CN114574724B - Directionally distributed SnO 2 /A 2 Sn 2 O 7 Preparation method of complex phase ceramic reinforced silver-based composite material - Google Patents
Directionally distributed SnO 2 /A 2 Sn 2 O 7 Preparation method of complex phase ceramic reinforced silver-based composite material Download PDFInfo
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Abstract
The invention relates to a preparation technology of a complex phase ceramic reinforced silver-based composite material, and aims to provide directionally distributed SnO 2 /A 2 Sn 2 O 7 A preparation method of a complex phase ceramic reinforced silver-based composite material. The present invention utilizes SnO 2 /A 2 Sn 2 O 7 In the complex phase ceramics A 2 Sn 2 O 7 The crystal structure similarity between the phase and the metal Ag phase realizes the hard phase SnO 2 /A 2 Sn 2 O 7 The mosaic reaction between the complex phase ceramic and the soft phase Ag achieves high-strength interface metallurgical bonding; snO with excellent electric and heat conducting properties prepared by utilizing sectional type hot-pressing reaction sintering technology 2 /A 2 Sn 2 O 7 The complex phase ceramic reinforced silver-base composite material solves the problem of traditional SnO 2 The reinforced silver-based composite material has the problems of poor phase interface combination, low density, poor electric and heat conductivity and the like. The prepared product has the characteristics of high phase interface bonding strength, fusiform directional distribution structure on the structure and the like, and can be used as an effective channel for quickly transmitting electron or phonon heat energy; the preparation process has simple conditions and is easy for batch synthesis.
Description
Technical Field
The invention relates to preparation of a complex phase ceramic reinforced silver-based composite material, in particular to SnO directionally distributed in a spindle shape 2 /A 2 Sn 2 O 7 A preparation method of a complex phase ceramic (A = Bi, sb, Y) reinforced silver-based composite material.
Background
The metal oxide reinforced silver-based composite material is a key core material in the current 5G communication and new energy switch devices, and the performance of the metal oxide reinforced silver-based composite material is directly related to the cycle service reliability of the 5G communication and new energy devices. SnO among the numerous metal oxide-reinforced silver-based composites 2 The reinforced silver-based composite material system is a main research hotspot at present, but the reinforced silver-based composite material system is easy to break in the plastic processing process and is difficult to be processed and molded smoothly; meanwhile, snO is arranged in the switching device for real working condition service process 2 The reinforcing phase and the silver matrix phase are easy to generate the phenomena of phase separation, segregation and the like, so that the switch device fails in advance, and even serious electrical safety accidents occur.
For this reason, the related scholars have conducted research work on the improvement of related optimization from the viewpoint of the modification of the reinforcing phase. Wang et al report states that compared to Ag/SnO 2 -La 2 O 3 、Ag/SnO 2 -TiO 2 In particular, ag/SnO 2 -Bi 2 O 3 The material shows the most appropriate electric contact performance and is expected to replace Ag/CdO to realize the application in the field of low-voltage electric appliances. Wu-Xinhe has systematically studied Ag/SnO 2 -Bi 2 O 3 The in-situ reaction synthesis method for preparing the electric contact material and the research on the electric service life performance thereof are Ag/SnO 2 -Bi 2 O 3 The mass production application of the electric contact material provides data support. In addition to the above-mentioned single element simple substance and single oxidationAs a doping modification technology, other researchers improve Ag/SnO through a co-doping technology 2 Electrical properties of the contact material. Zhengxianhua et al discovered that (CuO, fe) was prepared by a mechanical alloying process combined with a cold press-sinter-hot press process 2 O 3 ) Complex phase doping modified Ag/SnO 2 The material exhibits optimum conductive properties with a resistivity of at least 2.25 mu omega cm.
However, the above composite enhanced phase material or modified phase material still has the disadvantages of intrinsic electrical conductivity, intrinsic thermal conductivity and other physical properties, so that the enhanced modified silver-based electrical contact material formed by compounding the composite enhanced or modified material and the silver matrix phase is difficult to realize double superposition effect on electrical and thermal properties, and the modified silver-based electrical contact material with more excellent comprehensive electrical properties such as electrical and thermal conductivity, arc erosion resistance and the like cannot be prepared.
Therefore, the preparation of the novel electric contact material with excellent comprehensive performance has practical significance and meets the market demand.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a directionally distributed SnO 2 /A 2 Sn 2 O 7 A preparation method of a complex phase ceramic reinforced silver-based composite material (A = Bi, sb and Y).
