EP0876670A2 - Method of producing a shaped part from a silver-based contact material - Google Patents

Method of producing a shaped part from a silver-based contact material

Info

Publication number
EP0876670A2
EP0876670A2 EP97914051A EP97914051A EP0876670A2 EP 0876670 A2 EP0876670 A2 EP 0876670A2 EP 97914051 A EP97914051 A EP 97914051A EP 97914051 A EP97914051 A EP 97914051A EP 0876670 A2 EP0876670 A2 EP 0876670A2
Authority
EP
European Patent Office
Prior art keywords
silver
contact material
metal oxide
rhenium
iron
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
EP97914051A
Other languages
German (de)
French (fr)
Other versions
EP0876670B1 (en
Inventor
Franz Hauner
Günter Tiefel
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.)
Metaux Precieux Metalor SA
Original Assignee
Siemens AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Siemens AG filed Critical Siemens AG
Publication of EP0876670A2 publication Critical patent/EP0876670A2/en
Application granted granted Critical
Publication of EP0876670B1 publication Critical patent/EP0876670B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
    • H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
    • H01H11/048—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by powder-metallurgical processes
    • 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
    • H01H2001/02378—Composite material having a noble metal as the basic material and containing oxides containing iron-oxide as major component

Definitions

  • the invention relates to a method for producing a shaped piece from a silver-based contact material.
  • the invention further relates to such a contact material and a shaped piece made from such a contact material.
  • contact materials based on silver which contain certain active components, have long proven themselves. Both metals and metal oxides are known as active components which have a favorable influence on the switching properties of the contact material.
  • Representatives of the silver-based metallic contact materials are, for example, silver-nickel (AgNi) and silver-iron (AgFe). Silver-iron oxide (AgFe 2 ⁇ 3) may be mentioned as a representative of the oxidic contact materials.
  • oxidic contact materials have a lower tendency to weld than metallic contact materials, the latter have a longer service life, especially with small currents.
  • Silver-nickel contact materials in particular have good switching properties, but it is disadvantageous that the nickel dust which forms during production or during operation due to abrasion and that which forms as a switching product Nickel oxide can have a harmful effect on the human organism.
  • a silver-based contact material is known from EP 0 586 411 B1, which contains the metals iron and rhenium in mass proportions between 1% and 50% or between 0.01% and 5% as active components. It was recognized that rhenium improves the properties of such a contact material even in proportions below 1%.
  • the contact material mentioned is characterized by a low contact heating with stable heating behavior, acceptable welding tendency and a long service life in relation to predetermined switching currents.
  • the silver-iron-rhenium contact material is produced by mixing silver and iron-rhenium alloy powder or by mixing separate powders of silver, iron and rhenium.
  • the powder mixture is then processed by compression molding or extrusion and sintering into molded parts or semi-finished products.
  • the structure of such a material i.e. the size and the distribution of the active components in the silver matrix is predetermined by the grain size of the metal powder or alloy powder available on the market.
  • the use of coarse metal powders leads to a coarse-grained structure, of fine-grained metal powders to a fine-grained structure.
  • the finest iron powders produced in technically relevant quantities have an average grain size of approximately 5 ⁇ m.
  • Iron-rhenium powders are produced by atomizing a corresponding melt and also have an average grain size of approx. 5 ⁇ m or more.
  • the powder mixture is pressed into a molding by compression molding, which is produced by sintering and optionally further pressing Fitting is processed.
  • the shaped part can additionally be pressed with a layer of pure silver to securely connect the contact piece to the base by brazing.
  • the active components added in powder form with a uniform grain size are distributed irregularly over the silver matrix.
  • the structure of the fitting is largely isotropic.
  • the powder mixture is first pressed and / or sintered into a porous compact or slug.
  • the compact or slug optionally with a layer of pure silver (see above), is pressed by extrusion into a strand from which the shaped pieces are separated and possibly subjected to a subsequent treatment.
  • the powder grains of the silver and possibly the active components are deformed or aligned in the extrusion direction, as a result of which an anisotropic, namely linear structure is formed.
  • the contact material Due to the structure of the contact material, its electrical switching properties, e.g. Burning, contact resistance and welding force, largely determined.
  • WO 95/08833 A1 describes a method for connecting a contact piece made of a silver-metal oxide material to a carrier by brazing or welding.
  • the metal oxide of the contact material is at least partially reduced to metal in the region of the contact piece near the surface. A resulting structural change which has a favorable influence on the switching properties of the contact piece or the contact material is not achieved.
  • the method described is only suitable for the manufacture thin, weldable and solderable layers down to a few 100 ⁇ m.
  • the object of the invention is to provide a production method for a molded piece made of a contact material and such a contact material itself which has switching properties which are more favorable than the prior art. Furthermore, it is an object of the invention to provide a contact piece made of the contact material which, due to improved switching properties, is particularly suitable for a switching device in energy technology.
  • This object is achieved according to the invention with regard to the method for producing a shaped piece from a silver-based contact material by forming a powder mixture of silver and a metal oxide, which is processed into the shaped piece by powder metallurgy, and reducing the metal oxide to metal .
  • the invention is based on the knowledge that a contact material with a fine structure exhibits better switching behavior than a contact material with a coarse structure.
  • the range of properties of a contact material can be significantly improved by reducing the average grain size of the active components in the silver matrix.
  • Active components is less than 1 ⁇ m.
  • Such a contact material can, however, not be produced using known powder-metallurgical manufacturing processes using commercially available metal powders, the average grain size of which is in the range of a few microns.
  • metal oxide powders are available whose grain sizes are significantly smaller than 1 ⁇ m
  • the use of metal oxide powder instead of metal powder and subsequent reduction of the metal oxide enables a contact material to be obtained in which the average grain size the metallic active components are in the nanometer range.
  • the use of metal oxide powders can be carried out under less strict transport and processing regulations, since in contrast to metal oxide powders, many metal powders are self-igniting. In this way, the manufacturing costs can be reduced.
  • the reduction of the metal oxide advantageously takes place in the powder mixture, since a complete reduction of the metal oxide is made more difficult by the increasing compression of the powder mixture in subsequent work steps.
  • the reduction of the metal oxide can also take place in a blank of the shaped piece, which still has a sufficiently high porosity or gas permeability.
  • a blank is, for example, the slug to be made available in extrusion technology, which is subsequently pressed into an extrusion.
