CN107794389B - Silver tin oxide indium oxide electric contact material and preparation method thereof - Google Patents
Silver tin oxide indium oxide electric contact material and preparation method thereof Download PDFInfo
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- H01H1/02—Contacts characterised by the material thereof
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Abstract
The invention provides a silver tin oxide indium oxide electric contact material and a preparation method thereof, and the preparation method comprises the following steps: preparing AgSnIn-based alloy powder by smelting and atomizing; the rapid oxidation of the AgSnIn-based alloy powder is realized through high-energy ball milling-mechanical alloying to obtain AgSnO2In2O3A base intermediate powder; mixing AgSnO2In2O3Regulating and controlling the component ratio of the intermediate powder and the silver powder to obtain AgSnO with the same component as a finished material2In2O3Powder; mixing powder, ball milling, roasting, isostatic pressing, sintering and hot extrusion to obtain the required material. The invention forms conductive AgSnO by quickly oxidizing the melted and atomized AgSnIn-based alloy powder in high energy2In2O3The base intermediate powder has good wettability with matrix Ag, and can obtain AgSnO with high conductivity, good ductility and excellent processability2In2O3A strip or a wire.
Description
Technical Field
The invention relates to a preparation method of an electrical contact material in the technical field of materials, in particular to a silver tin oxide indium oxide electrical contact material and a preparation method thereof.
Background
The electric contact is a core element in an electric appliance switch, is used for connecting and disconnecting a circuit and loading current, is widely applied to low-voltage and high-voltage electric appliances such as an air switch, a relay, an alternating current and direct current contactor and the like, and relates to various fields of civil use, military use, aerospace, aviation and the like in modern society. With the rapid development of the electrical appliance industry, the application of the electrical switch puts higher requirements on the performance of the electrical contact material, such as low and stable contact resistance, wear resistance, good fusion welding resistance and arc erosion resistance, excellent conductivity and the like.
The silver cadmium oxide electric contact material widely used at present has excellent performance and lower material cost, especially has high cadmium oxide content, and the preparation process is mature and stable. Cadmium elements harmful to human bodies and the environment are contained in the silver cadmium oxide material, the cadmium element pollution problem exists in the production, assembly, use and recovery processes of the silver cadmium oxide material, and the development of the cadmium-free electric contact material with equivalent or even more excellent performance becomes a current research hotspot.
AgSnO2Is recognized as an environment-friendly electric contact functional material which is most hopeful to replace silver cadmium oxide. SnO2The silver-silver alloy has good thermal stability, is not easy to decompose under the action of electric arc, has poor wettability with molten liquid silver and larger density difference with the silver, and is easy to float to the surface of a contact to form enrichment. Due to SnO2The non-conductivity leads to the increase of contact resistance of the contact, causes temperature rise and influences the service performance of the electrical contact and even the electrical appliance. Simultaneous AgSnO2The material still has the defects of low elongation, difficult processing and forming and the like, and the large-scale application of the material is limited. AgSnO can be prepared by powder metallurgy, internal oxidation and chemical precipitation methods2A material. However, these processes have some disadvantages, such as SnO in powder metallurgy process2Uneven distribution in the silver matrix; the internal oxidation process needs to add elements for promoting the oxidation rate, such as indium, and has high requirements on equipment and high cost; the chemical precipitation method has long production period and higher cost.
Through retrieval, the research on the silver tin oxide electric contact material at home and abroad is as follows:
(1) preparation method of novel silver tin oxide wire material electrical contact material, CN101202169A
(2) Silver tin oxide indium oxide electrical contact wire and process for producing the same, CN1167835A
Document (1) describes a powder pre-oxidation process for preparing AgSnO2Method for producing a material, document (2) describes the production of a material in AgSnO2The influence of Zn, Cu, Ni and other elements added into the material on the material shows that the addition of trace elements is beneficial to AgSnO2The electrical contact performance of the material is improved, but the subsequent processing of the material and the like are less influenced.
