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EP0118717B2 - Sintered material for electrical contacts and its method of manufacture - Google Patents

Sintered material for electrical contacts and its method of manufacture Download PDF

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Publication number
EP0118717B2
EP0118717B2 EP84101010A EP84101010A EP0118717B2 EP 0118717 B2 EP0118717 B2 EP 0118717B2 EP 84101010 A EP84101010 A EP 84101010A EP 84101010 A EP84101010 A EP 84101010A EP 0118717 B2 EP0118717 B2 EP 0118717B2
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EP
European Patent Office
Prior art keywords
oxide
silver
sintered material
moo3
mass content
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EP84101010A
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German (de)
French (fr)
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EP0118717A1 (en
EP0118717B1 (en
Inventor
Horst Prof. Dr. Schreiner
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Siemens AG
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Siemens 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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9265—Special properties
    • Y10S428/929—Electrical contact feature
    • 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
    • Y10T428/1216—Continuous interengaged phases of plural metals, or oriented fiber containing
    • Y10T428/12174—Mo or W containing

Definitions

  • the invention relates to a sintered composite material for electrical contacts made of silver, tin oxide, bismuth oxide, copper oxide and a method for its manufacture.
  • AgCdO has proven itself very well for the production of electrical contact pieces for a large number of applications.
  • the CdO has been classified as a toxic material due to its environmental impact. An attempt is therefore made to replace CdO with another metal oxide.
  • tin oxide (SnO2) is a suitable replacement for cadmium oxide (CdO).
  • AgSnO2 contact materials do not yet have optimal values in all functionally important properties. So z. B. with AgSnO2 contact materials over AgCdO contact materials a firmly adhering oxide layer.
  • EP-A-0 024 349 discloses a material for electrical contacts made of silver, tin oxide and tungsten oxide as a further metal oxide.
  • DE-A-30 17 424 suggests that such a silver-based material with 5 to 20 wt.% Tin oxide and 0.05 to 5 wt.% Tungsten oxide additionally 0.1 to 5 wt.% Contains bismuth oxide. These materials are sintered and compacted from the powder mixture of silver and the individual metal oxides, so that a typical sintered structure with a statistical distribution of the metal oxides results.
  • a material for electrical contacts which consists of silver, tin oxide, bismuth oxide and copper oxide.
  • the copper oxide can optionally be replaced by zinc oxide. Both materials can be produced by the so-called internal oxidation of alloys initially produced, the oxidation taking place essentially by solid-state diffusion of oxygen.
  • a material which contains molybdenum oxide and / or germanium oxide in addition to silver and tin oxide, but no bismuth oxide and copper oxide, it being possible for the molybdenum oxide to be partially replaced by tungsten oxide.
  • This material is either powder metallurgically made from silver and the metal oxides or by internal oxidation of alloy sheets, whereby no statements have been made about the structure formation.
  • the invention has for its object to improve the known CdO-free silver contact pieces in such a way that the optimization of the contact properties with regard to arcing in the arc, low welding force and low contact resistance is made possible.
  • the invention thus provides a material in which the fact that tungsten and / or molybdenum is insoluble in silver is advantageously taken into account. By sublimating the corresponding oxides on the composite particles, the advantages of these metal oxide additives can nevertheless be exploited.
  • the mean particle sizes of the tin oxide, bismuth oxide and copper oxide precipitations in the silver regions are between 0.1 and 5 ⁇ m, in particular between 0.1 ⁇ m and 3 ⁇ m.
  • the tin oxide content is between 6 and 15% by mass
  • the bismuth oxide content is between 0.2 and 2% by weight
  • the copper oxide content is between 0.2 and 2% by weight
  • the proportion of subliming metal oxide additive is between 0.2 and 2% by weight .
  • a powder of particle size ⁇ 200 ⁇ m is produced from an AgSnBiCu alloy with 7.7% tin (Sn), 1% bismuth (Bi) and 1% copper (Cu).
  • a suitable procedure for this is e.g. B. the pressure atomization of the melt of this alloy.
  • the alloy powder obtained is completely internally oxidized, a composite powder of AgSnO2Bi2O3CuO having the appropriate composition being obtained.
  • the internal oxidation is carried out in air. wherein the annealing treatment is started at 500 ° C and is held at 800 ° C after one hour for the same time.
  • the composite powder is mixed with 0.8% by mass of tungsten oxide (WO3) in an agitator ball mill under acetone for one hour and thereby the WO3 is distributed on the surface of the composite powder particles.
  • WO3 tungsten oxide
  • a shaped body is produced by pressing, sintering and hot post-compression, the residual porosity of which is ⁇ 1.5%.
  • the contact properties such as arcing in the arc.
  • Welding force and contact resistance were measured under a condition described in the literature on a test switch and compared with a very good AgCdO quality.
  • the burn-up values are 25% lower, which leads to a corresponding improvement in the service life.
  • a corresponding saving in silver can be achieved by reducing the contact piece volume.
  • the welding force values were in the same range as for AgCdO 12 and the contact resistance was in the same fluctuation range.
  • Example 2 Made of an AgSnBiCu alloy with 7.7% tin (Sn) by mass, 1% by mass Bismuth (Bi) and 1% by mass of coupler (Cu), as in Example 1, is used to produce a powder with a particle size of ⁇ 200 ⁇ m by pressure atomization of the molten alloy.
  • a completely internally oxidized composite powder AgSnO2Bi2O3CuO is obtained under the conditions given in Example 1.
  • the composite powder is ground with 0.4% mass content of tungsten oxide powder (WO3) and 0.2% mass content of molybdenum oxide powder (MoO3) in an agitator ball mill under acetone for 1 h and the oxide additives are evenly distributed on the surface of the composite powder particles.
  • WO3 tungsten oxide powder
  • MoO3 molybdenum oxide powder

