EP0369283B1 - Sintered contact material for low-tension switchgear, particularly for contactors - Google Patents
Sintered contact material for low-tension switchgear, particularly for contactors Download PDFInfo
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- EP0369283B1 EP0369283B1 EP89120515A EP89120515A EP0369283B1 EP 0369283 B1 EP0369283 B1 EP 0369283B1 EP 89120515 A EP89120515 A EP 89120515A EP 89120515 A EP89120515 A EP 89120515A EP 0369283 B1 EP0369283 B1 EP 0369283B1
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- Prior art keywords
- bismuth
- oxide
- contact material
- sintered contact
- material according
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- 239000000463 material Substances 0.000 title claims description 31
- 239000000843 powder Substances 0.000 claims description 33
- 239000000956 alloy Substances 0.000 claims description 22
- 229910045601 alloy Inorganic materials 0.000 claims description 22
- 229910002115 bismuth titanate Inorganic materials 0.000 claims description 13
- 229910052797 bismuth Inorganic materials 0.000 claims description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 10
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 9
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 9
- 229910001887 tin oxide Inorganic materials 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 2
- HSGAUFABPUECSS-UHFFFAOYSA-N [Ag][Cu][Sn][Bi] Chemical compound [Ag][Cu][Sn][Bi] HSGAUFABPUECSS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910002118 Bi2Ti2O7 Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- IVQODXYTQYNJFI-UHFFFAOYSA-N oxotin;silver Chemical compound [Ag].[Sn]=O IVQODXYTQYNJFI-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- UXVJMYXIXYVFDD-UHFFFAOYSA-N oxotin oxotungsten silver Chemical compound [W]=O.[Sn]=O.[Ag] UXVJMYXIXYVFDD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
- H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
- H01H11/048—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by powder-metallurgical processes
Definitions
- the invention relates to a sintered contact material for low-voltage switching devices in energy technology, in particular for motor contactors, with silver (Ag), tin oxide (SnO2), bismuth oxide (Bi2O3) and copper oxide (CuO) made from an internally oxidized alloy powder (IOLP) of a silver-tin bismuth -Copper starting alloy, the tin oxide being present in mass fractions of 4 to 12% and the ratio of the mass fractions of tin oxide to bismuth oxide on the one hand and of tin oxide to copper oxide in the internally oxidized alloy powder, respectively, between 8: 1 and 12: 1.
- Contact materials based on silver-tin oxide have proven to be particularly advantageous for use in low-voltage switchgear in power engineering, for example in motor contactors, but also in circuit breakers.
- Contact pieces made of silver-tin oxide have a long service life in motor contactors, but have the disadvantage that thermally stable oxide layers form on the contact surfaces when exposed to arcing, which lead to increased contact resistance. This leads to inadmissibly high excess temperatures on the switching elements when the current is conducted in the switching device, which can lead to damage to the plastic parts.
- DE-OS 33 04 637 ( ⁇ EP-A-0 182 386), DE-OS 34 21 758 ( ⁇ EP-A-0 170 812) and DE-OS 34 21 759 ( ⁇ EP-A- 0 164 664) describes sintered contact materials of the constitution AgSnO2Bi2O3CuO made from internally oxidized alloy powders, which on the one hand meet the demands made today on the number of life cycles and on the other hand the switch-on capacity. These materials can have a relatively high proportion of bismuth oxide, which is introduced either via the internally oxidized alloy powder or via a separate admixture of the bismuth oxide to the internally oxidized alloy powder. However, these materials only reach acceptable values with regard to overtemperature if the total mass fraction of oxide is limited to 8% to 11%.
- materials for electrical contacts based on AgSnO2 which additionally contain a small proportion of compounds of refractory metals, namely vanadium oxide, molybdenum oxide or bismuth titanate and preferably still molybdenum carbide or tungsten carbide.
- Such materials are said to be just as effective as tungsten oxide to be able to lower the contact point temperature, but to guarantee this lower contact point temperature for a larger number of switching cycles than a silver-tin oxide-tungsten oxide material.
- the object of the invention is to further improve a material of the constitution AgSnO2Bi2O3CuO made from internally oxidized alloy powder.
