EP0774529A1 - Silver-iron material for electrical switch contacts - Google Patents

Silver-iron material for electrical switch contacts Download PDF

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Publication number
EP0774529A1
EP0774529A1 EP96117210A EP96117210A EP0774529A1 EP 0774529 A1 EP0774529 A1 EP 0774529A1 EP 96117210 A EP96117210 A EP 96117210A EP 96117210 A EP96117210 A EP 96117210A EP 0774529 A1 EP0774529 A1 EP 0774529A1
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Prior art keywords
oxide
silver
iron
weight
materials
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EP96117210A
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German (de)
French (fr)
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EP0774529B1 (en
Inventor
Wolfgang Dr. Weise
Willi Malikowski
Roger Wolmer
Peter Dr. Braumann
Andreas Koffler
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Evonik Operations GmbH
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Degussa GmbH
Degussa Huels AG
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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
    • 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

Definitions

  • the invention relates to silver-iron materials with further oxidic additives for electrical switch contacts.
  • Contact materials for use in electrical power engineering must have high erosion resistance, low welding force and low contact resistance.
  • the composite material silver-nickel has proven itself for switching currents of less than 100A. It has a high erosion resistance with very good excess temperature behavior.
  • a disadvantage of this material is that nickel, particularly in the form of dusts, can have harmful effects on the human organism.
  • Various iron has been proposed as an alternative to nickel.
  • DE-OS 38 16 895 describes the use of a silver-iron material for electrical contacts which, in addition to silver, contains 3 to 30% by weight of iron and a total of 0.05 to 5% by weight of one or more of the additives manganese, Contains copper, zinc, antimony, bismuth oxide, molybdenum oxide, tungsten oxide and chromium nitride. These materials show a significantly better overtemperature behavior with a good service life compared to simple silver-iron materials, but are still below the values of corresponding silver-nickel materials.
  • contact materials are disclosed, which besides Silver can contain 5 to 50% by weight of iron and up to 5% by weight of one or more of the oxides titanium oxide, zirconium oxide, niobium oxide, tantalum oxide, molybdenum oxide, tungsten oxide, manganese oxide, copper oxide and zinc oxide.
  • a contact material is known which contains iron oxide, zirconium oxide and tungsten oxide in addition to silver.
  • EP-PS 0 586 411 describes a contact material made of silver with 1 to 50% by weight of iron and 0.01 to 5% by weight of rhenium.
  • the materials consist of 0.5 to 4.5% by weight of iron and 0.05 to 2% by weight of one or more of the oxidic additives magnesium oxide, calcium oxide, yttrium oxide, lanthanum oxide, titanium oxide, zirconium oxide, Hafnium oxide, cerium oxide, niobium oxide, tantalum oxide, chromium oxide, manganese oxide, iron oxide, zinc oxide, aluminum oxide, indium oxide, silicon oxide and tin oxide, the rest being silver.
  • the oxidic additives magnesium oxide, calcium oxide, yttrium oxide, lanthanum oxide, titanium oxide, zirconium oxide, Hafnium oxide, cerium oxide, niobium oxide, tantalum oxide, chromium oxide, manganese oxide, iron oxide, zinc oxide, aluminum oxide, indium oxide, silicon oxide and tin oxide, the rest being silver.
  • oxidic components Preferably, 0.2 to 1.5% by weight of oxidic components are added.
  • the materials contain 0.2 to 1.2% by weight of magnesium oxide, calcium oxide, yttrium oxide, lanthanum oxide, titanium oxide, zirconium oxide, hafnium oxide, cerium oxide, niobium oxide, tantalum oxide, aluminum oxide and silicon oxide.
  • the iron content is between 0.5 and 2.5% by weight.
  • the silver-iron materials used to date with further additives normally contained between 10 and 20% by weight of iron.
  • the reduction in the iron content is accompanied by an improvement in the excess temperature behavior.
  • the welding behavior and the service life deteriorate as the iron content decreases.
  • the addition of the oxides mentioned in amounts between 0.05 to 2% by weight increases the service life and welding reliability disproportionately without the excess temperature value being impaired. It is advantageous for the overtemperature behavior if the iron content is below 4.5%.
  • the materials are resistance weldable and connections with copper base materials show high connection strengths. Materials whose iron content is less than 2.5% by weight and the amount of oxidic additives less than 1.2% by weight have proven particularly useful.
  • the materials can be manufactured economically and are comparable in their switching properties with the silver-nickel material, in particular the overtemperature shows values that the silver-nickel materials also achieve.
  • the materials are manufactured by powder metallurgy by mixing the corresponding powders, cold isostatic pressing, sintering and extrusion to form wires or profiles.

