WO2015074349A1 - 银金属氧化物石墨复合电触头材料的制备方法及其产品 - Google Patents

银金属氧化物石墨复合电触头材料的制备方法及其产品 Download PDF

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WO2015074349A1
WO2015074349A1 PCT/CN2014/072093 CN2014072093W WO2015074349A1 WO 2015074349 A1 WO2015074349 A1 WO 2015074349A1 CN 2014072093 W CN2014072093 W CN 2014072093W WO 2015074349 A1 WO2015074349 A1 WO 2015074349A1
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powder
silver
metal oxide
additive
graphite
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PCT/CN2014/072093
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English (en)
French (fr)
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万岱
翁桅
夏承东
杨昌麟
刘洋
柏小平
林万焕
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福达合金材料股份有限公司
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Publication of WO2015074349A1 publication Critical patent/WO2015074349A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver

Definitions

  • the invention relates to a method for producing electrical contact materials for low-voltage electrical appliances, in particular to a silver metal oxide graphite (AgMeOC) The preparation method and product of composite electric contact material.
  • AgMeOC silver metal oxide graphite
  • silver-based materials As electrical contact materials, and silver metal oxides (AgMeO , Me).
  • AgMeO silver metal oxides
  • Me silver metal oxides
  • the fusion between the contacts is one of the main failure modes.
  • a common method for improving the resistance of a material to fusion welding is to increase the content of the high melting point oxide component in the material or to precipitate the oxide particles in a needle shape (the needle direction is perpendicular to the working surface).
  • the solution will reduce the conductivity of the material and the degree of improvement is limited; the second scheme can be realized in the internal oxidation process material, but it is difficult to achieve in the powder metallurgy method (including the pre-oxidation method and the mixed powder method).
  • the AgMeO electrical contact material needs to add a layer of soldered silver to the soldering surface during the processing. The bonding between the AgMeO layer and the soldered silver layer is usually achieved by hot rolling.
  • Silver graphite is also an electrical contact material. Due to the presence of graphite, it has excellent resistance to fusion welding when a large current is applied, but AgC The material has poor electrical corrosion resistance and is generally used for small circuit breakers, protection switches and other electrical appliances.
  • the object of the present invention is to overcome the shortcomings and deficiencies of the prior art, and to provide a method for preparing a silver metal oxide graphite composite electrical contact material.
  • the silver metal oxide graphite composite electric contact material prepared by the method comprehensively utilizes the advantages of the silver metal oxide and the silver graphite (AgC) contact materials, thereby improving the anti-welding performance of the electrical contact material, so that It has a wider range of applications.
  • the method also solves the problem that metallurgical bonding cannot be formed between the soldered silver layer and the silver metal oxide graphite matrix due to the plasticity drop caused by the addition of graphite.
  • Another object of the present invention is to provide a silver metal oxide graphite composite electrical contact material prepared by the above method, Compared with silver metal oxide electrical contact materials, it can improve the anti-weld properties, and can be applied to small circuit breakers and protection switches instead of AgC materials to achieve silver-saving, or used in AC/DC contactors and circuit breakers instead of AgMeO. Materials to achieve the purpose of improving the resistance to fusion welding.
  • the prepared silver metal oxide graphite composite electrical contact material is a small sheet contact material, and includes the following steps:
  • step (1) inserting a partition longitudinally in a rubber sleeve closed at the bottom, so that the inner cavity of the rubber sleeve is divided into a large chamber and a small chamber, and the radial height ratio of the large chamber A to the small chamber B is controlled at 7:1 to 10:1.
  • the mixed powder disposed in the step (1) is charged into the large chamber, the silver powder for welding the silver layer is filled into the chamber, the separator is taken out, and the whole spindle is pressed into the isostatic pressing device, and the diameter of the spindle is controlled at 80 to 120 mm.
  • the length is controlled at 200 ⁇ 500mm, and the isostatic pressure is 50 ⁇ 300MPa;
  • the spindle is sintered at 600 ⁇ 900 °C for 1 ⁇ 6 hours under protective atmosphere conditions, and is recompressed in cold isostatic pressing equipment or hydraulic press, and the pressure of recompression is 20 ⁇ 300MPa;
  • the spindle is extruded into a strip at 600 ⁇ 900 °C for 1 to 6 hours under a protective atmosphere, and the strip width is 20 ⁇ 70 mm and the thickness is 2 ⁇ 10 mm;
  • the finished contact is obtained by the strip-slice method; or the finished contact is obtained by the die punching method.
  • the technical solution of the present invention may also be that the prepared silver metal oxide graphite composite electrical contact material is a large sheet contact material, and includes the following steps:
  • the mixed powder prepared in the step (1) is placed in a ball mill device for 2 to 24 hours;
  • the initial pressure compact is obtained by the compression molding method, and the relative density is controlled at 65% ⁇ 85%; at the initial pressure, a layer of silver powder is uniformly deposited on the surface of the mixed powder as the welded silver layer, and the thickness of the silver layer is controlled at the total thickness of the contact. 5% ⁇ 30%;
  • the initial pressure compact is sintered at 600 ⁇ 900 ° C for 2 to 5 hours under a protective atmosphere;
  • the technical solution of the present invention includes the following components, including a contact substrate and a solder silver layer.
  • the contact substrate comprises the following components:
  • Metal oxide 1-25%, graphite 0.05-5%, additive ⁇ 5%, balance is silver; specifically:
  • Option 1 includes the following components, in mass percent:
  • the additives include the following components in parts by mass:
  • Bi2O3 0.01 ⁇ 2.5; TeO2 0.1 ⁇ 2.5; Sb2O3 0.01 ⁇ 1.0; CuO 0.01 ⁇ 2.5.
  • Option 2 includes the following components, in mass percent:
  • the additives include the following components in parts by mass:
  • Option 3 includes the following components, in mass percent:
  • the additives include the following components in parts by mass:
  • Option 4 includes the following components, in mass percent:
  • the additives include the following components in parts by mass:
  • the above-mentioned protective atmosphere condition means protection with argon or nitrogen.
  • the AgMeOC electrical contact material also needs to add a layer of soldered silver on the soldered surface, this new material is less plastic than the AgMeO material of the same oxide content due to a certain amount of C.
  • the traditional hot-rolling composite method is used for the complex silver, and the AgMeOC layer needs to be more than 50% in order to ensure the joint strength. Cracks are generated that affect material utilization and subsequent processing.
  • the invention realizes complex silver by means of a rubber sleeve.
  • the contact area between the base layer and the silver layer powder is large, the atomic diffusion between the base material and the silver layer is realized by the extrusion deformation of the large deformation amount after heating. Metallurgical bonding of the AgMeOC layer to the soldered silver layer.
  • the invention has the advantages and positive effects: 1. Adding C to the AgMeO contact material can significantly improve the resistance of the contact and improve the reliability of the DC contactor; 2. Select the AgMeOC contact material with appropriate composition, It can replace AgC contact material in miniature circuit breaker and protection switch, improve the arc burning resistance of the contact, improve the electric life, reduce the silver content of the contact, and play a significant silver-saving effect; 3. Use powder suppression - Extrusion process, complex silver, the bonding strength between the welded silver layer and the AgMeOC matrix material is firm, and the silver layer distribution is relatively uniform, which solves the problem of difficulty in re-silvering of the AgMeOC contact material by extrusion; 4. Process designed by the present invention The route is simple, the material utilization rate is high, and the production cycle is short, which is suitable for mass production.