- the oxide content should be as high as possible and the overtemperature should be as high as possible low and in which the other properties are left in an optimal ratio to each other.
- the object is achieved according to the invention in the case of a contact material of the type mentioned at the outset by bismuth zirconate as a further metal oxide which is admixed with the internally oxidized alloy powder.
- Bismuth titanate may also be present within the scope of the invention.
- the bismuth zirconate is preferably present as a mixed oxide 2Bi2O3.3ZrO2 and the bismuth titanate in a stoichiometric compound Bi2Ti2O2.
- the mass fraction of bismuth zirconate and possibly bismuth titanate is between 0.1 and 5%, the total content of the oxides in mass fractions being a maximum of 20%.
- bismuth zirconate powder and / or bismuth titanate powder are added to an internally oxidized alloy powder of a predetermined composition, organic solvents, in particular propanol, being used when the internally oxidized alloy powder is mixed with the powder of the additional oxides.
- the lifetime switching number corresponds to the volume erosion of the contact material and the overtemperature corresponds to the contact resistance.
- alloys made of AgSnBiCu are melted at a temperature of approximately 1323 K (1050 ° C.). Alloy powders of the same composition are obtained by atomizing the melt with water in a pressure atomization system. After drying, the powders are sieved to ⁇ 300 ⁇ m. This portion is quantitatively internal oxidized in an oxygen-containing atmosphere at temperatures between 773 K (500 ° C) and 873 K (600 ° C), after which AgSnO2Bi2O3CuO powder the following composition can be obtained in percentages by mass:
- the specified AgSnO2Bi2O3CuO powders are powdered from bismuth zirconate (2Bi2O3.3ZrO2) and / or bismuth titanate (Bi2Ti2O7) added by wet mixing in a stirred ball mill using propanol and steel balls. After the mixture has dried, the steel balls are separated from the respective powder mixture by sieving.
- the starting powders for the contact piece production of the material examples given in the table are composed as follows:
- the internally oxidized alloy powder forms the basis with 100 percent by mass, to which the additional oxides are added in percentages by mass.
- the starting powder mixture produced is compressed with a pressure of, for example, 600 MPa and the pressed bodies obtained are at a temperature between 1123 K (850 ° C.) and 1148 K (875 ° C.) sintered in air for 2 h.
- the sintered contact pieces are hot pressed at a temperature of 923 K (650 ° C) and a pressure of, for example, 1000 MPa.
- the grain size which can be controlled by the sintering temperature and duration, runs as a front inside the AgSnO2Bi2O3CuO powder particles 1.
- the oxide precipitates 2 have an elongated, partly streak-like shape and are high in zirconate and / or titanium.
- the structure of the structure according to the figure has a favorable influence on the electrical conductivity of the oxide layers which form on the contact surfaces when exposed to arcing.
- two-layer finished molded parts are expediently manufactured with a solderable pure silver layer. These molded parts can be soldered directly onto the contact carrier, for example by motor contactors.
- the new materials which were produced by sintering an internally oxidized alloy powder with the addition of bismuth zirconate powder and / or bismuth titanate powder, in particular with a total mass fraction of about 12% oxide, result in the required improvement in the overtemperature behavior. Values from 60 K to 70 K were measured, the lifetime switching number remaining at the same high level of the prior art. The range of properties is thus improved overall, with silver being saved in every case.
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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)
- Powder Metallurgy (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Manufacture Of Switches (AREA)
Description
Die Erfindung bezieht sich auf einen Sinterkontaktwerkstoff für Niederspannungsschaltgeräte der Energietechnik, insbesondere für Motorschütze, mit Silber (Ag), Zinnoxid (SnO₂), Wismutoxid (Bi₂O₃) und Kupferoxid (CuO) hergestellt aus einem inneroxidierten Legierungspulver (IOLP) einer Silber-Zinn-Wismut-Kupfer-Ausgangslegierung, wobei das Zinnoxid in Massenanteilen von 4 bis 12 % vorhanden ist und das Verhältnis der Massenanteile von Zinnoxid zu Wismutoxid einerseits und von Zinnoxid zu Kupferoxid andererseits im inneroxidierten Legierungspulver jeweils zwischen 8:1 und 12:1 beträgt.The invention relates to a sintered contact material for low-voltage switching devices in energy technology, in particular for motor contactors, with silver (Ag), tin oxide (SnO₂), bismuth oxide (Bi₂O₃) and copper oxide (CuO) made from an internally oxidized alloy powder (IOLP) of a silver-tin bismuth -Copper starting alloy, the tin oxide being present in mass fractions of 4 to 12% and the ratio of the mass fractions of tin oxide to bismuth oxide on the one hand and of tin oxide to copper oxide in the internally oxidized alloy powder, respectively, between 8: 1 and 12: 1.
