EP0164664B1 - Sintered contact material for low-tension energy switchgear - Google Patents
Sintered contact material for low-tension energy switchgear Download PDFInfo
- Publication number
- EP0164664B1 EP0164664B1 EP85106748A EP85106748A EP0164664B1 EP 0164664 B1 EP0164664 B1 EP 0164664B1 EP 85106748 A EP85106748 A EP 85106748A EP 85106748 A EP85106748 A EP 85106748A EP 0164664 B1 EP0164664 B1 EP 0164664B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cuo
- mass
- contact material
- materials
- contact
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000463 material Substances 0.000 title claims abstract description 43
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 239000004332 silver Substances 0.000 claims abstract description 7
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract 8
- 239000000843 powder Substances 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 abstract description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 229910052797 bismuth Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010944 silver (metal) Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 239000010946 fine silver Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 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
- 239000012634 fragment Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
- H01H1/023—Composite material having a noble metal as the basic material
- H01H1/0237—Composite material having a noble metal as the basic material and containing oxides
- H01H1/02372—Composite material having a noble metal as the basic material and containing oxides containing as major components one or more oxides of the following elements only: Cd, Sn, Zn, In, Bi, Sb or Te
- H01H1/02376—Composite material having a noble metal as the basic material and containing oxides containing as major components one or more oxides of the following elements only: Cd, Sn, Zn, In, Bi, Sb or Te containing as major component SnO2
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
-
- 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
Definitions
- the invention relates to a low-voltage switchgear contact material of energy technology made of AgSn0 2 , Bi 2 0 3 and CuO.
- contact materials based on silver metal oxides have proven to be particularly advantageous.
- cadmium oxide was used as the active component, with these contact materials in particular fulfilling the desired electrical-technological properties and having proven themselves in long-term use of switching devices.
- cadmium is known to be one of the toxic heavy metals and when the contact pieces burn off, CdO is also released into the environment, efforts have been underway for some time to replace the CdO as completely as possible with other metal oxides.
- the substitute materials should have just as little arc burn-off, as well as low welding power and, in particular, low heating with continuous current flow, like the proven AgCdO contact materials.
- a contact material which is made especially of a silver alloy with 3 to 15 wt.% Tin, 0.01 to 1 wt.% Bismuth and 0.1 to 8.5 wt .-% copper is produced. If necessary, 0.01 to 0.5% by weight of one or more elements of the iron group may also be present in this material.
- the silver metal alloys are oxidized there as thin sheets at 650 ° C. for about 200 hours. Electrical contact pieces were produced from the contact materials produced in this way and tested with regard to the switching properties on the one hand and the mechanical properties on the other. The temperature behavior was not examined. If the starting alloys had the AgSnBiCu constitution, comparatively high tin contents (> 8.5%) were present.
- an electrical contact material with a metal component as the main component and the rest of a metal oxide as a secondary component is also known, in which the metal component is essentially silver with or without tin and the metal oxide component is essentially bismuth oxide and tin oxide, where the amount of bismuth in bismuth oxide is 1.5 to 6% by weight and the total amount of tin from the metal and metal oxide components is 0.1 to 6% by weight, based on the sum of the metal component and the metal content in the metal oxide component.
- the metal oxide component can contain copper or zinc oxide as an additive, in which case the metal of the additional oxide is 0.016 to 1.2% by weight, based on the sum of the metal component and the metals of the metal oxide components.
- the Sn0 2 content is usually low, in particular below 4% by weight. Only in one of the materials that can be taken from DE-A-27 54 335 (Example 18) does the Sn content be higher (4Bi-6Sn-1,2Cu-Ag), in which case the Sn0 2 volume content of the sum oxides is comparatively low .
- the object of the invention is therefore to specify specific materials of the constitution AgSn0 2 Bi 2 O 3 C U O for use in low-voltage switchgear in energy technology.
- the object is achieved with a material of the constitution AgSn0 2 Bi 2 O 3 C U O according to the invention in that the Sn0 2 mass fraction in the range from 4 to 8%, the Bi 2 0 3 mass fraction between 0.5 and 4% and the CuO mass fraction is between 0.3 and 1%, with the proviso that the contact material is a sintered material, available from an internally oxidized alloy powder (IOLP), where the volume fraction of total metal oxide is between 10 and 25% with an Sn0 2 volume fraction 70% of the total amount of oxide, and the ratio of the mass fraction in percent of Sn0 2 to CuO is between 8: 1 and 12 : 1 lies.
