CN108878179A - The contact material formula of siller tin oxide exacerbation rare earth - Google Patents
The contact material formula of siller tin oxide exacerbation rare earth Download PDFInfo
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- CN108878179A CN108878179A CN201810926171.5A CN201810926171A CN108878179A CN 108878179 A CN108878179 A CN 108878179A CN 201810926171 A CN201810926171 A CN 201810926171A CN 108878179 A CN108878179 A CN 108878179A
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-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
- C22C32/0094—Non-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 organic materials as the main non-metallic constituent, e.g. resin
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- 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
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Abstract
Siller tin oxide aggravates the contact material formula of rare earth, including GeO2、Gd2O3、Sm2O3And Y2One or more of O, wherein Sm2O3, Gd2O3、Y2O3And GeO2The addition total amount of four kinds of rare earths is 1.2%-1.5%, Sn content is 12%-16%, and the conductive plastics of 8%-15% is added, which is made by the SiO2 for adding Filamentous carbon black and complete coking in PC plastic and ABS plastic mixing material, Ag is surplus, which distributes according to weight.The invention has the advantages that:The addition of heavy rare earth optimizes the high-temperature stability of material, and contact is highly conductive, high-termal conductivity, and after conductive plastics molding, integral contact lightens, and can make it have good resistance to arc erosion energy.
Description
Technical field
The invention belongs to contact material fields, and in particular to the contact material formula of siller tin oxide exacerbation rare earth.
Background technique
Electrical contact is the core component of various high and low voltage electrical equipments, is widely used in Aeronautics and Astronautics, navigational field and civilian work
The various AC/DC contactors of industry, breaker, in relay change-over switch.The on-off that its performance directly affects entire electric appliance is held
Amount, service life and operational reliability etc..
Electrical contact material is many kinds of.Commonly mainly there are silver-base alloy and acid bronze alloy, wherein silver-base alloy electrical contact
Material is widely used in middle Smaller load(Less than 50A)Or under the conditions of light current(Less than 1A)Low-voltage electrical apparatus, car electrics and household
In electric appliance.Especially these electric appliances for having a large capacity and a wide range of relay and contactor, almost all use Ag base contact material.
In silver based contact material, AgCdO is due to good resistance to arc wear, resistance fusion welding, electric conductivity and leads
It is hot, and contact resistance is small and stability is high, referred to as " omnipotent contact material ".But since AgCdO contact material is producing, is making
With there is the harm of " cadmium poison " in removal process, to human body and natural environment with biggish harm and pollution.State thus
Border Electrotechnical Commission was issued in 2 months 2003《About being forbidden to use certain Hazardous Substances Directives in electronic electric equipment》.This refers to
It enables and coming into force from July 1st, 2006.Therefore, develop and develop the novel contact material with environmental protection and excellent electric contact performance
Material becomes the heat subject in the field.
AgSnO2It is that the area research is most, most promising new material.By the exploration of many years, AgSnO2Material exists
The performance of some aspects, such as electrical property under DC condition, even more than AgCdO.Developed countries are in AgSnO2Material
The improvement of performance and manufacturing process realizes stable industrialized production, completely instead of AgCdO.No matter in AC and DC
It is applied widely in electric appliance.And China is to AgSnO2Research, seriously lag behind foreign countries, the early 1990s just starts pair
The material carries out imitated and developmental research.But progress is slow, and every electrical performance indexes, mechanical and physical performance etc. and foreign material
Gap it is larger.It is embodied in:Electrical properties and the modelings such as resistance is big, temperature increases, resistance to electrical wear and resistance fusion welding, electric life are low
Property it is poor, hardly possible processing etc. mechanical and physical performances, be always restrict the widely applied Major Difficulties of the material.Therefore, electrician trade
Scientific research personnel also never stopped to the material carry out deeper into research.
A:SnO2Granular size and content are to AgSnO2The influence of contact material performance
SnO2Particle and content and the distribution in material matrix directly determine AgSnO2Every electrical property.SnO2Content is light
Micro- increase can be obviously improved AgSnO2Resistance fusion welding energy.
Work as SnO2When content is less than 7%, the fusion welding resisting ability of contact material is weaker, and works as SnO2When content is greater than 15%, then deposit
In the problem that temperature rise is excessively high, it is seen that SnO2Content has large effect to contact and anti-melting welding, electric life etc..