Für den Einsatz in Niederspannungsschaltgeräten der Energietechnik, beispielsweise in Motorschützen, aber auch in Leistungsschaltern haben sich Kontaktwerkstoffe auf der Basis von Silber-Zinnoxid als besonders vorteilhaft erwiesen. Kontaktstücke aus Silber-Zinnoxid erreichen in Motorschützen eine hohe Lebensdauerschaltzahl, haben aber den Nachteil, daß sich bei Lichtbogeneinwirkung auf den Kontaktflächen thermisch sehr stabile Oxidschichten ausbilden, die zu einem erhöhten Kontaktwiderstand führen. Dadurch treten bei Dauerstromführung im Schaltgerät unzulässig hohe Übertemperaturen an den Schaltgliedern auf, die insbesondere zu Schäden an den Kunststoffteilen führen können.Contact materials based on silver-tin oxide have proven to be particularly advantageous for use in low-voltage switchgear in power engineering, for example in motor contactors, but also in circuit breakers. Contact pieces made of silver-tin oxide have a long service life in motor contactors, but have the disadvantage that thermally stable oxide layers form on the contact surfaces when exposed to arcing, which lead to increased contact resistance. This leads to inadmissibly high excess temperatures on the switching elements when the current is conducted in the switching device, which can lead to damage to the plastic parts.
In der DE-OS 33 04 637 (≙ EP-A-0 182 386), der DE-OS 34 21 758 (≙ EP-A-0 170 812) und der DE-OS 34 21 759 (≙ EP-A-0 164 664) werden aus inneroxidierten Legierungspulvern hergestellte Sinterkontaktwerkstoffe der Konstitution AgSnO₂Bi₂O₃CuO beschrieben, die einerseits die heute gestellten Forderungen an die Lebensdauerschaltzahl und andererseits an das Einschaltvermögen erfüllen. Bei diesen Werkstoffen kann ein relativ hoher Wismutoxid-Anteil vorhanden sein, der entweder über das inneroxidierte Legierungspulver oder über eine separate Zumischung des Wismutoxides zum inneroxidierten Legierungspulver eingebracht wird. Allerdings erreichen diese Werkstoffe hinsichtlich der Übertemperatur nur dann akzeptable Werte, wenn der Gesamtmassenanteil an Oxid auf 8 % bis 11 % begrenzt wird.In DE-OS 33 04 637 (≙ EP-A-0 182 386), DE-OS 34 21 758 (≙ EP-A-0 170 812) and DE-OS 34 21 759 (≙ EP-A- 0 164 664) describes sintered contact materials of the constitution AgSnO₂Bi₂O₃CuO made from internally oxidized alloy powders, which on the one hand meet the demands made today on the number of life cycles and on the other hand the switch-on capacity. These materials can have a relatively high proportion of bismuth oxide, which is introduced either via the internally oxidized alloy powder or via a separate admixture of the bismuth oxide to the internally oxidized alloy powder. However, these materials only reach acceptable values with regard to overtemperature if the total mass fraction of oxide is limited to 8% to 11%.