Further, the inventor found that chinese patent invention patent 201210439786.8, publication No. CN102925738A, discloses a method for preparing silver tin oxide material but in the method: the component content of the raw materials adopted by smelting is not greatly different from that of the final finished product, namely the component content of the raw materials determines the component content of the final finished product, and the components of the material cannot be flexibly adjusted; and the patent prepares AgSnO by carrying out oxidation treatment while carrying out water atomization on AgSn-based powder2Base powders, generally cause the following problems:
1. the water atomization and the oxidation treatment can cause the AgSn-based powder (other elements are In, La, Bi, Zn, Ni and the like) of the atomized powder to be oxidized into AgSnO 2-based powder (In2O3, ZnO, CuO, Bi2O3 and the like) with lower efficiency and large energy consumption of equipment;
2. the technical treatment principle is similar to internal oxidation, so that the wettability of SnO2 and a matrix Ag is poor, the plasticity of the AgSnO2 material is poor, and subsequent material processing is not facilitated, such as subsequent plate rolling, wire extrusion, rivet preparation and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a silver tin oxide indium oxide electric contact material and a preparation method thereof, aiming at the original AgSnO2The preparation process of the material is improved, the rapid oxidation is realized by a high-energy ball milling-mechanical alloying method, and the large plastic deformation technology is assisted to prepare the AgSnO with the characteristics of enhanced phase dispersion distribution or fibrous structure2In2O3An environment-friendly electric contact material.
The invention is realized by the following technical scheme:
according to the inventionIn a first aspect, the invention provides a silver tin oxide indium oxide electrical contact material, which comprises the following components in percentage by weight: SnO24～13％，ZnO 0.01～0.4％，In2O32～5％，CuO 0.01～0.2％，NiO 0.01～0.5％，Bi2O30.01-0.5% and the balance of Ag.
Preferably, the oxide SnO2，ZnO，In2O3，CuO，NiO，Bi2O3The particle size of the particles is 5 nm-15 mu m.
Preferably, the silver-based electrical contact material has an obvious dispersion distribution or a fibrous structure, wherein the fibrous structure is formed by drawing and extruding a dispersion distribution reinforcing phase, namely a metal oxide formed after metal in an additive is oxidized, and the reinforcing phase is an oxide SnO2，ZnO，In2O3，CuO，NiO，Bi2O3And (3) granules.
According to a second aspect of the present invention, there is provided a method for preparing the above silver tin oxide indium oxide electrical contact material, wherein: the AgSnO is obtained by adopting the smelting atomized AgSnIn alloy powder to realize rapid oxidation through a high-energy ball milling-mechanical alloying technology2In2O3An intermediate powder having Ag coated SnO2In2O3Particle characteristics, SnO is avoided2In2O3The particles are in direct contact with the matrix silver, the intermediate powder has good wettability with the matrix silver, and the intermediate powder has conductivity, so that SnO is reduced2In2O3The particles adversely affect the properties of the electrical contact material. Then the intermediate powder and pure silver powder are mixed according to the composition ratio, and the AgSnO with the characteristics of enhanced phase dispersion distribution or fibrous tissue structure is obtained through the processes of powder mixing, ball milling, roasting, isostatic pressing, sintering, hot extrusion and the like2In2O3A strip or a wire.
Specifically, the method comprises the following steps:
firstly, putting a silver ingot, tin, indium, zinc, nickel, bismuth and copper into a smelting furnace for smelting according to the proportion, wherein the alloy raw materials in parts by weight are as follows: 35-85 parts of silver, 1-40 parts of tin, 1-20 parts of indium, 0.01-5 parts of zinc, 0.01-5 parts of nickel, 0.01-5 parts of bismuth and 0.01-5 parts of copper;
preferably, the smelting is carried out at the temperature of 900-1100 ℃ for 30-60 min.
Secondly, atomizing the smelted molten metal to prepare powder to obtain AgSnIn alloy powder;
preferably, the atomization pulverization is to utilize high-pressure gas or water to impact a molten liquid metal flow to atomize the molten liquid metal flow into metal droplets, and then cooling to obtain the AgSnIn alloy powder.