On mechanical and physical performance:SnO2Volume fraction, distribution situation, size and the powder granule shape of particle
Deng largely determining AgSnO2Processing performance.It needs to increase because of factors such as the electric current that uses of electric appliance are excessive again
SnO2Volume fraction when, then the demand on its material electrical property is obtained using the plasticity of expendable material as cost.But these
It is all often theoretic analysis, actually but not so.Therefore, to seek high electrical property, while machinery with higher again
Physical property often just needs to increase other elements to reach such purpose.
B:Additive is to AgSnO2The influence of contact material performance
A kind of contact material of excellent performance first has to low bulk resistor and low contact resistance, is just unlikely to contact in this way
Temperature rise when connecting and disjunction is unstable, and has stronger arc resistant ablation, resistance to electrical wear.External AgSnO at present2
Material nearly all contains multiple additives(Add copper, nickel, tungstic acid and rare earth element).
The use of additive can not only reduce the contact resistance of material, can also improve SnO2Particle and basis material
Surface moist.Such as addition copper oxide(CuO silver) can be improved to SnO2Liquid after CuO is added in the surface moist of particle
Silver penetrates into occurs metal oxide simultaneously in oxide particle gap(MeO) to the expanding in silver-colored region, firmly wet boundary is formed
The probability for forming the accumulation regions MeO is reduced in face, switch contact temperature rise when in use can be effectively reduced, to reduce AgSnO2Touching
The raising of head material contact resistance under arcing.
External common additive has WO3, MO2O3, InO3, Bi2O3, CuO, Li2O, Sn2O3Deng.In recent years in order to mention more greatly
The electrical property of high material begins to use some light rare earth elements, but it is total a bit, how using addition element or addition how much, then
According to the different type of electric appliance and different requirements, and meet the requirement of different performance.However, addition is any
Following state should not occur for additive:
a:The wet performance of oxide particle is influenced, with SnO2The additive not reacted with Ag.Add such additives
With the AgSnO of class additive in no addition2Material property is similar, and aggressivity is poor, and resistance fusion welding is general, and disjunction drag is low.
b:Increase angle of wetting, makes SnO2Particle surface is more difficult the additive being wet.The contact for adding such additives is burnt
Surface layer is silver-colored area and metal oxide two layers of tissue after erosion, and not containing the AgSnO of additive2Contact is compared, and electrical property deteriorates.
c:Reducing angle of wetting makes oxide particle be easier to wet additive.After the contact ablation for adding such additives
Surface topography should show as honeycomb and netted, and general surface is more smooth or smooth, that is to say, that such additive is added
The high temperature sublimability of material inner oxide is improved, this is also that light rare earth effect achieved is added, and largely improves touching
Head arc resistant ability.
d:The additive of compound can be formed with Ag.
Although current research makes people use and select certain understanding and reference to additive.But it is practical
It selects to consider the electric condition used, material preparation method and actual use experience etc. when additive.And it adds
The complexity of agent becomes an important factor for influencing contact material performance.It is also that it becomes the main of contact material key technology
Reason.No matter which kind of additive added so reacted from another side again, the action principle of additive is at present without unification
It is theoretical.
But by TG-DT A spectrum, the thermal stability of various additives must at 1500 DEG C or less energy and SnO2Hair
Raw combination reaction, can generate new phase constitution structure after combination reaction occurs.
Summary of the invention
Aiming at the shortcomings in the prior art, the present invention provides AgSnO2The contact material formula for aggravating rare earth, can be significantly
Improve the hot properties and stability of material.The arc resistant ablation ability of material is set to obtain very big promotion, to make contact
Reliability is further enhanced.
The invention is realized by the following technical scheme.
Siller tin oxide aggravates the contact material formula of rare earth, including GeO2、Gd2O3、Sm2O3And Y2One or more of O,
Wherein Sm2O3, Gd2O3,、Y2O3And GeO2The addition total amount of four kinds of rare earths is 1.2%-1.5%, and the conductive plastics of 8%-15% is added,
The conductive plastics is made by the SiO2 for adding Filamentous carbon black and complete coking in PC plastic and ABS plastic mixing material, and Ag is remaining
Amount, the proportion are distributed according to weight.The ratio of Filamentous carbon black and the SiO2 of complete coking are 1:1 obtained conductive plastics, addition are led
The contact of electric plastics not only has high conductivity, but also gravity greatly reduces.