In der DE-A-32 32 627 sind weiterhin Werkstoffe für elektrische Kontakte auf der Basis von AgSnO₂ beschrieben, welche zusätzlich noch einen kleinen Anteil von Verbindungen hochschmelzender Metalle enthalten, nämlich Vanadiumoxid, Molybdänoxid oder Wismuttitanat sowie vorzugsweise noch Molybdäncarbid oder Wolframcarbid. Solche Werkstoffe sollen ebenso wirksam wie Wolframoxid die Kontaktstellentemperatur zu senken vermögen, diese erniedrigte Kontaktstellentemperatur aber für eine größere Schaltspielzahl gewährleisten als ein Silber-Zinnoxid-Wolframoxid-Werkstoff.In DE-A-32 32 627 materials for electrical contacts based on AgSnO₂ are also described, which additionally contain a small proportion of compounds of refractory metals, namely vanadium oxide, molybdenum oxide or bismuth titanate and preferably still molybdenum carbide or tungsten carbide. Such materials are said to be just as effective as tungsten oxide to be able to lower the contact point temperature, but to guarantee this lower contact point temperature for a larger number of switching cycles than a silver-tin oxide-tungsten oxide material.
Aufgabe der Erfindung ist es demgegenüber, einen aus inneroxidiertem Legierungspulver hergestellten Werkstoff der Konstitution AgSnO₂Bi₂O₃CuO weiter zu verbessern. Dabei soll zwecks Silbereinsparung der Oxidanteil möglichst hoch und trotzdem die Übertemperatur möglichst niedrig und bei dem die übrigen Eigenschaften in einem optimalen Verhältnis zueinander belassen sind.In contrast, the object of the invention is to further improve a material of the constitution AgSnO₂Bi₂O₃CuO made from internally oxidized alloy powder. In order to save silver, the oxide content should be as high as possible and the overtemperature should be as high as possible low and in which the other properties are left in an optimal ratio to each other.
Die Aufgabe ist erfindungsgemäß bei einem Kontaktwerkstoff der eingangs genannten Art durch Wismutzirkonat als weiteres Metalloxid, das dem inneroxidierten Legierungspulver zugemischt ist, gelöst. Im Rahmen der Erfindung kann zusätzlich auch Wismuttitanat vorhanden sein. Vorzugsweise liegen das Wismutzirkonat als Mischoxid 2Bi₂O₃.3ZrO₂ und das Wismuttitanat in stöchiometrischer Verbindung Bi₂Ti₂O₇ vor. Dabei beträgt der Massenanteil an Wismutzirkonat und gegebenenfalls Wismuttitanat zwischen 0,1 und 5 %, wobei der Gesamtgehalt der Oxide in Massenanteilen maximal 20 % ist.The object is achieved according to the invention in the case of a contact material of the type mentioned at the outset by bismuth zirconate as a further metal oxide which is admixed with the internally oxidized alloy powder. Bismuth titanate may also be present within the scope of the invention. The bismuth zirconate is preferably present as a mixed oxide 2Bi₂O₃.3ZrO₂ and the bismuth titanate in a stoichiometric compound Bi₂Ti₂O₂. The mass fraction of bismuth zirconate and possibly bismuth titanate is between 0.1 and 5%, the total content of the oxides in mass fractions being a maximum of 20%.
Zur Herstellung eines solchen Werkstoffes wird einem inneroxidierten Legierungspulver vorgegebener Zusammensetzung Wismutzirkonatpulver und/oder Wismuttitanatpulver hinzugefügt, wobei beim Naßmischen des inneroxidierten Legierungspulvers mit dem Pulver der Zusatzoxide organische Lösungsmittel, insbesondere Propanol, verwendet werden.To produce such a material, bismuth zirconate powder and / or bismuth titanate powder are added to an internally oxidized alloy powder of a predetermined composition, organic solvents, in particular propanol, being used when the internally oxidized alloy powder is mixed with the powder of the additional oxides.
Im Rahmen der Erfindung ergab es sich überraschenderweise, daß speziell durch den Zusatz von Wismutzirkonatpulver und weiterhin von Wismuttitanatpulver zu einem inneroxidierten Legierungspulver aus AgSnO₂Bi₂O₃CuO gegenüber dem Stand der Technik bei hoher Lebensdauerschaltzahl eine Absenkung der Übertemperatur erreicht wird.In the context of the invention, it was surprisingly found that, in particular, the addition of bismuth zirconate powder and further of bismuth titanate powder to an internally oxidized alloy powder made of AgSnO₂Bi₂O₃CuO compared to the prior art results in a reduction in the excess temperature with a high number of life cycles.