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Contacts (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Switches (AREA)
  • Conductive Materials (AREA)

Abstract

AgCdO based contact elements are replaced in contactors and small circuit breakers with CdO-less type elements which exhibit little burn-off in the arc, a low welding force and minimal heating when carrying continuous current. However, known AgSnO2 contact materials do not have optimum values in all operationally important properties. In these contact materials a more firmly adhering oxide layer occurs as compared with AgCdO. The invention relates to a sintered compound material for electrical contacts, consisting of AgSnO2Bi2O3CuO and containing at least one other metal oxide additive which sublimes below the melting temperature of silver. The SnO2, Bi2O3 and CuO are globularly precipitated in silver material structure zones having a maximum diameter of 200 mu m, and the metal oxide additive is distributed on the surfaces of the boundary regions of these microscopic silver zones.

Description

Die Erfindung bezieht sich auf einen Sinterverbundwerkstoff für elektrische Kontakte aus Silber, Zinnoxid, Wismutoxid, Kupferoxid und ein Verfahren zu seiner Herstellund.The invention relates to a sintered composite material for electrical contacts made of silver, tin oxide, bismuth oxide, copper oxide and a method for its manufacture.

Für eine Vielzahl von Anwendungsfällen hat sich für das Herstellen von elektrischen Kontakt­stücken AgCdO sehr gut bewährt. Das CdO ist wegen seiner Umweltbelastung als toxischer Werkstoff eingestuft worden. Daher wird ver­sucht, CdO durch ein anderes Metalloxid zu ersetzen. Es hat sich gezeigt, daß Zinnoxid (SnO₂) ein geeigneter Ersatz für Cadmiumoxid (CdO) ist. Es hat sich aber auch gezeigt, daß AgSnO₂-Kontaktwerkstoffe noch nicht in allen funktionswichtigen Eigenschaften optimale Werte aufweisen. So tritt z. B. bei AgSnO₂-Kon­taktwerkstoffen gegenüber AgCdO-Kontaktwerk­stoffen eine fest haftende Oxidschïcht auf.AgCdO has proven itself very well for the production of electrical contact pieces for a large number of applications. The CdO has been classified as a toxic material due to its environmental impact. An attempt is therefore made to replace CdO with another metal oxide. It has been shown that tin oxide (SnO₂) is a suitable replacement for cadmium oxide (CdO). But it has also been shown that AgSnO₂ contact materials do not yet have optimal values in all functionally important properties. So z. B. with AgSnO₂ contact materials over AgCdO contact materials a firmly adhering oxide layer.

