EP0645049B1 - Matiere pour contacts electriques a base d'oxyde d'etain et d'argent ou d'oxyde de zinc et d'argent - Google Patents

Matiere pour contacts electriques a base d'oxyde d'etain et d'argent ou d'oxyde de zinc et d'argent Download PDF

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Publication number
EP0645049B1
EP0645049B1 EP93912924A EP93912924A EP0645049B1 EP 0645049 B1 EP0645049 B1 EP 0645049B1 EP 93912924 A EP93912924 A EP 93912924A EP 93912924 A EP93912924 A EP 93912924A EP 0645049 B1 EP0645049 B1 EP 0645049B1
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EP
European Patent Office
Prior art keywords
tin
oxide
oxides
carbides
silver
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
EP93912924A
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German (de)
English (en)
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EP0645049A1 (fr
Inventor
Volker Behrens
Thomas Honig
Andreas Kraus
Karl E. Saeger
Rainer Schmidberger
Theodor Staneff
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 Solutions GmbH
Original Assignee
Doduco GmbH and Co KG Dr Eugen Duerrwaechter
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Publication date
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Publication of EP0645049A1 publication Critical patent/EP0645049A1/fr
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Publication of EP0645049B1 publication Critical patent/EP0645049B1/fr
Anticipated expiration legal-status Critical
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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
    • 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

