CN107794389A - A kind of silver-tin oxide or indium oxide contact material and preparation method thereof - Google Patents

A kind of silver-tin oxide or indium oxide contact material and preparation method thereof Download PDF

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CN107794389A
CN107794389A CN201710981271.3A CN201710981271A CN107794389A CN 107794389 A CN107794389 A CN 107794389A CN 201710981271 A CN201710981271 A CN 201710981271A CN 107794389 A CN107794389 A CN 107794389A
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silver
powder
agsno
contact material
preparation
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CN107794389B (en
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张泽忠
陈晓
吴新合
穆成法
祁更新
陈林驰
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Wenzhou Hongfeng Electrical Alloy Co Ltd
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Wenzhou Hongfeng Electrical Alloy Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C5/00Alloys based on noble metals
    • C22C5/06Alloys based on silver
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14Treatment of metallic powder
    • B22F1/145Chemical treatment, e.g. passivation or decarburisation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0021Matrix based on noble metals, Cu or alloys thereof
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01HELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00Contacts
    • H01H1/02Contacts characterised by the material thereof
    • H01H1/021Composite material
    • H01H1/023Composite material having a noble metal as the basic material
    • H01H1/0237Composite material having a noble metal as the basic material and containing oxides
    • H01H1/02372Composite material having a noble metal as the basic material and containing oxides containing as major components one or more oxides of the following elements only: Cd, Sn, Zn, In, Bi, Sb or Te
    • H01H1/02376Composite material having a noble metal as the basic material and containing oxides containing as major components one or more oxides of the following elements only: Cd, Sn, Zn, In, Bi, Sb or Te containing as major component SnO2
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Powder Metallurgy (AREA)
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Abstract

The present invention provides a kind of silver-tin oxide or indium oxide contact material and preparation method thereof, and step is:It is atomized by melting and prepares AgSnIn base alloy powders;The Quick Oxidation of AgSnIn base alloy powders is realized by high-energy ball milling machinery alloying, obtains AgSnO2In2O3Base intermediate powder;By AgSnO2In2O3Intermediate powder and silver powder carry out composition proportion regulation and control, obtain the AgSnO for having identical component with finished-product material2In2O3Powder;Mixed powder, ball milling, roasting, isostatic pressed, sintering, hot extrusion, obtains material requested.The present invention aoxidizes the AgSnO to form conduction by the quick high energy of AgSnIn base alloy powders for being atomized melting2In2O3Base intermediate powder, there is good wetability with matrix Ag, the conductive high, AgSnO that ductility is good, processing characteristics is excellent can be obtained2In2O3Band or silk material.

Description

A kind of silver-tin oxide or indium oxide contact material and preparation method thereof
Technical field
The present invention relates to a kind of preparation method of the electrical contact material of field of material technology, specifically, one is referred to Kind silver-tin oxide or indium oxide contact material and preparation method thereof.
Background technology
Electrical contact is the core parts in electric switch, and it is responsible for the connecting and disconnecting of circuit, and times of load current Business, is widely used in the low pressure and High-Voltage Electrical Appliances such as air switch, relay, AC/DC contactor, is related to modern society Civilian, military, space flight and the every field such as aviation.With the fast development of electrical apparatus industry, the application of electric switch is for electricity The performance of contact material proposes requirements at the higher level, stablizes as contact resistance is low, wear-resistant, good resistance fusion welding and resistance to electric arc Aggressivity, and excellent electric conductivity etc..
Agcdo contact material widely used at present has fabulous performance and relatively low material cost, especially high It is even more so to aoxidize cadmium content, preparation technology is also very ripe and stably.Contain in silver cadmium oxide material and human body and environment are harmful to Cadmium element, and production in silver cadmium oxide material, assemble, use and reclaim during cadmium element pollution all be present and ask Topic, exploitation performance is quite or even more excellent no cadmium contact material turns into current study hotspot.
