EP0080641A1 - Method of producing preforms of cadmium-free silver-metal oxide compound materials for electric contacts - Google Patents

Method of producing preforms of cadmium-free silver-metal oxide compound materials for electric contacts Download PDF

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EP0080641A1
EP0080641A1 EP82110530A EP82110530A EP0080641A1 EP 0080641 A1 EP0080641 A1 EP 0080641A1 EP 82110530 A EP82110530 A EP 82110530A EP 82110530 A EP82110530 A EP 82110530A EP 0080641 A1 EP0080641 A1 EP 0080641A1
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Prior art keywords
powder
temperature range
metal oxide
sintering
cadmium
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EP82110530A
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German (de)
French (fr)
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EP0080641B1 (en
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Horst Dr.Prof. Schreiner
Bernhard Rothkegel
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Siemens AG
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Siemens AG
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    • 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

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  • the invention relates to a method for producing molded parts from cadmium-free silver-metal oxide composite materials with at least two metal oxide components for electrical contact pieces with a solderable or weldable second layer, in which pressure-atomized and then internally oxidized silver alloy powder (AgMe 1 Me 2 ) with Me 1 from zinc (Zn), tin (Sn) in an amount of 12 to 25 vol% oxide and Me 2 from at least one of the metals bismuth (Bi), lead (Pb), copper (Cu), indium ( In) in an amount of 0.1 to 2% by volume of oxide is pressed to give shaped articles and these are compressed by sintering in air or a neutral atmosphere and by subsequent pressing.
  • pressure-atomized and then internally oxidized silver alloy powder AgMe 1 Me 2
  • Me 1 from zinc
  • Sn tin
  • Me 2 from at least one of the metals bismuth (Bi), lead (Pb), copper (Cu)
  • indium ( In) in an amount of 0.1 to
  • the invention specifies a method with which it is possible to produce cadmium oxide-free AgSn0 2 or AgZnO contact materials as molded parts with a solderable or weldable second layer.
  • this object is achieved in that the pressure-atomized silver alloy powder is first ground dry or wet with simultaneous shaping in a mill, and then the internal oxidation is carried out in two stages in a first temperature range between 673 K and 773 K during 2 to 6 hours and in a second temperature range between 873 K and 1073 K for 0.5 to 2 hours and that sintering in a temperature range between 973 K and 1173 K.
  • the internally oxidized composite powder is subjected to grinding before sintering.
  • the degree of reshaping depends on the mill used, the grinding time and, in the case of wet grinding, also somewhat on the grinding liquid. Isopropanol has proven particularly suitable for wet grinding. The degree of deformation can be described microscopically by the change in the particle shape.
  • the AgMe alloy powders used usually show a rounded shape after production before grinding.
  • FIG. 1 and 2 show the cross section of a powder particle 11 before and 21 after grinding.
  • the average diameter 12 of the roundish particle 11 before grinding is reduced to approximately half the diameter 22 corresponding to the thickness of the platelet-shaped particle 21 formed after grinding.
  • the main criterion for grinding is forming, i.e. the change in particle shape during comminution.
  • the reduction in the average particle diameter is of minor importance.
  • the fill and tap densities also change during the milling treatment.
  • the desired reshaping of the powder particles was achieved with a ball mill in dry grinding and with an agitator ball mill in wet grinding.
  • a melt of the composition 91.8% by mass of Ag, 6% by mass of Zn and 2.2% by mass of Bi was produced from the metals silver, zinc and bismuth.
  • the homogenized alloy was ground in metal powder by pressure atomization with water.
  • the AgZnBi alloy powder of particle size ⁇ 0.2 mm was under Propanol was ground in a stirred ball mill with steel balls for 15 minutes.
  • the powder properties change as follows: bulk density from 3.33 g / cm 3 to 2.78 g / cm 3 and the tap density from 4.17 g / cm 3 to 3.85 g / cm 3 ; the flow time in the 60 ° funnel with a 4 mm nozzle diameter changes from 20 s / 100 g to 27 s / 100 g.
  • the particle shape has changed as a result of shaping in the manner shown schematically in FIGS. 1 and 2.
  • the powder is dried.
  • the internal oxidation was carried out by heating in air. First at 673 K for 2 hours and then at 873 K for 1 hour.
  • the completeness of the internal oxidation of the alloy powder to the AgZnOBi 2 O 3 composite powder was determined by increasing the weight and the oxide particles separated out in the powder particles were assessed in cross section. Complete internal oxidation was achieved, the precipitations of the oxide particles being in part in the particle size range ⁇ 0.5 ⁇ m and in part in particle sizes 0.5-2 ⁇ m.
  • the internally oxidized composite powder is mixed with 0.2% stearic acid ester as a pressure-relieving additive.
  • the ready-to-press powder was pressed on an automatic press to give two-layer molded contact pieces with a contact layer of 2.4 mm and a silver layer of about 0.3 mm thickness with a pressure of 600 MPa.
  • the size of the molded contact pieces was 15 x 16 x 2.5 mm3.
  • the compacts were sintered at 1023 K for 1 hour in air.
  • the contact pieces were compacted by cold pressing at 800 MPa. During a second sintering at 1123 K in air for 1 hour, the strength was further increased and the final shape of the contact pieces was obtained by a further cold pressing, the porosity being ⁇ 2%.
  • the bending strength of the contact pieces was? 1400 N.
  • the structure of this contact material shows a clear orientation in cross-section, which is not present in the same production of the contact piece from unground powder. By increasing the sintering temperature and time, the degree of alignment can be reduced.
  • the bending strength of a contact piece e.g. the size 15 x 16 x 2.5 mm 3
  • this is placed on round bars of 4 mm diameter, which are fixed at a distance of 12 mm, and in the middle with a bending punch with the radius 2 mm loaded to break.
  • the silver layer is on the pressure side.
  • the sintering conditions are chosen so that a minimum breaking strength is achieved.
  • the bending strength can be increased by increasing the sintering temperature and extending the sintering time.
  • the contact properties of the material were measured on a test switch under conditions as specified in "zfWerkstofftechnik / J. Of Materials Technology 7,381 to 389 (1976) on page 382 in the right column of Table 1.
  • the burnup value is around 20 mm3 about 30% cheaper than the contact material of the same composition made from unground powder.
  • Example 1 An AgSnBiCu alloy was processed into alloy powder in the same manner as described in Example 1. After wet grinding as in Example 1, the internal oxidation was carried out at 673 K for 6 hours and then at 873 K for 2 hours in air, a composite powder of the composition AgSnO 2 8.76 Bi 2 0 3 3.57 Cu0 0.98 was obtained. The production data as given in Example 1 could also be used here.

