CN109500392B - Preparation method of silver zinc oxide contact material for improving sintering property of ingot blank - Google Patents
Preparation method of silver zinc oxide contact material for improving sintering property of ingot blank Download PDFInfo
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- 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
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- B22F9/00—Making metallic powder or suspensions thereof
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- C22C5/06—Alloys based on silver
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
- H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
- H01H11/048—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by powder-metallurgical processes
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- B22F9/00—Making metallic powder or suspensions thereof
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- B22F2201/11—Argon
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- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
Abstract
The invention discloses a preparation method of a silver zinc oxide contact material for improving the sintering property of an ingot blank, which comprises the following steps: 1) according to the material proportion of the silver zinc oxide contact to be prepared, silver, zinc and additives with the same application amount are calculated and weighed, and are melted and atomized to prepare powder, so that silver-zinc alloy powder is obtained; 2) oxidizing the silver-zinc alloy powder to obtain silver-zinc oxide composite powder; 3) carrying out wet grinding on the silver zinc oxide composite powder under the condition of protective atmosphere to obtain ball-milled silver zinc oxide composite powder; 4) molding the ball-milled silver zinc oxide composite powder to obtain a silver zinc oxide green body; 5) sintering the obtained silver zinc oxide blank under the conditions that the oxygen partial pressure is more than or equal to 0.8Mpa and the temperature is 900-960 ℃ to obtain a silver zinc oxide ingot blank; 6) and carrying out hot extrusion on the obtained silver zinc oxide ingot blank to obtain a silver zinc oxide wire or strip. The silver zinc oxide contact material prepared by the method has uniform tissue and good processing performance.
Description
Technical Field
The invention relates to a preparation method of a silver zinc oxide contact, in particular to a preparation method of a silver zinc oxide contact material for improving the sintering property of an ingot blank.
Background
The electric contact is a core component of various high and low switches, electric appliances, instruments and meters and components, and is widely applied to high-capacity alternating current and direct current contactors, alternating current and direct current power relays, automobile electric appliances and medium and small-capacity low-voltage circuit breakers in the industrial fields of aerospace, aviation, automobiles and the like and the civil industry. Electrical contacts are of a wide variety and are commonly used in silver-based alloys and copper-based alloys. Among silver-based alloys, silver cadmium oxide contact materials have good arc wear resistance, fusion welding resistance, electrical conductivity, and thermal conductivity, and are called "universal contact materials" because of low contact resistance and high stability. However, the silver cadmium oxide material has the harm of cadmium toxicity in the production, use and recovery processes, so the development and development of novel environment-friendly materials with good electrical contact performance become the hot topic in the field.
The silver zinc oxide (AgZnO) contact material has excellent breaking performance, fusion welding resistance and arc erosion resistance, is non-toxic and environment-friendly, and is one of contact materials for replacing silver cadmium oxide. The preparation method of the silver zinc oxide contact material is roughly divided into a powder metallurgy method, an internal oxidation method, a chemical coprecipitation method and an atomization method. Each of these methods has disadvantages: the material prepared by the powder metallurgy method has low density, large contact resistance and high temperature; the surface and the internal structure of the material prepared by the internal oxidation method are not uniform, the oxide particles are seriously aggregated, and a lean oxidation layer is arranged in the middle; the chemical coprecipitation method has the problems of complex process, chemical pollution generated in the preparation process and the like. The atomization method process combines the advantages of a powder metallurgy method and an internal oxidation method, is suitable for mass production, has good application prospect, but improves the production efficiency of the silver zinc oxide and brings some defects such as difficult sintering, poor processing performance and the like.
