CN110391095A - Single side internal oxidized Ag tin oxide or indium oxide contact material and preparation method thereof - Google Patents

Single side internal oxidized Ag tin oxide or indium oxide contact material and preparation method thereof Download PDF

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Publication number
CN110391095A
CN110391095A CN201910786069.4A CN201910786069A CN110391095A CN 110391095 A CN110391095 A CN 110391095A CN 201910786069 A CN201910786069 A CN 201910786069A CN 110391095 A CN110391095 A CN 110391095A
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tin oxide
layer
indium oxide
single side
oxide
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CN110391095B (en
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穆成法
杨辉
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Zhejiang University ZJU
Wenzhou Hongfeng Electrical Alloy Co Ltd
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Zhejiang University ZJU
Wenzhou Hongfeng Electrical Alloy Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/0081—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for slabs; for billets
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/54—Furnaces for treating strips or wire
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/021—Composite material
    • H01H1/023—Composite material having a noble metal as the basic material
    • H01H1/0237—Composite material having a noble metal as the basic material and containing oxides
    • H01H1/02372—Composite 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
    • H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
    • H01H11/048—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by powder-metallurgical processes

Abstract

The present invention discloses a kind of single side internal oxidized Ag tin oxide or indium oxide contact material, including silver-tin oxide or indium oxide material body, the one side of the silver-tin oxide or indium oxide material body is the welding surface of included solder, the welding surface is made of AgSn layers or AgZn layers, the another side of the silver-tin oxide or indium oxide material body is oxide side, and the oxide side is AgSnO2In2O3Layer.The present invention also provides a kind of preparation methods of above-mentioned material, obtained single side internal oxidized Ag tin oxide or indium oxide contact material, subsequent welding processing is convenient and reliable, and obtained silver-tin oxide or indium oxide is single side oxidation, there is no intermediate " oxygen deprivation compound " region, Tissue distribution is uniform.

Description

Single side internal oxidized Ag tin oxide or indium oxide contact material and preparation method thereof
Technical field
The present invention relates to a kind of preparation methods of the electrical contact material of field of material technology, specifically, what is involved is one The included solder of kind, single side internal oxidized Ag tin oxide or indium oxide contact material and preparation method thereof.
Background technique
Contact material is that " connection-conduction-cutting " electric current and signal generation and transmission are undertaken in device for switching The performance of a kind of functional composite material of function carrier, contact material directly affects the reliability of electronic product, stability, essence Degree and service life.Internal oxidation prepares silver-tin oxide or indium oxide (AgSnO2-In2O3) material is due to its preferable electric life, excellent Resistance to arc erosion, wear resistance and resistance fusion welding, be widely used in each electric appliances.In recent years domestic and international correlative study and Report.Such as: 1) Chinese invention patent: a kind of preparation method of high-oxide content blade contact material, publication number: CN104404419B prepares high, Fu Yin circle with oxide content by combining conventional preparation techniques and high temperature diffusion annealing The tin-oxygen-silver electric contact material for the features such as face bond strength is high.2) Jiang Yibin etc., internal oxidation AgSnO2In2O3 electrical contact material Expect present Research, " electrical material " 2017, No.2；It describes internal oxidation technique, tissue, performance etc. and reviews internal oxidition Present Research has highlighted influence of the additive to internal oxidition and institutional framework.Patent 1) it introduces and improves siller tin oxide (hyperoxia Change content) and silver interface bond strength method and technique, but this method prepares siller tin oxide, welding surface Composite Pure silver layer, In It when subsequent welding processing, needs additionally to add solder or soldering paste, it is unstable to will lead to welding, and welding process is complex.Text Offer and 2) highlight interior tissue and additive relationship and Correlative Influence Factors, but for AgSnIn/Ag recombination process difficult point and Influence factor and high oxide (17% or more) content contact surface and temperature rise, and welding layer is then Composite Pure silver layer, changes speech It, contact needs to add solder and is welded, cause welding procedure more complicated in welding.To included solder internal oxidation Silver-tin oxide or indium oxide then without reference to and report.
