EP1043409B1 - Matériau composite préparé par métallurgie des poudres - Google Patents

Matériau composite préparé par métallurgie des poudres Download PDF

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Publication number
EP1043409B1
EP1043409B1 EP00107121A EP00107121A EP1043409B1 EP 1043409 B1 EP1043409 B1 EP 1043409B1 EP 00107121 A EP00107121 A EP 00107121A EP 00107121 A EP00107121 A EP 00107121A EP 1043409 B1 EP1043409 B1 EP 1043409B1
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EP
European Patent Office
Prior art keywords
composite material
matrix
refractory
metal
refractory component
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
EP00107121A
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German (de)
English (en)
Other versions
EP1043409A3 (fr
EP1043409A2 (fr
Inventor
Gerd Dipl.-Ing. Renner
Udo Dr. Dipl.-Chem. Siefken
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.)
Renner Louis GmbH
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Renner Louis GmbH
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Publication date
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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
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • 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

  • tungsten-silver and molybdenum-silver composites have been known as contact materials that are exposed to high electrical loads. These sintered materials combine the erosion resistance of the refractory refractory components W and Mo with the good electrical and thermal conductivity of the silver used as the matrix component.
  • Such contact materials are used as standard in the low-voltage power engineering as Abbrennessore in circuit breakers and as main contacts in circuit breakers.
  • a disadvantage of the first method is a remaining relatively high residual porosity, which may require further compression by re-pressing. Of the Forming degree by re-densification is relatively low. The result is a residual finite porosity.
  • Fine-grained refractory metal powders have a significantly higher oxygen content than coarse-grained powders. This complicates the wetting with matrix metal, which entails increased pore formation. Therefore, fine-grained materials tend to have a higher pore content than coarse-grained materials.
  • Another difficulty lies in the handling of fine refractory metal powders with an average particle size in the range of ⁇ 1 ⁇ m. These powders become pyrophoric and tend to spontaneously foul, burn or fume when processed in air.
  • a material produced by extrusion over the Einzelpreßtechnik also has the advantage that quasi an endless profile is generated, which can also be plated with the solder suitable for the connection technology during its manufacture.
  • This endless belt can then be integrated directly into the production line at the switch manufacturer.
  • the required contact pad is cut to length, fed to the carrier and connected, for example, by means of resistance soldering.
  • a disadvantage of both forming processes is that the starting pins, which are subjected to the forming must be sufficiently ductile. Otherwise, damage to the pressing or rolling equipment or to the profiles to be manufactured may occur during forming. With flat profiles, cracks and flaking at the edges can occur. Too brittle workpieces can not even be extruded even when warm. In any case, such errors are incompatible with a high material quality.
  • the forming technique of WAg or MoAg composites is limited to a technologically and economically less interesting high-silver content range.
  • A. Keil describes a.a.O. on p. 193 an extrusion of WAg sintered blocks produced by sintering powder mixtures below the melting point of silver is also seen, but the extrudability of the WAg is limited to tungsten parts ⁇ 30% by weight. Due to the high proportion of Ag, he believes that no stable and thus embrittling W skeletal body can form. The sintered body retains a sufficiently high ductility and remains extrudable.
  • JP-A-55 044558 discloses extruding a heat-resistant, electrically conductive material consisting of copper oxide or silver oxide alloy in the form of particles and W or Mo in the form of particles brought together, sintered and extruded.
  • the W or Mo surface is coated with Cu or Ag alloy. Neither in production nor application, this teaching aims at composites that are suitable for electrical contact materials.
  • the publication EP-A-0 806 489 relates to a process for producing a copper and a transition metal-containing composite, the process comprising sintering a compact of copper-containing and transition metal-containing particles in a reducing atmosphere, wherein the transition metal is preferably selected from tungsten and molybdenum and the compact contains sufficient chemically bound oxygen contains to improve the sintering of the compact.
  • the resulting composite material can be removed from the sintering furnace and used without further processing in a variety of electrical applications, preferably in electronic components.
  • the publication DE-A-1 106 965 relates to a process for the production of high density molded articles of silver composite, preferably having a sintered density of at least 95% and a Nachpreßêt of at least 99.8% of the compact density, characterized in that the pressed molded body is subjected to a pre-sintering in a hydrogen atmosphere, in terms of time and Temperature is measured so that the molding remains permeable to gas, and that the molding is then heated without sintering in vacuo for one hour to be selected between 850 ° C and the melting point of the silver sintering temperature and densely sintered and then nachgepreßt.
