EP2644723A1 - Composite material - Google Patents

Composite material Download PDF

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Publication number
EP2644723A1
EP2644723A1 EP12161247.7A EP12161247A EP2644723A1 EP 2644723 A1 EP2644723 A1 EP 2644723A1 EP 12161247 A EP12161247 A EP 12161247A EP 2644723 A1 EP2644723 A1 EP 2644723A1
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EP
European Patent Office
Prior art keywords
oxide
composite material
composite
sno
silver
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EP12161247.7A
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German (de)
French (fr)
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EP2644723B1 (en
Inventor
Michael Bender
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Umicore AG and Co KG
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Umicore AG and Co KG
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Priority to EP12161247.7A priority Critical patent/EP2644723B1/en
Priority to CN201380015121.7A priority patent/CN104245976B/en
Priority to PCT/EP2013/056345 priority patent/WO2013144112A1/en
Priority to US14/388,171 priority patent/US9928931B2/en
Priority to EP13715919.0A priority patent/EP2831298B1/en
Publication of EP2644723A1 publication Critical patent/EP2644723A1/en
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Publication of EP2644723B1 publication Critical patent/EP2644723B1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
    • 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
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
    • 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

Definitions

  • silver / metal and silver / metal oxide composites have proven themselves.
  • the silver / metal composite most commonly used is silver / nickel, which has its main application at lower currents.
  • the AgSnO 2 WO 3 / MoO 3 material is produced by powder metallurgy using the extrusion technique.
  • the powder metallurgical production has the advantage that additives of any kind and quantity can be used.
  • the material can be specifically optimized for certain properties, such as welding force or heating.
  • the combination of powder metallurgy with the extrusion technology allows a particularly high efficiency in the production of the contact pieces.
  • An internally oxidized AgSnO 2 / ln 2 O 3 material is also used. This material, described in DE-OS 24 28 147 , contains 5-10% SnO 2 and 1-6% In 2 O 3 .
  • a targeted change in the concentrations of the oxide additives to influence certain switching properties is often not always possible due to the oxidation kinetics.
  • This object is achieved by a metal composite material containing at least one metal and magnesium stannate.
  • Magnesium stannate, Mg 2 SnO 4 is a compound known from the literature, the preparation of which is described, for example, in US Pat Materials in Electronics, 16 (2005), pages 193 to 196 .
  • the present patent application also relates to the use of a composite material containing at least one metal and magnesium stannate for the production of electrical contact pieces, as well as electrical contacts comprising such a composite material as further described.
  • silver or silver alloys can be used as the metal.
  • Silver alone also has excellent properties for many applications.
  • the magnesium stannate is present in the composite as a disperse phase while the metal forms the continuous phase.
  • the magnesium stannate may have particle sizes of at least 1 ⁇ m.
  • At least 60% of the magnesium stannate have particle sizes of 1 .mu.m or more, which is advantageous in particular in the case of reshaping further processing, for example by extrusion.
  • contact pieces are individually sintered, instead of or in combination with magnesium stannate having a particle size of 1 ⁇ m or more, it is also possible to use particle sizes of 50 nm to less than 1000 nm, in particular 100 nm to 900 nm.
  • advantageously 60% of the magnesium stannate have particle sizes of 100 nm to 900 nm.
  • the composite material may have further oxides.
  • the composite material may additionally contain oxides from the group consisting of magnesium oxide, copper oxide, bismuth oxide, tellurium oxide, tin oxide, indium oxide, tungsten oxide, molybdenum oxide or combinations thereof, their mixed oxides or combinations thereof.
  • Bi 6 WO 12 can be contained as mixed oxide.
  • the above oxides may be contained in total up to 7 wt .-%, in particular up to 2 wt .-%.
  • the composite may be obtained by a manufacturing method selected from powder metallurgy production, internal oxidation or combinations thereof.
  • the material In powder metallurgy production of the material is by mixing a powder of the metal or an alloy with magnesium stannate and optionally other oxides, cold isostatic pressing the powder mixture, and sintering at temperatures of about 500 ° C to about 940 ° C and forming the sintered material, such as Extruding into wires or profiles, the composite obtained. It is advantageous if the magnesium stannate used and / or further oxides have more than 60% by weight before mixing with the silver powder has a particle size of more than 1 micron. In this case, too fine magnesium stannate or other oxides can be coarsened by a heat treatment in the z. B.
  • magnesium stannate or other oxides are annealed at temperatures of about 700 ° C to about 1400 ° C until more than 60 wt.% Of the magnesium stannate or other oxides have a particle size of more than 1 micron.
  • the use of these coarsened oxide powders, after sintering the compacts, provides a material which is more ductile than materials having smaller oxide particle sizes and therefore can be more easily deformed, which may be advantageous in further forming treatment, such as extrusion.
  • magnesium stannate (Mg 2 SnO 4 ) powders having smaller particle sizes may also be used, in which case additives such as sintering activators are advantageous, for example copper oxide CuO, nanoscale silver powder or other nanomaterials.
  • magnesium stannate can be used in which 60 wt.% Even before mixing with the metal powder have a particle size of at least 1 micron, but also magnesium stannate (Mg 2 SnO 4 ), in which 60% of magnesium stannate particle sizes of 50 nm to less than 1000 nm, in particular 60% of the magnesium stannate has particle sizes of 100 nm to 900 nm.
  • Mg 2 SnO 4 magnesium stannate
  • an alloy of silver with base metals is made pyrometallurgically and often heat treated in pure oxygen under overpressure to form a composite.
  • Such methods are known from the literature and described for example in EP 1505164 and EP 0508055 ,
  • the composite contains, in particular, silver and magnesium stannate, and moreover only conventional impurities.
  • the composite contains magnesium stannate in an amount of 0.2 to 20% by weight and ad 100% by weight of silver, as well as common impurities.
  • the composite material contains magnesium stannate, which has at least 60% of a particle size of 1 ⁇ m or more, in an amount of 0.2 to 20% by weight and ad 100% by weight of silver and conventional impurities.
  • the crushed powder mixture is calcined at 1400 ° C for 20 hours in air and then ground to a particle size (d50) of 2 microns (Fritsch Pulverisette 5, 2 mm ZrO 2 spheres, dry isopropanol).
  • d50 particle size of 2 microns
  • the resulting product was found to consist of 95.6% dimagnesium stannate (Mg 2 SnO 4 ) and 4.4% cassiterite (SnO 2 ).
  • FIG. 2 shows for both composites, which have an oxide content of 17,07 per cent by volume, the burnup in mg per switching operation.
  • the lower column shows the change at the fixed contact, the upper column at the moving contact.
  • magnesium stannate (Mg 2 SnO 4 ) and silver based composite exhibits improved burn off properties.
  • FIG. 3 shows for both composites the contact resistances in mOhm, which are given as mean values (respectively right column) and as 99% values. It can be seen that the averages are comparable, but the 99% values are significantly lower in the case of the magnesium stannate (Mg 2 SnO 4 ) and silver-based composite, and thus significantly improved over the silver-tin oxide material.
  • Mg 2 SnO 4 magnesium stannate