In order to solve the technical problem, the solution of the invention is as follows:
providing a directionally distributed SnO 2 /A 2 Sn 2 O 7 The preparation method of the complex phase ceramic reinforced silver-based composite material comprises the following steps:
(1) Synthesis of SnO 2 /A 2 Sn 2 O 7 Complex phase ceramic
Weighing Sn powder and A powder in a vacuum glove box according to the molar ratio Sn: A = 3; uniformly mixing the powder, introducing the powder into an alumina crucible reaction tank, and placing the alumina crucible reaction tank into a vacuum tube furnace; then carrying out in-situ internal oxidation reaction under the protection of argon atmosphere, wherein the reaction temperature is 800-950 ℃, and the reaction time is 12-45 h; after the reaction is finished, snO is obtained 2 /A 2 Sn 2 O 7 Complex phase ceramic powder;
(2) Preparation of SnO 2 /A 2 Sn 2 O 7 Complex phase ceramic reinforced silver-base composite powder
Weighing silver powder and SnO according to the mass ratio of 88 2 /A 2 Sn 2 O 7 Heterogeneous ceramic powder prepared from silver powder and SnO 2 /A 2 Sn 2 O 7 Putting the complex phase ceramic, the grinding balls and the absolute ethyl alcohol into a ball milling tank in sequence, and grinding for 10-25 h under the condition of the rotating speed of 200-300 rpm to obtain SnO 2 /A 2 Sn 2 O 7 Complex phase ceramic reinforced silver-based composite powder;
(3) Preparation of SnO 2 /A 2 Sn 2 O 7 Complex phase ceramic reinforced silver-base composite material
SnO 2 /A 2 Sn 2 O 7 Leading the complex phase ceramic silver-based composite powder into a hot-pressing mould, and carrying out secondary hot-pressing treatment; wherein the pressure of the primary hot pressing is 30-50 MPa, and the temperature is 830-920 ℃; the pressure of the secondary hot pressing is 60-80 MPa, and the temperature is 700-850 ℃; after the hot-pressing reaction is finished, treating in an air cooling mode to finally obtain SnO 2 /A 2 Sn 2 O 7 The complex phase ceramic reinforced silver-base composite material.
In a preferable embodiment of the present invention, in the step (1), the purity of the Sn powder, the Bi powder, the Sb powder, or the Y powder is greater than or equal to 99.99%; the average grain size of Sn powder is 50-150nm, and the average grain size of Bi powder, sb powder or Y powder is 70-200 nm.
In a preferred embodiment of the present invention, in the step (1), the pressure of argon is 0.3 to 0.7MPa.
In a preferred embodiment of the present invention, in the step (1), the temperature is raised at a rate of 2 to 5 ℃/min to a predetermined reaction temperature condition.
As a preferable scheme of the invention, in the step (2), the grinding balls and the ball milling tank are made of zirconia or agate; the grinding balls are comprised of two sizes,
ball:
mass ratio of spheres = 1.
As a preferred scheme of the present invention, in the step (2), the grinding balls are weighed according to a mass ratio of the grinding balls to the multiphase ceramic powder of 5-10, and the anhydrous ethanol is weighed according to a mass ratio of the anhydrous ethanol to the multiphase ceramic powder of 2.
Finally, aimed at obtaining SnO 2 /A 2 Sn 2 O 7 And testing the density, the electric conduction, the heat conduction, the interface wettability and the like of the complex-phase ceramic reinforced silver-based composite material.
The principle of the invention is described as follows:
the invention provides a new design idea of a complex-phase ceramic reinforced silver-based composite structure, and constructs and invents a SnO directionally distributed in a flow shuttle shape by utilizing respective technical advantages of an in-situ selective oxidation technology, a mechanical alloying process and a sectional type hot-pressing reaction sintering technology 2 /A 2 Sn 2 O 7 The complex phase ceramic reinforced silver-based composite material has remarkable structural innovation.
The invention makes full use of SnO 2 /A 2 Sn 2 O 7 In the complex phase ceramics A 2 Sn 2 O 7 The crystal structure similarity between the phase and the metal Ag phase realizes the hard SnO phase 2 /A 2 Sn 2 O 7 The mosaic reaction between the complex phase ceramic and the soft phase Ag achieves high-strength interface metallurgical bonding; snO with excellent electric and heat conducting properties prepared by utilizing sectional type hot-pressing reaction sintering technology 2 /A 2 Sn 2 O 7 The complex phase ceramic reinforced silver-base composite material solves the problem of traditional SnO 2 The reinforced silver-based composite material has the problems of poor phase interface combination, low density, poor electric and heat conductivity and the like.