- IOLP internally oxidized alloy powder
- the invention was based on the knowledge that a selection from those in GB-A-20 55 398 on the one hand and DE-A-27 54 335 on the other hand has surprisingly favorable temperature properties with regard to the concentration information provided there if the above parameters are met. It is particularly important that the material is produced by powder metallurgy using internally oxidized alloy powder.
- An alloy of AgSnBiCu of the specified composition is melted at 1353 K from 93.60% fine silver grains, 5.20% tin grains, 0.6% metallic bismuth as fragments and 0.6% copper in rod form.
- an alloy powder of the same composition is obtained.
- the powder fraction is sieved to ⁇ 200 ⁇ m. This proportion is internally oxidized in an oxygen-containing atmosphere between 723 K and 872 K, after which a composite powder of AgSn0 2 Bi 2 O 3 Cu0 of the composition in mass proportions of 92.10% Ag, 6.50% Sn0 2 , 0.66% Bi 2 0 3 and 0.74% CuO is obtained.
- Such a composite powder is quantitatively completely internally oxidized and is referred to as IOLP.
- the composite powder is used to produce contact pieces by pressing in a die with 600 MPa.
- the contact pieces are sintered at 1173 K for one hour in air.
- the contact pieces are compacted by hot pressing at 923 K at 900 MPa. Further compression and solidification is achieved by a second sintering at 1173 K for one hour in air and a subsequent cold compression at 800 MPa.
- Metallographic micrographs show that the structure of the contact material thus produced is fine and uniform with an average oxide particle size of 1.5 ⁇ m.
- Example 2 In a further exemplary embodiment, method steps as in Example 1 were selected; However, starting materials of the following composition in mass fractions were assumed: 93.96% fine silver grains, 4.00% tin grains, 1.64% metallic bismuth and 0.40% copper, from which an alloy is melted. Corresponding alloy powder is produced from this in the manner described above.
- an IOLP of AgSn0 2 Bi 2 O 3 Cu0 of the composition in mass fractions of 92.70% Ag, 5.01% Sn0 2 , 1.80% Bi 2 0 3 and 0.49% CuO is obtained.
- This IOLP is the starting material for the material and the contact pieces to be made from it.
- the structure of this material essentially corresponds to the material according to Example 1, except for a larger grain size.
- the welding force of the contact materials produced according to the invention was determined in a test switch.
- the measured values obtained essentially correspond to those of the AgCd012Bi 2 0 3 1.0 contact material produced from internally oxidized alloy powder.
- service life and heating tests were carried out in motor contactors.
- the key parameters are the AC4 service life switching numbers of the contact pieces and the overtemperature of the current paths. Compared to AgCd012Bi 2 0 3 1.0 materials, the lifespan switching numbers are about a factor of 1.8 higher, with the excess temperatures only showing up to 10 * C higher values.
- test data of the new materials are shown in the table in comparison to the known material.
- the tin content is reduced to a suitable range, and thus at least, based on the predetermined volume fraction of the sum metal oxides the relative Bi 2 0 3 proportion increases, which leads to unexpectedly good results.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Contacts (AREA)
- Manufacture Of Switches (AREA)
- Glass Compositions (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
Die Erfindung bezieht sich auf einen Niederspannungsschaltgeräte-Kontaktwerkstoff der Energietechnik aus AgSn02, Bi203 und CuO.The invention relates to a low-voltage switchgear contact material of energy technology made of AgSn0 2 , Bi 2 0 3 and CuO.
Mit der nicht vorveröffentlichten EP-A-0 118 708, die einen Stand der Technik gemäß Art. 54 (3) EPÜ definiert, wird ein solcher Werkstoff vorgeschlagen, bei dem der Volumenanteil an Summenmetalloxid zwischen 10 % und 25 % mit einem Sn02-Volumenanteil 70 % der Gesamtoxidmenge beträgt.With the unpublished EP-A-0 118 708, which defines a state of the art according to Art. 54 (3) EPC, such a material is proposed in which the volume fraction of total metal oxide is between 10% and 25% with an Sn02 volume fraction Is 70% of the total amount of oxide.
