CN115491539B - Enhanced AgSnO 2 Electric contact material and preparation method thereof - Google Patents
Enhanced AgSnO 2 Electric contact material and preparation method thereof Download PDFInfo
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- CN115491539B CN115491539B CN202211044123.6A CN202211044123A CN115491539B CN 115491539 B CN115491539 B CN 115491539B CN 202211044123 A CN202211044123 A CN 202211044123A CN 115491539 B CN115491539 B CN 115491539B
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
- H01H1/023—Composite material having a noble metal as the basic material
- H01H1/0237—Composite material having a noble metal as the basic material and containing oxides
- H01H1/02372—Composite material having a noble metal as the basic material and containing oxides containing as major components one or more oxides of the following elements only: Cd, Sn, Zn, In, Bi, Sb or Te
- H01H1/02376—Composite material having a noble metal as the basic material and containing oxides containing as major components one or more oxides of the following elements only: Cd, Sn, Zn, In, Bi, Sb or Te containing as major component SnO2
Abstract
The invention belongs to the technical field of metal matrix composite materials, and particularly relates to a reinforced AgSnO 2 An electric contact material and a preparation method thereof. The enhanced AgSnO of the invention 2 The electric contact material comprises the following components in percentage by mass: snO 2 10.0～11.5％；In 2 O 3 1.8～2.3％；CuO0.8～1.3％；Bi 2 O 3 0.8～1.7％；Bi 2 Sn 2 O 7 1.3 to 4.5 percent; the balance being silver and unavoidable impurities. The invention provides enhanced AgSnO 2 The electric contact material effectively improves the dispersibility of oxide particles in a silver matrix, thereby improving the enhanced AgSnO 2 Compactness and electrical conductivity of the electrical contact material.
Description
Technical Field
The invention belongs to the technical field of metal matrix composite materials, and particularly relates to a reinforced AgSnO 2 An electric contact material and a preparation method thereof.
Background
The electric contact material mainly functions to cut off and connect electric current or transfer charge information in an electric switch. As an important electrical contact material, silver metal oxide (AgMeO) is widely used in aviation relays, automobile relays, and low-voltage electric appliances due to its excellent properties.
The emergence of universal contact AgCdO materials enables silver-based electric contact functional composite materials to achieve a new milestone, but Cd and CdO steam have carcinogenic effects on human bodies, so related products containing Cd are limited by a plurality of developed countries and regions such as European Union, japan, USA and the like, and the AgCdO electric contact is strictly prohibited from being produced, imported and used by legislation.
AgSnO 2 The material is the most popular material for replacing AgCdO, but the ceramic oxide SnO 2 The silver is difficult to distribute in the silver matrix, and agglomeration is easy to occur, so that the density and the conductivity are directly lower.
Disclosure of Invention
In view of the above, the invention aims to provide a reinforced AgSnO 2 The invention provides an electric contact material and a preparation method thereof, and the enhanced AgSnO 2 The oxide particles in the electric contact material are highly dispersed in the silver matrix, thereby improving the enhanced AgSnO 2 Compactness and conductivity of the electrical contact material.
In order to realize the aim, the invention provides a reinforced AgSnO 2 The electric contact material comprises the following components in percentage by mass:
the balance being silver and unavoidable impurities.
Preferably, the enhanced AgSnO 2 The electric contact material comprises the following components in percentage by mass:
the balance being silver and unavoidable impurities.
The invention also provides the reinforced AgSnO 2 The preparation method of the electric contact material comprises the following steps:
performing first mixing on AgCu alloy powder, agIn alloy powder and AgSn alloy powder, and oxidizing the obtained first mixed powder to obtain first composite powder;
mixing Ag powder and Bi 2 O 3 Carrying out second mixing on the powder and the first composite powder, and sintering the obtained second mixed powder to obtain the reinforced AgSnO 2 An electrical contact material;
the temperature of the oxidation is 500-800 ℃, and the time is 4-8 h.
