CN101651054B - Preparation method of modified AgSnO2 electric contact material - Google Patents

Preparation method of modified AgSnO2 electric contact material Download PDF

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Publication number
CN101651054B
CN101651054B CN2009100949561A CN200910094956A CN101651054B CN 101651054 B CN101651054 B CN 101651054B CN 2009100949561 A CN2009100949561 A CN 2009100949561A CN 200910094956 A CN200910094956 A CN 200910094956A CN 101651054 B CN101651054 B CN 101651054B
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contact material
powder
preparation
silver
agsno
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CN101651054A (en
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冯晶
陈敬超
肖冰
阮进
于杰
周荣
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Abstract

The invention relates to a preparation method of a modified AgSnO2 electric contact material, in particular to a preparation method of a carbonate modified AgSnO2 electric contact material, belonging to the technical field of material metallurgy. The method comprises the following steps: adding 0.1-2.0 percent of carbonate powder relative to total weight to silver-tin kinetosome powder; mixing and grinding into 300 meshes and pressing into biscuits under the protective atmosphere of argon; sintering the biscuits at 500-800 DEG C for 4-10 hours; pressing the sintered ingots again, sintering the sintered ingots again at 500-800 DEG C for 5-10h; and finally, and extruding the ingots which are pressed and sintered again at 400-600 DEG C for formation. The modified AgSnO2 electric contact material can replace a toxic silver cadmium oxide electric contact material, favorably solves the temperature rise problem of the electric contact material and improves the comprehensive performance of the material; and the prepared electric contact composite material has lower cost, greater serviceable range and longer service life.