  • such a blank can also be a preliminary product for a molded part produced in the molding technology, before the molded part is produced therefrom by pressing and sintering again.
  • the reduction of the metal oxide is expediently achieved by heat treatment in a reducing atmosphere. It is particularly effective if the heat treatment is carried out in a temperature range of 500 ° C. below the melting point of silver, ie taking into account the admixed active components at a temperature between 500 ° C. and 1000 ° C., preferably at 700 ° C. becomes.
  • the reducing atmosphere can also be used as a protective gas for any sintering that may be required. Sintering and reduction can thereby Position of the contact material takes place in one operation.
  • the gas hydrogen (H 2 ) usually used for the sintering is advantageously also used as the reducing atmosphere.
  • the sintering and pressing processes necessary in powder metallurgical manufacturing processes can lead to a conglomeration of the active component supplied in powder form. This is particularly the case if the active component is supplied in the form of a powder of a metal oxide with very small grain sizes. Grain sizes of the active component that are favorable for the switching properties can be achieved in the contact material if a powder with a grain size of less than 1 ⁇ m, preferably from 100 to 500 nm, is used as the metal oxide.
  • Metal oxide is added. As described, the further metal oxide is reduced to a further metal. However, it is also conceivable to add the further metal oxide only after the powder mixture has been reduced. In this case, the contact material produced would have an oxidic active component.
  • the powder mixture is silver (Ag), iron oxide (Fe 2 0 3 / Fe 3 ⁇ 4) and rhenium (Re) or silver (Ag), rhenium oxide (Re) and iron (Fe) or silver
  • the object is achieved according to the invention by a silver-based contact material with at least one further metallic component, the mean grain size of which is smaller than 1 ⁇ m, preferably 100 to Is 500 nm.
  • a contact material has in particular a very low tendency to weld and a long service life.
  • the contact material has favorable switching properties if iron (Fe) and rhenium (Re) are provided as the active metal components. It is advantageous if iron (Fe) is in a mass fraction between 1 and 50% and rhenium (Re) in a mass fraction between 0.01 and 5%.
  • the object with regard to the contact piece is achieved according to the invention by a molded piece made of the contact material in the form of a contact piece.
  • the contact piece can additionally be provided with a layer of pure silver for secure connection of the contact piece to the base by brazing.
  • Such a contact piece is suitable for use in a switching device in power engineering, in particular for a low-voltage switch.
  • 3 shows a structure of an Ag (FeRe 95/5) 8, 8 material produced according to the extrusion technology according to the invention parallel to the extrusion direction; 4 structure of a Ag (FeRe 95/5) 8.8 material conventionally produced by the extrusion technology parallel to the extrusion direction.
  • a silver-iron-rhenium material is produced.
  • silver powder Ag is mixed with rhenium powder Re (grain size approx. 5 ⁇ m) and with iron oxide powder Fe 2 0 3 / Fe 3 ⁇ 4 (grain size smaller than 10 nm).
  • This powder mixture is further processed into a blank or slug which is annealed at a temperature of 700 ° C. under an H 2 atmosphere to reduce the iron oxide to iron.
  • the further processing into a contact piece takes place according to the extrusion technique described under known conditions.
  • the composition of the powder mixture is such that the sum of the mass fractions of the active components iron (Fe) and rhenium (Re) is 8.8% in the finished material, the ratio of iron to rhenium being 19/1.
  • the material is to be referred to as Ag (FeRe 95/5) 8.8 in the following, where the ratio 95/5 refers to the mixing ratio of iron and rhenium powder, which is due to the manufacturing process.
  • FIGS. 1 and 3 show the fine structure of an Ag (FeRe 95/5) 8,8 material produced in this way parallel or perpendicular to the extrusion direction.
  • the mean grain size of the rhenium and iron particles in the silver matrix is in a range significantly below 1 ⁇ m.
  • the difference in size of the active components embedded in the silver matrix is significant.
  • FIGS. 3 and 4 show the structure of an Ag (FeRe 95/5) 8, 8 material produced according to the invention or conventionally, parallel to the extrusion direction.
  • the sum of the welding force values is shown, the ordinate being divided logarithmically according to the Weibull function and the abscissa. Since the mechanical processing of AgFeRe contact materials during the first switching operations can be the cause of high welding power, the 99.8% value is used for comparison with conventionally manufactured AgFeRe materials.

Abstract

The invention concerns the production of a shaped part from a silver-based contact material. According to the invention, a powder mixture is formed from silver and a metal oxide and is processed powder-metallurgically to form the shaped part, the metal oxide being reduced to metal. Since metal oxide powders with a considerably finer grain size than metal powders are available, a contact material of which the metal incorporated as active component has an average grain size of less than 1 mu m can be obtained. Owing to the fine grain size, a contact material of this type has particularly advantageous switching properties.

Description

~„~™, PCT/DE97/00042 O 97/27601~ "~ ™ , PCT / DE97 / 00042 O 97/27601
Beschreibungdescription
Verfahren zur Herstellung eines Formstücks aus einem Kontakt- werkstoff auf SilberbasisProcess for producing a shaped part from a contact material based on silver
Die Erfindung betrifft ein Verfahren zur Herstellung eines Formstücks aus einem Kontaktwerkstoff auf Silberbasis. Die Erfindung betrifft weiter einen solchen Kontaktwerkstoff so¬ wie ein Formstück aus einem solchen Kontaktwerkstoff.The invention relates to a method for producing a shaped piece from a silver-based contact material. The invention further relates to such a contact material and a shaped piece made from such a contact material.
Für ein Kontaktstück in einem Niederspannungs-Schaltgerät der Energietechnik, z.B. in einem Leistungsschalter oder in einem Hilfsschütz, haben sich Kontaktwerkstoffe auf Silberbasis, die bestimmte Wirkkomponenten enthalten, seit langem bewährt. Alε Wirkkomponenten, welche die Schalteigenschaften des Kon- taktwerkstoffes günstig beeinflussen, sind sowohl Metalle als auch Metalloxide bekannt. Vertreter der metallischen Kontakt¬ werkstoffe auf Silberbasis sind beispielsweise Silber-Nickel (AgNi) und Silber-Eisen (AgFe) . Als Vertreter der oxidischen Kontaktwerkstoffe sei beispielhaft Silber-Eisenoxid (AgFe2θ3) genannt.For a contact piece in a low-voltage switching device in energy technology, for example in a circuit breaker or in an auxiliary contactor, contact materials based on silver, which contain certain active components, have long proven themselves. Both metals and metal oxides are known as active components which have a favorable influence on the switching properties of the contact material. Representatives of the silver-based metallic contact materials are, for example, silver-nickel (AgNi) and silver-iron (AgFe). Silver-iron oxide (AgFe 2 θ3) may be mentioned as a representative of the oxidic contact materials.
