EP0152606B1 - Contact material and production of electric contacts - Google Patents

Contact material and production of electric contacts Download PDF

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Publication number
EP0152606B1
EP0152606B1 EP84115754A EP84115754A EP0152606B1 EP 0152606 B1 EP0152606 B1 EP 0152606B1 EP 84115754 A EP84115754 A EP 84115754A EP 84115754 A EP84115754 A EP 84115754A EP 0152606 B1 EP0152606 B1 EP 0152606B1
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EP
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Prior art keywords
weight percent
tungsten
contact
contact material
silver
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EP84115754A
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German (de)
French (fr)
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EP0152606A2 (en
EP0152606A3 (en
Inventor
Joachim Grosse
Günter Tiefel
Wolfgang Haufe
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Siemens AG
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Siemens AG
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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

Definitions

  • the invention relates to a contact material, in particular for contact pieces in low-voltage switching devices, which consists of silver, tin oxide and other additives.
  • the invention relates to a method for manufacturing contact pieces from this material.
  • AgSn0 2 contacts have a lower erosion compared to 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.
  • EP-B1-0 024 349 a material based on AgSn0 2 is known, in which the excess temperature is reduced compared to the pure AgSn0 2 by adding tungsten oxide (W0 3 );
  • EP-B1-0 0 39 429 proposes bismuth oxide (Bi 2 0 3 ) as a further additive, with which the welding force is to be influenced favorably without increasing the contact resistance.
  • EP-A1-0 056 857 states that the overtemperature behavior can also allegedly be improved by molybdenum oxide (Mo03) and / or germanium oxide (Ge0 2 ).
  • Mo03 molybdenum oxide
  • Ge0 2 germanium oxide
  • Mo03 deteriorates the erosion behavior of AgSn0 2 in such a way that the contact life falls far below that of AgCdO.
  • These disadvantages do not occur when using Ge0 2 ; however, due to the high price of germanium oxide, which is a multiple of that of silver, the contact piece becomes significantly more expensive. This largely eliminates the economic advantage of using AgSn0 2 , namely saving silver due to the favorable burning behavior compared to AgCdO.
  • the object of the invention is therefore to develop an electrical contact material based on silver and tin oxide, in which the excess temperature compared to the known AgSnOr material is specifically reduced by adding further additives.
  • the aim is neither to significantly reduce the contact life nor to make the material excessively expensive.
  • the object is achieved in that the new material 5 to 20 mass% SnO 2 , 0.1 to 5 mass% Ta 2 0 5 , 0.1 to 5 mass% CuO. Contains 0.1 to 5 mass% Bi 2 0 3 and the balance silver.
  • tungsten or oxygen-containing tungsten compounds can also be present, the proportion of tungsten being 0.05 to 3% by mass.
  • the invention shows in particular the advantageous property of tantalum oxide in conjunction with bismuth oxide and predetermined amounts of CuO and optionally tungsten in the case of contact materials based on silver-tin oxide.
  • WO-A1-80 / 01434 has already suggested that tantalum oxide also be used in contact materials.
  • tantalum is used either as cadmium tantalum oxide or as tantalum oxide in conjunction with at least germanium. Because of the favorable wetting properties of the tantalum oxide, the contact erosion is favorably influenced in the material there. It was not previously recognized that tantalum oxide can be used as an additive in silver-tin oxide-based contact materials in conjunction with bismuth oxide.
  • the overtemperature in the contact material according to the invention is on the one hand up to about 20% lower than in AgSn0 2 11.5 W0 3 0.5; on the other hand, the welding force has values comparable to those of known AgCdO materials.
  • an optimized contact material with low overtemperature and a sufficient service life can now be used.
  • the materials according to the invention can be produced by known powder metallurgical processes.
  • the material is advantageously subjected to an extrusion into a strip after sintering, as a result of which a straightening structure is produced.
  • the directional structure runs parallel to the longitudinal edges, the contact pieces being able to be hard-soldered onto the contact carriers of the conventional switching devices.
  • Powders of the components Ag, SnO 2 , Ta 2 0 5 , CuO and Bi 2 0 3 are used as starting materials, a composition in mass fractions of 91.4% Ag, 7.5% Sn0 2 , 0.5% Ta 2 0 5 , 0.3% CuO and 0.3% Bi 2 0 3 is selected.
  • the powder batch is mixed and then subjected to powder metallurgical process steps from pressing, sintering and post-pressing with the usual pressures and temperatures: For example, 200 MPa have been used for pressing the powder, 850-900 ° C for one hour in air and 600 for pressing MPa proved to be suitable values.
  • a strip as a semi-finished product is produced from the blank by extrusion at 700 ° C, from which contact pieces with a directional structure parallel to the edges can be separated.
  • the contact pieces manufactured in this way can be hard-soldered directly onto the contact carriers of a conventional switching device.
  • Powders of the components are used as in Example 1, with a composition in proportions by mass of 87.7% Ag, 10.5% SnO 2 , 0.8% Ta 2 0 5 , 0.5% CuO and 0.5% Bi 2 0 3 is selected.
  • the other manufacturing steps correspond to those of Example 1.
  • powders of the components Ag, Sn0 2 , Ta 2 0 5 , CuO are used as starting materials.
  • Bi 2 0 3 and additionally powder made of pure tungsten are used.
  • a mixture with mass fractions of 91.7% Ag, 7.0% Sn0 2 , 0.5% Ta 2 0 5 , 0.3% CuO, 0.3% Bi 2 0 3 and 0.2% W is selected .
  • the powder batch is mixed and then subjected to the usual powder metallurgical process steps from pressing, sintering and post-pressing.
  • a strip as a semi-finished product is produced from the blank by extrusion, from which contact pieces with a parallel alignment structure can be separated.
  • Powders of the components are used as in Example 3, but now a composition in mass fractions with 87.5% Ag, 10.5% Sn0 2 , 0.8% Ta 2 0 5 , 0.5% CuO, 0.4% Bi 2 0 3 and 0.3% W is selected.
  • the contact pieces were connected until the original button was remelted due to arcing. This required a few thousand switching operations. Under the highest continuous current load permitted for the switchgear, the temperature on the movable contact piece was measured directly below the contact pieces. It has been shown that the influence of the contact material can best be detected at this point.
  • the excess temperatures measured at the connection terminals for the reference material AgSn0 2 11.5 W0 3 0.5 are 33% higher than for AgCd012, while the pure AgSn0 2 materials are more than 44% higher. It can be seen that the materials according to the invention have excess temperatures which are between 7 and 23% lower than those of the comparative material AgSn0 2 11.5 W0 3 0.5 and thus at best reach the temperatures of AgCdO.
  • the materials according to the invention with added tungsten are even above the comparative material AgSn0 2 11.5 W0 3 0.5, while the materials according to the invention without tungsten achieve switching numbers comparable to the corresponding pure AgSnO 2 materials, but are due to the most favorable overtemperature behavior of all examined AgSn0 Mark 2 materials (with the same oxide content).
  • Tests with tungsten-containing AgSn0 2 contact materials in various switching devices generally confirm the favorable service life behavior, but with certain AC switching devices, material shifting can occur, which can lead to premature failure of the switching device.
  • contact material is transferred from one contact piece to the opposite, so that the material-releasing contact piece limits the service life of the switching device by switching through to the carrier material before the prescribed number of switching operations has been reached.
  • the causes of this material shift are not yet known, but seem to be related to the addition of tungsten or oxygen-containing tungsten compounds, since they have not previously occurred with tungsten-free AgSn0 2 materials. For these reasons, the behavior with regard to material displacement must first be checked before using the tungsten-containing AgSn0 2 materials.
  • the material according to the invention can be used as a substitute for AgCdO without tungsten addition, which, with a volume reduction of approximately 20%, still has a favorable combustion behavior compared to AgCdO.
  • the materials according to the invention with added tungsten compared to AgSn0 2 11.5 W0 3 0.5 have a longer service life at a lower excess temperature, while the materials according to the invention without tungsten are characterized by a lack of material displacement, very favorable excess temperature and a longer service life compared to AgCdO, which, however, are not completely reached the values of Agsn0 2 11.5 W0 3 0.5.
  • the percentage composition of the material can be further varied with the special oxide combination Sn0 2 , Ta 2 0 5 , CuO and Bi 2 0 3 and optionally W.
  • the tungsten can be added either as pure tungsten or as tungsten oxide (WO 3 ) or other oxygen-containing tungsten compounds without the properties of the contact material being impaired.
  • the material costs of the individual additional components are only about 40% compared to Ge0 2, which has so far been found to be particularly favorable. This enables the object of the invention to create an inexpensive contact material with favorable temperature behavior. Overall, suitable contact pieces for switching devices can now be produced.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Contacts (AREA)

