EP0586410B1 - Silver-based contact material for use in power-engineering switchgear, and a method of manufacturing contacts made of this material - Google Patents
Silver-based contact material for use in power-engineering switchgear, and a method of manufacturing contacts made of this material Download PDFInfo
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- EP0586410B1 EP0586410B1 EP92909652A EP92909652A EP0586410B1 EP 0586410 B1 EP0586410 B1 EP 0586410B1 EP 92909652 A EP92909652 A EP 92909652A EP 92909652 A EP92909652 A EP 92909652A EP 0586410 B1 EP0586410 B1 EP 0586410B1
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- oxide
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- iron oxide
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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
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- 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
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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
- H01H2001/02378—Composite material having a noble metal as the basic material and containing oxides containing iron-oxide as major component
Definitions
- the invention relates to a silver-based contact material for use in switching devices in power engineering, in particular for contact pieces in low-voltage switches, wherein in addition to silver as active components, at least iron oxide as the main component and at least one further metal oxide as the secondary component are present.
- contact materials are known on the one hand of the silver-metal system (AgMe) and on the other hand of the silver-metal oxide (AgMeO) system.
- Representatives of the first system are, for example, silver-nickel (AgNi) or silver-iron (AgFe);
- Representatives of the second system are in particular silver-cadmium oxide (AgCdO) or silver-tin oxide (AgSnO2).
- there may be other metal oxides such as, in particular, bismuth oxide (Bi 2 O 3 ), copper oxide (CuO) and / or tantalum oxide (Ta 2 O 5 ).
- the practical usability of a contact material based on silver-metal or silver-metal oxide is determined by the so-called electrical contact property spectrum. Relevant parameters are the lifetime switching number on the one hand, which is determined by the erosion of the contact, and the so-called overtemperature, ie the contact heating at the contact bridge, which essentially results from the electrical resistance of the contact structure mentioned, on the other hand. A sufficiently low tendency to weld the contact pieces and corrosion resistance are also important, since long-term corrosion of the material in air switchgear can change the switching properties over time.
- an electrical contact material of the silver-metal oxide system is already known, which in addition to cadmium or tin oxide can also contain iron oxide.
- DE-C-38 16 895 describes the use of a silver-iron material with 3 to 30% by weight of iron and one or more of the additives manganese, copper, zinc, antimony, bismuth oxide, molybdenum oxide, tungsten oxide, chromium nitride Quantities totaling 0.05 to 5% by weight, balance silver, proposed for electrical contacts.
- DE-A-39 11 904 discloses a powder metallurgical process for producing a semi-finished product for electrical contacts from a silver-based composite material with iron, in which 5 to 50% by weight of iron is the first secondary component and 0 to 5% by weight. % of a second secondary component from one or more substances from the group which contains the metals titanium, zirconium, niobium, tantalum, molybdenum, manganese, copper and zinc as well as their oxides and their carbides.
- the iron in elemental form is obtained in particular by chemical precipitation.
- JP-A-1/055345 discloses a material of the type mentioned at the outset, which consists of a silver matrix distributed in 0.5 to 20 percent by weight of iron oxide particles, in which part of the iron oxide is formed by at least one of the oxides of nickel, cobalt, Chromium, molybdenum, tungsten, cadmium, zinc, antimony, tin, bismuth, indium, lead, manganese, beryllium, calcium, magnesium or copper is replaced.
- the contact pieces produced from this are said to be distinguished by good mechanical properties and high arc resistance for use in switches.
- the object is achieved according to the invention by the combination of iron oxide and rhenium oxide as the active component, the iron oxide as the main component being present in mass fractions between 1 and 50% and the secondary components in mass fractions between 0.01 and 5%.
- the object is achieved according to the invention by the combination of iron oxide with bismuth zirconate, by the combination of iron oxide with boron oxide or by the combination of iron oxide with zirconium oxide, the iron oxide as the main component likewise in mass fractions between 1 and 50% and the alternative secondary components in mass fractions between 0.01 and 5%.
- the iron oxide can have the constitution Fe 2 O 3 or Fe 3 O 4 , but optionally also a mixed form.
- EP-A-0 369 282 and EP-A-0 369 283 for sintered contact materials of the constitution AgSnO 2 Bi 2 O 3 CuO.
- these materials are not comparable to contact materials based on AgFe 2 O 3 / Fe 3 O 4 .
- iron oxide as the main active component in conjunction with one of the specified metal oxides as the secondary component improves the property spectrum as a contact material.
- the iron oxide is preferably present in mass fractions of less than 40%, in particular less than 30%.
- the rhenium oxide, bismuth zirconate, boron oxide or zirconium oxide can be present either individually or in combination with different weightings.
- a contact material of the type mentioned at the outset, in which the iron oxide is present in mass fractions of 2 to 20%, with an addition of 0.5 to 2 m% rhenium oxide, the remainder being silver, is particularly advantageous.
- the boron oxide is preferably boric acid.
- the table shows measured values for the overtemperature of the stressed materials, which was measured at the contact bridge of the switching device.
- the first column of the measured temperature values contains the maximum overtemperature and the second column of the measured temperature values contains the average bridge temperature, which is the temperature difference from room temperature.
- the table comprises three exemplary embodiments with meaningful compositions of the contact material claimed.
- the production of the actual material and the production of the relevant contact pieces can be carried out done according to different methods.
- the measured value of the materials according to the invention is compared with AgFe 2 O 3 6.4.
- An AgFe9 contact material is also listed in the table. The results are discussed in more detail below.
- a powder mixture is prepared by wet mixing the oxide powders. From the powder mixture, strips or wires of the material are first produced as semi-finished products for the contact pieces using the so-called extrusion technique.
