EP0170812B1 - Procédé pour la fabrication de matériau de contact fritté - Google Patents

Procédé pour la fabrication de matériau de contact fritté Download PDF

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Publication number
EP0170812B1
EP0170812B1 EP85106749A EP85106749A EP0170812B1 EP 0170812 B1 EP0170812 B1 EP 0170812B1 EP 85106749 A EP85106749 A EP 85106749A EP 85106749 A EP85106749 A EP 85106749A EP 0170812 B1 EP0170812 B1 EP 0170812B1
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EP
European Patent Office
Prior art keywords
bi2o3
sno2
powder
alloy
amount
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
EP85106749A
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German (de)
English (en)
Other versions
EP0170812A3 (en
EP0170812A2 (fr
Inventor
Bernhard Rothkegel
Wolfgang Haufe
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.)
Siemens AG
Original Assignee
Siemens AG
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Publication date
Application filed by Siemens AG filed Critical Siemens AG
Priority to AT85106749T priority Critical patent/ATE84906T1/de
Publication of EP0170812A2 publication Critical patent/EP0170812A2/fr
Publication of EP0170812A3 publication Critical patent/EP0170812A3/de
Application granted granted Critical
Publication of EP0170812B1 publication Critical patent/EP0170812B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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

Definitions

  • the invention relates to a method for producing a low-voltage switchgear contact material made of AgSnO2, Bi2O3 and CuO.
  • Contact materials based on silver-metal oxides have proven to be particularly advantageous for low-voltage switchgear in energy technology, for example in contactors or circuit breakers.
  • cadmium oxide was used as the active component, with these contact materials in particular fulfilling the desired electrical-technological properties and having proven themselves in long-term use of switching devices.
  • cadmium is known to be one of the toxic heavy metals and when the contact pieces burn up, CdO is also released into the environment, efforts have been underway for some time to replace the CdO as completely as possible with other metal oxides.
  • the substitute materials should have an equally small arc burnout, as well as low welding power and in particular low Heating with continuous current supply as the proven AgCdO contact materials exhibit.
  • a contact material which is made especially of a silver alloy with 3 to 15 wt.% Tin, 0.01 to 1 wt.% Bismuth and 0.1 to 8.5 wt .-% copper is produced. If necessary, 0.01 to 0.5% by weight of one or more elements of the iron group may also be present in this material.
  • the silver metal alloys are oxidized there as thin sheets at 650 ° C. for about 200 hours. Electrical contact pieces are produced from the contact materials produced in this way and with regard to the switching properties checked on the one hand and the mechanical properties on the other. The temperature behavior was not examined. If the starting alloys had the AgSnBiCu constitution, comparatively high tin contents (> 8.5%) were present.
  • an electrical contact material with a metal component as the main component and the rest of a metal oxide as a secondary component is also known, in which the metal component is essentially silver with or without tin and the metal oxide component is essentially bismuth oxide and tin oxide, where the amount of bismuth in bismuth oxide is 1.5 to 6% by weight and the total amount of tin from the metal and metal oxide components is 0.1 to 6% by weight, based on the sum of the metal component and the metal content in the metal oxide component.
  • the metal oxide component can contain copper or tin oxide as an additive, the metal of the additional oxide being 0.016 to 1.2% by weight, based on the sum of the metal component and the metals of the metal oxide component.
  • the SnO2 content is usually low, in particular below 4% by weight. Only with one of the DE-A-27 54 335 removable material (Example 18) is the Sn content higher (4Bi-6Sn-1,2Cu-Ag), in which case the SnO2 volume fraction of the sum oxides is comparatively low.
  • the object of the invention is therefore to specify a method with which a structure which is particularly suitable for use in low-voltage switching devices is produced.
  • the object is achieved in a method of the type mentioned above in that, on the one hand, an AgSnBiCu alloy of predetermined composition is used as the starting material, from which a composite powder of the constitution AgSnO2Bi2O3CuO is produced by atomization and internal oxidation, and on the other hand a separately produced metal oxide powder made of Bi2O3 is used, whereby the composition of the AgSnBiCu alloy and the amount of the separately produced Bi2O3 powder are chosen so that the volume fraction of bulk metal oxide in the sintered contact material is between 10 and 20% with a SnO2 volume fraction ⁇ 50% and ⁇ 70% of the total oxide quantity and the SnO2 -Share is in the range of 4 to 8% and that on the one hand the ratio of the mass proportions in% of SnO2 to CuO between 8: 1 and 12: 1 and on the other hand the ratio of the mass proportions in% of SnO2 to Bi2O3 between 1: 1 and 3: 1 lies.