Definitions

  • 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, additives in powder form are added to the material, which is generally produced by powder metallurgy, which leads to a lower temperature at the contact point.
  • Tungsten and molybdenum compounds have become known 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, EP-A-0024349).
  • Bismuth and germanium compounds 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 the additives because they have an embrittling effect.
  • Another disadvantage, in particular of the tungsten and molybdenum compounds, is that they - especially 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 a contact temperature that is as low as possible under constant current load should be achieved by specifically producing a structure in which areas in which little or no metal oxide is contained 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 present invention is based on the object of creating a material of the type mentioned at the outset which, by means of oxidic or carbide additives, exhibits heating behavior which is just as favorable as that of the known contact materials, but is less brittle.
  • Another advantage of the invention is that the lower proportion of the chosen additive increases the service life of contact pieces made of the material, because the additives, which, like the molybdenum oxide, tend to evaporate under the influence of an arc, lead to a lower proportion thanks to their lower proportion Blistering on the contact surface and thus less burning.
  • Such a material can 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 and / or part of the additive diffuses into the surface area of the tin oxide particles, a single-phase mixed oxide ( a new chemical compound) or a two-phase or multi-phase oxide mixture can be formed.
  • the reaction spraying process can also advantageously be used to obtain a tin oxide powder which is superficially coated with the other oxides by, in a modification of the procedure described above, suspending a finely divided tin oxide powder in the salt solution instead of a tin salt and this suspension in a hot oxidizing atmosphere sprays.
  • the material expediently contains 5 to 20% by weight, preferably 8 to 15% by weight, tin oxide, and thus the tin oxide as desired can be kept in suspension by the additives in the molten phase occurring under the action of arcing, the tin oxide powder should contain 0.01 to 10% by weight of the further oxidic or carbidic additive, but expediently not more than 5% by weight.
  • the addition of the other oxides and carbides should be chosen as low as possible in order not to exceed a contact point temperature specified under the specified conditions of use, for which much smaller quantities are sufficient than in the prior art.
  • a tin oxide powder which contains only 0.1 to 1.5% by weight of the further oxide or carbide is preferably used.
  • the tin oxide areas in the material are expediently less than 100 ⁇ m, preferably less than 10 ⁇ m in diameter, but should not be less than 0.5 ⁇ m in order not to cause the material to become solidified in dispersion.
  • Molybdenum oxide is particularly preferred as an additive because of its particularly favorable effect on the heating behavior.
  • the teaching according to the invention can be applied to contact materials based on silver with zinc oxide. In such materials, practically no additives are used today, but efforts have so far been made to reduce the contact point temperature by constructive measures. By using a zinc oxide enriched with further oxides and / or carbides according to the invention, a lowering of the contact point temperature can also be achieved with this type of material.
  • a tin oxide-molybdenum oxide composite powder with 1% by weight of molybdenum oxide is produced by spraying an aqueous solution of tin-II-chloride and molybdenum-IV-chloride in a reactor heated to approx. 950 ° C. oxidizing atmosphere, whereby a tin oxide-molybdenum oxide composite powder precipitates, in the powder particles of which the tin oxide and the molybdenum oxide are present in a very fine distribution.
  • 12% by weight of the molybdenum oxide-doped tin oxide powder thus produced are mixed intensively with 88 parts by weight of a silver powder with a particle size of less than 40 ⁇ m, a cylindrical block of 50 kg weight is pressed cold isostatically therefrom, sintered in air and in the process Maintained at 820 ° C for 1.5 hours.
  • the sintered block is coated with silver, placed hot in a reverse extrusion press and pressed through an extrusion die with a branching extrusion opening, resulting in two flat strands that have a silver-tin oxide surface on one side and a well-soldered one on the other side. and have weldable silver surface.
  • the strands are then rolled flat and then have a width of 8 cm and a thickness of 2 mm.
  • the first example is modified such that instead of a solution of tin-II-chloride and molybdenum-IV-chloride, a solution of molybdenum-IV-chloride is sprayed in which a tin oxide powder with a particle size smaller than 5 ⁇ m is suspended.
  • This wire is tapered to a diameter of 1.4 mm and then processed into contact rivets with a head diameter of 3.2 mm and a shaft diameter of 1.47 mm.
  • the new material proves to be clearly superior to the state-of-the-art contact materials both in the AC service life test and when switching DC lamp loads.
  • a mixed oxide powder is produced from an aqueous solution of zinc chloride and meta-tungstic acid by spraying the solution into a reactor heated to 1100 ° C.
  • the zinc-tungsten-oxide mixture obtained in this way has a tungsten oxide content of 1% by weight and an average particle diameter of 2.4 ⁇ m.
  • the oxide powder is mixed with silver powder and further processed into contact wafers.
  • An aqueous solution of tin acetate and ammonium heptamolybdate is sprayed into a reactor at a temperature of 800 ° C., thus obtaining an oxide powder with a molybdenum oxide content of 350 ppm and an average particle diameter of 1.9 ⁇ m.
  • This powder is used to produce a contact material, as in Example 1, which is subjected to a service life test in accordance with test category AC1 in a switching device with an output of 37 kW. This lifetime test is interrupted in order to carry out a warming test with continuous current.
  • FIG. 1 The result of this heating test is shown in FIG. 1 and compared with an analog test for a state-of-the-art material made of 88% by weight Ag, 11.6% by weight SnO2 and 0.4% by weight MoO3 (FIG. 2 ).
  • the heating behavior of the novel material is just as good as that of the conventional material, although the novel material, based on the entire contact material, only has a molybdenum oxide content of 42 ppm, while the state-of-the-art material for the same advantageous result requires an amount of molybdenum oxide of 0.4% by weight, that is around a hundred times as much.

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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)

Claims (18)