Description

A kind of modification AgSnO 2The preparation method of contact material
Technical field
The present invention relates to a kind of preparation method of contact material, particularly a kind of carbonate modification AgSnO 2The preparation method of contact material belongs to material smelting tech field.
Background technology
Contact material is the key factor that influences device for switching contact system functional reliability.And electrical contact is one of key element of electric equipment, and its function is to connect and cut off electric current.It is a carrying object; Be again component of machine, must have favorable conductive thermal conductivity and anti-electrical arc erosion, anti-melting welding, little electrical wear, low and stable contact resistance, not play chemical change, certain intensity is arranged and be easy to the general characters such as machining with working medium.
Known Ag-MeO series electrical contact material mainly contains AgCdO, AgSnO 2, AgZnO, AgSiO 2, silver-colored rare earth oxide (AgREO) etc.The characteristics of AgCdO contact material are: good, the anti-melting welding ability of anti-deterioration property is strong, contact resistance is low and stable; Has good serviceability; The electric current of using is pacified to several kilo-amperes from tens, is widely used in lying prostrate last kilovolt the multiple low-voltage electrical apparatus from several, once is called as " omnipotent contact ".And in AgCdO, rely on the volatilization and the O of Cd steam 2Overflow and cool off basis material and extinguish arcs, the decomposition temperature of CdO is lower than the fusing point of Ag, and CdO just can distil under lower temperature; The existence of CdO has improved the viscosity of melt surface thing simultaneously, can prevent that silver from being blown off by electric arc.But because cadmium metal steam is poisonous, contaminated environment, harmful, recent two decades comes, and many countries have all launched the research for cadmium material, have made significant headway, and that wherein the most rising is AgSnO 2Material.AgSnO 2Contact is as a kind of novel siluer metal oxide contact material; Part commercialization in the world; This material is except the characteristics with common metal oxide; Also have higher thermal stability (1925 ℃), good electric property, higher resistance fusion welding ability and arc resistance ability, be specially adapted in powerful contactor and the low tension switch, become the ideal candidates person who replaces the Ag-CdO electric contact material.Japan is from the research that proposed to actively develop after restriction uses the AgCdO contact " few cadmium, for cadmium " contact material in 1972, succeed in developing and produce in a large number the AgSn alloy add one or more elements such as Bi, Mn, Cu carry out in the AgSnO of oxidation 2Contact material.The contact of manufacturing has characteristics such as anti-deterioration property is good, contact resistance is low.Simultaneously, the U.S., Russia, France, Korea S etc. also actively develop AgSnO 2The development of contact material and product development work.
Known contact material patented technology and document mainly are the wild phases that changes in the silver-based material; For example: stifled state's (Chinese invention patent forever; 99115496.7) etc. application number: the people adopts chemical precipitation or sonochemistry to coat legal system to be equipped with silver and rare-earth oxidation composite powder; Through press forming, sintering, forging and pressing or extruding, combination property surpasses the AgCdO material; People such as F.huanner have studied Ag-Fe 2O 3The performance of material in low tension switch adds ZrO 2Ag-Fe 2O 3Material is in the drop-out current scope of 120-1000A, and its performance is superior to alternative AgCdO material (F.Hauner, et al., Ag-Fe and Ag-Fe 2O 3Contact materials for lowvotage switchgear [M], Proc.19 ThICEC, [Nuremberg, Germany], 317-323, Sept.1998); J.Wang etc. are at AgSnO 2The middle La that adds 2O 3, Bi 2O 3, result of study shows that the break-make property of material, average temperature rising are identical with AgCdO (12) material, and the average arc erosion amount is lower than AgCdO (12) material (J.Wang, et al., Study on a new contact material Ag-SnO 2-La 2O 3-Bi 2O 3[M], Proc.46 ThIEEE Holm Conf.on Electrical Contacts, 94-97, Sept.2001.).In these bibliographical informations, less to the interpolation of other phase beyond the oxide wild phase.
Known domestic development AgSnO 2Contact material institute of Guilin electricity section, Kunming Institute of Precious Metals, Tianjin electrical alloy factory, Shanghai Alloy Material General Plant, University Of Tianjin, Xi'an Communications University etc. are arranged.But some problems still exist, and like the material bad plasticity, are difficult to processing; Silver tin oxide material temperature rise, tin oxide can not be decomposed and caused the arc extinguishing effect than Agcdo difference; Tin oxide lamination etc. occurs with the wetability difference of silver.99104491.6) and " silver-colored rare earth oxide contact material technology of preparing " (application number: 02113216.X) proposed a kind of method for preparing siluer metal oxide (tin oxide, rare earth oxide) contact material through reactive synthesis technique the patent " synthesis method for preparing silver-tin dioxide " of inventor application (application number:; Improved the serviceability of siller tin oxide to a certain extent, but be still waiting aspect too high to improve in the material temperature rise.
Summary of the invention
Technical problem to be solved by this invention provides a kind of modification AgSnO 2The preparation method of contact material, alternative poisonous Agcdo contact material preferably resolves the problem of temperature rise of contact material; The combination property of material is improved; And the electric contact composite material cost of preparation is lower, and the scope of application is bigger, and useful life is longer.
Solving the scheme that technical problem of the present invention adopts is: in silver-colored tin matrix powder, add the carbonate powder that accounts for total weight 0.1~2.0%, under argon shield atmosphere, mix being milled down to 300 orders, be pressed into biscuit; 500 ℃~800 ℃ of control biscuit sintering temperatures, 4~10 hours time; The sintering ingot blank is pressed again, in 500 ℃~800 ℃ following resinterings, 5~10 hours time; At last to the repressing and re-sintering base 400 ℃~600 ℃ following extrusion modlings.
In the silver-colored tin matrix powder of described contact material, tin element accounts for 4~15% of total weight, and carbonate accounts for 0.1~2.0% of total weight, and surplus is a silver.
, described silver-colored tin matrix powder also is added with one or both powder in adjustment elemental tungsten, molybdenum, the copper when grinding; And tungsten accounts for below 0.5% of matrix powder total weight; Molybdenum accounts for below 0.3% of matrix powder total weight, and copper accounts for below 0.3% of matrix powder total weight, and particle size is less than 45 microns.
Described carbonate powder adopts sodium carbonate, one or both in potash or the calcium carbonate, and granularity is 1 micron~100 microns.
