CN1085346A - Low-resistivity Ag/SnO 2Electric contact material and preparation thereof - Google Patents
Low-resistivity Ag/SnO 2Electric contact material and preparation thereof Download PDFInfo
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- CN1085346A CN1085346A CN 93110497 CN93110497A CN1085346A CN 1085346 A CN1085346 A CN 1085346A CN 93110497 CN93110497 CN 93110497 CN 93110497 A CN93110497 A CN 93110497A CN 1085346 A CN1085346 A CN 1085346A
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Abstract
Low-resistivity Ag/SnO
2Electric contact material is at SnO
2Middle antimony dopant element is so that the SnO of insulation
2Be modified as the SnO of conduction
2Thereby reduced material resistance, high temperature resistance particularly, and improved its serviceability.Its preparation technology is with Sn-Sb preparation in proportion, melting, casting, obtains conducting electricity SnO with nitric acid oxidation, high-temperature calcination again
2Powder will conduct electricity SnO
2Powder is put into the molten device ultrasonic vibration of complexing silver nitrate with abundant dispersion SnO
2, splash into hydrazine hydrate solution then and obtain spongy Ag bag conduction SnO
2Powder.Technology of the present invention is simple, is suitable for suitability for industrialized production.
Description
The invention provides a kind of low-resistivity Ag/SnO
2Electric contact material and preparation thereof.
Electrician's contact plays a part connection, disjunction and transmission current as one of main original paper of device for switching.Ag/SnO
2Be that alloy material is a kind of novel electrical contact material, its resistance fusion welding, anti-electrical wear are good, the electric life height, nontoxic, can miniaturize the elements, it is alloy material that the utmost point is hopeful to replace traditional Ag/CdO, thereby receives domestic and international electrical alloy worker's concern in recent years always.Ag/SnO
2The preparation method have three kinds, the one, powder metallurgic method, it is with Ag powder, SnO
2Mechanical mixture such as powder, compression moulding then, sintering, extruding (or forging and pressing) are become a useful person; The 2nd, the alloy inner oxidation method is about to Ag-Sn and is smelted into alloy, rolling or extrusion bar, and selective oxidation obtains Ag/SnO then
2Material; The 3rd, the alloy powder internal oxidation, it combines the advantage of preceding two kinds of technologies, at first obtains the Ag-Sn alloy powder, and selective oxidation obtains Ag-SnO again
2Powder, last compression moulding, sintering, extruding (or forging and pressing) are become a useful person.Though the above-mentioned three therapeutic methods of traditional Chinese medicine has his own strong points, the deficiency that temperature rise is big when all existing contact to use, the life-span is not high (comparing) with Ag/CdO, its essence is because SnO
2Be insulator, make and use SnO
2Higher with the resistivity of material that Ag makes.In addition, the material structure that obtains of above-mentioned three kinds of methods is all not satisfactory: powder metallurgic method is difficult for obtaining uniform formation; Alloy inner oxidation easily produces the component segregation and the SnO of macroscopic view, microcosmic
2Microfissure very easily appears in lamination during plastic working, in addition, this method production cycle is long, and power consumption is big, and labor productivity is low; That form during oxidation in the powder is SnO
2It is insulation SnO that bag Ag particle, powder metallurgy add what obtain man-hour
2Isolate the tissue of Ag, crystal boundary is continuous SnO
2, a little less than the intergranular adhesion, being prone to the both macro and micro crackle during use, the resistivity of material is higher, and the useful life of contact is not long.
Purpose of the present invention aims to provide a kind of Ag/SnO of low-resistivity
2Electric contact material and preparation technology thereof are to overcome the above-mentioned deficiency of prior art.
Technical solution of the present invention is: start with from the improvement of the constituent element electrical property that constitutes contact material, the aspects such as preparation of composite powder, with the tin ash (SnO of insulation
2) modification makes the tin ash of conduction, does for silver-colored agent with the complexing liquor argenti nitratis ophthalmicus then, makes reducing agent system Ag bag SnO with hydrazine hydrate solution
2Composite powder, repressed at last, sintering, forging and pressing or extruding, annealing, machine work are become a useful person.