Durch die EP-A-0 024 349 ist ein Werkstoff für elektrische Kontakte aus Silber, Zinnoxid und Wolframoxid als einem weiteren Metalloxid bekannt. In Weiterbildung dieses Werk­stoffes wird mit der DE-A-30 17 424 vorgeschlagen, daß ein solcher Silberbasiswerkstoff mit 5 bis 20 Gew.-% Zinnoxid und 0,05 bis 5 Gew.-% Wolframoxid zusätzlich 0,1 bis 5 Gew.-% Wismutoxid enthält. Diese Werkstoffe werden aus der Pulvermischung von Silber und den einzelnen Metalloxiden gesintert und verdichtet, so daß sich ein typisches Sintergefüge mit statistischer Verteilung der Metalloxide ergibt.EP-A-0 024 349 discloses a material for electrical contacts made of silver, tin oxide and tungsten oxide as a further metal oxide. In a further development of this material, DE-A-30 17 424 suggests that such a silver-based material with 5 to 20 wt.% Tin oxide and 0.05 to 5 wt.% Tungsten oxide additionally 0.1 to 5 wt.% Contains bismuth oxide. These materials are sintered and compacted from the powder mixture of silver and the individual metal oxides, so that a typical sintered structure with a statistical distribution of the metal oxides results.

Aus der GB-A-2 055 398 ist ein Werkstoff für elektrische Kontakte bekannt, der aus Silber, Zinnoxid, Wismutoxid und Kupferoxid besteht. In dem aus der DE-A-27 54 335 vorbekannten Werkstoff entsprechender Konstitution kann fakultativ das Kupferoxid durch Zinkoxid ersetzt werden. Beide Werkstoffe können durch die sogenannte innere Oxidation von zunächst erzeugten Legierungen hergestellt werden, wobei die Oxidation im wesentlichen durch Festkörperdiffusion von Sauerstoff erfolgt.From GB-A-2 055 398 a material for electrical contacts is known which consists of silver, tin oxide, bismuth oxide and copper oxide. In the material of corresponding constitution known from DE-A-27 54 335, the copper oxide can optionally be replaced by zinc oxide. Both materials can be produced by the so-called internal oxidation of alloys initially produced, the oxidation taking place essentially by solid-state diffusion of oxygen.

Aus der DE-A-31 02 067 ist weiterhin ein Werkstoff bekannt, der neben Silber und Zinnoxid Molybdänoxid und/oder Germaniumoxid, aber kein Wismutoxid und Kupferoxid enthält, wobei das Molybdän­oxid teilweise durch Wolframoxid ersetzt werden kann. Dieser Werkstoff wird entweder pulvermetallurgisch aus Silber und den Metalloxiden oder durch innere Oxidation von Legierungsblechen hergestellt, wobei über die Gefügeausbildung keine Aussagen gemacht sind.From DE-A-31 02 067 a material is also known which contains molybdenum oxide and / or germanium oxide in addition to silver and tin oxide, but no bismuth oxide and copper oxide, it being possible for the molybdenum oxide to be partially replaced by tungsten oxide. This material is either powder metallurgically made from silver and the metal oxides or by internal oxidation of alloy sheets, whereby no statements have been made about the structure formation.

