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EP0164664A2 - Sintered contact material for low-tension energy switchgear - Google Patents

Sintered contact material for low-tension energy switchgear Download PDF

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Publication number
EP0164664A2
EP0164664A2 EP85106748A EP85106748A EP0164664A2 EP 0164664 A2 EP0164664 A2 EP 0164664A2 EP 85106748 A EP85106748 A EP 85106748A EP 85106748 A EP85106748 A EP 85106748A EP 0164664 A2 EP0164664 A2 EP 0164664A2
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EP
European Patent Office
Prior art keywords
cuo
contact material
sno
sintered contact
material according
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
EP85106748A
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German (de)
French (fr)
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EP0164664B1 (en
EP0164664A3 (en
Inventor
Bernhard Rothkegel
Wolfgang Haufe
Manfred Müller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Siemens Corp
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Siemens AG
Siemens Corp
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Priority to AT85106748T priority Critical patent/ATE84905T1/en
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Publication of EP0164664A3 publication Critical patent/EP0164664A3/en
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/021—Composite material
    • H01H1/023—Composite material having a noble metal as the basic material
    • H01H1/0237—Composite material having a noble metal as the basic material and containing oxides
    • H01H1/02372—Composite material having a noble metal as the basic material and containing oxides containing as major components one or more oxides of the following elements only: Cd, Sn, Zn, In, Bi, Sb or Te
    • H01H1/02376—Composite material having a noble metal as the basic material and containing oxides containing as major components one or more oxides of the following elements only: Cd, Sn, Zn, In, Bi, Sb or Te containing as major component SnO2
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the invention relates to a sintered contact material for low-voltage switchgear in power engineering from A g S n0 2 with Bi 2 0 3 and Cu0 as further metal oxide additives, the volume fraction of total metal oxide being between 10% and 25% with a SnO 2 volume fraction of 70% of the total oxide quantity .
  • Contact materials based on silver-metal oxides have proven to be particularly advantageous for low-voltage switchgear in energy technology, for example in contactors or circuit breakers.
  • cadmium oxide in particular was used as the active component, with these contact materials in particular fulfilling the desired electrical-technological properties and having proven themselves in the long-term use of switching devices.
  • cadmium is known to be one of the toxic heavy metals and when the contact pieces burn off, CdO is also released to the surrounding area, efforts have been underway for some time to replace the CdO as completely as possible with other metal oxides.
  • these materials should have an arc burn-up that is just as small, as well as low welding power and, in particular, low heating with continuous current flow, like the proven AgCdO materials for contact pieces.
  • a new sintered contact material for the above purpose based on AgSnO 2 has already been disclosed, in which Bi203 and CuO and optionally CdO are provided as further metal oxides and the volume fraction of total metal oxide is between 10% and 25% with a SnO 2 - Volume part is ⁇ 70% of the total amount of oxide.
  • the contact material is made by powder metallurgy from an internally oxidized alloy powder (so-called IOLP).
  • the material with the following composition is especially suitable for the cadmium-free alternative in mass fractions of 87.95% Ag, 9.97% SnO 2 , 0.98% Bi 2 0 3 and 1.10% CuO Tests have now shown that the specified material does not yet fully meet the needs of practice.
  • the object of the invention is therefore to provide a further material of the constitution AgSnO 2 Bi 2 O 3 CuO for the above-mentioned application.
  • the object is achieved in that the SnO 2 mass fraction is specifically in the range from 4% to 8 % .
  • the Bi 2 0 3 mass fraction is preferably between 0.5% and 4%, while the CuO mass fraction is between 0.3% and 1%; the rest is silver.
  • the ratio of the mass fractions in% of SnO 2 to CuO is preferably between 8: 1 and 12: 1.
  • GB-A-20 55 398 describes materials based on silver metal oxide, for the production of which sheets are produced from alloys, which are subsequently oxidized internally. So this is not a factory made with powder metallurgical processes substances, in particular not egleiterspulvern to the internal oxidation of L followed by compaction and sintering.
  • GB-A-20 55 398 specifies, inter alia, a composition in mass fractions of 90.8% Ag, 8.5% Sn, 0.2% Bi and 0.5% Cu for the starting alloy. Otherwise, in the prior art, further components, for example cobalt, iron or nickel, are still added to the specified four-component system.
  • the present invention was based on the surprising finding that the Sn0 2 content can be reduced and thus the Bi 2 0 3 content can be increased in order to obtain more favorable temperature properties than in the prior art.
  • An alloy of AgSnBiCu of the specified composition is melted at 1353 K from 93.60% fine silver grains, 5.20% tin grains, 0.6% metallic bismuth as fragments and 0.6% copper in rod form.
  • an alloy powder of the same composition is obtained.
  • the powder portion is sieved to L 200 ⁇ m.
  • This portion is internally oxidized in an oxygen-containing atmosphere between 723 K and 872 K, after which a composite powder of AgSnO 2 Bl 2 O 3 CuO of the composition in mass fractions of 92.10% Ag, 6.50% SnO 2 , 0.66% Bi 2 0 3 and 0.74% CuO is obtained.
  • Such a composite powder is quantitatively completely internally oxidized and is referred to as IOLP.
  • the composite powder is used to produce contact pieces by pressing in a die with 600 MPa.
  • the contact pieces are sintered at 1173 K for one hour in air.
  • the contact pieces are compacted by hot pressing at 923 K at 900 MPa. Further compression and solidification is achieved by a second sintering at 1173 K for one hour in air and a subsequent cold compression at 800 MPa.
  • Metallographic micrographs show that the structure of the contact material produced in this way is fine and uniform with an average oxide particle size of 1.5 ⁇ m.
  • method steps as in example 1 were selected; However, starting materials of the following composition in mass fractions were assumed: 93.96% fine silver grains, 4.00% tin grains, 1.64% metallic bismuth and 0.40% copper, from which an alloy is melted. Corresponding alloy powder is produced from this in the manner described above.
  • an IOLP of AgSnO 2 Bi 2 C 3 CuO of the composition in mass fractions of 92.70% Ag, 5.01% SnO 2 , 1.80% Bi 2 0 3 and 0.49% Cuo is obtained.
  • This IOLP is the starting material for the material and the contact pieces to be made from it.
  • This material essentially corresponds to that of the material except for a larger grain size
  • the welding force of the contact materials produced according to the invention was determined in a test switch.
  • the measured values obtained essentially correspond to those of the AgCd012Bi2031, O contact material produced from internally oxidized alloy powder.
  • service life and heating tests were carried out in motor contactors.
  • the key parameters are the AC4 service life switching numbers of the contact pieces and the overtemperature of the current paths. in the Compared to AgCdO 12 Bi 2 O 3 1.0 materials, the lifespan switching numbers are about a factor of 1.8 higher, with higher temperatures only showing up to 10 ° C higher temperatures.
  • test data of the new materials are shown in the table in comparison to the known material.
  • the tin content is reduced to a suitable range, starting from the predetermined volume fraction of the sum metal oxides, and thus at least the relative Bi 2 0 3 fraction is increased, which leads to unexpectedly good results.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Contacts (AREA)
  • Manufacture Of Switches (AREA)
  • Glass Compositions (AREA)
  • Powder Metallurgy (AREA)