Below the present invention is elaborated.
1, conduction SnO
2The preparation of powder:
(contain 1～15wt%) preparation of Sb amount, melting, be cast into laminarly, obtain the compound powder of tin pewter with excessive concentrated nitric acid oxidation, high-temperature calcination obtains conducting electricity SnO by proper proportion with Sn-Sb
2Powder, high-temperature calcination obtain conducting electricity SnO
2Powder, granularity 0.5～3 μ m, resistivity 0.1～10 Ω cm, its conductivity is than pure SnO
2(insulator) high 5～6 orders of magnitude.
650～750 ℃ of alloy melting temps, time 1～2hr; 800～1200 ℃ of calcining heats, calcination time 1～3hr.
2, preparation complexing liquor argenti nitratis ophthalmicus, hydrazine hydrate solution
With silver nitrate (AgNO
3) or (concentration 0.1～1.5M) is done for silver-colored agent, and uses the ammoniacal liquor complexing, PH=8～12 to get liquor argenti nitratis ophthalmicus with silvery; With hydrazine hydrate (N
2H
4H
2O) (concentration 1～5M) is made reducing agent reduction AgNO to solution
3
3, preparation Ag bag conduction SnO
2Composite powder
To conduct electricity SnO
2Powder is put into the complexing liquor argenti nitratis ophthalmicus, and ((10～60min) with abundant dispersed electro-conductive SnO for frequency 10～50KHz) certain hours in ultrasonic vibration
2Powder stirs also and suitably heats (20～80 ℃ of temperature), splashes into (or sprinkling) hydrazine hydrate solution then and obtains spongy Ag bag conduction SnO
2Powder, washing, drying finally obtain Ag/SnO
2Composite powder.
4, compression moulding, sintering, forging and pressing or extruding, annealing, machine work is become a useful person.
The cold compaction briquetting pressure is 200～500MPa, and sintering temperature is 850～900 ℃, time 1～3hr, and it is 9.85～9.95g/cm that forging and pressing, extruding or hot rolling obtain density
3Section bar, 500～800 ℃ annealing 1～3hr, punching press again, cold forging become contact.
The Ag/SnO that finally obtains
2(12) material property is, resistivity 2.3～2.5 μ cm, hardness HB760～1200MPa, density 9.85～9.95g/cm
3
Remove above-mentioned at SnO
2Outside the middle doped chemical Sb, also can be at SnO
2In (0.1～2wt%) waits element, obtains conduction SnO by the similar approach doped with Cu
2Powder.
Major advantage of the present invention is:
1, the present invention realizes the pure SnO that will insulate first
2Be modified as conduction SnO
2Powder is used for Ag/SnO
2In the contact, reduce the resistance of contact material, particularly high temperature resistance greatly, and then improved its serviceability.
2, also suitably heat, use hydrazine hydrate reduction AgNO with ultrasonic vibration, stirring for the first time
3To obtain epigranular, high degree of dispersion, composition is accurate, interface binding power is strong Ag bag conduction SnO
2Powder can obtain the splendid Ag/SnO of disperse effect by follow-up powder metallurgy processing technology
2Contact material.
3, may command conduction SnO of the present invention
2The granularity of powder (by the control vibration frequency) therefore can be prepared different SnO according to actual needs
2The Ag/SnO of granularity
2Contact material.
But 4, the present invention's adjusting process, control Ag bag conduction SnO
2The granularity of composite powder is to optimize moulding, sintering process.
5, the Ag/SnO for preparing of the present invention
2The material plastic deformation ability is good, and easily extrusion rolling becomes silk or sheet material.
6, the present invention is raw materials used is easy to get, and the technology letter is by single, easy row, and cost is lower, is suitable for suitability for industrialized production.
In addition, the ultrasonic vibration among the present invention prepares Ag bag SnO
2Powder technology also may be used in other Ag base contact material and other composite material.
Embodiment:
1, molten refining Sn-Sb alloy
Sn grain, Sb grain (2.5wt%) are inserted the crucible fusing, obtain the Sn-Sb alloy.