Der Erfindung liegt die Aufgabe zugrunde, die bekannten CdO-freien Silberkontaktstücke da­hingehend zu verbessern, daß die Optimierung der Kontakteigenschaften hinsichtlich Abbrand im Lichtbogen, kleine Schweißkraft und kleinen Kontaktwiderstand ermöglichtwird.The invention has for its object to improve the known CdO-free silver contact pieces in such a way that the optimization of the contact properties with regard to arcing in the arc, low welding force and low contact resistance is made possible.

Die Aufgabe ist erfindungsgemäß dadurch gelöst, daß

  • a) der AgSnO₂Bi₂O₃CuO-Werkstoff Wolframoxid (WO₃) und/oder Molybdänoxid (MoO₃) als sublimierenden Metalloxidzusatz enthält und
  • b1) das Zinnoxid (SnO₂), das Wismutoxid (Bi₂O₃) und das Kupferoxid (CuO) als globulare Ausscheidungen im Silber in Gefügebereichen bis höchstens 200 µm Durchmesser ausgeschieden sind, wogegen
  • b2 ) der sublimierende Metalloxidzusatz aus Wolframoxid ( WO₃ ) und/oder Molybdänoxid (MoO₃) in den Oberflächen der Grenz­bereiche dieser Silberbereiche verteilt ist.
    Die Herstellung eines solchen Sinterverbundwerkstoffes erfolgt mit folgenden Verfahrensschritten vor dem Pressen, Sintern und Verdichten zum Formkörper:
  • a) Ein Legierungspulver aus AgSnBiCu vorgegebener Zusammen­setzung wird zu einem AgSnO₂Bi₂O₃CuO-Verbundpulver inner­oxidiert
  • b) das AgSnO₂Bi₂O₃CuO-Verbundpulver wird mit WO₃- und/oder MoO₃-Pulver vorgegebener Menge in einer Rührwerksmühle unter Azeton gemischt,
  • c) dabei werden die WO₃- und/oder MoO₃-Pulverteilchen auf der Ober fläche der Verbundpulverteilchen aus AgSnO₂Bi₂O₃CuO ver­teilt.
The object is achieved in that
  • a) the AgSnO₂Bi₂O₃CuO material contains tungsten oxide (WO₃) and / or molybdenum oxide (MoO₃) as a subliming metal oxide additive and
  • b1) the tin oxide (SnO₂), the bismuth oxide (Bi₂O₃) and the copper oxide (CuO) are excreted as globular precipitates in silver in structural areas up to a maximum of 200 µm in diameter, whereas
  • b2) the subliming metal oxide addition of tungsten oxide (WO₃) and / or molybdenum oxide (MoO₃) is distributed in the surfaces of the border areas of these silver areas.
    Such a sintered composite material is produced using the following process steps before pressing, sintering and compacting to give the shaped body:
  • a) An alloy powder of AgSnBiCu given composition is internally oxidized to an AgSnO₂Bi₂O₃CuO composite powder
  • b) the AgSnO₂Bi₂O₃CuO composite powder is mixed with WO₃ and / or MoO₃ powder in a predetermined amount in an agitator mill under acetone,
  • c) the WO₃ and / or MoO₃ powder particles are distributed on the upper surface of the composite powder particles made of AgSnO₂Bi₂O₃CuO.

Mit der Erfindung ist also ein Werkstoff geschaffen, bei dem in vorteilhafter Weise dem Umstand Rechnung getragen wird, daß Wolfram und/oder Molybdän in Silber unlösbar ist. Durch die Sublimation der entsprechenden Oxide an den Verbundteilchen können aber trotzdem die Vorteile dieser Metalloxidzusätze aus­genutzt werden.The invention thus provides a material in which the fact that tungsten and / or molybdenum is insoluble in silver is advantageously taken into account. By sublimating the corresponding oxides on the composite particles, the advantages of these metal oxide additives can nevertheless be exploited.