Preferably, the rotation speed of the first mixing is 450-600 rpm, and the time is 4-12 h.
Preferably, the rotation speed of the second mixing is 300-600 rpm, and the time is 1-3 h.
Preferably, after the second mixing, the step of pressing the second mixed powder before sintering is further included.
Preferably, the pressing pressure is 500-800 MPa, and the dwell time is 5-10 min.
Preferably, the temperature for sintering is 95-850 ℃ and the time is 12-13 h.
Preferably, the sintering comprises sequentially performing a first sintering, a second sintering, a third sintering, a fourth sintering and a fifth sintering;
the heat preservation temperature of the first sintering is 95-120 ℃, and the heat preservation time is 1-1.2 h;
the heat preservation temperature of the second sintering is 290-320 ℃; the heat preservation time is 3 to 3.2 hours;
the heat preservation temperature of the third sintering is 490-520 ℃; the heat preservation time is 3 to 3.2 hours;
the heat preservation temperature of the fourth sintering is 690-720 ℃; the heat preservation time is 3 to 3.2 hours;
the heat preservation temperature of the fifth sintering is 820-850 ℃; the heat preservation time is 2-2.2 h.
The invention provides a reinforced AgSnO 2 The electric contact material comprises the following components in percentage by mass: snO 2 10.0～11.5％；In 2 O 3 1.8～2.3％；CuO 0.8～1.3％；Bi 2 O 3 0.8～1.7％；Bi 2 Sn 2 O 7 1.3 to 4.5 percent; the balance being silver and unavoidable impurities. The enhanced AgSnO of the invention 2 In AgSnO as electric contact material 2 In is introduced into the composite material 2 O 3 、CuO、Bi 2 O 3 And Bi 2 Sn 2 O 7 CuO enables reduction of SnO 2 Wetting angles between silver substrates improve wettability and promote SnO 2 Interdiffusion with the silver matrix to uniform the structure and enhance AgSnO 2 The electric contact material has uniform tissue distribution. Bi 2 O 3 With SnO 2 In situ reaction generates Bi 2 Sn 2 O 7 Thereby improving the oxide (Bi) 2 O 3 And SnO 2 ) The combination mode between the silver oxide and the silver matrix ensures that the distribution uniformity of the oxide in the silver matrix is higher. In addition, when AgSn alloy is oxidized, dense SnO is generated on the surface 2 Layer, preventing further oxidation of the alloy, in 2 O 3 Can promote the internal oxidation of the alloy to enable SnO 2 The layer-wrapped Sn continues to oxidize, thereby promoting SnO 2 The generation and diffusion of the oxides are realized, the oxides are uniformly distributed in the silver matrix, and the enhanced AgSnO is improved 2 Compactness and conductivity of the electrical contact material.
In addition, the data of the examples show that the enhanced AgSnO provided by the invention 2 The electric contact material has higher density, compactness, hardness and lower resistivity.
The invention also provides the enhanced AgSnO 2 The preparation method of the electric contact material comprises the following steps: carrying out first mixing on AgCu alloy powder, agIn alloy powder and AgSn alloy powder, and oxidizing the obtained first mixed powder to obtain first composite powder; mixing Ag powder and Bi 2 O 3 Carrying out second mixing on the powder and the first composite powder, and sintering the obtained second mixed powder to obtain the reinforced AgSnO 2 An electrical contact material; the temperature of the oxidation is 500-800 ℃, and the time is 4-8 h. The preparation method provided by the invention is environment-friendly, easy to operate and suitable for actual production.
Drawings
FIG. 1 is a schematic representation of the enhanced AgSnO prepared in example 3 2 A 100 x metallographic micrograph of the electrical contact material;
FIG. 2 is a schematic representation of the enhanced AgSnO prepared in example 1 2 XRD phase analysis pattern of the electrical contact material.
Detailed Description
The invention provides a reinforced AgSnO 2 The electric contact material comprises the following components in percentage by mass:
the balance being silver and unavoidable impurities.