Description

Die Erfindung bezieht sich auf einen Kontaktwerkstoff, insbesondere für Kontaktstücke in Niederspannungsschaltgeräten, welcher aus Silber, Zinnoxid und weiteren Zusätzen besteht. Daneben bezieht sich die Erfindung auf ein Verfahren zum Fertigen von Kontaktstücken aus diesem Werkstoff.The invention relates to a contact material, in particular for contact pieces in low-voltage switching devices, which consists of silver, tin oxide and other additives. In addition, the invention relates to a method for manufacturing contact pieces from this material.

Für Niederspannungsschaltgeräte der Energietechnik, z. B. in Schützen oder Selbstschaltern, haben sich in der Vergangenheit Kontaktwerkstoffe auf der Basis von Silbermetalloxiden (AgMeO). insbesondere AgCdO, als besonders vorteilhaft erwiesen. Da aber Cadmium bekanntermaßen zu den toxischen Schwermetallen zählt und beim Abbrand der Kontakstücke CdO auch an die nähere Umgebung abgegeben wird, sind seit einiger Zeit Bestrebungen im Gange, das CdO durch andere Metalloxide zu ersetzen. Diese Werkstoffe sollen einen ebenso kleinen Abbrand im Lichtbogen, sowie geringe Schweißkraft und insbesondere niedrige Erwärmung bei Dauerstromführung wie die bekannten AgCdO-Werkstoffe für Kontaktstücke aufweisen.For low-voltage switchgear in power engineering, e.g. Contactors based on silver metal oxides (AgMeO) have been used in the past, for example in contactors or automatic switches. especially AgCdO, proved to be particularly advantageous. 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 with other metal oxides. These materials are said to have an arc burn-up that is just as small, as well as low welding power and, in particular, low heating in the case of continuous current flow, like the known AgCdO materials for contact pieces.

