CN102321838B - Method for preparing Ag/SnO2 composite material - Google Patents
Method for preparing Ag/SnO2 composite material Download PDFInfo
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- CN102321838B CN102321838B CN 201110307129 CN201110307129A CN102321838B CN 102321838 B CN102321838 B CN 102321838B CN 201110307129 CN201110307129 CN 201110307129 CN 201110307129 A CN201110307129 A CN 201110307129A CN 102321838 B CN102321838 B CN 102321838B
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- sno
- sintering
- sno2
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Abstract
The invention relates to preparation of silver-based composite materials, and aims to provide a method for preparing an Ag/SnO2 composite material. The method comprises the following steps of: simultaneously dripping ammonia water and an acid aqueous solution of SnCl4.5H2O into a WC suspended aqueous solution with stirring, reacting, filtering and washing, performing vacuum drying, and calcining to obtain core-shell coated structure composite SnO2 particles; performing ball milling on the particles and silver powder and uniformly mixing to obtain mixed powder; performing isostatic pressing on the mixed powder to obtain a blank; and sintering, re-pressing and re-sintering in turn; and performing hot extrusion forming to obtain the Ag/SnO2 composite material. By the Ag/SnO2 composite material prepared by the method, composite particles are ensured to have good characteristics similar to those of SnO2, and a defect of performance degradation caused by component segregation in the using process of the traditional electric contact material can be effectively overcome by regulating a compounding ratio of SnO2 to WC, so that adverse effects of contact resistance increase and temperature rise on electrical usability after long-term use are eliminated.
Description
Technical field
The present invention relates to a kind of preparation method of silver-based composite material, specifically, is a kind of Ag/SnO
2The composite manufacture method.
Background technology
Contact material and element are the key foundation of electrical equipment industry, are undertaking the task of connection and breaking current, and its performance directly has influence on break-make capacity, work-ing life and the serviceability of whole set equipment.The Ag/CdO electric contact composite material also begins large-scale application from the fifties, have anti-electric arc, anti-melting welding, anti-electric and mechanical wear, corrosion-resistant and low contact resistance and the good advantages such as processibility, in larger operating voltage or range of current, all show good electrical contact performance, be called as " omnipotent contact material ", Ag/CdO electric contact composite material decades leading in occupation of market always after this.Enter 21st century, environment protection day by day is subject to countries in the world and payes attention to, and in February, 2003, European Union promulgated RoHS instruction and WEEE instruction, and the application that contains the Cd material in the electronic and electrical equipment is limited, and has started Ag/CdO and has substituted the upsurge that contact material is studied.Over past ten years, the researchist has carried out a large amount of research work around environment-friendly type without the Cd electric contact composite material, and wherein the most representative is Ag/SnO
2Material.
Usually, Ag/SnO
2Material is to adopt SnO
2Particle and Ag direct combination make, thus obtained Ag/SnO
2Have preferably anti-arc erosion, anti-melting welding and the performance such as wear-resistant.But, because SnO
2Density (6.38g/cm
3) than the density (10.53g/cm of matrix Ag
3) little, at Ag/SnO
2Matrix material is because of behind arc erosion forms little molten bath, SnO
2The meeting floating is enriched in material surface and forms the not SnO of easy conductive
2Slag causes the contact material contact resistance to increase, and surface temperature rise is too high, and electrical property is deteriorated.Therefore, improve Ag/SnO by new preparation method
2The microtexture of material with further acquisition better properties, becomes the technical problem that needs to be resolved hurrily.
Summary of the invention
The object of the invention is to overcome the deficiency of existing contact material system, Ag/SnO is provided
2A kind of new preparation method of matrix material.
Be the technical solution problem, the invention provides a kind of Ag/SnO
2The composite manufacture method specifically comprises the steps:
(1) with ammoniacal liquor and pH value is 1～3 SnCl under agitation condition
45H
2It is that the pH value that makes reaction system is that the mol ratio of 2～4, Sn and W is 1: 10～1: 4 in 5% the WC aqueous suspension that the acidic aqueous solution of O is added drop-wise to massfraction simultaneously; After reacting 1～12h under 50～90 ℃ of conditions, with suspension filtered, washing, calcine after the vacuum-drying, obtain to have the composite S nO of nucleocapsid clad structure
2Particle;
(2) with above-mentioned composite S nO
2Particle and silver powder ball milling mix composite S nO
2Particle accounts for 8%～20% of mixed powder total mass, obtains mixed powder;
(3) powder after will mixing is by waiting static pressure to be pressed into base substrate, then successively through oversintering, press again, resintering technique, last hot extrusion molding obtains Ag/SnO
2Matrix material.