SnO provided by the invention 2 /A 2 Sn 2 O 7 A introduced into complex phase ceramic 2 Sn 2 O 7 The phase has a similar crystal structure with the silver matrix phase, and belongs to a face-centered cubic system, so that a similar sliding system can be maintained, and plastic processing and forming are facilitated. Moreover, compared with the conventional methodSnO of (2) 2 SnO for the/Ag interface Structure 2 /A 2 Sn 2 O 7 The interface structure between the complex phase ceramic and the Ag matrix can obtain better matching degree, and is beneficial to improving SnO 2 The wetting characteristic of the interface between the reinforcing phase and the silver matrix phase is enhanced, and the bonding strength of the phase interface is improved.
In addition, the directional distribution structure provided by the invention has an effective channel for quickly transmitting the heat energy of electrons or phonons. The reason is that the directional distribution structure can reduce the scattering effect of carriers such as electrons or phonons and the like, and improve the effective transmission capability of the carriers.
Thus, the synthesis of SnO 2 /A 2 Sn 2 O 7 Formula design of complex phase ceramic and SnO 2 /A 2 Sn 2 O 7 The good interface structure matching degree of the complex phase ceramic and the Ag matrix phase is optimized, the preparation process of the directional distribution structure is realized, and the like, and the directionally distributed SnO is realized 2 /A 2 Sn 2 O 7 The performance of the complex phase ceramic reinforced silver-based composite material is improved to replace the traditional Ag/SnO 2 Materials provide a new material research direction.
Compared with the prior art, the invention has the beneficial effects that:
1. the product prepared by the invention has the characteristics of high phase interface bonding strength, fusiform directional distribution organization on the structure and the like, and can be used as an effective channel for quickly transmitting the heat energy of electrons or phonons;
2. the invention solves the problem of the traditional SnO 2 The problems of poor phase interface combination, low density, poor electric and heat conducting performance and the like of the reinforced silver-based composite material are solved;
3. the preparation process of the invention has simple conditions and is easy for batch synthesis.
Drawings
FIG. 1 is a SnO prepared in example 2 2 /Sb 2 Sn 2 O 7 SEM photograph of the composite ceramic reinforced silver-based composite material.
Detailed Description
The following describes an implementation of the present invention by way of specific embodiments.
In the following examples, powdery Sn (purity 99.99%) and a (purity 99.99%, a = Bi, sb or Y) were used as raw materials, and the average grain size of Sn powder was 50 to 150nm, and the average grain size of Bi powder, sb powder or Y powder was 70 to 200nm.
During grinding, the grinding balls and the ball-milling tank can be made of zirconium oxide or agate. The grinding balls are comprised of two sizes of,
ball:
the mass ratio of the spheres = 1. And (2) weighing the grinding balls according to the mass ratio of the grinding balls to the multiphase ceramic powder of 5-10.
Example 1:
(1)SnO 2 /Bi 2 Sn 2 O 7 synthesis of complex phase ceramics
Based on the calculation and analysis of internal oxidation thermodynamic parameters, according to the molar ratio of Sn to Bi = 3. Then, carrying out in-situ internal oxidation reaction under the conditions of high-purity argon atmosphere protection (Ar pressure is 0.3 MPa), internal oxidation temperature (800 ℃), internal oxidation time (45 h) and oxidation heating rate of 2 ℃/min, and preparing corresponding SnO after the reaction is finished 2 /Bi 2 Sn 2 O 7 Complex phase ceramic powder.
(2)SnO 2 /Bi 2 Sn 2 O 7 Preparing the complex phase ceramic reinforced silver-based composite powder.
Weighing chemical silver powder and SnO according to the mass ratio of 88 2 /A 2 Sn 2 O 7 Multiple-phase ceramic powder prepared from silver powder and SnO 2 /Bi 2 Sn 2 O 7 And sequentially placing the complex phase ceramic, the grinding balls and the alcohol into a ball milling tank, wherein the mass ratio of the grinding balls to the complex phase ceramic powder is 5. Under the condition that the ball milling rotating speed is 200rpmGrinding for 25h to prepare SnO 2 /Bi 2 Sn 2 O 7 The complex phase ceramic reinforced silver-base composite powder.