Während oxidische Kontaktwerkstoffe gegenüber metallischen Kontaktwerkstoffen eine geringere Verschweißneigung aufwei- sen, besitzen letztgenannte insbesondere bei kleinen Strömen eine höhere Lebensdauer.While oxidic contact materials have a lower tendency to weld than metallic contact materials, the latter have a longer service life, especially with small currents.
Zur Messung bestimmter Eigenschaften eines Kontaktwerktoffes wird üblicherweise ein in Z. f. Werkstofftechnik/J. of Mate- rials Technology 7, (1976), 381 bis 389 beschriebener Prüf¬ schalter herangezogen, in den jeweils ein Kontaktstück aus dem Kontaktwerkstoff eingesetzt wird.In order to measure certain properties of a contact material, usually one in Z. f. Materials technology / J. of Materials Technology 7, (1976), 381 to 389 test switch used, in each of which a contact piece made of the contact material is used.
Besonders Silber-Nickel-Kontaktwerkstoffe besitzen gute Schalteigenschaften, jedoch ist nachteilig, daß der sich bei der Herstellung oder während des Betriebs durch Abrieb bil¬ dende Nickelstaub sowie das sich als Schaltprodukt bildende Nickeloxid eine schädliche Auswirkung auf den menschlichen Organismus haben kann.Silver-nickel contact materials in particular have good switching properties, but it is disadvantageous that the nickel dust which forms during production or during operation due to abrasion and that which forms as a switching product Nickel oxide can have a harmful effect on the human organism.
Aus der EP 0 586 411 Bl ist ein Kσntaktwerkstoff auf Silber- basis bekannt, der die Metalle Eisen und Rhenium in Massen¬ anteilen zwischen 1 % und 50 % bzw. zwischen 0,01 % und 5 % als Wirkkomponenten enthält. Dabei wurde erkannt, daß Rhenium selbst in Massenanteilen unter 1 % die Eigenschaften eines derartigen Kontaktwerkstoffes verbessert. Der genannte Kon- taktwerkstoff zeichnet sich durch eine geringe Kontakterwär¬ mung mit stabilem Erwärmungsverhalten, vertretbare Ver- schweißneigung und hohe Lebensdauer in bezug auf vorgegebene Schaltstromstärken aus.A silver-based contact material is known from EP 0 586 411 B1, which contains the metals iron and rhenium in mass proportions between 1% and 50% or between 0.01% and 5% as active components. It was recognized that rhenium improves the properties of such a contact material even in proportions below 1%. The contact material mentioned is characterized by a low contact heating with stable heating behavior, acceptable welding tendency and a long service life in relation to predetermined switching currents.
Gemäß der EP 0 586 411 Bl wird der Silber-Eisen-Rhenium-Kon¬ taktwerkstoff durch Mischen von Silber- und Eisen-Rhenium-Le¬ gierungspulver oder durch Mischen von separaten Pulvern aus Silber, Eisen und Rhenium hergestellt. Die Pulvermischung wird anschließend durch Formpressen oder Strangpressen sowie Sintern zu Formteilen bzw. zu Halbzeugen verarbeitet. Das Ge¬ füge eines solchen Werkstoffes, d.h. die Größe und die Ver¬ teilung der Wirkkomponenten in der Silbermatrix, ist durch die Korngröße der am Markt erhältlichen Metallpulver bzw. Le¬ gierungspulver vorgegeben. Die Verwendung von groben Metall- pulvern führt zu einem grobkörnigen, von feinkörnigen Metal1- pulvern zu einem feinkörnigen Gefüge. Die feinsten, in tech¬ nisch relevanten Mengen hergestellten Eisen-Pulver haben eine mittlere Korngröße von ca. 5 um. Eisen-Rhenium-Pulver werden durch Verdüsen einer entsprechenden Schmelze hergestellt und besitzen ebenfalls eine mittlere Korngröße von ca. 5 μm oder mehr.According to EP 0 586 411 B1, the silver-iron-rhenium contact material is produced by mixing silver and iron-rhenium alloy powder or by mixing separate powders of silver, iron and rhenium. The powder mixture is then processed by compression molding or extrusion and sintering into molded parts or semi-finished products. The structure of such a material, i.e. the size and the distribution of the active components in the silver matrix is predetermined by the grain size of the metal powder or alloy powder available on the market. The use of coarse metal powders leads to a coarse-grained structure, of fine-grained metal powders to a fine-grained structure. The finest iron powders produced in technically relevant quantities have an average grain size of approximately 5 μm. Iron-rhenium powders are produced by atomizing a corresponding melt and also have an average grain size of approx. 5 μm or more.
Zur Herstellung eines Formstücks aus dem Kontaktwerkstoff sind im wesentlichen zwei verschiedene pulvermetallurgische Verfahren bekannt. Bei der Formteiltechnik wird die Pulvermi¬ schung durch Formpressen zu einem Formteil verpreßt, welches durch Sintern und ggf. weiteres Pressen zu einem fertigen Formstück verarbeitet wird. Für die Herstellung eines Form¬ stücks in Form eines Kontaktstücks kann das Formteil zusätz¬ lich mit einer Schicht aus Reinsilber zur sicheren Verbindung des Kontaktstücks mit der Unterlage durch Hartlöten verpreßt werden.Essentially two different powder metallurgical processes are known for producing a shaped piece from the contact material. In the molding technology, the powder mixture is pressed into a molding by compression molding, which is produced by sintering and optionally further pressing Fitting is processed. For the production of a shaped piece in the form of a contact piece, the shaped part can additionally be pressed with a layer of pure silver to securely connect the contact piece to the base by brazing.
In einem nach der Formteiltechnik hergestellten Formstück liegen die in Pulverform zugefügten Wirkkomponenten mit ein¬ heitlicher Korngröße unregelmäßig über die Silbermatrix ver- teilt vor. Das Gefüge des Formstücks ist weitgehend isotrop.In a molded part manufactured according to the molding technology, the active components added in powder form with a uniform grain size are distributed irregularly over the silver matrix. The structure of the fitting is largely isotropic.