Abstract

Gemäß der Erfingung wird zunächst ein druckverdüstes cadmiumfreies Silber-Legierungspulver AgMe1Me2 mit Me1...Zn,Sn; Me2... Bi,Pb,Cu,In unter gleichzeitigem Umformen in einer Mühle trocken oder naß gemalen. Anschließend wird eine innere Oxidation des Pulvers in zwei Stufen durchgeführt, und zwar in einem ersten Temperaturbereich zwischen 673 K und 773 K während 2 bis 6 Stunden und in einem zweiten Temperaturbereich zwischen 873 K und 1073 K für 0,5 bis 2 Stunden. Anschließend wird das inneroxidierte Pulver zu Formteilen gepreßt und diese durch Sintern in einem Temperaturbereich zwischen 973 K und 1173 K an Luft oder neutraler Atmosphäre und durch Nachpressen verdichtet. Es kann vorteilhaft sein, daß das inneroxodierte Verbundpulver vor dem Sintern einer weiteren Mahlung unterzogen wird.According to the invention, a pressure-atomized cadmium-free silver alloy powder AgMe1Me2 with Me1 ... Zn, Sn; Paint Me2 ... Bi, Pb, Cu, In dry or wet with simultaneous forming in a mill. An internal oxidation of the powder is then carried out in two stages, namely in a first temperature range between 673 K and 773 K for 2 to 6 hours and in a second temperature range between 873 K and 1073 K for 0.5 to 2 hours. The internally oxidized powder is then pressed into molded parts and these are compressed by sintering in a temperature range between 973 K and 1173 K in air or a neutral atmosphere and by re-pressing. It may be advantageous for the internally-oxidized composite powder to be subjected to a further grinding before sintering.

