CN100432250C - Preparation process of silver tin oxide electric contact material - Google Patents
Preparation process of silver tin oxide electric contact material Download PDFInfo
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- CN100432250C CN100432250C CNB2006100456397A CN200610045639A CN100432250C CN 100432250 C CN100432250 C CN 100432250C CN B2006100456397 A CNB2006100456397 A CN B2006100456397A CN 200610045639 A CN200610045639 A CN 200610045639A CN 100432250 C CN100432250 C CN 100432250C
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Abstract
The preparation process of silver-tin oxide electric contact material features the material comprising 150 mesh SnO2 powder in 2-12 wt% and 50-1000 mesh AgSn alloy powder with Sn content of 1-5 wt% for the rest. The preparation process includes no-air ball milling or forced mixing the said material to obtain compound powder, and forming before or after internal oxidation to produce the electric contact material. Thus process has powder metallurgy and internal oxidation and the prepared silver-tin oxide electric contact material has excellent electric performance and mechanical performance.
Description
Technical field:
The present invention relates to the technology of preparing of electrical contact material, a kind of siller tin oxide electric contact material preparation method is provided especially.
Background technology:
Along with the high speed development of modern industry, control apparatus industrialization, intelligent level are more and more higher, and the high voltage power transmission and transforming network load increases day by day, and low-voltage distribution system and Controlling System be the update of development and electronic industrial products constantly.Electric equipment products develop to the direction of large vol, small volume.Thereupon to electric equipment products the heart element---electrical contact material is had higher requirement, promptly require material under the situation of greatly arc heat and joule heating, melting welding does not take place, mechanical wear and anti-electric abrasioning performance are good; The metal that produces in breaking course splashes too much unsuitable, and the arc time is unsuitable oversize; Under the direct current environment for use, resistance fusion welding is good, and material transition is few, and contact resistance is low and stable.
Because the CdO in the AgCdO alloy can at high temperature decompose, play the effect of heat absorption, cooling, so it has good over-all properties, good processability has been widely used in low-voltage apparatus contact field in addition, poisons but AgCdO is easy to generate Cd in production and use, biology is caused damage, environment is polluted, and Europe and Japan launch respectively rules for this reason, forbid to use in household electrical appliance and car electrics the AgCdO contact.Simultaneously also because low-voltage apparatus miniaturization, high reliability, long-life requirement, shortcoming such as AgCdO also exposes resistance fusion welding can be poor, electrical arc erosion is serious, it is alternative to need the better silver contact material of performance.
At present, the Ag-based electrical contact material manufacturing process has two big classes: 1. alloy melting internal oxidation; 2. powder metallurgic method.Also can be divided into interior oxidation contact and powder metallurgy contact two big series according to its product of manufacturing process.Japan proposes and has issued somely to prepare AgSnO with inner oxidation method
2Patented technology, and this product put goods on the market; Germany has issued the employing powder metallurgy process and has prepared AgSnO
2Patent, product also puts goods on the market in batches; The domestic coating method that adopts is in addition produced AgSnO
2Patented technology.Compare AgSnO with AgCdO
2Having shown good arc ablation resistance performance, high thermal stability and good anti-melting welding ability, successfully be applied to rly., contactor and low-tension switch, is the non-toxic material that is expected to comprehensively substitute AgCdO most.
At present, it is generally acknowledged the sliver oxidized tin contactor materials density height that internal oxidation process is produced, resistivity is low, and electric life is the longest, and under AC3 and AC4 condition, its electric life is better than AgCdO with the contact of this prepared.Because it is long that the frequent electrical equipment of operations such as contactor, rly. requires the anti-electric mill of contact to undermine electric life, the therefore general contact product that adopts internal oxidation process to produce, its shortcoming is to show higher temperature rise in some occasions.
The employing powder metallurgical technique is produced, the siller tin oxide product that has added Tungsten oxide 99.999, molybdenum oxide or cupric oxide, approaching with internal oxidation aspect the contact temperature rise having better result, but having poor result in the AC3 longevity test aspect the AC4 longevity test.