Bei der Strangpreßtechnik wird die Pulvermischung zunächst zu einem porösen Preßling oder Butzen gepreßt und/oder gesin¬ tert. Der Preßling oder Butzen wird, gegebenenfalls mit einer Schicht aus Reinsilber (s.o.), durch Strangpressen zu einem Strang verpreßt, aus welchem die Formstücke abgetrennt und eventuell einer nachfolgenden Behandlung unterzogen werden.In the extrusion technique, the powder mixture is first pressed and / or sintered into a porous compact or slug. The compact or slug, optionally with a layer of pure silver (see above), is pressed by extrusion into a strand from which the shaped pieces are separated and possibly subjected to a subsequent treatment.
In einem nach der Strangpreßtechnik hergestellten Formstück sind die Pulverkörner des Silbers und ggf. der Wirkkomponen¬ ten in Strangpreßrichtung verformt bzw. ausgerichtet, wodurch sich ein anisotropes, nämlich zeiliges Gefüge ausbildet.In a molded part manufactured according to the extrusion technique, the powder grains of the silver and possibly the active components are deformed or aligned in the extrusion direction, as a result of which an anisotropic, namely linear structure is formed.
Durch das Gefüge des Kontaktwerkstoffs werden seine elektri- sehen Schalteigenschaften, z.B. Abbrand, Kontaktwiderstand und Schweißkraft, maßgeblich bestimmt.Due to the structure of the contact material, its electrical switching properties, e.g. Burning, contact resistance and welding force, largely determined.
In der WO 95/08833 AI wird ein Verfahren zum Verbinden eines Kontaktstückes aus einem Silber-Metalloxid-Werkstoff mit ei- nem Träger durch Hartlöten oder Schweißen beschrieben. Dabei wird im oberflächennahen Bereich des Kontaktstückes das Me¬ talloxid des Kontaktwerkstoffes wenigstens teilweise zu Me¬ tall reduziert. Eine daraus resultierende, die Schalteigen¬ schaften des Kontaktstückes bzw. des Kontaktwerkstoffes gün- stig beeinflussende Gefügeveränderung wird nicht erreicht.WO 95/08833 A1 describes a method for connecting a contact piece made of a silver-metal oxide material to a carrier by brazing or welding. The metal oxide of the contact material is at least partially reduced to metal in the region of the contact piece near the surface. A resulting structural change which has a favorable influence on the switching properties of the contact piece or the contact material is not achieved.
Das beschriebene Verfahren eignet sich lediglich zur Herstel- lung dünner, schweiß- und lötbarer Schichten bis zu wenigen 100 μm.The method described is only suitable for the manufacture thin, weldable and solderable layers down to a few 100 μm.
Aufgabe der Erfindung ist es, ein Herstellungsverfahren für ein Formstück aus einem Kontaktwerkstoff sowie einen solchen Kontaktwerkstoff selbst anzugeben, welcher gegenüber dem Stand der Technik günstigere Schalteigenschaften aufweist. Ferner ist es Aufgabe der Erfindung, ein Kontaktstück aus dem Kontaktwerkstoff anzugeben, welches sich durch verbesserte Schalteigenschaften besonders für ein Schaltgerät der Ener¬ gietechnik eignet .The object of the invention is to provide a production method for a molded piece made of a contact material and such a contact material itself which has switching properties which are more favorable than the prior art. Furthermore, it is an object of the invention to provide a contact piece made of the contact material which, due to improved switching properties, is particularly suitable for a switching device in energy technology.
Diese Aufgabe wird bezüglich des Verfahrens zur Herstellung eines Formstücks aus einem Kontaktwerkstoff auf Silberbasis erfindungsgemäß gelöst, indem eine Pulvermischung aus Silber und aus einem Metalloxid gebildet wird, welche pulvermetall¬ urgisch zu dem Formstück verarbeitet wird, und wobei das Me¬ talloxid zu Metall reduziert wird.This object is achieved according to the invention with regard to the method for producing a shaped piece from a silver-based contact material by forming a powder mixture of silver and a metal oxide, which is processed into the shaped piece by powder metallurgy, and reducing the metal oxide to metal .
Die Erfindung geht dabei von der Erkenntnis aus, daß ein Kon¬ taktwerkstoff mit einem feinen Gefüge ein besseres Schaltver¬ halten als ein Kontaktwerkstoff mit einem groben Gefüge auf¬ weist. Das Eigenschaftsspektrum eines Kontaktwerkstoffes läßt sich erheblich verbessern, indem die mittlere Korngröße der Wirkkomponenten in der Silbermatrix verringert wird.The invention is based on the knowledge that a contact material with a fine structure exhibits better switching behavior than a contact material with a coarse structure. The range of properties of a contact material can be significantly improved by reducing the average grain size of the active components in the silver matrix.
Umfangreiche Messungen lassen erwarten, daß die Schalteigen¬ schaften eines Kontaktwerkstoffes auf Silberbasis bzw. die Schalteigenschaften eines Formstücks aus dem Kontaktwerkstoff besonders günstig sind, falls die mittlere Korngröße derExtensive measurements can be expected that the switching properties of a silver-based contact material or the switching properties of a molded piece made of the contact material are particularly favorable if the average grain size of the
Wirkkomponenten kleiner als 1 μm ist. Ein derartiger Kontakt¬ werkstoff läßt sich mit bekannten pulvermetallurgischen Her¬ stellungsverfahren bei Verwendung handelsüblicher Metallpul¬ ver, deren mittlere Korngröße im Bereich einiger um liegt, allerdings nicht erzeugen. O 97/27601 P rtCT/ 'DE97 "/0«0"0»4•"2Active components is less than 1 μm. Such a contact material can, however, not be produced using known powder-metallurgical manufacturing processes using commercially available metal powders, the average grain size of which is in the range of a few microns. O 97/27601 P rt CT / 'DE97 "/ 0« 0 "0» 4 • "2
Da jedoch Metalloxid-Pulver verfügbar sind, deren Korngrößen wesentlich kleiner als 1 μm sind, läßt sich durch die Verwen¬ dung von Metalloxid-Pulver statt Metall-Pulver und anschlie¬ ßende Reduktion des Metalloxids ein Kontaktwerkstoff erzie- len, bei dem die mittlere Korngröße der metallischen Wirkkom¬ ponenten im Nanometer-Bereich liegt. Zudem kann bei der Ver¬ wendung von Metalloxid-Pulvern unter weniger strengen Trans¬ port- und Verarbeitungsvorschriften gearbeitet werden, da im Gegensatz zu Metalloxid-Pulvern viele Metall-Pulver selbst- entzündlich sind. Auf diese Weise lassen sich die Herstel¬ lungskosten reduzieren.However, since metal oxide powders are available whose grain sizes are significantly smaller than 1 μm, the use of metal oxide powder instead of metal powder and subsequent reduction of the metal oxide enables a contact material to be obtained in which the average grain size the metallic active components are in the nanometer range. In addition, the use of metal oxide powders can be carried out under less strict transport and processing regulations, since in contrast to metal oxide powders, many metal powders are self-igniting. In this way, the manufacturing costs can be reduced.