  1. Matière pour contacts électriques à base d'argent-oxyde d'étain, qui dans une matrice d'argent ou d'un alliage contenant principalement de l'argent, contient des domaines d'oxyde d'étain et d'autres oxydes et/ou carbures, caractérisée en ce que les autres oxydes et carbures sont contenus dans les domaines d'oxyde d'étain et/ou dans une zone limitrophe entre les domaines d'oxyde d'étain et la matrice d'argent,
    la fraction des autres oxydes et carbures pris ensemble représente jusqu'à 40% en poids par rapport à la masse d'oxyde d'étain,
    les autres oxydes et carbures sont des composés du molybdène, du tungstène, du bismuth, de l'antimoine, du germanium, du vanadium, du cuivre ou de l'indium,
    et la matrice d'argent, abstraction faite d'une fraction éventuellement soluble dans cette matrice, est exempte des autres oxydes et carbures.
  2. Matière selon la revendication 1, caractérisée en ce que la fraction d'oxyde d'étain et des autres oxydes et carbures pris ensemble représente de 5 à 20% en poids (par rapport au poids total de la matière).
  3. Matière selon la revendication 2, caractérisée en ce que la fraction d'oxyde d'étain et des autres oxydes et carbures pris ensemble représente de 8 à 15% en poids (par rapport au poids total de la matière).
  4. Matière selon l'une quelconque des revendications précédentes, caractérisée en ce que les domaines d'oxyde d'étain contiennent au moins 0,01% en poids (par rapport à la masse d'oxyde d'étain) des autres oxydes et/ou carbures.
  5. Matière selon l'une quelconque des revendications précédentes, caractérisée en ce que les domaines d'oxyde d'étain contiennent jusqu'à 10% en poids (par rapport à la quantité d'oxyde d'étain) des autres oxydes et/ou carbures.
  6. Matière selon l'une des revendications 1 à 4, caractérisée en ce que les domaines d'oxyde d'étain contiennent jusqu'à 5% en poids (par rapport à la masse d'oxyde d'étain) des autres oxydes et/ou carbures.
  7. Matière selon l'une des revendications 1 à 4, caractérisée en ce que les domaines d'oxydes d'étain contiennent jusqu'à 2,5% en poids (par rapport à la masse d'oxyde d'étain) des autres oxydes et/ou carbures.
  8. Matière selon la revendication 4, caractérisée en ce que les domaines d'oxyde d'étain contiennent de 0,1 à 1,5% des autres oxydes et/ou carbures.
  9. Matière selon l'une des revendications 1 à 8, qui est obtenue par mélange de poudre d'oxyde d'étain avec les autres oxydes et/ou carbures sous forme de poudre, calcination du mélange, de façon que par diffusion des autres oxydes et/ou carbures dans les particules de poudre d'oxyde d'étain, une poudre composite se forme, séparation de l'excédent d'autres oxydes et carbures de la poudre composite et insertion de la poudre composite dans une matrice d'argent ou d'un alliage contenant principalement de l'argent.
  10. Matière selon l'une des revendications 1 à 8, qui est obtenue par pulvérisation d'une solution d'un sel d'étain et d'un sel du métal ou des métaux, dont les oxydes doivent être contenus dans la matière en plus de l'oxyde d'étain, dans une atmosphère chaude et oxydante, dans laquelle les sels sont convertis en oxydes sous l'action de la chaleur, de façon que se dépose une poudre composite finement divisée, qui contient l'oxyde d'étain et les autres oxydes, et insertion de cette poudre composite dans une matrice d'argent ou d'un alliage contenant principalement de l'argent.
  11. Matière selon l'une des revendications 1 à 8, caractérisée en ce qu'elle contient avec les autres oxydes et/ou carbures des particules d'oxyde d'étain incrustées.
  12. Matière selon la revendication 11, caractérisée en ce que les particules d'oxyde d'étain incrustées avec les autres oxydes et/ou carbures sont obtenues par pulvérisation d'une suspension d'oxyde d'étain dans une solution d'un sel ou de sels du métal ou des métaux, dont les oxydes doivent être contenus en plus de l'oxyde d'étain dans la matière, dans une atmosphère chaude et oxydante, dans laquelle les sels sont convertis thermiquement en oxydes et se fixent aux particules d'oxyde d'étain provenant de la suspension.
  13. Matière selon l'une des revendications 1 à 8, qui est obtenue par pulvérisation d'une suspension d'oxyde d'étain et/ou d'un ou plusieurs oxydes et/ou carbures, qui doivent être contenus dans la matière en plus de l'oxyde d'étain, dans une solution d'un sel ou de sels du métal ou des métaux, dont les oxydes doivent être contenus sous forme de constituant oxydé résiduel dans la matière, dans une atmosphère chaude et oxydante, dans laquelle les sels sont convertis thermiquement en oxydes et se fixent aux particules d'oxyde et aux particules de carbure provenant de la suspension.
  14. Matière selon l'une quelconque des revendications précédentes, caractérisée en ce que ses domaines d'oxyde d'étain sont inférieurs en diamètre à 100 µm.
  15. Matière selon la revendication 14, caractérisée en ce que ses domaines d'oxyde d'étain n'excèdent pas en diamètre 10 µm.
  16. Matière selon l'une quelconque des revendications précédentes, caractérisée en ce que ses domaines d'oxyde d'étain ont un diamètre d'au moins 0,5 µm.
  17. Matière selon l'une quelconque des revendications précédentes, caractérisée en ce que l'étain est remplacé en tout ou partie par du zinc.
  18. Procédé pour la préparation d'une matière pour contacts électriques à base d'argent-oxyde d'étain selon la revendication 1 par
    - mélange d'une poudre d'argent ou d'un alliage contenant principalement de l'argent avec une poudre d'oxyde d'étain, dont les particules de poudre contiennent jusqu'à 40% en poids (par rapport à la masse d'oxyde d'étain) d'un oxyde et/ou d'un carbure de molybdène, tungstène, bismuth, antimoine, germanium, vanadium, cuivre ou indium,
    - compression
    - frittage.
EP93912924A 1992-06-10 1993-06-09 Matiere pour contacts electriques a base d'oxyde d'etain et d'argent ou d'oxyde de zinc et d'argent Expired - Lifetime EP0645049B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE4219333 1992-06-10
DE4219333 1992-06-10
DE4311399 1993-04-07
DE4311399 1993-04-07
PCT/EP1993/001453 WO1993026021A1 (fr) 1992-06-10 1993-06-09 Matiere pour contacts electriques a base d'oxyde d'etain et d'argent ou d'oxyde de zinc et d'argent