AgSnO2It is the generally acknowledged environment-friendly type electrical contact functional material for being most hopeful to substitute Agcdo.SnO2Thermostabilization Property it is good, be not easily decomposed under arcing, it is poor plus wetability of its silver with fused solution and larger with the density variation of silver, Easily float to contact surface and form enrichment.Due to SnO2It is non-conductive, cause contact resistance to increase, cause temperature rise, shadow Ring the electrical contact even performance of electrical equipment.AgSnO simultaneously2Material still has the shortcomings of elongation percentage is low, machine-shaping is difficult, Limit the large-scale application of the material.So far, powder metallurgy, internal oxidation and chemical precipitation method can be prepared AgSnO2Material.But these techniques all come with some shortcomings, such as SnO in powder metallurgical technique2The skewness in silver matrix; Internal oxidation technique needs to add the element for promoting oxidation rate, and such as indium, the requirement to equipment is high and cost is high;Chemical precipitation method Production cycle is grown, and cost is higher.
Through retrieval, the research on tin-oxygen-silver electric contact material is specific as follows both at home and abroad:
(1) novel silver tin oxide silk electrical contact material preparation method, CN101202169A
(2) silver-tin oxide or indium oxide electric contact wire rod and its production technology, CN1167835A
Document (1) describes a kind of powder pre-oxidation and prepares AgSnO2The method of material, document (2) are described in AgSnO2 The influences of the element to material such as Zn, Cu and Ni are added in material, the results showed that addition trace element is advantageous to AgSnO2Material Electrical contact performance raising, but the influence such as following process on material is smaller.
Further found in retrieval, Chinese patent patent of invention 201210439786.8, Publication No. CN102925738A, It discloses in a kind of preparation method of silver tin oxide material but this method:Used by melting material composition content with it is final The component content of finished product is more or less the same, i.e. the component content of its raw material determines the component content of final finished, can not flexibly adjust Save the component of material;And the patent is to carry out oxidation processes while using AgSn original washing powder body water atomizations to be prepared for AgSnO2Original washing powder Body, it will usually cause problems with:
1. water atomization carries out oxidation processes simultaneously, can cause to be atomized powder AgSn original washing powders body (other elements In, La, Bi, Zn, Ni etc.) it is oxidized to the less efficient and equipment power consumption of AgSnO2 original washing powders body (In2O3, ZnO, CuO, Bi2O3 etc.) greatly;
2. water atomization carries out oxidation processes simultaneously, AgSn original washing powder bodies are oxidized to AgSnO2 original washing powder bodies, this technical finesse For principle similar to internal oxidition, this easily causes, and SnO2 and matrix Ag wetability is poor, the plasticity of AgSnO2 materials is poor, is unfavorable for Follow-up material processing, the rolling of such as follow-up sheet material and the extruding of silk material, the preparation of rivet.
The content of the invention
The present invention is in view of the deficienciess of the prior art, provide a kind of silver-tin oxide or indium oxide contact material and its preparation Method, to original AgSnO2Material preparation process is improved, and quick oxygen is realized by high-energy ball milling-mechanical alloying method Change, and be aided with severe Plastic Deformation Methods, be prepared for the AgSnO with enhancing phase Dispersed precipitate or filamentary structure feature2In2O3 Environmentally friendly contact material.
The present invention is achieved by the following technical solutions:
According to the first aspect of the invention, the present invention provides a kind of silver-tin oxide or indium oxide contact material, what it was included Component and weight percentage are:SnO24~13%, ZnO 0.01~0.4%, In2O32~5%, CuO 0.01~ 0.2%, NiO 0.01~0.5%, Bi2O30.01~0.5%, surplus Ag.
Preferably, the oxide S nO2, ZnO, In2O3, CuO, NiO, Bi2O3The granularity of particle is 5nm~15 μm.
Preferably, the Ag-based electrical contact material has obvious Dispersed precipitate or filamentary structure, wherein filamentary structure By Dispersed precipitate enhancing mutually be additive in metal oxidation after formed metal oxide drawing, be extruded from, it is described Enhancing is mutually oxide S nO2, ZnO, In2O3, CuO, NiO, Bi2O3Particle.