Es wurde bisher versucht, das Cadmium durch Zinn oder Zink zu ersetzen. Die bekannten Vorschläge mit AgSn02- und AgZnO-Kontaktwerkstoffen konnten jedoch insgesamt nicht die hochwertigen Eigenschaften von AgCdO-Kontaktstücken erreichen. Insbesondere bei AgSn02 als Alternativwerkstoff zu AgCdO hat sich gezeigt, daß dieser aufgrund der höheren thermischen Stabilität von Sno2 nach Schaltbelastungen durch Bildung von Oxid-Deckschichten einen gegenüber AgCdO erhöhten Übergangswiderstand aufweist. Dadurch treten aber beim eingeschalteten, d. h. im stromführenden, Zustand des Schaltgerätes unzulässig hohe Temperaturen (Übertemperaturen) an den Kontaktstücken auf, die zu Schäden am Schaltgerät führen können. Dagegen weisen AgSn02-Kontakte 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 AgSn0 2 and AgZnO contact materials could not achieve the high-quality properties of AgCdO contact pieces. In particular with AgSn0 2 as an alternative material to AgCdO, it has been shown that due to the higher thermal stability of Sno 2 after switching loads due to the formation of oxide cover layers, it has a higher contact resistance than AgCdO. As a result, however, when the switchgear is switched on, ie when the switchgear is in a live state, inadmissibly high temperatures (excess temperatures) occur at the contact pieces, which can damage the switchgear. In contrast, AgSn0 2 contacts have a lower erosion compared to 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.

Aus der EP-B1-0 024 349 ist ein Werkstoff auf der Basis von AgSn02 bekannt, bei dem durch Zusatz von Wolframoxid (W03) die Übertemperatur gegenüber dem reinen AgSn02 gesenkt wird ; daneben wird mit der EP-B1-0 0 39 429 als weiterer Zusatz Wismutoxid (Bi203) vorgeschlagen, womit die Schweißkraft günstig beeinflußt werden soll, ohne den Kontaktwiderstand zu erhöhen.From EP-B1-0 024 349 a material based on AgSn0 2 is known, in which the excess temperature is reduced compared to the pure AgSn0 2 by adding tungsten oxide (W0 3 ); In addition, EP-B1-0 0 39 429 proposes bismuth oxide (Bi 2 0 3 ) as a further additive, with which the welding force is to be influenced favorably without increasing the contact resistance.

Darüber hinaus wird in der EP-A1-0 056 857 ausgeführt, daß das Übertemperaturverhalten angeblich auch durch Molybdänoxid (Mo03) und/oder Germaniumoxid (Ge02) verbessert werden kann. Es hat sich jedoch gezeigt, daß der Zusatz von Mo03 das Abbrandverhalten von AgSn02 derart verschlechtert, daß die Kontaktlebensdauer weit unter die von AgCdO abfällt. Diese Nachteile treten zwar beim Einsatz von Ge02 nicht auf ; allerdings wird aufgrund des hohen Preises von Germaniumoxid, der ein Mehrfaches von dem des Silbers beträgt, das Kontaktstück deutlich teuerer. Damit wird der wirtschaftliche Vorteil bei Ei-nsatz von AgSn02, namlich einer Einsparung von Silber aufgrund des günstigen Abbrandverhaltens gegenüber AgCdO, weitgehend wieder aufgehoben.In addition, EP-A1-0 056 857 states that the overtemperature behavior can also allegedly be improved by molybdenum oxide (Mo03) and / or germanium oxide (Ge0 2 ). However, it has been shown that the addition of Mo03 deteriorates the erosion behavior of AgSn0 2 in such a way that the contact life falls far below that of AgCdO. These disadvantages do not occur when using Ge0 2 ; however, due to the high price of germanium oxide, which is a multiple of that of silver, the contact piece becomes significantly more expensive. This largely eliminates the economic advantage of using AgSn0 2 , namely saving silver due to the favorable burning behavior compared to AgCdO.

Aufgabe der Erfindung ist es daher, einen elektrischen Kontaktwerkstoff auf der Basis von Silber und Zinnoxid zu entwickeln, bei dem durch Beimischung weiterer Zusätze speziell die Übertemperatur gegenüber dem bekannten AgSnOrWerkstoff gesenkt wird. Dabei soll weder die Kontaktlebensdauer entscheidend verringert noch der Werkstoff übermäßig verteuert werden.The object of the invention is therefore to develop an electrical contact material based on silver and tin oxide, in which the excess temperature compared to the known AgSnOr material is specifically reduced by adding further additives. The aim is neither to significantly reduce the contact life nor to make the material excessively expensive.