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Contacts (AREA)
  • Powder Metallurgy (AREA)

Abstract

The composite material comprises a metal and 0.2-60 vol.% of magnesium stannate. The magnesium stannate is present in an amount of 60 wt.%, and has a particle size of >= 1 mu m. The composite material further comprises oxides, and is obtained by a production method including powder metallurgical production and internal oxidation methods. An independent claim is included for a method for manufacturing a composite material.

Description

Für die Herstellung von elektrischen Kontakten in Niederspannungsschaltgeräten haben sich Silber/Metall- und Silber/Metalloxid-Verbundwerkstoffe bewährt. Als Silber/Metall-Verbundwerkstoff wird am häufigsten Silber/Nickel eingesetzt, dessen Hauptanwendungsgebiet bei niedrigeren Strömen liegt.For the production of electrical contacts in low-voltage switchgear, silver / metal and silver / metal oxide composites have proven themselves. The silver / metal composite most commonly used is silver / nickel, which has its main application at lower currents.

Bestimmte Zusätze, wie WO3 oder MoO3, haben sich bei Schaltgeräten, die hohen thermischen Belastungen standhalten müssen, bewährt. Besonders gut bewährte sich AgSnO2 mit diesen Zusätzen in Schaltgeräten mit Nennströmen von mehr als 100 A und unter sogenannter AC4-Belastung. Bei geringeren Schaltströmen ist allerdings die Lebensdauer dieser Werkstoffe relativ kurz.Certain additives, such as WO 3 or MoO 3 , have been proven in switching devices that have to withstand high thermal loads. AgSnO 2 proved to be particularly suitable with these accessories in switchgear with rated currents of more than 100 A and under so-called AC4 load. At lower switching currents, however, the life of these materials is relatively short.

Der AgSnO2WO3/MoO3-Werkstoff wird pulvermetallurgisch über die Strangpresstechnik hergestellt. Die pulvermetallurgische Herstellung hat den Vorteil, dass Zusätze beliebiger Art und Menge verwendet werden können. Damit kann der Werkstoff gezielt auf bestimmte Eigenschaften hin, wie z.B. Verschweisskraft oder Erwärmung, optimiert werden. Zudem erlaubt die Kombination von Pulvermetallurgie mit der Strangpresstechnik eine besonders hohe Wirtschaftlichkeit bei der Herstellung der Kontaktstücke. Ein innerlich oxidierter AgSnO2/ln2O3-Werkstoff findet ebenfalls Verwendung. Dieser Werkstoff, beschrieben in DE-OS 24 28 147 , enthält neben 5-10 % SnO2 noch 1-6 % In2O3. Eine gezielte Änderung der Konzentrationen der Oxidzusätze, um bestimmte Schalteigenschaften zu beeinflussen, ist häufig aufgrund der Oxidationskinetik nicht immer möglich.The AgSnO 2 WO 3 / MoO 3 material is produced by powder metallurgy using the extrusion technique. The powder metallurgical production has the advantage that additives of any kind and quantity can be used. Thus, the material can be specifically optimized for certain properties, such as welding force or heating. In addition, the combination of powder metallurgy with the extrusion technology allows a particularly high efficiency in the production of the contact pieces. An internally oxidized AgSnO 2 / ln 2 O 3 material is also used. This material, described in DE-OS 24 28 147 , contains 5-10% SnO 2 and 1-6% In 2 O 3 . A targeted change in the concentrations of the oxide additives to influence certain switching properties is often not always possible due to the oxidation kinetics.