According to the second aspect of the invention, there is provided a kind of preparation method of above-mentioned silver-tin oxide or indium oxide contact material, Wherein:The AgSnIn alloy powders being atomized using melting realize that Quick Oxidation obtains by high-energy ball milling-Mechanic Alloying Technology AgSnO2In2O3There is Ag to wrap up SnO for intermediate powder, the intermediate powder2In2O3Particle characteristic, avoid SnO2In2O3 Grain directly contacts with matrix silver, and intermediate powder has good wetability with matrix silver, and intermediate powder has conduction Property, reduce SnO2In2O3Adverse effect of the particle to contact material performance.Then the intermediate powder is entered with fine silver powder Row composition proportion, through techniques such as mixed powder, ball milling, roasting, isostatic pressed, sintering and hot extrusions, obtain with the disperse point of enhancing phase The AgSnO of cloth or bacillar structure architectural feature2In2O3Band or wire rod.
Specifically, methods described comprises the following steps:
The first step, silver ingot and tin, indium, zinc, nickel, bismuth, copper are placed in melting in smelting furnace in proportion, wherein the alloy used The parts by weight of raw material are:Silver is 35~85 parts, and tin is 1~40 part, and indium is 1~20 part, and zinc is 0.01~5 part, nickel 0.01 ~5 parts, bismuth is 0.01~5 part, and copper is 0.01~5 part;
Preferably, the melting, between smelting temperature is 900~1100 DEG C, 30~60min.
Second step, the molten metal after melting is subjected to powder by atomization, obtains AgSnIn alloy powders;
Preferably, the powder by atomization is to utilize gases at high pressure or water slug fused solution metal stream, it is atomized into gold Belong to droplet, then cooling obtains AgSnIn alloy powders.
3rd step, AgSnIn alloy powders are subjected to high-energy ball milling-mechanical alloying in high energy ball mill, realized quick Oxidation forms AgSnO2In2O3Intermediate powder;
Preferably, the high-energy ball milling-mechanical alloying, major parameter are:Ball milling ratio is 10~20, rotating speed 200~ 400r/min, 1~5h of time.
4th step, by silver powder and AgSnO2In2O3Intermediate powder, which pours into V-type, to be mixed mixed powder is carried out in powder machine, wherein silver powder with AgSnO2In2O3The AgSnO that the part by weight of intermediate powder is prepared needed for2In2O3Material composition calculates gained;
Preferably, the mixed powder, it is 2~6h, 30~100r/min of rotating speed to mix the powder time.
5th step, by the AgSnO after mixed powder2In2O3Powder carries out general milling;
Preferably, the ball milling, rotating speed are 30~100r/min, 10~30h of Ball-milling Time, ratio of grinding media to material 1~10.
6th step, the powder after ball milling is calcined;
Preferably, the roasting, temperature are 400~700 DEG C, 1~6h of time, and atmosphere is nitrogen or argon gas.
7th step, the powder after roasting is subjected to isostatic cool pressing;
Preferably, the isostatic pressed, isostatic pressed pressure are 80~300MPa.
8th step, the base substrate that isostatic cool pressing obtains is sintered;
Preferably, the sintering, sintering temperature are 800~930 DEG C, and soaking time is 10~20h.
9th step, the base substrate for sintering acquisition is subjected to hot extrusion, obtains having enhancing mutually in Dispersed precipitate or fibrous knot The silver-based electric contact band or wire rod of structure;
Preferably, the hot extrusion, base substrate heating-up temperature are 600~900 DEG C, and extrusion ratio is between 30~300, extruding speed Spend for 5~15cm/min, 300~500 DEG C of extrusion die preheating temperature.