The traditional process flow of the atomization method is roughly as follows: smelting, atomizing to prepare powder, oxidizing alloy powder, isostatic pressing, sintering, hot extrusion, drawing and finally preparing the finished product. Wherein the thermodynamic stability of ZnO is higher than that of Ag in the oxidation stage of alloy powder2Therefore, oxidation of Zn is preferred to oxidation of Ag. The ZnO is subjected to segregation on the surface of powder particles, and the contact and diffusion of Ag among the powder are hindered in the subsequent sintering process, so that the problems of difficult sintering of a blank, poor processing performance and the like are caused. For example, the invention patent with the publication number of CN101202168 discloses a novel silver zinc oxide contact material preparation process, which is to melt silver, zinc and additives in a medium frequency melting furnace according to a certain proportionMelting and atomizing the mixture into silver-zinc alloy powder, and then drying, oxidizing and tempering, isostatic pressing, sintering, extruding, drawing and the like the atomized alloy powder to obtain the silver-zinc oxide electrical contact. As mentioned above, the thermodynamic stability of ZnO is higher than that of Ag at normal pressure2O, so that the oxidation of Zn is prior to the oxidation of Ag, thereby causing the segregation of ZnO on the surface of powder particles and hindering the contact and diffusion of Ag among the powder particles in the subsequent sintering process, and the invention also has the defects of difficult sintering of a green body and poor processing performance.
Disclosure of Invention
The invention aims to provide a preparation method of a silver zinc oxide contact material for improving the sinterability of an ingot blank. The method wetly grinds the oxidized silver zinc oxide composite powder under the atmosphere protection condition and then forms the silver zinc oxide composite powder, and the obtained blank is sintered under the conditions of specific oxygen pressure and ultrahigh temperature, so that the sinterability of an ingot blank is effectively improved, and the silver zinc oxide contact material with uniform tissue and good processing performance is obtained.
In order to solve the technical problems, the preparation method of the silver zinc oxide contact material for improving the sintering property of the ingot blank, provided by the invention, comprises the following steps:
1) calculating the required silver, zinc and additive amount according to the material ratio of the silver zinc oxide contact to be prepared, weighing the silver, zinc and additive with corresponding amount, melting, atomizing and pulverizing to obtain silver-zinc alloy powder;
2) oxidizing the silver-zinc alloy powder to obtain silver-zinc oxide composite powder;
3) placing the silver zinc oxide composite powder in a ball mill, carrying out wet milling under the condition of protective atmosphere, and drying the obtained powder after the wet milling is finished to obtain the ball-milled silver zinc oxide composite powder;
4) molding the ball-milled silver zinc oxide composite powder to obtain a silver zinc oxide green body;
5) sintering the obtained silver zinc oxide blank under the conditions that the oxygen partial pressure is more than or equal to 0.8MPa and the temperature is 900-960 ℃ to obtain a silver zinc oxide ingot blank;
6) and carrying out hot extrusion on the obtained silver zinc oxide ingot blank to obtain a silver zinc oxide wire or a silver zinc oxide strip.
In the step 1) of the preparation method, in the obtained silver-zinc alloy powder, the additive accounts for 0-2% by mass, the zinc accounts for 1-20% by mass, and the balance is silver. The additive may be selected in the same manner as in the prior art, and specifically may be one or a combination of two or more selected from Cu, Bi, Ni, Sb and Te. In the step, the raw materials of silver, zinc and additives can be in the form of pure metal ingots or pure metal powder, for example, Ag can be pure Ag blocks or pure Ag powder.
In the step 2) of the preparation method, the operation during oxidation is the same as that in the prior art, and specifically, the silver-zinc alloy powder is placed in a high-pressure oxidation furnace and oxidized for 4-8 hours under the conditions that the oxygen partial pressure is 0.5-2 MPa and the temperature is 600-800 ℃. And crushing the material obtained after oxidation to obtain the silver zinc oxide composite powder.
In step 3) of the above production method, it is usually required to wet-grind the resulting powder to a particle size of 5 μm or less, preferably to wet-grind the resulting powder to a particle size of 2 μm or less, and more preferably to wet-grind the resulting powder to a particle size of 1 μm or less. The ball milling medium, the ball material mass ratio, the ball milling time and the like in the wet milling are the same as those in the prior art, and preferably, the ball material mass ratio is 3-10: 1, a ball milling medium is absolute ethyl alcohol, and the mass ratio of the medium to the material is 0.5-2: 1, the ball milling speed is 250-500 rmp, and the ball milling time is 6-15 h. The protective atmosphere is usually N2Or an inert gas (e.g., Ar, etc.). Drying the powder obtained after wet grinding is usually carried out at the temperature of 80-100 ℃, and the time is usually 6-10 h.