Die Aufgabe wird erfindungsgemäß dadurch gelöst, daß der neue Werkstoff 5 bis 20 Masse% SnO2, 0,1 bis 5 Masse% Ta205, 0,1 bis 5 Masse% CuO. 0,1 bis 5 Masse% Bi203 sowie als Rest Silber enthält. Gegebenenfalls können zusätzlich Wolfram oder sauerstoffhaltige Wolframverbindungen vorhanden sein, wobei der Anteil an Wolfram 0,05 bis 3 Masse% beträgt.The object is achieved in that the new material 5 to 20 mass% SnO 2 , 0.1 to 5 mass% Ta 2 0 5 , 0.1 to 5 mass% CuO. Contains 0.1 to 5 mass% Bi 2 0 3 and the balance silver. Optionally, tungsten or oxygen-containing tungsten compounds can also be present, the proportion of tungsten being 0.05 to 3% by mass.

Die Erfindung zeigt insbesondere die vorteilhafte Eigenschaft des Tantaloxides in Verbindung mit Wismutoxid sowie vorgegebenen Mengen CuO und gegebenenfalls Wolfram bei Kontaktwerkstoffen auf Silber-Zinnoxid-Basis. Zwar wurde bereits mit der WO-A1-80/01434 vorgeschlagen, in Kontaktwerkstoffen auch Tantaloxid zu verwenden. Allerdings wird beim Stand der Technik das Tantal entweder als Cadmiumtantaloxid oder als Tantaloxid in Verbindung mit wenigstens Germanium eingesetzt. Aufgrund der günstigen Benetzungseigenschaften des Tantaloxids wird beim dortigen Werkstoff der Kontaktabbrand günstig beeinflußt. Nicht erkannt war bisher, daß Tantaloxid als Zusatz in Kontaktwerkstoffen auf Silber-Zinnoxid-Basis in Verbindung mit Wismutoxid verwendet werden kann.The invention shows in particular the advantageous property of tantalum oxide in conjunction with bismuth oxide and predetermined amounts of CuO and optionally tungsten in the case of contact materials based on silver-tin oxide. WO-A1-80 / 01434 has already suggested that tantalum oxide also be used in contact materials. However, in the prior art, tantalum is used either as cadmium tantalum oxide or as tantalum oxide in conjunction with at least germanium. Because of the favorable wetting properties of the tantalum oxide, the contact erosion is favorably influenced in the material there. It was not previously recognized that tantalum oxide can be used as an additive in silver-tin oxide-based contact materials in conjunction with bismuth oxide.

Mit der Erfindung wurden nun Werkstoffe aufgefunden, die wenigstens die gleiche Lebensdauer wie ein AgCdO-Werkstoff und etwa die gleiche Lebensdauer wie ein AgSn02-Werkstoff mit W03-Zusatz haben. Überraschenderweise liegt aber beim erfindungsgemäßen Kontaktwerkstoff einerseits die Übertemperatur um bis zu etwa 20 % niedriger als bei AgSn0211,5 W030.5 ; andererseits hat die Schweißkraft etwa vergleichbare Werte wie die von bekannten AgCdO-Werkstoffen. Je nach Anwendungsfall bzw. Schaltgerätetyp läßt sich nunmehr ein optimierter Kontaktwerkstoff mit niedriger Übertemperatur und trotzdem ausreichender Lebensdauer einsetzen.With the invention, materials have now been found which have at least the same lifespan as an AgCdO material and approximately the same lifespan as an AgSn0 2 material with W0 3 addition. Surprisingly, however, the overtemperature in the contact material according to the invention is on the one hand up to about 20% lower than in AgSn0 2 11.5 W0 3 0.5; on the other hand, the welding force has values comparable to those of known AgCdO materials. Depending on the application or type of switchgear, an optimized contact material with low overtemperature and a sufficient service life can now be used.

Die erfindungsgemäßen Werkstoffe lassen sich nach bekannten pulvermetallurgischen Verfahren herstellen. Vorteilhafterweise wird zur Fertigung von Kontaktstücken der Werkstoff nach der Sinterung einem Strangpressen zu einem Band unterzogen, wodurch ein Richtgefüge entsteht. Bei aus diesem Band geschnittenen Kontaktstücken verläuft das Richtgefüge parallel zu den Längskanten, wobei die Kontaktstücke auf die Kontaktträger der herkömmlichen Schaltgeräte hart aufgelötet werden können. Anhand von Beispielen wird die Erfindung im einzelnen erläutert :The materials according to the invention can be produced by known powder metallurgical processes. To produce contact pieces, the material is advantageously subjected to an extrusion into a strip after sintering, as a result of which a straightening structure is produced. In the case of contact pieces cut from this band, the directional structure runs parallel to the longitudinal edges, the contact pieces being able to be hard-soldered onto the contact carriers of the conventional switching devices. The invention is explained in detail using examples:

Beispiel 1example 1

Als Ausgangsmaterialien werden Pulver der Komponenten Ag, SnO2, Ta205, CuO und Bi203 verwendet, wobei eine Zusammensetzung in Massenanteilen von 91,4 % Ag, 7,5 % Sn02, 0.5% Ta205, 0,3 % CuO und 0,3 % Bi203 gewählt wird.Powders of the components Ag, SnO 2 , Ta 2 0 5 , CuO and Bi 2 0 3 are used as starting materials, a composition in mass fractions of 91.4% Ag, 7.5% Sn0 2 , 0.5% Ta 2 0 5 , 0.3% CuO and 0.3% Bi 2 0 3 is selected.

Der Pulveransatz wird gemischt und anschließend pulvermetallurgischen Verfahrensschritten aus Pressen, Sintern und Nachpressen mit üblichen Drucken und Temperaturen unterzogen : Beispielsweise haben sich für das Pressen des Pulvers 200 MPa, für das Sintern 850-900°C bei einer Stunde an Luft und für das Nachpressen 600 MPa als geeignete Werte erwiesen. Aus dem Rohling wird durch Strangpressen bei 700°C ein Band als Halbzeug erzeugt, von dem Kontaktstücke mit kantenparallelem Richtgefüge abgetrennt werden können.The powder batch is mixed and then subjected to powder metallurgical process steps from pressing, sintering and post-pressing with the usual pressures and temperatures: For example, 200 MPa have been used for pressing the powder, 850-900 ° C for one hour in air and 600 for pressing MPa proved to be suitable values. A strip as a semi-finished product is produced from the blank by extrusion at 700 ° C, from which contact pieces with a directional structure parallel to the edges can be separated.

Die so gefertigten Kontaktstücke können direkt auf die Kontaktträger eines herkömmlichen Schaltgerätes hart aufgelötet werden.The contact pieces manufactured in this way can be hard-soldered directly onto the contact carriers of a conventional switching device.

Beispiel 2Example 2

Es werden Pulver der Komponenten wie bei Beispiel 1 verwendet, wobei eine Zusammensetzung in Massenanteilen von 87,7 % Ag, 10,5 % Sn02, 0,8 % Ta205, 0,5 % CuO und 0,5 % Bi203 gewählt wird. Die weiteren Hergtellungsschritte entsprechen denen von Beispiel 1.Powders of the components are used as in Example 1, with a composition in proportions by mass of 87.7% Ag, 10.5% SnO 2 , 0.8% Ta 2 0 5 , 0.5% CuO and 0.5% Bi 2 0 3 is selected. The other manufacturing steps correspond to those of Example 1.

Beispiel 3Example 3

Als Ausgangsmaterialien werden wiederum Pulver der Komponenten Ag, Sn02, Ta205, CuO. Bi203 und zusätzlich Pulver aus reinem Wolfram verwendet. Beispielsweise wird eine Mischung mit Massenanteilen von 91,7 % Ag, 7,0 % Sn02, 0,5 % Ta205, 0,3 % CuO, 0,3 % Bi203 und 0,2 % W gewählt. Der Pulveransatz wird gemischt und anschließend den üblichen pulvermetallurgischen Verfahrensschritten aus Pressen, Sintern und Nachpressen unterzogen. Aus dem Rohling wird durch Strangpressen ein Band als Halbzeug erzeugt, von dem Kontaktstücke mit kantenparallelem Richtgefüge abgetrennt werden können.In turn, powders of the components Ag, Sn0 2 , Ta 2 0 5 , CuO are used as starting materials. Bi 2 0 3 and additionally powder made of pure tungsten are used. For example, a mixture with mass fractions of 91.7% Ag, 7.0% Sn0 2 , 0.5% Ta 2 0 5 , 0.3% CuO, 0.3% Bi 2 0 3 and 0.2% W is selected . The powder batch is mixed and then subjected to the usual powder metallurgical process steps from pressing, sintering and post-pressing. A strip as a semi-finished product is produced from the blank by extrusion, from which contact pieces with a parallel alignment structure can be separated.

Beispiel 4Example 4

Es werden Pulver der Komponenten wie bei Beispiel 3 verwendet, wobei jetzt eine Zusammensetzung in Massenanteilen mit 87,5 % Ag, 10,5 % Sn02, 0,8 % Ta205, 0,5 % CuO, 0,4 % Bi203 und 0,3 % W gewählt wird.Powders of the components are used as in Example 3, but now a composition in mass fractions with 87.5% Ag, 10.5% Sn0 2 , 0.8% Ta 2 0 5 , 0.5% CuO, 0.4% Bi 2 0 3 and 0.3% W is selected.

Aus diesen Werkstoffen gefertigte Kontaktstücke wurden auf die Kontaktträger eines herkömmlichen Schaltgerätes hart aufgelötet.Contact pieces made from these materials were hard-soldered onto the contact carriers of a conventional switching device.