  • Figure 1 is a structural view of a rubber sleeve used in the process of the present invention:
  • Figure 2 is a cross-sectional view of a rubber sleeve used in the process of the present invention
  • A is a large chamber
  • B is a small chamber
  • 1 is a rubber sleeve
  • 2 is a partition.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • the AgCdO(10)+additive powder was prepared by a pre-oxidation process, and then AgCdO(10)+additive powder and 25 kg of C powder of 0.5% by weight were charged into a mixer for 4 hours.
  • the additive therein included 0.1% by weight of NiO powder and 2.0% of SnO2 powder.
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 9:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator is taken out and pressed into an integral spindle in an isostatic pressing apparatus.
  • the spindle has a diameter of 100 mm, a length of 300 mm, and an isostatic pressure of 150 MPa.
  • the spindle is sintered at 800 ° C for 6 hours under argon protection conditions, and recompressed in a cold isostatic press at a pressure of 150 MPa.
  • the spindle was heated to 850 ° C for 2 hours under argon protection and extruded into a strip.
  • the extruded strip was 70 mm wide and 3 mm thick.
  • the strip was cold rolled to a thickness of the finished product on a cold rolling mill, and cold-rolled to a thickness of 1.5 mm for annealing once, and argon gas was used for annealing at a temperature of 700 ° C for 0.5 hours.
  • a stripe-slice method is used to obtain a finished contact of 3.8 x 3.8 x 0.8 mm.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • the AgCdO(25)+additive powder was prepared by a pre-oxidation process, and then AgCdO(25)+additive powder and 20% by weight of C powder were charged into a mixer for 8 hours.
  • the additive therein included 0.5% by weight of ZnO powder and 1.0% of CuO powder.
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 8:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator was taken out and pressed into an integral spindle in an isostatic pressing apparatus, the spindle having a diameter of 90 mm, a length of 400 mm, and an isostatic pressure of 200 MPa.
  • the spindle is sintered at 900 ° C for 2 hours under argon protection conditions, and recompressed in a hydraulic press with a pressure of 20 MPa.
  • the spindle was heated to 750 ° C for 3 hours under nitrogen protection and extruded into a strip.
  • the extruded strip was 50 mm wide and 10 mm thick.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 7:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator is taken out and pressed into an integral spindle in an isostatic pressing apparatus.
  • the spindle has a diameter of 95 mm, a length of 350 mm, and an isostatic pressure of 220 MPa.
  • the spindle is sintered at 850 ° C for 4 hours under nitrogen protection and recompressed in a hydraulic press with a pressure of 30 MPa.
  • the spindle was heated to 600 ° C for 5 hours under argon gas protection and extruded into a strip.
  • the extruded strip was 70 mm wide and 8 mm thick.
  • the strip is cold rolled to the finished thickness on a cold rolling mill, cold rolled to a thickness of 6 mm, cold rolled to a thickness of 4 mm, and cold rolled to a thickness of 2 mm.
  • Each annealing is performed once, and nitrogen is used for annealing at a temperature of 500 ° C. , 2 hours.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 10:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator was taken out and pressed into an integral spindle in an isostatic pressing apparatus.
  • the spindle has a diameter of 110 mm, a length of 400 mm, and an isostatic pressure of 300 MPa.
  • the spindle is sintered at 600 ° C for 6 hours under nitrogen protection, and is recompressed in an isostatic press at a pressure of 250 MPa.
  • the strip was cold rolled to a thickness of the finished product on a cold rolling mill, and annealed once to a thickness of 2 mm by cold rolling, and argon gas was used for annealing at a temperature of 800 ° C for 1 hour.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • the mixed powder is ball milled in a ball mill for 12 hours for granulation.
  • the initial pressure compact is obtained by the compression molding method, and the relative density is controlled at 75%; at the initial pressure, a layer of silver powder is uniformly deposited on the surface of the mixed powder as the welded silver layer, and the thickness of the silver layer is controlled to 10% of the total thickness of the contact.
  • the AgCdO(5)+additive powder was prepared by a pre-oxidation process, and then AgCdO(5)+additive powder and 25 wt% of C powder were put into a mixer for 6 hours.
  • the additive therein included 1.0% by weight of CuO powder and 1.5% of SnO2 powder.
  • the mixed powder is ball milled in a ball mill for 6 hours for granulation.
  • the initial pressure compact is obtained by the compression molding method, and the relative density is controlled at 80%; at the initial pressure, a layer of silver powder is uniformly deposited on the surface of the mixed powder as the welded silver layer, and the thickness of the silver layer is controlled to 20% of the total thickness of the contact.
  • the AgSnO2(10)+additive powder was prepared by a pre-oxidation process, and then AgSnO2(10)+additive powder and 25 kg of C powder by weight of 0.5% were charged into a mixer for 4 hours.
  • the additive therein included 0.2% by weight of NiO powder and 4.0% of In2O3 powder.
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 9:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator is taken out and pressed into an integral spindle in an isostatic pressing apparatus.
  • the spindle has a diameter of 100 mm, a length of 300 mm, and an isostatic pressure of 150 MPa.
  • the spindle is sintered at 800 ° C for 6 hours under argon protection conditions, and recompressed in a cold isostatic press at a pressure of 150 MPa.
  • the spindle was heated to 850 ° C for 2 hours under argon protection and extruded into a strip.
  • the strip width was 60 mm and the thickness was 4 mm.
  • a stripe-slice method is used to obtain a finished contact of 3.8 x 3.8 x 0.8 mm.
  • AgSnO2(15)+additive powder was prepared by pre-oxidation process, and then AgSnO2(15)+additive powder and 25kg of C powder with a weight percentage of 0.3% were put into a mixer for 8 hours.
  • the additive therein included 0.5% by weight of WO3 powder and 1.0% of MoO3 powder.
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 8:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator was taken out and pressed into an integral spindle in an isostatic pressing apparatus, the spindle having a diameter of 90 mm, a length of 400 mm, and an isostatic pressure of 200 MPa.
  • the spindle is sintered at 900 ° C for 2 hours under argon protection conditions, and recompressed in a hydraulic press with a pressure of 20 MPa.
  • the spindle was heated to 750 ° C for 3 hours under nitrogen protection and extruded into a strip.
  • the extruded strip was 50 mm wide and 10 mm thick.
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 7:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator is taken out and pressed into an integral spindle in an isostatic pressing apparatus.
  • the spindle has a diameter of 95 mm, a length of 350 mm, and an isostatic pressure of 220 MPa.
  • the spindle is sintered at 850 ° C for 4 hours under nitrogen protection and recompressed in a hydraulic press with a pressure of 30 MPa.
  • the spindle was heated to 600 ° C for 5 hours under argon gas protection and extruded into a strip.
  • the extruded strip was 70 mm wide and 8 mm thick.
  • the strip is cold rolled to the finished thickness on a cold rolling mill, cold rolled to a thickness of 6 mm, cold rolled to a thickness of 4 mm, and cold rolled to a thickness of 2 mm.
  • Each annealing is performed once, and nitrogen is used for annealing at a temperature of 500 ° C. , 2 hours.