Es hat sich besonders bewährt, wenn die mittle­ren Teilchengroßen der Zinnoxid-, Wismutoxid­und Kupferoxidausscheidungen in den Silberbe­reichen zwischen 0,1 und 5 µm insbesondere zwischen 0,1 µm und 3 µm betragen.It has proven particularly useful if the mean particle sizes of the tin oxide, bismuth oxide and copper oxide precipitations in the silver regions are between 0.1 and 5 µm, in particular between 0.1 µm and 3 µm.

Weiterhin ist es vorteilhaft, daß der Zinnoxi­danteil zwischen 6 und 15% Massengehalt der Wismutoxidanteil zwischen 0,2 und 2% Massengehalt, der Kupferoxidanteil zwischen 0,2 und 2% Massengehalt und der Anteil an sublimie­renden Metalloxidzusatz zwischen 0,2 und 2% Massengehalt beträgt.It is also advantageous that the tin oxide content is between 6 and 15% by mass, the bismuth oxide content is between 0.2 and 2% by weight, the copper oxide content is between 0.2 and 2% by weight and the proportion of subliming metal oxide additive is between 0.2 and 2% by weight .

Als besonders geeignet hat sich für den subli­mierenden Metaltoxidzusatz Molybdänoxid (MoO₃) mit einem Anteil von 0,5% Massengehalt, oder Wolframoxid (WO₃), mit einem Anteil von 0,8% Massengehalt oder Wolframoxid (WO₃) mit einem Anteil von 0,5% Massengehalt und Mo­ lybdänoxid (MoO₃) mit einem Anteil von 0,2% Massengehalt erwiesen.Has been particularly suitable for the sublimating addition of malt oxide (MoO₃) with a proportion of 0.5% by mass, or tungsten oxide (WO₃) with a proportion of 0.8% by mass or tungsten oxide (WO₃) with a proportion of 0.5 % Mass content and mo Lybdenum oxide (MoO₃) with a proportion of 0.2% mass content proved.

Bei dem Kontaktwerkstoff gemäß dem Kenn­zeichen des Patentanspruches 1 wird eine Opti­mierung durch die Silberbereiche mit den globu­laren Oxidausscheidungen von Zinnoxid Wismu­toxid und Kupferoxid mit sehr günstigen Lichtbo­geneigenschaften und den an der Oberfläche dieser Silberbereiche liegenden sublimierenden Metalloxiden erreicht, die bei Lichtbogenbe­lastungen zu kleinen Silberinseln führen, aus denen die Metalloxide unter der Silberschmelz­temperatur sublimieren und dadurch eine ge­schlossene Deckschicht an Oxiden vermeiden. Dadurch wird eine deutliche Erniedrigung des Kontaktwiderstandes erzielt, ohne daß die Schweißkraft erhöht wird. An zwei Ausführungs­beispielen wird die Erfindung näher erläutert.In the case of the contact material according to the characterizing part of patent claim 1, optimization is achieved through the silver areas with the globular oxide precipitates of tin oxide bismuth oxide and copper oxide with very favorable arcing properties and the sublimating metal oxides lying on the surface of these silver areas, which lead to small silver islands from which arcing occurs sublimate the metal oxides below the silver melting temperature and thereby avoid a closed top layer of oxides. This results in a significant reduction in the contact resistance without increasing the welding force. The invention is explained in more detail using two exemplary embodiments.