- the process conditions with regard to temperature on the one hand and pressure on the other hand are chosen so that undesired evaporation of rhenium is taken into account.
- the proportions of silver, iron oxide and rhenium oxide can be varied using the same procedure.
- a material with the composition AgFe 2 O 3 5.7 ReO 2 2.2 was also investigated.
- the contact pieces are produced by molding technology.
- the further oxide as a side effect component is not rhenium oxide but, for example, zirconium oxide.
- a material with the composition AgFe 2 O 3 5.4ZrO 2 1.0 was examined in detail.
- molded parts are pressed from the powder mixture into contact pieces at a pressure of approx. 200 MPa.
- a pressure of approx. 200 MPa For secure connection technology of the contact piece to the contact piece carrier by brazing, it is again advantageous in this pressing process to press a second layer of pure silver together with the actual contact layer into a two-layer contact piece.
- the molded parts are then sintered at a temperature of approximately 850 ° C. for about an hour.
- the sintered bodies are then pressed at a pressure of approx. 1000 MPa and sintered again at approx. 800 ° C for about an hour.
- the contact pieces thus produced are again calibrated at a pressure of approx. 1000 MPa.
- the table shows that the first two examples of the material according to the invention each have an average bridge temperature which is above the value of AgFe9 and also AgFe 2 O 3 6.4. In contrast, the corresponding value in the third example is below the comparative examples. It should be noted that AgFe and AgFe 2 O 3 materials show a similar temperature behavior in this context. Overall, all values for the average bridge temperature are in a range of 70 ⁇ 5 K.
- the iron oxide can also be in the constitution Fe 3 O 4 or in a mixed form instead of the chemical constitution Fe 2 O 3 .
- the iron oxide in particular in mass fractions of 2 to 20%, the addition of rhenium oxide between 0.5 and 3 m%, the addition of bismuth zirconate between 0.05 and 3 m%, the addition of boric acid between 0, 05 and 0.5 m% and the addition of zirconium oxide should be between 0.05 and 2 m%.
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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)
- Conductive Materials (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Manufacture Of Switches (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
Abstract
Description
Die Erfindung bezieht sich auf einen Kontaktwerkstoff auf Silberbasis zur Verwendung in Schaltgeräten der Energietechnik, insbesondere für Kontaktstücke in Niederspannungsschaltern, wobei neben Silber als Wirkkomponenten wenigstens Eisenoxid als Hauptkomponente und wenigstens ein weiteres Metalloxid als Nebenkomponente vorhanden sind.The invention relates to a silver-based contact material for use in switching devices in power engineering, in particular for contact pieces in low-voltage switches, wherein in addition to silver as active components, at least iron oxide as the main component and at least one further metal oxide as the secondary component are present.
Für Kontaktstücke in Niederspannungsschaltgeräten der Energietechnik, z.B. in Leistungsschaltern sowie in Gleichstrom-, Motor- und Hilfsschützen, sind Kontaktwerkstoffe einerseits des Systems Silber-Metall (AgMe) und andererseits des Systems Silber-Metalloxid (AgMeO) bekannt. Vertreter des ersten Systems sind beispielsweise Silber-Nickel (AgNi) oder Silber-Eisen (AgFe); Vertreter des zweiten Systems sind inbesondere Silber-Cadmiumoxid (AgCdO) oder Silber-Zinnoxid (AgSnO2). Hinzu können weitere Metalloxide, wie insbesondere Wismutoxid (Bi2O3), Kupferoxid (CuO) und/oder Tantaloxid (Ta2O5), kommen.For contact pieces in low-voltage switching devices in energy technology, for example in circuit breakers and in direct current, motor and auxiliary contactors, contact materials are known on the one hand of the silver-metal system (AgMe) and on the other hand of the silver-metal oxide (AgMeO) system. Representatives of the first system are, for example, silver-nickel (AgNi) or silver-iron (AgFe); Representatives of the second system are in particular silver-cadmium oxide (AgCdO) or silver-tin oxide (AgSnO2). In addition, there may be other metal oxides, such as, in particular, bismuth oxide (Bi 2 O 3 ), copper oxide (CuO) and / or tantalum oxide (Ta 2 O 5 ).
Die praktische Verwendbarkeit eines Kontaktwerkstoffes auf Silber-Metall- bzw. Silber-Metalloxid-Basis wird durch das sogenannte elektrische Kontakteigenschaftsspektrum bestimmt. Maßgebliche Kenngrößen sind dabei die Lebensdauerschaltzahl einerseits, die durch den Abbrand des Schaltstückes bestimmt wird, und die sogenannte Übertemperatur, d.h. die Kontakterwärmung an der Kontaktbrücke, welche sich im wesentlichen aus dem elektrischen Widerstand des genannten Kontaktaufbaus ergibt, andererseits. Weiterhin wichtig sind eine hinreichend geringe Verschweißneigung der Kontaktstücke und eine Korrosionsbeständigkeit, da durch Langzeitkorrosion des Werkstoffes in Luftschaltgeräten sich die Schalteigenschaften mit der Zeit verändern können.The practical usability of a contact material based on silver-metal or silver-metal oxide is determined by the so-called electrical contact property spectrum. Relevant parameters are the lifetime switching number on the one hand, which is determined by the erosion of the contact, and the so-called overtemperature, ie the contact heating at the contact bridge, which essentially results from the electrical resistance of the contact structure mentioned, on the other hand. A sufficiently low tendency to weld the contact pieces and corrosion resistance are also important, since long-term corrosion of the material in air switchgear can change the switching properties over time.