In the step 4) of the preparation method, the ball-milled silver zinc oxide composite powder is molded by adopting the prior conventional technology to obtain a silver zinc oxide green body, the ball-milled silver zinc oxide composite powder is usually molded on an isostatic press, the isostatic pressure is controlled to be 50-200 MPa, the pressure maintaining time is 10-200 s,
in the step 5) of the preparation method, the sintering time is usually controlled to be 4-10 h. In order to further improve the processing performance of the obtained ingot blank, the sintering is preferably carried out under the conditions that the oxygen partial pressure is 1-2 Mpa and the temperature is 950-960 ℃, and the sintering time is preferably controlled to be 6-8 h.
In the step 6) of the preparation method, the operation of hot extrusion is the same as that of the prior art, specifically, the temperature of hot extrusion is 830-900 ℃, and the extrusion ratio is 190-270. After the silver zinc oxide wire or the silver zinc oxide strip is obtained, the required silver zinc oxide contact is manufactured according to the conventional process. For example, the wire or the strip is subjected to drawing (or rolling and compounding) for multiple times, annealing processing is carried out to the required size, and then the wire or the strip is processed (or punched by a punch) by a riveting machine to form the rivet-type (or sheet-type) contact.
Compared with the prior art, the invention is characterized in that:
1. the formed silver zinc oxide blank is placed under the conditions that the oxygen partial pressure is more than or equal to 0.8MPa and the temperature is 900-960 ℃, particularly under the conditions that the oxygen partial pressure is 1-2 MPa and the temperature is 950-960 ℃, and the melting point of silver is increased along with the increase of pressure, so that the melting point of silver is more than 962 ℃ in the technical scheme of the invention (the melting point of silver is 962 ℃ under the standard atmospheric pressure), and therefore, the ingot blank does not melt in the ultra-high temperature sintering process (under the standard atmospheric pressure, when the sintering temperature of the silver zinc oxide ingot blank reaches 960 ℃, the melting phenomenon even occurs above 950 ℃); on the other hand, the mutual sintering diffusion effect among the silver zinc oxide particles can be enhanced by sintering under the condition of ultrahigh temperature and high pressure, and the formation of sintering necks among the particles is promoted (according to the traditional sintering theory, the closer the sintering temperature is to the melting point of a substance, the more excellent sintering performance is obtained by sintering the substance), so that the processing performance of the material is improved, and further, the high-ductility silver zinc oxide ingot blank is obtained.
2. Oxidizing the atomized silver-zinc alloy powder, then placing the oxidized silver-zinc alloy powder into a ball mill to carry out high-energy wet grinding under the atmosphere protection condition, and breaking hard shells formed by segregation of ZnO on the surfaces of powder particles in the oxidation procedure to continuously expose metal bases in the hard shells, thereby playing a role in promoting sintering and further improving the processing performance of ingot blanks; on the other hand, the particle size is refined and crushed, the agglomeration phenomenon can not be generated, the problem of surface oxidation of powder particles can not be caused, a large number of microcracks can be generated in the wet grinding process of the particles, and a diffusion channel of oxygen is added for the subsequent oxidation process, so that the diffusion rate of oxygen atoms of the particles to the interior of the powder particles in the subsequent high-pressure rapid oxidation process is greater than the diffusion rate of zinc atoms from the interior of the particles to the boundary, the enrichment of zinc oxide on the particle surface is reduced, and the uniformity of material tissues is improved.
3. The method is simple and easy to control, and is suitable for industrial production.
Drawings
FIG. 1 is a picture of a silver zinc oxide ingot blank object obtained by sintering in step 5) in example 1 of the present invention;
FIG. 2 is a picture of a silver zinc oxide ingot blank object obtained by sintering in step 5) in comparative example 1;
FIG. 3 is a picture of a silver zinc oxide ingot blank object obtained by sintering in step 5) of comparative example 2;
FIG. 4 shows fracture morphology analysis and metallographic analysis of the silver zinc oxide ingot blank obtained in step 5) of example 1 and the silver zinc oxide ingot blank obtained in step 5) of comparative example 2, respectively; wherein, (a) is the fracture morphology of the silver zinc oxide ingot blank obtained in the step 5) of the comparative example 2, (b) is the metallographic structure of the silver zinc oxide ingot blank obtained in the step 5) of the comparative example 2, (c) is the fracture morphology of the silver zinc oxide ingot blank obtained in the step 5) of the example 1, and (d) is the metallographic structure of the silver zinc oxide ingot blank obtained in the step 5) of the example 1.