Thirdly, carrying out high-energy ball milling-mechanical alloying on the AgSnIn alloy powder in a high-energy ball mill to realize rapid oxidation to form AgSnO2In2O3Intermediate powder;
preferably, the high-energy ball milling-mechanical alloying has the following main parameters: the ball milling ratio is 10-20, the rotating speed is 200-400 r/min, and the time is 1-5 h.
Fourthly, mixing the silver powder with AgSnO2In2O3Pouring the intermediate powder into a V-shaped powder mixer for mixing, wherein the silver powder and the AgSnO are mixed2In2O3The weight proportion of the intermediate powder is according to the AgSnO prepared as required2In2O3Calculating the material components;
preferably, the powder mixing time is 2-6 h, and the rotating speed is 30-100 r/min.
Fifthly, mixing the AgSnO powder2In2O3Carrying out common ball milling on the powder;
preferably, the ball milling is carried out at the rotating speed of 30-100 r/min for 10-30 h, and the ball-to-material ratio is 1-10.
Sixthly, roasting the powder subjected to ball milling;
preferably, the roasting is carried out at the temperature of 400-700 ℃ for 1-6 h, and the atmosphere is nitrogen or argon.
Seventhly, carrying out cold isostatic pressing on the roasted powder;
preferably, the isostatic pressure is 80-300 MPa.
Eighthly, sintering the blank obtained by cold isostatic pressing;
preferably, the sintering temperature is 800-930 ℃, and the heat preservation time is 10-20 h.
Ninth, performing hot extrusion on the green body obtained by sintering to obtain a silver-based electric contact strip or wire with a reinforcing phase in a dispersion distribution or fibrous structure;
preferably, in the hot extrusion, the heating temperature of the blank is 600-900 ℃, the extrusion ratio is 30-300, the extrusion speed is 5-15 cm/min, and the preheating temperature of the extrusion die is 300-500 ℃.
The invention adopts the material design principle that the multicomponent oxide reinforcing phase is jointly reinforced, integrates the characteristics of the reinforcing phase of each element, and obtains the electric contact material which has excellent electric contact performance, good processing performance and low cost. Specifically, the effect of each element is as follows: oxidation of Sn to SnO2The particles can enhance the arc erosion resistance of the contact material; a small amount of In and Bi elements can improve the problem of over-high temperature rise In the use process of the contact material, can promote the oxidation rate and reduce the oxidation time; zn element can ensure that the contact material keeps good fusion welding resistance and good deformation processing performance; the Cu element can promote the oxidation rate and reduce the In dosage; the Ni element can refine crystal grains of the matrix Ag and improve the mechanical property of the contact material.
In the invention, the component content of the raw material used for smelting is greatly different from that of the final finished product, wherein AgSnIn-based intermediate powder is prepared by smelting and atomizing, the silver content of the AgSnIn-based intermediate powder is adjustable, and the AgSnIn-based intermediate powder and Ag powder are proportionally mixed to form the component content of the final finished product.
In the invention, oxidation is carried out while water atomization is carried out for preparing powder, so as to obtain oxide powder, and compared with the prior art that the oxide powder is mostly prepared by adopting an internal oxidation technology, the invention adopts more efficient and energy-saving high-energy ball milling-mechanical alloying for preparing the oxide powder.
Compared with the prior art, the invention has the following beneficial effects:
compared with the traditional powder metallurgy for preparing AgSnO2Compared with the electric contact material, the invention carries out scientific design on the raw material components, and the AgSnIn alloy powder which is smelted and atomized is rapidly oxidized by the high-energy ball milling-mechanical alloying technology to form AgSnO with a silver-coated enhanced phase structure2In2O3The intermediate powder improves the interface wettability of the oxide particles and the matrix silver, and eliminates the adverse effect on the mechanical property of the electrical contact due to poor interface wettability in the traditional powder metallurgy method. More importantly, AgSnO2In2O3The intermediate powder has conductivity, and is beneficial to improving the electrical property of the electrical contact material.
