EP0645049B1 - Material for electrical contacts based on silver-tin oxide or silver-zinc oxide - Google Patents
Material for electrical contacts based on silver-tin oxide or silver-zinc oxide Download PDFInfo
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- EP0645049B1 EP0645049B1 EP93912924A EP93912924A EP0645049B1 EP 0645049 B1 EP0645049 B1 EP 0645049B1 EP 93912924 A EP93912924 A EP 93912924A EP 93912924 A EP93912924 A EP 93912924A EP 0645049 B1 EP0645049 B1 EP 0645049B1
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- tin
- oxide
- oxides
- carbides
- silver
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/059—Making alloys comprising less than 5% by weight of dispersed reinforcing phases
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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
Definitions
- contact materials based on silver-tin oxide Due to their better environmental compatibility and their at least partially more favorable lifespan, contact materials based on silver-tin oxide have started to replace the previously preferred silver-cadmium oxide materials. Since the tin oxide tends to be poorly conductive when exposed to arcing because of its higher thermal resistance To form slag layers on the contact surface, however, the heating behavior under continuous current is unsatisfactory for contacts made of silver-tin oxide. In order to eliminate this disadvantage, additives in powder form are added to the material, which is generally produced by powder metallurgy, which leads to a lower temperature at the contact point.
- Tungsten and molybdenum compounds have become known in the patent literature as suitable additives in this sense (DE-A-29 33 338, DE-A-31 02 067, DE-A-32 32 627, EP-A-0024349).
- Bismuth and germanium compounds have also been mentioned as additives (DE-A-31 02 067 and DE-A-32 32 627).
- These additives help to wet the tin oxide particles so that when the contact piece surface melts locally under the action of a switching arc, the tin oxide remains in fine suspension. In addition to this positive effect with regard to the heating behavior under continuous current, these additives also have undesirable side effects.
- the plastic deformability of the silver-tin oxide contact materials which is not entirely satisfactory anyway, for the improvement of which, for example, a pretreatment of the tin oxide powder is carried out by annealing (DE-A-29 52 128) is made worse by the additives because they have an embrittling effect.
- Another disadvantage, in particular of the tungsten and molybdenum compounds, is that they - especially in switching operation under AC1 load (DIN 57660 part 102) - favor a material transfer that leads to accelerated combustion and thus to a reduction in the service life.
- a contact material with a low tendency to weld and a contact temperature that is as low as possible under constant current load should be achieved by specifically producing a structure in which areas in which little or no metal oxide is contained alternate with areas, in which all or the vast majority of the metal oxide component is contained in a fine distribution.
- a composite powder is produced which contains the predominant part of the tin oxide and the further oxides and / or carbides as well as part of the silver. This composite powder is mixed with the remaining silver powder and possibly with the smaller rest of the metal oxides, compacted, sintered and shaped. In this way, a material that can be used well is obtained, but by a relatively complex process.
- the present invention is based on the object of creating a material of the type mentioned at the outset which, by means of oxidic or carbide additives, exhibits heating behavior which is just as favorable as that of the known contact materials, but is less brittle.
- Another advantage of the invention is that the lower proportion of the chosen additive increases the service life of contact pieces made of the material, because the additives, which, like the molybdenum oxide, tend to evaporate under the influence of an arc, lead to a lower proportion thanks to their lower proportion Blistering on the contact surface and thus less burning.
- Such a material can be obtained by mixing tin oxide powder and the powdery additive with one another and annealing them together so that the tin oxide powder particles are wetted by the additive and / or part of the additive diffuses into the surface area of the tin oxide particles, a single-phase mixed oxide ( a new chemical compound) or a two-phase or multi-phase oxide mixture can be formed.
- the reaction spraying process can also advantageously be used to obtain a tin oxide powder which is superficially coated with the other oxides by, in a modification of the procedure described above, suspending a finely divided tin oxide powder in the salt solution instead of a tin salt and this suspension in a hot oxidizing atmosphere sprays.
- the material expediently contains 5 to 20% by weight, preferably 8 to 15% by weight, tin oxide, and thus the tin oxide as desired can be kept in suspension by the additives in the molten phase occurring under the action of arcing, the tin oxide powder should contain 0.01 to 10% by weight of the further oxidic or carbidic additive, but expediently not more than 5% by weight.
- the addition of the other oxides and carbides should be chosen as low as possible in order not to exceed a contact point temperature specified under the specified conditions of use, for which much smaller quantities are sufficient than in the prior art.
- a tin oxide powder which contains only 0.1 to 1.5% by weight of the further oxide or carbide is preferably used.
- the tin oxide areas in the material are expediently less than 100 ⁇ m, preferably less than 10 ⁇ m in diameter, but should not be less than 0.5 ⁇ m in order not to cause the material to become solidified in dispersion.
- Molybdenum oxide is particularly preferred as an additive because of its particularly favorable effect on the heating behavior.
- the teaching according to the invention can be applied to contact materials based on silver with zinc oxide. In such materials, practically no additives are used today, but efforts have so far been made to reduce the contact point temperature by constructive measures. By using a zinc oxide enriched with further oxides and / or carbides according to the invention, a lowering of the contact point temperature can also be achieved with this type of material.
- a tin oxide-molybdenum oxide composite powder with 1% by weight of molybdenum oxide is produced by spraying an aqueous solution of tin-II-chloride and molybdenum-IV-chloride in a reactor heated to approx. 950 ° C. oxidizing atmosphere, whereby a tin oxide-molybdenum oxide composite powder precipitates, in the powder particles of which the tin oxide and the molybdenum oxide are present in a very fine distribution.
- 12% by weight of the molybdenum oxide-doped tin oxide powder thus produced are mixed intensively with 88 parts by weight of a silver powder with a particle size of less than 40 ⁇ m, a cylindrical block of 50 kg weight is pressed cold isostatically therefrom, sintered in air and in the process Maintained at 820 ° C for 1.5 hours.
- the sintered block is coated with silver, placed hot in a reverse extrusion press and pressed through an extrusion die with a branching extrusion opening, resulting in two flat strands that have a silver-tin oxide surface on one side and a well-soldered one on the other side. and have weldable silver surface.
- the strands are then rolled flat and then have a width of 8 cm and a thickness of 2 mm.
- the first example is modified such that instead of a solution of tin-II-chloride and molybdenum-IV-chloride, a solution of molybdenum-IV-chloride is sprayed in which a tin oxide powder with a particle size smaller than 5 ⁇ m is suspended.
- This wire is tapered to a diameter of 1.4 mm and then processed into contact rivets with a head diameter of 3.2 mm and a shaft diameter of 1.47 mm.
- the new material proves to be clearly superior to the state-of-the-art contact materials both in the AC service life test and when switching DC lamp loads.
- a mixed oxide powder is produced from an aqueous solution of zinc chloride and meta-tungstic acid by spraying the solution into a reactor heated to 1100 ° C.
- the zinc-tungsten-oxide mixture obtained in this way has a tungsten oxide content of 1% by weight and an average particle diameter of 2.4 ⁇ m.