  • the document gives no indication of the particle size of the refractory component. Although molybdenum and tungsten are mentioned as added metals, in the examples only the ductile metal nickel in combination with silver is used.
  • the invention is therefore based on the object to develop a contact material, which is both inexpensive to manufacture, and improved material properties, i. shows a fine-grained, evenly distributed refractory fraction in the metal matrix with the lowest possible residual porosity. It is intended to provide a material which meets the increasing demands on electrical switching capacity and service life (number of switching cycles), in particular in low-voltage technology.
  • the invention should encompass the full range of technically important compositions. Of particular interest is the composition W / Ag 40/60 wt .-% to W / Ag 60/40 wt .-% or MoAg 40/60 wt .-% to MoAg 60/40 wt .-%.
  • the material should be superior in terms of its physical and technological values to the state-of-the-art materials and offer advantages in terms of handling and costs to the switch manufacturer when equipping the switchgear.
  • the invention is further based on the object to provide a method for producing such a contact material, which by a high degree of deformation ensures the desired compression of the material with a residual porosity ⁇ 0.5%.
  • the invention thus relates to a powder metallurgically produced composite material according to claim 1 and such a composite material in the form of a flat strip or endless belt according to claim 6.
  • Preferred embodiments of the composite material of the invention are the subject of claims 1 to 5 and a preferred embodiment of the composite material in the form of a flat strip or endless belt is the subject matter of claim 7.
  • the subject of the invention is the use of a composite material of the invention as an electrical contact material.
  • a refractory metal preferably W or Mo
  • W or Mo is weighed by powder metallurgy with at least one of the matrix metals Cu, Ag, Al in such a way that the refractory component preferably comprises 30-70% by weight of the mixture.
  • the refractory metal powder must be fine-grained with 0.1 to 1 micron average grain size.
  • a powdery sintering aid such as Ni, Co or Fe are added.
  • the weighed powders are homogenized by a method known to those skilled in the art and pressed isostatically to round bolts.
  • the resulting green compact is sintered under protective gas at a temperature above 600 ° C in such a way that a sintering shrinkage (volume contraction) of at least 10% occurs.
  • the still porous sintered body thus obtained is heated inductively and reduced by means of a suitable forming technique, such as extrusion (forward extrusion), rolling or Umschmieden to a suitable cross-section.
  • a suitable forming technique such as extrusion (forward extrusion), rolling or Umschmieden to a suitable cross-section.
  • extrusion forward extrusion
  • rolling or Umschmieden
  • brazing is the dimensionally desired profile (preferably flat strip) obtained and wound onto a coil as an endless belt.
  • the residual porosity of the finished material is ⁇ 0.5%.
  • the finished sintered bolt has a density of 12.0 g / cm 3 . This corresponds to a residual porosity of 7%.
  • the resulting wires are then further processed by fine rolling to a thickness of 1 mm or roll-rolled directly after extrusion with a suitable Ag brazing alloy and then finish-rolled to final strength.
  • Each rolling process is associated with a subsequent deburring and annealing.
  • the distribution of W in the Ag matrix is very uniform.
  • the material is virtually free of pores. Despite the extreme elongation in one axis due to extrusion and rolling, the longitudinal grinding shows only a small line texture. In other words, the material has no preferred direction in the arrangement of the W grains in the Ag matrix. It is virtually isotropic over the 3 spatial directions, i. the distribution is in the optimum.
  • Example 2 In a similar manner as in Example 1, 50 parts by weight of fine Ag powder ⁇ 60 microns grain size mixed with 50 parts by weight of submicron tungsten metal powder, ground and pressed into round bars. The green compact obtained is in turn sintered at a temperature of 700 ° C in such a way that the sintering shrinkage is 38.7 vol .-%. As a sintering aid 4 wt .-% Ni was added. The sintered billet has a density of 12.7 g / cm 3 . This corresponds to a residual porosity of 8%.
  • the obtained strip with 5 x 1 mm cross-section has the following chemical and physical properties.
  • typical values according to the prior art AgW 50/50 wt .-%, single-press technique, sintered in the liquid phase.
  • State of the art Ag analysis: [Wt .-%] 49.6 (50)
  • Hardness [HV], annealed 152 130 Micrograph longitudinal / transverse Fig. 3 / Fig. 4
  • the improvements in terms of grain size, distribution and pore poverty can be compared to a state-of-the-art comparative sanding (AgW 50/50 wt.%, Single-press technique, sintered in the liquid phase) (cf. Fig. 5 ).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Powder Metallurgy (AREA)
  • Contacts (AREA)
  • Manufacture Of Switches (AREA)
  • High-Tension Arc-Extinguishing Switches Without Spraying Means (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Claims (13)