Among the present invention, calcining temperature is 400～800 ℃ in the described step (1), and calcination time is 2h.
Among the present invention, described composite S nO
2The particle size range of particle is 0.05 μ m～1 μ m, and the particle size range of silver powder is 0.1～50 μ m.
Among the present invention, in the described ball-milling technology of step (2), the rotational speed of ball-mill scope is 50～200r/min, ratio of grinding media to material scope 1: 1～10: 1, Ball-milling Time 1～24h.
Among the present invention, wait static pressure pressure range 50～500MPa described in the step (3).
Among the present invention, sintering process described in the step (3) refers to sintering under the hydrogen atmosphere protection, 600～900 ℃ of sintering temperatures, sintering time 1～12h.
Among the present invention, multiple compression technology is to carry out hot pressing under 500～800 ℃ described in the step (3), pressure range 200～700MPa, soaking time 10～60min.
Among the present invention, resintering technique described in the step (3) refers under hydrogen atmosphere protection again sintering, 700～900 ℃ of sintering temperatures, sintering time 1～12h.
Among the present invention, described in the step (3) in the hot extrusion molding technique, 200～700 ℃ of mold preheating temperatures, 300～900 ℃ of blank temperatures, the extrusion ratio scope is 10～200, extrusion speed is 1～10cm/min.
With existing Ag/SnO
2The material preparation method is compared, and the invention has the beneficial effects as follows:
The Ag/SnO for preparing by the present invention
2Matrix material, its SnO
2The wild phase particle has take WC as nuclear, SnO
2Microcosmic composite structure for shell.This structure has guaranteed that on the one hand composite particles has and SnO
2Similar good characteristic is on the other hand because WC has higher density (15.63g/cm
3), therefore can be by adjusting SnO
2Make composite S nO with the compositely proportional of WC
2Particle has the density with Ag matrix phase coupling, thereby effectively overcomes traditional Ag/SnO
2The performance degradation that contact material in use causes because of component segregation, and then eliminate contact contact resistance increase, temperature rise behind life-time service and improve the disadvantageous effect to electric use properties.
Embodiment
Below the present invention is further described by example.
Ag/SnO provided by the invention
2The composite manufacture method specifically comprises the steps:
(1) with ammoniacal liquor and pH value is 1～3 SnCl under agitation condition
45H
2It is that the pH value that makes reaction system is that the mol ratio of 2～4, Sn and W is 1: 10～1: 4 in 5% the WC aqueous suspension that the acidic aqueous solution of O is added drop-wise to massfraction simultaneously; After reacting 1～12h under 50～90 ℃ of conditions, with suspension filtered, washing, calcine after the vacuum-drying, obtain to have the composite S nO of nucleocapsid clad structure
2Particle;
(2) with above-mentioned composite S nO
2Particle and silver powder ball milling mix composite S nO
2Particle accounts for 8%～20% of mixed powder total mass, obtains mixed powder;
(3) powder after will mixing is by waiting static pressure to be pressed into base substrate, then successively through oversintering, press again, resintering technique, last hot extrusion molding obtains Ag/SnO
2Matrix material.
Testing data among each embodiment sees the following form.
At last, it is also to be noted that, what more than enumerate only is part specific embodiment of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (7)
1. Ag/SnO
2The composite manufacture method specifically comprises the steps:
(1) with ammoniacal liquor and pH value is 1 ~ 3 SnCl under agitation condition
45H
2It is that the pH value that makes reaction system is that the mol ratio of 2～4, Sn and W is 1: 10～1: 4 in 5% the WC aqueous suspension that the acidic aqueous solution of O is added drop-wise to massfraction simultaneously; After reacting 1～12h under 50～90 ℃ of conditions, with suspension filtered, washing, calcine after the vacuum-drying, obtain to have the nucleocapsid clad structure take WC as nuclear, SnO
2Composite S nO for shell
2Particle;
(2) with above-mentioned composite S nO
2Particle and silver powder ball milling mix composite S nO
2Particle accounts for 8%～20% of mixed powder total mass, obtains mixed powder;
(3) powder after will mixing is by waiting static pressure to be pressed into base substrate, then successively through oversintering, press again, resintering technique, last hot extrusion molding obtains Ag/SnO
2Matrix material;
Calcining temperature is 400～800 ℃ in the described step (1), and calcination time is 2h;
Described composite S nO
2The particle size range of particle is 0.05 μ m ~ 1 μ m, and the particle size range of silver powder is 0.1～50 μ m.