Usually require difference according to electric switch function, current class etc., the material of selecting for use is also different.In addition, select for use asymmetric pairing also can improve the work-ing life of material.
Internal oxidation is that the AgSn alloy is heated under oxygen-enriched environment, passes through O
2Diffusion in Ag, at the inner stannic oxide particle that generates of alloy, this method can obtain meticulous stannic oxide particle distribution, but the component gradient that often has stannic oxide in the product, the surface is high, and is middle few, has rich stannic oxide district, the crystal boundary zone is segregation stannic oxide easily, thereby reduced the contact performance.And in the AgSn alloy when the content of Sn during greater than 4-5% (in metal element), unavoidably to form successive Sn oxide film at this alloy outside surface, thereby hinder oxygen and be penetrated into alloy inside, make the Sn of AgSn block alloy inside be difficult to interior oxidation, interior oxidation needs time long (needing several months), temperature height (500-750 degree), pressure big (general 10-200 normal atmosphere), consumes energy is many.In order to address these problems, usually to the In that wherein adds 0.5-5%, to promote interior oxidation.But the In price is high, and widespread use has the obstacle on the price, even and add prooxidant such as In, the AgSnO of 2mm
2Also need the oxidation of 200 hours ability complete.There is employing that the AgSn alloy atomization is made the AgSn alloy powder in recent years, the technology of oxidation in carrying out again.But the interior oxidation of the AgSn alloy powder that surpasses 4%Sn is still slow, still forms SnO simultaneously easily
2The particle situation of bag Ag, powder metallurgy adds man-hour, obtains SnO
2The tissue of isolating Ag, the rich SnO of crystal boundary
2, material mechanical performance is poor, is difficult to cold working (wire drawing, riveter nail etc.).
Summary of the invention:
The object of the present invention is to provide a kind of preparation method of siller tin oxide electric contact material, have both the advantage of powder metallurgy and interior oxidation, have good electrical property and mechanical property with the siller tin oxide electric contact material of this method preparation.
The invention provides a kind of preparation method of siller tin oxide electric contact material, it is characterized in that:
---the granularity with 2～12% weight is no more than 150 purpose SnO
2Powder, and the AgSn alloy powder of the granularity of surplus between 50～500 orders be raw material, wherein in the AgSn alloy powder tin content between 1～4% weight;
---above-mentioned raw materials powder secluding air ball milling or powerful mixing are prepared SnO
2The composite powder that is evenly distributed;
---above-mentioned composite powder reshaped through oxidation in earlier make contact material, perhaps make contact material through oxidation in being shaped again earlier.
Among the preparation method of siller tin oxide electric contact material of the present invention, described AgSn alloy powder can also contain one or several among Cu, Re, Zn, In, Bi, Sb or the Ce that is no more than 2% weight.
Among the preparation method of siller tin oxide electric contact material of the present invention, in the described AgSn alloy powder, tin content is preferably between 2～4% weight.
Among the preparation method of siller tin oxide electric contact material of the present invention, can also contain the WO that is no more than 1% weight in the described raw material powder
3, Bi
2O
3, MoO
3, In
2O
3, GeO
2, in CuO, WC, W, C or the bortz powder one or several.
Among the preparation method of siller tin oxide electric contact material of the present invention, the size range of described AgSn alloy powder is preferably between the 100-325 order.
Among the preparation method of siller tin oxide electric contact material of the present invention, reshape technology for oxidation in the described elder generation, parameter is chosen as: 400～800 ℃ of interior oxidizing temperatures, 1～100 hour time; Oxidizing temperature is 550 ℃ in being preferably, and the time is 5 hours.
Among the preparation method of siller tin oxide electric contact material of the present invention, for the described elder generation internal oxidation process again that is shaped, parameter is chosen as interior oxidizing temperature 500-750 ℃, time 1-200 hour.
Among the preparation method of siller tin oxide electric contact material of the present invention, for described ball-milling technology, ratio of grinding media to material is 5～50: 1, and the time is 1～20 hour.
