EP0660964B1 - Materiau pour contacts electriques a base d'argent-oxyde stannique ou d'argent-oxyde de zinc et son procede de fabrication - Google Patents

Materiau pour contacts electriques a base d'argent-oxyde stannique ou d'argent-oxyde de zinc et son procede de fabrication Download PDF

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Publication number
EP0660964B1
EP0660964B1 EP93920746A EP93920746A EP0660964B1 EP 0660964 B1 EP0660964 B1 EP 0660964B1 EP 93920746 A EP93920746 A EP 93920746A EP 93920746 A EP93920746 A EP 93920746A EP 0660964 B1 EP0660964 B1 EP 0660964B1
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EP
European Patent Office
Prior art keywords
tin oxide
silver
powder
mixture
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP93920746A
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German (de)
English (en)
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EP0660964A1 (fr
EP0660964B2 (fr
Inventor
Volker Behrens
Thomas Honig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Doduco Contacts and Refining GmbH
Original Assignee
Doduco GmbH and Co KG Dr Eugen Duerrwaechter
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Application filed by Doduco GmbH and Co KG Dr Eugen Duerrwaechter filed Critical Doduco GmbH and Co KG Dr Eugen Duerrwaechter
Publication of EP0660964A1 publication Critical patent/EP0660964A1/fr
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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 relates to a material for electrical contacts based on silver-tin oxide with the features specified in the preamble of claim 1.
  • a material for electrical contacts based on silver-tin oxide with the features specified in the preamble of claim 1.
  • Such a material is known from WO 80/01434; the material is obtained by mixing a powder of silver or an alloy containing mainly silver with tin oxide powder, compacting the mixture and sintering.
  • contact materials based on silver-tin oxide Due to their better environmental compatibility and their at least partially more favorable lifespan, contact materials based on silver-tin oxide have started to replace the previously preferred silver-cadmium oxide materials. Since the tin oxide tends to be poorly conductive when exposed to arcing because of its higher thermal resistance To form slag layers on the contact surface, however, the heating behavior under continuous current is unsatisfactory for contacts made of silver-tin oxide. In order to eliminate this disadvantage, it is known to add additives in powder form to the material produced by powder metallurgy, which lead to a lower temperature at the contact point.
  • Tungsten and molybdenum oxide and carbide have been mentioned in the patent literature as suitable additives in this sense (DE-A-29 33 338, DE-A-31 02 067, DE-A-32 32 627).
  • Bismuth and germanium oxide have also been mentioned as additives (DE-A-31 02 067 and DE-A-32 32 627).
  • These additives help to wet the tin oxide particles so that when the contact piece surface melts locally under the action of a switching arc, the tin oxide remains in fine suspension. In addition to this positive effect with regard to the heating behavior under continuous current, these additives also have undesirable side effects.
  • the plastic deformability of the silver-tin oxide contact materials which is not entirely satisfactory anyway, for the improvement of which, for example, a pretreatment of the tin oxide powder is carried out by annealing (DE-A-29 52 128) is made worse by these additives because they have an embrittling effect.
  • Another disadvantage, in particular of the tungsten and molybdenum compounds, is that they are particularly in switching operation under AC1 load (DIN 57660 part 102) favor a material transfer that leads to accelerated combustion and thus to a reduction in the service life.
  • a contact material with a low tendency to weld and the lowest possible contact temperature under continuous current is to be obtained by specifically producing a structure in which areas in which little or no metal oxide is present alternate with areas, in which all or the vast majority of the metal oxide component is contained in a fine distribution.
  • a composite powder is produced which contains the predominant part of the tin oxide and the further oxides and / or carbides as well as part of the silver. This composite powder is mixed with the remaining silver powder and possibly with the smaller rest of the metal oxides, compacted, sintered and shaped. In this way, a material that can be used well is obtained, but by a relatively complex process.
  • the oxides of tungsten, molybdenum, bismuth, vanadium and copper are mentioned as metal oxides.
  • the doped tin oxide powder is a composite powder which can be obtained by mixing the tin oxide powder with the powdered dopant, annealing the mixture so that the dopant and the tin oxide powder particles diffuse, and separating the excess of the dopant from the tin oxide powder.
  • P 42 19 333.8 discloses to spray a solution of a salt of tin and a salt of the metal or metals, from the oxides or carbides of which the dopant is supposed to consist, into a hot, oxidizing atmosphere , in which the salts are decomposed so that a fine-particle composite powder precipitates, the particles of which contain the tin oxide and the dopants.