Abstract

Silber-Eisen-Werkstoffe für elektrische Schaltkontakte mit Eigenschaften, die den Silber-Nickel-Werkstoffen sehr nahe kommen, bestehen aus 0,5 bis 4,5 Gew.% Eisen und 0,05 bis 2 Gew.% eines oder mehrerer der Oxide Magnesiumoxid, Calziumoxid, Yttriumoxid, Lanthanoxid, Titanoxid, Zirkoniumoxid, Hafniumoxid, Ceroxid, Nioboxid, Tantaloxid, Chromoxid, Manganoxid, Eisenoxid, Zinkoxid, Aluminiumoxid, Indiumoxid, Siliziumoxid und Zinnoxid, Rest Silber.Silver-iron materials for electrical switch contacts with properties that come very close to the silver-nickel materials consist of 0.5 to 4.5% by weight of iron and 0.05 to 2% by weight of one or more of the oxides magnesium oxide , Calcium oxide, yttrium oxide, lanthanum oxide, titanium oxide, zirconium oxide, hafnium oxide, cerium oxide, niobium oxide, tantalum oxide, chromium oxide, manganese oxide, iron oxide, zinc oxide, aluminum oxide, indium oxide, silicon oxide and tin oxide, the rest silver.

Description

Die Erfindung betrifft Silber-Eisen-Werkstoffe mit weiteren oxidischen Zusätzen für elektrische Schaltkontakte.The invention relates to silver-iron materials with further oxidic additives for electrical switch contacts.

Kontaktwerkstoffe für den Einsatz in der elektrischen Energietechnik müssen eine hohe Abbrandfestigkeit, geringe Verschweißkraft und niedrigen Kontaktwiderstand aufweisen. Für luftoffene Schaltgeräte der Niederspannungstechnik hat sich für Schaltströme von kleiner als 100A der Verbundwerkstoff Silber-Nickel bewährt. Er besitzt eine hohe Abbrandfestigkeit bei sehr gutem Übertemperaturverhalten.Contact materials for use in electrical power engineering must have high erosion resistance, low welding force and low contact resistance. For air-tight switchgear in low-voltage technology, the composite material silver-nickel has proven itself for switching currents of less than 100A. It has a high erosion resistance with very good excess temperature behavior.

Ein Nachteil dieses Werkstoffes liegt jedoch darin, daß Nickel insbesondere in Form von Stäuben schädliche Auswirkungen auf den menschlichen Organismus haben kann. Als Alternative zu Nickel ist verschiedentlich Eisen vorgeschlagen worden.A disadvantage of this material, however, is that nickel, particularly in the form of dusts, can have harmful effects on the human organism. Various iron has been proposed as an alternative to nickel.

In der DE-OS 38 16 895 wird die Verwendung eines Silber-Eisen-Werkstoffs für elektrische Kontakte beschrieben, der neben Silber 3 bis 30 Gew.% Eisen und insgesamt 0,05 bis 5 Gew.% von einem oder mehreren der Zusätze Mangan, Kupfer, Zink, Antimon, Wismutoxid, Molybdänoxid, Wolframoxid und Chromnitrid enthält. Diese Werstoffe zeigen ein deutlich besseres Übertemperaturverhalten bei guter Lebensdauer gegenüber einfachen Silber-Eisen-Werkstoffen, liegen jedoch noch unter den Werten entsprechender Silber-Nickel-Werkstoffe.DE-OS 38 16 895 describes the use of a silver-iron material for electrical contacts which, in addition to silver, contains 3 to 30% by weight of iron and a total of 0.05 to 5% by weight of one or more of the additives manganese, Contains copper, zinc, antimony, bismuth oxide, molybdenum oxide, tungsten oxide and chromium nitride. These materials show a significantly better overtemperature behavior with a good service life compared to simple silver-iron materials, but are still below the values of corresponding silver-nickel materials.