Abstract

AgSnO2-based contact materials with Bi2O3 and CuO as further metal oxide additives have already been proposed. In these, the volume fraction of metal oxide should be between 10% and 25% with an SnO2 volume fraction of >/=70% of the total oxide quantity. It is proposed to select the SnO2 mass fraction specifically in the range from 4% to 8%. The Bi2O3 mass fraction is here between 0.5% and 4%, and the CuO mass fraction is between 0.3% and 1%, the remainder being silver in each case. Contact pieces having surprisingly good electrical properties can be manufactured from such materials.

Description

Die Erfindung bezieht sich auf einen Sinterkontaktwerkstoff für Niederspannungsschaltgeräte der Energietechnik aus AgSn02 mit Bi203 und Cu0 als weitere Metalloxidzusätze, wobei der Volumenanteil an Summenmetalloxid zwischen 10 % und 25 % mit einem SnO2-Volumenanteil 70 % der Gesamtoxidmenge beträgt.The invention relates to a sintered contact material for low-voltage switchgear in power engineering from A g S n0 2 with Bi 2 0 3 and Cu0 as further metal oxide additives, the volume fraction of total metal oxide being between 10% and 25% with a SnO 2 volume fraction of 70% of the total oxide quantity .

Ein solcher Werkstoff ist unter anderem Gegenstand der älteren deutschen Patentanmeldung P 33 04 637.9.Such a material is, among other things, the subject of the older German patent application P 33 04 637.9.