Meanwhile, the invention combines scientific component design and adopts a preparation process with shorter period and lower cost, so that the prepared AgSnO2The electric contact material has excellent electrical property, greatly improves the elongation and the processability, can partially or completely replace the silver cadmium oxide to be applied to various application fields using the electric contact material, such as relays, circuit breakers, contactors and the like, and avoids the problem of environmental pollution in the production and application processes of the silver cadmium oxide electric contact material.
The raw material component content used for smelting is greatly different from the component content of a final finished product, the AgSnIn-based intermediate powder is prepared by smelting and atomizing, the silver content of the AgSnIn-based intermediate powder is adjustable, and the AgSnIn-based intermediate powder and the Ag powder are proportionally re-mixed to obtain the component content of the final finished product, so that the component adjustment of the whole material is very flexible and controllable.
The invention adopts more efficient and energy-saving high-energy ball milling-mechanical alloying to prepare the oxide powder, the process is simple, the cost is low, no special requirement is required on equipment, the AgSnO2In2O3 electric contact material prepared by the invention is environment-friendly, the fusion welding resistance, the arc erosion resistance and the electric conductivity of the electric contact material are greatly improved, and the processing performance is very excellent.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a flow chart of a preparation method according to an embodiment of the present invention;
FIG. 2 shows AgSnO formed by rapid oxidation after high-energy ball milling-mechanical alloying of AgSnIn alloy powder according to an embodiment of the present invention2In2O3Intermediate powder;
FIGS. 3a and 3b illustrate AgSnO after hot extrusion according to an embodiment of the present invention2In2O3Cross section and longitudinal section of the material under 1000 x.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical solution of the present invention, and a detailed embodiment and a specific operation process are given, but the scope of the present invention is not limited to the following examples.
As shown in FIG. 1, the production methods in the following examples of the present invention were carried out according to the procedures shown in FIG. 1.
Example 1:
with AgSnO2(8)In2O3(4) Preparation of the materials
1. Weighing 68Kg of silver ingot, placing the silver ingot in a medium-frequency induction furnace, heating the silver ingot to 1000 ℃ for melting, adding 10KgIn, 20KgSn, 0.5KgZn, 1KgNi, 0.3KgBi and 0.2KgCu, and homogenizing the silver ingot for 30 minutes to obtain a silver-based alloy melt;
2. atomizing at 1200 ℃ under the air pressure of 0.5MPa to prepare powder to obtain AgSnIn alloy powder;
3. placing the AgSnIn alloy powder into a high-energy ball mill, carrying out high-energy ball milling-mechanical alloying to realize rapid oxidation to obtain AgSnO2In2O3Intermediate powder; the ball milling ratio is 20, the rotating speed is 200r/min, and the time is 3 h; the AgSnO with a silver-coated reinforcing phase structure is formed by rapidly oxidizing the melted and atomized AgSnIn alloy powder by a high-energy ball milling-mechanical alloying technology2In2O3The intermediate powder improves the interface wettability of the oxide particles and the matrix silver, and eliminates the defects in the traditional powder metallurgy methodThe bad wettability of the interface has adverse effect on the mechanical property of the electrical contact.
4. The obtained AgSnO2In2O3The intermediate powder is mixed with 225.11Kg silver powder to obtain AgSnO2(8)In2O3(4) Powder;
5. pouring the proportioned powder into a V-shaped powder mixer for mixing at the rotating speed of 40r/min for 5 hours;
6. carrying out common ball milling on the powder after the powder mixing, wherein the ball milling rotation speed is 60r/min, the ball milling time is 20h, and the ball-to-material ratio is 10;
7. roasting the powder after the common ball milling at the temperature of 500 ℃ for 5 hours in the atmosphere of air;
8. pressing the calcined powder into a green body with the diameter of 90 ℃ under the isostatic pressure of 100 MPa;
9. sintering the green body at 820 ℃ for 12 h;
10. and carrying out hot extrusion on the sintered blank, wherein the extrusion ratio of the hot extrusion is 300, the extrusion speed is 5cm/min, and the preheating temperature of an extrusion die is 300 ℃.