Für Niederspannungsschaltgeräte der Energietechnik, z.B. in Schützen oder Selbstschaltern, haben sich Kontaktwerkstoffe auf der Basis von Silber-Metalloxiden (AgMeO) als besonders vorteilhaft erwiesen. In der Vergangenheit wurde als Wirkkomponente insbesondere Cadmiumoxid verwendet, wobei speziell diese Kontaktwerkstoffe die gewünschten elektrisch-technologischen Eigenschaften erfüllen und sich im praktischen Langzeiteinsatz von Schaltgeräten bewährt haben. Da aber Cadmium bekanntermaßen zu den toxischen Schwermetallen zählt und beim Abbrand der Kontaktstücke CdO auch an die Umgebung abgegeben wird, sind seit einiger Zeit Bestrebungen im Gange, das CdO möglichst vollständig durch andere Metalloxide zu ersetzen. Die Ersatzwerkstoffe sollen aber einen ebenso kleinen Abbrand im Lichtbogen, sowie geringe Schweißkraft und insbesondere geringe Erwärmung bei Dauerstromführung wie die bewährten AgCdO-Kontaktwerkstoffe aufweisen.For low-voltage switchgear in energy technology, e.g. In contactors or automatic switches, contact materials based on silver metal oxides (AgMeO) have proven to be particularly advantageous. In the past, in particular cadmium oxide was used as the active component, with these contact materials in particular fulfilling the desired electrical-technological properties and having proven themselves in long-term use of switching devices. However, since cadmium is known to be one of the toxic heavy metals and when the contact pieces burn off, CdO is also released into the environment, efforts have been underway for some time to replace the CdO as completely as possible with other metal oxides. However, the substitute materials should have just as little arc burn-off, as well as low welding power and, in particular, low heating with continuous current flow, like the proven AgCdO contact materials.
Es wurde bisher versucht, das Cadmium durch Zinn oder Zink zu ersetzen. Die bekannten Vorschläge mit AgSn02 und AgZnO-Kontaktwerkstoffen konnten jedoch insgesamt nicht die hochwertigen Eigenschaften von AgCdO-Kontaktstücken erreichen. Insbesondere bei Kontaktstücken aus AgS- n02 als Alternativwerkstoff zu AgCdO hat sich gezeigt, daß dieser aufgrund seiner höheren thermischen Stabilität nach Lichtbogeneinwirkung durch Bildung von Oxiddeckschichten einen gegenüber AgCdO erhöhten Übergangswiderstand aufweist. Dadurch treten im stromführenden Zustand des Schaltgerätes unzulässig hohe Übertemperaturen an den Schaltgliedern auf, die zu Schäden am Schaltgerät führen können. Andererseits weisen aber AgSn02-Kontaktstücke gegenüber AgCdO einen geringeren Abbrand auf, was zu einer erhöhten Kontaktlebensdauer führt. Daher kann vorteilhafterweise die Größe der benötigten Kontaktstücke im Vergleich zu AgCdO verringert werden, wodurch eine nicht unerhebliche Silbereinsparung erzielt wird.So far, attempts have been made to replace the cadmium with tin or zinc. However, the known proposals with AgSn0 2 and AgZnO contact materials could not achieve the high-quality properties of AgCdO contact pieces. In particular in the case of contact pieces made of AgS-n0 2 as an alternative material to AgCdO, it has been shown that this has an increased contact resistance compared to AgCdO due to its higher thermal stability after exposure to arcing through the formation of oxide cover layers. As a result, inadmissibly high excess temperatures occur on the switching elements when the switching device is live, which can lead to damage to the switching device. On the other hand, however, AgSn0 2 contact pieces have a lower erosion compared to AgCdO, which leads to an increased contact life. Therefore, the size of the required contact pieces can advantageously be reduced in comparison to AgCdO, whereby a not inconsiderable silver saving is achieved.
Es ist bekannt, zur Verbesserung von AgSn02-Basiswerkstoffen weitere Metalloxide als zusätzliche Wirkkomponenten vorzusehen. Aus der GB-A-20 55 398 ist ein Kontaktwerkstoff bekannt, der speziell aus einer Silber-Legierung mit 3 bis 15 Gew.-% Zinn, 0,01 bis 1 Gew.-% Wismut und 0,1 bis 8,5 Gew.-% Kupfer hergestellt wird. Gegebenenfalls können bei diesem Werkstoff noch 0,01 bis 0,5 Gew.-% von einem oder mehreren Elementen der Eisengruppe vorhanden sein. Zur Herstellung des Kontaktwerkstoffes mit Metalloxiden werden dort die Silber-Metallegierungen als dünne Bleche bei 650 ° C für etwa 200 Stunden oxidiert. Von den solchermaßen erzeugten Kontaktwerkstoffen wurden elektrische Kontaktstücke hergestellt und hinsichtlich der Schalteigenschaften einerseits und der mechanischen Eigenschaften andererseits geprüft. Das Temperaturverhalten wurde nicht untersucht. Sofern die Ausgangslegierungen die Konstitution AgSnBiCu hatten, waren dabei jeweils vergleichsweise hohe Zinngehalte (> 8,5 %) vorhanden.It is known to provide further metal oxides as additional active components to improve AgSnO 2 base materials. From GB-A-20 55 398 a contact material is known which is made especially of a silver alloy with 3 to 15 wt.% Tin, 0.01 to 1 wt.% Bismuth and 0.1 to 8.5 wt .-% copper is produced. If necessary, 0.01 to 0.5% by weight of one or more elements of the iron group may also be present in this material. To produce the contact material with metal oxides, the silver metal alloys are oxidized there as thin sheets at 650 ° C. for about 200 hours. Electrical contact pieces were produced from the contact materials produced in this way and tested with regard to the switching properties on the one hand and the mechanical properties on the other. The temperature behavior was not examined. If the starting alloys had the AgSnBiCu constitution, comparatively high tin contents (> 8.5%) were present.