In der DE-OS 27 54 335 wird ein Kontakfiiverkstoff beschrieben, der neben Silber 1,6 bis 6,5 Bi2O3 und 0,1 bis 7,5 SnO2 enthält. Dieser Werkstoff kann sowohl über die innere Oxidation als auch pulvermetallurgisch hergestellt werden. Derart hohe Bi2O3-Gehalte führen aber zu einer Versprödung, so dass der Werkstoff nur über Einzelsintern, nicht aber über die wirtschaftlichere Strangpresstechnik hergestellt werden kann. Aus der US 4,680,162 ist ein innerlich oxidierter AgSnO2-Werkstoff bekannt, der bei Zinngehalten von mehr als 4,5 % Zusätze an 0,1-5 Indium und 0,01-5 Wismut enthalten kann. Das Metallegierungspulver wird kompaktiert und anschliessend innerlich oxidiert. Durch diese Zusätze werden die bei innerlicher Oxidation üblichen inhomogenen Oxidausscheidungen unterbunden. Optimale Kontakteigenschaften zeigt dieser Werkstoff jedoch nicht.In the DE-OS 27 54 335 describes a Kontakfiiverkstoff containing 1.6 to 6.5 Bi 2 O 3 and 0.1 to 7.5 SnO 2 in addition to silver. This material can be produced both by internal oxidation and powder metallurgy. However, such high Bi 2 O 3 contents lead to embrittlement, so that the material can be produced only by individual sintering, but not by the more economical extrusion technology. From the US 4,680,162 is an internally oxidized AgSnO 2 material is known, which may contain at tin contents of more than 4.5% additions of 0.1-5 indium and 0.01-5 bismuth. The metal alloy powder is compacted and then internally oxidized. These additives inhibit the inhomogeneous oxide precipitations customary in internal oxidation. Optimal contact properties shows this Material not.

In der Veröffentlichung " Investigation into the Switching behaviour of new Silber-Tin-Oxide Contact materials in Proc. of the 14th Int. Conf. on EI. Contacts, Paris, 1988 June 20-24, S. 405-409 " wird über das Schaltverhalten pulvermetallurgisch hergestellter elektrischer Kontakte aus Silber-Zinnoxid berichtet, die weitere zwei Oxide aus der Reihe Wismutoxid, Indiumoxid, Kupferoxid, Molybdänoxid oder Wolframoxid enthalten können, wobei über die genaue Zusammensetzung dieser Werkstoffe nichts ausgesagt wird.In the publication " Investigation into the Switching behavior of new Silver-Tin-Oxide Contact materials in Proc. of the 14th Int. Conf. on EI. Contacts, Paris, 1988 June 20-24, pp. 405-409 "reported on the switching behavior of powder-metallurgical electrical contacts made of silver-tin oxide, which may contain two more oxides from bismuth oxide, indium oxide, copper oxide, molybdenum oxide or tungsten oxide, said nothing about the exact composition of these materials.

In der US 4,695,330 wird ein spezielles Verfahren zur Herstellung eines innerlich oxidierten Werkstoffes mit 0,5-12 Zinn, 0,5-15 Indium und 0,01-1,5 Wismut beschrieben. Die pulvermetallurgische Herstellung von Kontaktwerkstoffen auf Silber-Zinnoxid-Basis durch Mischen der Pulver, kaltisostatischem Pressen, Sintern und Strangpressen zu Halbzeug ist beispielsweise aus der DE 43 19 137 und DE 43 31 526 bekannt.In the US 4,695,330 describes a special process for producing an internally oxidized material with 0.5-12 tin, 0.5-15 indium and 0.01-1.5 bismuth. The powder metallurgical production of contact materials based on silver-tin oxide by mixing the powder, cold isostatic pressing, sintering and extrusion to semi-finished is, for example, from DE 43 19 137 and DE 43 31 526 known.

Aus der US 4,141,727 sind Kontaktwerkstoffe aus Silber bekannt, die Wismut-Zinnoxid als Mischoxidpulver enthalten. Weiterhin wird in der DE 29 52 128 das Zinnoxidpulver vor dem Vermischen mit Silberpulver bei 900°C bis 1600° C geglüht.From the US 4,141,727 Contact materials are known from silver containing bismuth tin oxide mixed oxide powder. Furthermore, in the DE 29 52 128 annealed the Zinnoxidpulver before mixing with silver powder at 900 ° C to 1600 ° C.

Durch ansteigende Anforderungen an die Kontaktwerkstoffe genügen die bekannten Materialien den Anforderungen nicht immer oder für alle Anwendungen.Due to increasing demands on the contact materials, the known materials do not always meet the requirements or for all applications.