Die Reduktion des Metalloxides erfolgt vorteilhafterweise in der Pulvermischung, da durch die zunehmende Verdichtung der Pulvermischung in nachfolgenden Arbeitsschritten eine voll¬ ständige Reduktion des Metalloxids erschwert ist.The reduction of the metal oxide advantageously takes place in the powder mixture, since a complete reduction of the metal oxide is made more difficult by the increasing compression of the powder mixture in subsequent work steps.
Die Reduktion des Metalloxids kann auch in einem Rohling des Formstücks erfolgen, welcher noch eine genügend hohe Porosi- tat bzw. Gasdurchlässigkeit aufweist. Ein solcher Rohling ist beispielsweise der in der Strangpreßtechnik bereitzustellende Butzen, der nachfolgend zu einem Strang verpreßt wird. Ebenso kann ein solcher Rohling aber auch ein in der Formteiltechnik hergestelltes Vorprodukt für ein Formteil sein, ehe aus die- sem durch erneutes Pressen und Sintern das Formteil herge¬ stellt wird.The reduction of the metal oxide can also take place in a blank of the shaped piece, which still has a sufficiently high porosity or gas permeability. Such a blank is, for example, the slug to be made available in extrusion technology, which is subsequently pressed into an extrusion. Likewise, such a blank can also be a preliminary product for a molded part produced in the molding technology, before the molded part is produced therefrom by pressing and sintering again.
Zweckmäßigerweise wird die Reduktion des Metalloxids durch eine Wärmebehandlung in einer reduzierenden Atmosphäre er- reicht. Besonders effektiv ist es, wenn die Wärmebehandlung in einem Temperaturbereich von 500 °C unterhalb des Schmelz¬ punktes von Silber, d.h. unter Berücksichtigung der beige¬ mischten Wirkkomponenten bei einer Temperatur zwischen 500 °C bis 1000 °C, vorzugsweise bei 700 °C, durchgeführt wird. Da- bei kann die reduzierende Atmosphäre gleichzeitig als Schutz¬ gas für eine eventuell erforderliche Sinterung herangezogen werden. Sinterung und Reduktion können dadurch bei der Her- Stellung des Kontaktwerkstoffes in einem Arbeitsgang erfol¬ gen.The reduction of the metal oxide is expediently achieved by heat treatment in a reducing atmosphere. It is particularly effective if the heat treatment is carried out in a temperature range of 500 ° C. below the melting point of silver, ie taking into account the admixed active components at a temperature between 500 ° C. and 1000 ° C., preferably at 700 ° C. becomes. The reducing atmosphere can also be used as a protective gas for any sintering that may be required. Sintering and reduction can thereby Position of the contact material takes place in one operation.
Vorteilhafterweise wird als reduzierende Atmosphäre auch das üblicherweise für die Sinterung eingesetzte Gas Wasserstoff (H2) verwendet.The gas hydrogen (H 2 ) usually used for the sintering is advantageously also used as the reducing atmosphere.
Durch die bei pulvermetallurgischen Herstellungsverfahren notwendigen Sinter- und Preßvorgänge kann es zu einer Konglo- meration der in Pulverform zugeführten Wirkkomponente kommen. Dies insbesondere, falls die Wirkkomponente in Form eines Pulvers eines Metalloxids mit sehr kleinen Korngrößen zuge¬ führt wird. Für die Schalteigenschaften günstige Korngrößen der Wirkkomponente lassen sich im Kontaktwerkstoff erzielen, wenn als Metalloxid ein Pulver mit einer Korngröße von klei¬ ner als 1 um, vorzugsweise von 100 bis 500 nm verwendet wird.The sintering and pressing processes necessary in powder metallurgical manufacturing processes can lead to a conglomeration of the active component supplied in powder form. This is particularly the case if the active component is supplied in the form of a powder of a metal oxide with very small grain sizes. Grain sizes of the active component that are favorable for the switching properties can be achieved in the contact material if a powder with a grain size of less than 1 μm, preferably from 100 to 500 nm, is used as the metal oxide.
Der hergestellte Kontaktwerkstoff bzw. das Formstück aus dem Kontaktwerkstoff weist vorteilhafte Schalteigenschaften auf, wenn der Pulvermischung ein weiteres Metall oder ein weiteresThe contact material or the molded part made of the contact material has advantageous switching properties if the powder mixture contains another metal or another
Metalloxid beigemischt wird. Dabei wird das weitere Metall¬ oxid, wie beschrieben, zu einem weiteren Metall reduziert. Es ist aber auch vorstellbar, das weitere Metalloxid erst nach der Reduktion der Pulvermischung beizumengen. Der herge- stellte Kontaktwerkstoff hätte in diesem Fall eine oxidische Wirkkomponente.Metal oxide is added. As described, the further metal oxide is reduced to a further metal. However, it is also conceivable to add the further metal oxide only after the powder mixture has been reduced. In this case, the contact material produced would have an oxidic active component.
Besonders vorteilhaft ist es, wenn der Pulvermischung Silber (Ag) , Eisenoxid (Fe203/Fe3θ4) und Rhenium (Re) oder Silber (Ag) , Rheniumoxid (Re) und Eisen (Fe) oder SilberIt is particularly advantageous if the powder mixture is silver (Ag), iron oxide (Fe 2 0 3 / Fe 3 θ4) and rhenium (Re) or silver (Ag), rhenium oxide (Re) and iron (Fe) or silver
(Ag) , Rheniumoxid (ReO) und Eisenoxid (Fe2θ3/Fe3θ4) zugeführt wird.(Ag), rhenium oxide (ReO) and iron oxide (Fe 2 θ3 / Fe3θ 4 ) is supplied.