Aus der DE-A-27 54 335 ist weiterhin ein elektrischer Kontaktwerkstoff mit einer Metallkomponente als Hauptkomponente und als Rest einem Metalloxid als Nebenkomponente bekannt, bei dem die Metallkomponente im wesentlichen Silber mit oder ohne Zinn und die Metalloxidkomponente im wesentlichen Wismutoxid und Zinnoxid sind, wobei die Menge des Wismuts im Wismutoxid 1,5 bis 6 Gew.-% und die Gesamtmenge des Zinns aus der Metall- und der Metalloxidkomponente 0,1 bis 6 Gew.-% bezogen auf die Summe der Metallkomponente und des Metallanteils in der Metalloxidkomponente betragen. Zusätzlich kann die Metalloxidkomponente Kupfer- oder Zinkoxid als Zusatz enthalten, wobei in diesem Fall das Metall des Zusatzoxids 0,016 bis 1,2 Gew.-% bezogen auf die Summe der Metallkomponente und der Metalle der Metalloxidkomponenten beträgt. Bei den im einzelnen beschriebenen Werkstoffen, die hinsichtlich Härte, Verschweißneigung und Abbrand untersucht wurden, ist der Sn02-Gehalt meist gering, insbesondere unter 4 Gew.-%. Lediglich bei einem der DE-A-27 54 335 entnehmbaren Werkstoff (Beispiel 18) liegt der Sn-Anteil höher (4Bi-6Sn-1,2Cu-Ag), wobei in diesem Fall der Sn02-Volumenanteil an den Summenoxiden vergleichsweise gering ist.From DE-A-27 54 335 an electrical contact material with a metal component as the main component and the rest of a metal oxide as a secondary component is also known, in which the metal component is essentially silver with or without tin and the metal oxide component is essentially bismuth oxide and tin oxide, where the amount of bismuth in bismuth oxide is 1.5 to 6% by weight and the total amount of tin from the metal and metal oxide components is 0.1 to 6% by weight, based on the sum of the metal component and the metal content in the metal oxide component. In addition, the metal oxide component can contain copper or zinc oxide as an additive, in which case the metal of the additional oxide is 0.016 to 1.2% by weight, based on the sum of the metal component and the metals of the metal oxide components. In the materials described in detail, which were examined with regard to hardness, tendency to weld and burn off, the Sn0 2 content is usually low, in particular below 4% by weight. Only in one of the materials that can be taken from DE-A-27 54 335 (Example 18) does the Sn content be higher (4Bi-6Sn-1,2Cu-Ag), in which case the Sn0 2 volume content of the sum oxides is comparatively low .
Erprobungen haben ergeben, daß die bekannten Werkstoffe noch nicht die Bedürfnisse der Praxis erfüllen. Aufgabe der Erfindung ist es daher, spezifische Werkstoffe der Konstitution AgSn02Bi2O3CUO für die Anwendung bei Niederspannungsschaltgeräten der Energietechnik anzugeben.Tests have shown that the known materials do not yet meet practical needs. The object of the invention is therefore to specify specific materials of the constitution AgSn0 2 Bi 2 O 3 C U O for use in low-voltage switchgear in energy technology.