The final material obtained in this example had the following composition: SnO27.6％，ZnO 0.19％，In2O33.7％，CuO0.07％，NiO 0.38％，Bi2O30.1 percent and the balance of Ag.
The properties of the material obtained in this example were: tensile strength of 330MPa, soft elongation of 25%, resistivity of 2.19 mu omega cm, soft hardness of 90HV, density of 9.8g/cm3The mean particle size of the reinforcing phase particles was 8 μm.
Example 2:
with AgSnO2(10)In2O3(4) Preparation of the materials
1. Weighing 64.05Kg of silver ingot, placing the silver ingot in a medium-frequency induction furnace, heating the silver ingot to 1100 ℃ for melting, adding 5KgIn, 10.72KgSn, 0.27KgZn, 0.33KgNi, 0.07KgBi and 0.03KgCu, and homogenizing the mixture for 35 minutes to obtain a silver-based alloy melt;
2. atomizing at 1250 ℃ under the air pressure of 0.6MPa to prepare powder to obtain AgSnIn alloy powder;
3. placing the AgSnIn alloy powder into a high-energy ball mill, carrying out high-energy ball milling-mechanical alloying to realize rapid oxidation to obtain AgSnO2In2O3Intermediate powder; the ball milling ratio is 15, the rotating speed is 300r/min, and the time is 2.5 h;
4. the obtained AgSnO2In2O3The intermediate powder is mixed with 62.06Kg silver powder to obtain AgSnO2(10)In2O3(4) Powder;
5. pouring the proportioned powder into a V-shaped powder mixer for mixing at the rotating speed of 50r/min for 4 hours;
6. carrying out common ball milling on the powder after the powder mixing, wherein the ball milling rotation speed is 70r/min, the ball milling time is 18h, and the ball-to-material ratio is 9;
7. roasting the powder after the common ball milling at the temperature of 600 ℃ for 4 hours in the atmosphere of air;
8. pressing the calcined powder into a green body with the diameter of 90 ℃ under the isostatic pressure of 90 MPa;
9. sintering the green body at 850 ℃ for 10 h;
10. and carrying out hot extrusion on the sintered blank, wherein the extrusion ratio of the hot extrusion is 260, the extrusion speed is 8cm/min, and the preheating temperature of an extrusion die is 280 ℃.
The final material obtained in this example had the following composition: SnO29.3％，ZnO 0.23％，In2O34.1％，CuO0.03％，NiO 0.3％，Bi2O30.05 percent and the balance of Ag.
The properties of the material obtained in this example were: tensile strength of 360MPa, soft elongation of 20%, resistivity of 2.21 mu omega cm, soft hardness of 95HV, density of 9.7g/cm3The mean particle size of the reinforcing phase particles was 10 μm.
Example 3:
with AgSnO2(7)In2O3(3) Preparation of the materials
1. Weighing 62.4Kg of silver ingot, placing the silver ingot in a medium-frequency induction furnace, heating the silver ingot to 1050 ℃ for melting, adding 2.67KgIn, 5.93KgSn, 0.3KgZn, 0.33KgNi, 0.1KgBi and 0.07KgCu, and homogenizing for 40 minutes to obtain a silver-based alloy melt;
2. atomizing at 1230 ℃ under the air pressure of 0.4MPa to prepare powder to obtain AgSnIn alloy powder;
3. placing the AgSnIn alloy powder into a high-energy ball mill, and carrying out high-energy ball milling-mechanical alloying rapid oxidation to obtain AgSnO2In2O3Intermediate powder; the ball milling ratio is 10, the rotating speed is 350r/min, and the time is 5 h;
4. the obtained AgSnO2In2O3The intermediate powder and 43.33Kg of silver powder are mixed to obtain AgSnO2(7)In2O3(3) Powder;
5. pouring the proportioned powder into a V-shaped powder mixer for mixing at the rotating speed of 45r/min for 4.5 hours;
6. carrying out common ball milling on the powder after the powder mixing, wherein the ball milling rotation speed is 75r/min, the ball milling time is 15h, and the ball-to-material ratio is 6;
7. roasting the powder after the common ball milling at 650 ℃ for 3.5h in the atmosphere of air;
8. pressing the calcined powder into a blank with the diameter of 90 ℃ under the isostatic pressure of 95 MPa;
9. sintering the blank at 830 ℃ for 11 h;
10. and carrying out hot extrusion on the sintered blank, wherein the extrusion ratio of the hot extrusion is 250, the extrusion speed is 10cm/min, and the preheating temperature of an extrusion die is 350 ℃.
