EP0170812A2 - 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
EP0170812A2
EP0170812A2 EP85106749A EP85106749A EP0170812A2 EP 0170812 A2 EP0170812 A2 EP 0170812A2 EP 85106749 A EP85106749 A EP 85106749A EP 85106749 A EP85106749 A EP 85106749A EP 0170812 A2 EP0170812 A2 EP 0170812A2
Authority
EP
European Patent Office
Prior art keywords
sno
contact material
sintered contact
oxide
volume fraction
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.)
Granted
Application number
EP85106749A
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German (de)
English (en)
Other versions
EP0170812A3 (en
EP0170812B1 (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
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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Filing date
Publication date
Application filed by Siemens AG, Siemens Corp 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

    • 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 sintered contact material for low-voltage switching devices in power engineering made of AgSn0 2 with Bi 2 0 3 and CuO as further. Metal oxides and a volume fraction of total metal oxide between 10% and 25%. In addition, the invention also relates to special processes for producing the material.
  • 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 in particular was used as the active component, with these contact materials in particular fulfilling the desired electrical-technological properties and having proven themselves in the long-term use of switching devices.
  • cadmium is known to be one of the toxic heavy metals and when the contact pieces burn off, CdO is also released to the surrounding area, efforts have been underway for some time to replace the CdO as completely as possible with other metal oxides.
  • these materials should have an arc burn-up that is just as small, as well as low welding power and, in particular, low heating with continuous current flow, like the proven AgCdO materials for contact pieces.
  • the object of the invention is therefore to specify a further material of the constitution AgSnO 2 Bi 2 O 3 CuO for the above-mentioned application and associated manufacturing processes.
  • the Sn0 2 volume fraction is ⁇ 70% of the total amount of oxide, the Sn0 2 mass fraction in the range between 4% and 8% and the ratio of the mass fraction in% of Sn0 2 to CuO between 8: 1 and 12: 1.
  • the volume of SnO 2 is preferably about 65% of the total amount of oxide, in any case being at least 50%.
  • compositions have mass fractions of either 6.33% Sn0 2 , 3.27% Bi 2 0 3 , 0.72% Cu0 or 6.47% Sn0 2 , 3.51% Bi203, 0.71% CuO and the balance each proven silver.
  • 0.64% of the bismuth oxide is present in the IOLP and 2.63% as a separate oxide.
  • GB-A-20 55 398 describes materials based on silver metal oxide, for the production of which sheets are produced from alloys, which are subsequently oxidized internally. This means that these are not powder metallurgy materials, especially not by internal oxidation of alloy powders.
  • a composition in mass fractions of 9 0, 8% Ag, 8.5% .sn, 0.2% Bi and 0.5% Cu is specified for the starting alloy. Otherwise, other components are still added to the four-component systems, for example cobalt, iron or nickel.
  • the present invention was based on the surprising finding that the Sn0 2 portion of the total amount of oxide must be reduced in order to further improve the temperature properties, to the extent that its relative volume fraction of the total amount of oxide is below 70%.
  • the Bi 2 0 3 proportion in the material is increased considerably, so that the ratio of the mass fractions of SnO 2 to Bi 2 0 3 is now between 1 and 3.
  • an alloy powder of a predetermined composition is internally oxidized.
  • the procedure can preferably be such that an alloy with a comparatively small amount of bismuth is first produced in a manner known per se and, after the oxidation, a separate powder of Bi 2 0 3 is added to the internally oxidized alloy powder.
  • This creates a very specific structure with different oxide particle sizes, with re-granulation taking place to form mixed oxides.