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 10:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator was taken out and pressed into an integral spindle in an isostatic pressing apparatus.
  • the spindle has a diameter of 110 mm, a length of 400 mm, and an isostatic pressure of 300 MPa.
  • the spindle is sintered at 600 ° C for 6 hours under nitrogen protection, and is recompressed in an isostatic press at a pressure of 250 MPa.
  • the strip was cold rolled to a thickness of the finished product on a cold rolling mill, and annealed once to a thickness of 2 mm by cold rolling, and argon gas was used for annealing at a temperature of 800 ° C for 1 hour.
  • the mixed powder is ball milled in a ball mill for 12 hours for granulation.
  • the initial pressure compact is obtained by the compression molding method, and the relative density is controlled at 75%; at the initial pressure, a layer of silver powder is uniformly deposited on the surface of the mixed powder as the welded silver layer, and the thickness of the silver layer is controlled to 10% of the total thickness of the contact.
  • the AgSnO2(12)+additive powder was prepared by a pre-oxidation process, and then AgSnO2(12)+additive powder and 25% by weight of C powder were put into a mixer for 1 hour.
  • the additives therein include 0.2% by weight of NiO powder, 4.0% of In2O3 powder, 0.5% of TeO2 powder, and 0.3% of MoO3 powder.
  • the mixed powder is ball milled in a ball mill for 8 hours for granulation.
  • the initial pressure compact was obtained by the compression molding method, and the relative density was controlled at 85%; at the initial pressure, a layer of silver powder was uniformly deposited on the surface of the mixed powder as the welded silver layer, and the thickness of the silver layer was controlled at 10% of the total thickness of the contact.
  • AgZnO (10) + additive powder was prepared by pre-oxidation process, and then AgZnO (10) + additive powder and 25 kg of C powder by weight of 0.5 kg were placed in a mixer for 4 hours.
  • the additive therein included 0.2% by weight of NiO powder and 1.0% of CuO powder.
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 9:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator is taken out and pressed into an integral spindle in an isostatic pressing apparatus.
  • the spindle has a diameter of 100 mm, a length of 300 mm, and an isostatic pressure of 150 MPa.
  • the spindle is sintered at 800 ° C for 6 hours under argon protection conditions, and recompressed in a cold isostatic press at a pressure of 150 MPa.
  • the spindle was extruded under argon gas treatment at 850 ° C for 2 hours and then extruded into a strip.
  • the extruded strip was 60 mm wide and 3 mm thick.
  • the strip was cold rolled to a thickness of the finished product in a cold rolling mill, and cold rolled to a thickness of 1.5 mm for annealing once, and argon gas was used for annealing at a temperature of 700 ° C for 1.5 hours.
  • a strip-slice method is used to obtain a finished contact of 3 ⁇ 2 ⁇ 0.8 mm.
  • Embodiment 14 is a diagrammatic representation of Embodiment 14:
  • AgZnO (20) + additive powder was prepared by pre-oxidation process, and then AgZnO (20) + additive powder and 25 kg of C powder with a weight percentage of 0.3% were placed in a mixer for 8 hours.
  • the additive therein included 0.2% by weight of WO3 powder and 0.3% of MoO3 powder.
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 8:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator was taken out and pressed into an integral spindle in an isostatic pressing apparatus, the spindle having a diameter of 90 mm, a length of 400 mm, and an isostatic pressure of 200 MPa.
  • the spindle is sintered at 900 ° C for 2 hours under argon protection conditions, and recompressed in a hydraulic press with a pressure of 20 MPa.
  • the spindle was heated at 750 ° C for 3 hours under nitrogen protection and extruded into a strip.
  • the extruded strip was 45 mm wide and 8 mm thick.
  • the strip is cold-rolled to the thickness of the finished product on a cold rolling mill, cold-rolled to a thickness of 6 mm, cold-rolled to a thickness of 4 mm, cold-rolled to a thickness of 2 mm, each annealed, and nitrogen-protected during annealing at a temperature of 300 ° C. , 4 hours.
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 7:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator is taken out and pressed into an integral spindle in an isostatic pressing apparatus.
  • the spindle has a diameter of 95 mm, a length of 450 mm, and an isostatic pressure of 220 MPa.
  • the spindle is sintered at 850 ° C for 4 hours under nitrogen protection and recompressed in a hydraulic press with a pressure of 30 MPa.
  • the spindle was heated at 700 ° C for 3 hours under argon protection and extruded into a strip.
  • the strip width was 60 mm and the thickness was 8 mm.
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 10:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator was taken out and pressed into an integral spindle in an isostatic pressing apparatus.
  • the spindle has a diameter of 100 mm, a length of 400 mm, and an isostatic pressure of 200 MPa.
  • the spindle is sintered at 700 ° C for 6 hours under nitrogen protection and recompressed in an isostatic press at a pressure of 200 MPa.
  • the spindle was extruded under a nitrogen atmosphere at 800 ° C for 2 hours and then extruded into a strip.
  • the strip width was 60 mm and the thickness was 3 mm.
  • the strip was cold rolled to a thickness of the finished product on a cold rolling mill, and annealed once at a thickness of 1.8 mm by cold rolling, and argon gas was used for annealing at a temperature of 800 ° C for 2 hours.
  • the initial pressure compact is obtained by the compression molding method, and the relative density is controlled at 70%; at the initial pressure, a layer of silver powder is uniformly deposited on the surface of the mixed powder as the welded silver layer, and the thickness of the silver layer is controlled to 5% of the total thickness of the contact.
  • AgZnO(1)+additive powder was prepared by pre-oxidation process, and then AgZnO(1)+additive powder and 25kg of C powder with a weight percentage of 5% were put into a mixer for 8 hours.
  • the additive therein included 1.5% by weight of WO3 powder and 0.5% of Sb2O3 powder.
  • the mixed powder is ball milled in a ball mill for 6 hours for granulation.
  • the initial pressure compact was obtained by the compression molding method, and the relative density was controlled at 80%; at the initial pressure, a layer of silver powder was uniformly coated on the surface of the mixed powder as the welded silver layer, and the thickness of the silver layer was controlled at 15% of the total thickness of the contact.
  • the AgCuO(10)+additive powder was prepared by a pre-oxidation process, and then AgCuO(10)+ additive powder and 25 kg of C powder by weight of 0.5% were placed in a mixer for 4 hours.
  • the additive therein included 0.2% by weight of NiO powder and 1.0% of ZnO powder.
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 9:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator is taken out and pressed into an integral spindle in an isostatic pressing apparatus.
  • the spindle has a diameter of 100 mm, a length of 300 mm, and an isostatic pressure of 150 MPa.
  • the spindle is sintered at 800 ° C for 6 hours under argon protection conditions, and recompressed in a cold isostatic press at a pressure of 150 MPa.
  • the spindle was heated to 850 ° C for 2 hours under argon protection and extruded into a strip.
  • the strip width was 60 mm and the thickness was 4 mm.
  • a stripe-slice method is used to obtain a finished contact of 3.8 x 3.8 x 0.9 mm.
  • Embodiment 20 is a diagrammatic representation of Embodiment 20.
  • AgCuO(20)+additive powder was prepared by pre-oxidation process, and then AgCuO(20)+additive powder and 25kg of C powder with a weight percentage of 0.3% were put into a mixer for 8 hours.