In the invention, the enhanced AgSnO 2 The electric contact material comprises 10.0-11.5% of SnO 2 Preferably 10.5 to 11.0%.
In the invention, the enhanced AgSnO 2 The electric contact material comprises 1.8 to 2.3 mass percent of In 2 O 3 Preferably 2.0 to 2.2%.
In the invention, the enhanced AgSnO 2 The electric contact material comprises 0.8-1.3% of CuO by mass percentage, and preferably 1.0-1.2%.
In the invention, the enhanced AgSnO 2 The electric contact material comprises 0.8 to 1.7 mass percent of Bi 2 O 3 Preferably 1.0 to 1.5%.
In the invention, the enhanced AgSnO 2 The electric contact material comprises 1.3-4.5 mass percent of Bi 2 Sn 2 O 7 Preferably 2.0 to 4.0%.
In the invention, the enhanced AgSnO 2 The electric contact material includes the balance of silver and inevitable impurities.
The invention also provides the reinforced AgSnO 2 The preparation method of the electric contact material comprises the following steps:
carrying out first mixing on AgCu alloy powder, agIn alloy powder and AgSn alloy powder, and oxidizing the obtained first mixed powder to obtain first composite powder;
mixing Ag powder and Bi 2 O 3 Carrying out second mixing on the powder and the first composite powder, and sintering the obtained second mixed powder to obtain the reinforced AgSnO 2 An electrical contact material.
The method comprises the steps of mixing AgCu alloy powder, agIn alloy powder and AgSn alloy powder for the first time, and oxidizing the obtained first mixed powder to obtain first composite powder.
In the present invention, the mass ratio of the AgCu alloy powder to the AgIn alloy powder is preferably 0.75 to 0.8:33.0 to 33.10, more preferably 0.799:33.08. in the present invention, the mass ratio of the AgIn alloy powder to the AgSn alloy powder is preferably 33.0 to 33.10:12 to 13, more preferably 33.08:12.603. in the present invention, the purities of the AgCu alloy powder, the AgIn alloy powder, and the AgSn alloy powder are independently preferably not less than 99.99%, and the particle sizes of the AgCu alloy powder, the AgIn alloy powder, and the AgSn alloy powder are independently preferably 40 to 45 μm, and more preferably 41 to 44 μm.
In the present invention, the first mixing is preferably performed by wet milling; the rotation speed of the first mixing is preferably 450 to 600rpm, more preferably 500 to 550rpm; the time is preferably 4 to 12 hours, more preferably 6 to 10 hours. In the present invention, the wet milling preferably has a ball to feed ratio of 1 to 5, more preferably 2 to 4. In the present invention, the wet milling medium is preferably absolute ethanol, and the mass ratio of the absolute ethanol to the mixed material is 2 to 4.
In the present invention, it is preferable to further perform drying before the oxidation, and in the present invention, the drying is preferably natural air drying to remove a medium for wet grinding.
In the invention, the temperature of the oxidation is 500-800 ℃, preferably 600-700 ℃; the time is preferably 4 to 8 hours, more preferably 5 to 7 hours.
After the first composite powder is obtained, ag powder and Bi are mixed 2 O 3 Carrying out second mixing on the powder and the first composite powder, and sintering the obtained second mixed powder to obtain the reinforced AgSnO 2 An electrical contact material.
In the present invention, the Ag powder and Bi 2 O 3 The mass ratio of the powder is preferably 2.2-2.5: 0.2 to 0.4, more preferably 2.271 to 2.471:0.2 to 0.4. In the present invention, the Ag powder and Bi 2 O 3 The purity of the powder is preferably more than or equal to 99.99 percent independently, and the Ag powder and the Bi powder 2 O 3 The particle size of the powder is independently preferably 40 to 45um, more preferably 41 to 44um.