The design of material principle that the present invention is mutually strengthened jointly using multivariant oxide enhancing, the spy of comprehensive each element enhancing phase Point, not only electrical contact performance is excellent for acquisition, and the contact material that processing characteristics is good, cost is cheap.Specifically, each element Effect it is as follows:Become SnO after Sn oxidations2Particle, the resistance to arc erosion ability of contact material can be strengthened;A small amount of In and Bi members Element can improve the problem of temperature rise during contact material use is too high, and can promote oxidation rate, reduce oxidization time; Zn elements can cause contact material to keep good deformation processing performance while keeping good resistance fusion welding;Cu elements can To promote oxidation rate, In dosages are reduced;Ni elements can refine matrix Ag crystal grain, improve the mechanical property of contact material.
In the present invention, the material composition content used in melting differs larger with the component content of final finished, wherein melting Prepared by atomization is AgSnIn base intermediate powders, and the silver content of the AgSnIn base intermediate powders is adjustable, with the AgSnIn bases Intermediate powder matches somebody with somebody the component content of formation final finished after powder with Ag powder again in proportion.
In the present invention, oxidation processes are carried out while oxidation is water atomization pulverization, obtain oxide powder, compared to existing Oxide powder is prepared using internal oxidition technology mostly in technology, the present invention is using more efficiently high-energy ball milling-machine with energy-conservation Tool alloying carries out preparing oxide powder.
Compared with prior art, the invention has the advantages that:
AgSnO is prepared with prior powder metallurgy2Contact material is compared, and the present invention on starting components due to carrying out Scientific design, the AgSnIn alloy powders that melting is atomized are realized by Quick Oxidation shape by high-energy ball milling-Mechanic Alloying Technology The AgSnO of enhancing phase structure is wrapped up into silver2In2O3Intermediate powder, improve the interface wet ability of oxide particle and matrix silver Characteristic, eliminate in prior powder metallurgy method because interface wet ability difference is to the adverse effect of electrical contact mechanical property.It is more important , AgSnO2In2O3Intermediate powder is conductive, is advantageous to the raising of electrical contact material electrical property.
Meanwhile the present invention combines the composition design of science, employs the preparation technology that the cycle is shorter, cost is lower so that The AgSnO of preparation2Contact material not only excellent electrical property, and elongation percentage is greatly improved with processability, can part Or all it is applied to the various application fields using electrical contact material such as relay, breaker and contactor instead of Agcdo, Avoid the problem of environmental pollution in the production and application process of silver cadmium oxide electrical contact material.
Material composition content used in melting of the present invention differs larger with the component content of final finished, because melting is atomized What is prepared is AgSnIn base intermediate powders, and the silver content of the AgSnIn base intermediate powders is adjustable, and among the AgSnIn bases Body powder and Ag powder are in proportion again with the component content that final finished is only after powder, so the constituent adjustment of whole material is very Flexibly, it is controllable.
The present invention uses and more efficiently carries out preparing oxide powder, this hair with high-energy ball milling-mechanical alloying of energy-conservation Bright technique is simple, and cost is cheap, to equipment without particular/special requirement, AgSnO2In2O3 contact materials environmental protection prepared by the present invention, its Resistance fusion welding, resistance to arc erosion and conductance are greatly improved, and processing characteristics is very excellent.
Brief description of the drawings
The detailed description made by reading with reference to the following drawings to non-limiting example, further feature of the invention, Objects and advantages will become more apparent upon:
Fig. 1 is preparation method flow chart in one embodiment of the invention;
Fig. 2 is formed by Quick Oxidation after one embodiment of the invention AgSnIn alloy powders high-energy ball milling-mechanical alloying AgSnO2In2O3Intermediate powder;
Fig. 3 a, 3b are AgSnO after one embodiment of the invention hot extrusion2In2O3Material 1000 × under cross section and longitudinal section Metallographic structure.
Embodiment
Embodiments of the invention are elaborated below:The present embodiment is carried out lower premised on technical solution of the present invention Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation Example.
As shown in figure 1, the preparation method in following examples of the present invention is implemented according to the flow shown in Fig. 1.
