin oxide-antimony oxide material.
  • Another advantage of the invention is that due to the lower proportion of the chosen additive the service life of contact pieces made of the material is increased, especially under AC1-test conditions.
  • the use of the invention Powder surprisingly leads to one less erosion than with conventional silver-tin oxide contact materials with pure metal oxide additives such as tungsten oxide, molybdenum oxide or bismuth oxide.
  • the tin oxide particles are superficially with the silver-metal-oxygen compounds busy. They promote the wetting of the tin oxide particles with the arc forming melt phase then particularly effective.
  • a tin oxide powder modified in this way can be obtained with advantage by using tin oxide powder and the powdery additive together mixed and glows together so that the tin oxide powder particles be wetted by the additive, whereby a Part of the addition also in the surface area of the Diffuse tin oxide particles and possibly a mixed oxide can form.
  • the material expediently contains 5 to 20% by weight, preferably 8 to 14 %
  • the tin oxide powder preferably with at least 0.1% by weight of the additive, but with no more than 2.5% by weight, preferably with not more than 1% by weight of the additive.
  • Silver molybdate is particularly preferred as an additive because of its particularly beneficial effect on the Heating behavior.
  • the glow of the mixture of tin oxide and the selected addition is conveniently made at oxygen-containing atmosphere, preferably in air at a Temperature between 500 ° C and 800 ° C, best at a temperature just above the melting point of the additive so that it becomes liquid and the tin oxide particles are wetted superficially.
  • the addition is then only there where its wetting Effect is desired, and can therefore be economical be used. With the small amounts, in the tin oxide particles stick to not yet with each other; but should it be in individual cases can occur by grinding to encounter.
  • the tin oxide and the additive can not only connected by glowing together but also by separating the additive on the tin oxide particles using chemical or physical deposition processes.
  • the teaching according to the invention can be transferred are based on contact materials based on silver with zinc oxide. In such materials are so far in in practice, no additives are used, but one endeavors to take constructive measures in the shaft device to achieve a reduction in the contact point temperature.
  • an additive combined zinc oxide powder can a lowering of the contact point temperature also with this type of material to reach.
  • the three examples can be modified accordingly that zinc oxide is used instead of tin oxide becomes.

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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)
  • Dispersion Chemistry (AREA)
  • Contacts (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Conductive Materials (AREA)

Abstract

PCT No. PCT/EP93/02511 Sec. 371 Date May 18, 1995 Sec. 102(e) Date May 18, 1995 PCT Filed Sep. 16, 1993 PCT Pub. No. WO94/07252 PCT Pub. Date Mar. 31, 1994A material for electric contacts based on silver-tin oxide is obtained by mixing a powder of silver or an alloy mainly containing silver with a powder consisting mainly of tin oxide and 0.01 to 10 wt. % (in relation to the quantity of tin oxide) of an additive consisting of one or more compounds containing silver, oxygen and a metal from sub-groups II to VI of the periodic system and/or antimony, bismuth, germanium, indium and gallium, compacting the mixture and sintering it. The tin oxide may be replaced by zinc oxide.

Description

Die Erfindung geht aus von einem Werkstoff für elektrische Kontakte auf der Basis von Silber-Zinnoxid mit den im Oberbegriff des Anspruchs 1 angegebenen Merkmalen. Ein solcher Werkstoff ist aus der WO 80/01434 bekannt; der Werkstoff wird erhalten durch Mischen eines Pulvers aus Silber oder einer hauptsächlich Silber enthaltenden Legierung mit ZinnoxidPulver, Verdichten der Mischung und Sintern.The invention is based on a material for electrical contacts based on silver-tin oxide with those specified in the preamble of claim 1 Features. Such a material is from WO 80/01434 known; the material is obtained by mixing a powder of silver or one mainly Silver containing alloy with tin oxide powder, compacting of mixing and sintering.