  • the additive therein included 0.05% by weight of WO3 powder and 0.1% of MoO3 powder.
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 8:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator was taken out and pressed into an integral spindle in an isostatic pressing apparatus, the spindle having a diameter of 90 mm, a length of 400 mm, and an isostatic pressure of 200 MPa.
  • the spindle is sintered at 900 ° C for 2 hours under argon protection conditions, and recompressed in a hydraulic press with a pressure of 20 MPa.
  • the spindle was heated at 750 ° C for 3 hours under nitrogen protection and extruded into a strip.
  • the extruded strip was 45 mm wide and 8 mm thick.
  • the strip is cold-rolled to the thickness of the finished product on a cold rolling mill, cold-rolled to a thickness of 6 mm, cold-rolled to a thickness of 4 mm, cold-rolled to a thickness of 2 mm, each annealed, and nitrogen-protected during annealing at a temperature of 300 ° C. , 4 hours.
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 7:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator is taken out and pressed into an integral spindle in an isostatic pressing apparatus.
  • the spindle has a diameter of 95 mm, a length of 350 mm, and an isostatic pressure of 220 MPa.
  • the spindle is sintered at 850 ° C for 4 hours under nitrogen protection and recompressed in a hydraulic press with a pressure of 30 MPa.
  • the spindle was heated to 600 ° C for 5 hours under argon gas protection and extruded into a strip.
  • the extruded strip was 55 mm wide and 8 mm thick.
  • the strip is cold rolled to the finished thickness on a cold rolling mill, cold rolled to a thickness of 6 mm, cold rolled to a thickness of 4 mm, and cold rolled to a thickness of 2 mm.
  • Each annealing is performed once, and nitrogen is used for annealing at a temperature of 500 ° C. , 2 hours.
  • the separator is placed in the rubber sleeve of the cold isostatic pressing device to form two chambers, and the height ratio of the large chamber A to the small chamber B is controlled at 10:1; the mixed powder is charged into the large chamber A, and the silver powder is loaded.
  • the separator was taken out and pressed into an integral spindle in an isostatic pressing apparatus.
  • the spindle has a diameter of 110 mm, a length of 400 mm, and an isostatic pressure of 300 MPa.
  • the spindle is sintered at 600 ° C for 6 hours under nitrogen protection, and is recompressed in an isostatic press at a pressure of 250 MPa.
  • the strip was cold rolled to a thickness of the finished product on a cold rolling mill, and annealed once to a thickness of 2 mm by cold rolling, and argon gas was used for annealing at a temperature of 800 ° C for 1 hour.
  • the mixed powder is ball milled in a ball mill for 12 hours for granulation.
  • the initial pressure compact is obtained by the compression molding method, and the relative density is controlled at 75%; at the initial pressure, a layer of silver powder is uniformly deposited on the surface of the mixed powder as the welded silver layer, and the thickness of the silver layer is controlled to 10% of the total thickness of the contact.
  • the AgCuO(19)+additive powder was prepared by a pre-oxidation process, and then AgCuO(19)+additive powder and 25% by weight of C powder were put into a mixer for 1 hour.
  • the additive therein included 0.2% by weight of NiO powder, 0.3% of WO3 powder, and 0.8% of TeO2 powder.
  • the mixed powder is ball milled in a ball mill for 8 hours for granulation.
  • the initial pressure compact was obtained by the compression molding method, and the relative density was controlled at 85%; at the initial pressure, a layer of silver powder was uniformly deposited on the surface of the mixed powder as the welded silver layer, and the thickness of the silver layer was controlled at 10% of the total thickness of the contact.
