EP0056857B1 - Material for electrical contacts - Google Patents

Material for electrical contacts Download PDF

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Publication number
EP0056857B1
EP0056857B1 EP81110185A EP81110185A EP0056857B1 EP 0056857 B1 EP0056857 B1 EP 0056857B1 EP 81110185 A EP81110185 A EP 81110185A EP 81110185 A EP81110185 A EP 81110185A EP 0056857 B1 EP0056857 B1 EP 0056857B1
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EP
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Prior art keywords
oxide
weight
gew
germanium
electrical contacts
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EP81110185A
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German (de)
French (fr)
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EP0056857A1 (en
Inventor
Wolfgang Dr. Böhm
Roger Wolmer
Willi Malikowski
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Evonik Operations GmbH
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Degussa GmbH
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Application filed by Degussa GmbH filed Critical Degussa GmbH
Priority to AT81110185T priority Critical patent/ATE7979T1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
    • 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

Definitions

  • the invention relates to a material for electrical contacts made of silver, tin oxide and one or more other metal oxides.
  • the object of the invention was to provide a material for electrical contacts made of silver, tin oxide and one or more other metal oxides, which has a long service life, an even lower tendency to weld and even lower temperatures when switching compared to the known contact materials.
  • the material contains 0.05 to 4% by weight of molybdenum oxide and / or germanium oxide.
  • the proportion of tin oxide is preferably 8-20% by weight.
  • 0.05 to 0.9% by weight of molybdenum oxide and 0.05 to 1.5% by weight of germanium oxide have proven to be preferred addition amounts. It is also possible to add about 0.2% by weight of tungsten oxide without losing the improved properties.
  • the materials based on AgSn0 2 with additions of molybdenum oxide and / or germanium oxide can be produced by powder metallurgy both by pressing and sintering individual contact pieces and by extruding sintered bolts.
  • Another special advantage of germanium oxide is that due to the solubility of germanium in silver, this additive can also be easily used for internally oxidized material.
  • Experimental concentrations of 0.1% Ge to AgSn 7.5 resulted in a uniform excretion of the metal oxides in the material. There was no formation of a covering layer.
  • germanium significantly accelerates the internal oxidation and that oxidation rates as with Ag / CdO can be achieved.
  • the maximum internally oxidizable base content is increased by adding germanium and thus the security against welding is improved.

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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)

Description

Die Erfindung betrifft einen Werkstoff für elektrische Kontakte aus Silber, Zinnoxid und einem oder mehreren weiteren Metalloxiden.The invention relates to a material for electrical contacts made of silver, tin oxide and one or more other metal oxides.

Für die Herstellung von elektrischen Kontaktstücken hat sich für die Vielzahl von Anwendungsfällen SilberKadmiumoxid bisher am besten bewährt. Aufgrund der Umweltbelastung durch Kadmiumoxid (CdO) wird jedoch verstärkt versucht, CdO durch ein anderes Metalloxid zu ersetzen. Bei diesen Untersuchungen zeigte sich, dass Zinnoxid (SnO2) ein geeigneter Ersatz für CdO ist. Aufgrund der höheren thermischen Stabilität von SnO2 gegenüber CdO ergibt sich zudem eine deutlich verminderte Abbrandrate, die zur längeren Lebensdauer im Schaltgerät führt. Ein sehr wesentlicher Nachteil von Ag/Sn02-Kontakten besteht jedoch darin, dass der Uebergangswiderstand am Kontakt nach einigen tausend Schaltungen durch Deckschichtbildung zu hoch wird. Dies führt dann in der Regel zu erhöhten Temperaturen (Uebertemperaturen) im Schaltgerät, die zur Zerstörung des Gerätes führen können und somit unzulässig sind.Up to now, silver-cadmium oxide has proven to be the best for the production of electrical contact pieces for a large number of applications. However, due to the environmental impact of cadmium oxide (CdO), efforts are increasingly being made to replace CdO with another metal oxide. These investigations showed that tin oxide (SnO 2 ) is a suitable replacement for CdO. Due to the higher thermal stability of SnO 2 compared to CdO, there is also a significantly reduced burn rate, which leads to a longer service life in the switchgear. A very important disadvantage of Ag / Sn0 2 contacts, however, is that the transition resistance at the contact becomes too high after a few thousand switching operations due to the formation of a covering layer. This then usually leads to increased temperatures (excessive temperatures) in the switching device, which can lead to the destruction of the device and are therefore inadmissible.