Aufgrund ihrer besseren Umweltverträglichkeit und ihrer zumindest teilweise günstigeren Lebensdauer haben Kontaktwerkstoffe auf der Basis von Silber-Zinnoxid begonnen, die bis dahin bevorzugten Silber-Cadmiumoxidwerkstoffe zu ersetzen. Da das Zinnoxid wegen seiner höheren thermischen Beständigkeit dazu neigt, unter Lichtbogeneinwirkung schlecht leitende Schlackeschichten an der Kontaktoberfläche zu bilden, ist jedoch das Erwärmungsverhalten unter Dauerstrom bei Kontakten aus Silber-Zinnoxid unbefriedigend. Um diesen Nachteil zu beseitigen, ist es bekannt, dem pulvermetallurgisch hergestellten Werkstoff Zusätze in Pulverform beigegeben, die zu einer niedrigeren Temperatur an der Kontaktstelle führen. Als geeignete Zusätze in diesem Sinn sind in der Patentliteratur vor allem Wolfram- und Molybdänoxid und -karbid genannt worden (DE-A-29 33 338, DE-A-31 02 067, DE-A-32 32 627). Als Zusätze sind ferner Wismut- und Germaniumoxid genannt worden (DE-A-31 02 067 und DE-A-32 32 627). Diese Zusätze helfen, Zinnoxidpartikel zu benetzen, so dass dann, wenn die Kontaktstückoberfläche unter der Wirkung eines Schaltlichtbogens lokal aufschmilzt, das Zinnoxid feinteilig in Suspension bleibt. Neben dieser positiven Wirkung hinsichtlich des Erwärmungsverhaltens unter Dauerstrom haben diese Zusätze jedoch auch unerwünschte Nebenwirkungen. Die ohnehin nicht ganz befriedigende plastische Verformbarkeit der Silber-Zinnoxid-Kontaktwerkstoffe, zu deren Verbesserung beispielsweise eine Vorbehandlung des Zinnoxidpulvers durch Glühen durchgeführt wird (DE-A-29 52 128), wird durch diese Zusätze noch verschlechtert, weil sie versprödend wirken. Das gilt insbesondere für Wismut- und Molybdänoxid. Ein weiterer Nachteil insbesondere der Wolfram- und Molybdänverbindungen besteht darin, dass sie insbesondere im Schaltbetrieb unter AC1-Belastung (DIN 57660 Teil 102) eine Materialübertragung begünstigen, die zu beschleunigtem Abbrand und damit zu einer Verringerung der Lebensdauer führt.Because of their better environmental compatibility and have at least partially more favorable lifespan Contact materials based on silver-tin oxide started the previously preferred silver-cadmium oxide materials to replace. Because of the tin oxide its higher thermal resistance tends to be poorly conductive when exposed to arcing To form slag layers on the contact surface is however the heating behavior under continuous current unsatisfactory for contacts made of silver-tin oxide. Around To overcome this disadvantage, it is known to powder metallurgy manufactured material additives in powder form added that to a lower temperature lead at the contact point. As suitable additives in this sense, tungsten and molybdenum oxide and carbide (DE-A-29 33 338, DE-A-31 02 067, DE-A-32 32 627). Bismuth and germanium oxide are also additives have been mentioned (DE-A-31 02 067 and DE-A-32 32 627). These additives help to wet tin oxide particles, so that if the contact piece surface under the Effect of a switching arc melts locally, the Tin oxide remains in fine suspension. Besides this positive effect in terms of heating behavior under continuous current, however, these additives have also undesirable side effects. The anyway not entirely satisfactory plastic deformability of the Silver-tin oxide contact materials, for their improvement for example pretreatment of the tin oxide powder is carried out by annealing (DE-A-29 52 128), is made worse by these additions because they look embrittling. This is especially true for bismuth and molybdenum oxide. Another disadvantage in particular of tungsten and molybdenum compounds in that they are particularly in switching mode AC1 load (DIN 57660 part 102) a material transfer favor the accelerated burnup and thus leads to a reduction in the service life.

Nach der Lehre der WO 89/09478 soll ein Kontaktwerkstoff mit geringer Verschweißneigung und möglichst niedriger Kontakttemperatur unter Dauerstrombelastung dadurch erhalten werden, dass man gezielt ein Gefüge herstellt, in welchem Bereiche, in denen kein oder nur sehr wenig Metalloxid enthalten ist, abwechseln mit Bereichen, in denen die gesamte oder der weit überwiegende Teil der Metalloxidkomponente in feiner Verteilung enthalten ist. Zu diesem Zweck wird unter anderem ein Verbundpulver hergestellt, welches den überwiegenden Teil des Zinnoxids und der weiteren Oxide und/oder Karbide sowie einen Teil des Silbers enthält. Dieses Verbundpulver wird mit dem restlichen Silberpulver und ggfs. mit dem kleineren Rest der Metalloxide vermischt, verdichtet, gesintert und umgeformt. Auf diese Weise erhält man zwar einen gut brauchbaren Werkstoff, jedoch nach einem verhältnismässig aufwendigen Verfahren. Als Metalloxide sind die Oxide von Wolfram, Molybdän, Wismut, Vanadium und Kupfer genannt.According to the teaching of WO 89/09478, a contact material with little tendency to weld and if possible low contact temperature under continuous current load be obtained by targeting one Fabricates in which areas where no or contains very little metal oxide with areas where all or the far predominant part of the metal oxide component in fine Distribution is included. For this purpose, among other things made a composite powder, which the predominant Part of the tin oxide and other oxides and / or carbides and part of the silver. This composite powder is mixed with the rest of the silver powder and possibly with the smaller rest of the metal oxides mixed, compacted, sintered and formed. To this Way you get a usable material, however, after a relatively complex Method. The oxides of tungsten are as metal oxides, Molybdenum, bismuth, vanadium and copper called.