The mixed powder of described contact material is in planetary ball mill, to grind, and abrading-ball and mill jar adopt a corundum or an agate material preparation, rotating speed 800rad/min~1500rad/min, ball milling time 4~hours 20 hours.
Described biscuit forming pressure is 400MPa~800MPa when adopting the two-way compacting of punching block, is 200MPa~300MPa when adopting cold isostatic compaction.
The concrete raw material of contact material of the present invention is: one or both in one or both in (1) silver powder+putty powder+sodium carbonate, calcium carbonate and the potash+tungsten, molybdenum, the copper; (2) one or both in one or both in silver powder+glass putty+silver oxide powder+sodium carbonate, calcium carbonate and the potash+tungsten, molybdenum, the copper; (3) one or both in one or both in silver-colored ashbury metal powder+silver oxide powder+sodium carbonate, calcium carbonate and the potash+tungsten, molybdenum, the copper.
The invention has the beneficial effects as follows:
When grinding, mechanical alloying makes oxide, and carbonate is evenly distributed in material, and the granules of stannic oxide wild phase can be according to production with performance requirement and the original position generation combines firmly with the formed interface of silver matrix, and the combination property of material is greatly improved;
Suitable technology can make the granules of stannic oxide original position generate; The disperse of additive is divided cloth and is accomplished through machining deformation; The content of additive can change according to the actual requirements easily; The interpolation of carbonate can not increase the difficult problem of tin-oxygen-silver electric contact material following process, promptly reasonably the low consumption of carbonate can not cause composite material intensity and plastic property than about-face.
Carbonate can decompose under arcing; Absorb certain heat and reduce the temperature of contact material, play certain arc extinguishing effect, and form after the carbonate decomposition oxide can with the carbon dioxide in air new carbonate of formation that reacts; Can continue in opening and closing circuit, to keep corresponding arc quenching effect; Recycled and bring into play its effect, the life-span that electrically contacts of the tin-oxygen-silver electric contact material after the modification improves greatly, has enlarged the scope of application of said material.
That raw material is prepared is simple, can under the condition of original production technology, add carbonate easily, technological process is controlled easily, with short production cycle, product cost is low, the life-span is long, and can realize production in enormous quantities, production process environmentally safe or of low pollution.
Description of drawings
Fig. 1 is a process chart of the present invention.
Embodiment
Embodiment one
Putty powder (percentage by weight) by 10%, 89.5% silver powder (percentage by weight); 0.4% sodium carbonate powder (percentage by weight); 0.1% copper powder (percentage by weight) is inserted powder in the ball grinder of corundum material, vacuumizes; Charge into argon gas, under argon shield atmosphere, carry out mechanical alloying.Planetary high-energy ball mill rotating speed 800rad/min, through after the mixing in 6 hours, two-way press forming becomes biscuit in punching block in planetary ball mill, and the biscuit forming pressure is 650MPa; Biscuit is through being sintered into ingot blank in 800 ℃, 4 hours; Ingot blank is pressed with the pressure of 500MPa again, and 700 ℃, 10 hours resinterings are squeezed into the line bar then under 600 ℃ temperature conditions, and last cold drawing becomes line (silk) material.
Embodiment two
Glass putty (percentage by weight) by 7%, 74% silver powder (percentage by weight); 18.5% silver oxide is a raw material, 0.4% potash powder (percentage by weight), and add 0.1% tungsten powder (percentage by weight); Powder is inserted in the ball grinder of corundum material; Vacuumize, charge into argon gas, under argon shield atmosphere, carry out mechanical alloying.Planetary high-energy ball mill rotating speed 600rad/min, through after the mixing in 10 hours, two-way press forming becomes biscuit in punching block in planetary ball mill, and the biscuit forming pressure is 650MPa; Biscuit is through being sintered into ingot blank in 800 ℃, 4 hours; Ingot blank is pressed with the pressure of 500MPa again, and 700 ℃, 8 hours resinterings are squeezed into the line bar then under 600 ℃ temperature conditions, and last cold drawing becomes line (silk) material.
Embodiment three
By silver-colored tin alloy powder 52% (wherein the weight percent content of tin be silver-colored tin alloy powder 24%); The potash powder (percentage by weight) of silver oxide powder 46.88%, 1.0%, and add 0.08%W (tungsten), 0.04%Mo (molybdenum) (percentage by weight); Powder is inserted in the ball grinder of corundum material; Vacuumize, charge into argon gas, under argon shield atmosphere, carry out mechanical alloying.Planetary high-energy ball mill rotating speed 500rad/min, through after the mixing in 9 hours, two-way press forming becomes biscuit in punching block in planetary ball mill, and the biscuit forming pressure is 500MPa; And further become biscuit, biscuit forming pressure 300MPa with isostatic cool pressing; Biscuit was sintered into ingot blank through 760 ℃, 7 hours, and ingot blank is pressed with 500MPa again, 800 ℃, 3 hours resinterings, and 550 ℃ are squeezed into the line bar, and last cold drawing becomes line (silk) material.
Embodiment four
Putty powder (percentage by weight) by 12%, 87.15% silver powder (percentage by weight); 0.8% sodium carbonate and Paris white (percentage by weight); 0.05% molybdenum powder (percentage by weight) is inserted powder in the ball grinder of corundum material, vacuumizes; Charge into argon gas, under argon shield atmosphere, carry out mechanical alloying.Planetary high-energy ball mill rotating speed 800rad/min, through after the mixing in 8 hours, two-way press forming becomes biscuit in punching block in planetary ball mill, and the biscuit forming pressure is 650MPa; And further become biscuit, biscuit forming pressure 300MPa with isostatic cool pressing; Biscuit is through being sintered into ingot blank in 800 ℃, 7 hours; Ingot blank is pressed with the pressure of 500MPa again, and 700 ℃, 8 hours resinterings are squeezed into the line bar then under 550 ℃ temperature conditions, and last cold drawing becomes line (silk) material.
Embodiment five
By silver-colored tin alloy powder 52% (wherein the weight percent content of tin be silver-colored tin alloy powder 24%); The potash of silver oxide powder 47.25%, 0.6% and Paris white (percentage by weight), and add 0.1%Cu (copper), 0.05%Mo (molybdenum) (percentage by weight); Powder is inserted in the ball grinder of corundum material; Vacuumize, charge into argon gas, under argon shield atmosphere, carry out mechanical alloying.Planetary high-energy ball mill rotating speed 600rad/min, through after the mixing in 9 hours, two-way press forming becomes biscuit in punching block in planetary ball mill, and the biscuit forming pressure is 500MPa; And further become biscuit, biscuit forming pressure 300MPa with isostatic cool pressing; Biscuit was sintered into ingot blank through 800 ℃, 9 hours, and ingot blank is pressed with 550MPa again, 780 ℃, 3 hours resinterings, and 550 ℃ are squeezed into the line bar, and last cold drawing becomes line (silk) material.