Die Aufgabe wird bei einem Werkstoff der Konstitution AgSn02Bi2O3CUO erfindungsgemäß dadurch gelöst, daß der Sn02-Massenanteil im Bereich von 4 bis 8 %, der Bi203-Massenanteil zwischen 0,5 und 4 % und der CuO-Massenanteil zwischen 0,3 und 1 % liegen, mit der Maßgabe, daß der Kontaktwerkstoff ein Sinterwerkstoff ist, erhältlich aus einem inneroxidierten Legierungspulver (IOLP), wobei der Volumenanteil an Summenmetalloxid zwischen 10 und 25 % mit einem Sn02-Volumenanteil 70 % der Gesamtoxidmenge beträgt, und daß das Verhältnis der Massenanteile in Prozent von Sn02 zu CuO zwischen 8 : 1 und 12 : 1 liegt.The object is achieved with a material of the constitution AgSn0 2 Bi 2 O 3 C U O according to the invention in that the Sn0 2 mass fraction in the range from 4 to 8%, the Bi 2 0 3 mass fraction between 0.5 and 4% and the CuO mass fraction is between 0.3 and 1%, with the proviso that the contact material is a sintered material, available from an internally oxidized alloy powder (IOLP), where the volume fraction of total metal oxide is between 10 and 25% with an Sn0 2 volume fraction 70% of the total amount of oxide, and the ratio of the mass fraction in percent of Sn0 2 to CuO is between 8: 1 and 12 : 1 lies.
Der Erfindung lag die Erkenntnis zugrunde, daß eine Auswahl aus den in der GB-A-20 55 398 einerseits und der DE-A-27 54 335 andererseits hinsichtlich der dort vorhandenen Konzentrationsangaben dann Überraschend günstige Temperatureigenschaften hat, wenn obige Parameter erfüllt sind. Dabei kommt es insbesondere darauf an, daß der Werkstoff pulvermetallurgisch über inneroxidierte Legierungspulver hergestellt ist.The invention was based on the knowledge that a selection from those in GB-A-20 55 398 on the one hand and DE-A-27 54 335 on the other hand has surprisingly favorable temperature properties with regard to the concentration information provided there if the above parameters are met. It is particularly important that the material is produced by powder metallurgy using internally oxidized alloy powder.
Weitere Einzelheiten und Vorteile der Erfindung ergeben sich aus der Beschreibung von Ausführungsbeispielen:
- Bei der Herstellung von Sinterkontaktwerkstoffen werden im allgemeinen nur die Massenanteile in % (Massengehalt) angegeben. Ausgehend von einem konstanten Volumenanteil an Silber, bietet sich für die Optimierung des Eigenschaftsspektrums eine Variation der Wirkkomponenten bei vorgegebenem Volumenanteil der Summenmetalloxide an. Dieser beträgt bei der Erfindung zwischen 10 % und 25 %, wobei der Volumenanteil von Sn02 70 % ist. Wegen der unterschiedlichen Dichte der Oxide ist es sachgerecht, einerseits die Volumenanteile der Summenmetalloxide, andererseits speziell die Massenanteile in % der einzelnen Komponenten anzugeben, wie es bei den nachfolgenden Beispielen ausgeführt ist.
- When manufacturing sintered contact materials, generally only the mass fractions are given in% (mass content). Starting from a constant volume fraction of silver, a variation of the active components with a given volume fraction of the sum metal oxides is appropriate for the optimization of the property spectrum. In the invention, this is between 10% and 25%, the volume fraction of Sn02 being 70%. Because of the different densities of the oxides, it is appropriate to indicate the volume fractions of the sum metal oxides on the one hand, and specifically the mass fractions in% of the individual components on the other hand, as explained in the following examples.
Aus 93,60 % Feinsilberkörnern, 5,20 % Zinnkörnern, 0,6 % metallischem Wismut als Bruchstücke und 0,6 % Kupfer in Stangenform wird eine Legierung aus AgSnBiCu der angegebenen Zusammensetzung bei 1353 K erschmolzen. Durch Zerstäuben der Schmelze in Wasser mit einer Druckverdüsungsanlage wird daraus ein gleich zusammengesetztes Legierungspulver erhalten. Nach dem Trocknen wird der Pulveranteil auf < 200 um abgesiebt. Dieser Anteil wird in sauerstoffhaltiger Atmosphäre zwischen 723 K und 872 K inneroxidiert, wonach ein Verbundpulver aus AgSn02Bi2O3Cu0 der Zusammensetzung in Massenanteilen von 92,10 % Ag, 6,50 % Sn02, 0,66 % Bi203 und 0,74 % CuO erhalten wird. Ein solches Verbundpulver ist quantitativ vollständig inneroxidiert und wird als sogenanntes IOLP bezeichnet.An alloy of AgSnBiCu of the specified composition is melted at 1353 K from 93.60% fine silver grains, 5.20% tin grains, 0.6% metallic bismuth as fragments and 0.6% copper in rod form. By atomizing the melt in water with a pressure atomization system, an alloy powder of the same composition is obtained. After drying, the powder fraction is sieved to <200 μm. This proportion is internally oxidized in an oxygen-containing atmosphere between 723 K and 872 K, after which a composite powder of AgSn0 2 Bi 2 O 3 Cu0 of the composition in mass proportions of 92.10% Ag, 6.50% Sn0 2 , 0.66% Bi 2 0 3 and 0.74% CuO is obtained. Such a composite powder is quantitatively completely internally oxidized and is referred to as IOLP.