Beschreibungdescription

Es war die Aufgabe, einen neuen Metall-Verbundwerkstoff bereit zu stellen, der beim Einsatz als Kontaktmaterial in elektrischen Schaltgeräten gegenüber verbreiteten silberbasierten Silber-Zinnoxid Verbundwerkstoffen ein verbessertes Abbrandverhalten und einen niedrigeren Kontaktwiderstand zeigt. Diese Aufgabe wird gelöst durch einen Metall-Verbundwerkstoff, welcher mindestens ein Metall und Magnesiumstannat enthält. Magnesiumstannat, Mg2SnO4, ist eine literaturbekannte Verbindung, deren Herstellung beispielsweise beschrieben ist in Materials in Electronics, 16 (2005), Seiten 193 bis 196 , Journal of Power Sources 97-98 (2001), Seiten 223-225 oder Ceramics International 27 (2001), Seiten 325 bis 334 . Zur Herstellung dieser Verbindung können Magnesiumoxid MgO und Zinnoxid SnO2 im entsprechenden molaren Verhältnis (also MgO:SnO2 = 2:1) intensiv vermischt werden (beispielsweise durch Nass- oder Trockenmahlung), optional getrocknet und dann für etwa 15 bis etwa 25 Stunden bei Temperaturen von etwa 1200°C bis etwa 1600°C kalziniert werden. An die Atmosphäre sind im Allgemeinen keine besonderen Anforderungen zu stellen, so daß an der Luft kalziniert werden kann. Auf diese Weise kann ein Gemisch aus Magnesiumstannat und Magnesiumoxid erhalten wie in Figur 1 dargestellt werden, wobei etwa 4,4% Magnesiumoxid mit etwa 95,6 % Magnesiumstannat vorliegen. Durch Einsetzen eines Überschusses von etwa 10% Magnesiumoxid können bis zu 98 % Magnesiumstannat Mg2SnO4 erreicht werden.It was the object to provide a new metal composite, which shows when used as contact material in electrical switching devices over common silver-based silver-tin oxide composite materials improved burn-off behavior and a lower contact resistance. This object is achieved by a metal composite material containing at least one metal and magnesium stannate. Magnesium stannate, Mg 2 SnO 4 , is a compound known from the literature, the preparation of which is described, for example, in US Pat Materials in Electronics, 16 (2005), pages 193 to 196 . Journal of Power Sources 97-98 (2001), pages 223-225 or Ceramics International 27 (2001), pages 325 to 334 , To prepare this compound, magnesium oxide MgO and tin oxide SnO 2 in the corresponding molar ratio (ie MgO: SnO 2 = 2: 1) can be intensively mixed (for example by wet or dry grinding), optionally dried and then at from about 15 to about 25 hours Temperatures of about 1200 ° C to about 1600 ° C calcined. To the atmosphere In general, there are no special requirements, so that it is possible to calcine in air. In this way, a mixture of magnesium stannate and magnesium oxide can be obtained as in FIG. 1 wherein about 4.4% magnesium oxide is present with about 95.6% magnesium stannate. By using an excess of about 10% magnesium oxide, up to 98% magnesium stannate Mg 2 SnO 4 can be achieved.

Die vorliegende Patentanmeldung betrifft auch die Verwendung eines Verbundwerkstoffs enthaltend mindestens ein Metall und Magnesiumstannat zur Herstellung von elektrischen Kontaktstücken, sowie elektrische Kontakte enthaltend einen solchen Verbundwerkstoff wie weiter beschrieben.The present patent application also relates to the use of a composite material containing at least one metal and magnesium stannate for the production of electrical contact pieces, as well as electrical contacts comprising such a composite material as further described.