Claims (9)

1. modification AgSnO 2The preparation method of contact material is characterized in that: in silver-colored tin matrix powder, contain the carbonate powder that accounts for total weight 0.1~2.0%, under argon shield atmosphere, mix being milled down to 300 orders,Be pressed into biscuit; 500 ℃~800 ℃ of control biscuit sintering temperatures, 4~10 hours time; The sintering ingot blank is pressed again, in 500 ℃~800 ℃ following resinterings, 5~10 hours time; At last to the repressing and re-sintering base 400 ℃~600 ℃ following extrusion modlings.
2. modification AgSnO according to claim 1 2The preparation method of contact material is characterized in that: in the silver-colored tin matrix powder of described contact material, tin element accounts for 4~15% of total weight, and carbonate accounts for 0.1~2.0% of total weight, and surplus is a silver.
3. modification AgSnO according to claim 2 2The preparation method of contact material; It is characterized in that: in described silver-colored tin matrix powder, also contain one or both powder in adjustment elemental tungsten, molybdenum, the copper; And tungsten accounts for below 0.5% of matrix powder total weight, and molybdenum accounts for below 0.3% of matrix powder total weight, and copper accounts for below 0.3% of matrix powder total weight; Particle size is less than 45 microns, and the adjustment element is added into when grinding the matrix powder.
4. modification AgSnO according to claim 2 2The preparation method of contact material is characterized in that: described carbonate powder adopts sodium carbonate, one or both in potash or the calcium carbonate, and granularity is 1 micron~100 microns.
5. modification AgSnO according to claim 2 2The preparation method of contact material; It is characterized in that: all powder raw materials of contact material grind in planetary ball mill; Abrading-ball and mill jar employing corundum or agate material preparation, rotating speed 800 rad/min~1500rad/min, 4 hours~20 hours ball milling time.
6. modification AgSnO according to claim 2 2The preparation method of contact material is characterized in that: the biscuit forming pressure is 400MPa~800MPa when adopting the two-way compacting of punching block, is 200 MPa~300MPa when adopting cold isostatic compaction.
7. according to claim 3,4,5 or 6 described modification AgSnO 2The preparation method of contact material is characterized in that: the concrete raw material of contact material is one or both in one or both in silver powder+putty powder+sodium carbonate, calcium carbonate and the potash+tungsten, molybdenum, the copper.
8. according to claim 3,4,5 or 6 described modification AgSnO 2The preparation method of contact material is characterized in that: the concrete raw material of contact material is one or both in one or both in silver powder+glass putty+silver oxide powder+sodium carbonate, calcium carbonate and the potash+tungsten, molybdenum, the copper.
9. according to claim 3,4,5 or 6 described modification AgSnO 2The preparation method of contact material is characterized in that: the concrete raw material of contact material is one or both in one or both in silver-colored ashbury metal powder+silver oxide powder+sodium carbonate, calcium carbonate and the potash+tungsten, molybdenum, the copper.
CN2009100949561A 2009-09-11 2009-09-11 Preparation method of modified AgSnO2 electric contact material Expired - Fee Related CN101651054B (en)

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US9287018B2 (en) * 2010-12-03 2016-03-15 Wenzhou Hongfeng Electrical Alloy Co., Ltd. Method of preparing silver-based electrical contact materials with fiber-like arrangement of reinforcing nanoparticles
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CN102319901B (en) * 2011-10-20 2013-04-24 福达合金材料股份有限公司 Preparation method for silver cadmium oxide electrical contact
CN102328086B (en) * 2011-10-20 2013-04-17 福达合金材料股份有限公司 Method for preparing silver tin oxide electrical contact
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CN1616164A (en) * 2004-11-30 2005-05-18 昆明理工大学 Process for preparing silver base poly phase composite oxide composite material
CN101053903A (en) * 2007-05-23 2007-10-17 福达合金材料股份有限公司 Method for preparing silver copper oxide electric contacting material

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CN1616164A (en) * 2004-11-30 2005-05-18 昆明理工大学 Process for preparing silver base poly phase composite oxide composite material
CN101053903A (en) * 2007-05-23 2007-10-17 福达合金材料股份有限公司 Method for preparing silver copper oxide electric contacting material

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