(3)SnO 2 /Bi 2 Sn 2 O 7 Preparation of complex phase ceramic reinforced silver-base composite material
SnO 2 /Bi 2 Sn 2 O 7 Leading the complex phase ceramic silver-based composite powder into a mold with the diameter of phi 12mm, and carrying out secondary hot pressing treatment; wherein the primary hot pressing pressure is 30MPa, and the primary hot pressing temperature is 830 ℃; the secondary hot pressing pressure is 60MPa, the secondary hot pressing temperature is 700 ℃, and after the hot pressing reaction sintering is finished, the secondary hot pressing is processed in an air cooling mode to finally obtain SnO 2 /A 2 Sn 2 O 7 The complex phase ceramic reinforced silver-base composite material.
And testing the finally prepared composite electric contact material according to the Archimedes principle and the specification of the national standard GB/T5586.2998, such as density, electric conduction, heat conduction, interface wettability and the like.
Example 2:
(1)SnO 2 /Sb 2 Sn 2 O 7 synthesis of complex phase ceramics
Based on the calculation and analysis of internal oxidation thermodynamic parameters, according to the Sn: sb molar ratio = 3. Then, carrying out in-situ internal oxidation reaction under the conditions of high-purity argon atmosphere protection (Ar pressure is 0.7 MPa), internal oxidation temperature (950 ℃), internal oxidation time (12 h), oxidation heating rate of 5 ℃/min and the like, and preparing corresponding SnO after the reaction is finished 2 /Sb 2 Sn 2 O 7 Complex phase ceramic powder.
(2)SnO 2 /Sb 2 Sn 2 O 7 Preparing the complex phase ceramic reinforced silver-based composite powder.
Weighing chemical silver powder and SnO according to the mass ratio of 88 2 /A 2 Sn 2 O 7 Multiple-phase ceramic powder prepared from silver powder and SnO 2 /Sb 2 Sn 2 O 7 The multiphase ceramic, the grinding balls and the alcohol are sequentially put into a ball milling tank, and the grinding balls and the multiphase ceramic are mixedThe mass ratio of the powder is 10. Grinding for 10h under the condition that the ball milling rotating speed is 300rpm to prepare SnO 2 /Sb 2 Sn 2 O 7 The complex phase ceramic reinforced silver-base composite powder.
(3)SnO 2 /Sb 2 Sn 2 O 7 Preparation of complex phase ceramic reinforced silver-base composite material
SnO 2 /Sb 2 Sn 2 O 7 Leading the complex phase ceramic silver-based composite powder into a mold with the diameter of phi 12mm, and carrying out secondary hot pressing treatment; wherein the primary hot pressing pressure is 50MPa, and the primary hot pressing temperature is 920 ℃; the secondary hot pressing pressure is 80MPa, the secondary hot pressing temperature is 850 ℃, and after the hot pressing reaction sintering is finished, the secondary hot pressing is processed in an air cooling mode to finally obtain SnO 2 /A 2 Sn 2 O 7 The complex phase ceramic reinforced silver-base composite material.
And testing the finally prepared composite electric contact material for compactness, electric conduction, heat conduction, interface wettability and the like according to the Archimedes principle and the specification of the national standard GB/T5586.2998.
FIG. 1 shows SnO prepared in this example 2 /Sb 2 Sn 2 O 7 SEM photograph of the composite ceramic reinforced silver-based composite material. As can be seen from the figure, snO 2 /Sb 2 Sn 2 O 7 The multiphase ceramic (dark gray part in SEM picture) is distributed in spindle-shaped orientation, and SnO is distributed in spindle-shaped 2 /Sb 2 Sn 2 O 7 The complex phase ceramics have a silver matrix phase (light gray portion in SEM photograph) distributed between them. The constructed fusiform directional distribution structure is beneficial to effective transmission of electrons or phonons, and the electric conduction and heat conduction characteristics of the silver-based composite material are improved.
Example 3:
(1)SnO 2 /Y 2 Sn 2 O 7 synthesis of complex phase ceramics
Based on the calculation and analysis of internal oxidation thermodynamic parameters, according to the Sn: Y molar ratio =3, weighing corresponding Sn powder and Y powder in a vacuum glove box, introducing the Sn powder and the Y powder into an alumina crucible reaction tank, and placing the alumina crucible reaction tank into a vacuum tube furnace. Then, the mixture was subjected to high-purity argon atmosphere protection (Ar pressure: 0.5 MPa), internal oxidation temperature (860 ℃ C.)Carrying out in-situ internal oxidation reaction under the conditions of internal oxidation time (32 h), oxidation heating rate of 3 ℃/min and the like, and preparing corresponding SnO after the reaction is finished 2 /Y 2 Sn 2 O 7 Complex phase ceramic powder.