Die Kontaktstücke wurden solange beschaltet, bis die ursprüngliche Schaltfläche durch Lichtbogeneinwirkung überall umgeschmolzen war. Dazu waren einige tausend Schaltspiele notwendig. Unter der höchsten, für das Schaltgerät zulässigen Dauerstrombelastung wurde zunächst die Temperatur am beweglichen Schaltstück direkt unterhalb der Kontaktstücke gemessen. Es hat sich gezeigt, daß an dieser Stelle der Einfluß des Kontaktwerkstoffes am besten erfaßt werden kann.The contact pieces were connected until the original button was remelted due to arcing. This required a few thousand switching operations. Under the highest continuous current load permitted for the switchgear, the temperature on the movable contact piece was measured directly below the contact pieces. It has been shown that the influence of the contact material can best be detected at this point.

Die oben beschriebenen Werkstoffe wurden einerseits mit einem AgCd012-Werkstoff und zusatzfreien AgSn02-Werkstoffen und andererseits mit dem aus der EP-B1-00 24 349 bekannten AgSn02 11.5 W03-Werkstoff verglichen, der nach dem dort beschriebenen Verfahren hergestellt wurde. Die Ergebnisse sind in der Tabelle zusammengestellt. Aufgetragen und für die einzelnen Werkstoffe die Maximalwerte speziell der Klemmenübertemperaturen, die durch die Übertemperatur am Schaltstück entstehen, sowie die AC 4-Lebensdauerschaltzahlen.The materials described above were compared on the one hand with an AgCd012 material and additive-free AgSn0 2 materials and on the other hand with the AgSn0 2 11.5 W0 3 material known from EP-B1-00 24 349, which was produced by the process described there. The results are summarized in the table. The maximum values, in particular of the terminal overtemperature caused by the overtemperature on the contact, as well as the AC 4 service life switching numbers are plotted and for the individual materials.

Diskussiondiscussion

Wie aus der Tabelle ersichtlich, liegen die an den Anschlußklemmen gemessenen Übertemperaturen für den Vergleichswerkstoff AgSn02 11.5 W030,5 um 33 % höher als für AgCd012, während die reinen AgSn02-Werkstoffe um mehr als 44 % höher liegen. Es zeigt sich, daß die erfindungsgemäßen Werkstoffe Übertemperaturen aufweisen, die zwischen 7 und 23 % niedriger sind als die des Vergleichswerkstoffes AgSn0211,5 W030.5 und damit günstigstenfalls bis an die Temperaturen von AgCdO heranreichen.As can be seen from the table, the excess temperatures measured at the connection terminals for the reference material AgSn0 2 11.5 W0 3 0.5 are 33% higher than for AgCd012, while the pure AgSn0 2 materials are more than 44% higher. It can be seen that the materials according to the invention have excess temperatures which are between 7 and 23% lower than those of the comparative material AgSn0 2 11.5 W0 3 0.5 and thus at best reach the temperatures of AgCdO.

Aus dem direkten Vergleich mit AgSn0212 bzw. AgSn028 kann, bezogen auf vergleichbaren Gesamtoxidgehalt, die temperatursenkende Wirkung der erfindungsgemäßen Zusätze ersehen werden. Auffällig ist, daß die erfindungsgemäßen Werkstoffe mit niedrigem Oxidgehalt ebenso wie die ohne Wolfram-Zusatz zu einer etwas niedrigeren Übertemperatur neigen. Aus dem Lebensdauervergleich ist zu ersehen, daß alle AgSn02-Werkstoffe trotz der Volumenreduzierung um ca. 20 % gegenüber AgCd012 eine höhere Schaltzahl erreichen. Dabei liegen die erfindungsgemässen Werkstoffe mit Wolframzusatz sogar noch über dem Vergleichswerkstoff AgSn0211,5 W030,5, während die erfindungsgemäßen Werkstoffe ohne Wolfram vergleichbare Schaltzahlen wie die entsprechenden reinen AgSnO2-Werkstoffe erreichen, sich jedoch durch das günstigste Übertemperaturverhalten aller untersuchten AgSn02-Werkstoffe (bei gleichem Oxidgehalt) auszeichnen.From direct comparison with AgSn0 2 12 or AgSn0 2 8, based on comparable total oxide content, the temperature-lowering effect of the additives according to the invention can be seen. It is striking that the materials according to the invention with a low oxide content, as well as those without the addition of tungsten, tend to have a somewhat lower excess temperature. From the life cycle comparison it can be seen that all AgSn0 2 materials achieve a higher number of operations in spite of the volume reduction of approx. 20% compared to AgCd012. The materials according to the invention with added tungsten are even above the comparative material AgSn0 2 11.5 W0 3 0.5, while the materials according to the invention without tungsten achieve switching numbers comparable to the corresponding pure AgSnO 2 materials, but are due to the most favorable overtemperature behavior of all examined AgSn0 Mark 2 materials (with the same oxide content).