Description

Die Erfindung bezieht sich auf ein Verfahren zum Herstellen von Formteilen aus cadmiumfreien Silber-Metalloxid-Verbundwerkstoffen mit mindestens zwei Metalloxid-Anteilen für elektrische Kontaktstücke mit einer Löt-oder schweißfähigen zweiten Schicht, bei dem druckverdüstes und anschließend inneroxidiertes Silber-Legierungspulver (AgMe1Me2) mit Me1 aus Zink (Zn), Zinn (Sn) in einer Menge von 12 bis 25 Vol-% Oxid und Me2 aus mindestens einem der Metalle Wismut (Bi), Blei (Pb), Kupfer (Cu), Indium (In) in einer Menge von 0,1 bis 2 Vol-% Oxid zu Formteilen gepreßt und diese durch Sintern an Luft oder neutraler Atmosphäre und durch Nachpressen verdichtet werden.The invention relates to a method for producing molded parts from cadmium-free silver-metal oxide composite materials with at least two metal oxide components for electrical contact pieces with a solderable or weldable second layer, in which pressure-atomized and then internally oxidized silver alloy powder (AgMe 1 Me 2 ) with Me 1 from zinc (Zn), tin (Sn) in an amount of 12 to 25 vol% oxide and Me 2 from at least one of the metals bismuth (Bi), lead (Pb), copper (Cu), indium ( In) in an amount of 0.1 to 2% by volume of oxide is pressed to give shaped articles and these are compressed by sintering in air or a neutral atmosphere and by subsequent pressing.

Cadmiumoxidfreie Silbermetalloxid-Kontaktwerkstoffe können bisher noch nicht alle Eigenschaftsforderungen, die an größere Schaltschütze gestellt werden, erfüllen. Kontaktwerkstoffe, z.B. aus AgSn02 in stranggepreßter Ausführung weisen z.B. parallel zur Strangpreßrichtung eine zu hohe Erwärmung und störende Materialwanderung auf. Während die zu hohe Erwärmung durch einen Wolframoxid (W03)-Zusatz gemindert werden kann, tritt die störende Materialwanderung bei großen Schaltschützen noch immer auf. Lediglich ein AgSn02-Kontaktwerkstoff, senkrecht zurStrangpreßrichtung eingesetzt, zeigte keine Materialwanderung; jedoch ist bei dieser Qualität die sichere Verbindungstechnik mit dem Träger noch nicht gelöst.Up to now, cadmium oxide-free silver metal oxide contact materials have not been able to meet all the property requirements placed on larger contactors. Contact materials, for example made of AgSn0 2 in an extruded version, have, for example parallel to the extrusion direction, excessive heating and disruptive material migration. While the excessive heating can be reduced by adding tungsten oxide (W0 3 ), the disruptive material migration still occurs with large contactors. Only one AgSn0 2 contact material, used perpendicular to the extrusion direction, showed no material migration; however, with this quality, the secure connection technology with the carrier has not yet been resolved.

Es ist Aufgabe der vorliegenden Erfindung - um eine geringere Umweltbelastung bei der Anwendung von Silber- metalloxid-Kontaktwerkstoffen zu erzielen - cadmiumoxidfreie Silbermetalloxid-Kontaktwerkstoffe mit etwa gleichem Eigenschaftsspektrum, wie Cadmiumoxid enthaltende Silbermetalloxid-Werkstoffe, herzustellen. Demnach gibt die Erfindung ein Verfahren an, mit dem es möglich ist, cadmiumoxidfreie AgSn02- oder AgZnO-Kontaktwerkstoffe als Formteile mit einer löt- oder schweißfähigen zweiten Schicht herzustellen.It is an object of the present invention - in order to achieve a lower environmental impact when using silver metal oxide contact materials - to produce cadmium oxide-free silver metal oxide contact materials with approximately the same property spectrum as silver metal oxide materials containing cadmium oxide. Accordingly, the invention specifies a method with which it is possible to produce cadmium oxide-free AgSn0 2 or AgZnO contact materials as molded parts with a solderable or weldable second layer.