The final material obtained in this example had the following composition: SnO26.5％，ZnO 0.3％，In2O32.8％，CuO0.07％，NiO 0.36％，Bi2O30.1 percent and the balance of Ag.
The properties of the material obtained in this example were: tensile strength 320MPa, soft state elongation 27%, resistivity 2.1 mu omega cm, soft state hardness 88HV, density 9.9g/cm3The mean particle size of the reinforcing phase particles was 6 μm.
Example 4:
with AgSnO2(5)In2O3(3) Preparation of the materials
1. Weighing 52.38Kg of silver ingot, placing the silver ingot in a medium-frequency induction furnace, heating the silver ingot to 1150 ℃ for melting, adding 2KgIn, 3.18KgSn, 0.086KgZn, 0.13KgNi, 0.09KgBi and 0.04KgCu, and homogenizing the silver ingot for 33 minutes to obtain a silver-based alloy melt;
2. atomizing at 1150 ℃ under the air pressure of 0.5MPa to prepare powder to obtain AgSnIn alloy powder;
3. placing the AgSnIn alloy powder into a high-energy ball mill, and carrying out high-energy ball milling-mechanical alloying rapid oxidation to obtain AgSnO2In2O3Intermediate powder; the ball milling ratio is 20, the rotating speed is 330r/min, and the time is 3 h;
4. the obtained AgSnO2In2O3The intermediate powder and 26.8Kg of silver powder are mixed to obtain AgSnO2(5)In2O3(3) Powder;
5. pouring the proportioned powder into a V-shaped powder mixer for mixing at the rotating speed of 37r/min for 6 hours;
6. carrying out common ball milling on the powder after the powder mixing, wherein the ball milling rotation speed is 80r/min, the ball milling time is 20h, and the ball-to-material ratio is 5;
7. roasting the powder after the common ball milling at 700 ℃ for 3 hours in the atmosphere of air;
8. pressing the calcined powder into a green body with the diameter of 90 ℃ under the isostatic pressure of 90 MPa;
9. sintering the green body at 860 ℃ for 10 h;
10. and carrying out hot extrusion on the sintered blank, wherein the extrusion ratio of the hot extrusion is 210, the extrusion speed is 12cm/min, and the preheating temperature of an extrusion die is 360 ℃.
The final material obtained in this example had the following composition: SnO24.8％，ZnO 0.13％，In2O32.8％，CuO0.06％，NiO 0.19％，Bi2O30.1 percent and the balance of Ag.
The properties of the material obtained in this example were: tensile strength of 300MPa, soft elongation of 30%, resistivity of 2.01 mu omega cm, soft hardness of 83HV, density of 9.96g/cm3The mean particle size of the reinforcing phase particles was 4 μm.
Referring to FIG. 2, the AgSnO formed by the rapid oxidation after the high-energy ball milling-mechanical alloying of the AgSnIn alloy powder according to one embodiment of the present invention2In2O3The intermediate powder has a silver-coated reinforcing phase structure, a large number of fine reinforcing phases (namely metal oxides) are embedded in or coated by flat silver particles, and the fine reinforcing phases are continuously coated to form AgSnO in the ball milling process2In2O3And (3) granules.