2, oxidation Sn-Sb alloy
Pour in the container that fills the Sn-Sb alloy with red fuming nitric acid (RFNA) (excessive), fully reaction with distilled water washing, drying, obtains white powder to obtain white precipitate, inserts to calcine under 1000 ℃ in the Muffle furnace finally to obtain pewter conduction SnO in 1 hour again
2Powder.
3, preparation Ag bag SnO
2Composite powder
The AgNO of preparation 0.9N concentration
3Solution is used the ammoniacal liquor combination, the hydrazine hydrate solution of preparation 1.7N.Press Ag: SnO
2=88: 12 ratio weighs up conduction SnO
2Powder calculates required AgNO
3The volume of solution is with the SnO that weighs up
2Powder is put into AgNO
3In the solution (container), will fill SnO again
2Powder and AgNO
3The container of solution places on the ultrasonic generator, fully vibrates more than the 30min, and supersonic frequency is 20KHz, stirs while shaking then, splashes into hydrazine hydrate solution, and reaction obtains sponge shape grey Ag-SnO
2Composite powder.Washing, drying finally obtain the taupe composite powder.
4, powder metallurgic method prepares contact material
Composite powder is placed shaping mould,, insert then in the Muffle furnace,, be warmed up to 880 ℃ of calcinings 1～2 hour again, obtain ρ ≈ 7.2～7.4g/cm to remove organic volatile substances at 450 ℃ of preheating 1hr with pressure σ=300～350MP cold forming
3Sintered body, forge hot or hot extrude obtain ρ＞9.5g/cm then
3Section bar, again under 700 ℃ of temperature annealing 1 hour, stamping cold forging becomes contact again.
As follows with the material physical property that above-mentioned technological process obtains:
Electricalresistivity=2.3～2.5 μ Ω cm Brinell hardness HB=880MPa
Density d=9.7～9.9g/cm
3
Claims (8)
1, a kind of low-resistivity electric contact material is by Ag, SnO
2By the composite powder that certain metallurgical technology makes, it is characterized in that forming the SnO of this composite powder
2In be doped with element antimony.
2, material according to claim 1 is characterized in that SnO
2The antimony amount that contains in the powder is 1～15%(wt).
3, material according to claim 1 is characterized in that forming the SnO of this composite powder
2Powder doped chemical copper, its copper content are 0.1～2%(wt).
4, a kind of low-resistivity Ag/SnO
2The preparation technology of electric contact material is characterized in that:
(1) with Sn-Sb by proper proportion preparation, melting is cast into thin slice, and obtains the compound powder of tin, antimony with nitric acid oxidation, high-temperature calcination obtains conducting electricity SnO
2Powder;
(2) will conduct electricity SnO
2Powder is put into the complexing liquor argenti nitratis ophthalmicus, and ultrasonic vibration is with abundant dispersed electro-conductive SnO
2Powder stirs, and splashes into hydrazine hydrate solution then and obtains spongy Ag bag conduction SnO
2Powder;
(3) compression moulding, sintering, forging and pressing or extruding, annealing, machine work are become a useful person.
5, technology according to claim 4 is characterized in that SnO
2In to contain the antimony amount be 1～15%(wt).
6, preparation technology according to claim 4, the smelting temperature that it is characterized in that Sn-Sb is 650～750 ℃, the time is 1～2hr; Calcining heat is 800～1200 ℃, and the time is 1～3hr.
7, preparation technology according to claim 4, the frequency that it is characterized in that ultrasonic vibration is 10～50KHz, time of vibration 10～60min.