Gemäß der Erfindung wird diese Aufgabe dadurch gelöst, daß zunächst das druckverdüste Silber-Legierungspulver unter gleichzeitigem Umformen in einer Mühle trocken oder naß gemahlen wird, daß anschließend die innere Oxidation in zwei Stufen durchgeführt wird in einem ersten Temperaturbereich zwischen 673 K und 773 K während 2 bis 6 Stunden und in einem zweiten Temperaturbereich zwischen 873 K und 1073 K während 0,5 bis 2 Stunden und daß in einem Temperaturbereich zwischen 973 K und 1173 K gesintert wird.According to the invention, this object is achieved in that the pressure-atomized silver alloy powder is first ground dry or wet with simultaneous shaping in a mill, and then the internal oxidation is carried out in two stages in a first temperature range between 673 K and 773 K during 2 to 6 hours and in a second temperature range between 873 K and 1073 K for 0.5 to 2 hours and that sintering in a temperature range between 973 K and 1173 K.

Es kann z.B. vorteilhaft sein, daß das inneroxidierte Verbundpulver vor dem Sintern einer Mahlung unterzogen wird.For example, be advantageous that the internally oxidized composite powder is subjected to grinding before sintering.

Anhand von Ausführungsbeispielen und der Zeichnung wird die Erfindung noch näher beschrieben. Es zeigen

  • FIG 1 in schematischer Darstellung im Querschnitt ein Pulverteilchen vor dem Mahlen.
  • FIG 2 in schematischer Darstellung im Querschnitt ein Pulverteilchen nach dem Mahlen.
The invention is described in more detail with reference to exemplary embodiments and the drawing. Show it
  • 1 shows a schematic representation in cross section of a powder particle before grinding.
  • 2 shows a schematic representation in cross section of a powder particle after grinding.

Beim Mahlen des AgMe-Legierungspulvers wird als wesentliches Kriterium eine gleichzeitige Umformung erzielt. Der Grad der Umformung hängt von der verwendeten Mühle, von der Mahldauer und bei Naßmahlung auch etwas von der Mahlflüssigkeit ab. Beim Naßmahlen hat sich Isopropanol als besonders geeignet erwiesen. Der Grad der Umformung kann an der Veränderung der Teilchenform mikroskopisch beschrieben werden. Die verwendeten AgMe-Legierungspulver zeigen nach der Herstellung vor dem Mahlen meist rundliche Form.When grinding the AgMe alloy powder, simultaneous forming is an important criterion. The degree of reshaping depends on the mill used, the grinding time and, in the case of wet grinding, also somewhat on the grinding liquid. Isopropanol has proven particularly suitable for wet grinding. The degree of deformation can be described microscopically by the change in the particle shape. The AgMe alloy powders used usually show a rounded shape after production before grinding.

In FIG 1 und FIG 2 ist der Querschnitt eines Pulverteilchens 11 vor und 21 nach dem Mahlen gezeigt. Der mittlere Durchmesser 12 des rundlichen Teilchens 11 vor dem Mahlen ist etwa auf den halben Durchmesser 22 entsprechend der Dicke des entstandenen plättchenförmigen Teilchens 21 nach dem Mahlen reduziert. Das Hauptkriterium bei der Mahlung ist die Umformung, d.h. die Veränderung der Teilchenform, während der Zerkleinerung. Die Verminderung des mittleren Teilchendurchmessers ist dagegen von untergeordneter Bedeutung. Bei der Mahlbehandlung ändern sich auch die Füll- und Klopfdichten. Die gewünschte Umformung der Pulverteilchen wurde bei Trockenmahlung mit einer Kugelmühle und bei Naßmahlung mit einer Rührwerkskugelmühle erzielt.1 and 2 show the cross section of a powder particle 11 before and 21 after grinding. The average diameter 12 of the roundish particle 11 before grinding is reduced to approximately half the diameter 22 corresponding to the thickness of the platelet-shaped particle 21 formed after grinding. The main criterion for grinding is forming, i.e. the change in particle shape during comminution. The reduction in the average particle diameter, however, is of minor importance. The fill and tap densities also change during the milling treatment. The desired reshaping of the powder particles was achieved with a ball mill in dry grinding and with an agitator ball mill in wet grinding.