It is well known that general internal oxidation siller tin oxide preparation process: AgSnIn melting → ingot casting → surface processing → heat Compound (multiple silver) → rolling → punching → internal oxidition etc..In the actual production process, due to compound Ag layers of one side of AgSnIn material strip, After punching, internal oxidition, oxygen is spread from two sides (including four kinds) to centre, is aoxidized, but when oxygen internally expands It dissipates simultaneously, Sn and In also can accordingly be spread to outside, so contact center region will form so-called " oxygen deprivation after internal oxidition Compound " bright band causes material structure uneven, and intermediate " oxygen deprivation compound " region, and oxide content is few or does not have oxygen Compound, there are very big hidden danger during product is on active service, it is most likely that will lead to product and occurs melting welding in use, causes Product failure.Simultaneously as last procedure of product is internal oxidition, it may be assumed that aoxidized in high temperature and high oxygen pressure environment, institute With internal oxidition contact, be difficult as powder powder mixing method contact (powder powder mixing method is to mix silver powder and tin oxide powder, So not needing to aoxidize) in material strip preceding working procedure composite solder；Otherwise compound upper solder layer is enabled, in later period oxidation process In, solder also can complete oxidation, included solder layer final purpose is not achieved.Therefore, general traditional internal oxidation prepares tin oxide Indium oxide contact or contact simple grain carry out burning multiple solder, complex process and inefficiency or increase in subsequent welding process It is welded with piece or soldering paste, causes Control Welding Process complex, and unstable.
Summary of the invention
The present invention in view of the deficiency of the prior art and defect, provides a kind of included solder single side internal oxidized Ag oxygen Change tin indium oxide contact material and preparation method thereof, wherein the weld interface of contact material be by AgSn (high Sn content) or AgZn (high Zn content) tissue, fusing point and conventional solder fusing point are close, and when welding does not need to increase solder；And obtain silver oxidation Tin indium oxide is single side oxidation, and there is no intermediate " oxygen deprivation compound " region, Tissue distribution is uniform.
In order to achieve the above object, the technical solution adopted by the present invention is that:
According to the first aspect of the invention, a kind of single side internal oxidized Ag tin oxide or indium oxide contact material is provided, including Silver-tin oxide or indium oxide material body, the one side of the silver-tin oxide or indium oxide material body are the welding surface of included solder, institute It states welding surface to be made of AgSn layers or AgZn layers, the another side of the silver-tin oxide or indium oxide material body is oxide side, described Oxide side is AgSnO2In2O3Layer.
Optionally, the silver-tin oxide or indium oxide material body is band or plate.
Optionally, the AgSn or AgZn layers, it is 8~25% that thickness, which accounts for overall thickness ratio,.
Optionally, the AgSn composition of layer: Sn content is in 15wt%~25wt%, surplus Ag.When Sn content is higher than 25wt%, AgSn fusing point are lower, so that subsequent batch internal oxidition temperature can only be at 600 degree hereinafter, otherwise weld interface will appear Fusing, production efficiency are lower；When Sn content is lower than 15wt%, AgSn fusing point is higher, so that welding difficulty is higher, because at this time Fusing point is higher by nearly 150 degree than normal solder melt point.
Optionally, the AgZn composition of layer: Zn content is in 15wt%~30wt%, surplus Ag.When Zn content is higher than 25wt%, AgZn fusing point are lower, so that subsequent batch internal oxidition temperature can only be at 600 degree hereinafter, otherwise weld interface will appear Fusing layering, production efficiency are lower；When Zn content is lower than 15wt%, AgZn fusing point is higher, so that welding difficulty is higher, because Fusing point is higher by nearly 100 degree than normal solder melt point at this time.
Optionally, described AgSn layers or AgZn layer, in which: have one layer of meagre SnO on AgSn layers described2Layer (thickness≤ 20μm)；There is one layer of meagre ZnO layer (thickness≤20 μm) on AgZn layers described；Prevent AgSn alloy, the further oxygen of AgZn alloy Change, facilitates storage and transport, when need to use, meagre SnO can effectively be removed by simple rubbing down2Layer or ZnO layer are exposed Fresh AgSn or AgZn welding surface, as solder layer during rear road welding sequence carry out using.