Aus der DE-A-1 608 211 ist bereits ein elektrisches Kontaktmaterial des Systems Silber-Metalloxid bekannt, das neben Cadmium- bzw. Zinnoxid auch Eisenoxid enthalten kann. Weiterhin wird mit der DE-C-38 16 895 die Verwendung eines Silber-Eisen-Werkstoffs mit 3 bis 30 Gew.-% Eisen und einen oder mehreren der Zusätze Mangan, Kupfer, Zink, Antimon, Wismutoxid, Molybdänoxid, Wolframoxid, Chromnitrid in Mengen von insgesamt 0,05 bis 5 Gew.-%, Rest Silber, für elektrische Kontakte vorgeschlagen. Daneben ist aus der DE-A-39 11 904 ein pulvermetallurgisches Verfahren zum Herstellen eines Halbzeugs für elektrische Kontakte aus einem Verbundwerkstoff auf Silberbasis mit Eisen bekannt, bei dem 5 bis 50 Gew.-% Eisen als erstem Nebenbestandteil und 0 bis 5 Gew.-% eines zweiten Nebenbestandteils aus einer oder mehreren Substanzen aus der Gruppe, welche die Metalle Titan, Zirkon, Niob, Tantal, Molybdän, Mangan, Kupfer und Zink sowie ihre Oxide und ihre Karbide enthält, verwendet werden. Das Eisen in elementarer Form wird dabei insbesondere durch chemisches Fällen erhalten. Schließlich ist aus der JP-A-1/055345 ein Werkstoff der eingangs genannten Art bekannt, der aus einer Silbermatrix in 0,5 bis 20 Gewichtsprozent verteilten Eisenoxidpartikeln besteht, bei dem ein Teil des Eisenoxids durch wenigstens eines der Oxide von Nickel, Kobalt, Chrom, Molybdän, Wolfram, Cadmium, Zink, Antimon, Zinn, Wismut, Indium, Blei, Mangan, Beryllium, Calcium, Magnesium oder Kupfer ersetzt ist. Die daraus hergestellten Kontaktstücke sollen sich zur Anwendung bei Schaltern durch gute mechanische Eigenschaften und hohe Lichtbogenbeständigkeit auszeichnen.From DE-A-1 608 211 an electrical contact material of the silver-metal oxide system is already known, which in addition to cadmium or tin oxide can also contain iron oxide. Furthermore, DE-C-38 16 895 describes the use of a silver-iron material with 3 to 30% by weight of iron and one or more of the additives manganese, copper, zinc, antimony, bismuth oxide, molybdenum oxide, tungsten oxide, chromium nitride Quantities totaling 0.05 to 5% by weight, balance silver, proposed for electrical contacts. In addition, DE-A-39 11 904 discloses a powder metallurgical process for producing a semi-finished product for electrical contacts from a silver-based composite material with iron, in which 5 to 50% by weight of iron is the first secondary component and 0 to 5% by weight. % of a second secondary component from one or more substances from the group which contains the metals titanium, zirconium, niobium, tantalum, molybdenum, manganese, copper and zinc as well as their oxides and their carbides. The iron in elemental form is obtained in particular by chemical precipitation. Finally, JP-A-1/055345 discloses a material of the type mentioned at the outset, which consists of a silver matrix distributed in 0.5 to 20 percent by weight of iron oxide particles, in which part of the iron oxide is formed by at least one of the oxides of nickel, cobalt, Chromium, molybdenum, tungsten, cadmium, zinc, antimony, tin, bismuth, indium, lead, manganese, beryllium, calcium, magnesium or copper is replaced. The contact pieces produced from this are said to be distinguished by good mechanical properties and high arc resistance for use in switches.
Bei den Werkstoffen des Standes der Technik werden meist nicht alle Anforderungen des Schalteigenschaftsspektrums gleichzeitig erfüllt. Letztendlich wird angestrebt, für den jeweiligen Anwendungsfall ein daran angepaßtes Optimum der jeweils wichtigsten Kenngrößen zu erreichen.In the case of the materials of the prior art, not all requirements of the switching property spectrum are usually met at the same time. Ultimately, the aim is to achieve an optimum of the most important parameters adapted to the respective application.
Ausgehend von obigen Anforderungen ist es Aufgabe der Erfindung, weitere Kontaktwerkstoffe auf Silber-Eisenoxid-Basis aufzufinden. Diese Werkstoffe sollen sich durch geringe Kontakterwärmung mit stabilem Erwärmungsverhalten, geringer Neigung zum Verschweißen und eine hoher Lebensdauer in bezug auf die Schaltstromstärken auszeichnen. Weiterhin soll eine gute Korrosionsbeständigkeit gegeben sein.Based on the above requirements, it is an object of the invention to provide further contact materials based on silver-iron oxide to find. These materials should be characterized by low contact heating with stable heating behavior, low tendency to weld and a long service life in relation to the switching currents. Good corrosion resistance should also be provided.
Die Aufgabe ist erfindungsgemäß durch die Kombination von Eisenoxid und Rheniumoxid als Wirkkomponente gelöst, wobei das Eisenoxid als Hauptkomponente in Massenanteilen zwischen 1 und 50 % und die Nebenkomponenten in Massenanteilen zwischen 0,01 und 5 % vorliegen. Alternativ wird die Aufgabe erfindungsgemäß durch die Kombination von Eisenoxid mit Wismutzirkonat, durch die Kombination von Eisenoxid mit Boroxid oder aber durch die Kombination von Eisenoxid mit Zirkonoxid gelöst, wobei das Eisenoxid als Hauptkomponente ebenfalls in Massenanteile zwischen 1 und 50 % und die alternativen Nebenkomponenten in Massenanteile zwischen 0,01 und 5 % vorliegen. Das Eisenoxid kann dabei die Konstitution Fe2O3 oder Fe3O4, gegebenenfalls aber auch eine Mischform haben.The object is achieved according to the invention by the combination of iron oxide and rhenium oxide as the active component, the iron oxide as the main component being present in mass fractions between 1 and 50% and the secondary components in mass fractions between 0.01 and 5%. Alternatively, the object is achieved according to the invention by the combination of iron oxide with bismuth zirconate, by the combination of iron oxide with boron oxide or by the combination of iron oxide with zirconium oxide, the iron oxide as the main component likewise in mass fractions between 1 and 50% and the alternative secondary components in mass fractions between 0.01 and 5%. The iron oxide can have the constitution Fe 2 O 3 or Fe 3 O 4 , but optionally also a mixed form.