Aus dem Verbundpulver werden durch Pressen in einer Matrize mit 600 MPa Kontaktstücke hergestellt. Für eine sichere Verbindungstechnik durch Hartlöten ist es dabei vorteilhaft, beim Pressen des Verbundpulvers eine zweite Schicht aus Reinsilber gemeinsam mit der Kontaktschicht zu einem Zweischichten-Kontaktstück zu verpressen. Die Sinterung der Kontaktstücke erfolgt bei 1173 K während einer Stunde an Luft. Durch Warmpressen bei 923 K mit 900 MPa werden die Kontaktstücke verdichtet. Eine weitere Verdichtung und Verfestigung wird durch eine zweite Sinterung bei 1173 K während einer Stunde an Luft und eine darauf folgende Kaltverdichtung mit 800 MPa erreicht.The composite powder is used to produce contact pieces by pressing in a die with 600 MPa. For a secure connection technique by brazing, it is advantageous to press a second layer of pure silver together with the contact layer into a two-layer contact piece when pressing the composite powder. The contact pieces are sintered at 1173 K for one hour in air. The contact pieces are compacted by hot pressing at 923 K at 900 MPa. Further compression and solidification is achieved by a second sintering at 1173 K for one hour in air and a subsequent cold compression at 800 MPa.
Metallographische Schliffbilder zeigen, daß das Gefüge des so erzeugten Kontaktwerkstoffes fein und gleichmäßig mit einer mittleren Oxidteilchengröße von 1,5 um ist.Metallographic micrographs show that the structure of the contact material thus produced is fine and uniform with an average oxide particle size of 1.5 μm.
Bei einem weiteren Ausführungsbeispiel wurden Verfahrensschritte wie bei Beispiel 1 gewählt; es wurde jedoch von Ausgangsmaterialien folgender Zusammensetzung in Massenanteilen ausgegangen: 93,96% Feinsilberkörner, 4,00 % Zinnkörner, 1,64 % metallisches Wismut und 0,40 % Kupfer, woraus eine Legierung erschmolzen wird. Daraus wird in oben beschriebener Weise entsprechendes Legierungspulver erzeugt.In a further exemplary embodiment, method steps as in Example 1 were selected; However, starting materials of the following composition in mass fractions were assumed: 93.96% fine silver grains, 4.00% tin grains, 1.64% metallic bismuth and 0.40% copper, from which an alloy is melted. Corresponding alloy powder is produced from this in the manner described above.
Nach innerer Oxidation des Legierungspulvers wird ein IOLP aus AgSn02Bi2O3Cu0 der Zusammensetzung in Massenanteilen von 92,70 % Ag, 5,01 % Sn02, 1,80 % Bi203 und 0,49 % CuO erhalten. Dieses IOLP ist Ausgangsmaterial für den Werkstoff und die daraus zu fertigenden Kontaktstücke.After internal oxidation of the alloy powder, an IOLP of AgSn0 2 Bi 2 O 3 Cu0 of the composition in mass fractions of 92.70% Ag, 5.01% Sn0 2 , 1.80% Bi 2 0 3 and 0.49% CuO is obtained. This IOLP is the starting material for the material and the contact pieces to be made from it.
Das Gefüge dieses Werkstoffes entspricht bis auf eine stärkere Umkörnung im wesentlichen dem Werkstoff nach Beispiel 1.The structure of this material essentially corresponds to the material according to Example 1, except for a larger grain size.
Von den erfindungsgemäß hergestellten Kontaktwerkstoffen wurde in einem Prüfschalter die Schweißkraft ermittelt. Die erhaltenen Meßwerte entsprechen im wesentlichen denen des aus inneroxidierten Legierungspulver hergestellten AgCd012Bi203 1,0-Kontaktwerkstoffes. Darüber hinaus wurden in Motorschützen Lebensdauer- und Erwärmungsprüfungen durchgeführt. Wesentliche Kenngrößen sind dabei die AC4-Lebensdauer- schaltzahlen der Kontaktstücke und die Übertemperatur der Strombahnen. Im Vergleich zum AgCd012Bi203 1,0-Werkstoffe liegen die Lebensdauerschaltzahlen etwa um den Faktor 1,8 höher, wobei sich bei den Übertemperaturen lediglich bis zu 10 * C höhere Werte ergaben.The welding force of the contact materials produced according to the invention was determined in a test switch. The measured values obtained essentially correspond to those of the AgCd012Bi 2 0 3 1.0 contact material produced from internally oxidized alloy powder. In addition, service life and heating tests were carried out in motor contactors. The key parameters are the AC4 service life switching numbers of the contact pieces and the overtemperature of the current paths. Compared to AgCd012Bi 2 0 3 1.0 materials, the lifespan switching numbers are about a factor of 1.8 higher, with the excess temperatures only showing up to 10 * C higher values.