Among the preparation method of siller tin oxide electric contact material of the present invention, described AgSn alloy powder can obtain by modes such as ball milling powder process after aerosolization, water atomization, the turning, is preferably to adopt the preparation of air atomizing method.
Key of the present invention is to consider the AgSnO of powder metallurgy preparation
2Product in the use with performance on the deficiency of internal oxidation, the advantage of oxidation and powder method in comprehensive, according to AgSn alloy oxidation characteristic, promptly at Sn content less than 4% o'clock, relevant with the thin and thick of AgSn alloying pellet size or sheet material this feature with interior oxidation of the easy oxidation of AgSn alloy will contain Sn less than 4% AgSn alloy powder (perhaps AgSnCu alloy powder) and SnO
2Powder (perhaps contains CuO, WO
3, MoO
2SnO
2Powder), isolated oxygen carries out ball milling in high energy ball mill, with SnO
2Powder is all even ultra-fine state disperse and is distributed in the silver-colored tin alloy powder matrix, and the total content of tin is between 5-20% in the composite powder.AgSn behind the ball milling and SnO
2Composite powder can directly carry out interior oxidation, also can make interior oxidation behind the finished product contact.Because SnO
2The disperse oxide compound that a small amount of Sn forms when making internal oxidation can't form continuous blocking layer, oxidation can easily be carried out constantly, oxidation can not form the gradient of inside and outside.Therefore product of the present invention promptly has very disperse and combines accurate SnO with silver
2, containing of having also that the back adds can increase stannic oxide and silver wetting W, Mo and the oxide compound of Cu, and the advantage of inner oxidation method is promptly arranged, and the advantage of powder method is also arranged, and what separate out on the crystal boundary is not stannic oxide but fine silver, and mechanical property is improved greatly.
Embodiment:
Embodiment 1
Adopt the preparation of air atomizing method to contain the AgSn alloy powder of 4%Sn, process is sieved granularity＜100 orders of silver-colored tin alloy powder; SnO with the chemical method preparation
2(containing 5%CuO) mixes with the AgSn powder, calculates SnO
2Final content is 10% in batch mixing, mixing is put into high energy ball mill and is vacuumized logical argon gas ball milling after 30 minutes in mixing tank, ratio of grinding media to material is 30: 1, ball mill speed is 500r/min, ball mill overcoat water-cooled, 2 hours time, powder oxidation and annealing 5 hours in 550 ℃ of air furnaces behind the ball milling, through cold pressing, sintering, hot pressing, resintering and multiple pressure, be squeezed into the silk of diameter 6mm, through cold-drawn to final size.
Embodiment 2
Adopt the preparation of air atomizing method to contain the AgSn alloy powder of 2%Sn, process is sieved granularity＜150 orders of silver-colored tin alloy powder; SnO with the chemical method preparation
2(contain 2%WO
3) mix with the AgSn powder, calculate SnO
2Final content is 10% in batch mixing; in mixing tank, mix after 30 minutes and put into high energy ball mill; vacuumize logical argon gas ball milling; ratio of grinding media to material is 20: 1; ball mill speed is 400r/min; 4 hours time; powder is annealed under argon shield atmosphere behind the ball milling; cold pressing, sintering, hot pressing, resintering and multiple pressure under argon shield atmosphere are squeezed into the plate of diameter 20 * 75mm; compound with the hot pressing of 5mm fine silver plate; a deflection is greater than 60%, through being cold rolled to final 3mm, and oxidation 5 hours in 500 degree in air furnace then.
Embodiment 3
Adopt the preparation of air atomizing method to contain the AgSnCu alloy powder of 4%Sn and 1%Cu, process is sieved granularity＜150 orders of silver-colored tin alloy powder; SnO with the chemical method preparation
2Mix with the AgSnCu powder, calculate SnO
2Final content is 12% in batch mixing, adds 1% In in addition
2O
3In mixing tank, mix after 30 minutes and put into high energy ball mill, vacuumize logical argon gas ball milling, ratio of grinding media to material is 20: 1, and ball mill speed is 400r/min, 4 hours time, powder oxidation and annealing 2 hours in 550 ℃ of air furnaces behind the ball milling, through cold pressing, sintering, hot pressing, resintering and multiple pressure, be squeezed into the silk of diameter 5mm, through cold-drawn to final size.