Die Verwendung von Wismutzirkonat einerseits und Zirkonoxid andererseits ist aus der EP-A-0 369 282 bzw. EP-A-0 369 283 für Sinterkontaktwerkstoffe der Konstitution AgSnO2Bi2O3CuO bekannt. Diese Werkstoffe sind aber nicht vergleichbar mit Kontaktwerkstoffen auf der Basis von AgFe2O3/Fe3O4.The use of bismuth zirconate on the one hand and zirconium oxide on the other hand is known from EP-A-0 369 282 and EP-A-0 369 283 for sintered contact materials of the constitution AgSnO 2 Bi 2 O 3 CuO. However, these materials are not comparable to contact materials based on AgFe 2 O 3 / Fe 3 O 4 .
Im Rahmen vorliegender Erfindung wurde dagegen erkannt, daß speziell Eisenoxid als Hauptwirkkomponente in Verbindung mit einem der angegebenen Metalloxide als Nebenkomponente das Eigenschaftsspektrum als Kontaktwerkstoff verbessert. Vorzugsweise liegt das Eisenoxid in Massenanteilen von weniger als 40 %, insbesondere weniger als 30 %, vor. Von den weiteren genannten Oxiden können das Rheniumoxid, Wismutzirkonat, Boroxid oder auch Zirkonoxid entweder einzeln oder in Kombination mit unterschiedlicher Gewichtung vorliegen.In the context of the present invention, however, it was recognized that especially iron oxide as the main active component in conjunction with one of the specified metal oxides as the secondary component improves the property spectrum as a contact material. The iron oxide is preferably present in mass fractions of less than 40%, in particular less than 30%. Of the other oxides mentioned, the rhenium oxide, bismuth zirconate, boron oxide or zirconium oxide can be present either individually or in combination with different weightings.
Besonders vorteilhaft ist ein Kontaktwerkstoff der eingangs genannten Art, bei dem das Eisenoxid in Massenanteilen von 2 bis 20 % vorliegt, mit einem Zusatz von 0,5 bis 2 m% Rheniumoxid, Rest Silber. Ebenfalls vorteilhaft ist bei einem Kontaktwerkstoff der eingangs genannten Art, bei dem das Eisenoxid in Massenanteilen 2 bis 20 % vorliegt, ein Zusatz von 0,05 bis 3 m% Wismutzirkonat oder ein Zusatz von 0,05 bis 0,5 m% Boroxid oder ein Zusatz von 0,05 bis 2 m% Zirkonoxid mit Silber als jeweiligem Rest. Das Boroxid ist vorzugsweise Borsäure.A contact material of the type mentioned at the outset, in which the iron oxide is present in mass fractions of 2 to 20%, with an addition of 0.5 to 2 m% rhenium oxide, the remainder being silver, is particularly advantageous. In the case of a contact material of the type mentioned at the beginning, in which the iron oxide is present in mass fractions of 2 to 20%, it is also advantageous to add 0.05 to 3 m% bismuth zirconate or to add 0.05 to 0.5 m% boron oxide or Add 0.05 to 2 m% zirconium oxide with silver as the respective residue. The boron oxide is preferably boric acid.
Weitere Einzelheiten und Vorteile der Erfindung ergeben sich aus der nachfolgenden Beschreibung von Ausführungsbeispielen. Dabei wird einerseits auf unterschiedliche Verfahren zur Herstellung des beanspruchten Werkstoffes und andererseits auf die beigefügte Tabelle mit Einzelbeispielen für konkrete Werkstoffzusammensetzungen gemäß der Erfindung eingegangen.Further details and advantages of the invention result from the following description of exemplary embodiments. On the one hand, different methods for producing the claimed material and, on the other hand, on the attached table with individual examples for specific material compositions according to the invention are discussed.
In der Tabelle sind Meßwerte für die Übertemperatur der beanspruchten Werkstoffe, die jeweils an der Kontaktbrücke des Schaltgerätes gemessen wurde, angegeben. In der ersten Spalte der Temperaturmeßwerte ist die maximale Übertemperatur und in der zweiten Spalte der Temperaturmeßwerte ist die mittlere Brückentemperatur enthalten, die sich jeweils als Temperaturdifferenz zur Raumtemperatur ergeben. Die Temperaturmeßwerte wurden in Schaltreihenversuchen in einem 15 kW-Schütz bis zu einer Schaltzahl von ns = 50.000 Schaltungen ermittelt.The table shows measured values for the overtemperature of the stressed materials, which was measured at the contact bridge of the switching device. The first column of the measured temperature values contains the maximum overtemperature and the second column of the measured temperature values contains the average bridge temperature, which is the temperature difference from room temperature. The temperature measured values were determined in series of switching tests in a 15 kW contactor up to a switching number of n s = 50,000 switching operations.