Aus dem Aufsatz von Christine Bourda et al. "PRO-PERTIES AND EFFECTS OF DOPING AGENTS USED IN AGSNO2 CONTACT MATERIALS", veröffentlicht in Proc. 16th Int. Conference on Electrical Contacts 7.-12.09.1992 in Loughborough, ist es bekannt, dass manche oxidische Zusätze mit Silber oder Zinnoxid reagieren; so wurde festgestellt, dass sich bei Temperaturen, die unter der Einwirkung eines Schaltlichtbogens erreicht werden, in einem aus Silberpulver, Zinnoxidpulver und Molybdänoxidpulver oder Antimonoxidpulver hergestellten Kontaktwerkstoff aus Silber und Molybdänoxid Silbermolybdat Ag2MoO4 und aus Silber und Antimonoxid Silber-Antimonat AgSbO3 entstehen kann. Zu diesen beiden Zusätzen ist jedoch in der Literaturstelle angemerkt, dass sie nach dem Ergebnis von diesbezüglichen Versuchen keinen Einfluß auf die Benetzbarkeit des Zinnoxids mit Silber haben, so dass nicht zu erwarten ist, dass sie das Erwärmungsverhalten von Kontakten unter Dauerstrom verbessem.From the essay by Christine Bourda et al. "PRO-PERTIES AND EFFECTS OF DOPING AGENTS USED IN AGSNO2 CONTACT MATERIALS", published in Proc. 16th Int. Conference on Electrical Contacts September 7-12, 1992 in Loughborough, it is known that some oxidic additives react with silver or tin oxide; It was found that at temperatures that are reached under the action of a switching arc, silver molybdate Ag 2 MoO 4 and silver and antimony oxide silver-antimonate AgSbO 3 form in a contact material made from silver powder, tin oxide powder and molybdenum oxide powder or antimony oxide powder can. Regarding these two additives, however, it is noted in the literature that, after the results of experiments in this regard, they have no influence on the wettability of the tin oxide with silver, so that it is not to be expected that they will improve the heating behavior of contacts under continuous current.

In der älteren, aber nicht vorveröffentlichten deutschen Patentanmeldung P 42 19 333.8 wurde bereits ein Werkstoff für elektrische Kontakte auf der Basis von Silber-Zinnoxid vorgeschlagen, der erhalten wird durch Mischen eines Pulvers aus Silber oder aus einer hauptsächlich Silber enthaltenden Legierung mit einem Zinnoxidpulver, dessen Pulverteilchen mit bis zu 5 Gew.-% eines Oxids oder Karbids von Molybdän, Wolfram, Wismut, Antimon, Germanium, Vanadium, Kupfer oder Indium dotiert sind, Verdichten der Mischung, Sintem und Umformen. Dabei ist das dotierte Zinnoxidpulver ein Verbundpulver, welches erhalten werden kann durch Mischen des Zinnoxidpulvers mit der pulverförmigen Dotierungssubstanz, Glühen der Mischung, so dass die Dotierungssubstanz und die Zinnoxidpulverteilchen diffundiert, und Abtrennen des Uberschusses der Dotierungssubstanz vom Zinnoxidpulver. Als weiteres Verfahren, dotiertes Zinnoxidpulver zu erhalten, ist in P 42 19 333.8 offenbart, eine Lösung eines Salzes von Zinn und eines Salzes des Metalles oder der Metalle, aus deren Oxiden oder Karbiden die Dotierungssubstanz bestehen soll, in eine heiße, oxidierende Atmosphäre zu sprühen, in welcher die Salze zersetzt werden, so dass ein feinteiliges Verbundpulver ausfällt, dessen Teilchen das Zinnoxid und die Dotierungssubstanzen enthält.In the older, but not prepublished German Patent application P 42 19 333.8 has already been a material for electrical contacts based on Silver-tin oxide is proposed which is obtained by Mixing a powder of silver or one mainly Alloy containing silver with a tin oxide powder, its powder particles with up to 5% by weight an oxide or carbide of molybdenum, tungsten, bismuth, Antimony, germanium, vanadium, copper or indium are doped, compacting the mixture, sintem and Forming. The doped tin oxide powder is one Composite powder, which can be obtained by Mix the tin oxide powder with the powder Dopant, annealing the mixture so that the Dopant and the tin oxide powder particles diffuse, and separating the excess dopant of tin oxide powder. As another method, To obtain doped tin oxide powder is in P 42 19 333.8 discloses a solution of a salt of tin and a salt of the metal or metals from which Oxides or carbides are the dopant in a hot, oxidizing atmosphere spray in which the salts are decomposed so that a fine-particle composite powder precipitates, its particles contains the tin oxide and the dopants.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, einen Werkstoff der eingangs genannten Art zu schaffen, der durch Zusätze ein ebenso günstiges Erwärmungsverhalten zeigt wie die bekannten Kontaktwerkstoffe, jedoch duktiler ist und im AC1-Schaltfall eine höhere Lebensdauer hat. Diese Aufgabe wird gelöst durch einen Werkstoff mit den im Anspruch 1 angegebenen Merkmalen. Ein besonders geeignetes Verfahren zum Herstellen eines solchen Werkstoffes ist Gegenstand des Anspruchs 8. Vorteilhafte Weiterbildungen der Erfindung sind Gegenstand der abhängigen Ansprüche.The present invention is based on the object a material of the type mentioned at the beginning create the addition of an equally favorable heating behavior shows how the known contact materials, however, is more ductile and one in the AC1 switching case has a longer lifespan. This task is solved by a material with the specified in claim 1 Features. A particularly suitable process for the manufacture of such a material is the subject of claim 8. Advantageous further developments the invention are the subject of the dependent claims.