Die Prüfdaten der neuen Werkstoffe sind in der Tabelle im Vergleich zum bekannten Werkstoff wiedergegeben.The test data of the new materials are shown in the table in comparison to the known material.
Bei Werkstoffen nach der Erfindung wird also, ausgehend vom vorgegebenen Volumenanteil der Summenmetalloxide, der Zinngehalt auf einen geeigneten Bereich erniedrigt und damit zumindest der relative Bi203-Anteil erhöht, was zu unerwartet guten Ergebnissen führt.
Claims (5)
with the proviso that
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT85106748T ATE84905T1 (en) | 1984-06-12 | 1985-05-31 | SINTERED CONTACT MATERIAL FOR LOW VOLTAGE SWITCHGEAR IN POWER ENGINEERING. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3421759 | 1984-06-12 | ||
| DE19843421759 DE3421759A1 (en) | 1984-06-12 | 1984-06-12 | SINTER CONTACT MATERIAL FOR LOW VOLTAGE SWITCHGEAR OF ENERGY TECHNOLOGY |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0164664A2 EP0164664A2 (en) | 1985-12-18 |
| EP0164664A3 EP0164664A3 (en) | 1988-03-23 |
| EP0164664B1 true EP0164664B1 (en) | 1993-01-20 |
Family
ID=6238160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85106748A Expired - Lifetime EP0164664B1 (en) | 1984-06-12 | 1985-05-31 | Sintered contact material for low-tension energy switchgear |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0164664B1 (en) |
| JP (1) | JPH0768593B2 (en) |
| AT (1) | ATE84905T1 (en) |
| BR (1) | BR8502760A (en) |
| DE (2) | DE3421759A1 (en) |
| ZA (1) | ZA854389B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE58909295D1 (en) * | 1988-11-17 | 1995-07-20 | Siemens Ag | Low-voltage switchgear sintered contact material of energy technology, especially for motor contactors. |
| DE58908359D1 (en) * | 1988-11-17 | 1994-10-20 | Siemens Ag | Sintered contact material for low-voltage switchgear in energy technology, especially for motor contactors. |
| DE4201940A1 (en) * | 1992-01-24 | 1993-07-29 | Siemens Ag | SINTER COMPOSITE FOR ELECTRICAL CONTACTS IN SWITCHGEAR OF ENERGY TECHNOLOGY |
| DE4331913A1 (en) * | 1993-09-20 | 1995-03-23 | Siemens Ag | Method for connecting a contact pad made of silver-metal oxide material to a metallic contact carrier |
| CN117102479B (en) * | 2023-10-18 | 2024-01-02 | 佛山通宝精密合金股份有限公司 | Preparation process of modified silver tin oxide and prepared modified silver tin oxide |
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 |
| JPS6018735B2 (en) * | 1977-12-15 | 1985-05-11 | 松下電器産業株式会社 | electrical contact materials |
| JPS6013051B2 (en) * | 1978-08-11 | 1985-04-04 | 中外電気工業株式会社 | Improvement of electrical contact material by internally oxidizing silver↓-tin↓-bismuth alloy |
| GB2055398B (en) * | 1979-08-01 | 1983-06-02 | Chugai Electric Ind Co Ltd | Electrical contact materials of internally oxidized ag-sn-bi alloy |
| JPS6027746B2 (en) * | 1979-09-19 | 1985-07-01 | 松下電器産業株式会社 | electrical contact materials |
| JPS57134532A (en) * | 1981-02-12 | 1982-08-19 | Chugai Electric Ind Co Ltd | Electrical contact material of silver-tin-bismuth alloy |
| JPS57181339A (en) * | 1981-05-02 | 1982-11-08 | Chugai Electric Ind Co Ltd | Electrical contact material of selectively and internally oxidized silver-tin alloy containing bismuth |
-
1984
- 1984-06-12 DE DE19843421759 patent/DE3421759A1/en not_active Withdrawn
-
1985
- 1985-05-31 DE DE8585106748T patent/DE3587004D1/en not_active Expired - Fee Related
- 1985-05-31 AT AT85106748T patent/ATE84905T1/en not_active IP Right Cessation
- 1985-05-31 EP EP85106748A patent/EP0164664B1/en not_active Expired - Lifetime
- 1985-06-11 JP JP60127036A patent/JPH0768593B2/en not_active Expired - Lifetime
- 1985-06-11 ZA ZA854389A patent/ZA854389B/en unknown
- 1985-06-11 BR BR8502760A patent/BR8502760A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0164664A2 (en) | 1985-12-18 |
| EP0164664A3 (en) | 1988-03-23 |
| DE3587004D1 (en) | 1993-03-04 |
| JPS619541A (en) | 1986-01-17 |
| ATE84905T1 (en) | 1993-02-15 |
| JPH0768593B2 (en) | 1995-07-26 |
| BR8502760A (en) | 1986-02-18 |
| DE3421759A1 (en) | 1985-12-12 |
| ZA854389B (en) | 1986-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0170812B1 (en) | Method for the manufacture of sintered contact material | |
| DE2659012A1 (en) | SINTER CONTACT MATERIAL MADE OF SILVER AND INCORPORATED METAL OXIDES | |
| DE2908923C2 (en) | Internally oxidized composite material for electrical contacts | |