- the oxide powder is mixed with silver powder and further processed into contact wafers.
- An aqueous solution of tin acetate and ammonium heptamolybdate is sprayed into a reactor at a temperature of 800 ° C., thus obtaining an oxide powder with a molybdenum oxide content of 350 ppm and an average particle diameter of 1.9 ⁇ m.
- This powder is used to produce a contact material, as in Example 1, which is subjected to a service life test in accordance with test category AC1 in a switching device with an output of 37 kW. This lifetime test is interrupted in order to carry out a warming test with continuous current.
- FIG. 1 The result of this heating test is shown in FIG. 1 and compared with an analog test for a state-of-the-art material made of 88% by weight Ag, 11.6% by weight SnO2 and 0.4% by weight MoO3 (FIG. 2 ).
- the heating behavior of the novel material is just as good as that of the conventional material, although the novel material, based on the entire contact material, only has a molybdenum oxide content of 42 ppm, while the state-of-the-art material for the same advantageous result requires an amount of molybdenum oxide of 0.4% by weight, that is around a hundred times as much.
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- Contacts (AREA)
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Abstract
Description
Die Erfindung geht aus von einem Werkstoff für elektrische Kontakte auf der Basis von Silber-Zinnoxid, bestehend aus Silber oder einer hauptsächlich Silber enthaltenden Legierung, Zinnoxid und weiteren Oxiden oder Karbiden von Wolfram, Molybdän, Vanadium, Wismut, Titan und/oder Kupfer. Ein solcher Werkstoff ist aus der WO 89/09478 bekannt.The invention is based on a material for electrical contacts based on silver-tin oxide, consisting of silver or an alloy containing mainly silver, tin oxide and other oxides or carbides of tungsten, molybdenum, vanadium, bismuth, titanium and / or copper. Such a material is known from WO 89/09478.
Aufgrund ihrer besseren Umweltverträglichkeit und ihrer zumindest teilweise günstigeren Lebensdauer haben Kontaktwerkstoffe auf der Basis von Silber-Zinnoxid begonnen, die bis dahin bevorzugten Silber-Cadmiumoxidwerkstoffe zu ersetzen. Da das Zinnoxid wegen seiner höheren thermischen Beständigkeit dazu neigt, unter Lichtbogeneinwirkung schlecht leitende Schlackenschichten an der Kontaktoberfläche zu bilden, ist jedoch das Erwärmungsverhalten unter Dauerstrom bei Kontakten aus Silber-Zinnoxid unbefriedigend. Um diesen Nachteil zu beseitigen, werden dem in der Regel pulvermetallurgisch hergestellten Werkstoff Zusätze in Pulverform beigegeben, die zu einer niedrigeren Temperatur an der Kontaktstelle führen. Als geeignete Zusätze in diesem Sinn sind in der Patentliteratur vor allem Wolfram- und Molybdänverbindungen bekanntgeworden (DE-A-29 33 338, DE-A-31 02 067, DE-A-32 32 627, EP-A-0024349). Als Zusätze sind ferner Wismut- und Germaniumverbindungen genannt worden (DE-A-31 02 067 und DE-A-32 32 627). Diese Zusätze helfen, Zinnoxidpartikel zu benetzen, so dass dann, wenn die Kontaktstückoberfläche unter der Wirkung eines Schaltlichtbogens lokal aufschmilzt, das Zinnoxid feinteilig in Suspension bleibt. Neben dieser positiven Wirkung hinsichtlich des Erwärmungsverhaltens unter Dauerstrom haben diese Zusätze jedoch auch unerwünschte Nebenwirkungen. Die ohnehin nicht ganz befriedigende plastische Verformbarkeit der Silber-Zinnoxid-Kontaktwerkstoffe, zu deren Verbesserung beispielsweise eine Vorbehandlung des Zinnoxidpulvers durch Glühen durchgeführt wird (DE-A-29 52 128), wird durch die Zusätze noch verschlechtert, weil diese versprödend wirken. Das gilt insbesondere für Wismut- und Molybdänoxid. Ein weiterer Nachteil insbesondere der Wolfram- und Molybdänverbindungen besteht darin, dass sie - insbesondere im Schaltbetrieb unter AC1-Belastung (DIN 57660 Teil 102) - eine Materialübertragung begünstigen, die zu beschleunigtem Abbrand und damit zu einer Verringerung der Lebensdauer führt.Due to their better environmental compatibility and their at least partially more favorable lifespan, contact materials based on silver-tin oxide have started to replace the previously preferred silver-cadmium oxide materials. Since the tin oxide tends to be poorly conductive when exposed to arcing because of its higher thermal resistance To form slag layers on the contact surface, however, the heating behavior under continuous current is unsatisfactory for contacts made of silver-tin oxide. In order to eliminate this disadvantage, additives in powder form are added to the material, which is generally produced by powder metallurgy, which leads to a lower temperature at the contact point. Tungsten and molybdenum compounds have become known in the patent literature as suitable additives in this sense (DE-A-29 33 338, DE-A-31 02 067, DE-A-32 32 627, EP-A-0024349). Bismuth and germanium compounds have also been mentioned as additives (DE-A-31 02 067 and DE-A-32 32 627). These additives help to wet the tin oxide particles so that when the contact piece surface melts locally under the action of a switching arc, the tin oxide remains in fine suspension. In addition to this positive effect with regard to the heating behavior under continuous current, these additives also have undesirable side effects. The plastic deformability of the silver-tin oxide contact materials, which is not entirely satisfactory anyway, for the improvement of which, for example, a pretreatment of the tin oxide powder is carried out by annealing (DE-A-29 52 128) is made worse by the additives because they have an embrittling effect. This applies in particular to bismuth and molybdenum oxide. Another disadvantage, in particular of the tungsten and molybdenum compounds, is that they - especially in switching operation under AC1 load (DIN 57660 part 102) - favor a material transfer that leads to accelerated combustion and thus to a reduction in the service life.
Nach der Lehre der WO 89/09478 soll ein Kontaktwerkstoff mit geringer Verschweißneigung und möglichst niedriger Kontakttemperatur unter Dauerstrombelastung dadurch erreicht werden, dass man gezielt ein Gefüge herstellt, in welchem Bereiche, in denen kein oder nur sehr wenig Metalloxid enthalten ist, abwechseln mit Bereichen, in denen die gesamte oder der weit überwiegende Teil der Metalloxidkomponente in feiner Verteilung enthalten ist. Zu diesem Zweck wird unter anderem ein Verbundpulver hergestellt, welches den überwiegenden Teil des Zinnoxids und der weiteren Oxide und/oder Karbide sowie einen Teil des Silbers enthält. Dieses Verbundpulver wird mit dem restlichen Silberpulver und ggfs. mit dem kleineren Rest der Metalloxide vermischt, verdichtet, gesintert und umgeformt. Auf diese Weise erhält man zwar einen gut brauchbaren Werkstoff, jedoch nach einem verhältnismässig aufwendigen Verfahren.According to the teaching of WO 89/09478, a contact material with a low tendency to weld and a contact temperature that is as low as possible under constant current load should be achieved by specifically producing a structure in which areas in which little or no metal oxide is contained alternate with areas, in which all or the vast majority of the metal oxide component is contained in a fine distribution. For this purpose, among other things, a composite powder is produced which contains the predominant part of the tin oxide and the further oxides and / or carbides as well as part of the silver. This composite powder is mixed with the remaining silver powder and possibly with the smaller rest of the metal oxides, compacted, sintered and shaped. In this way, a material that can be used well is obtained, but by a relatively complex process.