Die Erfindung verwendet in der pulvermetallurgischen Herstellung eines Kontaktwerkstoffs auf Silber-ZinnoxidBasis zusätzlich ein Pulver, das eine oder mehrere chemische Verbindungen von Silber, Sauerstoff und einem Metall aus den Nebengruppen II bis VI und/oder Antimon, Wismut, Germanium, Gallium und Indium enthält, insbesondere Silber-Wolfram-Sauerstoff-Verbindungen, Silber-Molybdän-Sauerstoff-Verbindungen, Silber-Antimon-Sauerstoff-Verbindungen, Silber-Wismut-Sauerstoff-Verbindungen und Silber-GermaniumSauerstoff-Verbindungen. Obwohl zu dieser Klasse von Verbindungen auch Silber-Antimonat und Silber-Molybdat gehören, von denen aus dem Aufsatz von Christine Bourda (s.o.) bekannt ist, dass sie sich in einem Silber-Zinnoxid-Molybdänoxid-Werkstoff bzw. Silber-Zinnoxid-Antimonoxid-Werkstoff bilden können und keinen günstigen Einfluß auf die Benetzbarkeit des Zinnoxids haben, erreicht man mit dem erfindungsgemäßen Kontaktwerkstoff überraschend doch eine wesentlich niedrigere Erwärmung der Kontaktstellen unter Dauerstrom als bei bekannten Kontakten mit mengenmäßig vergleichbarer Zusammensetzung. Es wird vermutet, dass das damit zusammenhängt, dass anders als von Christine Bourda (s.o.) berichtet, der Kontaktwerkstoff nicht wie üblich hergestellt wird, indem Silberpulver, Zinnoxidpulver und zusätzliche Metalloxidpulver miteinander gemischt und gesintert werden, sondern, indem von vornherein Pulver eingesetzt wird, welches anstelle eines reinen Metalloxids wie z.B. MoO3 eine Verbindung des Typs Silber-Metall-Sauerstoff wie Ag2MoO4 enthält, insbesondere, wenn diese Verbindung ganz oder teilweise mit den Zinnoxidpulverteilchen verbunden ist, d.h. ein Verbundpulver gebildet wird, in dessen Teilchen Zinnoxid und die Silber-Metall-Sauerstoff-Verbindung miteinander verbunden sind; dieses Verbundpulver wird dann mit Silberpulver gemischt und zu einem Kontaktwerkstoff gesintert.In the powder metallurgical production of a contact material based on silver-tin oxide, the invention additionally uses a powder which contains one or more chemical compounds of silver, oxygen and a metal from subgroups II to VI and / or antimony, bismuth, germanium, gallium and indium, in particular silver-tungsten-oxygen compounds, silver-molybdenum-oxygen compounds, silver-antimony-oxygen compounds, silver-bismuth-oxygen compounds and silver-germanium-oxygen compounds. Although this class of compounds also includes silver antimonate and silver molybdate, of which Christine Bourda (see above) is known to be in a silver-tin oxide-molybdenum oxide material or silver-tin oxide-antimony oxide material. Can form material and have no favorable influence on the wettability of the tin oxide, surprisingly achieved with the contact material according to the invention, however, a significantly lower heating of the contact points under constant current than with known contacts with a comparable composition in terms of quantity. It is believed that this is related to the fact that, unlike Christine Bourda (see above), the contact material is not produced as usual by mixing and sintering silver powder, tin oxide powder and additional metal oxide powders, but by using powder from the outset. which contains a compound of the type silver-metal-oxygen such as Ag 2 MoO 4 instead of a pure metal oxide such as MoO 3 , in particular if this compound is wholly or partly connected to the tin oxide powder particles, ie a composite powder is formed in the particles of which tin oxide and the silver-metal-oxygen compound are interconnected; this composite powder is then mixed with silver powder and sintered into a contact material.

Dadurch, dass erfindungsgemäss bei der pulvermetallurgischen Herstellung des Kontaktwerkstoffes mit dem Silberpulver ein Pulver gemischt wird, welches hauptsächlich aus Zinnoxid sowie aus einer oder mehreren Verbindungen vom Typ Silber-Sauerstoff-Metall besteht, werden entscheidende Vorteile erreicht. Überraschenderweise hat es sich nämlich gezeigt, dass man mit dem erfindungsgemäßen Kontaktwerkstoff eine bestimmte Senkung der Kontaktstellentemperatur unter vorgegebenen Bedingungen bereits mit einem wesentlich geringeren Anteil des gewählten Zusatzes als nach dem bisher bekannten Stand der Technik erreicht. Erste Erfahrungen mit erfindungsgemässen Kontaktwerkstoffen zeigen, dass eine bestimmte Senkung der Kontaktstellentemperatur erfindungsgemäss mit nur 1/2 bis zu 1/10 der Zusatzmenge erreicht werden kann, die im Stand der Technik benötigt wird. Das gilt auch für das Beispiel des Molybdänoxids dessen Anteil drastisch verringert werden kann, wenn es als Silbermolybdat eingesetzt wird, vorallem, wenn es an Zinnoxidpartikel gebunden ist.The fact that according to the invention in the powder metallurgical Production of the contact material with a powder is mixed with the silver powder, which mainly made of tin oxide and one or more Silver-oxygen-metal compounds decisive advantages are achieved. Surprisingly it has been shown that one a certain one with the contact material according to the invention Lowering the contact point temperature below given conditions already with an essential lower proportion of the chosen additive than after the previously known state of the art. First Experience with contact materials according to the invention show that a certain decrease in the contact point temperature according to the invention with only 1/2 up to 1/10 of the additional amount can be achieved in the State of the art is needed. That also applies to that Example of the molybdenum oxide whose proportion is drastic can be reduced when used as silver molybdate will, especially if it is bound to tin oxide particles is.