According to the second aspect of the invention, a kind of preparation of single side internal oxidized Ag tin oxide or indium oxide contact material is provided Method, comprising:
AgSnIn alloy spindle is processed into AgSnIn material strip or plate by S1；
The AgSnIn material strip or plate and AgZn band or AgSn band are carried out Compound Machining by S2, and wherein first layer is AgSnIn layers, the second layer is welding surface AgSn layers or AgZn layers；
The compound rear material strip of S3 or plate are diffused annealing, cold rolling by S3；
Material strip or plate progress internal oxidition after cold rolling is obtained included solder, the oxidation of single side internal oxidized Ag tin oxide by S4 Indium contact material.
Optionally, after S1, before S2 Compound Machining, AgSnIn material strip or plate surface are subjected to grinding and buffing.
Optionally, after S4, further comprise:
By material strip after internal oxidition or plate, welding carries out rubbing down, obtains the fresh face AgSn AgZn；
By material strip after rubbing down to punching and cleaning is carried out, the included solder used immediately, the oxidation of single side internal oxidized Ag are formed Tin indium oxide contact material.
Included solder, the single side internal oxidized Ag tin oxide or indium oxide contact material of above method preparation of the present invention, weldering Junction is formed by AgSn or AgZn layers, and subsequent welding processing is convenient and reliable, and obtained silver-tin oxide or indium oxide is single side oxygen Change, there is no intermediate " oxygen deprivation compound " region, Tissue distribution is uniform.It when need to use, can be effective by simple rubbing down Remove meagre SnO2Layer or ZnO layer, expose fresh AgSn or AgZn welding surface, as solder layer during rear road welding sequence into It exercises and uses.
The internal oxidition of the used method of the present invention and previous traditional material prepares AgSnO2Method have dramatically different, this hair The method of bright use is: obtaining AgSnIn material strip or plate using AgSnIn spindle, material strip or plate are then carried out compound add Then work is diffused annealing, cold rolling and internal oxidition to compound rear plate again.Due to AgSnIn material strip or plate compound AgSn again After (Sn content is in 15wt%~25wt%) layer or AgZn (Zn content is in 15wt%~30wt%) layer, in internal oxidition, do not have There is addition to promote oxidation In element or other rare earth elements, so that AgSn (Sn content >=15wt%) layer can form one layer on surface Fine and close SnO2Film prevents AgSn alloy from further aoxidizing；Likewise, in the industrial production find AgZn layers (Zn content >= 15wt%) in internal oxidition (such as within 2Mpa oxygen pressure, 720 DEG C of temperature or less), situation is similar with AgSn layers, AgZn layer surface Also layer of ZnO film is formed, industrial oxidation is difficult to realize.In this way, oxygen can only be diffused and be aoxidized by AgSnIn layers, also It is single side oxidation, therefore it is possible to prevente effectively from " oxygen deprivation compound " region among the two-sided oxidation of tradition is formed, further, oxidation Later AgSnO2In2O3/ AgSn or AgSnO2In2O3/ AgZn material strip or plate pass through welding surface rubbing down, can effectively remove welding Interface forms meagre SnO2Layer or ZnO layer make it expose fresh AgSn or AgZn welding surface, can be used as rear road welding sequence mistake In journey solder layer carry out using.On the contrary, traditional internal oxidation prepares silver-tin oxide or indium oxide, internal oxidition process contact center area Domain will form, and so-called " oxygen deprivation compound " bright band needs to increase additional solder work when causing material structure uneven, and welding Sequence, production process are complex and unstable.
Detailed description of the invention
Fig. 1 is conventional internal oxidation Ag88SnO2In2O3/ Ag metallographic structure figure；
Fig. 2 is Ag88SnO2In2O3/ AgSn metallographic structure aoxidizes, welding surface AgSn20 for single side；
Specific embodiment
Further description of the technical solution of the present invention below, and the following description is only to understand technical solution of the present invention It is used, is not used in and limits the scope of the invention, protection scope of the present invention is subject to claims.