Weitere Einzelheiten und Vorteile der Erfindung ergeben sich aus der nachfolgenden Beschreibung des Verfahrens zur Herstellung von Kontaktstücken aus dem neuen Werkstoff, wobei auf eine Figur und weiterhin eine Tabelle mit Einzelbeispielen für unterschiedliche Werkstoffzusammensetzungen Bezug genommen wird. Es zeigen die Figur ein typisches Gefügebild des neuen Werkstoffes und die Tabelle Meßwerte für die Lebensdauerschaltzahl und für die Übertemperatur.Further details and advantages of the invention result from the following description of the method for producing contact pieces from the new material, reference being made to a figure and also to a table with individual examples for different material compositions. The figure shows a typical microstructure of the new material and the table of measured values for the lifetime switching number and for the overtemperature.
Die Lebensdauerschaltzahl korrespondiert bekanntermaßen mit dem Volumenabbrand des Kontaktwerkstoffes und die Übertemperatur mit dem Kontaktwiderstand. Es sind vier Beispiele des Standes der Technik und fünf Ausführungsbeispiele der Erfindung gegenübergestellt.As is known, the lifetime switching number corresponds to the volume erosion of the contact material and the overtemperature corresponds to the contact resistance. Four examples of the prior art and five exemplary embodiments of the invention are compared.
Zur Herstellung der inneroxidierten Legierungspulver für die in der Tabelle angegebenen Beispiele werden Legierungen aus AgSnBiCu bei einer Temperatur von etwa 1323 K (1050°C) erschmolzen. Durch Zerstäuben der Schmelze mit Wasser in einer Druckverdüsungsanlage werden daraus gleich zusammengesetzte Legierungspulver erhalten. Nach dem Trocknen werden die Pulver auf < 300 µm abgesiebt. Dieser Anteil wird in sauerstoffhaltiger Atmosphäre bei Temperaturen zwischen 773 K (500°C) und 873 K (600°C) quantitativ inneroxidiert, wonach AgSnO₂Bi₂O₃CuO-Pulver folgender Zusammensetzung in Massenanteilen in Prozent erhalten werden:
Den angegebenen AgSnO₂Bi₂O₃CuO-Pulvern werden Pulver aus Wismutzirkonat (2Bi₂O₃.3ZrO₂) und/oder Wismuttitanat (Bi₂Ti₂O₇) durch Naßmischen in einer Rührwerkskugelmühle unter Verwendung von Propanol und Stahlkugeln zugesetzt. Nach dem Trocknen des Gemisches werden die Stahlkugeln von der jeweiligen Pulvermischung durch Absieben getrennt. Die Ausgangspulver für die Kontaktstückherstellung der in der Tabelle angegebenen Werkstoffbeispiele sind wie folgt zusammengesetzt:
Bei dieser Aufstellung bildet das inneroxidierte Legierungspulver die Basis mit 100 Massenanteilen in Prozent, zu denen die Zusatzoxide in Massenanteilen bezogen auf 100 % hinzugemischt werden. Bei der Herstellung der Kontaktstücke wird das erzeugte Ausgangspulvergemisch mit einem Preßdruck von z.B. 600 MPa verdichtet und werden die erhaltenen Preßkörper bei einer Temperatur zwischen 1123 K (850°C) und 1148 K (875°C) über 2 h an Luft gesintert. Zur Erzielung einer kleinen Restporosität werden die gesinterten Kontaktstücke bei einer Temperatur von 923 K (650°C) und einem Druck von z.B. 1000 MPa warm nachgepreßt. Eine weitere Verdichtung und Verfestigung wird durch eine zweite Sinterung bei einer Temperatur zwischen 1123 K (850°C) und 1148 K (875°C) während 2 h erreicht. Anschließend erfolgt als letzter Herstellschritt ein Kaltkalibrieren zur Endform bei einem Druck von z.B. 1000 MPa.In this list, the internally oxidized alloy powder forms the basis with 100 percent by mass, to which the additional oxides are added in percentages by mass. In the manufacture of the contact pieces, the starting powder mixture produced is compressed with a pressure of, for example, 600 MPa and the pressed bodies obtained are at a temperature between 1123 K (850 ° C.) and 1148 K (875 ° C.) sintered in air for 2 h. To achieve a small residual porosity, the sintered contact pieces are hot pressed at a temperature of 923 K (650 ° C) and a pressure of, for example, 1000 MPa. Further densification and solidification is achieved by a second sintering at a temperature between 1123 K (850 ° C) and 1148 K (875 ° C) for 2 hours. Then the last manufacturing step is a cold calibration to the final shape at a pressure of eg 1000 MPa.