Detailed Description
The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.
Example 1
1) Weighing the components according to the following mass percentage, placing the components in a medium-frequency induction smelting furnace to be smelted into uniform alloy melt, then atomizing the alloy melt by high-pressure water atomization equipment, drying the obtained powder slurry, and sieving the powder slurry by a 200-mesh sieve to obtain silver-zinc alloy powder;
Zn：12％；
addition of: 1% of Cu and 1% of Ni;
the balance of Ag;
2) placing the silver-zinc alloy powder in a high-pressure oxidation furnace, oxidizing for 6h under the conditions that the oxygen partial pressure is 1MPa and the temperature is 700 ℃, taking out, crushing, and sieving by a 100-mesh sieve to obtain silver-zinc oxide composite powder;
3) placing the silver zinc oxide composite powder in a high-energy ball mill, carrying out wet grinding treatment under the protection of an atmosphere (Ar) until the particle size of the obtained powder is 1-2 mu m, and placing the powder after wet grinding in an oven to dry for 10h at the temperature of 80 ℃ to obtain the ball-milled silver zinc oxide composite powder; during wet grinding, the ball material mass ratio is 8: 1, the ball milling medium is absolute ethyl alcohol, and the mass ratio of the medium to the material is 0.8: 1, ball milling rotation speed is 500rmp, and ball milling time is 15 h;
4) placing the ball-milled silver zinc oxide composite powder on an isostatic press for molding, controlling the isostatic pressure to be 50MPa, and keeping the pressure for 200s to obtain a silver zinc oxide green body;
5) placing the silver zinc oxide blank in a high-pressure oxidation furnace, and sintering for 6h under the conditions that the oxygen partial pressure is 0.8MPa and the temperature is 960 ℃, so as to obtain a silver zinc oxide ingot blank, wherein the material object is shown in figure 1, and as can be seen from the figure, the surface of the silver zinc oxide ingot blank obtained by sintering has metallic luster, which indicates that the blank sintering densification effect is good;
6) the silver zinc oxide ingot blank is processed into a wire by hot extrusion, and the wire is processed into a rivet type contact by a riveting machine after being drawn and annealed for a plurality of times to a required size.
Comparative example 1
Example 1 was repeated except that:
5) and (3) placing the silver zinc oxide blank in a high-pressure oxidation furnace, and heating to 960 ℃ under the condition of standard atmospheric pressure to sinter for 6 h. As a result: the silver base in the obtained ingot is already melted (since the melting point of silver is 961 ℃ under 1 standard atmospheric pressure, the sintered ingot is certainly melted at 960 ℃, and further qualified silver zinc oxide ingot cannot be obtained), and the obtained ingot is shown in figure 2. That is, this example did not yield a qualified ingot of silver zinc oxide for the subsequent process.
Comparative example 2
Example 1 was repeated except that:
5) and (3) placing the silver zinc oxide blank in a high-pressure oxidation furnace, and heating to 930 ℃ under the standard atmospheric pressure condition to sinter for 6 h. As a result: the silver zinc oxide ingot blank is obtained, and the substance is shown in figure 3, but the surface of the obtained ingot blank is still dark gray, which shows that the sintering densification effect of the blank at 930 ℃ is very undesirable.