Das gilt auch für weitere bekannte Kontaktwerkstoffe auf der Basis Silber-Eisen. In der DE-OS 39 11 904 werden beispielsweise Kontaktwerkstoffe geoffenbart, die neben Silber 5 bis 50 Gew.% Eisen und bis zu 5 Gew.% eines oder mehrerer der Oxide Titanoxid, Zirkoniumoxid, Nioboxid, Tantaloxid, Molybdänoxid, Wolframoxid, Manganoxid, Kupferoxid und Zinkoxid enthalten kann. Aus der DE-OS 43 43 550 ist ein Kontaktwerkstoff bekannt, der neben Silber Eisenoxid, Zirkoniumoxid und Wolframoxid enthält. In der EP-PS 0 586 411 wird ein Kontaktwerkstoff aus Silber mit 1 bis 50 Gew.% Eisen und 0,01 bis 5 Gew.% Rhenium beschrieben.This also applies to other known contact materials based on silver-iron. In DE-OS 39 11 904, for example, contact materials are disclosed, which besides Silver can contain 5 to 50% by weight of iron and up to 5% by weight of one or more of the oxides titanium oxide, zirconium oxide, niobium oxide, tantalum oxide, molybdenum oxide, tungsten oxide, manganese oxide, copper oxide and zinc oxide. From DE-OS 43 43 550 a contact material is known which contains iron oxide, zirconium oxide and tungsten oxide in addition to silver. EP-PS 0 586 411 describes a contact material made of silver with 1 to 50% by weight of iron and 0.01 to 5% by weight of rhenium.

Es war daher Aufgabe der vorliegenden Erfindung, Silber-Eisen-Werkstoffe mit weiteren oxidischen Zusätzen für elektrische Schaltkontakte zu finden, die in ihrer Verschweißneigung, Kontaktwiderstand und Lebensdauer den bekannten Silber-Nickel-Werkstoffen möglichst nahe kommen. Des weiteren muß der Werkstoff wirtschaftlich als Draht herstellbar sein und durch Widerstandschweißen auf Kontaktträgerstoffe aufgeschweißt werden können.It was therefore an object of the present invention to find silver-iron materials with further oxidic additives for electrical switch contacts, the welding tendency, contact resistance and service life of which are as close as possible to the known silver-nickel materials. Furthermore, the material must be economically producible as a wire and must be able to be welded onto contact carrier materials by resistance welding.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß die Werkstoffe aus 0,5 bis 4,5 Gew.% Eisen und 0,05 bis 2 Gew.% von einem oder mehreren der oxidischen Zusätze Magnesiumoxid, Calziumoxid, Yttriumoxid, Lanthanoxid, Titanoxid, Zirkoniumoxid, Hafniumoxid, Ceroxid, Nioboxid, Tantaloxid, Chromoxid, Manganoxid, Eisenoxid, Zinkoxid, Aluminiumoxid, Indiumoxid, Siliziumoxid und Zinnoxid, Rest Silber, bestehen.According to the invention, this object is achieved in that the materials consist of 0.5 to 4.5% by weight of iron and 0.05 to 2% by weight of one or more of the oxidic additives magnesium oxide, calcium oxide, yttrium oxide, lanthanum oxide, titanium oxide, zirconium oxide, Hafnium oxide, cerium oxide, niobium oxide, tantalum oxide, chromium oxide, manganese oxide, iron oxide, zinc oxide, aluminum oxide, indium oxide, silicon oxide and tin oxide, the rest being silver.

Vorzugsweise setzt man 0,2 bis 1,5 Gew.% oxidische Bestandteile zu.Preferably, 0.2 to 1.5% by weight of oxidic components are added.

Besonders bewährt hat es sich, wenn die Werkstoffe 0,2 bis 1,2 Gew.% Magnesiumoxid, Calziumoxid, Yttriumoxid, Lanthanoxid, Titanoxid, Zirkoniumoxid, Hafniumoxid, Ceroxid, Nioboxid, Tantaloxid, Aluminiumoxid und Siliziumoxid enthalten.It has proven particularly useful if the materials contain 0.2 to 1.2% by weight of magnesium oxide, calcium oxide, yttrium oxide, lanthanum oxide, titanium oxide, zirconium oxide, hafnium oxide, cerium oxide, niobium oxide, tantalum oxide, aluminum oxide and silicon oxide.

Es ist weiterhin von Vorteil, wenn der Eisengehalt zwischen 0,5 und 2,5 Gew.% liegt.It is also advantageous if the iron content is between 0.5 and 2.5% by weight.