Die EP-A 0 369 283 offenbart einen Sinterkontaktwerkstoff für Niederspannungsschaltgeräte der Energietechnik, insbesondere für Motorschütze, der Zusammensetzung AgSnO₂Bi₂O₃CuO. Er wird hergestellt durch innere Oxidation eines AgSnBiCu-Legierungspulvers, welches mit einer kleineren Menge Wismut-Zirkonat und/oder Wismut-Titanatpulver gemischt, gepreßt und gesintert wird. Dabei verarmen die AgSnO₂Bi₂O₃CuO-Partikel am Rand an Oxiden, so dass zwischen den Partikeln ein Silbernetzwerk entsteht, welches hohe Preßdichten ermöglicht. Sowohl die Herstellung des Legierungspulvers als auch dessen innere Oxidation sind jedoch aufwendig und machen das Verfahren teuer.EP-
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, einen Werkstoff der eingangs genannten Art zu schaffen, der durch oxidische oder karbidische Zusätze ein ebenso günstiges Erwärmungsverhalten zeigt wie die bekannten Kontaktwerkstoffe, jedoch weniger spröde ist.The present invention is based on the object of creating a material of the type mentioned at the outset which, by means of oxidic or carbide additives, exhibits heating behavior which is just as favorable as that of the known contact materials, but is less brittle.
Diese Aufgabe wird gelöst durch einen Werkstoff mit den in den Ansprüchen 1 oder 2 angegebenen Merkmalen. Vorteilhafte Weiterbildungen der Erfindung sind Gegenstand der abhängigen Ansprüche.This object is achieved by a material with the features specified in
Die Erfindung macht nicht den naheliegenden Versuch, neue Zusätze aufzufinden, die die Kontaktstellentemperatur senken, aber nicht oder weniger versprödend wirken, vielmehr werden erfindungsgemäss Zusätze verwendet, die zu diesem Zweck bereits bekannt sind und von denen man weiß, dass sie versprödend wirken. Erfindungsgemäss wird jedoch der gewählte Zusatz nicht als gesondertes Pulver neben Silberpulver und Zinnoxidpulver (DE-A-29 33 338, DE-A-31 02 067, DE-A-32 32 627) und auch nicht als Bestandteil eines Silber-Zinnoxid-Verbundpulvers eingesetzt, welches mit weiterem Silberpulver und ggfs. Metalloxidpulvern gemischt wird (WO 89/09478), vielmehr wird ein Werkstoff gebildet, welcher in einer aus Silber oder aus einer hauptsächlich Silber enthaltenden Legierung bestehenden Matrix Zinnoxidbereiche eingelagert, enthält, in welchen die weiteren Oxide und/oder Karbide an das Zinnoxid gebunden konzentriert sind und die Silbermatrix - abgesehen von etwaigen löslichen Anteilen - frei ist von den weiteren Oxiden und Karbiden. In diesen Zinnoxidbereichen können die Oxide als einphasiges Mischoxid oder als zweiphasiges oder mehrphasiges Oxidgemisch (z.B. in einem Teilchenverbund oder in einem Schichtverbund) vorliegen. Einen solchen Werkstoff stellt man bevorzugt rein pulvermetallurgisch her, indem man ein Silberpulver oder ein Silberlegierungspulver mit einem Verbundpulver mischt, in welchem die weiteren Oxide und/oder Karbide an das Zinnoxid gebunden sind, Formkörper daraus preßt und diese sintert und erforderlichenfalls nachverdichtet oder umformt. Es ist aber auch möglich, das Verbundpulver in eine Schmelze des Matrixmetalls einzurühren und diese dann erstarren zu lassen.The invention does not make the obvious attempt to find new additives which lower the contact point temperature, but which do not act or are less embrittling; rather, additives are used according to the invention which are already known for this purpose and which are known to be embrittling. According to the invention, however, the selected additive is not used as a separate powder in addition to silver powder and tin oxide powder (DE-A-29 33 338, DE-A-31 02 067, DE-A-32 32 627) and also not as a component of a silver-tin oxide composite powder used, which is mixed with further silver powder and possibly metal oxide powders (WO 89/09478), rather a material is formed which contains tin oxide regions embedded in a matrix consisting of silver or an alloy mainly containing silver, in which the further oxides and / or carbides are concentrated bound to the tin oxide and the silver matrix - apart from any soluble components - is free of the other oxides and carbides. In these tin oxide regions, the oxides can be present as a single-phase mixed oxide or as a two-phase or multi-phase oxide mixture (for example in a particle composite or in a layer composite). Such a material is preferably produced purely by powder metallurgy, by mixing a silver powder or a silver alloy powder with a composite powder in which the further oxides and / or carbides are bound to the tin oxide, pressed moldings therefrom and sintered and, if necessary, redensified or reshaped. However, it is also possible to stir the composite powder into a melt of the matrix metal and then allow it to solidify.
Überraschenderweise erreicht man erfindungsgemäss eine bestimmte Senkung der Kontaktstellentemperatur unter vorgegebenen Betriebsbedingungen bereits mit einem geringeren Anteil des gewählten oxidischen und/oder karbidischen Zusatzes zum Zinnoxid als bisher, so dass der Kontaktwerkstoff weniger spröde ist. Als weiterer Vorteil kommt hinzu, dass infolge des geringeren Anteils des elektrisch nicht leitenden Zusatzes der elektrische Widerstand des Kontaktwerkstoffes zusätzlich herabgesetzt wird, was einen weiteren Beitrag zur Senkung der Kontaktstellentemperatur leistet.Surprisingly, according to the invention, a certain reduction in the contact point temperature under predetermined operating conditions is achieved with a lower proportion of the chosen oxidic and / or carbidic additive to the tin oxide than before, so that the contact material is less brittle. Another advantage is that, due to the lower proportion of the electrically non-conductive additive, the electrical resistance of the contact material is additionally reduced, which makes a further contribution to lowering the contact point temperature.
Ein weiterer Vorteil der Erfindung liegt darin, dass durch den geringeren Anteil des gewählten Zusatzes die Lebensdauer von Kontaktstücken aus dem Werkstoff erhöht wird, denn die Zusätze, die wie das Molybdänoxid dazu neigen, unter Lichtbogeneinwirkung zu verdampfen, führen dank ihres geringeren Anteils zu einer geringeren Bläschenbildung an der Kontaktfläche und damit zu einem geringeren Abbrand.Another advantage of the invention is that the lower proportion of the chosen additive increases the service life of contact pieces made of the material, because the additives, which, like the molybdenum oxide, tend to evaporate under the influence of an arc, lead to a lower proportion thanks to their lower proportion Blistering on the contact surface and thus less burning.