Beispiel 1example 1

Aus den Metallen Silber, Zink und Wismut wurde eine Schmelze der Zusammensetzung 91,8 Massenprozent Ag, 6 Massenprozent Zn und 2,2 Massenprozent Bi hergestellt. Die homogenisierte Legierung wurde durch Druckverdüsung mit Wasser in Metallpulver zerkleinert. Das AgZnBi-Legierungspulver der Teilchengröße < 0,2 mm wurde unter Propanol in einer Rührwerkskugelmühle mit Stahlkugeln 15 Minuten lang gemahlen. Dabei ändern sich die Pulvereigenschaften wie folgt: Fülldichte von 3,33 g/cm3 zu 2,78 g/cm3 und die Klopfdichte von 4,17 g/cm3 zu 3,85 g/cm3; die Fließzeit im 60° Trichter bei 4 mm Düsendurchmesser ändert sich von 20 s/100 g zu 27 s/100 g. Bei der Mahlung hat sich die Teilchenform durch Umformung in der in den Figuren 1 und 2 schematisch dargestellten Weise geändert. Nach der Mahlung wird das Pulver getrocknet. Die innere Oxidation erfolgte durch Erwärmen an Luft. Zunächst bei 673 K für 2 Stunden und daran anschließend bei 873 K für 1 Stunde. Die Vollständigkeit der inneren Oxidation des Legierungspulvers zum AgZnOBi2O3-Verbundpulver wurde durch Gewichtszunahme festgestellt und die in den Pulverteilchen ausgeschiedenen Oxidteilchen im Querschliff beurteilt. Es wurde eine vollständige innere Oxidation erzielt, wobei die Ausscheidungen der Oxidteilchen zum Teil im Teilchengrößenbereich < 0,5 µm und zum Teil in Teilchengrößen 0,5-2 µm liegt. Das inneroxidierte Verbundpulver wird 'mit 0,2 %igem Stearinsäure-Ester als preßerleichternder Zusatz vermischt. Das preßfertige Pulver wurd auf einem Preßautomaten zu Zweischichten-Formteilkontaktstücken einer Kontaktschicht von 2,4 mm und einer Silberschicht von etwa 0,3 mm Dicke mit einem Druck von 600 MPa verpreßt. Die Größe der Formteilkontaktstücke betrug 15 x 16 x 2,5 mm3. Die Sinterung der Preßkörper erfolgte bei 1023 K während 1 Stunde an Luft. Durch Kaltnachpressen mit 800 MPa wurden die Kontaktstücke verdichtet. Während einer zweiten Sinterung bei 1123 K während 1 Stunde an Luft wurde die Festigkeit weiter gesteigert und durch ein weiteres Kaltnachpressen die Endform der Kontaktstücke erhalten, wobei die Porosität < 2 % betrug.A melt of the composition 91.8% by mass of Ag, 6% by mass of Zn and 2.2% by mass of Bi was produced from the metals silver, zinc and bismuth. The homogenized alloy was ground in metal powder by pressure atomization with water. The AgZnBi alloy powder of particle size <0.2 mm was under Propanol was ground in a stirred ball mill with steel balls for 15 minutes. The powder properties change as follows: bulk density from 3.33 g / cm 3 to 2.78 g / cm 3 and the tap density from 4.17 g / cm 3 to 3.85 g / cm 3 ; the flow time in the 60 ° funnel with a 4 mm nozzle diameter changes from 20 s / 100 g to 27 s / 100 g. During grinding, the particle shape has changed as a result of shaping in the manner shown schematically in FIGS. 1 and 2. After grinding, the powder is dried. The internal oxidation was carried out by heating in air. First at 673 K for 2 hours and then at 873 K for 1 hour. The completeness of the internal oxidation of the alloy powder to the AgZnOBi 2 O 3 composite powder was determined by increasing the weight and the oxide particles separated out in the powder particles were assessed in cross section. Complete internal oxidation was achieved, the precipitations of the oxide particles being in part in the particle size range <0.5 μm and in part in particle sizes 0.5-2 μm. The internally oxidized composite powder is mixed with 0.2% stearic acid ester as a pressure-relieving additive. The ready-to-press powder was pressed on an automatic press to give two-layer molded contact pieces with a contact layer of 2.4 mm and a silver layer of about 0.3 mm thickness with a pressure of 600 MPa. The size of the molded contact pieces was 15 x 16 x 2.5 mm3. The compacts were sintered at 1023 K for 1 hour in air. The contact pieces were compacted by cold pressing at 800 MPa. During a second sintering at 1123 K in air for 1 hour, the strength was further increased and the final shape of the contact pieces was obtained by a further cold pressing, the porosity being <2%.