Als Metall können insbesondere Silber oder Silberlegierungen eingesetzt werden. Gut geeignet sind beispielsweise Silber-Nickel-Legierungen. Silber alleine weist für viele Anwendungszwecke ebenfalls ausgezeichnete Eigenschaften auf. Magnesiumstannat kann im Allgemeinen in Mengen von 0,02 bis 60 Vol.%, oder 0,02 Vol.%, insbesondere 0,2 Vol.%, bis 25 Vol.%, (= bis 13 Gew.%), insbesondere 2 Vol.%, bis 25 Vol.%, oder 0,02 Vol.%, insbesondere 0,2 Vol.%, bis 60 Vol.%. (= bis Gew.%), insbesondere 2 Vol.%, bis 60 Vol.%. oder 0,02 Vol.%, insbesondere 0,2 Vol.%, bis 5 Vol.% (= bis 2,34 Gew.%), eingesetzt werden. Die zuzugebenden Mengen an Magnesiumstannat Mg2SnO4 können entsprechend der Anwendung in vorteilhaften Mengen ausgewählt werden, wobei für stranggepresste Werkstoffe der Zusatz von etwa 0,02 Vol.% bis 25 Vol.% (= 0 - 13 Gew.%), bei einzelgepressten Werkstoffen (ähnlich bekannten Ag/W und Ag/WC - Werkstoffen) 0,02 Vol% bis 60 Vol.%. (= 0 - 40 Gew.%) und bei Einsatz von Magnesiumstannat Mg2SnO4 als Additiv 0,02 Vol.% bis 5 Vol.% (= 0 - 2,34 Gew.%) besonders geeignet sind. Das Magnesiumstannat liegt im Verbundwerkstoff als disperse Phase vor, während das Metall die kontinuierliche Phase bildet. Das Magnesiumstannat kann Teilchengrößen von mindestens 1 µm aufweisen. Insbesondere weisen mindestens 60% des Mangesiumstannats Teilchengrößen von 1 µm oder mehr auf, was insbesondere bei umformender Weiterverarbeitung wie beispielsweise durch Strangpressen vorteilhaft ist. Werden Kontaktstücke einzeln gesintert, so können stattdessen oder in Kombination mit Magnesiumstannat mit einer Teilchengröße von 1 µm oder mehr auch Teilchengrößen von 50 nm bis kleiner 1000 nm, insbesondere 100 nm bis 900 nm verwendet werden. In diesem Fall weisen vorteilhaft 60 % des Magnesiumstannats Teilchengrößen von 100 nm bis 900 nm auf.In particular silver or silver alloys can be used as the metal. Well suited, for example, silver-nickel alloys. Silver alone also has excellent properties for many applications. Magnesium stannate may generally be used in amounts of 0.02 to 60% by volume, or 0.02% by volume, in particular 0.2% by volume, to 25% by volume, (= up to 13% by weight), in particular 2% by volume .%, to 25 vol.%, or 0.02 vol.%, in particular 0.2 vol.%, To 60 vol.%. (= to% by weight), in particular 2% by volume, up to 60% by volume. or 0.02% by volume, in particular 0.2% by volume, to 5% by volume (= up to 2.34% by weight). The quantities of magnesium stannate Mg 2 SnO 4 to be added can be selected according to the application in advantageous amounts, with the addition of about 0.02% by volume to 25% by volume (= 0-13% by weight) for extruded materials, for individually pressed articles Materials (similar to known Ag / W and Ag / WC materials) 0.02% to 60% by volume. (= 0 to 40% by weight) and when using magnesium stannate Mg 2 SnO 4 as an additive 0.02% by volume to 5% by volume (= 0 to 2.34% by weight) are particularly suitable. The magnesium stannate is present in the composite as a disperse phase while the metal forms the continuous phase. The magnesium stannate may have particle sizes of at least 1 μm. In particular, at least 60% of the magnesium stannate have particle sizes of 1 .mu.m or more, which is advantageous in particular in the case of reshaping further processing, for example by extrusion. If contact pieces are individually sintered, instead of or in combination with magnesium stannate having a particle size of 1 μm or more, it is also possible to use particle sizes of 50 nm to less than 1000 nm, in particular 100 nm to 900 nm. In this case, advantageously 60% of the magnesium stannate have particle sizes of 100 nm to 900 nm.

Zusätzlich kann der Verbundwerkstoff noch weitere Oxide aufweisen. Insbesondere kann der Verbundwerkstoff zusätzlich Oxide aus der Gruppe bestehend aus Magnesiumoxid, Kupferoxid, Wismutoxid, Telluroxid, Zinnoxid, Indiumoxid, Wolframoxid, Molybdänoxid oder deren Kombinationen, deren Mischoxide oder Kombinationen daraus enthalten. Als Mischoxid kann beispielsweise Bi6WO12 enthalten sein.In addition, the composite material may have further oxides. In particular, the composite material may additionally contain oxides from the group consisting of magnesium oxide, copper oxide, bismuth oxide, tellurium oxide, tin oxide, indium oxide, tungsten oxide, molybdenum oxide or combinations thereof, their mixed oxides or combinations thereof. For example, Bi 6 WO 12 can be contained as mixed oxide.

Die obigen Oxide können insgesamt zu bis zu 7 Gew.-%, insbesondere bis zu 2 Gew.-% enthalten sein.The above oxides may be contained in total up to 7 wt .-%, in particular up to 2 wt .-%.

Der Verbundwerkstoff kann durch eine Herstellungsweise ausgewählt aus pulvermetallurgischer Herstellung, innerer Oxidation oder deren Kombinationen erhalten werden.The composite may be obtained by a manufacturing method selected from powder metallurgy production, internal oxidation or combinations thereof.