  • Bi 2 0 3 distributions can further advantageously influence the electrical properties.
  • the sintered contact material according to the invention can also be produced by using alloy powder with a correspondingly high bismuth concentration as the starting material, from which a completely internally oxidized composite powder can be produced.
  • the mass fractions of the individual components are given in%, from which the volume fractions of the oxides result from the different densities.
  • 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 portion is sieved to ⁇ 200 ⁇ m.
  • This portion is internally oxidized in an oxygen-containing atmosphere between 773 K and 872 K, after which a composite powder of AgSnO 2 Bi 2 0 3 CuO of the composition in mass fractions of 92.10% Ag, 6.5% Sn0 2 , 0.66% Bi 2 0 3 and 0.74% CuO is obtained.
  • Such a composite powder is quantitatively internally oxidized and is referred to as IOLP.
  • the specified AgSn0 2 Bi 2 0 3 Cu0 composite powder was a My mass proportions talloxidzusatzj of 2.7% Bi 2 0 3 , based on the composite powder, by wet mixing under propanol in an agitator ball grinder added 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% SnO 2 , 3.27% Bi 2 0 3 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 purpose.
  • the outer areas of the former composite powder particles are grained with mixed oxide formation. In these areas there is a locally higher Bi 2 0 3 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 on average with a diameter (d) of about 2 ⁇ m, and on the other hand fine oxide deposits with a diameter (d) of ⁇ 1 ⁇ m, the latter inside the Particles of the former composite powder are arranged.
  • the single figure shows a metallographic micrograph (400: 1) with the structure of one produced in this way Material from which the typical distribution of the mixed oxide precipitates can be seen.
  • 1 denotes the areas 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.
  • areas 3 with coarse oxide precipitates 4, which have an average diameter of approximately 2 ⁇ m.
  • An alloy of AgSnBiCu in the specified composition is melted from 91.02% fine silver grains, 5.19% tin grains, 3.21% metallic bismuth as fragments and 0.58% copper in rod form.
  • an alloy powder of the same composition is obtained.
  • the powder fraction is sieved to ⁇ 200 ⁇ m and this fraction is internally oxidized in an oxygen-containing atmosphere between 723 K and 873 K.
  • a composite powder AgSnO 2 Bi 2 O 3 CuO of the composition in mass fractions of 89.31% Ag, 6.47% Sn0 2 , 3.51% Bi 2 0 3 and 0.71% CuO is obtained in this way.
  • a two-layer powder compact is immediately produced from the composite powder and is solidified by sintering, the residual porosity for suitable contact pieces being reduced by hot or cold compression.
  • Example 2 the structure of the material is very fine and uniform, with an average oxide excretion size of approximately 1.5 ⁇ m.
  • the welding force of the contact materials produced according to the invention was determined in a test switch.
  • the measured values obtained essentially correspond to those of an AgCd012Bi 2 0 3 1.0 contact material produced from internally oxidized alloy powder.
  • service life and heating tests were carried out in motor contactors.
  • the key parameters are the AC4 service life of the contact pieces and the overtemperature of the current paths. Compared to the AgCdO12Bi 2 O 3 1.0 material, the lifespan switching numbers are about a factor of 2.4 higher, 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 either by adding Bi 2 0 3 powder separately to the IOLP or by increasing the bismuth content in the starting alloy before the oxidation.
  • the volume fraction of total metal oxide which is decisive for the property spectrum after quantitative internal oxidation remains in the predetermined range. In all cases, unexpectedly good results were found in the electrical switching behavior.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (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)
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 true EP0170812A2 (fr) 1986-02-12
EP0170812A3 EP0170812A3 (en) 1988-03-23
EP0170812B1 EP0170812B1 (fr) 1993-01-20