Für Niederspannungsschaltgeräte der Energietechnik, z.B. in Schützen oder Selbstschaltern, haben sich Kontaktwerkstoffe auf der Basis von Silber-Metalloxiden (AgMeO) als besonders vorteilhaft erwiesen. In der Vergangenheit wurde als Wirkkomponente insbesondere Cadmiumoxid verwendet, wobei speziell diese Kontaktwerkstoffe die gewünschten elektrisch-technologischen Eigenschaften erfüllen und sich im praktischen Langzeiteinsatz von Schaltgeräten bewährt haben. Da aber Cadmium bekanntermaßen zu den toxischen Schwermetallen zählt und beim Abbrand der Kontaktstücke CdO auch an die nähere Umgebung abgegeben wird, sind seit einiger Zeit Bestrebungen im Gange, das CdO möglichst vollständig durch andere Metalloxide zu ersetzen. Diese Werkstoffe sollen aber einen ebenso kleinen Abbrand im Lichtbogen, sowie geringe Schweißkraft und insbesondere geringe Erwärmung bei Dauerstromführung wie die bewährten AgCdO-Werkstoffe für Kontaktstücke aufweisen.Contact materials based on silver-metal oxides (AgMeO) have proven to be particularly advantageous for low-voltage switchgear in energy technology, for example in contactors or circuit breakers. In the past, cadmium oxide in particular was used as the active component, with these contact materials in particular fulfilling the desired electrical-technological properties and having proven themselves in the long-term use of switching devices. However, since cadmium is known to be one of the toxic heavy metals and when the contact pieces burn off, CdO is also released to the surrounding area, efforts have been underway for some time to replace the CdO as completely as possible with other metal oxides. However, these materials should have an arc burn-up that is just as small, as well as low welding power and, in particular, low heating with continuous current flow, like the proven AgCdO materials for contact pieces.

Es wurde bisher versucht, das Cadmium durch Zinn oder Zink zu ersetzen. Die bekannten Vorschläge mit AgSnO2 und AgZnO-Kontaktwerkstoffen konnten jedoch insgesamt nicht die hochwertigen Eigenschaften von AgCdo-Kontaktstücken erreichen. Insbesondere bei Kontaktstücken aus AgSnO2 als Alternativwerkstoff zu AgCdO hat sich gezeigt, daß dieser aufgrund seiner höheren thermischen Stabilität nach Lichtbogeneinwirkung durch Bildung von Oxiddeckschichten einen gegenüber AgCdO-erhöhten Ubergangswiderstand aufweist. Dadurch treten im stromführenden Zustand des Schaltgerätes unzulässig hohe Ubertemperaturen an den Schaltgliedern auf, die zu Schäden am Schaltgerät führen können. Andererseits weisen aber AgSnO2-Kontaktstücke gegenüber AgCdO einen geringeren Abbrand auf, was zu einer erhöhten Kontaktlebensdauer führt. Daher kann vorteilhaft die Größe der benötigten Kontaktstücke im Vergleich zu AgCdO verringert werden, wodurch eine nicht unerhebliche Silbereinsparung erzielt wird.So far, attempts have been made to replace the cadmium with tin or zinc. However, the known proposals with AgSnO 2 and AgZnO contact materials could not achieve the high-quality properties of AgCdo contact pieces. In particular in the case of contact pieces made of AgSnO 2 as an alternative material to AgCdO, it has been shown that, owing to its higher thermal stability after exposure to arcing through the formation of oxide cover layers, this has an increased contact resistance compared to AgCdO. As a result, inadmissibly high excess temperatures occur on the switching elements when the switching device is live, which can lead to damage to the switching device. On the other hand, however, AgSnO 2 contact pieces have a lower erosion than AgCdO, which leads to an increased contact life. Therefore, the size of the required contact pieces can advantageously be reduced in comparison to AgCdO, whereby a not inconsiderable saving in silver is achieved.

Mit der älteren Patentanmeldung P 33 04 637.9 wurde bereits ein neuer Sinterkontaktwerktoff für obigen Zweck auf der Basis AgSnO2 offenbart, bei dem als weitere Metalloxide Bi203 und CuO sowie wahlweise CdO vorgesehen sind und der Volumenanteil an Summenmetalloxidzwischen 10% und 25 % mit einem SnO2-Volumenateil ≥70 % der Gesamtoxidmenge beträgt. Dabei wird der Kontaktwerkstoff pulvermetallurgisch aus einem inneroxidierten Legierungspulver (sogenanntes IOLP) hergestellt. Für die cadmiumfreie Alternative ist speziell der Werkstoff folgender Zusammensetzung in Massenanteilen von 87,95 % Ag, 9,97 % SnO2, 0,98 % Bi203 und 1,10 % CuO Erprobungen haben nun ergeben, daß der angegebene Werkstoff noch nicht voll den Bedürfnissen der Praxis genügt.With the older patent application P 33 04 637.9, a new sintered contact material for the above purpose based on AgSnO 2 has already been disclosed, in which Bi203 and CuO and optionally CdO are provided as further metal oxides and the volume fraction of total metal oxide is between 10% and 25% with a SnO 2 - Volume part is ≥70% of the total amount of oxide. The contact material is made by powder metallurgy from an internally oxidized alloy powder (so-called IOLP). The material with the following composition is especially suitable for the cadmium-free alternative in mass fractions of 87.95% Ag, 9.97% SnO 2 , 0.98% Bi 2 0 3 and 1.10% CuO Tests have now shown that the specified material does not yet fully meet the needs of practice.