Erste Erfahrungen mit dem erfindungsgemässen Kontaktwerkstoff zeigen, dass eine bestimmte Senkung der Kontaktstellentemperatur erfindungsgemäss sogar mit nur einem Viertel bis einem Fünftel der Zusatzmenge erreicht werden kann, die im Stand der Technik für eine gleich große Senkung der Kontaktstellentemperatur benötigt würde!Initial experience with the contact material according to the invention shows that, according to the invention, a certain reduction in the contact point temperature can even be achieved with only a quarter to a fifth of the additional amount which would be required in the prior art for an equally large reduction in the contact point temperature!
Mit besonders wenig zusätzlichem Oxid bzw. Karbid kommt man aus, wenn man dafür sorgt, dass diese Zusätze im Grenzbereich von den Zinnoxidbereichen zur Silbermatrix konzentriert sind. Einen solchen Werkstoff kann man dadurch erhalten, dass man Zinnoxidpulver und den pulverförmigen Zusatz miteinander vermischt und gemeinsam glüht, so dass die Zinnoxid-Pulverteilchen vom Zusatz benetzt werden und/oder ein Teil des Zusatzes in den Oberflächenbereich der Zinnoxidpartikel diffundiert, wobei ein einphasiges Mischoxid (also eine neue chemische Verbindung) oder ein zweiphasiges oder mehrphasiges Oxidgemisch gebildet werden kann. Für eine längere Lebensdauer von erfindungsgemässen Kontaktstücken ist es günstig, wenn die zusätzlichen Oxide und/oder Karbide sich nicht nur im Grenzbereich von den Zinnoxidbereichen zur Silbermatrix befinden, sondern wenn sich die zusätzlichen Oxide und/oder Karbide durchgehend in den Zinnoxidbereichen befinden. Vorzugsweise wird deshalb das Zinnoxidverbundpulver durch Anwendung eines Reaktionssprühverfahrens erhalten, indem man eine Lösung eines Salzes von Zinn und eines Salzes des Metalls oder der Metalle, aus deren Oxiden oder Karbiden der Zusatz bestehen soll, in eine heiße, oxidierende Atmosphäre sprüht, in welcher die Salze thermisch zersetzt werden, so dass ein feinteiliges Verbundpulver ausfällt, in welchem Zinnoxid und die Oxide oder Mischoxide der Zusatzmetalle in einem innigen Verbund vorliegen. Das Reaktionssprühverfahren ist beispielsweise in der DE-C-29 29 630, der US-A-3 510 291 und in der EP-A-0 012 202 offenbart. Ein karbidhaltiges Zinnoxidverbundpulver kann man erhalten, wenn man das Karbid als feines Pulver in der zu versprühenden Lösung suspendiert. Beim Versprühen der Suspension in einer heißen oxidierenden Atmosphäre lagern sich an den Karbidteilchen das Zinnoxid und die weiteren Oxide an, wobei die Verweilzeit in der heißen oxidierenden Atmosphäre so kurz gehalten wird, dass die reduzierende Wirkung der Karbide nicht zum Tragen kommt.You can get by with very little additional oxide or carbide if you ensure that these additives are concentrated in the border area from the tin oxide areas to the silver matrix. Such a material can be obtained by mixing tin oxide powder and the powdery additive with one another and annealing them together so that the tin oxide powder particles are wetted by the additive and / or part of the additive diffuses into the surface area of the tin oxide particles, a single-phase mixed oxide ( a new chemical compound) or a two-phase or multi-phase oxide mixture can be formed. For a longer service life of contact pieces according to the invention, it is advantageous if the additional oxides and / or carbides are not only located in the border area from the tin oxide areas to the silver matrix, but if the additional oxides and / or carbides are located continuously in the tin oxide areas. Preferably, therefore, the composite tin oxide powder is obtained by using a reaction spray method by making a solution of a salt of tin and a salt of the metal or the metals from whose oxides or carbides the additive is to be sprayed into a hot, oxidizing atmosphere in which the salts are thermally decomposed so that a finely divided composite powder precipitates in which tin oxide and the oxides or mixed oxides of the additive metals form an intimate composite available. The reaction spray method is disclosed, for example, in DE-C-29 29 630, US-A-3 510 291 and in EP-A-0 012 202. A carbide-containing tin oxide composite powder can be obtained by suspending the carbide as a fine powder in the solution to be sprayed. When the suspension is sprayed in a hot oxidizing atmosphere, the tin oxide and the other oxides attach to the carbide particles, the residence time in the hot oxidizing atmosphere being kept so short that the reducing effect of the carbides does not come into play.
Das Reaktionssprühverfahren kann mit Vorteil auch eingesetzt werden, um ein Zinnoxidpulver zu erhalten, welches oberflächlich mit den weiteren Oxiden überzogen ist, indem man in Abwandlung der vorstehend beschriebenen Verfahrensweise anstelle eines Zinnsalzes in der Salzlösung ein feinteiliges Zinnoxidpulver suspendiert und diese Suspension in eine heiße oxidierende Atmosphäre sprüht.The reaction spraying process can also advantageously be used to obtain a tin oxide powder which is superficially coated with the other oxides by, in a modification of the procedure described above, suspending a finely divided tin oxide powder in the salt solution instead of a tin salt and this suspension in a hot oxidizing atmosphere sprays.
Schließlich ist es auch möglich, einen Teil der Oxide, zu denen auch Zinnoxid gehören kann, ggfs. auch Karbide, die im Werkstoff als Zusatz enthalten sein sollen, in einer Lösung zu suspendieren, welche die Metalle für den restlichen Oxidbestandteil des Werkstoffs gelöst enthält, und die so gebildete Suspension nach dem Reaktionssprühverfahren zu versprühen. Auf diese Weise lassen sich Verbundpulver mit vielfältig abgewandeltem Aufbau herstellen, maßgeschneidert für den jeweiligen Verwendungszweck des Kontaktwerkstoffs.Finally, it is also possible to use some of the oxides, which may also include tin oxide, possibly also carbides, which should be contained in the material as an additive, to be suspended in a solution which contains the metals for the remaining oxide component of the material, and to spray the suspension formed in this way by the reaction spray process. In this way, composite powders with a varied structure can be produced, tailor-made for the respective intended use of the contact material.