Family

ID=6238159

Family Applications (1)

Application Number Title Priority Date Filing Date
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)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0369283A3 (fr) * 1988-11-17 1991-03-13 Siemens Aktiengesellschaft Matériau de contact fritté pour appareillages interrupteurs à basse tension de la technique de l'énergie, spécialement pour des contacteurs
EP0369282A3 (fr) * 1988-11-17 1991-03-13 Siemens Aktiengesellschaft Matériau de contact fritté dans appareillages interrupteurs à basse tension de la technique de l'énergie, spécialement pour des contacteurs
WO1993015517A1 (fr) * 1992-01-24 1993-08-05 Siemens Aktiengesellschaft Materiau composite fritte pour des contacts electriques d'appareils de commutation en technique des courants forts et procede pour sa 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

Families Citing this family (13)

* 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
JPH03504615A (ja) * 1988-03-26 1991-10-09 ドドウコ・ゲーエムベーハー＋コンパニー・ドクトル・オイゲン・デュルベヒテル 銀‐錫酸化物系複合材料から成る電気接点用半製品および粉末冶金によるその製法
US4834939A (en) * 1988-05-02 1989-05-30 Hamilton Standard Controls, Inc. Composite silver base electrical contact material
US4874430A (en) * 1988-05-02 1989-10-17 Hamilton Standard Controls, Inc. Composite silver base electrical contact material
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
DE4142374A1 (de) * 1991-12-20 1993-06-24 Siemens Ag Verfahren zum vorbeloten von kontaktstuecken fuer elektrische schaltgeraete
ATE139864T1 (de) * 1992-09-16 1996-07-15 Duerrwaechter E Dr Doduco Werkstoff für elektrische kontakte auf der basis von silber-zinnoxid oder silber-zinkoxid und verfahren zu seiner herstellung
US5796017A (en) * 1993-08-23 1998-08-18 Siemens Aktiengesellschaft Silver-based contact material, use of such a contact material, in switchgear for power engineering applications and method of manufacturing the contact material
DE19503182C1 (de) * 1995-02-01 1996-05-15 Degussa Sinterwerkstoff auf der Basis Silber-Zinnoxid für elektrische Kontakte und Verfahren zu dessen Herstellung
US6724292B2 (en) * 2001-07-18 2004-04-20 Nec Schott Components Corporation Thermal fuse
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

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH588152A5 (fr) * 1972-12-11 1977-05-31 Siemens Ag
US4141727A (en) * 1976-12-03 1979-02-27 Matsushita Electric Industrial Co., Ltd. Electrical contact material and method of making the same
DE2659012C3 (de) * 1976-12-27 1980-01-24 Siemens Ag, 1000 Berlin Und 8000 Muenchen Verfahren zum Herstellen eines Sinterkontaktwerkstoffes aus Silber und eingelagerten Metalloxiden
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
GB2055398B (en) * 1979-08-01 1983-06-02 Chugai Electric Ind Co Ltd Electrical contact materials of internally oxidized ag-sn-bi alloy
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
JPS57181340A (en) * 1982-02-02 1982-11-08 Chugai Electric Ind Co Ltd Electrical contact material of selectively and internally oxidized silver-tin alloy containing bismuth
JPS57145953A (en) * 1982-02-02 1982-09-09 Chugai Electric Ind Co Ltd Electrical contact material of silver-tin-bismuth alloy
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
US4452652A (en) * 1982-07-08 1984-06-05 Akira Shibata Electrical contact materials and their production method
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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0369283A3 (fr) * 1988-11-17 1991-03-13 Siemens Aktiengesellschaft Matériau de contact fritté pour appareillages interrupteurs à basse tension de la technique de l'énergie, spécialement pour des contacteurs
EP0369282A3 (fr) * 1988-11-17 1991-03-13 Siemens Aktiengesellschaft Matériau de contact fritté dans appareillages interrupteurs à basse tension de la technique de l'énergie, spécialement pour des contacteurs
WO1993015517A1 (fr) * 1992-01-24 1993-08-05 Siemens Aktiengesellschaft Materiau composite fritte pour des contacts electriques d'appareils de commutation en technique des courants forts et procede pour sa fabrication
US5486222A (en) * 1992-01-24 1996-01-23 Siemens Aktiengesellschaft Sintered composite materials for electric contacts in power technology switching devices and process for producing them
DE4331913A1 (de) * 1993-09-20 1995-03-23 Siemens Ag Verfahren zum Verbinden von einer Kontaktauflage aus Silber-Metalloxid-Werkstoff mit einem metallischen Kontaktträger
US5628448A (en) * 1993-09-20 1997-05-13 Siemens Aktiengesellschaft Process for bonding a contact layer of silver-metal oxide material and metal contact base, and suitable contact layer

Also Published As

Publication number Publication date
BR8502780A (pt) 1986-02-18
ATE84906T1 (de) 1993-02-15
DE3587005D1 (de) 1993-03-04
DE3421758A1 (de) 1985-12-12
EP0170812A3 (en) 1988-03-23
EP0170812B1 (fr) 1993-01-20
ZA854391B (en) 1986-02-26
JPH0672276B2 (ja) 1994-09-14
JPS6112841A (ja) 1986-01-21
US4855104A (en) 1989-08-08
US4764227A (en) 1988-08-16

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