Ein weiterer Nachteil dieser Ag/SnO2-Werkstoffe gegenüber Ag/CdO-Werkstoffen besteht in der geringeren Sicherheit gegen Verschweissen. Die Kräfte, die zum Zerreissen der Schweissbrücken erforderlich sind, sind teilweise doppelt so hoch wie die bei Ag/CdO-Kontakten. Damit besteht die Gefahr von Schaltstörungen bei Einsatz von Ag/Sn02,Another disadvantage of these Ag / SnO 2 materials compared to Ag / CdO materials is the lower security against welding. The forces required to tear the welding bridges are sometimes twice as high as with Ag / CdO contacts. There is therefore a risk of switching faults when using Ag / Sn0 2 ,

Es ist daher versucht worden, durch den Zusatz weiterer Metalloxide zu Ag/Sn02 die Verschweißsicherheit zu erhöhen, wobei beispielsweise Wismutoxid (DE-OS 27 54 335) oder Indiumoxid (DE-OS 24 28 147) verwendet werden. Diese Zusätze verbessern zwar die Verschweißsicherheit bedingen jedoch eine erhöhte Temperatur am Kontakt und am Schaltgerät, was die Lebensdauer der Geräte beeinträchtigt.Attempts have therefore been made to increase the welding security by adding further metal oxides to Ag / Sn0 2 , bismuth oxide (DE-OS 27 54 335) or indium oxide (DE-OS 24 28 147) being used, for example. Although these additives improve welding security, they require an increased temperature on the contact and on the switching device, which affects the service life of the devices.

Durch Zusatz von Wolframoxid (W03) zu Ag/Sn02 kann man erreichen (DE-AS 29 33 338), dass sowohl die Uebertemperatur als auch die Verschweisskraft gegenüber Ag/Sn02 vermindert werden. Dadurch erhält man einen mit Ag/CdO vergleichbaren Kontaktwerkstoff, der sogar eine erheblich höhere Lebensdauer erreicht. Wünschenswert sind jedoch Kontaktwerkstoffe, die noch geringere Verschweissneigungen und geringere Uebertemperaturen zeigen.By adding tungsten oxide (W0 3 ) to Ag / Sn0 2 it can be achieved (DE-AS 29 33 338) that both the excess temperature and the welding force compared to Ag / Sn0 2 are reduced. This results in a contact material comparable to Ag / CdO, which even achieves a considerably longer service life. However, contact materials that show even lower tendencies to weld and lower excess temperatures are desirable.

Aufgabe der Erfindung war es, einen Werkstoff für elektrische Kontakte aus Silber, Zinnoxid und einem oder mehreren weiteren Metalloxiden zu schaffen, der eine hohe Lebensdauer besitzt, eine noch geringere Verschweißneigung und noch niedrigere Temperaturen beim Schalten gegenüber den bekannten Kontaktwerkstoffen aufweist.The object of the invention was to provide a material for electrical contacts made of silver, tin oxide and one or more other metal oxides, which has a long service life, an even lower tendency to weld and even lower temperatures when switching compared to the known contact materials.

Diese Aufgabe wurde erfindungsgemäss dadurch gelöst, dass der Werkstoff 0,05 bis 4 Gew.% Molybdänoxid und/oder Germaniumoxid enthält. Vorzugsweise beträgt der Anteil an Zinnoxid 8-20 Gew.%.This object was achieved according to the invention in that the material contains 0.05 to 4% by weight of molybdenum oxide and / or germanium oxide. The proportion of tin oxide is preferably 8-20% by weight.