Referring to FIGS. 3a and 3b, an embodiment of the invention is AgSnO after hot extrusion2In2O3The cross section and the longitudinal section of the material are metallographic structures at 1000 x, reinforcing phase particles are in dotted and granular dispersion distribution, and the particle size is small; longitudinal section: the reinforcing phases are distributed in a fiber shape, the fibers are parallel to each other, the fiber distribution direction is along the extrusion or drawing direction of the silk material, and the fibers are small in diameter and short in length; the tissue has no holes and is compact.
The invention prepares AgSnO by adopting smelting atomization and high-energy ball milling2In2O3The base intermediate powder is energy-saving; AgSnO2In2O3The base intermediate powder has good wettability with the matrix Ag, has conductivity, and reduces SnO2In2O3The adverse effect of the particles on the mechanical and electrical properties of the electrical contact material.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and various changes and modifications, such as changes in the contents of components, preparation process parameters, etc., described in the present invention may be made by those skilled in the art within the scope of the appended claims without affecting the spirit of the present invention.
Claims (10)
1. A preparation method of a silver tin oxide indium oxide electric contact material is characterized by comprising the following steps:
firstly, putting a silver ingot and additives of tin, indium, zinc, nickel, bismuth and copper into a smelting furnace for smelting according to a proportion, wherein the weight parts of the adopted metal raw materials are as follows: 35-85 parts of silver, 1-40 parts of tin, 1-20 parts of indium, 0.01-5 parts of zinc, 0.01-5 parts of nickel, 0.01-5 parts of bismuth and 0.01-5 parts of copper;
secondly, atomizing the smelted molten metal to prepare powder to obtain AgSnIn-based alloy powder;
thirdly, carrying out high-energy ball milling-mechanical alloying on the AgSnIn-based alloy powder in a high-energy ball mill to realize rapid oxidation to form AgSnO with a silver-coated reinforcing phase structure2In2O3Intermediate powder;
fourthly, mixing the silver powder with AgSnO2In2O3Pouring the intermediate powder into a V-shaped powder mixer for mixing;
fifthly, mixing the AgSnO powder2In2O3Carrying out common ball milling on the powder;
sixthly, roasting the powder subjected to ball milling;
seventhly, carrying out cold isostatic pressing on the roasted powder;
eighthly, sintering the blank obtained by cold isostatic pressing;
ninth, performing hot extrusion on the blank obtained by sintering to obtain a silver-based electrical contact strip or wire with reinforced phase dispersion distribution or a fibrous structure;
the silver tin oxide indium oxide electric contact material comprises the following components in percentage by weight: SnO24～13％，ZnO 0.01～0.4％，In2O32～5％，CuO 0.01～0.2％，NiO 0.01～0.5％，Bi2O30.01-0.5% of Ag, and the balance of Ag;
the silver tin oxide indium oxide electric contact material has an obvious dispersion distribution or fibrous structure, wherein the fibrous structure is formed by drawing and extruding a dispersion distribution reinforcing phase, namely a metal oxide formed after metal in an additive is oxidized, and the reinforcing phase is an oxide SnO2，ZnO，In2O3，CuO，NiO，Bi2O3And (3) granules.
2. The method for preparing the silver tin oxide indium oxide electrical contact material according to claim 1, wherein in the first step, the melting temperature is 900-1100 ℃, and the melting time is 30-60 min.
3. The method for preparing the silver tin oxide indium oxide electrical contact material according to claim 1, wherein in the third step, the high-energy ball milling and mechanical alloying are carried out, wherein the ball milling ratio is 10-20, the rotating speed is 200-400 r/min, and the time is 1-5 h.
4. The method of preparing an Ag-Sn-O-in electrical contact material of claim 1 wherein in the fourth step, the Ag powder is mixed with AgSnO2In2O3The weight proportion of the intermediate powder is according to the AgSnO prepared as required2In2O3The material components are calculated, the powder mixing time is 2-6 h, and the rotating speed is 30-100 r/min.