In the present invention, the second mixing means is preferably wet milling; the rotation speed of the second mixing is preferably 300 to 600rpm, more preferably 400 to 550rpm; the time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours. In the present invention, the wet milling preferably has a ball to feed ratio of 1 to 5, more preferably 2 to 4. In the invention, the wet grinding medium is preferably absolute ethyl alcohol, and the mass ratio of the absolute ethyl alcohol to the second mixed powder is 2-4. In the present invention, after the wet milling, it is preferable to further include subjecting the material obtained by the wet milling to natural air drying.
In the present invention, before sintering, it is preferable to further include pressing the second mixed powder. In the present invention, the pressure of the pressing is preferably 500 to 800MPa, more preferably 600 to 700MPa; the dwell time is preferably 5 to 10min, more preferably 6 to 8min.
In the present invention, mechanical alloying of the raw materials is achieved during the first mixing and the second mixing.
In the invention, the temperature for keeping the sintering temperature is preferably 95-850 ℃, and more preferably 100-830 ℃; the time is preferably 12 to 13 hours, more preferably 12.5 hours. In the present invention, the sintering preferably includes sequentially performing a first sintering, a second sintering, a third sintering, a fourth sintering, and a fifth sintering.
In the invention, the heat preservation temperature of the first sintering is preferably 95-120 ℃, and more preferably 100-115 ℃; the time is 1 to 1.2 hours, more preferably 1.1 hour. In the present invention, the temperature increase rate for increasing the temperature to the first sintering temperature is preferably 15 to 20 ℃/min.
In the present invention, the temperature of the second sintering is preferably 290 to 320 ℃, more preferably 300 to 310 ℃; the holding time is preferably 3 to 3.2 hours, more preferably 3.1 hours. In the present invention, the rate of temperature increase to the second sintering temperature is preferably 15 to 20 ℃/min.
In the present invention, the temperature of the third sintering is preferably 490 to 520 ℃, more preferably 500 to 510 ℃; the holding time is preferably 3 to 3.2 hours, more preferably 3.1 hours. In the present invention, the rate of temperature increase to the third sintering temperature is preferably 15 to 20 ℃/min.
In the present invention, the temperature of the fourth sintering is preferably 690 to 720 ℃, more preferably 700 to 710 ℃; the holding time is preferably 3 to 3.2 hours, more preferably 3.1 hours. In the present invention, the rate of temperature rise to the fourth sintering temperature is preferably 15 to 20 ℃/min.
In the present invention, the temperature of the fifth sintering is preferably 820 to 850 ℃, and more preferably 830 to 840 ℃; the holding time is preferably 2 to 2.2 hours, more preferably 2.1 hours. In the present invention, the rate of temperature rise to the fifth sintering temperature is preferably 15 to 20 ℃/min.
In order to further illustrate the present invention, the following embodiments are provided to describe the technical solutions of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Placing 0.799g of AgCu alloy powder, 33.08g of AgIn alloy powder and 12.603g of AgSn alloy powder in a ball milling tank under an absolute ethyl alcohol medium for wet milling (the rotating speed is 600rpm, the time is 8h, and the ball-to-material ratio is 3: 1), and oxidizing the first mixed powder obtained by wet milling for 4h at the temperature of 800 ℃ to obtain first composite powder.
Mixing 2.471gAg powder, 0.2gBi 2 O 3 Placing the powder and the first composite powder in a ball milling tank under an absolute ethyl alcohol medium for wet milling (the rotating speed is 300r/min, the time is 4h, the ball-to-material ratio is 1); raising the temperature from 100 ℃ to 300 ℃, and preserving the heat for 3h at 300 ℃; heating from 300 ℃ to 500 ℃, and preserving heat for 3h at 500 ℃; heating from 500 ℃ to 700 ℃, and preserving heat for 3h at 700 ℃; raising the temperature from 700 ℃ to 830 ℃, and preserving the heat for 2h at 830 ℃ to obtain the enhanced AgSnO 2 An electrical contact material.
Example 2
Placing 0.799g of AgCu alloy powder, 33.08g of AgIn alloy powder and 12.603g of AgSn alloy powder in a ball milling tank under an absolute ethyl alcohol medium for wet milling (the rotating speed is 450rpm, the time is 4h, the ball-material ratio is 5.