Versuche mit wolframhaltigen AgSn02-Kontaktwerkstoffen in verschiedenen Schaltgeräten bestätigen zwar das günstige Lebensdauerverhalten im Allgemeinen, bei bestimmten Wechselstromschaltgeräten können jedoch Materialverlagerungen auftreten, die zu einem vorzeitigen Versagen des Schaltgerätes führen. Dabei wird Kontaktmaterial von dem einen Schaltstück auf das gegenüberliegende übertragen, so daß das materialabgebende Schaltstück die Lebensdauer des Schaltgerätes durch Durchschalten auf den Trägerwerkstoff vor Erreichen der vorgeschriebenen Schaltzahl begrenzt. Die Ursachen dieser Materialverlagerung sind bisher nicht bekannt, scheinen aber mit dem Zusatz von Wolfram oder sauerstoffhaltigen Wolframverbindungen im Zusammenhang zu stehen, da sie bei wolframfreien AgSn02-Werkstoffen bisher nicht auftraten. Aus diesen Gründen muß vor Einsatz der wolframhaltigen AgSn02-Werkstoffe zunächst das Verhalten bezüglich Materialverlagerung geprüft werden. Alternativ kann bei Auftreten der Materialverlagerung der erfindungsgemäße Werkstoff ohne Wolframzusatz als Ersatz für AgCdO eingesetzt werden, der bei einer Volumenreduzierung um ca. 20 % gegenüber AgCdO noch ein günstiges Abbrandverhalten aufweist.Tests with tungsten-containing AgSn0 2 contact materials in various switching devices generally confirm the favorable service life behavior, but with certain AC switching devices, material shifting can occur, which can lead to premature failure of the switching device. In this case, contact material is transferred from one contact piece to the opposite, so that the material-releasing contact piece limits the service life of the switching device by switching through to the carrier material before the prescribed number of switching operations has been reached. The causes of this material shift are not yet known, but seem to be related to the addition of tungsten or oxygen-containing tungsten compounds, since they have not previously occurred with tungsten-free AgSn0 2 materials. For these reasons, the behavior with regard to material displacement must first be checked before using the tungsten-containing AgSn0 2 materials. Alternatively, when the material shift occurs, the material according to the invention can be used as a substitute for AgCdO without tungsten addition, which, with a volume reduction of approximately 20%, still has a favorable combustion behavior compared to AgCdO.

Insgesamt weisen die erfindungsgemäßen Werkstoffe mit Wolframzusatz gegenüber AgSn0211,5 W030,5 eine höhere Lebensdauer bei niedrigerer Übertemperatur auf, während sich die erfindungsgemäßen Werkstoffe ohne Wolfram durch fehlende Materialverlagerung, sehr günstige Übertemperatur und gegenüber AgCdO höhere Lebensdauer auszeichnen, die jedoch nicht ganz die Werte von Agsn0211,5 W030.5 erreicht.Overall, the materials according to the invention with added tungsten compared to AgSn0 2 11.5 W0 3 0.5 have a longer service life at a lower excess temperature, while the materials according to the invention without tungsten are characterized by a lack of material displacement, very favorable excess temperature and a longer service life compared to AgCdO, which, however, are not completely reached the values of Agsn0 2 11.5 W0 3 0.5.

Es kann also belegt werden, daß die Mittelwerte der bei den erfindungsgemäßen Werkstoffen gemessenen Temperaturen erheblich unterhalb der Meßwerte beim AgSn0211,5 W030.5-Werkstoff liegen. Dieses Ergebnis ist umso überraschender, da nunmehr die bisher als unvermeidbar erachteten Materialwanderungen besser beherrscht werden können. Die Schweißkraft ergab bei allen Werkstoffen Werte in gleicher Größenordnung wie beim früher verwendeten AgCdO-Werkstoff.It can thus be demonstrated that the mean values of the temperatures measured for the materials according to the invention are considerably below the measured values for the AgSn0 2 11.5 W0 3 0.5 material. This result is all the more surprising since it is now possible to better manage material migration that was previously considered inevitable. The welding power for all materials resulted in values of the same order of magnitude as for the AgCdO material previously used.

In weiteren Beispielen kann die prozentuale Zusammensetzung des Werkstoffes mit der speziellen Oxidkombination Sn02, Ta205, CuO und Bi203 sowie gegebenenfalls W weiter variiert werden. Insbesondere können die prozentualen Verteilungen neben Silber bei 8 bis 14 Masse% Sn02, 0.2 bis 1,5 Masse% Ta205, 0,2 bis 1,5 Masse% CuO. 0,1 bis 1,2 Masse% Bi203 und gegebenenfalls 0.05 bis 1 Masse% Wolfram liegen. Zu letzterem hat sich gezeigt, daß das Wolfram entweder als Reinwolfram oder als Wolframoxid (W03) bzw. andere sauerstoffhaltige Wolframverbindungen zugesetzt werden kann, ohne daß die Eigenschaften des Kontaktwerkstoffes beeinträchtigt werden.In further examples, the percentage composition of the material can be further varied with the special oxide combination Sn0 2 , Ta 2 0 5 , CuO and Bi 2 0 3 and optionally W. In particular, the percentage distributions in addition to silver at 8 to 14 mass% Sn0 2 , 0.2 to 1.5 mass% Ta 2 0 5 , 0.2 to 1.5 mass% CuO. 0.1 to 1.2 mass% of Bi 2 0 3 and optionally 0.05 to 1 mass% of tungsten. For the latter, it has been shown that the tungsten can be added either as pure tungsten or as tungsten oxide (WO 3 ) or other oxygen-containing tungsten compounds without the properties of the contact material being impaired.