Beispiel 1example 1

Aus einer AgSnBiCu-Legierung mit 7,7% Massengehalt Zinn (Sn), 1% Massengehalt Wismut (Bi) und 1% Massengehalt Kupfer (Cu) wird ein Pulver der Teilchengröße < 200 µm hergestellt. Ein geeignetes verfahren dafür ist z. B. die Druckverdüsung der Schmelze dieser Legierung. Das erhaltene Legierungspulver wird vollständig inneroxidiert, wobei ein verbund­pulver AgSnO₂Bi₂O₃CuO entsprechender Zu­sammensetzung erhalten wird. Die innere Oxida­tion wird an Luft vorgenommen. wobei die Glühbehandlung bei 500°C begonnen wird und nach einer Stunde während der gleichen Zeit bei 800°C gehalten wird. Das verbundpulver wird mit 0,8% Massengehalt Wolframoxid (WO₃) in einer Rührwerkskugelmühle unter Azeton während einer Stunde gemischt und dabei das WO₃ auf der Oberfläche der Verbundpulverteil­chen verteilt.A powder of particle size <200 µm is produced from an AgSnBiCu alloy with 7.7% tin (Sn), 1% bismuth (Bi) and 1% copper (Cu). A suitable procedure for this is e.g. B. the pressure atomization of the melt of this alloy. The alloy powder obtained is completely internally oxidized, a composite powder of AgSnO₂Bi₂O₃CuO having the appropriate composition being obtained. The internal oxidation is carried out in air. wherein the annealing treatment is started at 500 ° C and is held at 800 ° C after one hour for the same time. The composite powder is mixed with 0.8% by mass of tungsten oxide (WO₃) in an agitator ball mill under acetone for one hour and thereby the WO₃ is distributed on the surface of the composite powder particles.

Nach Trocknen dieser Pulvermischung wird durch Pressen, Sintern und Warmnachverdichten ein Formkörper hergestellt, dessen Restporosität bei <1,5% liegt. Die Kontakteigenschaften wie Abbrand im Lichtbogen. Schweißkraft und Kon­taktwiderstand wurden unter in der Literatur be­schriebenen Bedingungen auf einem Prüf­schalter gemessen und mit einer sehr guten AgCdO-Qualität verglichen. Die Abbrandwerte lie­gen um 25% niedriger, womit eine entsprechende Verbesserung der Lebensdauer erreicht wird. Da­durch kann eine entsprechende Silbereinsparung durch Verkleinerung des Kontaktstückvolumens erzielt werden. Die Schweißkraftwerte lagen im gleichen Bereich wie bei AgCdO12 und auch der Kontaktwiderstand lag im gleichen Schwankungsbereich.After this powder mixture has dried, a shaped body is produced by pressing, sintering and hot post-compression, the residual porosity of which is <1.5%. The contact properties such as arcing in the arc. Welding force and contact resistance were measured under a condition described in the literature on a test switch and compared with a very good AgCdO quality. The burn-up values are 25% lower, which leads to a corresponding improvement in the service life. A corresponding saving in silver can be achieved by reducing the contact piece volume. The welding force values were in the same range as for AgCdO 12 and the contact resistance was in the same fluctuation range.

Beispiel 2Example 2

Aus einer AgSnBiCu-Legierung mit 7,7% Massengehalt Zinn (Sn), 1% Massengehalt Wismut (Bi) und 1% Massengenalt Kupler (Cu) wird wie bei Beispiel 1 ein Pulver der Teilcheng­röße < 200 µm durch Druckverdüsung der ge­schmolzenen Legierung hergestellt. Durch innere Oxidation des Legierungspulvers wird unter den in Beispiel 1 angegebenen Bedingungen ein voll­ständig inneroxidiertes Verbundpulver AgS­nO₂Bi₂O₃CuO erhalten. Das verbundpulver wird mit 0,4% Massengehalt Wolframoxid-Pulver (WO₃) und 0,2% Massengehalt Molybdänoxid­Pulver (MoO₃) in einer Rührwerkskugelmühle unter Azeton während 1 h gemahlen und die Oxidzusätze auf der Oberfläche der Verbund­pulverteilchen gleichmäßig verteilt. Nach Trock­nen der Pulvermischung wird durch Pressen. Sintern und Warmnachverdichten ein Form­körper hergestellt, dessen Restporosität bei < 1,5 % liegt. Die Kontakteigenschaften wurden auf einem in der Literatur beschriebenen Prüf­schalter gemessen, sie sind genauso hervorra­gend wie bei dem im Beispiel 1 beschriebenen Kontaktwerkstoff.Made of an AgSnBiCu alloy with 7.7% tin (Sn) by mass, 1% by mass Bismuth (Bi) and 1% by mass of coupler (Cu), as in Example 1, is used to produce a powder with a particle size of <200 μm by pressure atomization of the molten alloy. By internal oxidation of the alloy powder, a completely internally oxidized composite powder AgSnO₂Bi₂O₃CuO is obtained under the conditions given in Example 1. The composite powder is ground with 0.4% mass content of tungsten oxide powder (WO₃) and 0.2% mass content of molybdenum oxide powder (MoO₃) in an agitator ball mill under acetone for 1 h and the oxide additives are evenly distributed on the surface of the composite powder particles. After drying the powder mixture is by pressing. Sintering and hot post-compression molding are produced, the residual porosity of which is <1.5%. The contact properties were measured on a test switch described in the literature, they are just as excellent as in the contact material described in Example 1.