Bei pulvermetallurgischer Herstellung des Werkstoffs wird durch Mischen eines Pulvers aus dem Metall oder einer Legierung mit Magnesiumstannat und gegebenenfalls weiteren Oxiden, kaltisostatischem Pressen des Pulvergemischs, und Sintern bei Temperaturen von etwa 500°C bis etwa 940°C und Umformen des gesinterten Materials, etwa durch Strangpressen zu Drähten oder Profilen, der Verbundwerkstoff erhalten. Hierbei ist es vorteilhaft, wenn das verwendete Magnesiumstannat und/oder weitere Oxide zu mehr als 60 Gew.% bereits vor dem Vermischen mit dem Silberpulver eine Teilchengrösse von mehr als 1 µm aufweisen. Hierbei kann zu feines Magnesiumstannat oder auch andere Oxide durch eine Wärmebehandlung vergröbert werden in dem z. B. bei Temperaturen von etwa 700°C bis etwa 1400°C geglüht wird, bis mehr als 60 Gew.% des Magnesiumstannats bzw. der weiteren Oxide eine Teilchengrösse von mehr als 1 µm aufweisen. Die Verwendung dieser vergröberten Oxidpulver liefert nach dem Sintern der Presslinge einen Werkstoff, der duktiler ist als Werkstoffe mit geringeren Oxidteilchengrössen und kann daher leichter verformt werden, was bei weiterer umformender Behandlung vorteilhaft sein kann, wie zum Beispiel Strangpressen. Beim Einzelsintern von Kontakten können wie oben beschrieben auch Magnesiumstannat (Mg2SnO4) Pulver mit kleineren Teilchengrößen verwendet werden, wobei in diesem Fall Additive, wie Sinteraktivatoren vorteilhaft sind, zum Beispiel Kupferoxid CuO, nanoskaliges Silberpulver oder andere Nanomaterialien. In diesem Fall kann natürlich auch Magnesiumstannat verwendet werden, bei welchem 60 Gew.% bereits vor dem Vermischen mit dem Metallpulver eine Teilchengrösse von mindestens 1 µm aufweisen, aber auch Magnesiumstannat (Mg2SnO4), bei welchem 60 % des Magnesiumstannats Teilchengrößen von 50 nm bis weniger als 1000 nm, insbesondere 60 % des Magnesiumstannats Teilchengrößen von 100 nm bis 900 nm aufweist.In powder metallurgy production of the material is by mixing a powder of the metal or an alloy with magnesium stannate and optionally other oxides, cold isostatic pressing the powder mixture, and sintering at temperatures of about 500 ° C to about 940 ° C and forming the sintered material, such as Extruding into wires or profiles, the composite obtained. It is advantageous if the magnesium stannate used and / or further oxides have more than 60% by weight before mixing with the silver powder has a particle size of more than 1 micron. In this case, too fine magnesium stannate or other oxides can be coarsened by a heat treatment in the z. B. is annealed at temperatures of about 700 ° C to about 1400 ° C until more than 60 wt.% Of the magnesium stannate or other oxides have a particle size of more than 1 micron. The use of these coarsened oxide powders, after sintering the compacts, provides a material which is more ductile than materials having smaller oxide particle sizes and therefore can be more easily deformed, which may be advantageous in further forming treatment, such as extrusion. In individual sintering of contacts, as described above, magnesium stannate (Mg 2 SnO 4 ) powders having smaller particle sizes may also be used, in which case additives such as sintering activators are advantageous, for example copper oxide CuO, nanoscale silver powder or other nanomaterials. In this case, of course, magnesium stannate can be used in which 60 wt.% Even before mixing with the metal powder have a particle size of at least 1 micron, but also magnesium stannate (Mg 2 SnO 4 ), in which 60% of magnesium stannate particle sizes of 50 nm to less than 1000 nm, in particular 60% of the magnesium stannate has particle sizes of 100 nm to 900 nm.

Bei der Herstellung durch innere Oxidation wird beispielsweise eine Legierung aus Silber mit unedlen Metallen pyrometallurgisch hergestellt und oft in reinem Sauerstoff unter Überdruck wärmebehandelt, so daß ein Verbundwerkstoff entsteht. Derartige Verfahren sind literaturbekannt und beispielsweise beschrieben in EP 1505164 und EP 0508055 .For example, when produced by internal oxidation, an alloy of silver with base metals is made pyrometallurgically and often heat treated in pure oxygen under overpressure to form a composite. Such methods are known from the literature and described for example in EP 1505164 and EP 0508055 ,

In einer Ausführungsform enthält der Verbundwerkstoff insbesondere Silber und Magnesiumstannat und darüber hinaus lediglich übliche Verunreinigungen. In einer Ausführungsform enthält der Verbundwerkstoff Magnesiumstannat in einer Menge von 0,2 bis 20 Gew.-% und ad 100 Gew.-% Silber sowie übliche Verunreinigungen.In one embodiment, the composite contains, in particular, silver and magnesium stannate, and moreover only conventional impurities. In one embodiment, the composite contains magnesium stannate in an amount of 0.2 to 20% by weight and ad 100% by weight of silver, as well as common impurities.

In einer weiteren Ausführungsform der Erfindung enthält der Verbundwerkstoff Magnesiumstannat, welches zu mindestens 60% eine Teilchengröße von 1 µm oder mehr aufweist, in einer Menge von 0,2 bis 20 Gew.-% und ad 100 Gew.-% Silber sowie übliche Verunreinigungen.In a further embodiment of the invention, the composite material contains magnesium stannate, which has at least 60% of a particle size of 1 μm or more, in an amount of 0.2 to 20% by weight and ad 100% by weight of silver and conventional impurities.

BeispieleExamples Beispiel 1example 1 Herstellung von MagnesiumstannatProduction of magnesium stannate

13,03 g SnO2 und 6,97 g MgO wurden eingewogen und 2 x 5 Minuten bei 250 U/min nass vermahlen (Fritsch Pulverisette 5, 2 mm ZrO2-Kugeln, trockenes Isopropanol). Das Pulvergemisch wird im Trockenschrank (Temperatur) getrocknet und anschließend mit einem Mörser zerkleinert.13.03 g SnO 2 and 6.97 g MgO were weighed in and wet-ground for 2 × 5 minutes at 250 rpm (Fritsch Pulverisette 5, 2 mm ZrO 2 balls, dry isopropanol). The powder mixture is dried in a drying oven (temperature) and then comminuted with a mortar.