Bei obigen Werkstoffen wird nach der Sinterung ein spezifisches Gefüge mit unterschiedlichen Oxidteilchengrößen und -formen sowie Oxidkonzentrationen erhalten, das in der Figur in Anlehnung an ein lichtmikroskopisches Gefügebild wiedergegeben ist. Erkennbar sind die ehemaligen Teilchen des inneroxidierten Legierungspulvers 1 mit Oxidfeinausscheidungen 2 und angelagerten gröberen Oxidausscheidungen 3. Durch die Umkörnung der Oxidausscheidungen an den Grenzen des inneroxidierten Legierungspulvers aus AgSnO₂Bi₂O₃CuO entsteht ein umschließendes, nahezu oxidfreies Silbernetzwerk 4, das eine hohe Sinterverdichtung bewirkt und die es aufgrund ihrer Duktilität erlaubt, einen nahezu porenfreien Kontaktwerkstoff durch Kaltverdichten herzustellen.In the above materials, a specific structure with different oxide particle sizes and shapes and oxide concentrations is obtained after sintering, which is shown in the figure based on a light microscopic micrograph. The former particles of the inner-oxidized
Die Umkörnung, die durch die Sintertemperatur und Sinterdauer steuerbar ist, verläuft als Front ins Innere der AgSnO₂Bi₂O₃CuO-Pulverteilchen 1. In dieser Front besitzen die Oxidausscheidungen 2 eine längliche, zum Teil schlierenartige Form und sind hoch zirkonat- und/oder titanathaltig.The grain size, which can be controlled by the sintering temperature and duration, runs as a front inside the
Überraschenderweise führt der Gefügeaufbau gemäß der Figur zu einer günstigen Beeinflussung der elektrischen Leitfähigkeit der sich bei Lichtbogeneinwirkung auf den Kontaktflächen ausbildenden Oxidschichten.Surprisingly, the structure of the structure according to the figure has a favorable influence on the electrical conductivity of the oxide layers which form on the contact surfaces when exposed to arcing.
Zur Verwendung als Kontaktstücke in Niederspannungsschaltgeräten der Energietechnik werden zweckmäßigerweise Zweischichten-Fertigformteile mit einer lötfähigen Reinsilberschicht gefertigt. Diese Formteile können unmittelbar auf die Kontaktträger beispielsweise von Motorschützen aufgelötet werden.For use as contact pieces in low-voltage switchgear In energy technology, two-layer finished molded parts are expediently manufactured with a solderable pure silver layer. These molded parts can be soldered directly onto the contact carrier, for example by motor contactors.
Mit nach obiger Vorschrift hergestellten Kontaktstücken wurden Lebensdauer- und Erwärmungsprüfungen in Motorschützen durchgeführt. Es wurden Siemens-Schütze mit einem AC-3-Nennbetriebsstrom von 250 A verwendet. Wesentliche Kenngrößen sind dabei die Lebensdauerschaltzahl bei 4-fachem AC-3-Nennbetriebsstrom (4 x Ie AC-3=1000 A) und die maximale Übertemperatur der Anschlußschienen des Schaltgerätes bei Dauerführung des AC-1-Nennbetriebsstromes von IeAC-1=300 A. Die Messungen der Übertemperatur wurden während der Lebensdauerprüfung bis zu einer Schaltzahl von 5.10⁴ durchgeführt. Die zugehörigen Meßwerte sind in der Tabelle angegeben.With contact pieces manufactured according to the above regulation, service life and heating tests were carried out in motor contactors. Siemens contactors with an AC-3 nominal operating current of 250 A were used. Significant parameters are the number of lifespan cycles with 4-fold AC-3 nominal operating current (4 x I e AC-3 = 1000 A) and the maximum overtemperature of the switching device's connecting rails when the AC-1 nominal operating current is kept at I eAC-1 = 300 A. The measurements of the overtemperature were carried out during the service life test up to a switching number of 5.10⁴. The associated measured values are given in the table.