Shown in referring to Fig.1, for conventional internal oxidation Ag88SnO2In2O3/ Ag metallographic structure, it can be seen that traditional interior oxygen It is two-sided oxidation that change method, which prepares silver-tin oxide or indium oxide, and welding surface is fine silver, and internal oxidition process contact center region will form institute " oxygen deprivation compound " bright band is called, causes material structure uneven.Black portions are Ag88SnO above2In2O3Material, below white be Welding surface is Ag layers pure, and central area " white wire " is poor oxide region.
The embodiment of the present invention provides a kind of included solder, single side internal oxidized Ag tin oxide or indium oxide contact material, weldering Junction is formed by AgSn or AgZn layers, and subsequent welding processing is convenient and reliable, and obtained silver-tin oxide or indium oxide is single side oxygen Change, there is no intermediate " oxygen deprivation compound " region, Tissue distribution is uniform.As shown in Fig. 2, being Ag88SnO2In2O3/ AgSn metallographic Tissue aoxidizes, welding surface AgSn20 for single side.Black portions are Ag88SnO above in figure2In2O3Material, below grey be Welding surface is AgSn20 layers pure, without poor oxide region.
In the embodiment of the present invention, the melting of design and ingot casting are squeezed or are forged, polish and polish, is compound, at diffusion heat Reason, cold rolling, internal oxidition, rubbing down, punching and cleaning and etc., the parameter of concrete technology operation is alternatively, such as:
The first step, by Ag ingot, Sn ingot, In ingot, X element carry out melting and ingot casting.
Wherein parameter can use: Ag content for 83.5wt%~93.5wt%, Sn content be 5.5wt%~ 10.5wt%, In content are 2.5wt%~5wt%, and wherein X is that all can form alloy with Ag, Sn and can be improved its electricity Element of performance, X total weight content≤1.0%.X can be one of Zn, Bi, Cu, Ni and rare earth element or multiple combinations.
Above step is to obtain AgSnIn alloy spindle, and X belongs to selectable element, is able to ascend electrical property.When So, prior art preparation also can be directly used, or directly adopt existing AgSnIn alloy spindle product.The above is only this hairs A bright preferred embodiment.
The alloy spindle that the first step obtains is squeezed or is forged, is processed into AgSnIn material strip or plate by second step.
In this step, following parameter can be preferably used: squeeze temperature: between 550 degree~750 degree, leading in heating process N2 or charcoal protection；It forges between 550 degree~750 degree of temperature, heating process leads to N2 or charcoal protection.
In this step, material strip or plate thickness can be between 18mm~30mm, and thickness is according to final finished AgSnIn layers It calculates and obtains with AgSn (high Sn content) or AgZn (high Zn content) thickness degree proportion requirement.
AgSnIn material strip or plate surface are carried out grinding and buffing processing by third step, this step is option.Wherein polish It can be using wire brush or resin brush as polishing brush.
4th step, will treated material strip or plate, carry out two layers of cold compound or two layers of hot Compound Machining；
In this step, compound tense, one layer is AgSnIn layers, another layer of AgSn (high Sn content) or AgZn (high Zn content) layer (welding surface), wherein AgSn composition of layer: Ag content is in 75wt%~85wt%, surplus Sn；AgZn composition of layer: Ag content exists 70wt%~85wt%, surplus Zn.It is 8~25% that AgSn or AgZn thickness degree, which accounts for overall thickness ratio,.
Compound tense, when stock size foundation is cold rolled to finished product material band or plate, welding surface requirement welding layer thickness (such as cold rolling 0.15mm is required to finished product) calculate acquisition.AgSn layers or the degree foundation finished product material welding layer requirement of AgZn thickness, in conjunction with AgSnIn Material strip or plate thickness calculate proportion and obtain.
In this step, two layers of cold compound tense, for deflection between 60%~80%, material strip or strip width can be in 30mm Between~90mm.
In this step, two layers of hot compound tense, for deflection between 40%~70%, temperature control can be 500 degree~750 Between degree, H2, N2 or Ar protection.
5th step, will be compound after obtained material strip be diffused annealing.Wherein diffusion annealing parameter can use: temperature exists Between 450 degree~750 degree, the time 4~12 hours, lead to H2、N2Or Ar gas shield.