2. described Ag/SnO according to claim 1
2The composite manufacture method is characterized in that, in the described ball-milling technology of step (2), the rotational speed of ball-mill scope is 50～200r/min, ratio of grinding media to material scope 1: 1 ~ 10: 1, Ball-milling Time 1～24h.
3. described Ag/SnO according to claim 1
2The composite manufacture method is characterized in that, waits static pressure pressure range 50～500MPa described in the step (3).
4. described Ag/SnO according to claim 1
2The composite manufacture method is characterized in that, sintering process described in the step (3) refers to sintering under the hydrogen atmosphere protection, 600～900 ℃ of sintering temperatures, sintering time 1～12h.
5. described Ag/SnO according to claim 1
2The composite manufacture method is characterized in that, multiple compression technology is to carry out hot pressing under 500～800 ℃ described in the step (3), pressure range 200～700MPa, soaking time 10～60min.
6. described Ag/SnO according to claim 1
2The composite manufacture method is characterized in that, resintering technique described in the step (3) refers under hydrogen atmosphere protection again sintering, 700～900 ℃ of sintering temperatures, sintering time 1～12h.
7. described Ag/SnO according to claim 1
2The composite manufacture method is characterized in that, described in the step (3) in the hot extrusion molding technique, and 200～700 ℃ of mold preheating temperatures, 300～900 ℃ of blank temperatures, the extrusion ratio scope is 10～200, extrusion speed is 1～10cm/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110307129 CN102321838B (en) | 2011-10-11 | 2011-10-11 | Method for preparing Ag/SnO2 composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110307129 CN102321838B (en) | 2011-10-11 | 2011-10-11 | Method for preparing Ag/SnO2 composite material |
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| Publication Number | Publication Date |
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| CN102321838A CN102321838A (en) | 2012-01-18 |
| CN102321838B true CN102321838B (en) | 2013-02-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110307129 Expired - Fee Related CN102321838B (en) | 2011-10-11 | 2011-10-11 | Method for preparing Ag/SnO2 composite material |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102528055B (en) * | 2012-02-13 | 2013-12-04 | 中国科学院宁波材料技术与工程研究所 | Preparation method for silver and stannic oxide composite powder and application thereof |
| CN105551811B (en) * | 2016-01-18 | 2018-05-15 | 吉林大学 | The porous SnO of graded structure2And TiO2The Ag@C nanos ball of cladding, preparation method and applications |
| CN106041061B (en) * | 2016-07-06 | 2018-06-26 | 同济大学 | A kind of preparation method of the low-loss composite magnetic powder core of high-performance |
| CN106181132B (en) * | 2016-07-15 | 2018-07-20 | 哈尔滨工业大学深圳研究生院 | A kind of high-temp solder preparation method based on Ag@Sn nucleocapsid structures |
| CN106636723B (en) * | 2016-12-30 | 2018-04-20 | 衢州学院 | One kind is with La1‑xSrxInO3Microballoon is the Ag base electrical contact material preparation methods of enhancing phase |
| CN108330315B (en) * | 2018-02-13 | 2019-12-06 | 浙江大学 | Superplastic Ag/SnO2 alloy material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417817A (en) * | 2002-11-05 | 2003-05-14 | 天津大学 | Nano silver-tin oxide electric contact and its prepn |
| CN101649399A (en) * | 2009-07-20 | 2010-02-17 | 温州宏丰电工合金有限公司 | Preparation method of tin-oxygen-silver electric contact material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6455358A (en) * | 1987-08-26 | 1989-03-02 | Matsushita Electric Works Ltd | Electric contact material |
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2011
- 2011-10-11 CN CN 201110307129 patent/CN102321838B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417817A (en) * | 2002-11-05 | 2003-05-14 | 天津大学 | Nano silver-tin oxide electric contact and its prepn |
| CN101649399A (en) * | 2009-07-20 | 2010-02-17 | 温州宏丰电工合金有限公司 | Preparation method of tin-oxygen-silver electric contact material |
Non-Patent Citations (1)
| Title |
|---|
| JP昭64-55358A 1989.03.02 |
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