Die zerkleinerte Pulvermischung wird bei 1400°C 20 Stunden an Luft kalziniert und anschließend bis zu einer Partikelgröße (d50) von 2 µm gemahlen (Fritsch Pulverisette 5, 2 mm ZrO2-Kugeln, trockenes Isopropanol). Durch Röntgenbeugung am Reaktionsprodukt und Rietveld-Verfeinerung wurde festgestellt, daß das entstandene Produkt zu 95,6 % aus Dimagnesiumstannat (Mg2SnO4) und zu 4,4 % aus Cassiterite (SnO2) besteht.The crushed powder mixture is calcined at 1400 ° C for 20 hours in air and then ground to a particle size (d50) of 2 microns (Fritsch Pulverisette 5, 2 mm ZrO 2 spheres, dry isopropanol). By X-ray diffraction on the reaction product and Rietveld refinement, the resulting product was found to consist of 95.6% dimagnesium stannate (Mg 2 SnO 4 ) and 4.4% cassiterite (SnO 2 ).

Herstellung des Verbundwerkstoffs enthaltend Mg2SnO4 Preparation of the composite containing Mg 2 SnO 4

914,4 g Silberpulver (Umicore, verdüstes Silberpulver, auf <42 µm abgesiebt) werden mit 17,07 Volumenprozent Mg2SnO4-Pulver (85,6 g) in einem Mischaggregat (MTI-Mischer 8 Min., 1000 U/min) gemischt. Die Pulvermischung wird in eine plastische zylinderförmige Form gefüllt und bei einem Druck von 800 bar kaltisostatisch zu einem Bolzen gepresst. Dieser Bolzen wird 2 h bei 820 °C gesintert und anschließend stranggepresst.914.4 g of silver powder (Umicore, atomized silver powder, sieved to <42 microns) with 17.07 volume percent Mg 2 SnO 4 powder (85.6 g) in a mixing unit (MTI mixer 8 min., 1000 U / min ) mixed. The powder mixture is transformed into a plastic filled cylindrical shape and pressed at a pressure of 800 bar cold isostatic to a bolt. This stud is sintered for 2 h at 820 ° C and then extruded.

Vergleichsbeispiel 2: Herstellung des Verbundwerkstoffs enthaltend SnO2 Comparative Example 2 Production of the Composite Material Containing SnO 2

880 g Silberpulver (gleiches Silberpulver wie in Beispiel 1) werden mit 120 g entsprechend 17,07 Vol.% SnO2-Pulver in einem Mischaggregat (MTI-Mischer , 8 Min., 1000 U/min) gemischt. Die Pulvermischung wird in eine plastische zylinderförmige Form gefüllt und bei einem Druck von 800 bar kaltisostatisch zu einem Bolzen gepresst. Dieser Bolzen wird 2 h bei 820 °C gesintert und anschließend stranggepresst.880 g of silver powder (same silver powder as in Example 1) are mixed with 120 g corresponding to 17.07% by volume SnO 2 powder in a mixing unit (MTI mixer, 8 min., 1000 U / min). The powder mixture is filled into a plastic cylindrical shape and cold isostatically pressed into a bolt at a pressure of 800 bar. This stud is sintered for 2 h at 820 ° C and then extruded.

Es wurden mit Proben beider Verbundwerkstoffe Zugversuche gemäß EN ISO 6892-1 durchgeführt und die Bruchdehnung bei beiden Verbundwerkstoffen zu 27% bestimmt.Tensile tests according to EN ISO 6892-1 were carried out with samples of both composites and the elongation at break for both composites was determined to be 27%.

Aus den hergestellten Verbundwerkstoffen werden nach dem Strangpressen Kontaktstücke gefertigt (5 mm Draht, Halbzeug, wird aufgelötet und abgedreht, dann geschaltet) und mit diesen Kontaktstücken Schaltversuche in einem Ausschalter mit 500 Schaltungen, einer Stromstärke von 350 A und Blasfeld: 30 mT/kA durchgeführt. Die Ergebnisse sind in Figuren 2 und 3 dargestellt.From the produced composite materials are produced after extrusion contact pieces (5 mm wire, semi-finished, soldered and turned off, then switched) and with these contacts switching experiments in a circuit breaker with 500 circuits, a current of 350 A and Blasfeld: 30 mT / kA performed , The results are in Figures 2 and 3 shown.

Figur 2 zeigt für beide Verbundwerkstoffe, die einen Oxidgehalt von je 17,07 Volumenprozent aufweisen, den Abbrand in mg pro Schaltvorgang. Die jeweils untere Säule zeigt die Veränderung am festen Kontakt, die obere Säule am beweglichen Kontakt. FIG. 2 shows for both composites, which have an oxide content of 17,07 per cent by volume, the burnup in mg per switching operation. The lower column shows the change at the fixed contact, the upper column at the moving contact.

Es ist erkennbar, daß der auf Magnesiumstannat (Mg2SnO4) und Silber basierende Verbundwerkstoff verbesserte Abbrandeigenschaften zeigt.It can be seen that the magnesium stannate (Mg 2 SnO 4 ) and silver based composite exhibits improved burn off properties.

Figur 3 zeigt für beide Verbundwerkstoffe die Kontaktwiderstände in mOhm, die als Mittelwerte (jeweils rechte Säule) und als 99%-Werte angegeben sind. Es ist ersichtlich, daß die Mittelwerte vergleichbar, die 99%-Werte jedoch bei dem auf Magnesiumstannat (Mg2SnO4) und Silber basierenden Verbundwerkstoff deutlich niedriger und damit gegenüber dem Silber-Zinnoxid -Werkstoff erheblich verbessert sind. FIG. 3 shows for both composites the contact resistances in mOhm, which are given as mean values (respectively right column) and as 99% values. It can be seen that the averages are comparable, but the 99% values are significantly lower in the case of the magnesium stannate (Mg 2 SnO 4 ) and silver-based composite, and thus significantly improved over the silver-tin oxide material.