Embodiment 4
Adopt the air atomizing method to prepare the AgSnCu alloy powder that contains 4%Sn and 1%Cu, the granularity of alloy powder＜150 orders; SnO with the chemical method preparation
2Mix with the AgSnCu powder, add 0.3% Bi in addition
2O
3, calculate SnO
2, CuO and Bi
2O
3Content final in batch mixing is 15%, mixes after 30 minutes in mixing tank and puts into high energy ball mill, vacuumizes logical argon gas ball milling, and ratio of grinding media to material is 20: 1, and ball mill speed is 400r/min, and 4 hours time, powder places the vacuum hotpressing machine behind the ball milling, vacuumizes 10
-1Par also remains to 700 ℃, continues 1 hour, is warmed up to 780 degree hot pressing to fine and close, takes out the silk that is squeezed into diameter 5mm, arrives final size through cold-drawn, on rivet driver with AgSnO
2Make composite rivet, AgSnO greatly with Cu
2Thickness be 200 μ m, composite rivet 500 ℃ of oxidations 3 hours, is taken out the back at ammonia dissolving atmosphere (75%H
2And 25%N
2) 450 ℃ of copper reductions with oxidation.
Claims (10)
1, a kind of preparation method of siller tin oxide electric contact material is characterized in that:
---the granularity with 2～12% weight is no more than 150 purpose SnO
2Powder, and the AgSn alloy powder of the granularity of surplus between 50～1000 orders be raw material, wherein in the AgSn alloy powder tin content between 1～4% weight;
---above-mentioned raw materials powder secluding air ball milling or powerful mixing are prepared SnO
2The composite powder that is evenly distributed;
---above-mentioned composite powder reshaped through oxidation in earlier make contact material, perhaps make contact material through oxidation in being shaped again earlier.
2, according to the preparation method of the described siller tin oxide electric contact material of claim 1, it is characterized in that: in the described AgSn alloy powder, contain among Cu, Re, Zn, In, Bi, Sb or the Ce that is no more than 2% weight one or several.
3, according to the preparation method of claim 1 or 2 described siller tin oxide electric contact materials, it is characterized in that: in the described AgSn alloy powder, tin content is between 2～4% weight.
4, according to the preparation method of claim 1 or 2 described siller tin oxide electric contact materials, it is characterized in that: also contain the WO that is no more than 1% weight in the described raw material powder
3, Bi
2O
3, MoO
3, In
2O
3, GeO
2, in CuO, WC, W, C or the bortz powder one or several.
5, according to the preparation method of claim 1 or 2 described siller tin oxide electric contact materials, it is characterized in that: the size range of described AgSn alloy powder is between 80～325 orders.
6, according to the preparation method of claim 1 or 2 described siller tin oxide electric contact materials, it is characterized in that: reshape technology for oxidation in the described elder generation, 400～800 ℃ of interior oxidizing temperatures, 1～100 hour time.
7, according to the preparation method of the described siller tin oxide electric contact material of claim 6, it is characterized in that: oxidizing temperature is 550 ℃ in described, and the time is 5 hours.
8, according to the preparation method of claim 1 or 2 described siller tin oxide electric contact materials, it is characterized in that: for the described elder generation internal oxidation process again that is shaped, 500～850 ℃ of interior oxidizing temperatures, 1～200 hour time.
9, according to the preparation method of claim 1 or 2 described siller tin oxide electric contact materials, it is characterized in that: for described ball-milling technology, ratio of grinding media to material is 5～50: 1, and the time is 1～20 hour.
10, according to the preparation method of claim 1 or 2 described siller tin oxide electric contact materials, it is characterized in that: described AgSn alloy powder adopts the preparation of aerosolization method.