  • the sintered compact is pressed into a ⁇ 20 ⁇ 2mm finished contact in a recompression die, and the pressure of recompression is 14T/cm2.

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Abstract

公开了一种银金属氧化物石墨复合电触头材料的制备方法及其产品，其技术方案主要是包括以下组分，包括有触头基体和焊接银层，该触头基体包括以下组分：金属氧化物1-25%，石墨0.05-5%，添加物≤5%，余量为银。该材料具有的优点和积极效果包括有（1）在AgMeO触头材料中添加C，可以明显提高触头的抗熔焊性，提高直流接触器的可靠性；（2）选择适当成分的AgMeOC触头材料，可以在小型断路器和保护开关中替代AgC触头材料，提高触头的抗电弧烧损能力，提高电寿命，同时降低触头银含量，起到明显的节银效果等等。

Description

银金属氧化物石墨复合电触头材料的制备方法 及其产品 技术领域
本发明涉及一种低压电器用电触头材料的生产方法，尤其是指一种银金属氧化物石墨（ AgMeOC ）复合电触头材料的制备方法及其产品 。
 背景技术
目前低压电器行业中大多以银基材料作为电触头材料，而其中银金属氧化物（ AgMeO ， Me 指代金属）材料由于其具有优良的抗电弧侵蚀性、抗熔焊性和低而稳定的接触电阻的综合电性能，在整个电触头材料体系中占有重要的地位。
在电触头接触过程中，触头间的熔焊是其主要失效形式之一。通常的提高材料抗熔焊性能的方法是提高材料中高熔点氧化物成分的含量，或者使氧化物颗粒呈针状析出（针状方向垂直于工作面）。但是方案一会降低材料的导电性能，而且可提高的程度有限；方案二在内氧化工艺材料中可以实现，但是在粉末冶金法（包括预氧化法和混粉法）工艺中却很难实现。由于金属氧化物与焊料及铜合金之间的润湿性较差， AgMeO 电触头材料在加工过程中需要在焊接面增加一层焊接银层，通常是通过热轧复合方式实现 AgMeO 层与焊接银层之间的结合。
银石墨（ AgC ）也是一种电触头材料，由于石墨的存在，在接通大电流时具有优良的抗熔焊性，但是 AgC 材料耐电腐蚀性能略差，一般多用于小型断路器、保护开关等电器。
技术问题
本发明的目的是为了克服现有技术存在的缺点和不足，而提供一种银金属氧化物石墨复合电触头材料的制备方法。通过该方法制备的银金属氧化物石墨复合电触头材料综合利用了银金属氧化物和银石墨（AgC）两种触头材料各自的优势，提高电触头材料的抗熔焊性能，使其具有更广泛的应用，另外，该方法还解决了因其添加了石墨而造成的塑性下降而导致的焊接银层与银金属氧化物石墨基体之间无法形成冶金结合的问题。
本发明的另一个目提供一种利用上述方法制备的银金属氧化物石墨复合电触头材料， 相较银金属氧化物电触头材料，提高抗熔焊性，可应用于小型断路器和保护开关中替代AgC材料达到节银的目的，或者应用于交流/直流接触器、断路器中替代AgMeO材料，达到提高抗熔焊性能的目的。
 技术解决方案
为实现上述第一个目的，本发明的技术方案是该制备的银金属氧化物石墨复合电触头材料为小型片状触点材料，包括以下工序：
（1）混合粉体配置，采用预氧化工艺制备银金属氧化物粉和添加物粉，然后将银金属氧化物粉、添加物粉与石墨粉混合均匀；或者直接将Ag粉、金属氧化物粉、石墨粉、添加物粉混合均匀；该混合粉体中的各组分质量比为：
金属氧化物 1-25%，石墨 0.05-5%，添加物 ≤5%，余量为银；
（2）在一底部封闭的橡胶套中纵向插入隔板，使橡胶套的内腔分隔成大室和小室，大室A与小室B的径向高度比控制在7:1~10:1，将步骤（1）配置的混合粉体装入大室，将焊接银层成型用银粉装入小室，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径控制在80~120mm，长度控制在200~500mm，等静压压力50~300MPa；
（3）锭子在保护气氛条件下，600~900℃烧结1~6小时，冷等静压设备或者液压机中复压，复压压力20~300MPa；
（4）锭子在保护气氛条件下，在600~900℃加热1~6小时后挤压成带材，挤压带材宽度20~70mm，厚度2~10mm；
（5）挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，中途退火至少一次，退火时采用保护气氛，温度300~800℃，时间0.5~8小时；
（6）采用分条-切片方法获得成品触点；或者采用模具冲制方法获得成品触点。
本发明的技术方案还可以是该制备的银金属氧化物石墨复合电触头材料为大型片状触点材料，包括以下工序：
（1）混合粉体制备，采用预氧化工艺制备银金属氧化物粉和添加物粉，然后将银金属氧化物粉、添加物粉和石墨粉混合均匀；或者直接将Ag粉、金属氧化物粉、石墨粉、添加物粉混合均匀；该混合粉体中的各组分质量比为：
金属氧化物 1-25%，石墨 0.05-5%，添加物 ≤5%，余量为银；
（2）制粒，将步骤（1）制备的混合粉体放入球磨设备中球磨2~24小时；
（3）采用模压成型方法获得初压压坯，相对密度控制在65%~85%；初压时在混合粉表面均匀铺一层银粉作为焊接银层，银层厚度控制在触点总厚度的5%~30%；
（4）初压压坯在保护气氛条件下于600~900℃烧结2~5小时；
（5）烧结后的压坯在复压模具中压制成为成品触点，复压压力6~14T/cm2。
为实现本发明的另一个目的，本发明的技术方案是包括以下组分，包括有触头基体和焊接银层， 该触头基体包括以下组分：
金属氧化物 1-25%，石墨 0.05-5%，添加物 ≤5%，余量为银；具体为：
方案1 包括以下组分，以质量百分比计：
CdO 1-25%；石墨 0.05~5%；添加物≤5%，余量为银，
其中添加物包括以下组分，以质量份数计：
NiO 0.1~0.5 ； SnO2 0.05~2.0； ZnO 0.01~2.5；
Bi2O3 0.01~2.5；TeO2 0.1~2.5；Sb2O3 0.01~1.0；CuO 0.01~2.5。
方案2 包括以下组分，以质量百分比计：
SnO2 1-15%；石墨 0.05~5%；添加物≤5%，余量为银，
其中添加物包括以下组分，以质量份数计：
NiO 0.1~0.5； WO3 0.05~2.0；ZnO 0.01~2.5；Bi2O3 0.01~2.5；TeO2 0.1~2.5；Sb2O3 0.01~1.0；CuO 0.01~2.5；In2O3 0.1~5.0；MoO3 0.05~2.0。
方案3 包括以下组分，以质量百分比计：
ZnO 1-20% ；石墨 0.05~5%；添加物≤5%；余量为银，
其中添加物包括以下组分，以质量份数计：
NiO 0.1~0.5； WO3 0.05~2.0；CuO 0.01~2.5；Bi2O3 0.01~2.5；
TeO2 0.1~2.5；Sb2O3 0.01~1.0；SnO2 0.01~2.0；MoO3 0.05~2.0。
方案4 包括以下组分，以质量百分比计：
CuO 1-20% ；石墨 0.05~5%；添加物≤5%；余量为银，
其中添加物包括以下组分，以质量份数计：
NiO 0.1~0.5； WO3 0.05~2.0；ZnO 0.01~2.5；Bi2O3 0.01~2.5；
TeO2 0.1~2.5；Sb2O3 0.01~1.0；SnO2 0.01~2.0；MoO3 0.05~2.0。
本发明，上述的保护气氛条件是指采用氩气或者氮气保护。
另外，由于AgMeOC电触头材料同样需要在焊接面增加一层焊接银层，由于含有一定量的C，这种新型材料与相同氧化物含量的AgMeO材料相比塑性要差。采用预氧化法或者混粉法生产小规格触点时，由于基体材料的塑性较差，采用传统的热轧复合方法进行复银，为保障结合强度一次性变形量需要达到50%以上，AgMeOC层会产生裂纹影响材料利用率和后续的加工。本发明采用橡胶套的方式实现复银，由于基体层与银层粉体之间接触面积大，通过加热后大变形量的挤压变形，使基体材料与银层之间实现原子扩散，实现了AgMeOC层与焊接银层的冶金结合。
 有益效果
本发明具有的优点和积极效果：1、在AgMeO触头材料中添加C，可以明显提高触头的抗熔焊性，提高直流接触器的可靠性；2、选择适当成分的AgMeOC触头材料，可以在小型断路器和保护开关中替代AgC触头材料，提高触头的抗电弧烧损能力，提高电寿命，同时降低触头银含量，起到明显的节银效果；3、采用粉体压制-挤压工艺复银，焊接银层与AgMeOC基体材料之间的结合强度牢固，银层分布较均匀，解决了挤压法AgMeOC触头材料的复银困难的问题；4、本发明设计的工艺路线简单，材料利用率高，生产周期短，适合大批量生产。
下面结合说明书附图和具体实施方式对本发明做进一步介绍。
 附图说明
图1 本发明工艺所用的橡胶套结构图：
图2 本发明工艺所用的橡胶套横剖图；
图中A为大室 、B为小室、1为橡胶套，2为隔板。
 本发明的最佳实施方式
下面通过实施例对本发明进行具体的描述，只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限定，该领域的技术工程师可根据上述发明的内容对本发明作出一些非本质的改进和调整。