Das überraschende Auftreten einer Verringerung der Übertemperatur am Kontaktstück bei Verwendung von Tantaloxid hat sich auch gezeigt bei Werkstoffen, die neben Silber 5 bis 20 Masse% Sn02, 0,1 bis 5 Masse% Ta205, 0,1 bis 5 Masse% CuO, 0,1 bis 5 Masse% Bi203 und gegebenenfalls 0,05 bis 3 Masse% W enthält.The surprising occurrence of a reduction in the excess temperature at the contact piece when using tantalum oxide has also been shown in materials which, in addition to silver, contain 5 to 20% by mass Sn0 2 , 0.1 to 5% by mass Ta 2 0 5 , 0.1 to 5% by mass CuO, 0.1 to 5 mass% Bi 2 0 3 and optionally 0.05 to 3 mass% W contains.

Bei den erfindungsgemäßen Werkstoffen ist vorteilhaft, daß die Materialkosten der einzelnen Zusatzkomponenten gegenüber dem bisher als besonders günstig herausgestellten Ge02 nur etwa 40 % betragen. Damit läßt sich das Ziel der Erfindung, einen preisgünstigen Kontaktwerkstoff.mit günstigem Temperaturverhalten zu schaffen, erreichen. Insgesamt lassen sich nunmehr geeignete Kontaktstücke für Schaltgeräte erzeugen.In the materials according to the invention it is advantageous that the material costs of the individual additional components are only about 40% compared to Ge0 2, which has so far been found to be particularly favorable. This enables the object of the invention to create an inexpensive contact material with favorable temperature behavior. Overall, suitable contact pieces for switching devices can now be produced.

(Siehe Tabelle Seite 5 f.)(See table on page 5 f.)

Figure imgb0001
Figure imgb0001

Claims (12)

1. Contact material, in particular but not exclusively for contact elements in low-voltage switchgear, which consists of silver, tin oxide and further additives, characterised in that in addition to silver, it contains 5 to 20 % Sn02, 0.1 to 5 weight percent Ta205, 0.1 to 5 weight percent CuO, and 0.1 to 5 weight percent Bi203.
2. A contact material as claimed in Claim 1, characterised in that tungsten or oxygen-containing tungsten compounds are additionally provided, the tungsten component being from 0.05 to 3 weight percent.
3. A contact material as claimed in Claim 1, characterised in that in addition to silver, it contains 7 to 14 weight percent Sn02' 0.2 to 1.5 weight percent Ta205, 0.2 to 1.5 weight percent CuO. and 0.1 to 1.2 weight percent Bi203.
4. A contact material as claimed in Claim 2 and 3, characterised in that the tungsten component contains 0.05 to 1 weight percent.
5. A contact material as claimed in Claim 3, characterised in that it contains 7.5 weight percent Sn02, 0.5 weight percent Ta20s, 0.3 weight percent CuO, 0.3 weight percent Bi203, the remainder being silver.
6. A contact material as claimed in Claim 3, characterised in that it contains 10.5 weight percent Sn02, 0.8 weight percent Ta205, 0.5 percent CuO, 0.5 weight percent Bi203, the remainder being silver.
7. A contact material as claimed in Claim 2 and 3, characterised in that it contains 7.0 percent Sno2, 0.5 percent Ta205, 0.5 percent CuO, 0.3 percent Bi203, 0.2 percent W, the remainder being silver.
8. A contact material as claimed in Claim 3, characterised in that it contains 10.5 weight percent Sn02, 0.8 weight percent Ta205, 0.5 weight percent CuO, 0.4 weight percent Bi203, 0.3 weight percent W, the remainder being silver.
9. A contact material as claimed in Claim 2, characterised in that the oxygen-containing tungsten compound is an oxide (W03).
10. A process for the production of contact elements from a contact material as claimed in Claim 1 or one of Claims 2 to 9. characterised in that when the individual components have been mixed to form a powder mixture, the material is produced by compression, sintering and re-compression ; and that a strip having an orientated structure is then produced by extrusion as a semi-finished product, and contact elements are separated from the strip in such manner that the orientated structure extends parallel to the longitudinal edges of the contact element.
11. A process as claimed in Claim 10, characterised in that the tungsten is added to the powder mixture in the form of tungsten powder.
12. A process as claimed in Claim 10, characterised in that the tungsten is added to the powder mixture in the form of tungsten oxide powder (WO3). ,
EP84115754A 1984-01-30 1984-12-18 Contact material and production of electric contacts Expired EP0152606B1 (en)

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