(2)SnO 2 /Y 2 Sn 2 O 7 Preparing the complex phase ceramic reinforced silver-based composite powder.
Weighing chemical silver powder and SnO according to the mass ratio of 88 2 /A 2 Sn 2 O 7 Heterogeneous ceramic powder prepared from silver powder and SnO 2 /Y 2 Sn 2 O 7 And sequentially placing the complex phase ceramic, the grinding balls and the alcohol into a ball milling tank, wherein the mass ratio of the grinding balls to the complex phase ceramic powder is 7. Grinding for 22h under the condition that the ball milling rotating speed is 250rpm to prepare SnO 2 /Y 2 Sn 2 O 7 The complex phase ceramic reinforced silver-base composite powder.
(3)SnO 2 /Y 2 Sn 2 O 7 Preparation of complex phase ceramic reinforced silver-base composite material
SnO 2 /Y 2 Sn 2 O 7 Leading the complex phase ceramic silver-based composite powder into a mold with the diameter of phi 12mm, and carrying out secondary hot pressing treatment; wherein the primary hot pressing pressure is 42MPa, and the primary hot pressing temperature is 850 ℃; the secondary hot pressing pressure is 75MPa, the secondary hot pressing temperature is 780 ℃, and after the hot pressing reaction sintering is finished, the secondary hot pressing reaction sintering is processed in an air cooling mode to finally obtain SnO 2 /A 2 Sn 2 O 7 The complex phase ceramic reinforced silver-base composite material.
And (3) carrying out performance tests on the finally prepared composite electric contact material such as density, electric conduction, heat conduction, interface wettability and the like according to the Archimedes principle and the specification of the national standard GB/T5586.2998.
Analysis of comparative examples and test results:
in the invention, snO 2 /A 2 Sn 2 O 7 The regulation and control of A-site atoms in the complex phase ceramic synthesizes SnO through in-situ selective oxidation 2 /A 2 Sn 2 O 7 (A = Bi, sb or Y) complex phase ceramic material is constructed by utilizing a mechanical alloying method and combining a segmented hot-pressing reaction sintering technologyFusiform directionally distributed SnO 2 /A 2 Sn 2 O 7 The complex phase ceramic reinforced silver-base composite material. As a control, the existing Ag/SnO is used 2 -La 2 O 3 、Ag/SnO 2 -TiO 2 、Ag/SnO 2 -Bi 2 O 3 As a blank control, the specific test method was the same as in each example.
SnO in examples 2 /A 2 Sn 2 O 7 The physical properties of the complex phase ceramic reinforced silver-based composite material and the blank control group are shown in table 1.
TABLE 1
As can be seen from comparative performance analysis (see Table 1), examples 1-3 all have significant performance advantages in terms of compactness, resistivity, interfacial wettability, etc., as compared with the blank control group. SnO compared with blank control group 2 -La 2 O 3 、SnO 2 -TiO 2 、 SnO 2 -Bi 2 O 3 In contrast, examples 1-3 are relatively high in density, on average 1-3 percentage points higher; a marked decrease in resistivity, in particular SnO 2 /Sb 2 Sn 2 O 7 The resistivity of the composite ceramic silver-based composite material is reduced to 2.07 mu omega cm (the resistivity in the industry is basically 2.2 mu omega cm), and the excellent performance has certain relevance with good interface wettability and a flow shuttle-shaped directional distribution structure. And the data measured in examples 1-3 also has certain performance advantages compared with a blank control group in terms of thermal conductivity, and the data has certain relevance with the flow shuttle-shaped directional distribution structure constructed by the invention, so that an effective channel for quickly transmitting the electronic or phonon heat energy is formed.
In particular SnO in example 2 2 /Sb 2 Sn 2 O 7 The complex phase ceramic reinforced silver-based composite material has the best performance and can replace the traditional AgSnO 2 An electrical contact material. Therefore, the novel composite material has the advantages of 5G communication, new energy and other fieldsHas wide application prospect.