Example 2
1) Weighing the components according to the following mass percentage, placing the components in a medium-frequency induction smelting furnace to be smelted into uniform alloy melt, then atomizing the alloy melt by high-pressure water atomization equipment, drying the obtained powder slurry, and sieving the powder slurry by a 200-mesh sieve to obtain silver-zinc alloy powder;
Zn：8％；
addition of: 0.3 percent of Cu and 0.2 percent of Ni;
the balance of Ag;
2) placing the silver-zinc alloy powder in a high-pressure oxidation furnace, oxidizing for 4 hours under the conditions that the oxygen partial pressure is 2MPa and the temperature is 800 ℃, taking out, crushing, and sieving by a 100-mesh sieve to obtain silver-zinc oxide composite powder;
3) placing the silver zinc oxide composite powder in a high-energy ball mill, carrying out wet grinding treatment under the protection of an atmosphere (Ar) until the particle size of the obtained powder is 2-4 mu m, and placing the powder after wet grinding in an oven to dry for 6h at the temperature of 100 ℃ to obtain the ball-milled silver zinc oxide composite powder; during wet grinding, the ball material mass ratio is 3: 1, the ball milling medium is absolute ethyl alcohol, and the mass ratio of the medium to the material is 1: 1, ball milling rotation speed is 250rmp, and ball milling time is 10 h;
4) placing the ball-milled silver zinc oxide composite powder on an isostatic press for molding, controlling the isostatic pressure to be 100MPa, and keeping the pressure for 10s to obtain a silver zinc oxide green body;
5) placing the silver zinc oxide blank in a high-pressure oxidation furnace, and sintering for 6h under the conditions that the oxygen partial pressure is 2MPa and the temperature is 960 ℃ to obtain a silver zinc oxide ingot blank;
6) the silver zinc oxide ingot blank is processed into a plate by hot extrusion, and the plate is processed into a sheet contact by a punch after being rolled and annealed for a plurality of times to the required size.
Example 3
1) Weighing the components according to the following mass percentage, placing the components in a medium-frequency induction smelting furnace to be smelted into uniform alloy melt, then atomizing the alloy melt by high-pressure water atomization equipment, drying the obtained powder slurry, and sieving the powder slurry by a 200-mesh sieve to obtain silver-zinc alloy powder;
Zn：10％；
addition of: 0.1 percent of Sb;
the balance of Ag;
2) placing the silver-zinc alloy powder in a high-pressure oxidation furnace, oxidizing for 8 hours under the conditions that the oxygen partial pressure is 0.5MPa and the temperature is 800 ℃, taking out, crushing, and sieving by a 100-mesh sieve to obtain silver-zinc oxide composite powder;
3) placing the silver zinc oxide composite powder in a high-energy ball mill, carrying out wet grinding treatment under the protection of an atmosphere (Ar) until the particle size of the obtained powder is 3-5 mu m, and placing the powder after wet grinding in an oven to dry for 9h at the temperature of 90 ℃ to obtain the ball-milled silver zinc oxide composite powder; during wet grinding, the ball material mass ratio is 5: 1, the ball milling medium is absolute ethyl alcohol, and the mass ratio of the medium to the material is 10: 1, ball milling rotation speed is 400rmp, and ball milling time is 10 h;
4) placing the ball-milled silver zinc oxide composite powder on an isostatic press for molding, controlling the isostatic pressure to be 80MPa, and keeping the pressure for 100s to obtain a silver zinc oxide green body;
5) placing the silver zinc oxide blank in a high-pressure oxidation furnace, and sintering for 4h under the conditions that the oxygen partial pressure is 1MPa and the temperature is at the temperature to obtain a silver zinc oxide ingot blank;
6) the silver zinc oxide ingot blank is processed into a wire by hot extrusion, and the wire is processed into a rivet type contact by a riveting machine after being drawn and annealed for a plurality of times to a required size.
Example 4
1) Weighing the components according to the following mass percentage, placing the components in a medium-frequency induction smelting furnace to be smelted into uniform alloy melt, then atomizing the alloy melt by high-pressure water atomization equipment, drying the obtained powder slurry, and sieving the powder slurry by a 200-mesh sieve to obtain silver-zinc alloy powder;
Zn：20％；
addition of: 0 percent;
the balance of Ag;
step 2), 3), 4) are the same as in example 3;
5) placing the silver zinc oxide blank in a high-pressure oxidation furnace, and sintering for 6h under the conditions that the oxygen partial pressure is 1MPa and the temperature is 950 ℃ to obtain a silver zinc oxide ingot blank;
6) the silver zinc oxide ingot blank is processed into a wire by hot extrusion, and the wire is processed into a rivet type contact by a riveting machine after being drawn and annealed for a plurality of times to a required size.