Claims (8)

1. A sintered material for electrical contacts consisting of silver, tin oxide, bismuth oxide, copper oxide (AgSnO₂Bi₂O₃CuO), characterised in that
a) the AgSnO₂Bi₂O₃CuO - material contains tungsten oxide (WO₃) and/or molybdenum oxide (MoO₃) as sublimed metal oxide addition and
b1) the tin oxide (SnO₂), the bismuth oxide (Bi₂O₃) and the copper oxide (CuO) are separated as globular separations in the silver in structural regions of at least 200µm diameter, with in contrast
b2) the tungsten oxide (WO₃) and/or molybdenum oxide (MoO₃) sublimed metal oxide addition being distributed in the surfaces of the boundary regions of these silver regions.
2. A sintered material according to claim 1 characterised in that the average particle sizes of the tin oxide, bismuth oxide and copper oxide separations in the silver regions amount to between 0.1 and 5µm.
3. A sintered material according to claim 2, characterised in that the average particle sizes of the tin oxide, bismuth oxide and copper oxide separations in the silver regions are between 0.1µm and 3µm.
4. A sintered material according to one of the forgoing claims, characterised in that the tin oxide component amounts to between 6 and 15% mass content, the bismuth oxide component amounts to between 0.2 and 2% mass content, the copper oxide component amounts to between 0.2 and 2% mass content, and that the content of sublimed metal oxide addition amounts to between 0.2 and 2% mass content.
5. A sintered material according to one of the forgoing claims characterised in that the added molybdenum oxide component (MoO₃) is provided in a mass content of 0.5%.
6. A sintered material according to one of claims 1 to 4, characterised in that the added tungsten oxide component (WO₃) provided in a mass content of 0.8%.
7. A sintered material according to one of claims 1 to 4 characterised in that the added tungsten oxide component (WO₃) is provided in a mass content of 0.5% and at the same time the added molybdenum oxide component (MoO₃) is provided in a mass content of 0.2%.
8. Process for the production of a sintered material according to one of claims no.s 1 to 7 with the following processing steps before the pressing, sintering and compressing to form shaped bodies:
a) an alloy powder consisting of AgSnBiCu of predetermined composition is internally oxidised to a AgSnO₂Bi₂O₃CuO composite powder,
b) the AgSnO₂Bi₂O₃Cuo composite powder is mixed with WO₃ and/or MoO₃ powder of predetermined quantity in a rotary mill under acetone,
c) the WO₃ and/or MoO₃ particles are then distributed on the surface of the AgSnO₂Bi₂O₃Cuo composite particles.
EP84101010A 1983-02-16 1984-02-01 Sintered material for electrical contacts and its method of manufacture Expired - Lifetime EP0118717B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84101010T ATE20506T1 (en) 1983-02-16 1984-02-01 SINTERED COMPOSITE MATERIAL FOR ELECTRICAL CONTACTS AND PROCESS FOR ITS MANUFACTURE.