  1. Matériau composite obtenu par métallurgie des poudres, constitué par une matrice en argent, un additif en grains en au moins un métal réfractaire (composant réfractaire) contenu dans cette matrice, et, le cas échéant en guise d'adjuvant de frittage, au moins un métal qui s'allie aussi bien avec le composant réfractaire qu'avec le métal de la matrice, matériau composite dans lequel la proportion du composant réfractaire est a 30 a 70% en poids, rapportée à la masse totale du matériau composite, dans lequel le composant réfractaire présente une grosseur de grain moyenne de 0,1 - 1,0 µm et est réparti de manière uniforme dans la matrice, et dans lequel l'adjuvant de frittage est additionné selon une quantité d'au plus 6% en poids, et le composite présente une porosité résiduelle < 0,5%.
  2. Matériau composite selon la revendication 1, caractérisé en ce que la proportion en composant réfractaire vaut 40 - 60% en poids rapportée à la masse totale du matériau composite.
  3. Matériau composite selon l'une des revendications 1 ou 2, caractérisé en ce que le composant réfractaire est constitué par au moins l'un des métaux W et Mo.
  4. Matériau composite selon l'une des revendications 1 3, caractérisé en ce que l'adjuvant de frittage est additionné selon une quantité de 0,3 à 4% en poids.
  5. Matériau composite selon la revendication 4, caractérisé en ce que l'adjuvant de frittage est constitué de Ni, Co ou Fe.
  6. Matériau composite obtenu par métallurgie des poudres, sous la forme d'un ruban plat ou d'une bande sans fin, constitué par une matrice en argent ou en cuivre, un additif en grains en au moins un métal réfractaire (composant réfractaire) contenu dans cette matrice, et, le cas échéant en guise d'adjuvant de frittage, au moins un métal qui s'allie aussi bien avec le composant réfractaire qu'avec le métal de la matrice, matériau dans lequel la proportion du composant réfractaire est > 30 à 70% en poids, rapportée à la masse totale du matériau composite, dans lequel le composant réfractaire présente une grosseur de grain moyenne de 0,1 - 1,0 µm et est réparti de manière uniforme dans la matrice, et dans lequel l'adjuvant de frittage est additionné dans une quantité d'au plus 6% en poids, et le composite présente une porosité résiduelle < 0,5%.
  7. Matériau composite selon la revendication 6, caractérisé en ce qu'il est plaqué avec un métal d'apport de brasage fort.
  8. Procédé de production d'un matériau composite selon l'une des revendications 1 à 5, caractérisé en ce qu'un mélange sous forme de poudre, constitué par au moins un métal réfractaire avec une grosseur de grain moyenne de 0,1 - 1,0 µm et de l'argent en tant que métal de matrice, le cas échéant avec addition de l'adjuvant de frittage, est compressé et est aggloméré par frittage en phase solide ou liquide à une température au-dessus de 600°C, de façon qu'il se produise une contraction ou un retrait de frittage de 10 - 50% en volume, et en ce que le corps de frittage obtenu est soumis à un formage de façon à ce que la porosité résiduelle se situe à une valeur <0,5%.
  9. Procédé selon la revendication 8, caractérisé en ce que la contraction ou le retrait de frittage vaut de 30-40% en volume.
  10. Procédé selon l'une des revendications 8 ou 9, caractérisé en ce que le formage est effectué par extrusion, laminage ou forgeage.
  11. Procédé de production d'un matériau composite sous la forme d'un ruban plat ou d'une bande sans fin, selon la revendication 6, caractérisé en ce qu'un mélange sous forme de poudre, constitué par au moins un métal réfractaire avec une grosseur de grain moyenne de 0,1-1,0 µm et de l'argent ou du cuivre en tant que métal de matrice, le cas échéant avec addition de l'adjuvant de frittage, est compressé et est aggloméré par frittage en phase solide ou liquide à une température au-dessus de 600°C, de façon qu'il se produise une contraction ou un retrait de frittage de 10 - 50% en volume, en ce que le corps de frittage obtenu est soumis à un formage de façon à ce que la porosité résiduelle se situe à une valeur < 0,5%, et en ce qu'est effectué un formage supplémentaire par laminage en obtenant un ruban plat ou une bande sans fin.
  12. Procédé selon la revendication 11, caractérisé en ce que le ruban plat ou la bande sans fin est plaqué avec un placage de métal d'apport de brasage approprié.
  13. Utilisation d' un matériau composite selon l'une des revendications 1 à 7 en tant que matériau de contact électrique.
EP00107121A 1999-04-09 2000-04-07 Matériau composite préparé par métallurgie des poudres Expired - Lifetime EP1043409B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19916082A DE19916082C2 (de) 1999-04-09 1999-04-09 Pulvermetallurgisch hergestellter Verbundwerkstoff, Verfahren zu dessen Herstellung sowie dessen Verwendung
DE19916082 1999-04-09