Material strip after annealing is carried out cold rolling by the 6th step.Wherein parameter can use: cold rolling single track deformation amount controlling is 5% Between~30%.It is also possible to multi-pass cold rolling.
Material strip after cold rolling is carried out internal oxidition by the 7th step, obtains included solder, single side internal oxidized Ag tin oxide or indium oxide electricity Contact material.
In this step, internal oxidition can preferably use following parameter: for 550 degree~720 degree, the voltage-controlled system of oxygen exists oxidizing temperature Between 0.8Mpa~2Mpa, oxidization time combines oxidation technology parameter to calculate and obtains according to cold-rolling thickness.
Certainly, after above-mentioned 7th step, included solder, single side internal oxidized Ag tin oxide or indium oxide can also be in electrical contact Material carries out rubbing down, removes welding surface oxide layer, then carry out punching and cleaning, obtains included solder, the list that can be used immediately Face internal oxidized Ag tin oxide or indium oxide contact material.
It should be noted that being preferred implementation step and condition of the invention above, the invention is not limited to above-mentioned steps Rapid and condition.
The detailed technical operation of the present invention is illustrated below by way of the embodiment of concrete application.
Embodiment one
To prepare Ag (92) SnO2-In2O3/ AgSn20 and Ag (92) SnO2-In2O3For/AgZn20 electrical contact material
The first step, by Ag ingot, Sn ingot, In ingot, additive Ni carry out melting and ingot casting.Wherein Ag content is 93.5wt%, Sn content is 4.7wt%, and In content is 2.5wt%, and Ni content is 0.3wt%.
Second step carries out the alloy spindle that the first step obtains to be squeezed into AgSnIn material strip, wherein squeezing temperature is 750 Degree leads to N2Protection.Material strip width is 30mm, with a thickness of 20mm.
Third step, by the processing of AgSnIn material strip row grinding and buffing, polishing brush uses resin brush.
4th step, by third step treated material strip, carry out two layers it is cold compound, compound preceding layer is AgSnIn layer, is stocked up Thickness 20mm；Another layer AgSn20 layers (Ag content 80wt%), stock thickness 1.74mm (requires welding surface multiple according to finished product thickness The silver-colored thickness accounting 8.0% of layer, which calculates, to be obtained)；Alternatively, another layer is AgZn20 layers (Ag content 80wt%) stock thickness 1.8mm (requiring welding surface cladding silver thickness accounting 8.25% to calculate according to finished product thickness to obtain)；Composite deformation amount 80%, all material strips Width 30mm, compound rear material strip thickness 4.36mm.
The material strip that 4th step obtains after compound is diffused annealing, wherein 750 degree of temperature by the 5th step, and the time 4 hours, Logical N2Gas shield.
Material strip after annealing is carried out cold rolling by the 6th step, and wherein cold rolling single track deformation amount controlling is rolled down within 30% Product require thickness 1.8mm.
7th step, carries out internal oxidition for material strip after cold rolling, wherein 700 degree of oxidizing temperature, and oxygen presses 0.8Mpa, oxidization time 160 hours, obtain single side internal oxidized Ag tin oxide or indium oxide contact material.Due to AgSnIn material strip at compound AgSn layers or After AgZn layers, when internal oxidition, does not add promotion oxidation In element or other rare earth elements, so that AgSn layers can be in surface shape At one layer of densification SnO2Film prevents AgSn alloy from further aoxidizing；Likewise, AgZn layers in internal oxidition surface also form one layer ZnO film is difficult to realize industrial oxidation.In this way, oxygen can only be diffused and be aoxidized by AgSnIn layers, that is, single side oxygen Change, therefore it is possible to prevente effectively from " oxygen deprivation compound " region among the two-sided oxidation of tradition is formed.
The welding surface elder generation rubbing down of material strip after internal oxidition is removed oxide layer by the 8th step, then carries out punching and cleaning, punching Size 8mm × 8mm is in electrical contact product obtained from band solder, single side internal oxidized Ag tin oxide or indium oxide.