Die vier Vergleichswerkstoffe des oben abgehandelten Standes der Technik, die durch Sinterung von inneroxidierten Legierungspulvern hergestellt wurden, sind eingangs aufgelistet. Die Meßwerte zeigen, daß bezüglich Übertemperatur Werkstoffe der Konstitution AgSnO₂Bi₂O₃CuO und AgSnO₂Bi₂O₃CuO + Bi₂O₃ Werte unterhalb von 80 K nicht erreichen, was in der Praxis in manchen Fällen als unbefriedigend angesehen wird.The four comparison materials of the prior art dealt with above, which were produced by sintering internally oxidized alloy powders, are listed at the beginning. The measured values show that materials of the constitution AgSnO₂Bi₂O₃CuO and AgSnO₂Bi₂O₃CuO + Bi₂O₃ do not reach values below 80 K, which in practice is considered unsatisfactory in some cases.
Hier ergeben nun die neuen Werkstoffe, die durch Sinterung eines inneroxidierten Legierungspulvers unter Zumischung von Wismutzirkonatpulver und/oder Wismuttitanatpulver hergestellt wurden, insbesondere bei einem Gesamtmassenanteil von etwa 12 % Oxid, die geforderte Verbesserung des Übertemperaturverhaltens. Es wurden Werte von 60 K bis 70 K gemessen, wobei die Lebensdauerschaltzahl auf dem gleichen hohen Niveau des Standes der Technik bleibt. Damit ist das Eigenschaftspektrum insgesamt verbessert, wobei sich in jedem Fall eine Silbereinsparung ergibt.
Claims (9)
- Sintered contact material for low voltage switchgear for power engineering, in particular for a motor contactor, containing silver (Ag), tin oxide (SnO₂), bismuth oxide (Bi₂O₃) and copper oxide (CuO) and produced from an internally oxidised alloy powder (IOAP) of a silver-tin-bismuth-copper starting alloy, the tin oxide content being from 4 to 12% by weight and the ratio of tin oxide to bismuth oxide on the one hand and of tin oxide to copper oxide on the other hand as weight percentages in the internally oxidised alloy powder being in each case between 8:1 and 12:1, characterised by bismuth zirconate (2Bi₂O₃.3ZrO₂) as a further metal oxide which is admixed with the internally oxidised alloy powder.
- Sintered contact material according to claim 1, characterised in that in addition bismuth titanate (Bi₂Ti₂O₇) is present.
- Sintered contact material according to claim 1 and claim 2, characterised in that the bismuth zirconate is present as a mixed oxide and the bismuth titanate as a stoichiometric compound.
- Sintered contact material according to claim 1 and claim 2, characterised in that the total amount of bismuth zirconate and bismuth titanate is between 0.1 and 5% by weight.
- Sintered contact material according to claim 3, characterised in that the total amount of bismuth zirconate and bismuth titanate is between 0.5 and 4% by weight.
- Sintered contact material according to claim 4, characterised in that the amount of bismuth zirconate is between 0.5 and 3% by weight.
- Sintered contact material according to claim 2, characterised in that the amount of bismuth titanate is between 0.1 and 2% by weight.
- Sintered contact material according to one of the preceding claims, characterised in that the total oxide content of oxides amounts to at most 20% by weight.