Es wurde überraschenderweise gefunden, dass Molybdänoxid und vor allem Germaniumoxid die Uebertemperatur im Schaltgerät gegenüber Wolframoxid noch weiter absenken und auch die Verschweisskraft merklich vermindern, obwohl weder die Schmelz-, Siede- und Sublimationspunkte noch die Go-Werte ein solches Verhalten dieser beiden Oxide nahelegen. Andere Metalloxide mit dem Wolframoxid ähnlicheren thermodynamischen Eigenschaften steigern nämlich die Uebertemperatur.It was surprisingly found that molybdenum oxide and above all germanium oxide lower the excess temperature in the switching device compared to tungsten oxide and also noticeably reduce the welding force, although neither the melting, boiling and sublimation points nor the G o values suggest such behavior of these two oxides . Other metal oxides with thermodynamic properties similar to the tungsten oxide increase the excess temperature.

Als bevorzugte Zusatzmengen haben sich 0,05 bis 0,9 Gew.% Molybdänoxid und 0,05 bis 1,5 Gew.% Germaniumoxid erwiesen. Auch ist es möglich, etwa 0,2 Gew.% Wolframoxid beizugeben, ohne dass die verbesserten Eigenschaften verloren gehen.0.05 to 0.9% by weight of molybdenum oxide and 0.05 to 1.5% by weight of germanium oxide have proven to be preferred addition amounts. It is also possible to add about 0.2% by weight of tungsten oxide without losing the improved properties.

Die Werkstoffe auf der Basis AgSn02 mit Zusätzen von Molybdän-Oxid und/oder Germanium-Oxid können pulvermetallurgisch sowohl durch Pressen und Sintern von Einzelkontaktstücken als auch durch Strangpressen gesinterter Bolzen hergestellt werden. Bei Germaniumoxid kommt als weiterer besonderer Vorteil hinzu, dass aufgrund der Löslichkeit von Germanium in Silber dieser Zusatz auch leicht für innerlich oxidiertes Material vorgesehen werden kann. Versuchsweise eingebrachte Konzentrationen von 0,1 % Ge zu AgSn 7,5 ergaben eine gleichmässige Ausscheidung der Metalloxide im Werkstoff. Eine Deckschichtbildung trat nicht ein. Ueberraschenderweise wurde sogar gefunden, dass Germanium eine deutliche Beschleunigung der inneren Oxidation bewirkt und Oxidationsgeschwindigkeiten wie bei Ag/CdO erreicht werden. Ausserdem wird durch einen Germaniumzusatz der maximal innerlich oxidierbare Unedelgehalt erhöht und damit die Sicherheit gegen Verschweissen verbessert.The materials based on AgSn0 2 with additions of molybdenum oxide and / or germanium oxide can be produced by powder metallurgy both by pressing and sintering individual contact pieces and by extruding sintered bolts. Another special advantage of germanium oxide is that due to the solubility of germanium in silver, this additive can also be easily used for internally oxidized material. Experimental concentrations of 0.1% Ge to AgSn 7.5 resulted in a uniform excretion of the metal oxides in the material. There was no formation of a covering layer. Surprisingly, it was even found that germanium significantly accelerates the internal oxidation and that oxidation rates as with Ag / CdO can be achieved. In addition, the maximum internally oxidizable base content is increased by adding germanium and thus the security against welding is improved.

Es werden folgende Beispiele für den erfindungsgemässen Werkstoff angegeben :