Bezüglich des Kontaktwerkstoffes wird die Aufgabe erfindungs- gemäß gelöst durch einen Kontaktwerkstoff auf Silberbasis mit zumindest einer weiteren metallischen Komponente, deren mitt¬ lere Korngröße kleiner als 1 um ist, vorzugsweise 100 bis 500 nm beträgt. Ein derartiger Kontaktwerkstoff weist neben sehr guten Schalteigenschaften insbesondere eine sehr geringe Verschweißneigung sowie eine hohe Lebensdauer auf .With regard to the contact material, the object is achieved according to the invention by a silver-based contact material with at least one further metallic component, the mean grain size of which is smaller than 1 μm, preferably 100 to Is 500 nm. In addition to very good switching properties, such a contact material has in particular a very low tendency to weld and a long service life.
Günstige Schalteigenschaften besitzt der Kontaktwerkstoff, wenn als metallische Wirkkomponenten Eisen (Fe) und Rhenium (Re) vorgesehen sind. Dabei ist es vorteilhaft, wenn Eisen (Fe) in Massenanteilen zwischen 1 und 50 % und Rhenium (Re) in Massenanteilen zwischen 0,01 und 5 % vorliegen.The contact material has favorable switching properties if iron (Fe) and rhenium (Re) are provided as the active metal components. It is advantageous if iron (Fe) is in a mass fraction between 1 and 50% and rhenium (Re) in a mass fraction between 0.01 and 5%.
Die Aufgabe bezüglich des Kontaktstücks wird erfindungsgemäß gelöst durch ein Formstück aus dem Kontaktwerkstoff in Ge¬ stalt eines Kontaktstückes. Dabei kann das Kontaktstück zu¬ sätzlich mit einer Schicht aus Reinsilber zur sicheren Ver- bindung des Kontaktstücks mit der Unterlage durch Hartlöten versehen sein. Ein derartiges Kontaktstück eignet sich für die Verwendung in einem Schaltgerät der Energietechnik, ins¬ besondere für einen Niederspannungsschalter.The object with regard to the contact piece is achieved according to the invention by a molded piece made of the contact material in the form of a contact piece. The contact piece can additionally be provided with a layer of pure silver for secure connection of the contact piece to the base by brazing. Such a contact piece is suitable for use in a switching device in power engineering, in particular for a low-voltage switch.
Durch die folgenden Untersuchungsergebnisse sowie durch eineBy the following test results as well as by a
Zeichnung wird ein Ausführungsbeispiel der Erfindung näher erläutert.Drawing an embodiment of the invention is explained in more detail.
Dabei zeigen:Show:
FIG 1 Gefüge eines erfindungsgemäß nach der Strangpre߬ technik hergestellten Ag (FeRe 95/5) 8, 8-Werkstof- fes senkrecht zur Strangpreßrichtung;1 structure of an Ag (FeRe 95/5) 8, 8 material manufactured according to the extrusion technique according to the invention perpendicular to the extrusion direction;
FIG 2 Gefüge eines konventionell nach der Strangpreßtech¬ nik hergestellten Ag (FeRe 95/5) 8,8-Werkstoffes senkrecht zur Strangpreßrichtung;2 structure of an Ag (FeRe 95/5) 8,8 material conventionally produced according to the extrusion technology perpendicular to the direction of extrusion;
FIG 3 Gefüge eines erfindungsgemaß nach der Strangpreß- technik hergestellten Ag (FeRe 95/5) 8, 8-Werkstof- fes parallel zur Strangpreßrichtung; FIG 4 Gefüge eines konventionell nach der Strangpreßtech¬ nik hergestellten Ag (FeRe 95/5) 8,8-Werkstoffes parallel zur Strangpreßrichtung.3 shows a structure of an Ag (FeRe 95/5) 8, 8 material produced according to the extrusion technology according to the invention parallel to the extrusion direction; 4 structure of a Ag (FeRe 95/5) 8.8 material conventionally produced by the extrusion technology parallel to the extrusion direction.
Als Ausführungsbeispiel der Erfindung wird ein Silber-Eisen- Rhenium-Werkstoff hergestellt. Dazu wird Silberpulver Ag mit Rheniumpulver Re (Korngröße ca. 5 um) und mit Eisenoxid-Pul¬ ver Fe203/Fe3θ4 (Korngröße kleiner als 10 nm) vermischt. Die¬ ses Pulvergemisch wird zu einem Rohling oder Butzen weiter- verarbeitet, welcher bei einer Temperatur von 700 °C unter einer H2-Atmosphäre zur Reduktion des Eisenoxids zu Eisen ge¬ glüht wird. Die Weiterverarbeitung zu einem Kontaktstück ge¬ schieht nach der beschriebenen Strangpreßtechnik unter be¬ kannten Bedingungen.As an exemplary embodiment of the invention, a silver-iron-rhenium material is produced. For this purpose, silver powder Ag is mixed with rhenium powder Re (grain size approx. 5 μm) and with iron oxide powder Fe 2 0 3 / Fe 3 θ 4 (grain size smaller than 10 nm). This powder mixture is further processed into a blank or slug which is annealed at a temperature of 700 ° C. under an H 2 atmosphere to reduce the iron oxide to iron. The further processing into a contact piece takes place according to the extrusion technique described under known conditions.
Die Zusammensetzung der Pulvermischung ist derart, daß die Summe der Massenanteile der Wirkkomponenten Eisen (Fe) und Rhenium (Re) 8,8 % im fertigen Werkstoff beträgt, wobei das Verhältnis von Eisen zu Rhenium 19/1 gewählt ist. Der Werk- stoff soll im folgenden mit Ag (FeRe 95/5) 8,8 bezeichnet werden, wobei sich die Angabe des Verhältnisses 95/5 auf das fertigungstechnisch bedingte Mischungsverhältnis von Eisen- und Rhenium-Pulver bezieht.The composition of the powder mixture is such that the sum of the mass fractions of the active components iron (Fe) and rhenium (Re) is 8.8% in the finished material, the ratio of iron to rhenium being 19/1. The material is to be referred to as Ag (FeRe 95/5) 8.8 in the following, where the ratio 95/5 refers to the mixing ratio of iron and rhenium powder, which is due to the manufacturing process.