Die Biegebruchkraft der Kontaktstücke betrug ? 1400 N. Das Gefüge dieses Kontaktwerkstoffes zeigt im Querschliff eine deutliche Ausrichtung, die bei der gleichen Herstellung des Kontaktstückes aus ungemahlenem Pulver nicht vorhanden ist. Durch Erhöhen der Sintertemperatur und der Sinterzeit kann der Grad der Ausrichtung verringert werden.The bending strength of the contact pieces was? 1400 N. The structure of this contact material shows a clear orientation in cross-section, which is not present in the same production of the contact piece from unground powder. By increasing the sintering temperature and time, the degree of alignment can be reduced.

Bei der Bestimmung der Biegebruchkraft eines Kontaktstückes, z.B. der Größe 15 x 16 x 2,5 mm3, wird dieses auf Rundstäbe von 4 mm Durchmesser, die im Abstand von 12 mm festgelegt sind, aufgelegt und in der Mitte mit einem Biegestempel mit dem Radius 2 mm bis zum Bruch belastet. Bei einem Zweischichtkontaktstück mit einer Silberschicht ist die Silberschicht auf der Druckseite. Die Sinterbedingungen werden so gewählt, daß eine Mindestbruchkraft erreicht wird. Durch Erhöhung der Sintertemperatur und Verlängerung der Sinterzeit kann die Biegebruchkraft erhöht werden.When determining the bending strength of a contact piece, e.g. the size 15 x 16 x 2.5 mm 3 , this is placed on round bars of 4 mm diameter, which are fixed at a distance of 12 mm, and in the middle with a bending punch with the radius 2 mm loaded to break. In the case of a two-layer contact piece with a silver layer, the silver layer is on the pressure side. The sintering conditions are chosen so that a minimum breaking strength is achieved. The bending strength can be increased by increasing the sintering temperature and extending the sintering time.

Die Kontakteigenschaften des Werkstoffes wurden auf einem Prüfschalter bei Bedingungen gemessen, wie sie in "z.f.Werkstofftechnik/J. of Materials Technology 7,381 bis 389 (1976) auf Seite 382 in der rechten Spalte der Tabelle 1 angegeben sind. Der Abbrandwert liegt mit 20 mm3 um etwa 30 % günstiger als bei dem Kontaktwerkstoff gleicher Zusammensetzung aus ungemahlenem Pulver.The contact properties of the material were measured on a test switch under conditions as specified in "zfWerkstofftechnik / J. Of Materials Technology 7,381 to 389 (1976) on page 382 in the right column of Table 1. The burnup value is around 20 mm3 about 30% cheaper than the contact material of the same composition made from unground powder.

Dadurch ergibt sich eine Silbereinsparung von etwa 1/3. Die Kontaktwiderstandswerte lagen mit dem RK1-Wert nach dem prellenden Einschalten als 99,8 %-Wert der Verteilungskurve bei 0,2 mΩ, was einer zulässigen Erwärmung im Schaltgerät entspricht.This results in a silver saving of about 1/3. The contact resistance values with the R K1 value after the bouncing switch-on as a 99.8% value of the distribution curve were 0.2 mΩ, which corresponds to a permissible temperature rise in the switchgear.

Beispiel 2Example 2

Eine AgSnBiCu-Legierung wurde in der gleichen Weise zu Legierungspulver verarbeitet, wie bereits im Beispiel 1 beschrieben wurde. Nach der Naßmahlung wie in Beispiel 1 erfolgte die innere Oxidation bei 673 K 6 Stunden lang und daran anschließend bei 873 K 2 Stunden lang an Luft, wobei ein Verbundpulver der Zusammensetzung AgSnO2 8,76 Bi203 3,57 Cu0 0,98 erhalten wurde. Die Herstellungsdaten, wie sie im Beispiel 1 angegeben sind, konnten auch hier angewendet werden.An AgSnBiCu alloy was processed into alloy powder in the same manner as described in Example 1. After wet grinding as in Example 1, the internal oxidation was carried out at 673 K for 6 hours and then at 873 K for 2 hours in air, a composite powder of the composition AgSnO 2 8.76 Bi 2 0 3 3.57 Cu0 0.98 was obtained. The production data as given in Example 1 could also be used here.