  • 1. Ein Werkstoff mit 88 Gew.% Ag, 11,5 Gew.% Sn02 und 0,5 Gew.% Mo03 wird pulvermetallurgisch hergestellt und durch Pressen, Sintern und Nachpressen zu Kontaktauflagen verarbeitet.
  • 2. Eine Legierung aus Silber mit Zinn und Germanium wird zu Blech von 3 mm Dicke verarbeitet und bei 820 °C 30 Stunden bei 9 bar mit Sauerstoff innerlich oxidiert, wobei ein Werkstoff mit 88 Gew.% Ag, 11,5 Gew.% Sn02 und 0,5 Gew.% Ge02 entsteht..
  • 3. Ein Gemisch aus 88 Gew.% Ag, 11,5 Gew.% Sn02, 0,3 Gew.% Mo03 und 0,2 Gew.% Ge02 wird auf bekannte Weise pulvermetallurgisch verarbeitet und zu Kontaktauflagen verpresst.
  • 4. Ein Gemisch aus 88 Gew.% Ag, 11,3 Gew.% Sn02, 0,2 Gew.% W03, 0,3 Gew.% Mo03 und 0,2 Gew.% Ge02 wird auf bekannter Weise zu Kontaktauflagen verarbeitet.
  • 5. Die Schaltversuche dieser Werkstoffe zeigt die folgende Tabelle, wobei einige bekannte Kontaktwerkstoffe zum Vergleich herangezogen werden.
    Figure imgb0001
The following examples are given for the material according to the invention:
  • 1. A material with 88% by weight of Ag, 11.5% by weight of Sn0 2 and 0.5% by weight of Mo03 is produced by powder metallurgy and processed into contact layers by pressing, sintering and subsequent pressing.
  • 2. An alloy of silver with tin and germanium is processed to sheet 3 mm thick and internally oxidized at 820 ° C. for 30 hours at 9 bar with oxygen, a material with 88% by weight Ag, 11.5% by weight Sn0 2 and 0.5 wt.% Ge0 2 is formed ..
  • 3. A mixture of 88% by weight of Ag, 11.5% by weight of Sn0 2 , 0.3% by weight of Mo03 and 0.2% by weight of Ge0 2 is processed in a known manner by powder metallurgy and pressed into contact layers.
  • 4. A mixture of 88 wt.% Ag, 11.3 wt.% Sn0 2 , 0.2 wt.% W0 3 , 0.3 wt.% Mo03 and 0.2 wt.% Ge0 2 is added in a known manner Contact orders processed.
  • 5. The switching tests of these materials are shown in the following table, whereby some known contact materials are used for comparison.
    Figure imgb0001

Claims (5)

1. A material for electrical contacts which consists of silver, tin oxide and one or more other metal oxides, characterised in that it contains from 0.05 to 4 % by weight of molybdenum oxide (Mo03) and/or germanium oxide (GeO2).
2. A material according to claim 1, characterised in that the proportion of tin oxide is from 8 to 20 %, by weight.
3. A material according to claim 1 or 2, characterised in that the proportion of molybdenum oxide (Mo03) is from 0.05 to 0.9 %, by weight.
4. A material according to one of claims 1 to 3, characterised in that the proportion of germanium oxide (GeO2) is from 0.05 to 1.5 %, by weight.
5. A material according to one of claims 1 to 4, characterised in that it contains a proportion of about 0.2 %, by weight of tungsten oxide (WO3).
EP81110185A 1981-01-23 1981-12-05 Material for electrical contacts Expired EP0056857B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81110185T ATE7979T1 (en) 1981-01-23 1981-12-05 MATERIAL FOR ELECTRICAL CONTACTS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19813102067 DE3102067A1 (en) 1981-01-23 1981-01-23 MATERIAL FOR ELECTRICAL CONTACTS
DE3102067 1981-01-23

Publications (2)

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EP0056857A1 EP0056857A1 (en) 1982-08-04
EP0056857B1 true EP0056857B1 (en) 1984-06-13

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ID=6123147

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US (1) US4410491A (en)
EP (1) EP0056857B1 (en)
JP (1) JPS57143460A (en)
AR (1) AR227957A1 (en)
AT (1) ATE7979T1 (en)
AU (1) AU544021B2 (en)
BR (1) BR8200159A (en)
CA (1) CA1183373A (en)
CS (1) CS231185B2 (en)
DE (2) DE3102067A1 (en)
DK (1) DK149786C (en)
ES (1) ES8305528A1 (en)
HU (1) HU186467B (en)
MX (1) MX7462E (en)
NO (1) NO157317C (en)
PL (1) PL137714B1 (en)
PT (1) PT74022B (en)
YU (1) YU43508B (en)
ZA (1) ZA82349B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4331526C3 (en) * 1992-09-16 2003-11-06 Ami Doduco Gmbh Material for electrical contacts based on silver-tin oxide or silver-zinc oxide and method for producing a composite powder therefor