Aufgabe der Erfindung ist es daher, einen weiteren Werkstoff der Konstitution AgSnO2Bi2O3CuO für obengenannte Anwendung anzugeben.The object of the invention is therefore to provide a further material of the constitution AgSnO 2 Bi 2 O 3 CuO for the above-mentioned application.

Die Aufgabe wird erfindungsgemäß dadurch gelöst, daß der SnO2-Massenanteil speziell im Bereich von 4 % bis 8 % liegt. Dabei liegt der Bi203-Massenanteil vorzugsweise zwischen 0,5 % und 4 % , während der CuO-Massenanteil zwischen 0,3 % und 1 % liegt; als Rest ist jeweils Silber vorhanden. Vorzugsweise beträgt das Verhältnis der Massenanteile in % von Sn02 zu CuO zwischen 8:1 und 12:1.The object is achieved in that the SnO 2 mass fraction is specifically in the range from 4% to 8 % . The Bi 2 0 3 mass fraction is preferably between 0.5% and 4%, while the CuO mass fraction is between 0.3% and 1%; the rest is silver. The ratio of the mass fractions in% of SnO 2 to CuO is preferably between 8: 1 and 12: 1.

Die vergleichsweise günstigen Eigenschaften von Werkstoffen der Konstitution AgSnO2Bi2O3CuO sind bereits seit einiger Zeit erkannt: Neben der älteren Patentanmeldung P 33 04 637.9 werden solche Werkstoffe auch in der DE-OS 27 54 335 angegeben. Bei den dort beschriebenen Werkstoffen wird jedoch immer ein vergleichsweise geringer Sn02-Massenanteil gewählt, der meist unter 4 % liegt. Lediglich bei einem, der DE-OS 27.54 335 entnehmbaren Werkstoff (Beispiel 18) liegt der Sn-Anteil höher; jedoch beträgt in diesem Fall der SnO2-Volumenanteil an den Summenoxiden weniger als 70 %, so daß ein anderes Eigenschaftsspektrum zu erwarten ist. Daneben sind in der GB-A-20 55 398 Werkstoffe auf Silbermetalloxidbasis beschrieben, zu deren Herstellung aus Legierungen Bleche erzeugt werden, welche anschließend inneroxidiert werden. Hier handelt es sich also nicht mit pulvermetallurgische Verfahren hergestellte Werkstoffe, insbesondere nicht um die innere Oxidation von Legierungspulvern mit anschließender Verdichtung und Sinterung. Bei der GB-A-20 55 398 ist für die Ausgangslegierung unter anderem eine Zusammensetzung in Massenanteilen von 90,8 % Ag, 8,5 % Sn, 0,2 % Bi und 0,5 % Cu angegeben. Ansonsten werden beim Stand der Technik zu dem angegebenen Vierstoffsystem immer noch weitere Komponenten, beispielsweise Kobalt, Eisen oder Nickel, hinzulegiert.The comparatively favorable properties of materials of the constitution AgSnO 2 Bi 2 O 3 CuO have been recognized for some time: in addition to the older patent application P 33 04 637.9, such materials are also specified in DE-OS 27 54 335. In the materials described there, however, a comparatively small Sn0 2 mass fraction is selected, which is usually less than 4%. Only in the case of a material which can be found in DE-OS 27.54 335 (Example 18) is the Sn content higher; however, in this case the SnO 2 volume fraction of the bulk oxides is less than 70%, so that a different spectrum of properties can be expected. In addition, GB-A-20 55 398 describes materials based on silver metal oxide, for the production of which sheets are produced from alloys, which are subsequently oxidized internally. So this is not a factory made with powder metallurgical processes substances, in particular not egierungspulvern to the internal oxidation of L followed by compaction and sintering. GB-A-20 55 398 specifies, inter alia, a composition in mass fractions of 90.8% Ag, 8.5% Sn, 0.2% Bi and 0.5% Cu for the starting alloy. Otherwise, in the prior art, further components, for example cobalt, iron or nickel, are still added to the specified four-component system.