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DE19833305270 DE3305270A1 (en) 1983-02-16 1983-02-16 SINTER COMPOSITE FOR ELECTRICAL CONTACTS AND METHOD FOR THE PRODUCTION THEREOF
DE3305270 1983-02-16

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EP (1) EP0118717B2 (en)
JP (1) JPS59173910A (en)
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Publication number Priority date Publication date Assignee Title
DE3304637A1 (en) * 1983-02-10 1984-08-16 Siemens AG, 1000 Berlin und 8000 München SINTER CONTACT MATERIAL FOR LOW VOLTAGE SWITCHGEAR
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
US4680162A (en) * 1984-12-11 1987-07-14 Chugai Denki Kogyo K.K. Method for preparing Ag-SnO system alloy electrical contact material
JPH06104873B2 (en) * 1986-07-08 1994-12-21 富士電機株式会社 Silver-metal oxide contact material and manufacturing method thereof
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
US4904317A (en) * 1988-05-16 1990-02-27 Technitrol, Inc. Erosion resistant Ag-SnO2 electrical contact material
JP2849663B2 (en) * 1988-12-26 1999-01-20 田中貴金属工業株式会社 Electrical contact material and manufacturing method thereof
DE4201940A1 (en) * 1992-01-24 1993-07-29 Siemens Ag SINTER COMPOSITE FOR ELECTRICAL CONTACTS IN SWITCHGEAR OF ENERGY TECHNOLOGY
US5258052A (en) * 1992-06-18 1993-11-02 Advanced Metallurgy Incorporated Powder metallurgy silver-tin oxide electrical contact material
DE59303090D1 (en) * 1992-09-16 1996-08-01 Duerrwaechter E Dr Doduco MATERIAL FOR ELECTRICAL CONTACTS BASED ON SILVER-TINNOXIDE OR SILVER-ZINCOXIDE AND METHOD FOR THE PRODUCTION THEREOF
DE19503182C1 (en) * 1995-02-01 1996-05-15 Degussa Sintered material used as electrical contacts for switching amperage rating
US5846288A (en) * 1995-11-27 1998-12-08 Chemet Corporation Electrically conductive material and method for making
US20060028895A1 (en) * 2004-08-09 2006-02-09 Carl Taussig Silver island anti-fuse
CN104942277A (en) * 2014-03-31 2015-09-30 三菱电机株式会社 Preparing method for novel nanometer doped Ag/SnO2 electrical contact material
CN110096839A (en) * 2019-05-17 2019-08-06 西北大学 A kind of method that hot compaction action intensity quantitatively calculates
CN112259278B (en) * 2020-10-19 2022-05-03 西安工程大学 A kind of preparation method of particle composite fiber reinforced copper tin oxide contact material

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US4141727A (en) * 1976-12-03 1979-02-27 Matsushita Electric Industrial Co., Ltd. Electrical contact material and method of making the same
JPS6013051B2 (en) * 1978-08-11 1985-04-04 中外電気工業株式会社 Improvement of electrical contact material by internally oxidizing silver↓-tin↓-bismuth alloy
GB2055398B (en) * 1979-08-01 1983-06-02 Chugai Electric Ind Co Ltd Electrical contact materials of internally oxidized ag-sn-bi alloy
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
FR2499760B1 (en) * 1981-02-12 1990-08-10 Chugai Electric Ind Co Ltd MATERIAL FOR MAKING ELECTRICAL CONTACTS

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ATE20506T1 (en) 1986-07-15
EP0118717A1 (en) 1984-09-19
EP0118717B1 (en) 1986-06-18
US4551301A (en) 1985-11-05
DE3460230D1 (en) 1986-07-24
JPS59173910A (en) 1984-10-02
DE3305270A1 (en) 1984-08-16
JPH0586006B2 (en) 1993-12-09

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