Figuren 1 und 3 zeigen die feine Struktur eines derart herge¬ stellten Ag (FeRe 95/5) 8,8-Werkstoffes parallel bzw. senk¬ recht zur Strangpreßrichtung. Die mittlere Korngröße der Rhe¬ nium- und Eisenpartikel in der Silbermatrix (gemessen senk¬ recht zur Strangpreßrichtung, s Fig. 1) liegt in einem Be- reich deutlich unter 1 um. Im Vergleich zu einem konventio¬ nell hergestellten Ag (FeRe 95/5) 8,8-Werkstoff, dessen Ge¬ füge senkrecht zur Strangpreßrichtung in Fig. 2 dargestellt ist, ist der Größenunterschied der in die Silbermatrix einge¬ betteten Wirkkomponenten signifikant. Ebenso wird dies auch in den Figuren 3 und 4 ersichtlich, die das Gefüge eines er¬ findungsgemäß bzw. konventionell hergestellten Ag (FeRe 95/5) 8, 8-Werkstoffes parallel zur Strangpreßrichtung zeigen. Als ein für das Schaltverhalten des Werkstoffs signifikanter Parameter wird die Schweißkraft des Werkstoffs nach Z. f. Werkstofftechnik/J. of Materials Technology 7, (1976) 381 bis 389 mit folgenden Prüfbedingungen getestet:FIGS. 1 and 3 show the fine structure of an Ag (FeRe 95/5) 8,8 material produced in this way parallel or perpendicular to the extrusion direction. The mean grain size of the rhenium and iron particles in the silver matrix (measured perpendicular to the extrusion direction, see FIG. 1) is in a range significantly below 1 μm. In comparison to a conventionally produced Ag (FeRe 95/5) 8.8 material, the structure of which is shown perpendicular to the extrusion direction in FIG. 2, the difference in size of the active components embedded in the silver matrix is significant. This can also be seen in FIGS. 3 and 4, which show the structure of an Ag (FeRe 95/5) 8, 8 material produced according to the invention or conventionally, parallel to the extrusion direction. The welding strength of the material according to Z. f. Materials technology / J. of Materials Technology 7, (1976) 381 to 389 tested with the following test conditions:
- Probenabmessung: 10 mm x 10 mm- Sample dimensions: 10 mm x 10 mm
- Kontaktfläche: ballig R = 80 mm- Contact surface: spherical R = 80 mm
- Oberflächenzustand: gedreht- Surface condition: turned
- Schließgeschwindigkeit: 1 m/sek. - Kontaktkraft: 60 N- Closing speed: 1 m / sec. - Contact force: 60 N.
- Prellzeit der ersten drei Sprünge: 5 msek.- Bounce time of the first three jumps: 5 msec.
- Trenngeschwindigkeit: 7,4 x 10"" m/sek.- separation speed: 7.4 x 10 " " m / sec.
- PrüfSpannung: 220 V- Test voltage: 220 V
- Einschalt- und Ausschaltstrom: 1000 A - Schaltzahl 1000.- Inrush and inrush current: 1000 A - Number of operations 1000.
Die Schweißkraftwerte werden in ihrer Summenhäufigkeit darge¬ stellt, wobei die Ordinate nach der Weibull-Funktion und die Abszisse logarithmisch geteilt ist. Da bei AgFeRe-Kontakt- Werkstoffen bei den ersten Schaltvorgängen die mechanische Bearbeitung Ursache hoher Schweißkraft sein kann, wird zum Vergleich mit konventionell hergestellten AgFeRe-Werkstoffen der 99,8 %-Wert herangezogen.The sum of the welding force values is shown, the ordinate being divided logarithmically according to the Weibull function and the abscissa. Since the mechanical processing of AgFeRe contact materials during the first switching operations can be the cause of high welding power, the 99.8% value is used for comparison with conventionally manufactured AgFeRe materials.
Es ergibt sich:The result is:
Erfindungsgemäßes Verfahren, Ag (FeRe 95/5) 8, 8-Werkstoff:Process according to the invention, Ag (FeRe 95/5) 8, 8 material:
Schweißkraft: 237 N (99,8 %)Welding force: 237 N (99.8%)
Konventionelles Verfahren, Ag (FeRe 95/5) 8,8-Werkstoff mit groben Gefüge:Conventional process, Ag (FeRe 95/5) 8,8 material with rough structure:
Schweißkraft: 530 N (99,8 %) . Dieses Ergebnis bedeutet ein um 55 % verbessertes Schweißver¬ halten des erfindungsgemäß hergestellen AgFeRe-Kontaktwerk- stoffes gegenüber einem konventionell hergestellten. Welding force: 530 N (99.8%). This result means a 55% improved welding behavior of the AgFeRe contact material produced according to the invention compared to a conventionally produced one.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung eines Formstücks aus einem Kon¬ taktwerkstoff auf Silberbasis, bei dem eine Pulvermischung aus Silber und aus einem Metalloxid gebildet wird, welche pulvermetallurgisch zu dem Formstück verarbeitet wird, und wobei das Metalloxid zu Metall reduziert wird.1. A method for producing a molded part from a contact material based on silver, in which a powder mixture of silver and a metal oxide is formed, which is processed by powder metallurgy to form the molded part, and wherein the metal oxide is reduced to metal.
2. Verfahren nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t, daß das Me¬ talloxid in der Pulvermischung reduziert wird.2. The method of claim 1, d a d u r c h g e k e n n z e i c h n e t that the metal oxide is reduced in the powder mixture.
3. Verfahren nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t, daß das Me- talloxid in einem Rohling des Formstücks reduziert wird.3. The method according to claim 1, that the metal oxide is reduced in a blank of the shaped part.
4. Verfahren nach einem der Ansprüche 1 bis 3, d a d u r c h g e k e n n z e i c h n e t, daß die Reduk¬ tion des Metalloxids durch eine Wärmebehandlung in einer re- duzierenden Atmosphäre erfolgt.4. The method according to any one of claims 1 to 3, that the reduction of the metal oxide takes place by heat treatment in a reducing atmosphere.