Preferably, the Sm2O3, Gd2O3,、Y2O3And GeO2The addition total amount of four kinds of rare earths is 1.3 %.
Preferably, the Sn content is 12%.
Compared with prior art:(1)The increase and decrease of the additional amount of heavy rare earth, makes AgSnO2The melting temperature of material becomes
Change, improves the hot properties and stability of material.(2)Heavy rare earth changes material materials microstructure structure, in the metallographic structure of material
It forms fine particle and strengthens phase structure, keep highly conductive, the high-termal conductivity of Ag.
Detailed description of the invention
Fig. 1 is heavy rare earth GeO of the invention2、Gd2O3、Sm2O3And Y2O3It is bent to the differential thermal of contact material when different additional amounts
Line.
Fig. 2 is different GeO of the invention2、Gd2O3、Sm2O3And Y2O3Content and material melting point, temperature variation curve.
Specific embodiment
The contact material formula of siller tin oxide exacerbation rare earth, which is characterized in that including GeO2、Gd2O3、Sm2O3And Y2In O
One or more, wherein Sm2O3, Gd2O3,、Y2O3And GeO2The addition total amount of four kinds of rare earths is 1.2%-1.5%, and 8%-15% is added
Conductive plastics, the conductive plastics is by adding the SiO2 of Filamentous carbon black and complete coking in PC plastic and ABS plastic mixing material
It is made, Ag is surplus, which distributes according to weight.
Rare earth element has special physical and chemical property.Make alterant and High-Temperature Strengthening agent in non-ferrous metal
Deng extensive use.Rare earth element is added such as in Cu stronger deoxidation, refines the effect of crystal grain.
According to the requirement of different electric appliances, suitable rare earth material is selected to reach the effect of reinforcing to the microstructure of silver
It answers.Stability of corresponding electrical property and alloy phase etc. can accomplish maximum quantization(The superiority of performance).But rare earth element
Aggregation is precipitated on crystal boundary easily in structure, reduces the intensity and toughness of alloy(Plasticity), this is also how to determine additional amount
Quantification problem.
In common rare earth or(Light rare earth)AgSnO is added2On the basis of having obtained better effects, using addition heavy rare earth
Research equally uses pre-oxidation process, the results showed that:Heavy rare earth element, such as Sm is added2O3, Gd2O3,、Y2O3And GeO2Deng four kinds
The addition total amount of rare earth is 1.2%-1.5%, and Sn content is 12%-16 %, and Ag is surplus, which distributes according to weight.The technique
AgSnO can be overcome2The poor processability of alloy, the problems such as unstable quality.On electrical property, addition heavy rare earth is greatly reduced
AgSnO after element2The lower bulk resistor of slider material and contact resistance.Resistance to electrical arc erosion characteristic is promoted20% or so, temperature rise drop
Low effect becomes apparent from.Through practical installation test, high current is substantially met(Greater than 40A) requirement of the superior performance of DC relay.
AgSnO2The difference of material preparation process and technology of preparing, causes AgSnO2The conduction of material, hot property and anti-molten
The huge difference of weldering property.Its main cause can be summarized as Ag matrix and SnO2The change of essence has occurred in the bonding state of particle
Change.Chemical synthesis, reaction synthesis are reviewed, the processes such as chemical codeposition and mechanical alloying are all based on powder metallurgy
Technique.Process is more and cumbersome, and we use the higher heavy rare earth element of fusing point such as germanium dioxide instead on the basis of light rare earth
(GeO2), gadolinium oxide(Gd2O3), samarium oxide(Sm2O3), yttrium oxide(Y2O3) etc., it can effectively improve light rare earth(As La, Ce,
Re, Nd etc.)To SnO2The inadequate state of the wellability of particle, makes SnO2Particle occurs in the state of complete wet with Ag substantial
Diffusion.Intermetallic compound is generated with Ag phase simultaneously, refines the metallographic in material structure more.Mechanical and physical performance obtains
More preferable to improve, plasticity and processing performance obtain optimization and improve.The addition of dystectic heavy rare earth element simultaneously makes material entirety
Hot properties, such as resistance to electrical arc erosion, arc resistant heat sealability all obtain larger promotion.