Die Tabelle umfaßt drei Ausführungsbeispiele mit aussagekräftigen Zusammensetzungen des beanspruchten Kontaktwerkstoffes. Dabei kann die Herstellung des eigentlichen Werkstoffes und die Fertigung der diesbezüglichen Kontaktstücke nach teilweise unterschiedlichen Methoden erfolgen. Der Meßwert der erfindungsgemäßen Werkstoffe wird mit AgFe2O3 6,4 verglichen. Außerdem ist in der Tabelle ein AgFe9-Kontaktwerkstoff angeführt. Auf die Ergebnisse wird weiter unten im einzelnen eingegangen.The table comprises three exemplary embodiments with meaningful compositions of the contact material claimed. The production of the actual material and the production of the relevant contact pieces can be carried out done according to different methods. The measured value of the materials according to the invention is compared with AgFe 2 O 3 6.4. An AgFe9 contact material is also listed in the table. The results are discussed in more detail below.
Zur Herstellung eines Kontaktwerkstoffes AgFe2O3 5,7 ReO2 1,1 werden entsprechende Anteile von Silberpulver, Eisenoxidpulver und Rheniumoxidpulver gemischt. Dazu werden handelsübliche Oxidpulver von Eisen oder Rhenium verwendet.Appropriate proportions of silver powder, iron oxide powder and rhenium oxide powder are mixed to produce a contact material AgFe 2 O 3 5.7 ReO 2 1.1. Commercial oxide powders of iron or rhenium are used for this.
Durch Naßmischen der Oxidpulver wird eine Pulvermischung zubereitet. Aus der Pulvermischung werden zunächst über die sogenannte Strangpreßtechnik Bänder oder Drähte des Werkstoffes als Halbzeug für die Kontaktstücke hergestellt. Die Verfahrensbedingungen hinsichtlich Temperatur einerseits und Druck andererseits werden dabei so gewählt, daß einer unerwünschten Verdampfung von Rhenium Rechnung getragen wird. Für eine sichere Verbindungstechnik ist es vorteilhaft, nach dem Zweischichten-Strangpreßverfahren Bänder mit einer lötfähigen Silberschicht herzustellen. Von dem so erzeugten Halbzeug lassen sich dann Kontaktstücke mit Richtgefüge abtrennen.A powder mixture is prepared by wet mixing the oxide powders. From the powder mixture, strips or wires of the material are first produced as semi-finished products for the contact pieces using the so-called extrusion technique. The process conditions with regard to temperature on the one hand and pressure on the other hand are chosen so that undesired evaporation of rhenium is taken into account. For secure connection technology, it is advantageous to use the two-layer extrusion process to produce tapes with a solderable silver layer. Contact pieces with a directional structure can then be separated from the semi-finished product thus produced.
Bei einem gleichen verfahrensmäßigen Vorgehen können die Anteile von Silber, Eisenoxid und Rheniumoxid variiert werden. Weiterhin untersucht wurde ein Werkstoff der Zusammensetzung AgFe2O35,7 ReO22,2.The proportions of silver, iron oxide and rhenium oxide can be varied using the same procedure. A material with the composition AgFe 2 O 3 5.7 ReO 2 2.2 was also investigated.
In einem anderen Verfahren werden die Kontaktstücke durch Formteiltechnik hergestellt. Dies ist insbesondere vorteilhaft, wenn das weitere Oxid als Nebenwirkkomponente nicht Rheniumoxid, sondern beispielsweise Zirkonoxid ist. Hierzu werden wiederum entsprechende Anteile von Silberpulver, Eisenoxidpulver und das Zirkonoxidpulver miteinander gemischt. Im einzelnen wurde ein Werkstoff der Zusammensetzung AgFe2O35,4ZrO21,0 untersucht.In another process, the contact pieces are produced by molding technology. This is particularly advantageous if the further oxide as a side effect component is not rhenium oxide but, for example, zirconium oxide. Appropriate proportions of silver powder, Iron oxide powder and the zirconium oxide powder mixed together. A material with the composition AgFe 2 O 3 5.4ZrO 2 1.0 was examined in detail.
Es kann weiterhin vorteihaft sein, neben Silberpulver und Eisenoxidpulver als weiteren Zusatz ein Pulver aus einer Mischung von zwei oder mehreren Komponenten aus Rheniumoxid, Wismutzirkonat, Boroxid und Zirkonoxid zu verwenden. Bei geeigneter Abstimmung der Anteile einer solchen Mischung können jeweils die Vorteile der einzelnen Zusatzoxide miteinander kombiniert werden.In addition to silver powder and iron oxide powder, it can also be advantageous to use a powder composed of a mixture of two or more components of rhenium oxide, bismuth zirconate, boron oxide and zirconium oxide as a further additive. With a suitable coordination of the proportions of such a mixture, the advantages of the individual additional oxides can be combined with one another.
Nach Naßmischen über einen geeigneten Zeitraum werden aus der Pulvermischung Formteile bei einem Druck von ca. 200 MPa zu Kontaktstücken gepreßt. Für eine sichere Verbindungstechnik des Kontaktstückes mit dem Kontaktstückträger durch Hartlöten ist es wiederum vorteilhaft, bei diesem Preßvorgang eine zweite Schicht aus Reinsilber gemeinsam mit der eigentlichen Kontaktschicht zu einem Zweischichten-Kontaktstück zu verpressen.After wet mixing for a suitable period of time, molded parts are pressed from the powder mixture into contact pieces at a pressure of approx. 200 MPa. For secure connection technology of the contact piece to the contact piece carrier by brazing, it is again advantageous in this pressing process to press a second layer of pure silver together with the actual contact layer into a two-layer contact piece.
Anschließend erfolgt eine Sinterung der Formteile bei einer Temperatur von ca. 850 °C etwa eine Stunde. Zur Erzielung einer möglichst geringen Porosität der fertigen Kontaktstücke werden anschließend die Sinterkörper bei einem Druck von ca. 1000 MPa nachgepresst und nochmals bei ca. 800 °C etwa eine Stunde gesintert. Das Kalibrieren der so herstellten Kontaktstücke erfolgt wiederum bei einem Druck von ca. 1000 MPa.The molded parts are then sintered at a temperature of approximately 850 ° C. for about an hour. To achieve the lowest possible porosity of the finished contact pieces, the sintered bodies are then pressed at a pressure of approx. 1000 MPa and sintered again at approx. 800 ° C for about an hour. The contact pieces thus produced are again calibrated at a pressure of approx. 1000 MPa.