Dies führt auch dazu, dass der Kontaktwerkstoff weniger spröde, d.h. duktiler ist. Als weiterer Vorteil kommt hinzu, dass infolge des geringeren Anteils des elektrisch nicht leitenden Zusatzes der elektrische Widerstand des Kontaktwerkstoffes zusätzlich herabgesetzt wird, was nochmal einen Beitrag zur Senkung der Kontaktstellentemperatur leistet.This also leads to the contact material less brittle, i.e. is more ductile. Another advantage In addition, due to the lower proportion of the electrically non-conductive addition of electrical resistance of the contact material is also reduced is what will help reduce the Contact point temperature.

Ein weiterer Vorteil der Erfindung liegt darin, dass durch den geringeren Anteil des gewählten Zusatzes die Lebensdauer von Kontaktstücken aus dem Werkstoff erhöht wird, und zwar insbesondere unter AC1-Prüfbedingungen. Der Einsatz des erfindungsgemäßen Pulvers führt überraschenderweise zu einem geringeren Abbrand als bei herkömmlichen Silber-Zinnoxid-Kontaktwerkstoffen mit reinen Metalloxidzusätzen wie Wolframoxid, Molybdänoxid oder Wismutoxid.Another advantage of the invention is that due to the lower proportion of the chosen additive the service life of contact pieces made of the material is increased, especially under AC1-test conditions. The use of the invention Powder surprisingly leads to one less erosion than with conventional silver-tin oxide contact materials with pure metal oxide additives such as tungsten oxide, molybdenum oxide or bismuth oxide.

Die Zinnoxidpartikel werden oberflächlich mit den Silber-Metall-Sauerstoffverbindungen belegt. Sie fördern das Benetzen der Zinnoxidpartikel mit der unter Lichtbogeneinwirkung sich bildenden schmelzflüssigen Phase dann besonders wirksam. Ein in dieser Weise modifiziertes Zinnoxidpulver kann man mit Vorteil dadurch erhalten, dass man Zinnoxidpulver und den pulverförmigen Zusatz miteinander vermischt und zusammen glüht, so dass die Zinnoxidpuiverteilchen vom Zusatz benetzt werden, wobei ein Teil des Zusatzes auch in den Oberflächenbereich der Zinnoxidpartikel diffundieren und darin ggfs. ein Mischoxid bilden kann.The tin oxide particles are superficially with the silver-metal-oxygen compounds busy. They promote the wetting of the tin oxide particles with the arc forming melt phase then particularly effective. A tin oxide powder modified in this way can be obtained with advantage by using tin oxide powder and the powdery additive together mixed and glows together so that the tin oxide powder particles be wetted by the additive, whereby a Part of the addition also in the surface area of the Diffuse tin oxide particles and possibly a mixed oxide can form.

Um die nötige Sicherheit gegen ein Verschweißen der Kontaktstücke zu bieten, die von Silber-Zinnoxid-Werkstoffen verlangt wird, enthält der Werkstoff zweckmässigerweise 5 bis 20 Gew.-%, vorzugsweise 8 bis 14 Gew.-% Zinnoxid, und damit das Zinnoxid wie gewünscht durch die Zusätze in der unter Lichtbogeneinwirkung auftretenden schmelzflüssigen Phase in Suspension gehalten werden kann, ist das Zinnoxidpulver vorzugsweise mit mindestens 0,1 Gew.-% des Zusatzes, aber mit nicht mehr als 2,5 Gew.-%, am besten mit nicht mehr als 1 Gew.-% des Zusatzes verbunden.To provide the necessary security against welding of the contact pieces on offer, made of silver-tin oxide materials the material expediently contains 5 to 20% by weight, preferably 8 to 14 % By weight of tin oxide, and thus the tin oxide as desired through the additives in the under the influence of arcs occurring molten phase in suspension can be held is the tin oxide powder preferably with at least 0.1% by weight of the additive, but with no more than 2.5% by weight, preferably with not more than 1% by weight of the additive.

Als Zusatz besonders bevorzugt ist Silbermolybdat wegen seiner besonderes günstigen Wirkung auf das Erwärmungsverhalten.Silver molybdate is particularly preferred as an additive because of its particularly beneficial effect on the Heating behavior.