  • the present invention has for its object to provide a material of the type mentioned, which shows by additions a favorable heating behavior as the known contact materials, but is more ductile and has a longer service life in the AC1 switching case.
  • This object is achieved by a material with the features specified in claim 1.
  • a particularly suitable method for producing such a material is the subject of claim 9.
  • Advantageous developments of 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 Can form material and have no favorable influence on the wettability of the tin oxide can be achieved
  • the contact material according to the invention a significantly lower heating of the contact points under continuous current than with known contacts with a composition of comparable quantity. It is believed that this is due to the fact that, unlike Christine Bourda (see above), the contact material is not produced in the usual way by mixing and sintering silver powder, tin oxide powder and additional metal oxide powder, but rather by using powder from the outset.
  • a powder is mixed with the silver powder in the powder-metallurgical production of the contact material, said powder consisting mainly of tin oxide and one or more compounds of the silver-oxygen-metal type, decisive advantages are achieved.
  • a certain lowering of the contact point temperature under predetermined conditions can be achieved with a significantly lower proportion of the chosen additive than according to the previously known prior art.
  • Contact materials show that, according to the invention, a certain reduction in the contact point temperature can be achieved with only 1/2 to 1/10 of the additional amount required in the prior art. This also applies to the example of molybdenum oxide, the proportion of which can be drastically reduced if it is used as silver molybdate, especially if it is bound to tin oxide particles.
  • the contact material is less brittle, i.e. is more ductile.
  • Another advantage is that, due to the lower proportion of the electrically non-conductive additive, the electrical resistance of the contact material is additionally reduced, which again contributes to lowering the contact point temperature.
  • Another advantage of the invention is that the lower proportion of the selected additive increases the service life of contact pieces made of the material, in particular under AC1 test conditions.
  • the use of the powder according to the invention surprisingly results in less burnup than in 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 preferably coated at least superficially with the silver-metal-oxygen compounds. They then particularly effectively promote the wetting of the tin oxide particles with the molten phase which forms under the action of an arc.
  • One in this Modified tin oxide powder can advantageously be obtained by mixing tin oxide powder and the powdery additive with one another and annealing them together, so that the tin oxide powder particles are wetted by the additive, some of the additive also diffusing into the surface area of the tin oxide particles and possibly a mixed oxide therein can form.
  • the material expediently contains 5 to 20% by weight, preferably 8 to 14% by weight, and thus the tin oxide as desired can be kept in suspension by the additives in the molten phase which occurs under the action of arcing, the tin oxide powder is preferably with at least 0.1% by weight of the additive, but with not more than 2.5% by weight, preferably with no more connected as 1% by weight of the additive.
  • Silver molybdate is particularly preferred as an additive because of its particularly favorable effect on the heating behavior.
  • the annealing of the mixture of tin oxide and the selected additive is advantageously carried out under an oxygen-containing atmosphere, preferably in air at a temperature between 500 ° C and 800 ° C, preferably at a temperature just above the melting point of the additive, so that it becomes liquid and the Tin Oxide Particles superficially wetted.
  • the additive is then only where its wetting-promoting effect is desired and can therefore be used sparingly. With the small amounts in which it is used, the tin oxide particles do not stick together yet; but should this happen in individual cases, you can counter this by grinding.
  • the tin oxide and the additive can be combined not only by annealing together, but also by depositing the additive on the tin oxide particles using chemical or physical deposition processes.
  • the teaching according to the invention can be applied to contact materials based on silver with zinc oxide.
  • no additives have been used in practice so far, but efforts have been made to reduce the contact point temperature by constructive measures in the switching device.
  • a zinc oxide powder combined with an additive according to the invention a reduction in the contact point temperature can also be achieved with this type of material.
  • the three examples can be modified so that zinc oxide is used instead of tin oxide.