Es ist auch möglich, zur Herstellung geeigneter Silber-Metalloxid-Pulvermischungen ein Langzeitmischen der Silber- und Einzeloxidpulver nach Art des sogenannte mechanischen Legierens anzuwenden. Dadurch werden die Gefügeeigenschaften des fertigen Werkstoffes vorteilhaft beeinflußt. Die Fertigung der Kontaktstücke kann jeweils wiederum alternativ durch Strangpreßtechnik oder Formteiltechnik erfolgen. Speziell bei Verwendung von Rheniumoxid als zusätzlicher Wirkkomponente muß wiederum einer möglichen Verdampfung von Rhenium Rechnung getragen werden. Diese Gefahr besteht bei Zirkonoxid nicht.It is also possible to produce long-term mixing of the silver and single oxide powders in the manner of what is known as mechanical to produce suitable silver-metal oxide powder mixtures Alloying. As a result, the structural properties of the finished material are advantageously influenced. The contact pieces can in each case alternatively be produced by extrusion technology or molding technology. Especially when using rhenium oxide as an additional active component, possible evaporation of rhenium must be taken into account. This danger does not exist with zirconium oxide.
Die Tabelle zeigt, daß bei den beiden ersten Beispielen des erfindungsgemäßen Werkstoffes jeweils eine mittlere Brückentemperatur vorliegt, die über dem Wert von AgFe9 und auch AgFe2O36,4 liegt. Demgegenüber liegt der entsprechende Wert beim dritten Beispiel unter den Vergleichsbeispielen. Festzuhalten ist, daß AgFe- und AgFe2O3-Werkstoffe in diesem Zusammenhang ein ähnliches Temperaturverhalten zeigen. Insgesamt liegen alle Werte für die mittlere Brückentemperatur in einem Bereich von 70 ± 5 K.The table shows that the first two examples of the material according to the invention each have an average bridge temperature which is above the value of AgFe9 and also AgFe 2 O 3 6.4. In contrast, the corresponding value in the third example is below the comparative examples. It should be noted that AgFe and AgFe 2 O 3 materials show a similar temperature behavior in this context. Overall, all values for the average bridge temperature are in a range of 70 ± 5 K.
Abgesehen von der mittleren Brückentemperatur zeigt sich aber nun, daß die maximale Übertemperatur bei allen erfindungsgemäßen Werkstoffen signifikant unter den Vergleichsbeispielen liegt. Insbesondere die statistisch auftretenden Maximawerte der Übertemperatur, die zu Schaden im Schaltgerät führen können, konnten aber bisher kaum beherrscht werden.Apart from the average bridge temperature, however, it can now be seen that the maximum excess temperature for all materials according to the invention is significantly lower than the comparative examples. In particular, the statistically occurring maximum values of overtemperature, which can lead to damage in the switchgear, have so far hardly been mastered.
Aus den Meßwerten läßt sich also die Erkenntnis ableiten, daß ein Zusatz von entweder Rheniumoxid oder insbesondere von Zirkonoxid das Temperaturverhalten eines AgFe2O3-Werkstoffes entscheidend stabilisiert. Letzteres drückt sich in der deutlich niedrigeren maximalen Übertemperatur aus.From the measured values it is therefore possible to derive the knowledge that the addition of either rhenium oxide or in particular zirconium oxide decisively stabilizes the temperature behavior of an AgFe 2 O 3 material. The latter is expressed in the significantly lower maximum overtemperature.
Gemäß Tabelle wurden im einzelnen AgFe2O3ReO2- und AgFe2O3ZrO2-Werkstoffe untersucht. Der gleiche positive Einfluß wie von Rheniumoxid oder Zirkonoxid kann auch von anderen geeigneten Oxidzusätzen erwartet werden. Beispielsweise können als geeignete Nebenkomponenten zum Eisenoxid auch Wismutzirkonat (2Bi2O3 × 3ZrO2) oder Borsäure (H3BO4) verwendet werden. Auch Mischungen der einzelnen Komponenten sind möglich.According to the table, AgFe 2 O 3 ReO 2 and AgFe 2 O 3 ZrO 2 materials were examined in detail. The same positive influence as that of rhenium oxide or zirconium oxide can also be expected from other suitable oxide additives. For example, bismuth zirconate (2Bi 2 O 3 × 3ZrO 2 ) or boric acid (H 3 BO 4 ) can also be used as suitable secondary components to the iron oxide. Mixtures of the individual components are also possible.
Bei den erfindungsgemäßen Werkstoffen kann das Eisenoxid anstatt der chemischen Konstitution Fe2O3 auch in der Konstitution Fe3O4 oder in einer Mischform vorliegen. Im einzelnen zeigt sich, daß das Eisenoxid insbesondere in Massenanteilen von 2 bis 20 %, der Zusatz von Rheniumoxid zwischen 0,5 und 3 m%, der Zusatz von Wismutzirkonat zwischen 0,05 und 3 m%, der Zusatz von Borsäure zwischen 0,05 und 0,5 m% und der Zusatz von Zirkonoxid zwischen 0,05 und 2 m% liegen sollte.
