CN105779801B - A kind of graphene enhances silver-colored nickel electric contact composite material and preparation method thereof - Google Patents
A kind of graphene enhances silver-colored nickel electric contact composite material and preparation method thereof Download PDFInfo
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- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
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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
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
- B22F2003/208—Warm or hot extruding
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
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- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
The present invention, which discloses a kind of graphene, enhances silver-colored nickel electric contact composite material and preparation method thereof, this method is that silver-colored graphene oxide composite powder is prepared with chemical method, metal nickel powder is mixed with silver-colored graphene oxide composite powder again, obtaining graphene by reduction treatment, powder metallurgy, Hot-extrusion enhances silver-colored nickel electric contact composite material.Graphene prepared by the present invention enhances silver-colored nickel electric contact composite material while holding AgNi original performance, its conductivity and fusion welding resisting ability can be improved, reduce contact resistance, the preparation method is easy to operate, technique is easily-controllable, easily accomplishes scale production.
Description
Technical field
The present invention relates to a kind of preparation methods of the metal-base composites of field of material technology, specifically, be related to
It is that a kind of graphene enhances silver-colored nickel electric contact composite material and preparation method thereof.
Background technique
Graphene because of its unusual conduction, heating conduction, high hardness, intensity and corrosion resistance etc. and become grind
Study carefully hot spot, and with the gradually breakthrough of the problems such as mass production and large scale, graphene will be applied at first mobile device,
The fields such as aerospace, new energy battery.Although the research and development of graphene reinforced metal-matrix composite is slow, graphene
Excellent conductive, thermally conductive and mechanical performance will bring major transformation to metal-base composites performance boost.It is related in recent years
Research report is continuously increased.
The Chinese invention patent of Publication No. CN 1848323A, provides a kind of silver-nickel electric contact producing technology, it is
Silver-colored nickel electric contact raw material powder is prepared using " co-precipitation-ball-milling method ", powder preparation engineering includes stock, displacement reaction, powder
End cleaning and drying sieving, liquid waste processing, ball mill grinding and reduction treatment process；Again through green compact, sintering, multiple pressure and extruding work
Sequence obtains silver nickel composite material.The present invention is complicated, especially in its powder preparation process, easily brings impurity, and
The material resistance is high, and electrical contact performance is bad, needs further to improve.
The Chinese invention patent of Publication No. CN 103466611B, provides a kind of graphene load nano silver-nickel alloy
The preparation method of composite granule is prepared for graphene oxide using oxidation-reduction method, then by graphene and silver ion and nickel ion
It restores to obtain graphene nano silver-nickel composite granule through reducing agent after mixing.The invention is simple, does not add any surface and repairs
Agent is adornd, graphene distribution is relatively uniform.But nickel is easily oxidized, no since particle is tiny in the obtained composite powder of this method
Conducive to storing and applying, the application of the composite material is largely limited.
The Chinese invention patent of Publication No. CN 104700961A provides a kind of graphene/silver composite material and its system
Preparation Method, is successively added reducing agent and silver nitrate in graphene oxide solution, restore silver powder obtained directly with oxygen in solution
Graphite alkene is compound, tentatively obtains graphene oxide/argentum composite powder, is dried reduction and obtains graphene/argentum composite powder, then leads to
Cross powder metallurgy, hot extrusion, rolling technique obtain the compound bulk of graphene/silver, composite wire material, composite strip.The invention system
Graphene dispersion is uniform in standby composite material, and matrix and reinforcement interface cohesion are good.It but is merely enhancing with graphene
The anti electric arc corrosion ability of phase, composite material is poor, and materials loss rate is high, can not be applied on a large scale, can be only applied to specified conditions
Although the addition of graphene can improve conductive, the thermally conductive and mechanicalness of material to a certain extent in the studies above
Can, but its process controllability, material property etc. still need to further improve.
Therefore, realize that High-performance graphene enhances silver-colored nickel with the good production technology means of a kind of environmental protection, low cost, controllability
The preparation of contact material not only has important scientific research value, but also is with a wide range of applications.
Summary of the invention
In view of the deficiency of the prior art and defect, providing a kind of graphene, to enhance silver-colored nickel electrical contact multiple by the present invention
Condensation material and preparation method thereof.The present invention is used as basis material using silver, and graphene is as the first reinforced phase, and metallic nickel is as the
Two reinforced phases, prepare that consistency is high, conduct electricity very well, fusion welding resisting ability is strong, the low silver/graphite alkene/nickel of contact resistance
(AgGRNi) composite material.Meanwhile this method is simple, and process controllability is good, and it is at low cost, easily accomplish scale production, the silver
Based composites even tissue, performance are stablized.
The present invention is achieved by the following technical solutions:
The present invention is silver-colored graphene oxide composite powder first to be prepared with chemical method, then metal nickel powder and silver are aoxidized stone
Black alkene composite powder mixing obtains preparation AgGRNi composite material by reduction treatment, powder metallurgy, Hot-extrusion.AgGRNi
Composite material can be improved its conductivity and fusion welding resisting ability, reduce contact resistance while holding AgNi original performance, should
Preparation method is easy to operate, technique is easily-controllable, easily accomplishes scale production.
To achieve the above object, graphene of the present invention enhances the preparation method of silver-colored nickel electric contact composite material, packet
Include following steps:
Silver/graphene oxide composite powder is mixed with nickel powder, obtains silver/graphene oxide/nickel composite powder by the first step
Body；
Silver/graphene oxide/nickle composite powder is restored, obtains AgGRNi composite powder by second step；
The AgGRNi composite powder is formed, sintering processes using PM technique, is obtained high cause by third step
The AgGRNi composite material of density, i.e. graphene enhance silver-colored nickel electric contact composite material.
Preferably, in the first step: the silver/graphene oxide composite powder is made by chemical synthesis.Specifically, oxygen
Graphite alkene solution is mixed with reducing agent solution, and then the mixed liquor is mixed with silver nitrate solution, and then is sufficiently mixed reaction and is obtained
The suspension for obtaining silver-colored/graphene oxide composite powder, through the pure silver/graphene oxide composite powder of sedimentation, washing, dry acquisition.
It is furthermore preferred that the reducing agent is in the non-toxic, environmental friendlies reducing agents such as ascorbic acid, glucose, citric acid, oxalic acid
One or more.The concentration of reducing agent solution and silver nitrate solution is 0.1mol/L-1mol/L, graphene oxide solution
Mass concentration is 0.5%-1.8%, and graphene oxide additive amount accounts for the 0.3wt%-5wt% of composite material gross mass.
Preferably, in the first step, silver/graphene oxide composite powder is mixed with nickel powder: with V-type batch mixer
Or silver/graphite alkene composite powder is uniformly mixed by ball mill with metallic nickel powder, mixing time is 3-8 hours, the wherein addition of nickel
Amount accounts for the 1wt%-30wt% of composite material gross mass.
Preferably, it in the second step, since the oxygen-containing group of surface of graphene oxide can hinder the transmission of electronics, reduces
The electric conductivity of composite material needs to carry out reduction treatment to silver/graphene oxide composite powder.The process adds in a hydrogen atmosphere
Thermal reduction, heating temperature are 450 DEG C -700 DEG C, and heating time 3-12 hour obtains silver/graphite alkene composite powder.
Preferably, in the third step, powder metallurgy process includes isostatic cool pressing and sintering process, and hydrostatic pressure is
0.6GPa-6GPa, sintering temperature are 500 DEG C -900 DEG C, and sintering time is 3-12 hours, and sintering atmosphere is hydrogen.
As a preferred embodiment, after third step, further comprise step 4: by the AgGRNi composite material into
Row extrusion process, material structure further densify, and obtain AgGRNi silk material.
Preferably, in the 4th step, the temperature of hot extrusion is 500 DEG C -800 DEG C, extrusion ratio 20-80.
The present invention also provides a kind of AgGRNi composite materials prepared by the above method.
In the present invention, control graphene, the additive amount of Ni and the pattern partial size of silver matrix can be convenient, it is preferred that oxidation
Graphene additive amount is 0.3wt%-5wt%, and the additive amount of Ni is 1wt%-30wt%, and surplus is silver, electronation preparation
Morphologies are spherical shape, and partial size is 0.2 μm -8 μm.Graphene reinforcing effect is obvious, can better meet different application demands.
Further, graphene oxide additive amount is preferably 0.5wt%-0.8wt%, and the additive amount of Ni is preferably 10wt%-35wt%.
Compared with prior art, the invention has the benefit that
(1) it is restored using hydrogen silver/graphene oxide/nickle composite powder, obtains silver/graphite alkene/nickel composite powder, it should
Process is also restored the oxide of part of nickel while redox graphene, is conducive to improve composite material
Electric conductivity.
(2) sintering processes in powder metallurgy process, whole process use hydrogen shield, ensure that the structure of graphene is not broken
It is bad, also ensure that nickel is not oxidized.
(3) addition of graphene effectively improves resistance fusion welding energy, temperature characteristic of traditional AgNi material etc., and reduces
Its contact resistance.
(4) further, silver/graphene oxide composite powder is prepared using chemical method, it is ensured that graphene oxide it is uniform
Dispersion, and composite effect is good.
The present invention passes through the technologies such as between PM technique, chemical synthesising technology and Hot-extrusion and cooperates,
The AgGRNi composite material haveing excellent performance can be prepared, a series of problem in science and technical problem are breached.Compared to no graphite
The AgNi electric contact composite material of alkene enhancing, the electric life of AgGRNi composite material contact improve 15%~30%, contact electricity
Resistance reduces 5%~20%, and melting welding power reduces by 15%~30%.
The present invention realizes High-performance graphene enhancing silver with the good production technology means of a kind of environmental protection, low cost, controllability
The preparation of nickel contact material not only has important scientific research value, but also is with a wide range of applications.
Detailed description of the invention
Fig. 1 is the preparation technology flow chart of the AgGRNi composite material of preferred embodiment of the present invention.
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.
As shown in Figure 1, the figure is the preparation technology flow chart of the AgGRNi composite material of preferred embodiment of the present invention,
The preparation process of AgGRNi composite material can successively be carried out according to the process, can also select to carry out it according to practical application request
In separate step.
Embodiment one
The basic operational steps that the present embodiment 1 prepares AgGRNi composite material are as follows:
I) material composition of AgGRNi composite material
The material composition of AgGRNi composite material is mainly metallic silver, metallic nickel and graphene, and wherein graphene oxide adds
Dosage is 0.5wt%, and the additive amount of nickel is 10wt%, and surplus is silver.
II) prepare the basic step of AgGRNi composite material (attached drawing 1 is shown in process flow)
1) 0.1mol/L silver nitrate solution and 0.1mol/L ascorbic acid solution (or glucose or citric acid or oxalic acid are prepared
It is one or more of)；
2) 2.5L ascorbic acid solution is taken to mix with 24.6g mass concentration for 0.5% graphene oxide solution, ion stirring
5-10 minutes, 2L silver nitrate solution is taken to be added in above-mentioned mixed liquor, continues ion stirring.Silver nitrate and ascorbic acid occur also
Original reaction, generates Argent grain, and graphene oxide is adsorbed by silver powder, obtains silver/graphene oxide suspension.By silver/graphite oxide
Alkene suspension centrifuge washing 5-10 times, freeze-drying obtains silver/graphene oxide composite powder.
3) V-type batch mixer is used, gained silver/graphene oxide composite powder is mixed with 2.5g nickel powder, mixing time is 5 small
When, obtain silver/graphene oxide/nickel composite powder.
4) in a hydrogen atmosphere by silver/graphene oxide/nickel composite powder, 450 DEG C of heating restore 3 hours, obtain AgGRNi
Composite powder.
5) AgGRNi composite powder compression moulding is obtained AgGRNi billet, which is placed using isostatic cool pressing technology
In sintering furnace, lower 850 DEG C of hydrogen atmosphere are sintered 10 hours, obtain the AgGRNi composite material of high compaction.
Embodiment 2
With embodiment 1 main difference is that: the present embodiment 2 increases hot extrusion process, and it is compound to obtain AgGRNi
Silk material.
I) material composition of AgGRNi composite material
The material composition of AgGRNi composite material is mainly metallic silver, tin oxide and graphene, and wherein graphene oxide adds
Dosage is 0.3wt%, and the additive amount of nickel is 15wt%, and surplus is silver.
II) prepare the basic step of AgGRNi composite material (attached drawing 1 is shown in process flow)
1) 0.2mol/L silver nitrate solution and 0.2mol/L ascorbic acid solution are prepared；
2) 2.5L ascorbic acid solution is taken to mix with 25.1g mass concentration for 0.6% graphene oxide solution, ion stirring
5-10 minutes, 2L silver nitrate solution is taken to be added in above-mentioned mixed liquor, continues ion stirring.Silver nitrate and ascorbic acid occur also
Original reaction, generates Argent grain, and graphene oxide is adsorbed by silver powder, obtains silver/graphene oxide suspension.By silver/graphite oxide
Alkene suspension centrifuge washing 5-10 times, freeze-drying obtains silver/graphene oxide composite powder.
3) V-type batch mixer is used, gained silver/graphite alkene composite powder is mixed with 7.5g nickel powder, mixing time is 6.5 small
When, obtain silver/graphene oxide/nickel composite powder.
4) in a hydrogen atmosphere by silver/graphene oxide/nickel composite powder, 500 DEG C of heating restore 4 hours, obtain AgGRNi
Composite powder.
5) AgGRNi composite powder compression moulding is obtained AgGRNi billet, which is placed using isostatic cool pressing technology
In sintering furnace, lower 850 DEG C of hydrogen atmosphere are sintered 12 hours, obtain the AgGRNi composite material of high compaction.
6) the AgGRNi composite material after high density powder metallurgy is subjected to hot extrusion, extrusion temperature is
500 DEG C, extrusion ratio 40 obtains AgGRNi composite wire material.Resulting materials are subjected to basic physics performance test, find resistivity
It is 2.2；Vickers hardness hv is 90；Tensile strength is 210MPa；Elongation percentage is 19%.In addition, the silk material is prepared into rivet contact
Afterwards, electric life compares AgNi1520% is promoted, contact resistance reduces by 10%.
Embodiment 3
With embodiment 2 main difference is that: reducing agent is using the mixed of ascorbic acid and glucose in the present embodiment 3
Reducing agent solution is closed, the additive amount of graphene and nickel has been changed simultaneously, has obtained AgGRNi composite wire material.
I) material composition of AgGRNi composite material
The material composition of AgGRNi composite material is mainly metallic silver, metallic nickel and graphene, and wherein graphene oxide adds
Dosage is 0.8wt%, and the additive amount of nickel is 35wt%, and surplus is silver.
II) prepare the basic step of AgGRNi composite material (attached drawing 1 is shown in process flow)
1) the mixing reducing agent solution of 0.2mol/L silver nitrate solution and 0.2mol/L ascorbic acid and glucose is prepared,
Middle ascorbic acid and glucose quality ratio are 2:1；
2) 2.5L mixing reducing agent solution is taken to mix with 50g mass concentration for 0.8% graphene oxide solution, ion stirring
5-10 minutes, 2L silver nitrate solution is taken to be added in above-mentioned mixed liquor, continues ion stirring.Silver nitrate and ascorbic acid occur also
Original reaction, generates Argent grain, and graphene oxide is adsorbed by silver powder, obtains silver/graphene oxide suspension.By silver/graphite oxide
Alkene suspension centrifuge washing 5-10 times, freeze-drying obtains silver/graphene oxide composite powder.
3) V-type batch mixer is used, gained silver/graphite alkene composite powder is mixed with 21g nickel powder, mixing time is 7 hours, is obtained
To silver/graphene oxide/nickel composite powder.
4) in a hydrogen atmosphere by silver/graphene oxide/nickel composite powder, 700 DEG C of heating restore 5 hours, obtain AgGRNi
Composite powder.
5) AgGRNi composite powder compression moulding is obtained AgGRNi billet, which is placed using isostatic cool pressing technology
In sintering furnace, lower 900 DEG C of hydrogen atmosphere are sintered 8 hours, obtain the AgGRNi composite material of high compaction.
6) the AgGRNi composite material after high density powder metallurgy is subjected to hot extrusion, extrusion temperature is
750 DEG C, extrusion ratio 60 obtains AgGRNi composite wire material.Resulting materials are subjected to basic physics performance test, find resistivity
It is 2.6；Vickers hardness hv is 115；Tensile strength is 210MPa；Elongation percentage is 15%.In addition, the silk material is prepared into rivet contact
Afterwards, melting welding power compares AgNi3020% is reduced, contact resistance reduces by 16%.
Embodiment 4
With embodiment 3 main difference is that: the present embodiment 4 changes the additive amount of graphene and nickel, obtains height
The AgGRNi composite wire material of graphene content.
I) material composition of AgGRNi composite material
The material composition of AgGRNi composite material is mainly metallic silver, metallic nickel and graphene, and wherein graphene oxide adds
Dosage is 5wt%, and the additive amount of nickel is 1wt%, and surplus is silver.
II) prepare the basic step of AgGRNi composite material (attached drawing 1 is shown in process flow)
1) the mixing reducing agent solution of 0.2mol/L silver nitrate solution and 0.2mol/L ascorbic acid and glucose is prepared,
Middle ascorbic acid and glucose quality ratio are 2:1；
2) 2.5L mixing reducing agent solution is taken to mix with 167g mass concentration for 1.5% graphene oxide solution, ion stirs
It mixes 5-10 minutes, 2L silver nitrate solution is taken to be added in above-mentioned mixed liquor, continue ion stirring.Silver nitrate and ascorbic acid occur
Reduction reaction generates Argent grain, and graphene oxide is adsorbed by silver powder, obtains silver/graphene oxide suspension.By silver/oxidation stone
Black alkene suspension centrifuge washing 5-10 times, freeze-drying, obtains silver/graphene oxide composite powder.
3) V-type batch mixer is used, gained silver/graphite alkene composite powder is mixed with 0.5g nickel powder, mixing time is 7 hours,
Obtain silver/graphene oxide/nickel composite powder.
4) in a hydrogen atmosphere by silver/graphene oxide/nickel composite powder, 600 DEG C of heating restore 5 hours, obtain AgGRNi
Composite powder.
5) AgGRNi composite powder compression moulding is obtained AgGRNi billet, which is placed using isostatic cool pressing technology
In sintering furnace, lower 500 DEG C of hydrogen atmosphere are sintered 8 hours, obtain the AgGRNi composite material of high compaction.
6) the AgGRNi composite material after high density powder metallurgy is subjected to hot extrusion, extrusion temperature is
550 DEG C, extrusion ratio 80 obtains AgGRNi composite wire material.Resulting materials are subjected to basic physics performance test, find resistivity
It is 2.1；Vickers hardness hv is 90；Tensile strength is 180MPa；Elongation percentage is 19%.In addition, the silk material is prepared into rivet contact
Afterwards, melting welding power compares AgNi3030% is reduced, contact resistance reduces by 20%.
It should be understood that above-described embodiment is only a part of embodiment of the invention, graphene of the present invention
Enhancing silver-colored nickel electric contact composite material includes all systems suitable for the product, such as changes the preparation formula of matrix silver, may be used also
To be the combination of other silver salt solutions and reducing agent, graphene and nickel reinforcement are also possible to a kind of any other adding manner,
The formula of final composite material should be designed according to practical application request.
It is discussed in detail although the contents of the present invention have passed through above preferred embodiment, but it should be appreciated that above-mentioned
Description should not be regarded as limitation of the present invention.After those skilled in the art have read above content, for of the invention
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (6)
1. the preparation method that a kind of graphene enhances silver-colored nickel electric contact composite material, it is characterised in that the following steps are included:
Silver/graphene oxide composite powder is mixed with nickel powder, obtains silver/graphene oxide/nickle composite powder by the first step；
Wherein the additive amount of nickel accounts for the 10wt%-30wt% or 35wt% of composite material gross mass；
The silver/graphene oxide composite powder is made by chemical synthesis；The chemical synthesis refers to: by graphite oxide
Alkene solution is mixed with reducing agent solution, and then the mixed liquor is mixed with silver nitrate solution, and then is sufficiently mixed reaction and is obtained silver/oxygen
The suspension of graphite alkene composite powder, through the pure silver/graphene oxide composite powder of sedimentation, washing, dry acquisition；
The reducing agent is one or more of ascorbic acid, glucose, citric acid, oxalic acid non-toxic, environmental friendly reducing agent；Institute
The concentration for stating reducing agent solution and silver nitrate solution is 0.1mol/L-1mol/L；
The mass concentration of the graphene oxide solution is 0.5%-1.8%, and graphene oxide additive amount accounts for the total matter of composite material
The 0.3wt%-5wt% of amount；
Silver/graphene oxide/nickle composite powder is restored, obtains AgGRNi composite powder by second step；
The AgGRNi composite powder is formed, sintering processes using PM technique, is obtained high-compactness by third step
AgGRNi composite material, i.e. graphene enhances silver-colored nickel electric contact composite material.
2. the preparation method that graphene as described in claim 1 enhances silver-colored nickel electric contact composite material, which is characterized in that first
Described to mix silver/graphene oxide composite powder with nickel powder in step, incorporation time is 3-8 hours.
3. the preparation method that graphene as described in claim 1 enhances silver-colored nickel electric contact composite material, which is characterized in that second
Described to restore silver/graphene oxide composite powder in step, refer to: heating reduction, heating temperature are in a hydrogen atmosphere
450 DEG C -700 DEG C, heating time 3-12 hour.
4. the preparation method that graphene as described in claim 1 enhances silver-colored nickel electric contact composite material, which is characterized in that third
In step, the PM technique includes isostatic cool pressing and sintering process, hydrostatic pressure 0.6GPa-6GPa, sintering temperature
It is 500 DEG C -900 DEG C, sintering time is 3-12 hours, and sintering atmosphere is hydrogen.
5. graphene according to any one of claims 1-4 enhances the preparation method of silver-colored nickel electric contact composite material, feature
It is, further comprises step 4: the AgGRNi composite material is carried out extrusion process, material structure after third step
Further densification, obtains AgGRNi silk material.
6. a kind of graphene such as any one of claim 1-5 the method preparation enhances silver-colored nickel electric contact composite material.
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| CN106363190B (en) * | 2016-09-18 | 2018-10-19 | 东莞市中一合金科技有限公司 | A kind of silver-nickel-graphite alkene alloy material and preparation method thereof |
| CN108218412A (en) * | 2017-12-23 | 2018-06-29 | 南京悠谷新材料科技有限公司 | A kind of preparation method of zinc-silver metallic composite |
| CN108531764B (en) * | 2018-04-13 | 2020-07-28 | 上海和伍复合材料有限公司 | Silver tungsten carbide graphene electrical contact material and preparation method thereof |
| CN108441668B (en) * | 2018-04-13 | 2021-02-26 | 上海和伍复合材料有限公司 | Silver-tungsten electric contact material and preparation method thereof |
| CN112620640B (en) * | 2020-12-09 | 2023-01-31 | 温州宏丰电工合金股份有限公司 | Preparation method of AgNi electrical contact material based on recycling of AgC scrap |
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| CN101992303A (en) * | 2010-10-29 | 2011-03-30 | 江苏大学 | Method for preparing graphene/Ni nano composite material |
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| CN105420530A (en) * | 2015-12-09 | 2016-03-23 | 哈尔滨工业大学 | Preparation method for graphene-reinforced nickel-based composite materials |
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| CN101992303A (en) * | 2010-10-29 | 2011-03-30 | 江苏大学 | Method for preparing graphene/Ni nano composite material |
| CN102350505A (en) * | 2011-09-22 | 2012-02-15 | 浙江师范大学 | Preparation method for nickel/graphene nanometer compound material |
| CN102385938A (en) * | 2011-11-10 | 2012-03-21 | 电子科技大学 | Metal matrix graphene composite electrical contact material and preparation method thereof |
| CN103466611A (en) * | 2013-09-29 | 2013-12-25 | 黑龙江大学 | Method for preparing graphene load nano silver-nickel alloy composite powder materials |
| CN104700961A (en) * | 2015-03-18 | 2015-06-10 | 上海和伍新材料科技有限公司 | Graphene/silver composite material and preparation method thereof |
| CN105420530A (en) * | 2015-12-09 | 2016-03-23 | 哈尔滨工业大学 | Preparation method for graphene-reinforced nickel-based composite materials |
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