Claims (2)

1. Verfahren zum Herstellen von Formteilen aus cadmiumfreien Silber-Metalloxid-Verbundwerkstoffen mit mindestens zwei Metalloxid-Anteilen für elektriche Kontaktstücke mit einer löt- oder schweißfähigen zweiten Schicht, bei dem druckverdüstes und anschließend inneroxidiertes Silber-Legierungspulver (AgMe1Me2) mit Me1 aus Zink (Zn), Zinn (Sn) in einer Menge von 12 bis 25 Vol-% Oxid und Me2 aus mindestens einem der Metalle Wismut (Bi), Blei (Pb), Kupfer (Cu), Indium (In) in einer Menge von 0,1 bis 2 Vol-% Oxid zu Formteilen gepreßt und diese durch Sintern an Luft oder neutraler Atmosphäre und durch Nachpressen verdichtet werden, dadurch gekennzeichnet, daß zunächst das druckverdüste Silber-Legierungspulver unter gleichzeitigem Umformen in einer Mühle trocken oder naß gemahlen wird, daß anschließend die innere Oxidation in zwei Stufen durchgeführt wird in einem ersten Temperaturbereich zwischen 673 K und 773 K während 2 bis 6 Stunden und in einem zweiten Temperaturbereich zwischen 873 K und 1073 K während 0,5 bis 2 Stunden und daß in einem Temperaturbereich zwischen 973 K und 1173 K gesintert wird.1.Method for producing molded parts from cadmium-free silver-metal oxide composite materials with at least two metal oxide components for electrical contact pieces with a solderable or weldable second layer, in which pressure-atomized and then internally oxidized silver alloy powder (AgMe 1 Me 2 ) with Me 1 from zinc (Zn), tin (Sn) in an amount of 12 to 25 vol% oxide and Me 2 from at least one of the metals bismuth (Bi), lead (Pb), copper (Cu), indium (In) in one Quantity of 0.1 to 2% by volume of oxide is pressed into shaped parts and these are compressed by sintering in air or a neutral atmosphere and by repressing, characterized in that the pressure-atomized silver alloy powder is first milled dry or wet in a mill with simultaneous shaping that the internal oxidation is then carried out in two stages in a first temperature range between 673 K and 773 K for 2 to 6 hours and in a second temperature range between 87 3 K and 1073 K for 0.5 to 2 hours and that sintering in a temperature range between 973 K and 1173 K. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet , daß das inneroxidierte Verbundpulver vor dem Sintern einer Mahlung unterzogen wird.2. The method according to claim 1, characterized in that the internally oxidized composite powder is subjected to grinding before sintering.
EP82110530A 1981-11-26 1982-11-15 Method of producing preforms of cadmium-free silver-metal oxide compound materials for electric contacts Expired EP0080641B1 (en)

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DE3146972 1981-11-26
DE19813146972 DE3146972A1 (en) 1981-11-26 1981-11-26 METHOD FOR PRODUCING MOLDED PARTS FROM CADMIUM-FREE SILVER METAL OXIDE COMPOSITIONS FOR ELECTRICAL CONTACTS

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EP0080641A1 true EP0080641A1 (en) 1983-06-08
EP0080641B1 EP0080641B1 (en) 1985-08-28

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JP (1) JPS5896801A (en)
BR (1) BR8206819A (en)
DE (2) DE3146972A1 (en)

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DE3265890D1 (en) 1985-10-03
US4609525A (en) 1986-09-02
EP0080641B1 (en) 1985-08-28
DE3146972A1 (en) 1983-06-01
BR8206819A (en) 1983-10-04
JPS646259B2 (en) 1989-02-02
JPS5896801A (en) 1983-06-09

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