Claims (11)
- Silver-based contact material for use in power engineering switchgear, in particular for contacts in low-voltage switches, wherein, in addition to silver, there are present as active components at least iron oxide (Fe2O3/Fe3O4) as main component and at least one further metal oxide as secondary component, characterised by the combination of iron oxide (Fe2O3/Fe3O4) and rhenium oxide (ReO2) as active components, wherein the iron oxide (Fe2O3/Fe3O4) is present in proportions of between 1 and 50% by weight and the rhenium oxide is present in proportions of between 0.01 and 5% by weight.
- Silver-based contact material for use in power engineering switchgear, in particular for contacts in low-voltage switches, wherein, in addition to silver, there are present as active components at least iron oxide (Fe2O3/Fe3O4) as main component and at least one further metal oxide as secondary component, characterised by the combination of iron oxide (Fe2O3/Fe3O4) and bismuth zirconate (2Bi2O3x3ZrO2) as active components, wherein the iron oxide (Fe2O3/Fe3O4) is also present in proportions of between 1 and 50% by weight and the bismuth zirconate (2Bi2O3x3ZrO2) is present in proportions of between 0.01 and 5% by weight.
- Silver-based contact material for use in power engineering switchgear, in particular for contacts in low-voltage switches, wherein, in addition to silver, there are present as active components at least iron oxide (Fe2O3/Fe3O4) as main component and at least one further metal oxide as secondary component, characterised by the combination of iron oxide (Fe2O3/Fe3O4) and boron oxide (H2BO4) as active components, wherein the iron oxide (Fe2O3/Fe3O4) is present at between 1 and 50% and the boron oxide (H2BO4) is present at between 0.01 and 5%.
- Silver-based contact material for use in power engineering switchgear, in particular for contacts in low-voltage switches, wherein, in addition to silver, there are present as active components at least iron oxide (Fe2O3/Fe3O4) as main component and at least one further metal oxide as secondary component, characterised by the combination of iron oxide (Fe2O3/Fe3O4) and zirconium oxide (ZrO2) as active components, wherein the iron oxide (Fe2O3/Fe3O4) is present in proportions of between 1 and 50% by weight and the zirconium oxide (ZrO2) is present in proportions of between 0.01 and 5% by weight.
- Contact material according to claims 1 to 5, characterised in that the iron oxide (Fe2O3/Fe3O4) is present in proportions of less than 40% by weight.
- Contact material according to claim 5, characterised in that the iron oxide (Fe2O3/Fe3O4) is present in proportions of less than 30% by weight.
- Contact material according to claims 1 to 4, characterised by iron oxide (Fe2O3/Fe304) in proportions of 2 to 20% by weight, with an addition of 0.5 to 3% rhenium oxide (ReO2), balance silver.
- Contact material according to claim 2, characterised by iron oxide (Fe2O3/Fe3O4) in proportions of 2 to 20% by weight, with an addition of 0.05 to 3% bismuth zirconate (2Bi2O3x3ZrO2), balance silver.
- Contact material according to claim 3, characterised by iron oxide (Fe2O3/Fe3O4) in proportions of 2 to 20% by weight, with an addition of 0.05 to 0.5% boron oxide (H2BO4), balance silver.
- Contact material according to claim 9, characterised in that the boron oxide (H2BO4) is boric acid.
- Contact material according to claim 4, characterised by iron oxide (Fe2O3/Fe3O4) in proportions of 2 to 20% by weight, with an addition of 0.05 to 2% zirconium oxide (ZrO2), balance silver.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4117311A DE4117311A1 (en) | 1991-05-27 | 1991-05-27 | CONTACT MATERIAL ON A SILVER BASE FOR USE IN SWITCHGEAR DEVICES IN ENERGY TECHNOLOGY |
DE4117311 | 1991-05-27 | ||
PCT/DE1992/000388 WO1992022080A1 (en) | 1991-05-27 | 1992-05-14 | Silver-based contact material for use in power-engineering switchgear, and a method of manufacturing contacts made of this material |
Publications (2)
Publication Number | Publication Date |
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EP0586410A1 EP0586410A1 (en) | 1994-03-16 |
EP0586410B1 true EP0586410B1 (en) | 1996-10-30 |
Family
ID=6432544
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Application Number | Title | Priority Date | Filing Date |
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EP92909652A Expired - Lifetime EP0586410B1 (en) | 1991-05-27 | 1992-05-14 | Silver-based contact material for use in power-engineering switchgear, and a method of manufacturing contacts made of this material |
Country Status (9)
Country | Link |
---|---|
US (1) | US5429656A (en) |
EP (1) | EP0586410B1 (en) |
JP (1) | JP3280968B2 (en) |
AT (1) | ATE144857T1 (en) |
BR (1) | BR9206065A (en) |
DE (2) | DE4117311A1 (en) |
DK (1) | DK0586410T3 (en) |
ES (1) | ES2094354T3 (en) |
WO (1) | WO1992022080A1 (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE136394T1 (en) * | 1992-06-10 | 1996-04-15 | Duerrwaechter E Dr Doduco | MATERIAL FOR ELECTRICAL CONTACTS BASED ON SILVER-TIN OXIDE OR SILVER-ZINC OXIDE |
US5796017A (en) * | 1993-08-23 | 1998-08-18 | Siemens Aktiengesellschaft | Silver-based contact material, use of such a contact material, in switchgear for power engineering applications and method of manufacturing the contact material |