Die bisher verwendeten Silber-Eisenwerkstoffe mit weiteren Zusätzen enthielten normalerweise zwischen 10 und 20 Gew.% Eisen. Es hat sich aber gezeigt, daß mit der Reduzierung des Eisengehaltes eine Verbesserung des Übertemperaturverhalten einhergeht. Gleichzeitig wird aber das Verschweißverhalten und die Lebensdauer mit abnehmendem Eisen-Gehalt verschlechtert. Überraschenderweise hat es sich nun gezeigt, daß durch Zusatz genannter Oxide in Mengen zwischen 0,05 bis 2 Gew.% die Lebensdauer und Verschweißsicherheit überproportional steigen, ohne das der Übertemperaturwert verschlechtert wird. Dabei ist es für das Übertemperaturverhalten von Vorteil, wenn der Eisen-Gehalt unter 4,5 % liegt. Die Werkstoffe sind widerstandsschweißbar und Verbindungen mit Kupfer-Trägerwerkstoffen zeigen hohe Verbindungsfestigkeiten. Besonders bewährt haben sich Werkstoffe, deren Eisen-Gehalt unter 2,5 Gew.% und die Menge der oxidischen Zusätze unter 1,2 Gew.% liegen.The silver-iron materials used to date with further additives normally contained between 10 and 20% by weight of iron. However, it has been shown that the reduction in the iron content is accompanied by an improvement in the excess temperature behavior. At the same time, however, the welding behavior and the service life deteriorate as the iron content decreases. Surprisingly, it has now been shown that the addition of the oxides mentioned in amounts between 0.05 to 2% by weight increases the service life and welding reliability disproportionately without the excess temperature value being impaired. It is advantageous for the overtemperature behavior if the iron content is below 4.5%. The materials are resistance weldable and connections with copper base materials show high connection strengths. Materials whose iron content is less than 2.5% by weight and the amount of oxidic additives less than 1.2% by weight have proven particularly useful.

Die Werkstoffe lassen sich wirtschaftlich herstellen und sind in allen Schalteigenschaften mit dem Silber-Nickel-Wersktoff vergleichbar, insbesondere die Übertemperatur zeigt Werte, die auch die Silber-Nickel-Werkstoffe erzielen.The materials can be manufactured economically and are comparable in their switching properties with the silver-nickel material, in particular the overtemperature shows values that the silver-nickel materials also achieve.

Dies wurde durch elektrische Schaltversuche in serienmäßigen Schützen nachgewiesen. Die Versuche wurden in einem 5,5 KW-Schütz unter den Schaltbedingungen AC1 nach DIN VDE 0660 durchgeführt. Die Übertemperaturmessung erfolgte an den Kontaktbrücken bei einer Strombelastung von 20 A und wurde jeweils nach 200.000 Schaltungen gemessen. Die Werkstoffe und die Ergebnisse der mit diesen Werkstoffen durchgeführten Schaltversuche nach einer Gesamtschaltbelastung von 600.000 Schaltspielen sind in folgender Tabelle enthalten und zeigen die Verbesserung der erfindungsgemäßen Werkstoffe hinsichtlich der Kontakterwärmung gegenüber den bekannten Werkstoffen AgNi20 und AgFe8,5Zn1,5. Tabelle Werkstoff Mittlere Übertemperatur in K AgNi20 90 AgFe8,5Zn1,5 116 AgFe4MgO1 95 AgFe2MgO0,5 87 AgFe4Y2O3 1 100 AgFe2Y2O30,5 88 AgFe4CeO1 102 AgFe2CeO0,5 91 AgFe4Ta2O51 109 AgFe2Ta2O50,5 99 AgFe4ZnO1 107 AgFe2ZnO0,5 98 AgFe4Al2O31 102 AgFe2Al2O30,5 91 AgFe4SnO21 107 AgFe2SnO20,5 97 AgFe2SiO20,5 94 This has been proven by electrical switching tests in standard contactors. The tests were carried out in a 5.5 KW contactor under the switching conditions AC1 according to DIN VDE 0660. The overtemperature measurement was carried out at the contact bridges at a current load of 20 A and was measured after every 200,000 switching operations. The materials and the results of the switching tests carried out with these materials after a total switching load of 600,000 switching cycles are shown in the following table and show the improvement in Materials according to the invention with regard to contact heating compared to the known materials AgNi20 and AgFe8.5Zn1.5. table material Average overtemperature in K AgNi20 90 AgFe8.5Zn1.5 116 AgFe4MgO1 95 AgFe2MgO0.5 87 AgFe4Y 2 O 3 1 100 AgFe2Y 2 O 3 0.5 88 AgFe4CeO1 102 AgFe2CeO0.5 91 AgFe4Ta 2 O 5 1 109 AgFe2Ta 2 O 5 0.5 99 AgFe4ZnO1 107 AgFe2ZnO0.5 98 AgFe4Al 2 O 3 1 102 AgFe2Al 2 O 3 0.5 91 AgFe4SnO 2 1 107 AgFe2SnO 2 0.5 97 AgFe2SiO 2 0.5 94

Die Herstellung der Werkstoffe erfolgt pulvermetallurgisch durch Mischen der entsprechenden Pulver, kaltisostatischem Pressen, Sintern und Strangpressen zu Drähten oder Profilen.The materials are manufactured by powder metallurgy by mixing the corresponding powders, cold isostatic pressing, sintering and extrusion to form wires or profiles.