实施例一：
a) 采用预氧化工艺制备AgCdO（10）+添加物粉，然后将AgCdO（10）+添加物粉与重量百分比0.5%的C粉共25kg装入混粉机中混合4小时。其中添加物包括重量百分比0.1%的NiO粉，2.0%的SnO2粉。
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在9:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径100mm，长度300mm，等静压压力150MPa。
c) 锭子在氩气保护条件下，800℃烧结6小时，在冷等静压机中复压，复压压力150MPa。
d) 锭子在氩气保护条件下，850℃加热2小时后挤压成带材，挤压带材宽度70mm，厚度3mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至1.5mm厚度退火一次，退火时采用氩气保护，温度700℃，时间0.5小时。
f) 采用分条-切片方法获得3.8×3.8×0.8mm规格成品触点。
实施例二：
a) 采用预氧化工艺制备AgCdO（25）+添加物粉，然后将AgCdO（25）+添加物粉与重量百分比2%的C粉共20kg装入混粉机中混合8小时。其中添加物包括重量百分比0.5%的ZnO粉，1.0%的CuO粉。
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在8:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径90mm，长度400mm，等静压压力200MPa。
c) 锭子在氩气保护条件下，900℃烧结2小时，在液压机中复压，复压压力20MPa。
d) 锭子在氮气保护条件下，750℃加热3小时后挤压成带材，挤压带材宽度50mm，厚度10mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至7mm厚度、冷轧至4mm厚度、冷轧至2mm厚度时各退火一次，退火时采用氩气保护，温度300℃，时间4小时。
f) 采用模具冲制方法获得Φ3.5×1mm规格成品触点。
实施例三：
a) 直接将21.625kg Ag粉、3.0kg CdO粉、0.25kg C粉、0.025kg NiO粉、0.050kg TeO2粉、0.050kg SnO2粉装入混粉机中混合12小时。
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在7:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径95mm，长度350mm，等静压压力220MPa。
c) 锭子在氮气保护条件下，850℃烧结4小时，在液压机中复压，复压压力30MPa。
d) 锭子在氩气保护条件下，600℃加热5小时后挤压成带材，挤压带材宽度70mm，厚度8mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至6mm厚度、冷轧至4mm厚度、冷轧至2mm厚度时各退火一次，退火时采用氮气保护，温度500℃，时间2小时。
f) 采用模具冲制方法获得Φ3×0.8mm规格成品触点。
实施例四：
a) 直接将21.125kg Ag粉、3.75kg CdO粉、0.125kg C粉装入混粉机中混合6小时。
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在10:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径110mm，长度400mm，等静压压力300MPa。
c) 锭子在氮气保护条件下，600℃烧结6小时，在等静压机中复压，复压压力250MPa。
d) 锭子在氮气保护条件下，800℃加热1.5小时后挤压成带材，挤压带材宽度50mm，厚度4mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至2mm厚度时退火一次，退火时采用氩气保护，温度800℃，时间1小时。
f) 采用分条-切片方法获得3.5×3.5×0.5mm规格成品触点。
实施例五：
a) 直接将19.25kg Ag粉、5.0kg CdO粉、0.5kg C粉、0.050kg Sb2O3粉、0.100kg SnO2粉、0.100kg Bi2O3粉装入混粉机中混合10小时。
b) 混合粉体放入球磨设备中球磨12小时，制粒。
c) 采用模压成型方法获得初压压坯，相对密度控制在75%；初压时在混合粉表面均匀铺一层银粉作为焊接银层，银层厚度控制在触点总厚度的10%。
d) 初压压坯在氮气保护条件下于900℃烧结5小时。
e) 烧结后的压坯在复压模具中压制成为25×10×2mm成品触点，复压压力10T/cm2。
实施例六：
a) 采用预氧化工艺制备AgCdO（5）+添加物粉，然后将AgCdO（5）+添加物粉与重量百分比3%的C粉共25kg装入混粉机中混合6小时。其中添加物包括重量百分比1.0%的CuO粉，1.5%的SnO2粉。
b) 混合粉体放入球磨设备中球磨6小时，制粒。
c) 采用模压成型方法获得初压压坯，相对密度控制在80%；初压时在混合粉表面均匀铺一层银粉作为焊接银层，银层厚度控制在触点总厚度的20%。
d) 初压压坯在氩气保护条件下于850℃烧结4小时。
e) 烧结后的压坯在复压模具中压制成为20×15×4mm成品触点，复压压力6T/cm2。
实施例七：
a) 采用预氧化工艺制备AgSnO2（10）+添加物粉，然后将AgSnO2（10）+添加物粉与重量百分比0.5%的C粉共25kg装入混粉机中混合4小时。其中添加物包括重量百分比0.2%的NiO粉，4.0%的In2O3粉。
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在9:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径100mm，长度300mm，等静压压力150MPa。
c) 锭子在氩气保护条件下，800℃烧结6小时，在冷等静压机中复压，复压压力150MPa。
d) 锭子在氩气保护条件下，850℃加热2小时后挤压成带材，挤压带材宽度60mm，厚度4mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至2.0mm厚度退火一次，退火时采用氮气保护，温度700℃，时间1小时。
f) 采用分条-切片方法获得3.8×3.8×0.8mm规格成品触点。
实施例八：
a) 采用预氧化工艺制备AgSnO2（15）+添加物粉，然后将AgSnO2（15）+添加物粉与重量百分比0.3%的C粉共25kg装入混粉机中混合8小时。其中添加物包括重量百分比0.5%的WO3粉，1.0%的MoO3粉。
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在8:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径90mm，长度400mm，等静压压力200MPa。
c) 锭子在氩气保护条件下，900℃烧结2小时，在液压机中复压，复压压力20MPa。
d) 锭子在氮气保护条件下，750℃加热3小时后挤压成带材，挤压带材宽度50mm，厚度10mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至7mm厚度、冷轧至4mm厚度、冷轧至2mm厚度时各退火一次，退火时采用氩气保护，温度300℃，时间4小时。
f) 采用模具冲制方法获得Φ3.5×1mm规格成品触点。
实施例九：
a) 直接将21.625kg Ag粉、3.0kg SnO2粉、0.25kg C粉、0.025kg NiO粉、0.050kg Bi2O3粉、0.050kg CuO粉装入混粉机中混合12小时。
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在7:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径95mm，长度350mm，等静压压力220MPa。
c) 锭子在氮气保护条件下，850℃烧结4小时，在液压机中复压，复压压力30MPa。
d) 锭子在氩气保护条件下，600℃加热5小时后挤压成带材，挤压带材宽度70mm，厚度8mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至6mm厚度、冷轧至4mm厚度、冷轧至2mm厚度时各退火一次，退火时采用氮气保护，温度500℃，时间2小时。
f) 采用模具冲制方法获得Φ3×0.8mm规格成品触点。
实施例十：
a) 直接将21.125kg Ag粉、3.75kg SnO2粉、0.125kg C粉装入混粉机中混合6小时。
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在10:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径110mm，长度400mm，等静压压力300MPa。