Four, AgSnO2Several big key technologies of+heavy rare earth material
a:The contact resistance problem of material
The contact resistance of material is smaller, in contact galvanization because of Joule effect caused by temperature rise with regard to smaller.Contact resistance packet
Containing " contraction protein " and " film resistance ", the increase of any of which resistance can be such that total contact resistance increases, and lead to temperature rise
It is excessively high.
Heavy rare earth and SnO is added2Particle can be effectively formed intermetallic compound.And the wettable SnO of this intermetallic compound2
Particle surface is easily spread with Ag matrix(Chemical affinity interaction).The effect of heavy rare earth so then changes SnO completely2
Particle is only a field trash originally and is embedded in the effect for only serving a skeleton in Ag matrix.Its envelope-bulk to weight ratio is according to Ag matrix
Interior certain volume, so that the reduction of conduction, heat-conducting area under certain current density, to make material bulk resistor
Change, that is, contact resistance become larger, temperature characteristic degenerates, and arc characteristic degenerates(Transition ablation of the electric arc to contact material surface).
b:The raising of contact resistance and arc erosion(Damage)It is relevant
On the one hand due to the raising of contact resistance so that the surface temperature rise of slider material improves, great change occurs for contact surface structure
Become, the scaling loss of electric arc destroys SnO2The combination interface of particle and Ag matrix, makes SnO2Particle is exposed to the surface layer of material, contact
Surface shows uneven, so that contact condition of the contact in the secondary connection of switch is changed, the contact surface of out-of-flatness
Subsequent poor contact is caused, to form the formation of bigger contact resistance and higher temperature rise, is recycled several times, contact
It is i.e. entirely ineffective and scrap.
And heavy rare earth element then changes disadvantages described above, makes SnO2Particle and Ag matrix form firm diffusion bond face,
To reduce the bulk resistor and surface contacted resistance of material.Joule effect is not generated in temperature rise thus.Simultaneously as being added
Heavy rare earth greatly improves the mechanical performance and non-deformability of material, reaches to the Grain Refinement Effect of materials microstructure
Its electrical property is neither influenced, and enhances the arc resistant scaling loss when cut-offfing, resistance fusion welding.
Heavy rare earth changes materials microstructure structure, and fine particle, that is, hardening constituent knot is formed in the metallographic structure of material
Structure, maintains highly conductive, the high-termal conductivity of Ag, and can make it have good resistance to arc erosion energy.The hair of this and light rare earth
Life manages the difference for having matter:Heavy rare earth optimizes the high-temperature stability of material.
The Sm of Fig. 1 different content2O3, Gd2O3,、Y2O3And GeO2Dopant material differential thermal curve
When(Sm2O3, Gd2O3,、Y2O3And GeO2)Additional amount when increasing to 0.8% by 0.2 %, the Curie temperature of contact material by
102 DEG C are increased to 130 DEG C(Sm2O3, Gd2O3,、Y2O3And GeO2)Additional amount when being more than 0.8% Curie temperature increase again to
180℃。
This reactions vary sample occurred when light rare earth elements is added, the additional amount of light rare earth how much the heat with material
Stream nothing is substantially change.Illustrate heavy rare earth(Sm2O3, Gd2O3,、Y2O3And GeO2 )The how much changeable material of additional amount heat flow value,
Variation i.e. on fusing point improves the melting temperature of material.
In terms of another side, heavy rare earth Sm2O3, Gd2O3,、Y2O3And GeO2Additional amount increase and decrease, the fusing point temperature of material
Degree also changes at any time, that is to say, that Sm2O3, Gd2O3,、Y2O3And GeO2Addition substantially increase the hot properties of material and steady
It is qualitative.The arc resistant ablation ability of material is set to obtain very big promotion, so that the reliability of contact be made to be further enhanced.
Fig. 2 show different Sm2O3, Gd2O3,、Y2O3And GeO2Content and material melting point, temperature variation curve;
Electrical contact material described in us is the critical material in device for switching, be because device for switching main performance such as:It connects
The size of logical breaking current and the length of electric life, temperature rise size of contact etc. determine the quality of contact material.But due to
Extremely complex situation can be encountered in use, and other than having mechanical force and frictional force, electric current flows through contact and generates
Thermal energy, the scaling loss of electric arc or the material generated by the change of current polarity transfer etc. various factors all can to material occur shadow
It rings.It is also different to different Effect of Materials.So must also make in conjunction with switch during the developmental research of material
It is combined closely with condition and a variety of different contact phenomenas, could develop and remove new material.