The present embodiment is finally in electrical contact product obtained from band solder, single side internal oxidized Ag tin oxide or indium oxide, wherein wherein It is about 0.15mm that contact welding surface, which carries solder layer, is that single side aoxidizes inside contact, even tissue, without " oxygen deprivation compound " Area, compared with the two-sided oxidation of tradition is with " oxygen deprivation compound " layer, contact electric life improves 10%.
Embodiment two
To prepare Ag (80) SnO2-In2O3/ AgSn25 and Ag (80) SnO2-In2O3For/AgZn30 electrical contact material
The first step, by Ag ingot, Sn ingot, In ingot, additive Cu and Ni element carry out melting and ingot casting.Wherein Ag content is 83.5wt%, Sn content are 10.5wt%, and In content is 5wt%, and additive Cu is 0.5wt%, Ni 0.5wt%.
The alloy spindle that the first step obtains is squeezed, AgSnIn material strip or plate is processed into, wherein squeezing by second step 550 degree of temperature, charcoal protection；Plate thickness 18mm.
AgSnIn material strip or plate surface are carried out grinding and buffing processing by third step, wherein polishing brush uses steel wire Brush.This step also can be omitted.
4th step, will treated material strip or plate, two layers of hot Compound Machining, wherein 500 degree of temperature, N2Protection, it is compound Before, one layer is AgSnIn layers, and stock up thickness 18mm；Another layer AgSn25 layers (Ag content 75wt%), stock thickness 6.0mm (according to It requires welding layer thickness accounting 25% to calculate according to finished product thickness to obtain)；Alternatively, another layer is AgZn30 layers of (Ag content 70wt%), it stocks up thickness 2.0mm (requiring welding layer thickness accounting 10% to calculate according to finished product thickness to obtain)；Composite deformation amount 70%, all material strips or strip width 30mm, it is compound after material strip thickness 6mm.
The material strip that 4th step obtains after compound is diffused annealing, wherein 450 degree of temperature by the 5th step, and the time 12 hours, Logical Ar gas shield.
Material strip after annealing is carried out cold rolling by the 6th step, and wherein cold rolling single track deformation amount controlling is within 5%；It is rolled down into Product require thickness 1.8mm.
7th step, carries out internal oxidition for material strip after cold rolling, wherein 550 degree of oxidizing temperature, and oxygen presses 2Mpa, oxidization time 220 Hour.
The welding surface elder generation rubbing down of material strip after internal oxidition is removed oxide layer by the 8th step, then carries out punching and cleaning, punching At diameter square contact size 5mm × 5mm, acquisition can carry solder, the electrical contact of single side internal oxidized Ag tin oxide or indium oxide produces Product.
The present embodiment is finally in electrical contact product obtained from band solder, single side internal oxidized Ag tin oxide or indium oxide, wherein wherein It is about 0.18mm that contact welding surface, which carries solder layer,.It is that single side aoxidizes inside contact, even tissue, without " oxygen deprivation compound " Area, compared with the two-sided oxidation of tradition is with " oxygen deprivation compound " layer, contact electric life improves 15%.
Embodiment three
To prepare Ag (88) SnO2-In2O3/ AgSn15 and Ag (80) SnO2-In2O3For/AgZn15 electrical contact material
The first step, by Ag ingot, Sn ingot, In ingot, additive Zn element carry out melting and ingot casting.Wherein Ag content is 89.5wt%, Sn content are 5.5wt%, and In content is 4.5wt%, and additive Zn is 0.5wt%.
The alloy spindle that the first step obtains is forged, is processed into AgSnIn plate by second step, wherein 750 degree are forged, Charcoal protection, plate thickness 18mm.
AgSnIn plate surface is carried out grinding and buffing processing by third step, wherein polishing brush uses wire brush.
4th step, will treated plate, carry out two layers it is cold compound, compound preceding layer is AgSnIn layer, stock thickness 18mm；Another layer AgSn15 layers (Ag content 85wt%), stock thickness 6mm (requires welding layer thickness accounting according to finished product thickness 25% calculates acquisition)；Alternatively, another layer is AgZn15 layers (Ag content 85wt%), stock thickness 2.0mm is (according to finished product thickness It is obtained it is required that welding layer thickness accounting 10% calculates)；Composite deformation amount 60%, all strip width 90mm, compound rear material strip are thick Spend 8mm.