Mixing 2.471gAg powder, 0.2gBi 2 O 3 Placing the powder and the first composite powder in a ball milling tank under an absolute ethyl alcohol medium for wet milling (the rotating speed is 300r/min, the time is 4h, the ball-to-material ratio is 1); heating from 100 ℃ to 300 ℃, and preserving heat for 3h at 300 ℃; raising the temperature from 300 ℃ to 50 DEG CKeeping the temperature at 0 ℃ for 3h at 500 ℃; heating from 500 ℃ to 700 ℃, and preserving heat for 3h at 700 ℃; raising the temperature from 700 ℃ to 830 ℃, and preserving the heat for 2h at 830 ℃ to obtain the enhanced AgSnO 2 An electrical contact material.
Example 3
Placing 0.799g of AgCu alloy powder, 33.08g of AgIn alloy powder and 12.603g of AgSn alloy powder in a ball milling tank under an absolute ethyl alcohol medium for wet milling (the rotating speed is 600rpm, the time is 12h, the ball-material ratio is 5.
Mixing 2.271gAg powder and 0.4gBi 2 O 3 Wet grinding the powder and the first composite powder under an absolute ethyl alcohol medium (the rotating speed is 300r/min, the time is 4h, the ball-to-material ratio is 1); heating from 100 ℃ to 300 ℃, and preserving heat for 3h at 300 ℃; raising the temperature from 300 ℃ to 500 ℃, and preserving the heat for 3h at 500 ℃; heating from 500 ℃ to 700 ℃, and preserving heat for 3h at 700 ℃; raising the temperature from 700 ℃ to 830 ℃, and preserving the heat for 2h at 830 ℃ to obtain the enhanced AgSnO 2 An electrical contact material.
The invention relates to the reinforced AgSnO prepared in the examples 1-3 2 The density, hardness and resistivity of the electric contact material were tested, wherein the density was measured by Archimedes drainage method and the theoretical density of the material was 9.7189g/cm 3 The density is calculated by adopting a rho actual/rho theory, measuring the hardness of the material by adopting a micro Vickers hardness tester, and measuring the resistivity of the material by adopting an eddy current conductivity meter. The test results are shown in Table 1. As can be seen from Table 1: the reinforced AgSnO prepared by the invention 2 The electric contact material has higher density, compactness, hardness and lower resistivity.
TABLE 1 enhanced AgSnO obtained in examples 1 to 3 2 Density, hardness and resistivity of electric contact material
The number of hardness tests in table 1 was 6, with the minimum and maximum values reported in the table.
FIG. 1 is a schematic representation of the enhanced AgSnO obtained in example 3 2 A metallographic micrograph of the electrical contact material 100 × is shown in fig. 1: the enhanced AgSnO prepared by the invention 2 The electric contact material has uniform tissue distribution, basically uniform silver matrix size and no obvious defects such as air hole cracks and the like.
FIG. 2 shows the reinforced AgSnO obtained in example 1 2 XRD phase analysis diagram of electric contact material, as can be seen from figure 2, the enhanced AgSnO prepared by the invention 2 The main component phase of the electric contact material comprises Ag and SnO 2 、In 2 O 3 、CuO、Bi 2 O 3 And Bi 2 Sn 2 O 7 . It was confirmed that Bi was formed during the preparation 2 Sn 2 O 7 。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements should also be considered as the protection scope of the present invention.
Claims (9)
1. Enhanced AgSnO 2 The electric contact material is characterized by comprising the following components in percentage by mass:
the balance of silver and inevitable impurities; the reinforced AgSnO 2 The preparation method of the electric contact material comprises the following steps:
performing first mixing on AgCu alloy powder, agIn alloy powder and AgSn alloy powder, and oxidizing the obtained first mixed powder to obtain first composite powder;
mixing Ag powder and Bi 2 O 3 Carrying out second mixing on the powder and the first composite powder, and sintering the obtained second mixed powder to obtain the reinforced AgSnO 2 An electrical contact material;
the temperature of the oxidation is 500-800 ℃, and the time is 4-8 h.