Um die nötige Sicherheit gegen ein Verschweißen der Kontaktstücke zu bieten, die von Silber-Metalloxid-Werkstoffen verlangt wird, enthält der Werkstoff zweckmässigerweise 5 bis 20 Gew.-%, vorzugsweise 8 bis 15 Gew.-% Zinnoxid, und damit das Zinnoxid wie gewünscht durch die Zusätze in der unter Lichtbogeneinwirkung auftretenden schmelzflüssigen Phase in Suspension gehalten werden kann, sollte das Zinnoxidpulver 0,01 bis 10 Gew.-% des weiteren oxidischen oder karbidischen Zusatzes enthalten, zweckmässigerweise aber nicht mehr als 5 Gew.-%. Im Hinblick darauf, dass der Werkstoff möglichst wenig spröde sein soll, wählt man den Zusatz der weiteren Oxide und Karbide so niedrig wie möglich, um eine unter den vorgegebenen Einsatzbedingungen vorgegebene Kontaktstellentemperatur nicht zu überschreiten, wozu wesentlich geringere Mengen genügen als beim Stand der Technik. Vorzugsweise verwendet man ein Zinnoxidpulver, welches nur 0,1 bis 1,5 Gew.-% des weiteren Oxids oder Karbids enthält.In order to provide the necessary security against welding of the contact pieces, which is required of silver-metal oxide materials, the material expediently contains 5 to 20% by weight, preferably 8 to 15% by weight, tin oxide, and thus the tin oxide as desired can be kept in suspension by the additives in the molten phase occurring under the action of arcing, the tin oxide powder should contain 0.01 to 10% by weight of the further oxidic or carbidic additive, but expediently not more than 5% by weight. In view of the fact that the material should be as brittle as possible, the addition of the other oxides and carbides should be chosen as low as possible in order not to exceed a contact point temperature specified under the specified conditions of use, for which much smaller quantities are sufficient than in the prior art. A tin oxide powder which contains only 0.1 to 1.5% by weight of the further oxide or carbide is preferably used.
Die Zinnoxidbereiche im Werkstoff sind zweckmäßigerweise kleiner als 100 µm, vorzugsweise kleiner als 10 µm im Durchmesser, sollten aber nicht kleiner sein als 0,5 µm, um keine Dispersionsverfestigung des Werkstoffs zu bewirken.The tin oxide areas in the material are expediently less than 100 μm, preferably less than 10 μm in diameter, but should not be less than 0.5 μm in order not to cause the material to become solidified in dispersion.
Als Zusatz besonders bevorzugt ist Molybdänoxid wegen seiner besonders günstigen Wirkung auf das Erwärmungsverhalten.Molybdenum oxide is particularly preferred as an additive because of its particularly favorable effect on the heating behavior.
Die erfindungsgemässe Lehre kann übertragen werden auf Kontaktwerkstoffe auf der Basis von Silber mit Zinkoxid. In solchen Werkstoffen werden heute praktisch noch keine Zusätze verwendet, sondern man bemüht sich bisher, durch konstruktive Maßnahmen eine Senkung der Kontaktstellentemperatur zu erreichen. Durch Verwenden eines erfindungsgemäss mit weiteren Oxiden und/oder Karbiden angereicherten Zinkoxids läßt sich auch bei diesem Werkstofftyp eine Senkung der Kontaktstellentemperatur erreichen.The teaching according to the invention can be applied to contact materials based on silver with zinc oxide. In such materials, practically no additives are used today, but efforts have so far been made to reduce the contact point temperature by constructive measures. By using a zinc oxide enriched with further oxides and / or carbides according to the invention, a lowering of the contact point temperature can also be achieved with this type of material.
1.
Ein Zinnoxid-Molybdänoxid-Verbundpulver mit 1 Gew.-% Molybdänoxid wird hergestellt durch Versprühen einer wässrigen Lösung von Zinn-II-Chlorid und Molybdän-IV-Chlorid in einem auf ca. 950°C aufgeheizten Reaktor mit oxidierender Atmosphäre, wobei ein Zinnoxid-Molybdänoxid-Verbundpulver ausfällt, in dessen Pulverteilchen das Zinnoxid und das Molybdänoxid in sehr feiner Verteilung vorliegen.1.
A tin oxide-molybdenum oxide composite powder with 1% by weight of molybdenum oxide is produced by spraying an aqueous solution of tin-II-chloride and molybdenum-IV-chloride in a reactor heated to approx. 950 ° C. oxidizing atmosphere, whereby a tin oxide-molybdenum oxide composite powder precipitates, in the powder particles of which the tin oxide and the molybdenum oxide are present in a very fine distribution.
12 Gew.-% Teile des so hergestellten, mit Molybdänoxid dotierten Zinnoxidpulvers werden mit 88 Gew.-Teilen eines Silberpulvers mit einer Teilchengröße kleiner als 40 µm intensiv gemischt, daraus kalt isostatisch ein zylindrischer Block von 50 kg Gewicht gepreßt, in Luft gesintert und dabei 1,5 Stunden bei einer Temperatur von 820°C gehalten. Der gesinterte Block wird mit Silber ummantelt, heiß in eine Rückwärtsstrangpresse eingelegt und durch eine Strangpreßmatrize mit einer sich verzweigenden Auspreßöffnung hindurchgepreßt, wodurch zwei flache Stränge entstehen, die auf der einen Seite eine Silber-Zinnoxid-Oberfläche und auf der anderen Seite eine gut löt- und schweißbare Silberoberfläche haben. Die Stränge werden anschließend platt gewalzt und haben dann eine Breite von 8 cm und eine Dicke von 2 mm.12% by weight of the molybdenum oxide-doped tin oxide powder thus produced are mixed intensively with 88 parts by weight of a silver powder with a particle size of less than 40 μm, a cylindrical block of 50 kg weight is pressed cold isostatically therefrom, sintered in air and in the process Maintained at 820 ° C for 1.5 hours. The sintered block is coated with silver, placed hot in a reverse extrusion press and pressed through an extrusion die with a branching extrusion opening, resulting in two flat strands that have a silver-tin oxide surface on one side and a well-soldered one on the other side. and have weldable silver surface. The strands are then rolled flat and then have a width of 8 cm and a thickness of 2 mm.
2.
Das erste Beispiel wird dahingehend abgewandelt, dass anstelle einer Lösung von Zinn-II-Chlorid und Molybdän-IV-Chlorid eine Lösung von Molybdän-IV-Chlorid versprüht wird, in welcher ein Zinnoxidpulver mit einer Teilchengröße kleiner als 5 µm suspendiert ist.2nd
The first example is modified such that instead of a solution of tin-II-chloride and molybdenum-IV-chloride, a solution of molybdenum-IV-chloride is sprayed in which a tin oxide powder with a particle size smaller than 5 μm is suspended.
Nach Beispiel 1 hergestellte Kontaktstücke zeigen erst nach einer sehr viel größeren Zahl von Schaltspielen einen Anstieg der Kontaktstellentemperatur. Vermutlich hängt das mit der anderen Struktur des Zinnoxid/Molybdänoxidverbundpulvers zusammen, möglicherweise auch mit einer Mischoxidbildung.Contact pieces manufactured according to Example 1 only show an increase in the contact point temperature after a very large number of switching cycles. This is probably related to the other structure of the tin oxide / molybdenum oxide composite powder, possibly also to the formation of a mixed oxide.
3.