Publications (2)

Publication Number Publication Date
EP0645049A1 EP0645049A1 (fr) 1995-03-29
EP0645049B1 true EP0645049B1 (fr) 1996-04-03

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EP93912924A Expired - Lifetime EP0645049B1 (fr) 1992-06-10 1993-06-09 Matiere pour contacts electriques a base d'oxyde d'etain et d'argent ou d'oxyde de zinc et d'argent

Country Status (8)

Country Link
US (1) US5610347A (fr)
EP (1) EP0645049B1 (fr)
JP (1) JP2896428B2 (fr)
CN (1) CN1036099C (fr)
AT (1) ATE136394T1 (fr)
DE (1) DE59302122D1 (fr)
ES (1) ES2086945T3 (fr)
WO (1) WO1993026021A1 (fr)

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CN102350502B (zh) * 2011-10-27 2013-01-09 福达合金材料股份有限公司 物理冶金包覆法银氧化锡的制备方法
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EP2644723B1 (fr) * 2012-03-26 2017-01-18 Umicore AG & Co. KG Matière active composite
CN102936668A (zh) * 2012-11-08 2013-02-20 哈尔滨工业大学 一种TCO/Cu电接触材料
CN102912177A (zh) * 2012-11-08 2013-02-06 哈尔滨工业大学 一种TCO/Ag电接触材料
CN103589898B (zh) * 2013-11-22 2015-06-24 福达合金材料股份有限公司 银金属氧化物碳化钨复合电触头材料的制备方法及其产品
CN103700532B (zh) * 2013-12-30 2015-10-14 桂林电器科学研究院有限公司 一种喷雾干燥制备银氧化锡电触头材料的方法
CN105728714B (zh) * 2014-12-12 2018-12-04 施耐德电气工业公司 银-金属氧化物电触头材料的制备方法、装置以及应用

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Also Published As

Publication number Publication date
JP2896428B2 (ja) 1999-05-31
CN1036099C (zh) 1997-10-08
ES2086945T3 (es) 1996-07-01
DE59302122D1 (de) 1996-05-09
US5610347A (en) 1997-03-11
WO1993026021A1 (fr) 1993-12-23
JPH08503998A (ja) 1996-04-30
EP0645049A1 (fr) 1995-03-29
CN1085687A (zh) 1994-04-20
ATE136394T1 (de) 1996-04-15

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