Claims (4)

Silber-Eisen-Werkstoffe mit weiteren oxidischen Zusätzen für elektrische Schaltkontakte,
dadurch gekennzeichnet,
daß sie aus 0,5 bis 4,5 Gew.% Eisen und 0,05 bis 2 Gew.% von einem oder mehreren der oxidischen Zusätze Magnesiumoxid, Calziumoxid, Yttriumoxid, Lanthanoxid, Titanoxid, Zirkoniumoxid, Hafniumoxid, Ceroxid, Nioboxid, Tantaloxid, Chromoxid, Manganoxid, Eisenoxid, Zinkoxid, Aluminiumoxid, Indiumoxid, Siliziumoxid und Zinnoxid, Rest Silber, bestehen.Silver-iron materials with further oxidic additives for electrical switch contacts,
characterized by
that they consist of 0.5 to 4.5% by weight of iron and 0.05 to 2% by weight of one or more of the oxidic additives magnesium oxide, calcium oxide, yttrium oxide, lanthanum oxide, titanium oxide, zirconium oxide, hafnium oxide, cerium oxide, niobium oxide, tantalum oxide, Chromium oxide, manganese oxide, iron oxide, zinc oxide, aluminum oxide, indium oxide, silicon oxide and tin oxide, the rest silver. Silber-Eisen-Werkstoffe nach Anspruch 1,
dadurch gekennzeichnet,
daß sie 0,2 bis 1,5 Gew.% oxidischer Bestandteile enthalten.Silver-iron materials according to claim 1,
characterized by
that they contain 0.2 to 1.5% by weight of oxidic constituents. Silber-Eisen-Werkstoffe nach Anspruch 1,
dadurch gekennzeichnet,
daß sie 0,2 bis 1,2 Gew.% Magnesiumoxid, Calziumoxid, Yttriumoxid, Lanthanoxid, Titanoxid, Zirkoniumoxid, Ceroxid, Nioboxid, Tantaloxid, Aluminiumoxid und Siliziumoxid enthalten.Silver-iron materials according to claim 1,
characterized by
that they contain 0.2 to 1.2% by weight of magnesium oxide, calcium oxide, yttrium oxide, lanthanum oxide, titanium oxide, zirconium oxide, cerium oxide, niobium oxide, tantalum oxide, aluminum oxide and silicon oxide. Silber-Eisen-Werkstoffe nach Anspruch 1 bis 3,
dadurch gekennzeichnet,
daß der Eisengehalt zwischen 0,5 bis 2,5 Gew.% liegt.Silver-iron materials according to claims 1 to 3,
characterized by
that the iron content is between 0.5 to 2.5% by weight.
EP96117210A 1995-11-20 1996-10-26 Silver-iron material for electrical switch contacts Expired - Lifetime EP0774529B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19543222A DE19543222C1 (en) 1995-11-20 1995-11-20 Silver@-iron material contg. oxide additives
DE19543222 1995-11-20

Publications (2)

Publication Number Publication Date
EP0774529A1 true EP0774529A1 (en) 1997-05-21
EP0774529B1 EP0774529B1 (en) 2000-03-29

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EP96117210A Expired - Lifetime EP0774529B1 (en) 1995-11-20 1996-10-26 Silver-iron material for electrical switch contacts

Country Status (5)

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US (1) US5841044A (en)
EP (1) EP0774529B1 (en)
JP (1) JPH09171735A (en)
DE (2) DE19543222C1 (en)
ES (1) ES2146825T3 (en)

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PATENT ABSTRACTS OF JAPAN vol. 18, no. 377 (C - 1225) 15 July 1994 (1994-07-15) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112760513A (en) * 2020-12-30 2021-05-07 宁波东大神乐电工合金有限公司 Silver tin oxide electrical contact material and preparation process thereof

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DE59604827D1 (en) 2000-05-04
JPH09171735A (en) 1997-06-30
ES2146825T3 (en) 2000-08-16
EP0774529B1 (en) 2000-03-29
US5841044A (en) 1998-11-24
DE19543222C1 (en) 1997-02-20

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