5. Verfahren nach Anspruch 4, d a d u r c h g e k e n n z e i c h n e t, daß die Wärme¬ behandlung bei einer Temperatur von 500 bis 1000 °C, Vorzugs- weise bei 700 °C, erfolgt.5. The method according to claim 4, which also means that the heat treatment is carried out at a temperature of 500 to 1000 ° C, preferably at 700 ° C.
6. Verfahren nach einem der Ansprüche 4 bis 5, d a d u r c h g e k e n n z e i c h n e t, daß die redu¬ zierende Atmosphäre Wasserstoff (H2) ist.6. The method according to any one of claims 4 to 5, characterized in that the reducing atmosphere is hydrogen (H 2 ).
7. Verfahren nach einem der Ansprüche 1 bis 6, d a d u r c h g e k e n n z e i c h n e t, daß als Me¬ talloxid ein Pulver mit einer Korngröße kleiner als 1 um, vorzugsweise von 100 bis 500 nm, verwendet wird. 7. The method according to any one of claims 1 to 6, characterized in that a powder with a grain size smaller than 1 .mu.m, preferably from 100 to 500 nm, is used as metal oxide.
8. Verfahren nach einem der Ansprüche 1 bis 7, d a d u r c h g e k e n n z e i c h n e t, daß der Pul¬ vermischung ein weiteres Metall oder ein weiteres Metalloxid beigemischt wird.8. The method according to any one of claims 1 to 7, so that a further metal or a further metal oxide is added to the powder mixture.
9. Verfahren nach Anspruch 8, d a d u r c h g e k e n n z e i c h n e t, daß der Pul¬ vermischung Silber (Ag) , Eisenoxid (Fe203/Fe304) und Rhenium (Re) oder Silber (Ag) , Rheniumoxid (ReO) und Eisen oder Sil- ber (Ag) , Rheniumoxid (ReO) und Eisenoxid (Fe203/Fe304) zuge¬ führt wird.9. The method according to claim 8, characterized in that the powder mixture silver (Ag), iron oxide (Fe 2 0 3 / Fe 3 0 4 ) and rhenium (Re) or silver (Ag), rhenium oxide (ReO) and iron or sil - About (Ag), rhenium oxide (ReO) and iron oxide (Fe 2 0 3 / Fe 3 0 4 ) is supplied.
10. Kontaktwerkstoff auf Silberbasis mit zumindest einer wei¬ teren metallischen Komponente, deren mittlere Korngröße klei- ner als 1 um ist, vorzugsweise zwischen 100 und 500 nm liegt.10. Silver-based contact material with at least one further metallic component, the average grain size of which is smaller than 1 μm, preferably between 100 and 500 nm.
11. Kontaktwerkstoff nach Anspruch 10, d a d u r c h g e k e n n z e i c h n e t , daß als weitere metallische Komponenten Eisen (Fe) und/oder Rhenium (Re) vor- gesehen sind.11. Contact material according to claim 10, d a d u r c h g e k e n n z e i c h n e t that as further metallic components iron (Fe) and / or rhenium (Re) are provided.
12. Kontaktwerkstoff nach Anspruch 11, d a d u r c h g e k e n n z e i c h n e t , daß das Eisen (Fe) in Massenanteilen zwischen 1 % und 50 % und das Rhenium (Re) in Massenanteilen zwischen 0,01 % und 5 % vorliegt.12. Contact material according to claim 11, so that the iron (Fe) is present in mass proportions between 1% and 50% and the rhenium (Re) in mass proportions between 0.01% and 5%.
13. Formstück aus einem Kontaktwerkstoff nach einem der An¬ sprüche 10 bis 12.13. Shaped piece made of a contact material according to one of claims 10 to 12.
14. Formstück nach Anspruch 13, welches als Kontaktstück für ein Schaltgerät der Energietech¬ nik, insbesondere für einen Niederspannungsschalter, ausge¬ bildet ist. 14. Molding according to claim 13, which is formed as a contact piece for a switching device of the energy technology, in particular for a low-voltage switch.
EP97914051A 1996-01-26 1997-01-13 Method of producing a shaped part from a silver-based contact material Expired - Lifetime EP0876670B1 (en)

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DE19602812A DE19602812C1 (en) 1996-01-26 1996-01-26 Method for producing a shaped piece from a silver-based contact material and shaped piece
DE19602812 1996-01-26
PCT/DE1997/000042 WO1997027601A2 (en) 1996-01-26 1997-01-13 Method of producing a shaped part from a silver-based contact material

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JP3825275B2 (en) * 2001-04-13 2006-09-27 株式会社日立製作所 Electrical contact member and its manufacturing method
US20070018526A1 (en) * 2004-06-18 2007-01-25 Tanaka Kikinzoku Kogyo K.K. Relay for sealed ac load and ag-base contact element material for use therein

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US2145690A (en) * 1937-09-24 1939-01-31 Mallory & Co Inc P R Electric contact material
US2664618A (en) * 1944-04-22 1954-01-05 Fansteel Metallurgical Corp Electrical contact
US3135601A (en) * 1961-11-16 1964-06-02 Martin Marietta Corp Alumina-silver alloy
US3505065A (en) * 1968-08-12 1970-04-07 Talon Inc Method of making sintered and infiltrated refractory metal electrical contacts
GB1536847A (en) * 1976-07-12 1978-12-20 Square D Co Electrically conductive composite materials
GB1524074A (en) * 1976-07-12 1978-09-06 Square D Co Electrically conductive composite materials
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US5286441A (en) * 1989-12-26 1994-02-15 Akira Shibata Silver-metal oxide composite material and process for producing the same
DE4117311A1 (en) * 1991-05-27 1992-12-03 Siemens Ag CONTACT MATERIAL ON A SILVER BASE FOR USE IN SWITCHGEAR DEVICES IN ENERGY TECHNOLOGY
DE4117312A1 (en) * 1991-05-27 1992-12-03 Siemens Ag SILVER-BASED CONTACT MATERIAL FOR USE IN SWITCHGEAR DEVICES OF ENERGY TECHNOLOGY AND METHOD FOR THE PRODUCTION OF CONTACT PIECES FROM THIS MATERIAL
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BR9707202A (en) 1999-04-06
WO1997027601A3 (en) 1997-10-09
DE59707280D1 (en) 2002-06-20
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DE19602812C1 (en) 1997-07-31
ES2176718T3 (en) 2002-12-01

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