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3232627A1 (en) * 1981-09-24 1983-04-07 Doduco KG Dr. Eugen Dürrwächter, 7530 Pforzheim Material for electrical contacts
DE3304637A1 (en) * 1983-02-10 1984-08-16 Siemens AG, 1000 Berlin und 8000 München SINTER CONTACT MATERIAL FOR LOW VOLTAGE SWITCHGEAR
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
DE3466122D1 (en) * 1984-01-30 1987-10-15 Siemens Ag Contact material and production of electric contacts
DE3435289A1 (en) * 1984-09-26 1986-04-03 Wilo-Werk Gmbh & Co Pumpen- Und Apparatebau, 4600 Dortmund Connecting box for a pump motor
US4817695A (en) * 1987-12-02 1989-04-04 Wingert Philip C Electrical contact material of Ag, SnO2, GeO2 and In2 O.sub.3
US4904317A (en) * 1988-05-16 1990-02-27 Technitrol, Inc. Erosion resistant Ag-SnO2 electrical contact material
JP2896428B2 (en) * 1992-06-10 1999-05-31 ドドウコ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・ウント・コンパニー・ドクトル・オイゲン・デュルベヒテル Material and manufacturing method for electrical contact having silver and tin oxide or silver and zinc oxide as main components
US5258052A (en) * 1992-06-18 1993-11-02 Advanced Metallurgy Incorporated Powder metallurgy silver-tin oxide electrical contact material
FR2893632B1 (en) * 2005-11-18 2008-01-25 Commissariat Energie Atomique SULFURIZED RESISTANT SILVER COATING, DEPOSITION METHOD AND USE
CN109252064B (en) * 2018-10-15 2020-05-22 浙江工业大学 Doped modified Ag/SnO2Composite electric contact material and preparation method thereof

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US3933485A (en) * 1973-07-20 1976-01-20 Chugai Denki Kogyo Kabushiki-Kaisha Electrical contact material
US3933486A (en) * 1974-02-12 1976-01-20 Chugai Denki Kogyo Kabushiki-Kaisha Silver-metal oxide composite and method of manufacturing the same
JPS51121795A (en) * 1975-04-17 1976-10-25 Nippon Tungsten Co Ltd Ag-tin oxide-system electric contact material
JPS523193A (en) * 1975-06-24 1977-01-11 Sumitomo Electric Ind Ltd Electric contact material
US4141727A (en) * 1976-12-03 1979-02-27 Matsushita Electric Industrial Co., Ltd. Electrical contact material and method of making the same
DE2659012C3 (en) * 1976-12-27 1980-01-24 Siemens Ag, 1000 Berlin Und 8000 Muenchen Process for producing a sintered contact material from silver and embedded metal oxides
DE2933338C3 (en) * 1979-08-17 1983-04-28 Degussa Ag, 6000 Frankfurt Material for electrical contacts and process for their manufacture

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4331526C3 (en) * 1992-09-16 2003-11-06 Ami Doduco Gmbh Material for electrical contacts based on silver-tin oxide or silver-zinc oxide and method for producing a composite powder therefor

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Publication number Publication date
ZA82349B (en) 1982-12-29
CA1183373A (en) 1985-03-05
BR8200159A (en) 1982-11-03
AU7798681A (en) 1982-07-29
PL234697A1 (en) 1982-10-25
AU544021B2 (en) 1985-05-16
NO157317C (en) 1988-02-24
DE3102067A1 (en) 1982-08-19
ES508715A0 (en) 1983-04-01
PT74022B (en) 1983-04-29
DK149786C (en) 1987-04-13
YU43508B (en) 1989-08-31
DK149786B (en) 1986-09-29
ATE7979T1 (en) 1984-06-15
JPS57143460A (en) 1982-09-04
JPH0325493B2 (en) 1991-04-08
US4410491A (en) 1983-10-18
NO157317B (en) 1987-11-16
MX7462E (en) 1988-12-22
CS231185B2 (en) 1984-10-15
ES8305528A1 (en) 1983-04-01
DE3164233D1 (en) 1984-07-19
EP0056857A1 (en) 1982-08-04
AR227957A1 (en) 1982-12-30
HU186467B (en) 1985-08-28
YU302681A (en) 1983-12-31
DK21982A (en) 1982-07-24
PL137714B1 (en) 1986-07-31
CS842681A2 (en) 1984-02-13
NO814101L (en) 1982-07-26
PT74022A (en) 1981-12-01

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