Vorliegender Erfindung lag nun die überraschende Erkenntnis zugrunde,daß der Sn02-Anteil erniedrigt und damit der Bi203-Anteil erhöht werden kann, um günstigere Temperatureigenschaften als beim Stand der Technik zu erhalten.The present invention was based on the surprising finding that the Sn0 2 content can be reduced and thus the Bi 2 0 3 content can be increased in order to obtain more favorable temperature properties than in the prior art.

Weitere Einzelheiten und Vorteile der Erfindung ergeben sich aus der Beschreibung zweier labormäßig realisierter Sinterkontaktwerkstoffe. Bei deren Herstellung werden im allgemeinen nur die Massenanteile in % (Massengehalt) angegeben. Ausgehend von einem konstanten Volumenanteil an Silber, bietet sich für die Optimierung des Eigenschaftsspektrums die Variation der Wirkkomponenten bei vorgegebenem Volumenanteil der Summenmetall oxide am Dieser beträgt bei der Erfindung zwischen 10 % und 25 %, wobei der Volumenanteil von SnO2 ≥ 70 % ist. Da die Dichte der Oxide unterschiedlich ist, hat es sich in der Praxis bewährt, einerseits die Volumenanteile der Summenmetalloxide und andererseits speziell die Massenanteile in % der einzelnen Komponenten wie bei den nachfolgenden Beispielen anzugeben.Further details and advantages of the invention result from the description of two sintered contact materials which have been implemented in the laboratory. When they are manufactured, only the mass fractions are generally given in% (mass content). Starting from a constant volume fraction of silver, the optimization of the property spectrum offers the variation of the active components for a given volume fraction of the sum metal oxides in the invention is between 10% and 25%, the volume fraction of SnO 2 being ≥ 70%. Since the density of the oxides is different, it has proven useful in practice to specify the volume fractions of the sum metal oxides on the one hand and, on the other hand, specifically the mass fractions in% of the individual components, as in the examples below.

Beispiel 1:Example 1:

Aus 93,60 % Feinsilberkörnern, 5,20 % Zinnkörnern, 0,6 % metallischem Wismut als Bruchstücke und 0,6 % Kupfer in Stangenform wird eine Legierung aus AgSnBiCu der angegebenen Zusammensetzung bei 1353 K erschmolzen. Durch Zerstäuben der Schmelze in Wasser mit einer Druckverdüsungsanlage wird daraus ein gleich zusammengesetztes Legierungspulver erhalten. Nach dem Trocknen wird der Pulveranteil auf L 200 µm abgesiebt. Dieser Anteil wird in sauerstoffhaltiger Atmosphäre zwischen 723 K und 872 K inneroxidiert, wonach ein Verbundpulver aus AgSnO2Bl2O3CuO der Zusammensetzung in Massenanteilen von 92,10 % Ag, 6,50 % SnO2, 0,66 % Bi203 und 0,74 % CuO erhalten wird. Ein solches Verbundpulver ist quantitativ vollständig inneroxidiert und wird als sogenanntes IOLP bezeichnet.An alloy of AgSnBiCu of the specified composition is melted at 1353 K from 93.60% fine silver grains, 5.20% tin grains, 0.6% metallic bismuth as fragments and 0.6% copper in rod form. By atomizing the melt in water with a pressure atomization system, an alloy powder of the same composition is obtained. After drying, the powder portion is sieved to L 200 µm. This portion is internally oxidized in an oxygen-containing atmosphere between 723 K and 872 K, after which a composite powder of AgSnO 2 Bl 2 O 3 CuO of the composition in mass fractions of 92.10% Ag, 6.50% SnO 2 , 0.66% Bi 2 0 3 and 0.74% CuO is obtained. Such a composite powder is quantitatively completely internally oxidized and is referred to as IOLP.

Aus dem Verbundpulver werden durch Pressen in einer Matrize mit 600 MPa Kontaktstücke hergestellt. Für eine sichere Verbindungstechnik durch Hartlöten ist es dabei vorteilhaft, beim Pressen des Verbundpulvers eine zweite Schicht aus Reinsilber gemeinsam mit der Kontaktschicht zu einem Zweischichten-Kontaktstück zu verpressen. Die Sinterung der Kontaktstücke erfolgt bei 1173 K während einer Stunde an Luft. Durch Warmpressen bei 923 K mit 900 MPa werden die Kontaktstücke verdichtet. Eine weitere Verdichtung und Verfestigung wird durch eine zweite Sinterung bei 1173 K während einer Stunde an Luft und eine darauf folgende Kaltverdichtung mit 800 MPa erreicht.The composite powder is used to produce contact pieces by pressing in a die with 600 MPa. For a secure connection technique by brazing, it is advantageous to press a second layer of pure silver together with the contact layer into a two-layer contact piece when pressing the composite powder. The contact pieces are sintered at 1173 K for one hour in air. The contact pieces are compacted by hot pressing at 923 K at 900 MPa. Further compression and solidification is achieved by a second sintering at 1173 K for one hour in air and a subsequent cold compression at 800 MPa.