| EP0182386B1 (en) | Method of producing contact parts | |
| EP0118717B2 (en) | Sintered material for electrical contacts and its method of manufacture | |
| EP0586411B1 (en) | Silver-based contact material for use in power-engineering switchgear, and a method of manufacturing contacts made of this material | |
| EP0774529B1 (en) | Silver-iron material for electrical switch contacts | |
| EP0152606B1 (en) | Contact material and production of electric contacts | |
| EP0725154B1 (en) | Sintered material based on silver-tinoxide for electrical contacts and process for its production | |
| DE3027732A1 (en) | CONTACT FOR A VACUUM CIRCUIT BREAKER | |
| EP0164664B1 (en) | Sintered contact material for low-tension energy switchgear | |
| EP0369283B1 (en) | Sintered contact material for low-tension switchgear, particularly for contactors | |
| EP0715765B1 (en) | Silver-based contact material, use of such a contact material in switchgear for power-engineering applications and method of manufacturing the contact material | |
| DE3538684A1 (en) | ELECTRICAL CONTACT MATERIAL | |
| EP0369282B1 (en) | Sintered contact material in low-tension switchgear, particularly for contactors | |
| EP0660964B1 (en) | Material for electric contacts based on silver-tin oxide or silver-zinc oxide and process for its production | |
| EP0064191B1 (en) | Compound material for electrical contacts, and method for its manufacture | |
| EP0064181A1 (en) | Contact material from a copper alloy, and method for its production | |
| DE3116442C2 (en) | Sintered contact material | |
| DE3405218C2 (en) | ||
| DE1930859A1 (en) | Powder metal compositions and processes for their preparation | |
| DE19608490C1 (en) | Contact material made of silver and active components, molded part made therefrom and process for producing the molded part | |
| EP0172442A2 (en) | Expulsion chamber for an electric switching device, particularly for application in low-voltage energy technics | |
| DE3346632A1 (en) | Process for the production of highly erosion-resistant composite materials for electrical contacts | |
| DE2642690A1 (en) | SINTER CONTACT MATERIAL FOR ELECTRICAL CONTACTS |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Designated state(s): AT CH DE FR GB IT LI NL SE |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT CH DE FR GB IT LI NL SE |
|
| 17P | Request for examination filed |
Effective date: 19880425 |
|
| 17Q | First examination report despatched |
Effective date: 19900618 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT CH DE FR GB IT LI NL SE |
|
| REF | Corresponds to: |
Ref document number: 84905 Country of ref document: AT Date of ref document: 19930215 Kind code of ref document: T |
|
| REF | Corresponds to: |
Ref document number: 3587004 Country of ref document: DE Date of ref document: 19930304 |
|
| ET | Fr: translation filed | ||
| ITF | It: translation for a ep patent filed | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19930421 Year of fee payment: 9 |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19930419 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19930531 Year of fee payment: 9 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Effective date: 19940531 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19941201 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
| EAL | Se: european patent in force in sweden |
Ref document number: 85106748.8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19960419 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19960514 Year of fee payment: 12 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19970531 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19970601 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19970819 Year of fee payment: 13 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19970531 |
|
| EUG | Se: european patent has lapsed |
Ref document number: 85106748.8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19980529 Year of fee payment: 14 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980531 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980531 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19980720 Year of fee payment: 14 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000131 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000301 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |