CN104538214A - Copper-based contact material based on graphene enhanced foamy copper - Google Patents

Copper-based contact material based on graphene enhanced foamy copper Download PDF

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Publication number
CN104538214A
CN104538214A CN201410754620.4A CN201410754620A CN104538214A CN 104538214 A CN104538214 A CN 104538214A CN 201410754620 A CN201410754620 A CN 201410754620A CN 104538214 A CN104538214 A CN 104538214A
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CN
China
Prior art keywords
copper
graphene
foam copper
foam
powder
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Application number
CN201410754620.4A
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Chinese (zh)
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CN104538214B (en
Inventor
刘立强
翁桅
林万焕
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Zhejiang Fuda Alloy Materials Technology Co Ltd
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Fuda Alloy Materials Co Ltd
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Classifications

    • 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
    • H01H1/025—Composite material having copper as the basic material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • 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
    • C22C32/0005—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 at least one oxide and at least one of carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper

Abstract

The invention discloses a copper-based contact material based on enhanced graphene foamy copper. The material is mainly composed of copper alloy and graphene, the copper alloy comprises 0.01-10 wt% of oxide, 0.01-2 wt% of carbide and the balance copper or copper alloy, the graphene is evenly distributed on the inner surface walls of holes which are communicated with one another in precursor foamy copper prepared through the copper alloy, and the outer surface of the foamy copper, and the thickness of the graphene is within the range of 10 nanometers. The foamy copper is prepared into a silver-free contact material after follow-up densification. The copper-based contact material has the advantages of being low and stable in contact resistance, good in electrical arc erosion resistance and good in welding resistance, and can take the place of an existing silver-based contact material to be applied to low-voltage circuit breakers, contactors and relays.

Description

Based on the copper base slider material of Graphene reinforced foam copper
Technical field
The invention belongs to electrical contact material field, specifically refer to a kind of copper base slider material based on Graphene reinforced foam copper.
Background technology
Contact material is the critical material of the electrical equipment such as various switch, relay, contactor, plays a part connection, disjunction and transmission current.A large amount of contact material used is silver-based material both at home and abroad at present, and its cost is high.Although there is part copper base contact material, its antioxygenic property is poor and electric life is short.Main cause is that copper is exposed at contact surface, thus causes low temperature non-oxidizability poor, and under arcing, arcing is comparatively serious.
By retrieval, following Patent design is to copper base slider material
1, CN1224768A copper-base silver-less and cadmium-less alloy material for low-voltage electrical contact, mainly adopts reinforcing material (diamond etc.) and additive (Zn, Sn etc.) to improve copper base slider material electrical property.
2, CN1767105A cleaning environment-friendly type copper-base contact material for low-voltage electrical apparatus and contact preparation method thereof mainly adopt increase material (rare earth oxide) and additive (thulium) to improve copper base slider material electrical property.
3, the copper-based material of CN101335102A electric contacts mainly adopts Copper substrate interpolation the 5th, six subgroup elements and rare earth element method to improve electrical property.
4, the preparation method of a CN102324335A composite electric contact material discloses a kind of copper base slider material, and main feature is carbon nano-tube coated copper.
5, CN102218540A Graphene and metal nano compound are without powder and manufacture method thereof.
More than in invention, front 3 comparison patents all adopt reinforcing material and additive method to improve copper base slider material, but are not improved Copper substrate, thus make such material in use, copper is easy to exposedly to be oxidized in air and electric arc, affects contact resistance.Comparison patent 4 proposes the slider material of carbon nano-tube coated copper; but there is complicated process of preparation in this material, employing copper sheet is the copper particle that raw material brings thick (carbon nano-tube cannot arrive the effect protected completely), material internal contains part silver and cannot realize completely without problems such as patinas, is difficult to industrially be applied.Comparison patent 5 proposes the material of Graphene and metal-powder compound, but Graphene is the microplate type adopted, and unrealized graphene coated is in surface of metal particles, thus cannot reach the coated of metallic particles 100%.
Add graphite with conventional powder mixing method equally to compare with the copper base slider material of carbon nano-tube with band Graphene prepared by carbon nano-tube, material prepared by these class methods cannot ensure have Graphene or carbon nano-tube distribution between each reinforcing material and basis material, so just there is the unsteadiness of capability and performance.
Summary of the invention
The object of the invention is the shortcoming and defect existed to overcome prior art, and provide a kind of and can solve that copper base slider material non-oxidizability is poor, the larger problem of arcing make a kind of copper base slider material based on Graphene reinforced foam copper of distributing equilibrium between reinforcing material and basis material.
For achieving the above object, mechanism of the present invention and scheme are for blank is through compacting or rolling repeatedly with Graphene reinforced foam copper, make its density arrive more than 99% of solid density, be prepared into copper base slider material, this Graphene reinforced foam copper includes foam copper and Graphene.
Described foam copper comprises following component: the copper powder of 0.01-10wt% oxidate powder, 0.01-2wt% carbide powder, surplus or copper alloy powder, the foam-like distribution hole of mutual UNICOM is provided with in this foam copper, its porosity 50%-90%, described oxidate powder is SnO 2, CuO, ZnO, Fe 2o 3, rare earth one or several combination, described carbide is the one or more combination in tungsten carbide, vanadium carbide, boron carbide;
Described graphene uniform cover be distributed in the inner UNICOM of foam copper internal pore surface wall on and foam copper outer surface on, the cladding thickness of Graphene is within 10 nanometer range.
Further setting is that in described copper alloy powder, copper content is more than 95%, and this copper alloy powder is the one of CuAl, CuZn, CuNi, CuB, CuTe, CuRE; Or this copper alloy is at least two group element combinations in Cu and Al, Zn, Ni, B, Te, RE.
Further setting is described stone Graphene reinforced foam copper is obtained by following technique: the growing graphene layer in the inner wall surface and foam copper outer surface of foam copper inner UNICOM hole with chemical vapour deposition (CVD) or wet method liquid-phase reduction graphite oxide technique.
Copper base slider material of the present invention make use of on internal pore surface wall that graphene uniform is distributed in the inner UNICOM of foam copper and foam copper surface, make copper or copper alloy not exposed in outside, hinder the oxidation of copper, solve conventional copper base slider material and cannot solve low temperature antioxygenic property.Due to the high-specific surface area of Graphene, under arcing, there is not precipitation or floating and assemble, slider material ablation layer stable components in the reinforcing material (oxide, carbide) of graphene coated, ensure that the stability of contact resistance in military service process in metal bath; Due to the distinctive anti-melting welding ability of carbon that Graphene has, improve the resistance fusion welding energy of copper-based material.The high conduction performance of Graphene, also ensures that the volume resistivity of copper base slider material is lower.
Slider material of the present invention has more excellent oxidation resistance and anti-scorching ability with conventional copper base contact relatively, can be applied in low-voltage circuit breaker, contactor and relay.
Below in conjunction with embodiment, the present invention is described further.
Embodiment
Below by embodiment, the present invention is specifically described; only be used to further illustrate the present invention; can not be interpreted as limiting the scope of the present invention, the technician in this field can make some nonessential improvement and adjustment according to the content of foregoing invention to the present invention.
embodiment 1
CuTeWCSnO 2each quality of materials percentage of/GRN is: foam copper alloying component: WC:1, SnO 2: 1, all the other surpluses are CuTe, and wherein in CuTe alloy, Cu content is 99.5%, and surplus is Te.Graphene thickness in 10 nanometers, the 70-90% on graphite coat foam copper surface.Preparation technology is: CuTe powder, WC powder, SnO 2powder and pore creating material homogenizing mix powder, compacting sintering pore-creating, and porosity, at 50-90%, is prepared into foam copper block, and the organic pore-forming agents wherein in foam copper all must remove in sintering process.This block chemical vapor deposition graphene in tube type resistance furnace, carbon source is methane, and the graphene layer THICKNESS CONTROL of vapour deposition is in 10 nanometer range.The pore wall made is follow-up through repeat-rolling and compacting with the foam copper of Graphene, is prepared into the copper alloy slider material of the DB of relative density more than 99%.Copper base contact density prepared by this composition is 8.62g/cm 3, resistivity is 2.28 μ Ω .cm, hardness is HV112.
embodiment 2
CuB 4cSnO 2each quality of materials percentage of/GRN is: foam copper alloying component: B 4c:0.5, SnO 2: 0.3, all the other are the Cu of the graphene coated being no more than 10 nanometer thickness, the 80-95% on graphite coat foam copper surface.Preparation technology is: Cu powder, B4C powder, SnO2 powder and pore creating material homogenizing mix powder, follow-uply carry out sintering pore-creating, be prepared into the ball-type foam copper of porosity at 80-95%, this foam copper adds in the graphite oxide dispersion of high dispersive, under hydrazine hydrate reduction, make graphene uniform steady production on the pore wall of the inner UNICOM of foam copper, graphene layer THICKNESS CONTROL is in 10 nanometers, foam copper bulky grain, through compacting further, rolling, multiple pressure, is prepared into the copper alloy slider material of relative density more than 99%.Copper base contact density prepared by this composition is 8.67g/cm 3, resistivity is 2.19 μ Ω .cm, hardness is HV107
The invention is not restricted to above embodiment.

Claims (3)

1. the copper base slider material based on Graphene reinforced foam copper, it is characterized in that: with Graphene reinforced foam copper for blank is through compacting or rolling repeatedly, its density is made to arrive more than 99% of solid density, be prepared into copper base slider material, this Graphene reinforced foam copper includes foam copper and Graphene
Described foam copper comprises following component: the copper powder of 0.01-10wt% oxidate powder, 0.01-2wt% carbide powder, surplus or copper alloy powder, the foam-like distribution hole of mutual UNICOM is provided with in this foam copper, its porosity 50%-90%, described oxidate powder is SnO 2, CuO, ZnO, Fe 2o 3, rare earth one or several combination, described carbide is the one or more combination in tungsten carbide, vanadium carbide, boron carbide;
Described graphene uniform cover be distributed in the inner UNICOM of foam copper internal pore surface wall on and foam copper outer surface on, the cladding thickness of Graphene is within 10 nanometer range.
2. the copper base slider material based on Graphene reinforced foam copper according to claim 1, it is characterized in that: in described copper alloy powder, copper content is more than 95%, this copper alloy powder is the one of CuAl, CuZn, CuNi, CuB, CuTe, CuRE; Or this copper alloy is at least two group element combinations in Cu and Al, Zn, Ni, B, Te, RE.
3. the copper base slider material based on Graphene reinforced foam copper according to claim 1, is characterized in that: described stone Graphene reinforced foam copper is obtained by following technique: the growing graphene layer in the inner wall surface and foam copper outer surface of foam copper inner UNICOM hole with chemical vapour deposition (CVD) or wet method liquid-phase reduction graphite oxide technique.
CN201410754620.4A 2014-12-11 2014-12-11 The copper-based slider material of foam copper is strengthened based on Graphene Active CN104538214B (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105702387A (en) * 2016-04-08 2016-06-22 上海和伍复合材料有限公司 Graphene enhancement silver/metallic oxide electrical contact composite material and preparation method thereof
CN105695776A (en) * 2016-02-26 2016-06-22 济南大学 Preparation method for graphene reinforced copper-matrix electrical contact material
WO2017008716A1 (en) * 2015-07-13 2017-01-19 严利容 New type of silver-based low-voltage contact material and method for fabrication thereof
CN106736259A (en) * 2016-11-11 2017-05-31 陕西斯瑞新材料股份有限公司 A kind of preparation method of inexpensive looped network moving knife contact
TWI613070B (en) * 2015-11-20 2018-02-01 佛騰國際有限公司 High conductivity graphane-metal composite and methods of manufacture
CN109897985A (en) * 2019-03-05 2019-06-18 天津工业大学 Three-dimensional continuous graphite alkene/carbon/carbon-copper composite material and preparation method thereof
CN115255372A (en) * 2022-08-31 2022-11-01 河南机电职业学院 Powder making device for alloy powder and application of powder making device in preparation of copper-based solder

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT201700020699A1 (en) * 2017-03-14 2018-09-14 Vincenzo Tagliaferri Electrical contacts with inserts in metal foam electrodeposited with graphene.

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CN101781724A (en) * 2010-02-04 2010-07-21 西安理工大学 Method for preparing superfine foam copper by coordination compound
CN101885060A (en) * 2010-06-22 2010-11-17 上海中希合金有限公司 High-performance copper-diamond electrical contact material and preparation process thereof
CN102176338A (en) * 2011-03-10 2011-09-07 中国科学院上海硅酸盐研究所 Graphene/copper nanowire composite electric-conducting material and preparation method thereof
CN102400006A (en) * 2010-09-16 2012-04-04 北京有色金属研究总院 Foamy carbon/copper matrix or aluminum matrix composite material and preparation method thereof

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US20030015811A1 (en) * 1997-09-02 2003-01-23 Klett James W. Pitch-based carbon foam heat sink with phase change material
US6679933B1 (en) * 1998-12-16 2004-01-20 Victorian Rail Track Low resistivity materials with improved wear performance for electrical current transfer and methods for preparing same
CN101781724A (en) * 2010-02-04 2010-07-21 西安理工大学 Method for preparing superfine foam copper by coordination compound
CN101885060A (en) * 2010-06-22 2010-11-17 上海中希合金有限公司 High-performance copper-diamond electrical contact material and preparation process thereof
CN102400006A (en) * 2010-09-16 2012-04-04 北京有色金属研究总院 Foamy carbon/copper matrix or aluminum matrix composite material and preparation method thereof
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017008716A1 (en) * 2015-07-13 2017-01-19 严利容 New type of silver-based low-voltage contact material and method for fabrication thereof
TWI613070B (en) * 2015-11-20 2018-02-01 佛騰國際有限公司 High conductivity graphane-metal composite and methods of manufacture
TWI682848B (en) * 2015-11-20 2020-01-21 佛騰國際有限公司 High conductivity graphene-metal composite and methods of manufacture
CN105695776A (en) * 2016-02-26 2016-06-22 济南大学 Preparation method for graphene reinforced copper-matrix electrical contact material
CN105695776B (en) * 2016-02-26 2017-06-06 济南大学 A kind of Graphene strengthens the preparation method of copper-based electrical contact material
CN105702387A (en) * 2016-04-08 2016-06-22 上海和伍复合材料有限公司 Graphene enhancement silver/metallic oxide electrical contact composite material and preparation method thereof
CN106736259A (en) * 2016-11-11 2017-05-31 陕西斯瑞新材料股份有限公司 A kind of preparation method of inexpensive looped network moving knife contact
CN109897985A (en) * 2019-03-05 2019-06-18 天津工业大学 Three-dimensional continuous graphite alkene/carbon/carbon-copper composite material and preparation method thereof
CN115255372A (en) * 2022-08-31 2022-11-01 河南机电职业学院 Powder making device for alloy powder and application of powder making device in preparation of copper-based solder
CN115255372B (en) * 2022-08-31 2024-01-02 河南机电职业学院 Powder preparation device of alloy powder and application of powder preparation device in preparation of copper-based solder

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Effective date of registration: 20220127

Address after: 325025 No. 308, Binhai fifth road, Wenzhou Economic and Technological Development Zone, Wenzhou City, Zhejiang Province

Patentee after: Zhejiang Fuda alloy material technology Co.,Ltd.

Address before: No. 518, Binhai 4th Road, Binhai Park, Wenzhou Economic and Technological Development Zone, Zhejiang Province, 325000

Patentee before: FUDA ALLOY MATERIALS Co.,Ltd.