Das Glühen der Mischung aus Zinnoxid und dem gewählten Zusatz erfolgt zweckmässigerweise unter sauerstoffhaltiger Atmosphäre, bevorzugt an Luft bei einer Temperatur zwischen 500°C und 800°C, am besten bei einer Temperatur knapp oberhalb des Schmelzpunktes des Zusatzes, so dass dieser flüssig wird und die ZinnoxidTeilchen oberflächlich benetzt. Der Zusatz befindet sich dann nur dort, wo seine benetzungsfördernde Wirkung erwünscht ist, und kann deshalb sparsamst eingesetzt werden. Bei den geringen Mengen, in denen er eingesetzt wird, verkleben die Zinnoxidpartikel miteinander noch nicht; sollte das aber doch im Einzelfall vorkommen, kann man dem durch einen Mahlvorgang begegnen.The glow of the mixture of tin oxide and the selected addition is conveniently made at oxygen-containing atmosphere, preferably in air at a Temperature between 500 ° C and 800 ° C, best at a temperature just above the melting point of the additive so that it becomes liquid and the tin oxide particles are wetted superficially. The addition is then only there where its wetting Effect is desired, and can therefore be economical be used. With the small amounts, in the tin oxide particles stick to not yet with each other; but should it be in individual cases can occur by grinding to encounter.

Das Zinnoxid und der Zusatz können nicht nur durch gemeinsames Glühen miteinander verbunden werden, sondern auch durch Abscheiden des Zusatzes auf den Zinnoxidpartikeln unter Anwendung chemischer oder physikalischer Abscheideverfahren.The tin oxide and the additive can not only connected by glowing together but also by separating the additive on the tin oxide particles using chemical or physical deposition processes.

Die erfindungsgemässe Lehre kann übertragen werden auf Kontaktwerkstoffe auf der Basis von Silber mit Zinkoxid. In solchen Werkstoffen werden bisher in der Praxis noch keine Zusätze verwendet, sondern man bemüht sich, durch konstruktive Maßnahmen im Schaftgerät eine Senkung der Kontaktstellentemperatur zu erreichen. Durch Verwenden eines erfindungsgemäss mit einem Zusatz verbundenen Zinkoxidpulvers läßt sich auch bei diesem Werkstofftyp eine Senkung der Kontaktstellentemperatur erreichen.The teaching according to the invention can be transferred are based on contact materials based on silver with zinc oxide. In such materials are so far in in practice, no additives are used, but one endeavors to take constructive measures in the shaft device to achieve a reduction in the contact point temperature. By using an according to the invention an additive combined zinc oxide powder can a lowering of the contact point temperature also with this type of material to reach.

Beispiele:Examples:

  • 1. Aus 100 Gewichtsteilen Zinnoxidpulver mit einer Teilchengröße < 7 µm nach FSSS (FSSS = Fisher Sub-Sieve Sizer) und 0,5 Gewichtsteilen Disilbermonomolybdat Ag2MoO4 ähnlicher oder gleicher Teilchengröße wird durch trockenes Mischen eine Pulvermischung hergestellt. Diese Pulvermischung wird in flachen Keramikschalen unter Luft ca. 1 Stunde bei 600°C geglüht und dadurch das Zinnoxidpulver mit dem Ag2MoO4 benetzt. 12 Gewichtsteile der geglühten Mischung werden mit 88 Gewichtsteilen Silberpulver von etwa 20 µm Teilchengröße (FSSS-Wert) gemischt. Die Mischung wird kaltisostatisch mit einem Druck von 200MPa zu einem Block gepreßt und anschließend 2 Stunden bei 700°C an Luft gesintert. Der gesinterte Block wird durch Vorwärtsstrangpressen zu einem 5 mm dikken Band umgeformt. Das Band wird dann durch Warmwalzplattieren mit einem lötbaren Silber-Rükken versehen und durch Kaltwalzen auf die gewünschte Enddicke gewalzt. Aus diesem Band können nach Bedarf entweder durch Abhacken, Stanzen oder Trennschneiden Kontaktplättchen gebildet werden.1. A powder mixture is produced from 100 parts by weight of tin oxide powder with a particle size of <7 μm according to FSSS (FSSS = Fisher Sub-Sieve Sizer) and 0.5 parts by weight of disilbermonomolybdate Ag 2 MoO 4 of similar or identical particle size. This powder mixture is annealed in flat ceramic bowls in air for about 1 hour at 600 ° C and thereby the tin oxide powder is wetted with the Ag 2 MoO 4 . 12 parts by weight of the annealed mixture are mixed with 88 parts by weight of silver powder with a particle size of about 20 μm (FSSS value). The mixture is cold isostatically pressed to a block at a pressure of 200MPa and then sintered in air at 700 ° C. for 2 hours. The sintered block is formed into a 5 mm thick band by forward extrusion. The strip is then provided with a solderable silver backing by hot roll cladding and rolled to the desired final thickness by cold rolling. Contact strips can be formed from this band as required, either by chopping, punching or cutting.
  • 2. Aus 100 Gewichtsteilen Zinnoxidpulver mit einer Teilchengröße < 7 µm nach FSSS und 1 Gewichtsteil Silbertetrawolframat Ag8W4O16 ähnlicher oder gleicher Teilchengröße wird durch trockenes Mischen eine Pulvermischung hergestellt. Diese Pulvermischung wird in flachen Keramikschalen unter Luft ca. 1 Stunde bei 700°C geglüht und dadurch das Zinnoxidpulver mit dem Ag8W4O16 benetzt. 10 Gewichtsteile der geglühten Mischung werden mit 90 Gewichtsteilen Silberpulver mit einer Teilchengröße von ca. 20 µm (nach FSSS) gemischt. Die Mischung wird kaltisostatisch mit einem Druck von 200MPa zu zylindrischen Blöcken gepreßt und in Luft bei 700°C 2 Stunden gesintert. Der gesinterte Block wird mit Silber unmantelt, heiß in eine Rückwärtsstrangpresse eingelegt und durch eine Mehrfachmatrize stranggepreßt (DE-OS 34 26 240). Dadurch werden flache Stränge erhalten, die einseitig eine gut löt- und schweißbare Silberoberfläche haben. Durch Kaltwalzen wird die gewünschte Enddicke erhalten. Aus diesem Band können nach Bedarf durch Abhacken, Stanzen oder Trennschneiden Kontaktplättchen gebildet werden.2. A powder mixture is produced by dry mixing from 100 parts by weight of tin oxide powder with a particle size <7 μm according to FSSS and 1 part by weight of silver tetrahydrofuran Ag 8 W 4 O 16 . This powder mixture is annealed in flat ceramic bowls in air for approx. 1 hour at 700 ° C and thereby the tin oxide powder is wetted with the Ag 8 W 4 O 16 . 10 parts by weight of the annealed mixture are mixed with 90 parts by weight of silver powder with a particle size of approximately 20 μm (according to FSSS). The mixture is cold isostatically pressed at a pressure of 200MPa into cylindrical blocks and sintered in air at 700 ° C for 2 hours. The sintered block is coated with silver, hot placed in a reverse extrusion press and extruded through a multiple die (DE-OS 34 26 240). As a result, flat strands are obtained which have a silver surface that is easy to solder and weld. The desired final thickness is obtained by cold rolling. Contact strips can be formed from this band as required by chopping, punching or cutting.
  • 3. Das Beispiel 1 wird dahingehend abgewandelt, dass aus 119,5 Gewichtsteilen eines Zinnoxidpulvers mit einer Teilchengröße kleiner als 7 µm und 0,5 Gewichtsteile Ag2MoO4 mit einer mittleren Teilchengröße von 40 µm eine Mischung hergestellt wird, die bei 600°C geglüht wird. Dabei verteilt sich das Ag2MoO4 auf den Zinnoxidpartikeln. Im übrigen wird wie im Beispiel 1 verfahren.3. Example 1 is modified in such a way that a mixture is prepared from 119.5 parts by weight of a tin oxide powder with a particle size of less than 7 μm and 0.5 part by weight of Ag 2 MoO 4 with an average particle size of 40 μm is annealed. The Ag 2 MoO 4 is distributed on the tin oxide particles. Otherwise the procedure is as in Example 1.

    • Mit so hergestellten Kontaktstücken werden in einem Schaltgerät mit einer Leistung von 37 kW Lebensdauerprüfungen nach der Prüfkategorie AC1 durchgeführt. Nach 200.000 Schaltspielen wurde die Lebensdauer-Prüfung unterbrochen für eine Untersuchung der Erwärmung der Kontaktstücke bei Dauerstromführung. Dabei zeigte sich, dass die Erwärmung mit durchschnittlich 70-90°K nicht höher war als bei einem konventionell hergestellten Werkstoff der Zusammensetzung Ag88/SnO211,6/MoO30,4 mit einem rund zehnmal so hohen Molybdänoxidanteil.With contact pieces manufactured in this way, endurance tests according to test category AC1 are carried out in a switching device with an output of 37 kW. After 200,000 switching cycles, the service life test was interrupted for an examination of the heating of the contact pieces with continuous current. It was shown that the heating with an average of 70-90 ° K was not higher than that of a conventionally produced material with the composition Ag88 / SnO 2 11.6 / MoO 3 0.4 with a molybdenum oxide content that was around ten times higher.

    Die drei Beispiele können dahingehend abgewandelt werden, dass anstelle von Zinnoxid Zinkoxid eingesetzt wird.The three examples can be modified accordingly that zinc oxide is used instead of tin oxide becomes.

    Claims (13)