  • a predetermined amount is
  • the present invention was based on the knowledge that the SnO2 portion of the total amount of oxide can be reduced with the method according to the invention. This creates a very specific structure with different oxide particle sizes, with re-granulation taking place to form mixed oxides.
  • the electrical properties can be further advantageously influenced by different Bi2O3 distributions.
  • An alloy of AgSnBiCu is melted in the specified composition at 1353 K from 93.60% fine silver grains, 5.20% tin grains, 0.60% metallic bismuth as fragments and 0.60% copper in rod form.
  • an alloy powder of the same composition is obtained.
  • the powder fraction is sieved to ⁇ 200 ⁇ m. This proportion is internally oxidized in an oxygen-containing atmosphere between 773 K and 872 K, after which a composite powder of AgSnO2Bi2O3CuO the composition in mass fractions of 92.10% Ag, 6.5% SnO2, 0.66% Bi2O3 and 0.74% CuO is obtained.
  • Such a composite powder is quantitatively internally oxidized and is referred to as IOLP.
  • the specified AgSnO2Bi2O3CuO composite powder was a metal oxide additive in mass fractions of 2.7% Bi2O3, based on the composite powder, added by wet mixing under propanol in a stirred ball mill using steel balls. After drying, the steel balls were separated from the powder mixture of composite powder and bismuth oxide powder by sieving. The composition of the starting material for the contact material (composite powder and bismuth oxide) is then in mass fractions 89.68% Ag, 6.33% SnO2, 3.27% Bi2O3 and 0.72% CuO.
  • two-layer molded parts with a solderable silver layer are expediently produced for use as contact pieces for low-voltage switchgear in power engineering, the contact pieces being solidified by sintering in air, hot compression, sintering and cold compression to form a practically non-porous material. Process technologies customary in the prior art are used for this.
  • the outer areas of the former composite powder particles are grained with mixed oxide formation. In these areas, there is a locally higher Bi2O3 concentration than inside the particles.
  • the structure of a material produced in this way shows oxide deposits in two distributions: On the one hand, there are coarse oxide deposits with an average diameter ( d ) of about 2 ⁇ m, and on the other hand fine oxide precipitates with a diameter (d) of ⁇ 1 ⁇ m, the latter being arranged inside the particles of the former composite powder.
  • the single figure shows a metallographic micrograph (400: 1) with the structure of a material produced in this way, from which the typical distribution of the mixed oxide precipitates can be seen.
  • 1 in each case means the regions which have arisen from the alloy powder after internal oxidation.
  • the fine oxide precipitates 2 present in these areas have a diameter of ⁇ 1 ⁇ m and are essentially statistically distributed. Between areas 1 there are areas 3 with coarse oxide precipitates 4, which have an average diameter of approximately 2 ⁇ m.
  • the welding force of the contact material produced according to the invention is determined in a test switch.
  • the measured values obtained essentially correspond to those of an AgCdO12Bi2O31.0 contact material made from internally oxidized alloy powder.
  • service life and heating tests were carried out in motor contactors.
  • the key parameters are the AC4 lifetime switching number of the contact pieces and the overtemperature of the current paths. In comparison to the AgCdO12Bi2O31.0 material, the lifetime switching numbers are higher by a factor of 2.4, with higher temperatures only showing up to about 10 ° C.
  • the comparison values are compiled in the table.
  • the relative tin content is reduced, inter alia, by specifically increasing the bismuth content. This can be done in particular by the separate addition of Bi2O3 powder to the IOLP.
  • the volume fraction of total metal oxide which is decisive for the property spectrum after quantitative internal oxidation remains in the predetermined range. Unexpectedly good results were found in the electrical switching behavior.

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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)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • High-Tension Arc-Extinguishing Switches Without Spraying Means (AREA)

Claims (7)