Eine Zinn-Legierung mit 2 Gew.-% Kupfer sowie 1 Gew.-% Wismut wird auf 580°C erhitzt und mittels einer Zweistoffdüse in einen Reaktor mit sauerstoffhaltiger Atmosphäre gesprüht, die sich auf Zimmertemperatur befindet. Es entsteht ein Mischoxidpulver mit einem Teilchendurchmesser von 4,5 µm nach Fisher.
10 Gew.-% dieses Mischoxidpulvers werden mit einem Silberpulver, Teilchendurchmesser kleiner als 40 µm, gemischt, aus der Mischung ein zylinderförmiger Block isostatisch mit einem Druck von 7,85.10 N/m kalt gepreßt, bei 790°C an Luft für zwei Stunden gesintert und anschließend mit einer Strangpresse vorwärts zu einem Draht mit einem Durchmesser von 5 mm stranggepreßt. Dieser Draht wird durch Ziehen auf einen Durchmesser von 1,4 mm verjüngt und anschließend zu Kontaktnieten mit einem Kopfdurchmesser von 3,2 mm bei einem Schaftdurchmesser von 1,47 mm verarbeitet. In ein Relais eingebaut, erweist sich der neue Werkstoff sowohl bei der Wechselstrom-Lebensdauerprüfung als auch beim Schalten von Gleichstrom-Lampenlast als den dem Stand der Technik entsprechenden Kontaktwerkstoffen deutlich überlegen.3rd
A tin alloy with 2% by weight of copper and 1% by weight of bismuth is heated to 580 ° C. and sprayed into a reactor with an oxygen-containing atmosphere which is at room temperature by means of a two-component nozzle. A mixed oxide powder with a particle diameter of 4.5 µm is produced according to Fisher.
10% by weight of this mixed oxide powder are mixed with a silver powder, particle diameter smaller than 40 μm, a cylindrical block is cold pressed isostatically from the mixture with a pressure of 7.85.10 N / m, sintered at 790 ° C. in air for two hours and then extruded forward into a 5 mm diameter wire with an extruder. This wire is tapered to a diameter of 1.4 mm and then processed into contact rivets with a head diameter of 3.2 mm and a shaft diameter of 1.47 mm. Installed in a relay, the new material proves to be clearly superior to the state-of-the-art contact materials both in the AC service life test and when switching DC lamp loads.
4.
Aus einer wässrigen Lösung von Zinkchlorid und Meta-Wolframsäure wird ein Mischoxidpulver hergestellt, indem die Lösung in einen auf 1100°C aufgeheizten Reaktor gesprüht wird. Das auf diese Weise gewonnene Zink-Wolfram-Oxidgemisch hat einen Wolframoxidanteil von 1 Gew.-% und einen mittleren Teilchendurchmesser von 2,4 µm.
Das Oxidpulver wird wie in Beispiel 1 mit Silberpulver vermischt und zu Kontaktplättchen weiterverarbeitet.4th
A mixed oxide powder is produced from an aqueous solution of zinc chloride and meta-tungstic acid by spraying the solution into a reactor heated to 1100 ° C. The zinc-tungsten-oxide mixture obtained in this way has a tungsten oxide content of 1% by weight and an average particle diameter of 2.4 μm.
As in Example 1, the oxide powder is mixed with silver powder and further processed into contact wafers.
5.
Eine wässrige Lösung von Zinnacetat und Ammoniumheptamolybdat wird in einen Reaktor bei einer Temperatur von 800°C versprüht und so ein Oxidpulver mit einem Molybdänoxidgehalt von 350 ppm und einem mittleren Teilchendurchmesser von 1,9 µm erhalten.
Mit diesem Pulver wird wie in Beispiel 1 ein Kontaktwerkstoff hergestellt, der in einem Schaltgerät mit einer Leistung von 37 kW einer Lebensdauerprüfung nach Prüfkategorie AC1 unterzogen wird. Diese Lebendauerprüfung wird zur Durchführung einer Erwärmungsprüfung bei Dauerstromführung unterbrochen.5.
An aqueous solution of tin acetate and ammonium heptamolybdate is sprayed into a reactor at a temperature of 800 ° C., thus obtaining an oxide powder with a molybdenum oxide content of 350 ppm and an average particle diameter of 1.9 μm.
This powder is used to produce a contact material, as in Example 1, which is subjected to a service life test in accordance with test category AC1 in a switching device with an output of 37 kW. This lifetime test is interrupted in order to carry out a warming test with continuous current.
Das Ergebnis dieser Erwärmungsprüfung ist in Figur 1 dargestellt und mit einer analogen Prüfung für einen dem Stand der Technik entsprechenden Werkstoff aus 88 Gew.-% Ag, 11,6 Gew.-% SnO₂ und 0,4 Gew-% MoO₃ verglichen (Figur 2).The result of this heating test is shown in FIG. 1 and compared with an analog test for a state-of-the-art material made of 88% by weight Ag, 11.6% by weight SnO₂ and 0.4% by weight MoO₃ (FIG. 2 ).
Wie zu erkennen ist, ist das Erwärmungsverhalten des neuartigen Werkstoffes genau so gut wie das des herkömmlichen Werkstoffes, obwohl der neuartige Werkstoff, bezogen auf den gesamten Kontaktwerkstoff, lediglich einen Molybdänoxidanteil von 42 ppm aufweist, während der dem Stand der Technik entsprechende Werkstoff für das gleiche vorteilhafte Ergebnis eine Molybdänoxidmenge von 0,4 Gew.-% benötigt, also rund einhundertmal so viel.As can be seen, the heating behavior of the novel material is just as good as that of the conventional material, although the novel material, based on the entire contact material, only has a molybdenum oxide content of 42 ppm, while the state-of-the-art material for the same advantageous result requires an amount of molybdenum oxide of 0.4% by weight, that is around a hundred times as much.
6.
Eine wässrige Lösung von Zinnchlorid, Wismutoxid und Kupferchlorid wird in einen Reaktor mit einer Temperatur von 1200°C versprüht und so ein Mischoxidpulver mit einem Wismutoxidgehalt von 0,8 Gew.-% und einem Kupferoxidgehalt von 1,5 Gew.-% sowie einer mittleren Teilchengröße von 3 µm erhalten. Hieraus werden analog zu Beispiel 1 Kontaktplättchen hergestellt. Hierbei zeigt sich, dass der neuartige Kontaktwerkstoff im Gegensatz zu solchen, die auf dem herkömmlichen pulvermetallurgischem Weg hergestellt werden und Wismutoxid enthalten, gut verformbar ist. Die erhaltenen Kontaktplättchen werden in einem Motorschütz nach Prüfkategorie AC3 einer elektrischen Lebensdauerprüfung unterzogen. Figur 3 zeigt den Gesamtabbrand der Kontaktstücke als Funktion der Schaltspielzahl für den neuartigen Werkstoff als auch für einen dem Stand der Technik entsprechenden. Wie zu erkennen, liegt der Masseverlust bei dem neuartigen Werkstoff wesentlich unterhalb dem des herkömmlichen Werkstoffes, was zu einer Verlängerung der elektrischen Lebensdauer um etwa 50 % führt. Kontaktplättchen aus Silber-Zinnoxid-Kupferoxid-Wismutoxid lassen sich nach konventionellen pulvermetallurgischen Verfahren nur schwer herstellen, weil das versprödend wirkende Wismutoxid beim Verformen des Kontaktwerkstoffs zu Rissen führt.6.