Embodiment 1:
With AgSnO2(8)In2O3(4) exemplified by prepared by material
1st, 68Kg silver ingots are weighed, are placed in intermediate frequency furnace after being warming up to 1000 DEG C of fusings, addition 10KgIn, 20KgSn, 0.5KgZn, 1KgNi, 0.3KgBi and 0.2KgCu, silver-base alloy liquation was obtained after homogenization through 30 minutes;
2nd, under 0.5MPa air pressures, 1200 DEG C of powder by atomizations obtain AgSnIn alloy powders;
3rd, AgSnIn alloy powders are put into high energy ball mill, carry out high-energy ball milling-mechanical alloying and realize quick oxygen Change and obtain AgSnO2In2O3Intermediate powder;Ball milling ratio is 20, rotating speed 200r/min, time 3h;Closed by high-energy ball milling-machinery The AgSnIn alloy powders that melting is atomized are realized that Quick Oxidation forms silver parcel enhancing phase structure by aurification technology AgSnO2In2O3Intermediate powder, the interface wet ability characteristic of oxide particle and matrix silver is improved, eliminates conventional powder Because interface wet ability difference is to the adverse effect of electrical contact mechanical property in metallurgical method.
4th, by the AgSnO of acquisition2In2O3Intermediate powder carries out composition proportion with 225.11Kg silver powder and obtains AgSnO2(8) In2O3(4) powder;
5th, the powder after proportioning is poured into the mixed powder machine of V-type and carries out mixed powder, rotating speed 40r/min, time 5h;
6th, the powder after mixed powder is subjected to general milling, rotational speed of ball-mill 60r/min, Ball-milling Time 20h, ratio of grinding media to material 10;
7th, the powder after general milling is calcined, temperature is 500 DEG C, and time 5h, atmosphere is air;
The 8th, powder after roasting is pressed into a diameter of 90 base substrate under isostatic pressed 100MPa;
9th, base substrate is sintered, temperature is 820 DEG C, soaking time 12h;
10th, the base substrate after sintering is subjected to hot extrusion, the extrusion ratio of hot extrusion is 300, extrusion speed 5cm/min, is squeezed 300 DEG C of compression mould preheating temperature.
The final material that the present embodiment obtains, its composition are:SnO27.6%, ZnO 0.19%, In2O33.7%, CuO 0.07%, NiO 0.38%, Bi2O30.1%, surplus Ag.
The material property that the present embodiment is obtained is:Tensile strength 330MPa, soft state elongation percentage 25%, the μ of resistivity 2.19 Ω cm, soft state hardness 90HV, density 9.8g/cm3, the particle mean size of enhancing phase particle is 8 μm.
Embodiment 2:
With AgSnO2(10)In2O3(4) exemplified by prepared by material
1st, 64.05Kg silver ingots are weighed, are placed in intermediate frequency furnace after being warming up to 1100 DEG C of fusings, addition 5KgIn, 10.72KgSn, 0.27KgZn, 0.33KgNi, 0.07KgBi and 0.03KgCu, silver-base alloy was obtained after homogenization through 35 minutes and is melted Liquid;
2nd, under 0.6MPa air pressures, 1250 DEG C of powder by atomizations obtain AgSnIn alloy powders;
3rd, AgSnIn alloy powders are put into high energy ball mill, carry out high-energy ball milling-mechanical alloying and realize quick oxygen Change and obtain AgSnO2In2O3Intermediate powder;Ball milling ratio is 15, rotating speed 300r/min, time 2.5h;
4th, by the AgSnO of acquisition2In2O3Intermediate powder carries out composition proportion with 62.06Kg silver powder and obtains AgSnO2(10) In2O3(4) powder;
5th, the powder after proportioning is poured into the mixed powder machine of V-type and carries out mixed powder, rotating speed 50r/min, time 4h;
6th, the powder after mixed powder is subjected to general milling, rotational speed of ball-mill 70r/min, Ball-milling Time 18h, ratio of grinding media to material 9;
7th, the powder after general milling is calcined, temperature is 600 DEG C, and time 4h, atmosphere is air;
The 8th, powder after roasting is pressed into a diameter of 90 base substrate under isostatic pressed 90MPa;
9th, base substrate is sintered, temperature is 850 DEG C, soaking time 10h;
10th, the base substrate after sintering is subjected to hot extrusion, the extrusion ratio of hot extrusion is 260, extrusion speed 8cm/min, is squeezed 280 DEG C of compression mould preheating temperature.