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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)
  • Conductive Materials (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Claims (14)

  1. Matériau pour contacts électriques à base d'argent et d'oxyde d'étain, que l'on obtient par
    - mélange à une poudre d'oxyde d'étain, d'une poudre d'argent ou d'un alliage contenant essentiellement de l'argent,
    - compression du mélange, et
    - frittage,
    caractérisé en ce que, pour fabriquer le mélange, on utilise en outre une poudre qui contient de 0,01 à 10 % en poids, par rapport à la quantité de l'oxyde d'étain, d'un ou plusieurs composés constitués d'argent, d'oxygène et d'un métal des groupes secondaires II-VI du Tableau Périodique et/ou d'antimoine, de bismuth, de germanium, d'indium et de gallium.
  2. Matériau selon la revendication 1, caractérisé en ce que les composés sont combinés à l'oxyde d'étain pour donner des particules composites d'une poudre composite.
  3. Matériau selon la revendication 1 ou 2, caractérisé en ce qu'il contient de 5 à 20 % en poids d'oxyde d'étain.
  4. Matériau selon la revendication 3, caractérisé en ce qu'il contient de 8 à 14 % en poids d'oxyde d'étain.
  5. Matériau selon l'une des revendications précédentes, caractérisé en ce que l'additif est présent en une quantité d'au moins 0,1 % en poids.
  6. Matériau selon l'une des revendications précédentes, caractérisé en ce que l'additif est présent en une quantité non supérieure à 2,5 % en poids.
  7. Matériau selon la revendication 6, caractérisé en ce que l'additif est présent en une quantité non supérieure à 1 % en poids.
  8. Matériau selon l'une des revendications précédentes, caractérisé en ce que les composés contenus dans l'additif contiennent un métal du groupe du tungstène, du molybdène, du vanadiums de l'antimoine, du bismuth et du germaniums, le molybdène étant particulièrement préféré.
  9. Procédé pour fabriquer un matériau pour contacts électriques à base d'argent et d'oxyde d'étain, que l'on obtient par mélange d'une poudre d'argent ou d'un alliage contenant essentiellement de l'argent à une poudre d'oxyde d'étain et à une poudre supplémentaire contenant de 0,01 à 10 % en poids, par rapport à la quantité de l'oxyde d'étain, d'un ou plusieurs composés constitués d'argent, d'oxygène et d'un métal des groupes secondaires II-VI du Tableau Périodique et/ou d'antimoine, de bismuth, de germanium, d'indium et de gallium, compression du mélange et frittage selon l'une des revendications précédentes, caractérisé en ce que la poudre constituée essentiellement d'oxyde d'étain et de l'additif est obtenue par
    - mélange de la poudre d'oxyde d'étain à l'additif sous forme de poudre, et
    - recuit du mélange.
  10. Procédé selon la revendication 9, caractérisé en ce que le mélange est recuit à l'air.
  11. Procédé selon la revendication 9 ou 10, caractérisé en ce que le mélange est recuit entre 500 et 800°C.
  12. Procédé selon l'une des revendications 9 à 11, caractérisé en ce que le mélange est recuit à une température supérieure au point de fusion de l'additif.
  13. Procédé selon l'une des revendications 9 à 12, caractérisé en ce que le matériau, après frittage, est soumis à une post-compression et/ou une déformations
  14. Matériau selon l'une des revendications 1 à 8, ou préparé selon l'une des revendications 9 à 13, caractérisé en ce que l'oxyde d'étain est remplacé par l'oxyde de zinc.
EP93920746A 1992-09-16 1993-09-16 Materiau pour contacts electriques a base d'argent-oxyde stannique ou d'argent-oxyde de zinc et son procede de fabrication Expired - Lifetime EP0660964B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4231022 1992-09-16
DE4231022 1992-09-16
PCT/EP1993/002511 WO1994007252A1 (fr) 1992-09-16 1993-09-16 Materiau pour contacts electriques a base d'argent-oxyde stannique ou d'argent-oxyde de zinc et son procede de fabrication

Publications (3)

Publication Number Publication Date
EP0660964A1 EP0660964A1 (fr) 1995-07-05
EP0660964B1 true EP0660964B1 (fr) 1996-06-26
EP0660964B2 EP0660964B2 (fr) 2003-01-08

Family

ID=6468120

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93920746A Expired - Lifetime EP0660964B2 (fr) 1992-09-16 1993-09-16 Materiau pour contacts electriques a base d'argent-oxyde stannique ou d'argent-oxyde de zinc et son procede de fabrication

Country Status (7)

Country Link
US (1) US5822674A (fr)
EP (1) EP0660964B2 (fr)
JP (1) JP3441074B2 (fr)
AT (1) ATE139864T1 (fr)
DE (2) DE4331526C3 (fr)
ES (1) ES2091633T5 (fr)
WO (1) WO1994007252A1 (fr)

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EP0369283B1 (fr) * 1988-11-17 1994-09-14 Siemens Aktiengesellschaft Matériau de contact fritté pour appareillages interrupteurs à basse tension de la technique de l'énergie, spécialement pour des contacteurs
EP0435655B1 (fr) * 1989-12-26 1998-02-25 Sumitomo Metal Mining Company Limited Matériau composite d'argent et d'un oxyde métallique et son procédé de préparation
DE4319137A1 (de) * 1992-06-10 1993-12-16 Duerrwaechter E Dr Doduco Werkstoff für elektrische Kontakte auf der Basis von Silber-Zinnoxid oder Siler-Zinkoxid

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Publication number Publication date
DE59303090D1 (de) 1996-08-01
DE4331526A1 (de) 1994-03-17
EP0660964A1 (fr) 1995-07-05
ATE139864T1 (de) 1996-07-15
JP3441074B2 (ja) 2003-08-25
US5822674A (en) 1998-10-13
JPH08504292A (ja) 1996-05-07
EP0660964B2 (fr) 2003-01-08
ES2091633T3 (es) 1996-11-01
DE4331526C2 (de) 1998-07-30
WO1994007252A1 (fr) 1994-03-31
ES2091633T5 (es) 2003-09-01
DE4331526C3 (de) 2003-11-06

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