Metallographische Schliffbilder zeigen, daß das Gefüge des so erzeugten Kontaktwerkstoffes fein und gleichmäßig mit einer mittleren Oxidteilchengröße von 1,5 µm ist.Metallographic micrographs show that the structure of the contact material produced in this way is fine and uniform with an average oxide particle size of 1.5 μm.

Beispiel 2:Example 2:

Bei einem weiteren Ausführungsbeispiel wurden Verfahrensschritte wie bei Beispiel 1 gewählt; es wurde jedoch von Ausgangsmaterialien folgender Zusammensetzung in Massenanteilen ausgegangen: 93,96% Feinsilberkörner, 4,00 % Zinnkörner, 1,64 % metallisches Wismut und 0,40 % Kupfer, woraus eine Legierung erschmolzen wird. Daraus wird in oben beschriebener Weise entsprechendes Legierungspulver erzeugt.In a further exemplary embodiment, method steps as in example 1 were selected; However, starting materials of the following composition in mass fractions were assumed: 93.96% fine silver grains, 4.00% tin grains, 1.64% metallic bismuth and 0.40% copper, from which an alloy is melted. Corresponding alloy powder is produced from this in the manner described above.

Nach innerer Oxidation des Legierungspulvers wird ein IOLP aus AgSnO2Bi2C3CuO der Zusammensetzung in Massenanteilen von 92,70 % Ag, 5,01 % SnO2, 1,80 % Bi203 und 0,49 % Cuo erhalten. Dieses IOLP ist Ausgangsmaterial für den Werkstoff und die daraus zu fertigenden Kontaktstücke.After internal oxidation of the alloy powder, an IOLP of AgSnO 2 Bi 2 C 3 CuO of the composition in mass fractions of 92.70% Ag, 5.01% SnO 2 , 1.80% Bi 2 0 3 and 0.49% Cuo is obtained. This IOLP is the starting material for the material and the contact pieces to be made from it.

Das Gefüge dieses Werkstoffes entspricht bis auf eine stärkere Umkörnung im wesentlichen dem Werkstoff nachThe structure of this material essentially corresponds to that of the material except for a larger grain size

Beispiel 1.Example 1.

Von den erfindungsgemäß hergestellten Kontaktwerkstoffen wurde in einem Prüfschalter die Schweißkraft ermittelt. Die erhaltenen Meßwerte entsprechen im wesentlichen denen des aus inneroxidierten Legierungspulver hergestellten AgCd012Bi2031,O-Kontaktwerkstoffes. Darüber hinaus wurden in Motorschützen Lebensdauer- und Erwärmungsprüfungen durchgeführt. Wesentliche Kenngrößen sind dabei die AC4-Lebensdauerschaltzahlen der Kontaktstücke und die Ubertemperatur der Strombahnen. Im Vergleich zum AgCdO12Bi2O31,0-Werkstoffe liegen die Lebensdauerschaltzahlen etwa um den Faktor 1,8 höher, wobei sich bei den Ubertemperaturen lediglich bis zu 10 °C höhere Werte ergaben.The welding force of the contact materials produced according to the invention was determined in a test switch. The measured values obtained essentially correspond to those of the AgCd012Bi2031, O contact material produced from internally oxidized alloy powder. In addition, service life and heating tests were carried out in motor contactors. The key parameters are the AC4 service life switching numbers of the contact pieces and the overtemperature of the current paths. in the Compared to AgCdO 12 Bi 2 O 3 1.0 materials, the lifespan switching numbers are about a factor of 1.8 higher, with higher temperatures only showing up to 10 ° C higher temperatures.

Die Prüfdaten der neuen Werkstoffe sind in der Tabelle im Vergleich zum bekannten Werkstoff wiedergegeben.The test data of the new materials are shown in the table in comparison to the known material.

Bei Werkstoffen nach der Erfindung wird also, ausgehend vom vorgegebenen Volumenanteil der Summenmetalloxide, der Zinngehalt auf einen geeigneten Bereich erniedrigt und damit zumindest der relative Bi203-Anteil erhöht, was zu unerwartet guten Ergebnissen führt.