    1. Material for electric contacts on the basis of silver-tin oxide, obtained through
      mixing of a powder of silver or of a mainly silver containing alloy with tin oxide powder,
      compacting the mixture, and
      sintering,
      characterized in that for the production of the mixture an additional powder is used containing 0.01 to 10 weight % based upon the quantity of tin oxide of one or more compounds consisting of silver, oxygen and a metal from subgroups II to VI of the Periodic Table and/or antimony, bismuth, germanium, indium and galium, and that the compounds together with the tin oxide are bound to compound particles of a compound powder.
    2. Material according to claim 1, characterized in that it contains 5 to 20 weight % of tin oxide.
    3. Material according to claim 2, characterized in that it contains 8 to 14 weight % of tin oxide.
    4. Material according to any of the preceding claims, characterized in that it contains at least 0.1 weight % of the admixture.
    5. Material according to any of the preceding claims, characterized in that it contains the admixture in an amount not exceeding 2.5 weight %.
    6. Material according to claim 5, characterized in that it contains the admixture in an amount not exceeding 1 weight %.
    7. Material according to any of the preceding claims, characterized in that the compounds contained in the admixture include a metal from the group tungsten, molybdenum, vanadium, antimony, bismuth and germanium, where molybdenum is particularly preferred.
    8. Process for the production of a material for electric contacts on the basis of silver-tin oxide through mixing of a powder of silver or of a mainly silver containing alloy with tin oxide powder and an additional powder which contains 0.01 to 10 weight % based upon the quantitiy of tin oxide of one or more compounds consisting of silver, oxygen and of metal selected from the subgroups II to VI of the Periodic Table and/or antimony, bismuth, germanium, indium and gallium, compacting the mixture and sintering it, according to any of the preceding claims, characterized in that the powder, mainly consisting of tin oxide and of the admixture, is obtained through
      mixing of the tin oxide powder with the admixture in powder form and
      annealing of the mixture
    9. Process according to claim 8, characterized in that the mixture is annealed in air.
    10. Process according to claim 8 or 9, characterized in that the mixture is annealed between 500°C and 800°C.
    11. Process according to any of the claims 8 through 10, characterized in that the mixture is annealed at a temperature above the melting temperature of the admixture.
    12. Process according to any of the claims 8 through 11, characterized in that after sintering the material is again compacted andlor transformed.
    13. Material according to any of the claims 1 through 7 or produced according to any of the claims 8 through 12, characterized in that tin oxide is replaced by zinc oxide.
    EP93920746A 1992-09-16 1993-09-16 Material for electric contacts based on silver-tin oxide or silver-zinc oxide and process for its production Expired - Lifetime EP0660964B2 (en)

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    DE2952128C2 (en) * 1979-12-22 1984-10-11 Degussa Ag, 6000 Frankfurt Process for the pretreatment of the powder for sintered and extruded semifinished products made of silver-tin oxide for electrical contacts
    DE3017424C2 (en) * 1980-05-07 1987-01-15 Degussa Ag, 6000 Frankfurt Material for electrical contacts
    DE3102067A1 (en) * 1981-01-23 1982-08-19 Degussa Ag, 6000 Frankfurt MATERIAL FOR ELECTRICAL CONTACTS
    DE3232627A1 (en) * 1981-09-24 1983-04-07 Doduco KG Dr. Eugen Dürrwächter, 7530 Pforzheim Material for electrical contacts
    DE3146972A1 (en) * 1981-11-26 1983-06-01 Siemens AG, 1000 Berlin und 8000 München METHOD FOR PRODUCING MOLDED PARTS FROM CADMIUM-FREE SILVER METAL OXIDE COMPOSITIONS FOR ELECTRICAL CONTACTS
    DE3305270A1 (en) * 1983-02-16 1984-08-16 Siemens AG, 1000 Berlin und 8000 München SINTER COMPOSITE FOR ELECTRICAL CONTACTS AND METHOD FOR THE PRODUCTION THEREOF
    DE3402091C2 (en) * 1984-01-21 1994-01-13 Rau Gmbh G Composite material for electrical contact pieces
    DE3421758A1 (en) * 1984-06-12 1985-12-12 Siemens AG, 1000 Berlin und 8000 München SINTER CONTACT MATERIAL FOR LOW VOLTAGE SWITCHGEAR IN ENERGY TECHNOLOGY AND METHOD FOR THE PRODUCTION THEREOF
    DE3426240A1 (en) * 1984-07-17 1986-01-30 Doduco KG Dr. Eugen Dürrwächter, 7530 Pforzheim Method for the production of a band-shaped semi-finished product for electrical contacts from a composite material and an apparatus for carrying out the method
    WO1989009478A1 (en) * 1988-03-26 1989-10-05 Doduco Gmbh + Co. Dr. Eugen Dürrwächter Semifinished product for electrical contacts, made of a composite material based on silver and tin oxide, and powder metallurgical process for producing it
    DE58908359D1 (en) * 1988-11-17 1994-10-20 Siemens Ag Sintered contact material for low-voltage switchgear in energy technology, especially for motor contactors.
    CA2033139A1 (en) * 1989-12-26 1991-06-27 Akira Shibata Silver-metal oxide composite material and process for producing the same
    DE4319137A1 (en) * 1992-06-10 1993-12-16 Duerrwaechter E Dr Doduco Material for electrical contacts based on silver-tin oxide or siler-zinc oxide

    Also Published As

    Publication number Publication date
    DE4331526C3 (en) 2003-11-06
    ES2091633T5 (en) 2003-09-01
    ES2091633T3 (en) 1996-11-01
    EP0660964A1 (en) 1995-07-05
    ATE139864T1 (en) 1996-07-15
    EP0660964B1 (en) 1996-06-26
    JP3441074B2 (en) 2003-08-25
    DE4331526A1 (en) 1994-03-17
    WO1994007252A1 (en) 1994-03-31
    US5822674A (en) 1998-10-13
    JPH08504292A (en) 1996-05-07
    DE4331526C2 (en) 1998-07-30
    DE59303090D1 (en) 1996-08-01

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