2. The enhanced AgSnO of claim 1 2 The electric contact material is characterized by comprising the following components in percentage by mass:
the balance being silver and unavoidable impurities.
3. The enhanced AgSnO of claim 1 2 The preparation method of the electric contact material is characterized by comprising the following steps of:
carrying out first mixing on AgCu alloy powder, agIn alloy powder and AgSn alloy powder, and oxidizing the obtained first mixed powder to obtain first composite powder;
mixing Ag powder and Bi 2 O 3 Secondly mixing the powder with the first composite powder, and sintering the obtained second mixed powder to obtain the reinforced AgSnO 2 An electrical contact material;
the temperature of the oxidation is 500-800 ℃, and the time is 4-8 h.
4. The method according to claim 3, wherein the first mixing is performed at a rotation speed of 450 to 600rpm for 4 to 12 hours.
5. The method of claim 3, wherein the second mixing is performed at a speed of 300 to 600rpm for 1 to 3 hours.
6. The method according to claim 3, wherein the step of sintering further comprises pressing the second mixed powder.
7. The production method according to claim 6, wherein the pressure of the pressing is 500 to 800MPa, and the dwell time is 5 to 10min.
8. The preparation method according to claim 3, wherein the sintering is carried out at a temperature of 95-850 ℃ for 12-13 h.
9. The production method according to claim 3 or 8, wherein the sintering includes sequentially performing a first sintering, a second sintering, a third sintering, a fourth sintering, and a fifth sintering;
the heat preservation temperature of the first sintering is 95-120 ℃, and the heat preservation time is 1-1.2 h;
the heat preservation temperature of the second sintering is 290-320 ℃; the heat preservation time is 3 to 3.2 hours;
the heat preservation temperature of the third sintering is 490-520 ℃; the heat preservation time is 3 to 3.2 hours;
the heat preservation temperature of the fourth sintering is 690-720 ℃; the heat preservation time is 3 to 3.2 hours;
the heat preservation temperature of the fifth sintering is 820-850 ℃; the heat preservation time is 2-2.2 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6027747B2 (en) * | 1979-10-15 | 1985-07-01 | 松下電器産業株式会社 | electrical contact materials |
| DE19503182C1 (en) * | 1995-02-01 | 1996-05-15 | Degussa | Sintered material used as electrical contacts for switching amperage rating |
| JP4089252B2 (en) * | 2002-03-11 | 2008-05-28 | オムロン株式会社 | DC load contact structure and switch having the structure |
| CN100402195C (en) * | 2006-04-07 | 2008-07-16 | 桂林金格电工电子材料科技有限公司 | Silver composite tin oxide contact material and its preparation technology |
| CN101649399B (en) * | 2009-07-20 | 2010-12-29 | 温州宏丰电工合金股份有限公司 | Preparation method of tin-oxygen-silver electric contact material |
| 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 |
| US8691612B2 (en) * | 2010-12-10 | 2014-04-08 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Method of creating micro-scale silver telluride grains covered with bismuth nanoparticles |
| CN102820152A (en) * | 2012-08-21 | 2012-12-12 | 福达合金材料股份有限公司 | Method for preparing silver tin oxide electric contact material through jetting co-deposition |
| CN103589897B (en) * | 2013-11-22 | 2015-11-25 | 福达合金材料股份有限公司 | Preparation method of siluer metal oxide tungsten composite electric contact material and products thereof |
| CN107794389B (en) * | 2017-10-20 | 2020-04-28 | 温州宏丰电工合金股份有限公司 | Silver tin oxide indium oxide electric contact material and preparation method thereof |
| CN110643847B (en) * | 2019-10-18 | 2021-08-27 | 宁波汉博贵金属合金有限公司 | Preparation method of silver tin oxide electric contact material |
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