An aqueous solution of tin chloride, bismuth oxide and copper chloride is sprayed into a reactor at a temperature of 1200 ° C. and thus a mixed oxide powder with a bismuth oxide content of 0.8% by weight and a copper oxide content of 1.5% by weight and an average Obtained particle size of 3 microns. From this, contact plates are produced analogously to Example 1. This shows that the new type of contact material, in contrast to those which are produced by the conventional powder metallurgical method and contain bismuth oxide, is easily deformable. The contact plates obtained are subjected to an electrical endurance test in a motor contactor according to test category AC3. FIG. 3 shows the total erosion of the contact pieces as a function of the number of switching cycles for the novel material as well as for one corresponding to the prior art. As can be seen, the mass loss in the novel material is significantly below that of the conventional material, which leads to an extension of the electrical Lifespan by about 50%. Contact plates made of silver-tin oxide-copper oxide-bismuth oxide are difficult to produce by conventional powder metallurgy processes because the embrittling bismuth oxide leads to cracks when the contact material is deformed.
Claims (18)
- A material for electrical contacts taking silver-tin oxide as basis, that contains tin-oxide areas and other oxides and/or carbides in a matrix consisting of silver or of an alloy mainly consisting of silver, characterized in that the other oxides and/or carbides are contained in the tin-oxide areas and/or in a boundary area between the tin-oxide areas and the silver matrix,
that the total fraction of the other oxides and carbides amounts of up to 40 per cent by weight relative to the amount of the tin oxide,
that the other oxides and carbides are those of molybdenum, tungsten, bismuth, antimony, germanium, vanadium, copper or indium,
and that the silver matrix - apart from an eventually soluble fraction contained therein - is free of the other oxides and carbides. - A material according to claim 1, characterized in that the total fraction of the tin oxide and of the other oxides and carbides amounts to 5 to 20 per cent by weight (relative to the total weight of the material).
- A material according to claim 2, characterized in that the total fraction of the tin oxide and of the other oxides and carbides amounts to 8 to 15 per cent by weight (relative to the total weight of the material).
- A material according to any of the above claims, characterized in that the tin-oxide areas contain at least 0.01 per cent by weight (relative to the amount of the tin oxide) of the other oxides and/or carbides.
- A material according to any of the above claims, characterized in that the tin-oxide areas contain up to 10 per cent by weight (relative to the amount of the tin oxide) of the other oxides and/or carbides.
- A material according to any of the claims 1 to 4, characterized in that the tin-oxide areas contain up to 5 per cent by weight (relative to the amount of the tin oxide) of the other oxides and/or carbides.
- A material according to any of the claims 1 to 4, characterized in that the tin-oxide areas contain up to 2.5 per cent by weight (relative to the amount of the tin oxide) of the other oxides and/or carbides.
- A material according to claim 4, characterized in that the tin-oxide areas contain 0.1 to 1.5 per cent by weight of the other oxides and/or carbides.
- A material according to any of the claims 1 to 8 that is obtained by mixing of tin-oxide powder with the other pulverized oxides and/or carbides, calcining of the mixture so that by diffusion of the other oxides and/or carbides into the tin-oxide powder particles there is produced a composite powder, separating of the excess of the other oxides and carbides from the composite powder, and the incorporating of the composite powder into a matrix consisting of silver or of a mainly silver-containing alloy.
- A material according to any of the claims 1 to 8 that is obtained by spraying of a solution of a tin salt and a salt of the metal or of the metals, the oxides or carbides of which the material shall contain in addition to the tin oxide, into a hot, oxidizing atmosphere in which, by the application of heat, the salts are converted into oxides, resulting in the precipitation of a finely divided composite powder, and incorporating of the composite powder into a matrix consisting of silver or of a mainly silver-containing alloy.
- A material according to any of the claims 1 to 8, characterized in that it contains tin-oxide particles coated with the other oxides and/or carbides.
- A material according to claim 11, characterized in that the tin-oxide particles coated with the other oxides and/or carbides are obtained by spraying into a hot, oxidizing atmosphere a suspension of tin oxide in a solution of a salt of the metal or of the salts of the metals, the oxides of which, in addition to the tin oxide, the material shall contain; in this hot, oxidizing atmosphere, the salts are thermally converted into oxides and settle down on the tin-oxide particles stemming from the suspension.
- A material according to any of the claims 1 to 8 that is obtained by spraying into a hot, oxidizing atmosphere a suspension of tin oxide and/or one or several oxides and/or carbides, that the material shall contain in addition to the tin oxide, in a solution of a salt of the metal or of the salts of the metals, the oxides of which shall be contained in the material as a residual, oxidizing component; in this hot, oxidizing atmosphere, the salts are thermally converted into oxides and settle down on the oxide particles and/or carbide particles stemming from the suspension.
- A material according to any of the above claims, characterized in that its tin-oxide areas have a diameter of less than 100 µm.
- A material according to claim 14, characterized in that its tin-oxide areas have a diameter of not more than 10 µm.
- A material according to any of the above claims, characterized in that its tin-oxide areas have a diameter of at least 0.5 µm.
- A material according to any of the above claims, characterized in that the tin is either fully or partly replaced byzinc.