The material strip that 4th step obtains after compound is diffused heat treatment by the 5th step, and wherein for temperature at 650 degree, the time 5 is small When, lead to H2Gas shield.
Material strip after annealing is carried out cold rolling by the 6th step, and wherein cold rolling single track deformation amount controlling is rolled down within 10% Product require thickness 2.0mm.
7th step, carries out internal oxidition for material strip after cold rolling, wherein 600 degree of oxidizing temperature, and oxygen presses 2Mpa, oxidization time 140 Hour.
The welding surface elder generation rubbing down of material strip after internal oxidition is removed oxide layer by the 8th step, then carries out punching and cleaning, punching At the contact diameter 6.5mm, product is in electrical contact obtained from band solder, single side internal oxidized Ag tin oxide or indium oxide.
The present embodiment is finally in electrical contact product obtained from band solder, single side internal oxidized Ag tin oxide or indium oxide, wherein wherein It is about 0.20mm that contact welding surface, which carries solder layer,.It is that single side aoxidizes inside contact, even tissue, without " oxygen deprivation compound " Area, compared with the two-sided oxidation of tradition is with " oxygen deprivation compound " layer, contact electric life improves 8%.
Example IV
To prepare Ag (85) SnO2-In2O3/ AgSn15 and Ag (80) SnO2-In2O3For/AgZn15 electrical contact material
The first step, by Ag ingot, Sn ingot, In ingot, additive Ni element carry out melting and ingot casting, and wherein Ag content is 87wt%, Sn content are 9.7wt%, and In content is 3wt%, and additive Ni is 0.3wt%.
The alloy spindle that the first step obtains is forged, is processed into AgSnIn plate by second step, wherein 550 degree are forged, N2Protection, plate thickness 22mm.
AgSnIn plate surface is carried out grinding and buffing processing by third step, wherein polishing brush uses wire brush.
4th step, will treated plate, two layers of hot Compound Machining, wherein 750 degree of temperature, Ar is protected, before compound, one layer It is AgSnIn layers, stock up thickness 18mm；Another layer AgSn17 layers (Ag content 83wt%), stock thickness 2.0mm is (thick according to finished product Degree requires welding layer thickness accounting 10% to calculate acquisition)；Alternatively, another layer is AgZn25 layers (Ag content 75wt%), stock is thick Spend 2.0mm (requiring welding layer thickness accounting 10% to calculate according to finished product thickness to obtain)；Composite deformation amount 40%, all plates are wide Spend 30mm, compound rear material strip thickness 12mm.
The material strip that 4th step obtains after compound is diffused heat treatment by the 5th step, and wherein for temperature at 600 degree, the time 8 is small When, lead to N2Gas shield.
Material strip after annealing is carried out cold rolling again by the 6th step, and wherein cold rolling single track deformation amount controlling is within 15%, rolling Thickness 3.0mm is required to finished product.
7th step, carries out internal oxidition for material strip after cold rolling, wherein 720 degree of oxidizing temperature, and oxygen presses 1.0Mpa, oxidization time 320 hours.
The welding surface elder generation rubbing down of material strip after internal oxidition is removed oxide layer by the 8th step, then carries out punching and cleaning, punching At diameter contact size diameter 15mm, i.e., included solder, single side internal oxidized Ag tin oxide or indium oxide are in electrical contact product.
The present embodiment is finally in electrical contact product obtained from band solder, single side internal oxidized Ag tin oxide or indium oxide, wherein wherein It is about 0.30mm that contact welding surface, which carries solder layer,.It is that single side aoxidizes inside contact, even tissue, without " oxygen deprivation compound " Area, compared with the two-sided oxidation of tradition is with " oxygen deprivation compound " layer, contact electric life improves 20%.
The foregoing is merely part preferred embodiments of the invention, not do any limit to technical scope of the invention System it may also be possible to apply the invention for included solder, the single side internal oxidized Ag tin oxide or indium oxide electrical contact material of other compositions proportion The preparation of material.Any modification made all within the spirits and principles of the present invention, equivalent replacement and improvement etc. should be included in this Within the protection scope of invention.