Claims (14)

Verbundwerkstoff enthaltend mindestens ein Metall und Magnesiumstannat Mg2SnO4.Composite comprising at least one metal and magnesium stannate Mg 2 SnO 4 . Verbundwerkstoff nach Anspruch 1, wobei das Metall Silber oder eine Silberlegierung ist.The composite of claim 1, wherein the metal is silver or a silver alloy. Verbundwerkstoff nach Anspruch 1 oder 2, wobei 0,2 bis 60 Volumenprozent Magnesiumstannat enthalten sind.The composite of claim 1 or 2, wherein 0.2 to 60 volume percent magnesium stannate is included. Verbundwerkstoff nach einem oder mehreren der Ansprüche 1 bis 3, wobei der Verbundwerkstoff ein elektrischer Kontaktwerkstoff ist.Composite material according to one or more of claims 1 to 3, wherein the composite material is an electrical contact material. Verbundwerkstoff nach einem oder mehreren der Ansprüche 1 bis 4, wobei mindestens 60 Gew.-% des im Verbundwerkstoff vorhandenen Magnesiumstannats eine Teilchengröße von 1 µm oder mehr aufweist.A composite according to one or more of claims 1 to 4, wherein at least 60% by weight of the magnesium stannate present in the composite has a particle size of 1 μm or more. Verbundwerkstoff nach einem oder mehreren der Ansprüche 1 bis 5, enthaltend weitere Oxide.Composite material according to one or more of claims 1 to 5, containing further oxides. Verbundwerkstoff nach einem oder mehreren der Ansprüche 1 bis 6, wobei zusätzlich Oxide aus der Gruppe bestehend aus Magnesiumoxid, Kupferoxid, Wismutoxid, Telluroxid, Zinnoxid, Indiumoxid, Wolframoxid, Molybdänoxid oder deren Kombinationen enthalten sind.Composite material according to one or more of claims 1 to 6, wherein additionally oxides from the group consisting of magnesium oxide, copper oxide, bismuth oxide, tellurium oxide, tin oxide, indium oxide, tungsten oxide, molybdenum oxide or combinations thereof are contained. Verbundwerkstoff nach einem oder mehreren der Ansprüche 1 bis 7, erhältlich durch eine Herstellungsweise ausgewählt aus pulvermetallurgischer Herstellung, innerer Oxidation oder deren Kombinationen.Composite material according to one or more of claims 1 to 7, obtainable by a production method selected from powder metallurgy production, internal oxidation or combinations thereof. Verwendung eines Verbundwerkstoffs nach einem oder mehreren der Ansprüche 1 bis 8 zur Herstellung von elektrischen Kontaktstücken.Use of a composite material according to one or more of claims 1 to 8 for the production of electrical contact pieces. Elektrischer Kontakt enthaltend einen Verbundwerkstoff nach einem oder mehreren der Ansprüche 1 bis 8.Electrical contact containing a composite material according to one or more of claims 1 to 8. Verfahren zur Herstellung eines Verbundwerkstoffes aus Metall und Magnesiumstannat Mg2SnO4 durch Vermischen von pulverförmigem Magnesiumstannat Mg2SnO4 mit mindestens einem Metallpulver und gegebenenfalls weiteren Oxiden, Pressen der Mischung um einen Preßling zu erhalten und Sintern des Preßlings um einen Sinterling zu erhalten.A process for producing a composite material of metal and Magnesiumstannat Mg 2 SnO 4 made by mixing powdered Magnesiumstannat Mg 2 SnO 4 with at least one metal powder and optionally other oxides, Pressing the mixture to obtain a compact and sintering the compact around a sintered compact. Verfahren nach Anspruch 11, wobei der erhaltene Sinterling in einem weiteren Verfahrensschritt umgeformt, insbesondere stranggepreßt, wird,A process according to claim 11, wherein the resulting sintered compact is transformed, in particular extruded, in a further process step, Verfahren nach Anspruch 11, wobei der Sinterling ein Kontaktstück ist.The method of claim 11, wherein the sintered article is a contact piece. Verfahren nach Anspruch 13, wobei der Sinterling zusätzlich Kupferoxid enthält.The method of claim 13, wherein the sintered article additionally contains copper oxide.
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CN103613118A (en) * 2013-11-15 2014-03-05 广东光华科技股份有限公司 Preparation method of high-purity magnesium stannate powder
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CN103681015B (en) * 2013-11-28 2015-12-02 昆明理工大学 A kind of complex-phase metallic oxide strengthens the preparation method of Ag-based electrical contact material
CN103710556A (en) * 2013-12-27 2014-04-09 桂林电器科学研究院有限公司 Process for preparing silver tin oxide contact material through powder rolling method
CN115537594A (en) * 2022-10-28 2022-12-30 台州慧模科技有限公司 Silver-based electrical contact material and preparation method thereof

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