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 |
DE4343550A1 (en) * | 1993-12-20 | 1995-06-22 | Siemens Ag | Contact material based on silver for use in switching devices of power engineering |
US5846288A (en) * | 1995-11-27 | 1998-12-08 | Chemet Corporation | Electrically conductive material and method for making |
DE19602812C1 (en) * | 1996-01-26 | 1997-07-31 | Siemens Ag | Method for producing a shaped piece from a silver-based contact material and shaped piece |
DE19608490C1 (en) * | 1996-03-05 | 1997-09-04 | Siemens Ag | Contact material made of silver and active components, molded part made therefrom and process for producing the molded part |
ES2187801T3 (en) * | 1996-08-01 | 2003-06-16 | Metalor Technologies Int | PROCEDURE FOR MANUFACTURING A PRODUCT WITH A SILVER-BASED CONTACTING MATERIAL, CONTACT MATERIAL AND PRODUCT OBTAINED WITH THIS CONTACT MATERIAL. |
DE60107578T2 (en) * | 2001-07-18 | 2005-12-22 | Nec Schott Components Corp., Koka | THERMAL FUSE |
US6757963B2 (en) * | 2002-01-23 | 2004-07-06 | Mcgraw-Edison Company | Method of joining components using a silver-based composition |
EP1381065A1 (en) * | 2002-07-12 | 2004-01-14 | Metalor Technologies International S.A. | Electrical contact material and its method of manufacture |
WO2005124804A1 (en) * | 2004-06-18 | 2005-12-29 | Tanaka Kikinzoku Kogyo K.K. | RELAY FOR SEALED AC LOAD AND Ag-BASE CONTACT ELEMENT MATERIAL FOR USE THEREIN |
EP2124236A1 (en) * | 2008-05-22 | 2009-11-25 | Metalor Technologies International S.A. | Use of an electric contact material to blow an electric arc |
JP6145285B2 (en) * | 2012-03-22 | 2017-06-07 | 日本タングステン株式会社 | Electrical contact material, method for producing the same, and electrical contact |
CN112475295B (en) * | 2020-09-30 | 2022-11-15 | 浙江福达合金材料科技有限公司 | Silver ferric oxide electric contact material with oxide particles dispersed and distributed and preparation method thereof |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
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US2394501A (en) * | 1942-09-12 | 1946-02-05 | Square D Co | Electrical contact |
US3607244A (en) * | 1967-03-11 | 1971-09-21 | Sumitomo Electric Industries | Electric contact material and method of making the same |
DE2310784B2 (en) * | 1973-03-03 | 1975-03-13 | Fa. Dr. Eugen Duerrwaechter Doduco, 7530 Pforzheim | Process for the production of a ductile silver-metal oxide semi-finished product |
DE2446698C2 (en) * | 1974-09-30 | 1983-04-14 | Siemens AG, 1000 Berlin und 8000 München | Two-layer sintered contact piece for electrical switching devices |
JPS5913578B2 (en) * | 1977-01-25 | 1984-03-30 | 日本科学冶金株式会社 | electrical contact materials |
US4369063A (en) * | 1981-11-12 | 1983-01-18 | Ciba-Geigy Corporation | Silver containing conductive coatings |
JPH06104873B2 (en) * | 1986-07-08 | 1994-12-21 | 富士電機株式会社 | Silver-metal oxide contact material and manufacturing method thereof |
YU46258B (en) * | 1987-06-06 | 1993-05-28 | Degussa Ag. | APPLICATION OF SILVER IRON MATERIAL FOR ELECTRICAL CONTACTS |
DE3816895A1 (en) * | 1987-06-06 | 1988-12-22 | Degussa | Use of a silver-iron material for electric contacts |
JPS6455345A (en) * | 1987-08-25 | 1989-03-02 | Chugai Electric Ind Co Ltd | Silver-iron oxide sintered electrical contact material |
DE3911904A1 (en) * | 1988-04-16 | 1989-12-14 | Duerrwaechter E Dr Doduco | Powder-metallurgical process for producing a semifinished product for electric contacts from a silver-based composite with iron |
WO1989010417A1 (en) * | 1988-04-20 | 1989-11-02 | Siemens Aktiengesellschaft | Sintered contact material based on silver for use in power engineering switchgear, in particular for contact pieces in low-voltage switches |
DE58908359D1 (en) * | 1988-11-17 | 1994-10-20 | Siemens Ag | Sintered contact material for low-voltage switchgear in energy technology, especially for motor contactors. |
DE58909295D1 (en) * | 1988-11-17 | 1995-07-20 | Siemens Ag | Low-voltage switchgear sintered contact material of energy technology, especially for motor contactors. |
-
1991
- 1991-05-27 DE DE4117311A patent/DE4117311A1/en not_active Withdrawn
-
1992
- 1992-05-14 DE DE59207467T patent/DE59207467D1/en not_active Expired - Fee Related
- 1992-05-14 WO PCT/DE1992/000388 patent/WO1992022080A1/en active IP Right Grant
- 1992-05-14 ES ES92909652T patent/ES2094354T3/en not_active Expired - Lifetime
- 1992-05-14 EP EP92909652A patent/EP0586410B1/en not_active Expired - Lifetime
- 1992-05-14 JP JP50896092A patent/JP3280968B2/en not_active Expired - Fee Related
- 1992-05-14 DK DK92909652.7T patent/DK0586410T3/en active
- 1992-05-14 BR BR9206065A patent/BR9206065A/en not_active IP Right Cessation
- 1992-05-14 US US08/142,441 patent/US5429656A/en not_active Expired - Lifetime
- 1992-05-14 AT AT92909652T patent/ATE144857T1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
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JPH06507447A (en) | 1994-08-25 |
ES2094354T3 (en) | 1997-01-16 |
US5429656A (en) | 1995-07-04 |
EP0586410A1 (en) | 1994-03-16 |
DE59207467D1 (en) | 1996-12-05 |
JP3280968B2 (en) | 2002-05-13 |
WO1992022080A1 (en) | 1992-12-10 |
ATE144857T1 (en) | 1996-11-15 |
BR9206065A (en) | 1994-11-29 |
DK0586410T3 (en) | 1997-04-14 |
DE4117311A1 (en) | 1992-12-03 |
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