Claims (10)

1. a kind of single side internal oxidized Ag tin oxide or indium oxide contact material, it is characterised in that: including silver-tin oxide or indium oxide material Expect ontology, the one side of the silver-tin oxide or indium oxide material body is the welding surface of included solder, and the welding surface is by AgSn layers Or AgZn layers of composition, the another side of the silver-tin oxide or indium oxide material body is oxide side, and the oxide side is AgSnO2In2O3Layer.
2. single side internal oxidized Ag tin oxide or indium oxide contact material according to claim 1, it is characterised in that: described AgSn or AgZn layers, it is 8~25% that thickness, which accounts for overall thickness ratio,；
The AgSn composition of layer: Sn content is in 15wt%~25wt%, surplus Ag；
The AgZn composition of layer: Zn content is in 15wt%~30wt%, surplus Ag.
3. single side internal oxidized Ag tin oxide or indium oxide contact material according to claim 1 or 2, it is characterised in that: institute State AgSn layers or AgZn layers, in which:
There is the SnO of a layer thickness≤20 μm on the AgSn layer2Layer；
There is the ZnO layer of a layer thickness≤20 μm on the AgZn layer.
4. a kind of preparation method of any one of claim 1-3 single side internal oxidized Ag tin oxide or indium oxide contact material, It is characterized by comprising:
AgSnIn alloy spindle is processed into AgSnIn material strip or plate by S1；
The AgSnIn material strip or plate and AgZn band or AgSn band are carried out Compound Machining by S2, and wherein first layer is AgSnIn layers, the second layer is welding surface AgSn layers or AgZn layers；
The compound rear material strip of S3 or plate are diffused annealing, cold rolling by S3；
Material strip or plate progress internal oxidition after cold rolling is obtained included solder, single side internal oxidized Ag tin oxide or indium oxide electricity by S4 Contact material.
5. the preparation method of single side internal oxidized Ag tin oxide or indium oxide contact material according to claim 4, feature Be: in S1, the alloy spindle is processed into AgSnIn material strip or plate using extruding or forging, in which:
The extruding, temperature are 550 degree~750 degree, and N is led in heating process2Or charcoal protection；
The forging, forging temperature is 550 degree~750 degree, and heating process leads to N2Or charcoal protection.
6. the preparation method of single side internal oxidized Ag tin oxide or indium oxide contact material according to claim 4, feature It is: in S2, AgSnIn material strip or plate is subjected to two layers of Compound Machining, using cold compound or hot compound, in which:
Described cold compound, deflection is between 60%~80%；
The heat is compound, and for deflection between 40%~70%, temperature controls the H between 500 degree~750 degree2, N2 or Ar protect Shield；
The AgSn composition of layer: Ag content is in 75wt%~85wt%, surplus Sn；
The AgZn composition of layer: Ag content is in 70wt%~85wt%, surplus Zn.
7. the preparation method of single side internal oxidized Ag tin oxide or indium oxide contact material according to claim 4, feature Be: in S3, the diffusion annealing, wherein temperature leads to H between 450 degree~750 degree2、N2Or Ar gas shield.
8. the preparation method of single side internal oxidized Ag tin oxide or indium oxide contact material according to claim 4, feature Be: in S3, the cold rolling, wherein single track deformation amount controlling is between 5%~30%.
9. the preparation method of single side internal oxidized Ag tin oxide or indium oxide contact material according to claim 4, feature Be: in S4, the internal oxidition, wherein between 550 degree~720 degree of oxidizing temperature, the voltage-controlled system of oxygen is between 0.8Mpa~2Mpa.
10. according to the preparation side of the described in any item single side internal oxidized Ag tin oxide or indium oxide contact materials of claim 4-9 Method, it is characterised in that: further include following one or two kinds of features:
After S1, before S2 Compound Machining, AgSnIn material strip or plate surface are subjected to grinding and buffing processing；
After S4, further comprise:
By material strip after internal oxidition or plate, welding carries out rubbing down, obtains the fresh face AgSn AgZn；
By material strip after rubbing down to punching and cleaning is carried out, included solder, the single side internal oxidized Ag tin oxide oxygen used immediately is formed Change indium contact material.
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