c) 锭子在氮气保护条件下，600℃烧结6小时，在等静压机中复压，复压压力250MPa。
d) 锭子在氮气保护条件下，800℃加热1.5小时后挤压成带材，挤压带材宽度50mm，厚度4mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至2mm厚度时退火一次，退火时采用氩气保护，温度800℃，时间1小时。
f) 采用分条-切片方法获得3.5×3.5×0.5mm规格成品触点。
实施例十一：
a) 直接将22.25kg Ag粉、2.0kg SnO2粉、0.5kg C粉、0.050kg NiO粉、0.200kg TeO2粉装入混粉机中混合10小时。
b) 混合粉体放入球磨设备中球磨12小时，制粒。
c) 采用模压成型方法获得初压压坯，相对密度控制在75%；初压时在混合粉表面均匀铺一层银粉作为焊接银层，银层厚度控制在触点总厚度的10%。
d) 初压压坯在氮气保护条件下于900℃烧结5小时。
e) 烧结后的压坯在复压模具中压制成为25×10×2mm成品触点，复压压力10T/cm2。
实施例十二：
a) 采用预氧化工艺制备AgSnO2（12）+添加物粉，然后将AgSnO2（12）+添加物粉与重量百分比1%的C粉共25kg装入混粉机中混合1小时。其中添加物包括重量百分比0.2%的NiO粉，4.0%的In2O3粉，0.5%的TeO2粉，0.3%的MoO3粉。
b) 混合粉体放入球磨设备中球磨8小时，制粒。
c) 采用模压成型方法获得初压压坯，相对密度控制在85%；初压时在混合粉表面均匀铺一层银粉作为焊接银层，银层厚度控制在触点总厚度的10%。
d) 初压压坯在氩气保护条件下于650℃烧结2小时。
e) 烧结后的压坯在复压模具中压制成为30×20×4mm成品触点，复压压力14T/cm2。
实施例十三：
a) 采用预氧化工艺制备AgZnO（10）+添加物粉，然后将AgZnO（10）+添加物粉与重量百分比0.5%的C粉共25kg装入混粉机中混合4小时。其中添加物包括重量百分比0.2%的NiO粉，1.0%的CuO粉。
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在9:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径100mm，长度300mm，等静压压力150MPa。
c) 锭子在氩气保护条件下，800℃烧结6小时，在冷等静压机中复压，复压压力150MPa。
d) 锭子在氩气保护条件下，850℃加热2小时后挤压成带材，挤压带材宽度60mm，厚度3mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至1.5mm厚度退火一次，退火时采用氩气保护，温度700℃，时间1.5小时。
f) 采用分条-切片方法获得3×2×0.8mm规格成品触点。
实施例十四：
a) 采用预氧化工艺制备AgZnO（20）+添加物粉，然后将AgZnO（20）+添加物粉与重量百分比0.3%的C粉共25kg装入混粉机中混合8小时。其中添加物包括重量百分比0.2%的WO3粉，0.3%的MoO3粉。
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在8:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径90mm，长度400mm，等静压压力200MPa。
c) 锭子在氩气保护条件下，900℃烧结2小时，在液压机中复压，复压压力20MPa。
d) 锭子在氮气保护条件下，750℃加热3小时后挤压成带材，挤压带材宽度45mm，厚度8mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至6mm厚度、冷轧至4mm厚度、冷轧至2mm厚度时各退火一次，退火时采用氮气保护，温度300℃，时间4小时。
f) 采用模具冲制方法获得Φ8×1SR30mm规格成品触点。
实施例十五：
a) 直接将21.625kg Ag粉、3.0kg ZnO粉、0.25kg C粉、0.025kg NiO粉、0.050kg Bi2O3粉、0.050kg Sb2O3粉装入混粉机中混合12小时。
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在7:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径95mm，长度450mm，等静压压力220MPa。
c) 锭子在氮气保护条件下，850℃烧结4小时，在液压机中复压，复压压力30MPa。
d) 锭子在氩气保护条件下，700℃加热3小时后挤压成带材，挤压带材宽度60mm，厚度8mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至6mm厚度、冷轧至4mm厚度、冷轧至2mm厚度时各退火一次，退火时采用氮气保护，温度700℃，时间2小时。
f) 采用模具冲制方法获得Φ8×1mm规格成品触点。
实施例十六：
a) 直接将20.375kg Ag粉、4.50kg ZnO粉、0.125kg C粉装入混粉机中混合8小时。
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在10:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径100mm，长度400mm，等静压压力200MPa。
c) 锭子在氮气保护条件下，700℃烧结6小时，在等静压机中复压，复压压力200MPa。
d) 锭子在氮气保护条件下，800℃加热2小时后挤压成带材，挤压带材宽度60mm，厚度3mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至1.8mm厚度时退火一次，退火时采用氩气保护，温度800℃，时间2小时。
f) 采用分条-切片方法获得6×6×1mm规格成品触点。
实施例十七：
a) 直接将22.25kg Ag粉、2.0kg ZnO粉、0.5kg C粉、0.050kg NiO粉、0.025kg TeO2粉、0.025kg WO3粉、0.025kg CuO粉、0.050kg MoO3粉、0.075kg SnO2粉装入混粉机中混合9小时。
b) 混合粉体放入球磨设备中球磨11小时，制粒。
c) 采用模压成型方法获得初压压坯，相对密度控制在70%；初压时在混合粉表面均匀铺一层银粉作为焊接银层，银层厚度控制在触点总厚度的5%。
d) 初压压坯在氩气保护条件下于880℃烧结3小时。
e) 烧结后的压坯在复压模具中压制成为Φ20×2mm成品触点，复压压力10T/cm2。
实施例十八：
a) 采用预氧化工艺制备AgZnO（1）+添加物粉，然后将AgZnO（1）+添加物粉与重量百分比5%的C粉共25kg装入混粉机中混合8小时。其中添加物包括重量百分比1.5%的WO3粉，0.5%的Sb2O3粉。
b) 混合粉体放入球磨设备中球磨6小时，制粒。
c) 采用模压成型方法获得初压压坯，相对密度控制在80%；初压时在混合粉表面均匀铺一层银粉作为焊接银层，银层厚度控制在触点总厚度的15%。
d) 初压压坯在氩气保护条件下于850℃烧结4小时。
e) 烧结后的压坯在复压模具中压制成为25×10×2mm成品触点，复压压力8T/cm2。
实施例十九：
a) 采用预氧化工艺制备AgCuO（10）+添加物粉，然后将AgCuO（10）+添加物粉与重量百分比0.5%的C粉共25kg装入混粉机中混合4小时。其中添加物包括重量百分比0.2%的NiO粉，1.0%的ZnO粉。
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在9:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径100mm，长度300mm，等静压压力150MPa。
c) 锭子在氩气保护条件下，800℃烧结6小时，在冷等静压机中复压，复压压力150MPa。
d) 锭子在氩气保护条件下，850℃加热2小时后挤压成带材，挤压带材宽度60mm，厚度4mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至2.0mm厚度退火一次，退火时采用氮气保护，温度700℃，时间1小时。
f) 采用分条-切片方法获得3.8×3.8×0.9mm规格成品触点。
实施例二十：
a) 采用预氧化工艺制备AgCuO（20）+添加物粉，然后将AgCuO（20）+添加物粉与重量百分比0.3%的C粉共25kg装入混粉机中混合8小时。其中添加物包括重量百分比0.05%的WO3粉，0.1%的MoO3粉。
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在8:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径90mm，长度400mm，等静压压力200MPa。