5. The method for preparing the silver tin oxide indium oxide electrical contact material according to claim 1, wherein in the fifth step, the ball milling rotation speed is 30-100 r/min, the ball milling time is 10-30 h, and the ball-to-material ratio is 1-10.
6. The method of making a silver tin oxide indium oxide electrical contact material of any of claims 1-5, having one or more of the following characteristics:
in the sixth step, roasting is carried out at the temperature of 400-700 ℃ for 1-6 h;
in the seventh step, the isostatic pressure is 80-300 MPa;
and in the eighth step, sintering is carried out at the sintering temperature of 800-930 ℃ for 10-20 h.
7. The method for preparing an Ag-Sn-O-InO electrical contact material according to any one of claims 1 to 5, wherein in the ninth step, the hot extrusion green body is heated at a temperature of 600 to 900 ℃, the extrusion ratio is 30 to 300, the extrusion speed is 5 to 15cm/min, and the extrusion die preheating temperature is 300 to 500 ℃.
8. A silver tin oxide indium oxide electrical contact material prepared by the method of any one of claims 1 to 7.
9. The silver tin oxide indium oxide electrical contact material of claim 8, which comprises the following components in weight percent: SnO24～13％，ZnO 0.01～0.4％，In2O32～5％，CuO 0.01～0.2％，NiO0.01～0.5％，Bi2O30.01-0.5% and the balance of Ag.
10. The silver tin oxide indium oxide electrical contact material of claim 9, having one or more of the following characteristics:
said oxide SnO2，ZnO，In2O3，CuO，NiO，Bi2O3The particle size of the particles is 5 nm-15 mu m;
the silver-based electrical contact material has an obvious dispersed distribution or a fibrous structure, wherein the fibrous structure is formed by drawing and extruding a dispersed reinforcing phase, namely a metal oxide formed by oxidizing metal in an additive, and the reinforcing phase is an oxide SnO2，ZnO，In2O3，CuO，NiO，Bi2O3And (3) granules.
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| CN110423908B (en) * | 2019-08-23 | 2020-12-04 | 温州宏丰电工合金股份有限公司 | Silver oxide, tin oxide and indium oxide electric contact material capable of rapidly oxidizing silver and preparation method |
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| CN114438366A (en) * | 2021-12-28 | 2022-05-06 | 温州中希电工合金有限公司 | Preparation method of silver tin oxide indium oxide electric contact material |
| CN114360948B (en) * | 2022-01-10 | 2024-08-02 | 温州宏丰特种材料有限公司 | Silver tin oxide indium oxide electric contact composite material and preparation method thereof |
| CN115491539B (en) * | 2022-08-30 | 2023-04-18 | 昆明理工大学 | Enhanced AgSnO 2 Electric contact material and preparation method thereof |
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| CN116837247B (en) * | 2023-05-22 | 2024-02-06 | 贵研中希（上海）新材料科技有限公司 | Preparation method of electric contact noble metal material for new energy field |
| CN117107100B (en) * | 2023-08-28 | 2024-01-30 | 昆明理工大学 | Method for reinforcing silver-based material by metal oxide with core-shell structure |
| CN117127046B (en) * | 2023-08-30 | 2024-04-16 | 昆明理工大学 | SnO (tin oxide)2@In2O3Preparation method of reinforced silver-based composite material |
| CN117026004B (en) * | 2023-08-31 | 2024-01-12 | 昆明理工大学 | ZnO@In 2 O 3 Reinforced silver-based composite material and preparation method thereof |
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| JP2005036264A (en) * | 2003-07-18 | 2005-02-10 | Sumitomo Electric Ind Ltd | Electrical contact and contact breaker using it |
| CN101707153B (en) * | 2009-09-24 | 2011-12-28 | 温州宏丰电工合金股份有限公司 | Preparation method of fine-particle stannic oxide reinforced Ag-based electrical contact material |
| CN102031408B (en) * | 2010-12-30 | 2012-08-22 | 温州宏丰电工合金股份有限公司 | Method for preparing silver-based oxide electrical contact material with fibrous structure |
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