  1. Procédé de fabrication d'un matériau de contact pour appareil interrupteur basse tension, qui est essentiellement exempt de pores et qui est constitué d'AgSnO₂, de Bi₂O₃ et de CuO par frittage, densification à chaud et/ou densification à froid successifs, le cas échéant répétés, de poudre servant de matière de départ pour la fabrication de pièces de contact, qui consiste à utiliser comme matière de départ
    - d'une part, un alliage AgSnBiCu de composition donnée, produit par l'atomisation et l'oxydation interne d'une poudre composite de constitution AgSnO₂Bi₂O₃CuO, et
    - d'autre part, une poudre d'oxyde métallique produite indépendamment, à base de Bi₂O₃,
    - la composition de l'alliage d'AgSnBiCu et la quantité de poudre de Bi₂O₃ produite indépendamment étant telles que dans le matériau de contact fritté
    - la proportion en volume de la somme des oxydes métalliques est comprise entre 10 et 25 % avec une proportion en volume de SnO₂ supérieure ou égale à 50 % et inférieure à 70 % de la quantité totale des oxydes et
    - la proportion pondérale de SnO₂ est comprise entre 4 et 8 %,
    alors que
    - d'une part, le rapport des proportions pondérales en pourcentage de SnO₂ à CuO est compris entre 8:1 et 12:1 et
    - d'autre part, le rapport des proportions pondérales en pourcentage de SnO₂ à Bi₂O₃ est compris entre 1:1 et 3:1.
  2. Procédé suivant la revendication 1, caractérisé en ce que la concentration de l'alliage d'AgSnBiCu et la quantité de poudre de Bi₂O₃ produite indépendamment sont telles que la proportion en volume de SnO₂ représente 65 % environ de la quantité totale des oxydes.
  3. Procédé suivant la revendication 2, caractérisé en ce que la concentration de l'alliage d'AgSnBiCu et la quantité de poudre de Bi₂O₃ produite indépendamment sont telles que le rapport en pourcentage de SnO₂ à CuO est de 9:1 environ.
  4. Procédé suivant la revendication 2, caractérisé en ce que la concentration de l'alliage d'AgSnBiCu et la quantité de la poudre de Bi₂O₃ produite indépendamment sont telles que le rapport des proportions pondérales en pourcentage de SnO₂ à Bi₂O₃ est de 9:5 environ.
  5. Procédé suivant la revendication 1, caractérisé en ce qu'il consiste à ajouter à une composition donnée à l'avance de poudre d'AgSnO₂Bi₂O₃CuO une quantité donnée à l'avance de poudre de Bi₂O₃.
  6. Procédé suivant l'une des revendications précédentes, caractérisé en ce que, pour préparer l'alliage d'AgSnBiCu, on fond et l'on atomise sous pression 96,60 % d'argent fin, 5,2 % d'étain, 0,60 % de bismuth métallique et 0,60 % de cuivre, l'addition d'oxyde métallique de 2,63 % de Bi₂O₃ à la poudre de l'alliage, après oxydation intérieure complète en la poudre composite AgSnO₂Bi₂O₃CuO, étant effectuée après mélange par voie humide dans un broyeur à brassage.
  7. Procédé suivant la revendication 6, caractérisé en ce qu'il consiste à utiliser, pour le mélange par voie humide, des solvants organiques, par exemple du propanol.
EP85106749A 1984-06-12 1985-05-31 Procédé pour la fabrication de matériau de contact fritté Expired - Lifetime EP0170812B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85106749T ATE84906T1 (de) 1984-06-12 1985-05-31 Verfahren zur herstellung von sinterkontaktwerkstoffen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843421758 DE3421758A1 (de) 1984-06-12 1984-06-12 Sinterkontaktwerkstoff fuer niederspannungsschaltgeraete der energietechnik und verfahren zu dessen herstellung
DE3421758 1984-06-12

Publications (3)

Publication Number Publication Date
EP0170812A2 EP0170812A2 (fr) 1986-02-12
EP0170812A3 EP0170812A3 (en) 1988-03-23
EP0170812B1 true EP0170812B1 (fr) 1993-01-20

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ID=6238159

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EP85106749A Expired - Lifetime EP0170812B1 (fr) 1984-06-12 1985-05-31 Procédé pour la fabrication de matériau de contact fritté

Country Status (7)