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| CNB2006100456397A CN100432250C (en) | 2006-01-12 | 2006-01-12 | Preparation process of silver tin oxide electric contact material |
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|---|---|---|---|
| CNB2006100456397A CN100432250C (en) | 2006-01-12 | 2006-01-12 | Preparation process of silver tin oxide electric contact material |
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| CN100432250C true CN100432250C (en) | 2008-11-12 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102041474B (en) * | 2010-12-20 | 2013-03-06 | 昆明理工大学 | Preparation method for nano precious metal particle modified tin dioxide gas sensitive material |
| CN102176336B (en) * | 2010-12-30 | 2012-11-14 | 温州宏丰电工合金股份有限公司 | Preparation method of silver-based oxide electrical contact material with filamentary structure |
| CN102509654B (en) * | 2011-10-27 | 2015-03-11 | 福达合金材料股份有限公司 | Preparation method for silver stannic oxide wire |
| CN102568643B (en) * | 2012-03-01 | 2013-09-18 | 郴州市金贵银业股份有限公司 | AgSnO contact material and preparation method thereof |
| CN103695696B (en) * | 2013-12-30 | 2016-05-11 | 桂林电器科学研究院有限公司 | A kind of preparation method containing additive siller tin oxide electric contact material |
| CN104493175B (en) * | 2014-12-30 | 2016-04-13 | 桂林电器科学研究院有限公司 | A kind of preparation method of the siller tin oxide electric contact material containing additive |
| CN104588672A (en) * | 2015-01-12 | 2015-05-06 | 重庆川仪自动化股份有限公司 | Preparation method of in-situ doped copper-bearing tin oxide powder and silver tin oxide material |
| CN105458273A (en) * | 2015-11-26 | 2016-04-06 | 浙江工业大学 | Method for promoting oxidation of Ag-Sn alloy powder through high energy ball milling method |
| CN108493024A (en) * | 2018-05-22 | 2018-09-04 | 东北大学 | A kind of silver-tin electrical contact material and preparation method thereof |
| CN109252064B (en) * | 2018-10-15 | 2020-05-22 | 浙江工业大学 | Doped modified Ag/SnO2Composite electric contact material and preparation method thereof |
| US20220328260A1 (en) * | 2019-09-13 | 2022-10-13 | Tanaka Kikinzoku Kogyo K.K. | Dc high-voltage relay, and contact material for dc high-voltage relay |
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|---|---|---|---|---|
| JPH06136473A (en) * | 1992-10-21 | 1994-05-17 | Chugai Electric Ind Co Ltd | Internally oxidized electrical contact material of ag-sn alloy |
| JPH07188809A (en) * | 1993-12-27 | 1995-07-25 | Ishifuku Metal Ind Co Ltd | Silver-tin oxide contact material and its production |
| CN1425790A (en) * | 2003-01-09 | 2003-06-25 | 陈达峰 | Process for preparing silver tin oxide material |
| JP2005166339A (en) * | 2003-12-01 | 2005-06-23 | Mitsubishi Material Cmi Kk | Electric contact made of internal silver oxide/oxide system material for downsized electromagnetic relay with high conductivity |
| CN1635582A (en) * | 2003-12-30 | 2005-07-06 | 中南大学 | Electric contact material for electric locomotive and method for preparing same |
-
2006
- 2006-01-12 CN CNB2006100456397A patent/CN100432250C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06136473A (en) * | 1992-10-21 | 1994-05-17 | Chugai Electric Ind Co Ltd | Internally oxidized electrical contact material of ag-sn alloy |
| JPH07188809A (en) * | 1993-12-27 | 1995-07-25 | Ishifuku Metal Ind Co Ltd | Silver-tin oxide contact material and its production |
| CN1425790A (en) * | 2003-01-09 | 2003-06-25 | 陈达峰 | Process for preparing silver tin oxide material |
| JP2005166339A (en) * | 2003-12-01 | 2005-06-23 | Mitsubishi Material Cmi Kk | Electric contact made of internal silver oxide/oxide system material for downsized electromagnetic relay with high conductivity |
| CN1635582A (en) * | 2003-12-30 | 2005-07-06 | 中南大学 | Electric contact material for electric locomotive and method for preparing same |
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| CN100999789A (en) | 2007-07-18 |
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