The final material that the present embodiment obtains, its composition are:SnO29.3%, ZnO 0.23%, In2O34.1%, CuO 0.03%, NiO 0.3%, Bi2O30.05%, surplus Ag.
The material property that the present embodiment is obtained is:Tensile strength 360MPa, soft state elongation percentage 20%, the μ of resistivity 2.21 Ω cm, soft state hardness 95HV, density 9.7g/cm3, the particle mean size of enhancing phase particle is 10 μm.
Embodiment 3:
With AgSnO2(7)In2O3(3) exemplified by prepared by material
1st, 62.4Kg silver ingots are weighed, are placed in intermediate frequency furnace after being warming up to 1050 DEG C of fusings, addition 2.67KgIn, 5.93KgSn, 0.3KgZn, 0.33KgNi, 0.1KgBi and 0.07KgCu, silver-base alloy liquation was obtained after homogenization through 40 minutes;
2nd, under 0.4MPa air pressures, 1230 DEG C of powder by atomizations obtain AgSnIn alloy powders;
3rd, AgSnIn alloy powders are put into high energy ball mill, carry out high-energy ball milling-mechanical alloying Quick Oxidation and obtain Obtain AgSnO2In2O3Intermediate powder;Ball milling ratio is 10, rotating speed 350r/min, time 5h;
4th, by the AgSnO of acquisition2In2O3Intermediate powder carries out composition proportion with 43.33Kg silver powder and obtains AgSnO2(7) In2O3(3) powder;
5th, the powder after proportioning is poured into the mixed powder machine of V-type and carries out mixed powder, rotating speed 45r/min, time 4.5h;
6th, the powder after mixed powder is subjected to general milling, rotational speed of ball-mill 75r/min, Ball-milling Time 15h, ratio of grinding media to material 6;
7th, the powder after general milling is calcined, temperature is 650 DEG C, and time 3.5h, atmosphere is air;
The 8th, powder after roasting is pressed into a diameter of 90 base substrate under isostatic pressed 95MPa;
9th, base substrate is sintered, temperature is 830 DEG C, soaking time 11h;
10th, the base substrate after sintering is subjected to hot extrusion, the extrusion ratio of hot extrusion is 250, extrusion speed 10cm/min, is squeezed 350 DEG C of compression mould preheating temperature.
The final material that the present embodiment obtains, its composition are:SnO26.5%, ZnO 0.3%, In2O32.8%, CuO 0.07%, NiO 0.36%, Bi2O30.1%, surplus Ag.
The material property that the present embodiment is obtained is:Tensile strength 320MPa, soft state elongation percentage 27%, the μ of resistivity 2.1 Ω cm, soft state hardness 88HV, density 9.9g/cm3, the particle mean size of enhancing phase particle is 6 μm.