Country Link
US (2) US4764227A (fr)
EP (1) EP0170812B1 (fr)
JP (1) JPH0672276B2 (fr)
AT (1) ATE84906T1 (fr)
BR (1) BR8502780A (fr)
DE (2) DE3421758A1 (fr)
ZA (1) ZA854391B (fr)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3421758A1 (de) * 1984-06-12 1985-12-12 Siemens AG, 1000 Berlin und 8000 München Sinterkontaktwerkstoff fuer niederspannungsschaltgeraete der energietechnik und verfahren zu dessen herstellung
JPS63286541A (ja) * 1987-05-18 1988-11-24 Tanaka Kikinzoku Kogyo Kk Ａｇ酸化物系電気接点材料
DE3909384A1 (de) * 1988-03-26 1989-10-19 Duerrwaechter E Dr Doduco Halbzeug fuer elektrische kontakte aus einem verbundwerkstoff auf silber-zinnoxid-basis und pulvermetallurgisches verfahren zu seiner herstellung
US4874430A (en) * 1988-05-02 1989-10-17 Hamilton Standard Controls, Inc. Composite silver base electrical contact material
US4834939A (en) * 1988-05-02 1989-05-30 Hamilton Standard Controls, Inc. Composite silver base electrical contact material
EP0369282B1 (fr) * 1988-11-17 1995-06-14 Siemens Aktiengesellschaft Matériau de contact fritté dans appareillages interrupteurs à basse tension de la technique de l'énergie, spécialement pour des contacteurs
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
US5091100A (en) * 1990-08-20 1992-02-25 Nalco Chemical Company Fatty triglyceride-in-water solid film high temperature prelube emulsion for hot rolled steel
BR9407450A (pt) * 1993-08-23 1996-11-12 Siemens Ag Material para contatos à base de prata utilização de um tal material para contatos em um dispositivo comutador da eletrotécnica e processo para a confecção deste material para contatos
DE4142374A1 (de) * 1991-12-20 1993-06-24 Siemens Ag Verfahren zum vorbeloten von kontaktstuecken fuer elektrische schaltgeraete
DE4201940A1 (de) * 1992-01-24 1993-07-29 Siemens Ag Sinterverbundwerkstoff fuer elektrische kontakte in schaltgeraeten der energietechnik
WO1994007252A1 (fr) * 1992-09-16 1994-03-31 Doduco Gmbh + Co. Dr. Eugen Dürrwächter Materiau pour contacts electriques a base d'argent-oxyde stannique ou d'argent-oxyde de zinc et son procede de fabrication
DE4331913A1 (de) * 1993-09-20 1995-03-23 Siemens Ag Verfahren zum Verbinden von einer Kontaktauflage aus Silber-Metalloxid-Werkstoff mit einem metallischen Kontaktträger
DE19503182C1 (de) * 1995-02-01 1996-05-15 Degussa Sinterwerkstoff auf der Basis Silber-Zinnoxid für elektrische Kontakte und Verfahren zu dessen Herstellung
JP4383859B2 (ja) * 2001-07-18 2009-12-16 エヌイーシー ショット コンポーネンツ株式会社 温度ヒューズ
JP4089252B2 (ja) * 2002-03-11 2008-05-28 オムロン株式会社 直流負荷用接点構成および該構成を有した開閉器
CN115710653B (zh) * 2022-11-09 2023-08-29 浙江福达合金材料科技有限公司 银金属氧化物电触头材料的制备方法

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JPS6018735B2 (ja) * 1977-12-15 1985-05-11 松下電器産業株式会社 電気接点材料
JPS6013051B2 (ja) * 1978-08-11 1985-04-04 中外電気工業株式会社 銀↓−錫↓−ビスマス系合金を内部酸化した電気接点材料の改良
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JPS6027746B2 (ja) * 1979-09-19 1985-07-01 松下電器産業株式会社 電気接点材料
JPS57134532A (en) * 1981-02-12 1982-08-19 Chugai Electric Ind Co Ltd Electrical contact material of silver-tin-bismuth alloy
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DE3205857A1 (de) * 1982-02-18 1983-08-25 Chugai Denki Kogyo K.K., Tokyo Material fuer elektrische kontakte aus innen oxidierter ag-sn-bi-legierung
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DE3304637A1 (de) * 1983-02-10 1984-08-16 Siemens AG, 1000 Berlin und 8000 München Sinterkontaktwerkstoff fuer niederspannungsschaltgeraete
DE3305270A1 (de) * 1983-02-16 1984-08-16 Siemens AG, 1000 Berlin und 8000 München Sinterverbundwerkstoff fuer elektrische kontakte und verfahren zu seiner herstellung
DE3466122D1 (en) * 1984-01-30 1987-10-15 Siemens Ag Contact material and production of electric contacts
DE3421758A1 (de) * 1984-06-12 1985-12-12 Siemens AG, 1000 Berlin und 8000 München Sinterkontaktwerkstoff fuer niederspannungsschaltgeraete der energietechnik und verfahren zu dessen herstellung

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DE2754335A1 (de) * 1976-12-03 1978-06-08 Matsushita Electric Ind Co Ltd Elektrischer kontaktwerkstoff und verfahren zu dessen herstellung

Also Published As

Publication number Publication date
DE3421758A1 (de) 1985-12-12
BR8502780A (pt) 1986-02-18
US4764227A (en) 1988-08-16
US4855104A (en) 1989-08-08
DE3587005D1 (de) 1993-03-04
EP0170812A3 (en) 1988-03-23
JPS6112841A (ja) 1986-01-21
ATE84906T1 (de) 1993-02-15
ZA854391B (en) 1986-02-26
JPH0672276B2 (ja) 1994-09-14
EP0170812A2 (fr) 1986-02-12

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