- Sintered contact material according to claim 6, characterised in that the amount of all oxides is about 12% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3838950 | 1988-11-17 | ||
| DE3838950 | 1988-11-17 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0369283A2 EP0369283A2 (en) | 1990-05-23 |
| EP0369283A3 EP0369283A3 (en) | 1991-03-13 |
| EP0369283B1 true EP0369283B1 (en) | 1994-09-14 |
Family
ID=6367374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89120515A Expired - Lifetime EP0369283B1 (en) | 1988-11-17 | 1989-11-06 | Sintered contact material for low-tension switchgear, particularly for contactors |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4980125A (en) |
| EP (1) | EP0369283B1 (en) |
| JP (1) | JP2810162B2 (en) |
| BR (1) | BR8905828A (en) |
| DE (1) | DE58908359D1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4117311A1 (en) * | 1991-05-27 | 1992-12-03 | Siemens Ag | CONTACT MATERIAL ON A SILVER BASE FOR USE IN SWITCHGEAR DEVICES IN ENERGY TECHNOLOGY |
| DE4201940A1 (en) * | 1992-01-24 | 1993-07-29 | Siemens Ag | SINTER COMPOSITE FOR ELECTRICAL CONTACTS IN SWITCHGEAR OF ENERGY TECHNOLOGY |
| 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 |
| JP3441074B2 (en) * | 1992-09-16 | 2003-08-25 | ドドウコ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・ウント・コンパニー・ドクトル・オイゲン・デュルベヒテル | Member for electrical contact based on silver-tin oxide or silver-zinc oxide and method for producing the same |
| DE19503182C1 (en) * | 1995-02-01 | 1996-05-15 | Degussa | Sintered material used as electrical contacts for switching amperage rating |
| US20090202855A1 (en) * | 2008-01-09 | 2009-08-13 | Saxton David M | Porous sliding bearing and method of construction thereof |
| US8320089B1 (en) | 2009-04-16 | 2012-11-27 | Musco Corporation | Apparatus, method, and system for integrating ground fault circuit interrupters in equipment-grounded high voltage systems |
| CN108772053B (en) * | 2018-06-29 | 2020-12-15 | 辽宁石油化工大学 | Bismuth titanate/bismuth oxide photocatalyst and preparation method and application thereof |
| CN113502414B (en) * | 2021-06-10 | 2022-01-07 | 暨南大学 | High-thermal-conductivity aviation aluminum alloy and application thereof in preparation of ultra-large-area LED light source radiator |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4141727A (en) * | 1976-12-03 | 1979-02-27 | Matsushita Electric Industrial Co., Ltd. | Electrical contact material and method of making the same |
| DE3232627A1 (en) * | 1981-09-24 | 1983-04-07 | Doduco KG Dr. Eugen Dürrwächter, 7530 Pforzheim | Material for electrical contacts |
| DE3146972A1 (en) * | 1981-11-26 | 1983-06-01 | Siemens AG, 1000 Berlin und 8000 München | METHOD FOR PRODUCING MOLDED PARTS FROM CADMIUM-FREE SILVER METAL OXIDE COMPOSITIONS 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 |
| EP0152606B1 (en) * | 1984-01-30 | 1987-09-09 | Siemens Aktiengesellschaft | Contact material and production of electric contacts |
| DE3421758A1 (en) * | 1984-06-12 | 1985-12-12 | Siemens AG, 1000 Berlin und 8000 München | SINTER CONTACT MATERIAL FOR LOW VOLTAGE SWITCHGEAR IN ENERGY TECHNOLOGY AND METHOD FOR THE PRODUCTION THEREOF |
| DE3421759A1 (en) * | 1984-06-12 | 1985-12-12 | Siemens AG, 1000 Berlin und 8000 München | SINTER CONTACT MATERIAL FOR LOW VOLTAGE SWITCHGEAR OF ENERGY TECHNOLOGY |
-
1989
- 1989-11-06 EP EP89120515A patent/EP0369283B1/en not_active Expired - Lifetime
- 1989-11-06 DE DE58908359T patent/DE58908359D1/en not_active Expired - Fee Related
- 1989-11-15 JP JP1295181A patent/JP2810162B2/en not_active Expired - Lifetime
- 1989-11-17 US US07/438,740 patent/US4980125A/en not_active Expired - Fee Related
- 1989-11-17 BR BR898905828A patent/BR8905828A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JP2810162B2 (en) | 1998-10-15 |
| DE58908359D1 (en) | 1994-10-20 |
| EP0369283A2 (en) | 1990-05-23 |
| BR8905828A (en) | 1990-06-12 |
| US4980125A (en) | 1990-12-25 |
| EP0369283A3 (en) | 1991-03-13 |
| JPH02185937A (en) | 1990-07-20 |
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