Embodiment 4:
With AgSnO2(5)In2O3(3) exemplified by prepared by material
1st, 52.38Kg silver ingots are weighed, are placed in intermediate frequency furnace after being warming up to 1150 DEG C of fusings, addition 2KgIn, 3.18KgSn, 0.086KgZn, 0.13KgNi, 0.09KgBi and 0.04KgCu, silver-base alloy was obtained after homogenization through 33 minutes and is melted Liquid;
2nd, under 0.5MPa air pressures, 1150 DEG C of powder by atomizations obtain AgSnIn alloy powders;
3rd, AgSnIn alloy powders are put into high energy ball mill, carry out high-energy ball milling-mechanical alloying Quick Oxidation and obtain Obtain AgSnO2In2O3Intermediate powder;Ball milling ratio is 20, rotating speed 330r/min, time 3h;
4th, by the AgSnO of acquisition2In2O3Intermediate powder carries out composition proportion with 26.8Kg silver powder and obtains AgSnO2(5) In2O3(3) powder;
5th, the powder after proportioning is poured into the mixed powder machine of V-type and carries out mixed powder, rotating speed 37r/min, time 6h;
6th, the powder after mixed powder is subjected to general milling, rotational speed of ball-mill 80r/min, Ball-milling Time 20h, ratio of grinding media to material 5;
7th, the powder after general milling is calcined, temperature is 700 DEG C, and time 3h, atmosphere is air;
The 8th, powder after roasting is pressed into a diameter of 90 base substrate under isostatic pressed 90MPa;
9th, base substrate is sintered, temperature is 860 DEG C, soaking time 10h;
10th, the base substrate after sintering is subjected to hot extrusion, the extrusion ratio of hot extrusion is 210, extrusion speed 12cm/min, is squeezed 360 DEG C of compression mould preheating temperature.
The final material that the present embodiment obtains, its composition are:SnO24.8%, ZnO 0.13%, In2O32.8%, CuO 0.06%, NiO 0.19%, Bi2O30.1%, surplus Ag.
The material property that the present embodiment is obtained is:Tensile strength 300MPa, soft state elongation percentage 30%, the μ of resistivity 2.01 Ω cm, soft state hardness 83HV, density 9.96g/cm3, the particle mean size of enhancing phase particle is 4 μm.
Reference picture 2, for Quick Oxidation institute after one embodiment of the invention AgSnIn alloy powders high-energy ball milling-mechanical alloying The AgSnO of formation2In2O3There is silver parcel to strengthen phase structure, a large amount of tiny enhancing phase (i.e. metals for intermediate powder, the powder Oxide) it is embedded in inside flat Argent grain or is wrapped up by Argent grain, in mechanical milling process, constantly it is wrapped to form AgSnO2In2O3Particle.
Reference picture 3a, 3b, it is AgSnO after one embodiment of the invention hot extrusion2In2O3Material 1000 × under cross section with The metallographic structure of longitudinal section, enhancing phase particle is in point-like, graininess Dispersed precipitate, and grain diameter is tiny;Longitudinal section:Strengthen phase It is distributed in threadiness, parallel to each other between fiber, Direction of fibre distribution is extruded along silk material or drawing direction, fibre diameter is tiny, Length is short;Tissue is without hole, dense structure.
The present invention prepares AgSnO using melting atomization+high-energy ball milling2In2O3Base intermediate powder, energy-conservation; AgSnO2In2O3The wetability of base intermediate powder and matrix Ag is good and conductive, reduces SnO2In2O3Particle is to electricity The adverse effect of contact material mechanics and electric property.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, for example change heretofore described constituent content, preparation technology parameter etc. and can realize, this area skill Art personnel can make various deformations or amendments within the scope of the claims, and this has no effect on the substantive content of the present invention.

Claims (10)

1. a kind of preparation method of silver-tin oxide or indium oxide contact material, it is characterised in that comprise the following steps:
The first step, silver ingot and additive metallic tin, indium, zinc, nickel, bismuth, copper are placed in melting in smelting furnace in proportion, wherein using The parts by weight of raw metal be:Silver is 35~85 parts, and tin is 1~40 part, and indium is 1~20 part, and zinc is 0.01~5 part, nickel For 0.01~5 part, bismuth is 0.01~5 part, and copper is 0.01~5 part;
Second step, the molten metal after melting is subjected to powder by atomization, obtains AgSnIn base alloy powders;
3rd step, AgSnIn base alloy powders are subjected to high-energy ball milling-mechanical alloying in high energy ball mill, realize quick oxygen Change the AgSnO for forming silver parcel enhancing phase structure2In2O3Intermediate powder;
4th step, by silver powder and AgSnO2In2O3Intermediate powder pours into the mixed powder machine of V-type and carries out mixed powder;
5th step, by the AgSnO after mixed powder2In2O3Powder carries out general milling;
6th step, the powder after ball milling is calcined;
7th step, the powder after roasting is subjected to isostatic cool pressing;
8th step, the base substrate that isostatic cool pressing obtains is sintered;
9th step, the base substrate for sintering acquisition is subjected to hot extrusion, obtains the silver with enhancing phase Dispersed precipitate or filamentary structure Base electric contact band or wire rod.