c) 锭子在氩气保护条件下，900℃烧结2小时，在液压机中复压，复压压力20MPa。
d) 锭子在氮气保护条件下，750℃加热3小时后挤压成带材，挤压带材宽度45mm，厚度8mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至6mm厚度、冷轧至4mm厚度、冷轧至2mm厚度时各退火一次，退火时采用氮气保护，温度300℃，时间4小时。
f) 采用模具冲制方法获得Φ6×0.9SR30mm规格成品触点。
实施例二十一：
a) 直接将21.625kg Ag粉、3.0kg CuO粉、0.25kg C粉、0.050kg NiO粉、0.025kg Bi2O3粉、0.050kg Sb2O3粉装入混粉机中混合12小时
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在7:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径95mm，长度350mm，等静压压力220MPa。
c) 锭子在氮气保护条件下，850℃烧结4小时，在液压机中复压，复压压力30MPa。
d) 锭子在氩气保护条件下，600℃加热5小时后挤压成带材，挤压带材宽度55mm，厚度8mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至6mm厚度、冷轧至4mm厚度、冷轧至2mm厚度时各退火一次，退火时采用氮气保护，温度500℃，时间2小时。
f) 采用模具冲制方法获得Φ6×0.9mm规格成品触点。
实施例二十二：
a) 直接将20.375kg Ag粉、4.50kg CuO粉、0.125kg C粉装入混粉机中混合6小时。
b) 在冷等静压设备橡胶套中放入隔板，使其形成大小两室，大室A与小室B的高度比控制在10:1；将混合粉体装入大室A中，将银粉装入小室B中，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径110mm，长度400mm，等静压压力300MPa。
c) 锭子在氮气保护条件下，600℃烧结6小时，在等静压机中复压，复压压力250MPa。
d) 锭子在氮气保护条件下，800℃加热1.5小时后挤压成带材，挤压带材宽度50mm，厚度4mm。
e) 挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，冷轧至2mm厚度时退火一次，退火时采用氩气保护，温度800℃，时间1小时。
f) 采用分条-切片方法获得3.5×3.5×0.5mm规格成品触点。
实施例二十三：
a) 直接将22.25kg Ag粉、2.0kg CuO粉、0.5kg C粉、0.050kg NiO粉、0.025kg TeO2粉、0.025kg WO3粉、0.025kg ZnO粉、0.050kg MoO3粉、0.075kg SnO2粉装入混粉机中混合10小时。
b) 混合粉体放入球磨设备中球磨12小时，制粒。
c) 采用模压成型方法获得初压压坯，相对密度控制在75%；初压时在混合粉表面均匀铺一层银粉作为焊接银层，银层厚度控制在触点总厚度的10%。
d) 初压压坯在氮气保护条件下于900℃烧结5小时。
e) 烧结后的压坯在复压模具中压制成为Φ17.5×2mm成品触点，复压压力10T/cm2。
实施例二十四：
a) 采用预氧化工艺制备AgCuO（19）+添加物粉，然后将AgCuO（19）+添加物粉与重量百分比1%的C粉共25kg装入混粉机中混合1小时。其中添加物包括重量百分比0.2%的NiO粉，0.3%的WO3粉，0.8%的TeO2粉。
b) 混合粉体放入球磨设备中球磨8小时，制粒。
c) 采用模压成型方法获得初压压坯，相对密度控制在85%；初压时在混合粉表面均匀铺一层银粉作为焊接银层，银层厚度控制在触点总厚度的10%。
d) 初压压坯在氩气保护条件下于650℃烧结2小时。
烧结后的压坯在复压模具中压制成为Φ20×2mm成品触点，复压压力14T/cm2。
 本发明的实施方式
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Claims (7)

  1. 一种银金属氧化物石墨复合电触头材料的制备方法，其特征在于：该制备的银金属氧化物石墨复合电触头材料为小型片状触点材料，包括以下工序：
    （1）混合粉体配置，采用预氧化工艺制备银金属氧化物粉和添加物粉，然后将银金属氧化物粉、添加物粉与石墨粉混合均匀；或者直接将Ag粉、金属氧化物粉、石墨粉、添加物粉混合均匀；该混合粉体中的各组分质量比为：
    金属氧化物 1-25% 石墨 0.05-5% 添加物 ≤5%，余量为银；
    （2）在一底部封闭的橡胶套中纵向插入隔板，使橡胶套的内腔分隔成大室和小室，大室（A）与小室（B）的径向高度比控制在7:1~10:1，将步骤（1）配置的混合粉体装入大室，将焊接银层成型用银粉装入小室，抽出隔板，在等静压设备中压制成整体的锭子，锭子直径控制在80~120mm，长度控制在200~500mm，等静压压力50~300MPa；
    （3）锭子在保护气氛条件下，600~900℃烧结1~6小时，冷等静压设备或者液压机中复压，复压压力20~300MPa；
    （4）锭子在保护气氛条件下，在600~900℃加热1~6小时后挤压成带材，挤压带材宽度20~70mm，厚度2~10mm；
    （5）挤压带材去除头尾后，在冷轧机上冷轧至成品厚度，中途退火至少一次，退火时采用保护气氛，温度300~800℃，时间0.5~8小时；
    （6）采用分条-切片方法获得成品触点；或者采用模具冲制方法获得成品触点。
  2. 一种银金属氧化物石墨复合电触头材料的制备方法，其特征在于：该制备的银金属氧化物石墨复合电触头材料为大型片状触点材料，包括以下工序：
    （1）混合粉体制备，采用预氧化工艺制备银金属氧化物粉和添加物粉，然后将银金属氧化物粉、添加物粉和石墨粉混合均匀；或者直接将Ag粉、金属氧化物粉、石墨粉、添加物粉混合均匀；该混合粉体中的各组分质量比为：
    金属氧化物 1-25% 石墨 0.05-5% 添加物 ≤5%，余量为银；
    （2）制粒，将步骤（1）制备的混合粉体放入球磨设备中球磨2~24小时；
    （3）采用模压成型方法获得初压压坯，相对密度控制在65%~85%；初压时在混合粉表面均匀铺一层银粉作为焊接银层，银层厚度控制在触点总厚度的5%~30%；
    （4）初压压坯在保护气氛条件下于600~900℃烧结2~5小时；
    （5）烧结后的压坯在复压模具中压制成为成品触点，复压压力6~14T/cm2。
  3. 一种如权利要求1或2所制备的银金属氧化物石墨复合电触头材料，其特征在于：包括有触头基体和焊接银层， 该触头基体包括以下组分：
    金属氧化物 1-25% 石墨 0.05-5% 添加物 ≤5%，余量为银。
  4. 根据权利要求3所述的一种银金属氧化物石墨复合电触头材料，其特征在于包括以下组分，以质量百分比计：
    CdO 1-25%；石墨 0.05~5%；添加物≤5%，余量为银，
    其中添加物包括以下组分，以质量份数计：
    NiO 0.1~0.5 ； SnO2 0.05~2.0； ZnO 0.01~2.5；
    Bi2O3 0.01~2.5；TeO2 0.1~2.5；Sb2O3 0.01~1.0；CuO 0.01~2.5。
  5. 根据权利要求3所述的一种银金属氧化物石墨复合电触头材料，其特征在于包括以下组分，以质量百分比计：
    SnO2 1-15%；石墨 0.05~5%；添加物≤5%，余量为银，
    其中添加物包括以下组分，以质量份数计：
    NiO 0.1~0.5； WO3 0.05~2.0；ZnO 0.01~2.5；Bi2O3 0.01~2.5；TeO2 0.1~2.5；Sb2O3 0.01~1.0；CuO 0.01~2.5；In2O3 0.1~5.0；MoO3 0.05~2.0。
  6. 根据权利要求3所述的一种银金属氧化物石墨复合电触头材料，其特征在于包括以下组分，以质量百分比计：
    ZnO 1-20% ；石墨 0.05~5%；添加物≤5%；余量为银，
    其中添加物包括以下组分，以质量份数计：
    NiO 0.1~0.5； WO3 0.05~2.0；CuO 0.01~2.5；Bi2O3 0.01~2.5；
    TeO2 0.1~2.5；Sb2O3 0.01~1.0；SnO2 0.01~2.0；MoO3 0.05~2.0。
  7. 根据权利要求3所述的一种银金属氧化物石墨复合电触头材料，其特征在于包括以下组分，以质量百分比计：
    CuO 1-20% ；石墨 0.05~5%；添加物≤5%；余量为银，
    其中添加物包括以下组分，以质量份数计：
    NiO 0.1~0.5； WO3 0.05~2.0；ZnO 0.01~2.5；Bi2O3 0.01~2.5；
    TeO2 0.1~2.5；Sb2O3 0.01~1.0；SnO2 0.01~2.0；MoO3 0.05~2.0。
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