- A method to produce a material for electrical contacts taking silver-tin oxide as basis according to claim 1, by- mixing a powder of silver or a mainly silver-containing alloy with a tin-oxide powder, of which the powder particles contain up to 40 weight per cent (relative to the amount of the tin-oxide) of an oxide and/or carbide of molybdenum, tungsten, bismuth, antimony, germanium, vanadium, copper, or indium,- compacting and sintering.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4219333 | 1992-06-10 | ||
| DE4219333 | 1992-06-10 | ||
| DE4311399 | 1993-04-07 | ||
| DE4311399 | 1993-04-07 | ||
| PCT/EP1993/001453 WO1993026021A1 (en) | 1992-06-10 | 1993-06-09 | Material for electrical contacts based on silver-tin oxide or silver-zinc oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0645049A1 EP0645049A1 (en) | 1995-03-29 |
| EP0645049B1 true EP0645049B1 (en) | 1996-04-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93912924A Expired - Lifetime EP0645049B1 (en) | 1992-06-10 | 1993-06-09 | Material for electrical contacts based on silver-tin oxide or silver-zinc oxide |
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| Country | Link |
|---|---|
| US (1) | US5610347A (en) |
| EP (1) | EP0645049B1 (en) |
| JP (1) | JP2896428B2 (en) |
| CN (1) | CN1036099C (en) |
| AT (1) | ATE136394T1 (en) |
| DE (1) | DE59302122D1 (en) |
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| WO (1) | WO1993026021A1 (en) |
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| BR9407450A (en) * | 1993-08-23 | 1996-11-12 | Siemens Ag | Silver-based contact material using such a contact material in an electrotechnical switching device and process for making this contact material |
| US5846288A (en) * | 1995-11-27 | 1998-12-08 | Chemet Corporation | Electrically conductive material and method for making |
| JP4383859B2 (en) * | 2001-07-18 | 2009-12-16 | エヌイーシー ショット コンポーネンツ株式会社 | Thermal fuse |
| DE112004000163T5 (en) * | 2003-01-21 | 2006-03-02 | Osram Sylvania Inc., Danvers | Electrochemical displacement deposition process for the production of metal composite powders |
| CN100341082C (en) * | 2005-01-10 | 2007-10-03 | 宁波凌日表面工程有限公司 | Method for controlling additive distribution uniformity of silver-tin anhydride electride contact material |
| US7709759B2 (en) * | 2005-07-15 | 2010-05-04 | Abb Research Ltd. | Contact element and a contact arrangement |
| CN100402195C (en) * | 2006-04-07 | 2008-07-16 | 桂林金格电工电子材料科技有限公司 | Silver composite tin oxide contact material and its preparation technology |
| CN102350502B (en) * | 2011-10-27 | 2013-01-09 | 福达合金材料股份有限公司 | Preparation method of silver-stannic oxide by using physical metallurgical coating method |
| WO2013142765A1 (en) * | 2012-03-23 | 2013-09-26 | Technic, Inc. | Silver antimony coatings and connectors |
| EP2644723B1 (en) * | 2012-03-26 | 2017-01-18 | Umicore AG & Co. KG | Composite material |
| CN102936668A (en) * | 2012-11-08 | 2013-02-20 | 哈尔滨工业大学 | TCO/Cu electrical contact material |
| CN102912177A (en) * | 2012-11-08 | 2013-02-06 | 哈尔滨工业大学 | TCO/Ag electric contact material |
| CN103589898B (en) * | 2013-11-22 | 2015-06-24 | 福达合金材料股份有限公司 | Preparation method of compound electric contact material containing silver, metal oxide and tungsten carbide and product thereof |
| CN103700532B (en) * | 2013-12-30 | 2015-10-14 | 桂林电器科学研究院有限公司 | A kind of spraying dry prepares the method for siller tin oxide electric contact material |
| CN105728714B (en) * | 2014-12-12 | 2018-12-04 | 施耐德电气工业公司 | Preparation method, device and the application of silver-metallic oxide electrical contact material |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3933485A (en) * | 1973-07-20 | 1976-01-20 | Chugai Denki Kogyo Kabushiki-Kaisha | Electrical contact material |
| GB1461176A (en) * | 1974-04-11 | 1977-01-13 | Plessey Inc | Method of producing powdered materials |
| JPS5351128A (en) * | 1976-10-21 | 1978-05-10 | Nat Res Inst Metals | Electric contact materials |
| US4141727A (en) * | 1976-12-03 | 1979-02-27 | Matsushita Electric Industrial Co., Ltd. | Electrical contact material and method of making the same |
| US4150982A (en) * | 1978-03-13 | 1979-04-24 | Chugai Denki Kogyo Kabushiki-Kaisha | AG-Metal oxides electrical contact materials containing internally oxidized indium oxides and/or tin oxides |
| DE2929630C2 (en) * | 1979-07-21 | 1983-12-15 | Dornier System Gmbh, 7990 Friedrichshafen | Process for the production of silver powder |
| DE2933338C3 (en) * | 1979-08-17 | 1983-04-28 | Degussa Ag, 6000 Frankfurt | Material for electrical contacts and process for their manufacture |
| DE2952128C2 (en) * | 1979-12-22 | 1984-10-11 | Degussa Ag, 6000 Frankfurt | Process for the pretreatment of the powder for sintered and extruded semifinished products made of silver-tin oxide for electrical contacts |
| DE3017424A1 (en) * | 1980-05-07 | 1981-11-12 | Degussa Ag, 6000 Frankfurt | MATERIAL FOR ELECTRICAL CONTACTS |
| DE3102067A1 (en) * | 1981-01-23 | 1982-08-19 | Degussa Ag, 6000 Frankfurt | MATERIAL FOR ELECTRICAL CONTACTS |
| DE3304637A1 (en) * | 1983-02-10 | 1984-08-16 | Siemens AG, 1000 Berlin und 8000 München | SINTER CONTACT MATERIAL FOR LOW VOLTAGE SWITCHGEAR |
| DE3438547C2 (en) * | 1984-10-20 | 1986-10-02 | Dornier System Gmbh, 7990 Friedrichshafen | Heat treatment process for pre-alloyed, two-phase tungsten powder |
| DE3909384A1 (en) * | 1988-03-26 | 1989-10-19 | Duerrwaechter E Dr Doduco | Semi-finished part for electrical contacts comprising a composite material based on silver/tin oxide and a powder metallurgical process for the production thereof |
| EP0369283B1 (en) * | 1988-11-17 | 1994-09-14 | Siemens Aktiengesellschaft | Sintered contact material for low-tension switchgear, particularly for contactors |
| DE69032065T2 (en) * | 1989-12-26 | 1998-10-29 | Sumitomo Metal Mining Co | Composite of silver and metal oxide and method of manufacturing the same |
| US5286441A (en) * | 1989-12-26 | 1994-02-15 | Akira Shibata | Silver-metal oxide composite material and process for producing the same |
| DE4117311A1 (en) * | 1991-05-27 | 1992-12-03 | Siemens Ag | CONTACT MATERIAL ON A SILVER BASE FOR USE IN SWITCHGEAR DEVICES IN ENERGY TECHNOLOGY |
-
1993
- 1993-06-09 JP JP6501112A patent/JP2896428B2/en not_active Expired - Fee Related
- 1993-06-09 US US08/356,222 patent/US5610347A/en not_active Expired - Lifetime
- 1993-06-09 AT AT93912924T patent/ATE136394T1/en not_active IP Right Cessation
- 1993-06-09 ES ES93912924T patent/ES2086945T3/en not_active Expired - Lifetime
- 1993-06-09 WO PCT/EP1993/001453 patent/WO1993026021A1/en active IP Right Grant
- 1993-06-09 EP EP93912924A patent/EP0645049B1/en not_active Expired - Lifetime
- 1993-06-09 DE DE59302122T patent/DE59302122D1/en not_active Expired - Lifetime
- 1993-06-10 CN CN93108295A patent/CN1036099C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| WO1993026021A1 (en) | 1993-12-23 |
| CN1036099C (en) | 1997-10-08 |
| ES2086945T3 (en) | 1996-07-01 |
| US5610347A (en) | 1997-03-11 |
| ATE136394T1 (en) | 1996-04-15 |
| DE59302122D1 (en) | 1996-05-09 |
| EP0645049A1 (en) | 1995-03-29 |
| JP2896428B2 (en) | 1999-05-31 |
| CN1085687A (en) | 1994-04-20 |
| JPH08503998A (en) | 1996-04-30 |
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