Switch when suiting circuit contact can generate arc erosion, under the different loading condition of different modes of operation, electric arc
Influence of the process and erosion of erosion to contact resistance, is all different including each minor change in performance.And
When contact closure, spring is inevitably generated.Material from anode to cathode occurs because of liquid bridge and short arc for contact material
Transfer.Increase contact resistance because of the dynamic melting welding of generation again simultaneously.
And dynamic melting welding and erosion pattern depend mainly on load shock current characteristics and arcing time.
Different contact materials and different technique processing methods, it is different when to above-mentioned influence.
As in car direct current road, AgSnO2After+heavy rare earth contact material test operation number reaches 100,000 times,
The erosion of contact surface and material transfer are minimum.It is resistant to big dash current and corrodes, and keeps smooth contact surface and minimum
Net transfer.This is because this material, which has, has higher fusing point and higher temperature stability than not aggravating rare earth material,
The uniform oxide of disperse(Fusing point is all larger than 1500 DEG C)With low resistivity.The generation corroded can thus be prevented.
According to electrical contact and switching arc theory analysis, the operation of contact material and the electric heating of contained composition, mechanical, chemistry
Equal characterisitic parameters are related.The resistivity of the composition as contained by the contact resistance of contact and temperature rise and material, thermal conductivity.Resistance temperature system
Number, hardness, coefficient of elasticity, chemical affinity etc. are related.The tension of composition contained by the resistance fusion welding of contact, corrosion resistance and material
Intensity, fusing point, boiling point, fusing and gasification latent heat specific heat, decomposition temperature, electron work functon etc. are related.Therefore, contact material is ground
It is also the biggish field of difficulty that system, which is always most active field in Electrical Contact & Electrical Arc subject,.
Protection scope of the present invention includes but is not limited to embodiment of above, and protection scope of the present invention is with claims
Subject to, replacement, deformation, the improvement that those skilled in the art that any pair of this technology is made is readily apparent that each fall within of the invention
Protection scope.
Claims (3)
1. the contact material formula of siller tin oxide exacerbation rare earth, which is characterized in that including GeO2、Gd2O3、Sm2O3And Y2One in O
Kind is several, wherein Sm2O3, Gd2O3,、Y2O3And GeO2The addition total amount of four kinds of rare earths is 1.2%-1.5%, is added 8%-15%'s
Conductive plastics, the conductive plastics is by adding the SiO2 system of Filamentous carbon black and complete coking in PC plastic and ABS plastic mixing material
, Ag is surplus, which distributes according to weight.
2. the contact material formula that siller tin oxide according to claim 1 aggravates rare earth, which is characterized in that described
Sm2O3, Gd2O3,、Y2O3And GeO2The addition total amount of four kinds of rare earths is 1.3 %.
3. the contact material formula that siller tin oxide according to claim 1 aggravates rare earth, which is characterized in that described
SnO2Sn content is 12%.
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CN1281904A (en) * | 1999-07-26 | 2001-01-31 | 中国人民解放军国防科学技术大学 | Silver heavy rake earth metal oxide electric contact material and its preparation process |
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CN106893291A (en) * | 2015-12-18 | 2017-06-27 | 比亚迪股份有限公司 | Plastics composite and plastic products and plastic basis material surface selective metallization method |
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US4578215A (en) * | 1983-08-12 | 1986-03-25 | Micro-Circuits Company | Electrical conductivity-enhancing and protecting material |
JPH0831253A (en) * | 1994-05-11 | 1996-02-02 | Tanaka Kikinzoku Kogyo Kk | Electric contact material |
CN1281904A (en) * | 1999-07-26 | 2001-01-31 | 中国人民解放军国防科学技术大学 | Silver heavy rake earth metal oxide electric contact material and its preparation process |
CN1624838A (en) * | 2004-12-08 | 2005-06-08 | 昆明贵金属研究所 | Silver-tin oxide electrical contact material and preparation method thereof |
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