Claims (6)
1. Directionally distributed SnO 2 /A 2 Sn 2 O 7 The preparation method of the complex phase ceramic reinforced silver-based composite material is characterized by comprising the following steps:
(1) Synthesis of SnO 2 /A 2 Sn 2 O 7 Complex phase ceramic
Weighing Sn powder and A powder in a vacuum glove box according to the molar ratio Sn: A =3, wherein A = Bi, sb or Y; uniformly mixing the powder, introducing the powder into an alumina crucible reaction tank, and placing the alumina crucible reaction tank into a vacuum tube furnace; then carrying out in-situ internal oxidation reaction under the protection of argon atmosphere, wherein the reaction temperature is 800-950 ℃, and the reaction time is 12-45 h; after the reaction is finished, snO is obtained 2 /A 2 Sn 2 O 7 Complex phase ceramic powder;
(2) Preparation of SnO 2 /A 2 Sn 2 O 7 Complex phase ceramic reinforced silver-base composite powder
Weighing silver powder and SnO according to the mass ratio of 88 2 /A 2 Sn 2 O 7 Multiple-phase ceramic powder prepared from silver powder and SnO 2 /A 2 Sn 2 O 7 Sequentially putting the complex phase ceramic, the grinding balls and the absolute ethyl alcohol into a ball milling tank, and grinding for 10-25 h under the condition of the rotating speed of 200-300 rpm to obtain SnO 2 /A 2 Sn 2 O 7 Complex phase ceramic reinforced silver-base composite powder;
(3) Preparation of SnO 2 /A 2 Sn 2 O 7 Complex phase ceramic reinforced silver-base composite material
SnO 2 /A 2 Sn 2 O 7 Leading the complex phase ceramic silver-based composite powder into a hot-pressing mould, and carrying out secondary hot-pressing treatment; wherein the pressure of the primary hot pressing is 30-50 MPa, and the temperature is 830-920 ℃; the pressure of the secondary hot pressing is 60-80 MPa, and the temperature is 700-850 ℃; after the hot-pressing reaction is finished, treating in an air cooling mode to finally obtain SnO 2 /A 2 Sn 2 O 7 The complex phase ceramic reinforced silver-base composite material.
2. The method according to claim 1, wherein in the step (1), the purity of the Sn, bi, sb or Y powder is greater than or equal to 99.99%; the average grain size of Sn powder is 50-150nm, and the average grain size of Bi powder, sb powder or Y powder is 70-200 nm.
3. The method according to claim 1, wherein in the step (1), the pressure of the argon gas is 0.3 to 0.7MPa.
4. The method as set forth in claim 1, wherein in the step (1), the temperature is raised to the predetermined reaction temperature condition at a rate of 2-5 ℃/min.
5. The method according to claim 1, wherein in the step (2), the grinding balls and the ball milling pot are made of zirconium oxide or agate; the grinding balls are comprised of two sizes of,
ball:
mass ratio of spheres = 1.
6. The method according to claim 1, wherein in the step (2), the grinding balls are weighed according to a mass ratio of the grinding balls to the complex phase ceramic powder of 5-10.
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| US4141727A (en) * | 1976-12-03 | 1979-02-27 | Matsushita Electric Industrial Co., Ltd. | Electrical contact material and method of making the same |
| JPS5484810A (en) * | 1977-11-18 | 1979-07-06 | Matsushita Electric Ind Co Ltd | Electric contact material |
| JPH09134632A (en) * | 1995-09-05 | 1997-05-20 | Tanaka Kikinzoku Kogyo Kk | Electric contact material and clad rivet contact or clad cross bar contact, and automobile relay and television power supply relay using the same |
| CN1830599A (en) * | 2006-04-07 | 2006-09-13 | 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 |
| CN102074278A (en) * | 2010-12-09 | 2011-05-25 | 温州宏丰电工合金股份有限公司 | Preparation method of particle-aligned reinforced silver based contact material |
| CN113073226A (en) * | 2021-03-24 | 2021-07-06 | 国网河北能源技术服务有限公司 | Cu-TiC electric contact composite material and preparation method thereof |
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2022
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|---|---|---|---|---|
| US4141727A (en) * | 1976-12-03 | 1979-02-27 | Matsushita Electric Industrial Co., Ltd. | Electrical contact material and method of making the same |
| JPS5484810A (en) * | 1977-11-18 | 1979-07-06 | Matsushita Electric Ind Co Ltd | Electric contact material |
| JPH09134632A (en) * | 1995-09-05 | 1997-05-20 | Tanaka Kikinzoku Kogyo Kk | Electric contact material and clad rivet contact or clad cross bar contact, and automobile relay and television power supply relay using the same |
| CN1830599A (en) * | 2006-04-07 | 2006-09-13 | 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 |
| CN102074278A (en) * | 2010-12-09 | 2011-05-25 | 温州宏丰电工合金股份有限公司 | Preparation method of particle-aligned reinforced silver based contact material |
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