The flexural strength and other properties of the silver zinc oxide ingot obtained in step 5) of examples 1 to 4 and the silver zinc oxide ingot obtained in comparative example 2 were measured, and the results are shown in table 1 below:
table 1:
fracture morphology analysis and metallographic analysis are respectively carried out on the silver zinc oxide ingot blank obtained in the step 5) of the example 1 and the silver zinc oxide ingot blank obtained in the step 5) of the comparative example 2, and the results are shown in fig. 4, wherein (a) is the fracture morphology of the silver zinc oxide ingot blank obtained in the step 5) of the comparative example 2, (b) is the metallographic structure of the silver zinc oxide ingot blank obtained in the step 5) of the comparative example 2, (c) is the fracture morphology of the silver zinc oxide ingot blank obtained in the step 5) of the example 1, and (d) is the metallographic structure of the silver zinc oxide ingot blank obtained in the step 5) of the example 1. As can be seen from fig. 4, for the sintered compact of the comparative example, the powders are hardly sintered together, the fracture is completely brittle and separated along the powder particle boundary, the fracture surface retains the characteristics of the original powder particle, and a large number of ZnO particles are distributed on the particle surface, and the composition analysis of the interior of the large-particle grain (or particle) shows that the tin content in the interior is extremely low, and the majority is enriched on the powder particle surface (as shown in fig. 4a and 4 b). However, the powder of the sintered compact prepared by the process of the present invention has been completely sintered together to form a dense structure, and the fracture of the compact is characterized by plastic fracture with a large number of dimples, and the original powder particles are not distinguished at all in the fracture surface (as shown in fig. 4c and 4 d). The ZnO particles are distributed on the grain boundary and also distributed in a large amount in the crystal grains, which remarkably improves the distribution state of the second phase particles and is beneficial to improving the processing performance, plasticity and electrical property of the material.
Claims (7)
1. A preparation method of a silver zinc oxide contact material for improving the sinterability of an ingot blank comprises the following steps:
1) calculating the required silver, zinc and additive amount according to the material ratio of the silver zinc oxide contact to be prepared, weighing the silver, zinc and additive with corresponding amount, melting, atomizing and pulverizing to obtain silver-zinc alloy powder;
2) oxidizing the silver-zinc alloy powder to obtain silver-zinc oxide composite powder;
3) placing the silver zinc oxide composite powder in a ball mill, carrying out wet milling under the condition of protective atmosphere, and drying the obtained powder after the wet milling is finished to obtain the ball-milled silver zinc oxide composite powder;
4) molding the ball-milled silver zinc oxide composite powder to obtain a silver zinc oxide green body;
5) sintering the obtained silver zinc oxide blank under the conditions that the oxygen partial pressure is more than or equal to 0.8MPa and the temperature is 950-960 ℃ to obtain a silver zinc oxide ingot blank;
6) and carrying out hot extrusion on the obtained silver zinc oxide ingot blank to obtain a silver zinc oxide wire or a silver zinc oxide strip.
2. The method of claim 1, wherein: in the step 1), in the obtained silver-zinc alloy powder, the additive accounts for 0-2% by mass, the zinc accounts for 1-20% by mass, and the balance is silver.
3. The method of claim 1, wherein: in the step 1), the additive is one or a combination of more than two selected from Cu, Bi, Ni, Sb and Te.
4. The method of claim 1, wherein: in the step 3), wet grinding is carried out until the grain diameter of the obtained powder is less than or equal to 5 mu m.
5. The production method according to any one of claims 1 to 4, characterized in that: in the step 5), the sintering time is 4-10 h.
6. The method of claim 5, wherein: in the step 5), sintering is carried out under the conditions that the oxygen partial pressure is 1-2 MPa and the temperature is 950-960 ℃.
7. The method of claim 6, wherein: in the step 5), the sintering time is 6-8 h.
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| CN103643074B (en) * | 2013-12-06 | 2015-12-09 | 桂林电器科学研究院有限公司 | A kind of preparation method of flaky AgSnO2 contact |
| CN108010772B (en) * | 2017-12-08 | 2019-05-24 | 福达合金材料股份有限公司 | A kind of method that microwave heating prepares tin-oxygen-silver electric contact material |
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| CN101241804A (en) * | 2007-11-23 | 2008-08-13 | 中南大学 | A silver-ZnO electric contact and its making method |
| JP2010073540A (en) * | 2008-09-19 | 2010-04-02 | Tanaka Holdings Kk | Combined structure of sliding contact member used for automotive dc switch |
| CN104404419A (en) * | 2014-11-03 | 2015-03-11 | 福达合金材料股份有限公司 | Preparation method of high-oxide content flake-like contact material |
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