8, preparation technology according to claim 4 is characterized in that cold compaction briquetting pressure 200～500MPa, 850～900 ℃ of sintering temperatures, time 1～3hr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93110497A CN1035089C (en) | 1993-03-03 | 1993-03-03 | Electrical low-resistivity Ag/SnO2 contact material and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93110497A CN1035089C (en) | 1993-03-03 | 1993-03-03 | Electrical low-resistivity Ag/SnO2 contact material and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1085346A true CN1085346A (en) | 1994-04-13 |
| CN1035089C CN1035089C (en) | 1997-06-04 |
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ID=4988358
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93110497A Expired - Fee Related CN1035089C (en) | 1993-03-03 | 1993-03-03 | Electrical low-resistivity Ag/SnO2 contact material and preparation thereof |
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|---|---|
| CN (1) | CN1035089C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049998C (en) * | 1994-04-25 | 2000-03-01 | 中国人民解放军国防科学技术大学 | SiC crystal fibres reinforced silver base contact material and it prepn. method |
| CN101510479B (en) * | 2009-03-18 | 2010-08-25 | 中国船舶重工集团公司第七二五研究所 | Method for preparing siller tin oxide electric contact material |
| CN102528055A (en) * | 2012-02-13 | 2012-07-04 | 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 |
| CN102633499A (en) * | 2012-04-28 | 2012-08-15 | 东莞市中一合金科技有限公司 | Preparation method of silver tin oxide or silver tin oxide and indium oxide material |
| TWI453173B (en) * | 2007-11-02 | 2014-09-21 | Agc Flat Glass Na Inc | Transparent conductive oxide coating for thin film photovoltaic applications and methods of making the same |
| CN104867622A (en) * | 2015-05-22 | 2015-08-26 | 西北有色金属研究院 | Preparation method of AgSnO2 multi-core composite wire rod |
| CN105695791A (en) * | 2016-02-25 | 2016-06-22 | 昆明贵金属研究所 | Novel silver rare earth oxide alloy and preparing method thereof |
| CN105908108A (en) * | 2016-04-14 | 2016-08-31 | 西安工程大学 | Preparation method of tin oxide fiber reinforced silver-based electric contact alloy |
-
1993
- 1993-03-03 CN CN93110497A patent/CN1035089C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049998C (en) * | 1994-04-25 | 2000-03-01 | 中国人民解放军国防科学技术大学 | SiC crystal fibres reinforced silver base contact material and it prepn. method |
| TWI453173B (en) * | 2007-11-02 | 2014-09-21 | Agc Flat Glass Na Inc | Transparent conductive oxide coating for thin film photovoltaic applications and methods of making the same |
| US9181124B2 (en) | 2007-11-02 | 2015-11-10 | Agc Flat Glass North America, Inc. | Transparent conductive oxide coating for thin film photovoltaic applications and methods of making the same |
| CN101510479B (en) * | 2009-03-18 | 2010-08-25 | 中国船舶重工集团公司第七二五研究所 | Method for preparing siller tin oxide electric contact material |
| CN102528055A (en) * | 2012-02-13 | 2012-07-04 | 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 |
| 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 |
| CN102633499A (en) * | 2012-04-28 | 2012-08-15 | 东莞市中一合金科技有限公司 | Preparation method of silver tin oxide or silver tin oxide and indium oxide material |
| CN102633499B (en) * | 2012-04-28 | 2014-04-30 | 东莞市中一合金科技有限公司 | Preparation method of silver tin oxide or silver tin oxide and indium oxide material |
| CN104867622A (en) * | 2015-05-22 | 2015-08-26 | 西北有色金属研究院 | Preparation method of AgSnO2 multi-core composite wire rod |
| CN104867622B (en) * | 2015-05-22 | 2016-08-24 | 西北有色金属研究院 | A kind of AgSnO2the preparation method of Multicore composite material |
| CN105695791A (en) * | 2016-02-25 | 2016-06-22 | 昆明贵金属研究所 | Novel silver rare earth oxide alloy and preparing method thereof |
| CN105695791B (en) * | 2016-02-25 | 2017-12-15 | 昆明贵金属研究所 | A kind of new silver rare earth oxide alloy and preparation method thereof |
| CN105908108A (en) * | 2016-04-14 | 2016-08-31 | 西安工程大学 | Preparation method of tin oxide fiber reinforced silver-based electric contact alloy |
| CN105908108B (en) * | 2016-04-14 | 2017-12-19 | 西安工程大学 | A kind of method for preparing tin oxide fibre enhancing silver-based electric contact alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1035089C (en) | 1997-06-04 |
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