Figure imgb0001
In the case of materials according to the invention, the tin content is reduced to a suitable range, starting from the predetermined volume fraction of the sum metal oxides, and thus at least the relative Bi 2 0 3 fraction is increased, which leads to unexpectedly good results.
Figure imgb0001

Claims (8)

1. Sinterkontaktwerkstoff für Niederspannungsschaltgeräte der Energietechnik aus AgSnO2 mit Bi203 und CuO als weitere Metalloxidzusätze, wobei der Volumenanteil an Summenmetalloxid zwischen 10 % und 25 % mit einem SnO2-Volumenanteil ≥ 70 % der Gesamtoxidmenge beträgt, dadurch gekennzeichnet , daß der SnO2-Massenanteil speziell im Bereich von 4 % bis 8 % liegt.1. Sintered contact material for low-voltage switching devices in power engineering made of AgSnO 2 with Bi 2 0 3 and CuO as further metal oxide additives, the volume fraction of total metal oxide being between 10% and 25% with a SnO 2 volume fraction ≥ 70% of the total oxide quantity, characterized in that SnO 2 mass fraction is specifically in the range from 4% to 8%. 2. Sinterkontaktwerkstoff nach Anspruch 1, dadurch gekennzeichnet , daß der Bi203-Massenanteil zwischen 0,5 % und 4 % liegt.2. Sintered contact material according to claim 1, characterized in that the Bi 2 0 3 mass fraction is between 0.5% and 4%. 3. Sinterkontaktwerkstoff nach Anspruch 1, dadurch gekennzeichnet , daß der CuO-Massenanteil zwischen 0,3 % und 1 % liegt.3. Sintered contact material according to claim 1, characterized in that the CuO mass fraction is between 0.3% and 1%. 4. Sinterkontaktwerkstoff nach Anspruch 3, dadurch gekennzeichnet , daß das Verhältnis der Massenanteile in % von SnO2 zu CuO zwischen 8:1 und 12:1 liegt.4. Sintered contact material according to claim 3, characterized in that the ratio of the mass fractions in% of SnO 2 to CuO is between 8: 1 and 12: 1. 5. Sinterkontaktwerkstoff nach Anspruch 4, dadurch gekennzeichnet , daß das Verhältnis der Massenanteile in % von SnO2 zu CuO etwa 9:1 beträgt.5. Sintered contact material according to claim 4, characterized in that the ratio of the mass fractions in% of SnO 2 to CuO is approximately 9: 1. 6. Sinterkontaktwerkstoff nach Anspruch 5, dadurch gekennzeichnet , daß er in Massenanteilen 6,5 % SnO2, 0,66 % Bi203, 0,74 % CuO und als Rest Silber enthält.6. Sintered contact material according to claim 5, characterized in that it contains 6.5% SnO 2 , 0.66% Bi 2 0 3 , 0.74% CuO and the balance silver in mass fractions. 7. Sinterkontaktwerkstoff nach Anspruch 4, dadurch gekennzeichnet , daß das Verhältnis der Massenanteile in % von SnO2 zu CuO etwa 10:1 beträgt.7. sintered contact material according to claim 4, characterized in that the ratio of the mass fractions in% of SnO 2 to CuO is about 10: 1. 8. Sinterkontaktwerkstoff nach Anspruch 7 . dadurch gekennzeichnet , daß er in Massenanteilen 5,01 % SnO2, 1,80 % Bi2O3, 0,49 % CuO und als Rest Silber enthält.8. sintered contact material according to claim 7. characterized in that it contains 5.01% SnO 2 , 1.80% Bi 2 O 3 , 0.49% CuO in mass fractions and silver as the balance.
EP85106748A 1984-06-12 1985-05-31 Sintered contact material for low-tension energy switchgear Expired - Lifetime EP0164664B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85106748T ATE84905T1 (en) 1984-06-12 1985-05-31 SINTERED CONTACT MATERIAL FOR LOW VOLTAGE SWITCHGEAR IN POWER ENGINEERING.