Publications (3)

Publication Number Publication Date
EP1043409A2 EP1043409A2 (fr) 2000-10-11
EP1043409A3 EP1043409A3 (fr) 2003-12-17
EP1043409B1 true EP1043409B1 (fr) 2008-06-18

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Application Number Title Priority Date Filing Date
EP00107121A Expired - Lifetime EP1043409B1 (fr) 1999-04-09 2000-04-07 Matériau composite préparé par métallurgie des poudres

Country Status (5)

Country Link
US (1) US6312495B1 (fr)
EP (1) EP1043409B1 (fr)
JP (1) JP2000319734A (fr)
DE (2) DE19916082C2 (fr)
ES (1) ES2307476T3 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7192551B2 (en) * 2002-07-25 2007-03-20 Philip Morris Usa Inc. Inductive heating process control of continuous cast metallic sheets
US20060086441A1 (en) * 2004-10-27 2006-04-27 University Of Cincinnati Particle reinforced noble metal matrix composite and method of making same
US9694562B2 (en) 2010-03-12 2017-07-04 Xtalic Corporation Coated articles and methods
US20110220511A1 (en) * 2010-03-12 2011-09-15 Xtalic Corporation Electrodeposition baths and systems

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1106965B (de) * 1957-02-12 1961-05-18 Siemens Ag Verfahren zur Herstellung dicht gesinterter Formkoerper aus Silberverbundwerkstoff
US3685134A (en) * 1970-05-15 1972-08-22 Mallory & Co Inc P R Method of making electrical contact materials
US3992199A (en) * 1973-12-03 1976-11-16 P. R. Mallory & Co., Inc. Method of making electrical contact materials
JPS6032699B2 (ja) * 1978-09-27 1985-07-30 住友電気工業株式会社 耐熱導電材料並びにその製造方法
US4249944A (en) * 1979-04-09 1981-02-10 Fansteel Inc. Method of making electrical contact material
US4810289A (en) * 1988-04-04 1989-03-07 Westinghouse Electric Corp. Hot isostatic pressing of high performance electrical components
US5413751A (en) * 1993-04-14 1995-05-09 Frank J. Polese Method for making heat-dissipating elements for micro-electronic devices
US5439638A (en) * 1993-07-16 1995-08-08 Osram Sylvania Inc. Method of making flowable tungsten/copper composite powder
US5846288A (en) * 1995-11-27 1998-12-08 Chemet Corporation Electrically conductive material and method for making
US5831186A (en) * 1996-04-01 1998-11-03 Square D Company Electrical contact for use in a circuit breaker and a method of manufacturing thereof
US5686676A (en) * 1996-05-07 1997-11-11 Brush Wellman Inc. Process for making improved copper/tungsten composites
DE19828692A1 (de) * 1997-06-27 1999-01-07 Ami Doduco Gmbh Verfahren zum Granulieren von Zinnoxidpulver und damit hergestellte Kontaktwerkstoffe auf der Basis von Silber-Zinnoxid
DE19833620A1 (de) * 1998-07-25 2000-01-27 Ticona Gmbh Abtrennung von Trioxan aus gasförmigen Gemischen mit Formaldehyd

Also Published As

Publication number Publication date
US6312495B1 (en) 2001-11-06
EP1043409A3 (fr) 2003-12-17
DE19916082C2 (de) 2001-05-10
DE19916082A1 (de) 2000-10-19
EP1043409A2 (fr) 2000-10-11
DE50015204D1 (de) 2008-07-31
JP2000319734A (ja) 2000-11-21
ES2307476T3 (es) 2008-12-01

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