2. the preparation method of silver-tin oxide or indium oxide contact material as claimed in claim 1, it is characterised in that the first step In, between the smelting temperature is 900~1100 DEG C, smelting time is 30~60min.
3. the preparation method of silver-tin oxide or indium oxide contact material as claimed in claim 1, it is characterised in that the 3rd step In, the high-energy ball milling-mechanical alloying, wherein ball milling ratio are 10~20, and rotating speed be 200~400r/min, the time for 1~ 5h。
4. the preparation method of silver-tin oxide or indium oxide contact material as claimed in claim 1, it is characterised in that the 4th step In, silver powder and AgSnO2In2O3The AgSnO that the part by weight of intermediate powder is prepared needed for2In2O3Material composition calculates institute , the mixed powder time is 2~6h, and rotating speed is 30~100r/min.
5. the preparation method of silver-tin oxide or indium oxide contact material as claimed in claim 1, it is characterised in that the 5th step In, the rotational speed of ball-mill is 30~100r/min, and Ball-milling Time is 10~30h, and ratio of grinding media to material is 1~10.
6. the preparation method of the silver-tin oxide or indium oxide contact material as described in claim any one of 1-6, it is characterised in that With following one or more features:
In-the six step, the roasting, temperature is 400~700 DEG C, and the time is 1~6h.
In-the seven step, the isostatic pressed pressure is 80~300MPa.
In-the eight step, the sintering, sintering temperature is 800~930 DEG C, and soaking time is 10~20h.
7. the preparation method of the silver-tin oxide or indium oxide contact material as described in claim any one of 1-6, it is characterised in that In 9th step, the hot extrusion base substrate heating-up temperature be 600~900 DEG C, extrusion ratio between 30~300, extrusion speed be 5~ 15cm/min, 300~500 DEG C of extrusion die preheating temperature.
A kind of 8. silver-tin oxide or indium oxide contact material prepared using any one of claim 1-8 methods described.
9. silver-tin oxide or indium oxide contact material as claimed in claim 8, it is characterised in that the weight of its component and each component Measuring percentage composition is:SnO24~13%, ZnO 0.01~0.4%, In2O32~5%, CuO 0.01~0.2%, NiO 0.01~0.5%, Bi2O30.01~0.5%, surplus Ag.
10. silver-tin oxide or indium oxide contact material as claimed in claim 9, it is characterised in that have following a kind of or more Kind feature:
- oxide S the nO2, ZnO, In2O3, CuO, NiO, Bi2O3The granularity of particle is 5nm~15 μm;
- the Ag-based electrical contact material has obvious Dispersed precipitate or filamentary structure, and wherein filamentary structure is by Dispersed precipitate Enhancing mutually be additive in metal oxidation after formed metal oxide drawing, be extruded from, the enhancing is mutually oxygen Compound SnO2, ZnO, In2O3, CuO, NiO, Bi2O3Particle.
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CN109231259B (en) * 2018-10-09 2020-11-13 湖南工业大学 Method for preparing ultrafine ITO powder from metal indium and metal tin
CN109231259A (en) * 2018-10-09 2019-01-18 湖南工业大学 A kind of method that indium metal and metallic tin prepare ultra-fine ITO powder
CN110423908A (en) * 2019-08-23 2019-11-08 温州宏丰电工合金股份有限公司 One kind can quickly aoxidize silver-tin oxide or indium oxide contact material and preparation method
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EP3799977A1 (en) * 2019-10-01 2021-04-07 ABB Schweiz AG Method for manufacturing an ag-based electrical contact material, an electrical contact material and an electrical contact obtained therewith
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