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DE3421759 1984-06-12
DE19843421759 DE3421759A1 (en) 1984-06-12 1984-06-12 SINTER CONTACT MATERIAL FOR LOW VOLTAGE SWITCHGEAR OF ENERGY TECHNOLOGY

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JP (1) JPH0768593B2 (en)
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ZA (1) ZA854389B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0369283A2 (en) * 1988-11-17 1990-05-23 Siemens Aktiengesellschaft Sintered contact material for low-tension switchgear, particularly for contactors
EP0369282A2 (en) * 1988-11-17 1990-05-23 Siemens Aktiengesellschaft Sintered contact material in low-tension switchgear, particularly for contactors
WO1993015517A1 (en) * 1992-01-24 1993-08-05 Siemens Aktiengesellschaft Sintered composite materials for electric contacts in power technology switching devices and process for producing them
DE4331913A1 (en) * 1993-09-20 1995-03-23 Siemens Ag Method for connecting a contact pad made of silver-metal oxide material to a metallic contact carrier
CN117102479A (en) * 2023-10-18 2023-11-24 佛山通宝精密合金股份有限公司 Preparation process of modified silver tin oxide and prepared modified silver tin oxide

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DE2754335A1 (en) * 1976-12-03 1978-06-08 Matsushita Electric Ind Co Ltd ELECTRICAL CONTACT MATERIAL AND METHOD FOR MANUFACTURING IT
FR2433054A1 (en) * 1978-08-11 1980-03-07 Chugai Electric Ind Co Ltd AG-SN-BI ALLOYS WITH INTERNAL OXIDATION FOR IMPROVED ELECTRICAL CONTACTS
GB2055398A (en) * 1979-08-01 1981-03-04 Chugai Electric Ind Co Ltd Electrical contact materials of internally oxidized Ag-Sn-Bi alloy

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JPS6018735B2 (en) * 1977-12-15 1985-05-11 松下電器産業株式会社 electrical contact materials
JPS6027746B2 (en) * 1979-09-19 1985-07-01 松下電器産業株式会社 electrical contact materials
JPS57134532A (en) * 1981-02-12 1982-08-19 Chugai Electric Ind Co Ltd Electrical contact material of silver-tin-bismuth alloy
JPS57181339A (en) * 1981-05-02 1982-11-08 Chugai Electric Ind Co Ltd Electrical contact material of selectively and internally oxidized silver-tin alloy containing bismuth

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DE2754335A1 (en) * 1976-12-03 1978-06-08 Matsushita Electric Ind Co Ltd ELECTRICAL CONTACT MATERIAL AND METHOD FOR MANUFACTURING IT
FR2433054A1 (en) * 1978-08-11 1980-03-07 Chugai Electric Ind Co Ltd AG-SN-BI ALLOYS WITH INTERNAL OXIDATION FOR IMPROVED ELECTRICAL CONTACTS
GB2055398A (en) * 1979-08-01 1981-03-04 Chugai Electric Ind Co Ltd Electrical contact materials of internally oxidized Ag-Sn-Bi alloy

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0369283A2 (en) * 1988-11-17 1990-05-23 Siemens Aktiengesellschaft Sintered contact material for low-tension switchgear, particularly for contactors
EP0369282A2 (en) * 1988-11-17 1990-05-23 Siemens Aktiengesellschaft Sintered contact material in low-tension switchgear, particularly for contactors
EP0369283A3 (en) * 1988-11-17 1991-03-13 Siemens Aktiengesellschaft Sintered contact material for low-tension switchgear, particularly for contactors
EP0369282A3 (en) * 1988-11-17 1991-03-13 Siemens Aktiengesellschaft Sintered contact material in low-tension switchgear, particularly for contactors
WO1993015517A1 (en) * 1992-01-24 1993-08-05 Siemens Aktiengesellschaft Sintered composite materials for electric contacts in power technology switching devices and process for producing them
US5486222A (en) * 1992-01-24 1996-01-23 Siemens Aktiengesellschaft Sintered composite materials for electric contacts in power technology switching devices and process for producing them
DE4331913A1 (en) * 1993-09-20 1995-03-23 Siemens Ag Method for connecting a contact pad made of silver-metal oxide material to a metallic contact carrier
US5628448A (en) * 1993-09-20 1997-05-13 Siemens Aktiengesellschaft Process for bonding a contact layer of silver-metal oxide material and metal contact base, and suitable contact layer
CN117102479A (en) * 2023-10-18 2023-11-24 佛山通宝精密合金股份有限公司 Preparation process of modified silver tin oxide and prepared modified silver tin oxide
CN117102479B (en) * 2023-10-18 2024-01-02 佛山通宝精密合金股份有限公司 Preparation process of modified silver tin oxide and prepared modified silver tin oxide

Also Published As

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EP0164664B1 (en) 1993-01-20
DE3421759A1 (en) 1985-12-12
EP0164664A3 (en) 1988-03-23
JPS619541A (en) 1986-01-17
BR8502760A (en) 1986-02-18
DE3587004D1 (en) 1993-03-04
JPH0768593B2 (en) 1995-07-26
ZA854389B (en) 1986-02-26
ATE84905T1 (en) 1993-02-15

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