CN110125385A - A kind of preparation method of the graphene Cu-base composites based on fabricated in situ - Google Patents
A kind of preparation method of the graphene Cu-base composites based on fabricated in situ Download PDFInfo
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- CN110125385A CN110125385A CN201910299341.6A CN201910299341A CN110125385A CN 110125385 A CN110125385 A CN 110125385A CN 201910299341 A CN201910299341 A CN 201910299341A CN 110125385 A CN110125385 A CN 110125385A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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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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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The preparation method of the present invention relates to a kind of graphene Cu-base composites based on fabricated in situ.The present invention first passes through solution impregnation technology in electrolytic copper powder surface coated high molecular solid-state carbon source, then by chemical vapor deposition process in Copper Powder Surface in-situ preparation graphene, further, using mechanical ball mill technique by graphene ball milling into inside copper particle, graphene copper composite powders are obtained, the second best in quality graphene Cu-base composites are finally obtained using powder metallurgy forming and deformation processing technique.The present invention is solid-state carbon source in electrolytic copper powder surface in situ synthesizing graphite alkene using macromolecule, and it is evenly dispersed in copper powder to realize graphene, saves graphene raw material cost.Present invention process is simple, solves the problems, such as graphene uniform dispersion and graphene and copper interface cohesion, largely saves graphene raw material cost, is highly suitable for High-performance graphene Cu-base composites mass production preparation.
Description
Technical field
The preparation method of the present invention relates to a kind of graphene Cu-base composites based on fabricated in situ, belongs to compound
The preparation technical field of metal material.
Background technique
Cu-base composites have excellent conductive, thermally conductive and mechanical property, are widely used in electronic package material, rub
Wipe material, conduction and contact material.The reinforcement of traditional Cu-base composites mainly includes ceramic particle, carbon material etc.,
Such as silicon carbide, aluminium oxide, graphite, diamond.Ceramic particle high mechanical strength is non-conductive, can seriously be cut using it as reinforcement
The electric conductivity of weak Copper substrate.A kind of honeycomb planar nanometer material formed by carbon atom with sp2 hybrid form of graphene
Material has good conductive, thermally conductive and mechanical property.Single-layer graphene theoretical strength is up to 130Gpa, and thermal coefficient is high
Up to 5000W/ (mK), graphene resistivity only 10-6 Ω cm.Copper substrate intensity can be being improved using graphene as reinforcement
While do not weaken its conductive, heating conduction, be the ideal reinforcement of Cu-base composites.
Cu-base composites are prepared using graphene as reinforcement, two big difficulties: (1) graphene specific surface area must be overcome
Greatly, itself is easy to reunite, and graphene and copper powder density difference are very big, and graphene is difficult to be dispersed in Copper substrate；(2) graphite
Alkene and Copper substrate, that is, nonwetting also do not chemically react, and graphene is difficult to be formed in conjunction with good interface with Copper substrate.At this stage,
By graphene dispersion, into Copper substrate, there are mainly four types of methods, are mechanical ball mill/stirring, chemical/electrochemical synthesis, copper powder respectively
Surface modification and Copper Powder Surface growth in situ graphene technique.Wherein mechanical ball mill technique is difficult to realize uniformly dividing for graphene
It dissipates, chemical/electrochemical process yield is low and environment is unfriendly, and Copper Powder Surface modified technique can introduce extra impurity, copper powder table
Face fabricated in situ technique can utmostly realize graphene being uniformly distributed in metallic matrix, and largely save graphene raw material
Cost is that ideal mass prepares high-strength highly-conductive Cu-base composites preparation process.
Patent CN201711125991.6- it is a kind of using CVD method directly the method for Copper Powder Surface coated graphite alkene,
A kind of method that graphene enhancing Cu-base composites are efficiently prepared in situ of CN201410066469.50- with carbonaceous gas is
Carbon source grows graphene in Copper Powder Surface, and treatment process or the device is complicated, treatment temperature is high, copper powder easy-sintering together,
Subsequent composite molding processing difficulties.Patent CN201510227782.7 prepares stone in Copper Powder Surface situ catalytic solid carbon source
A kind of preparation of three-dimensional grapheme in-stiu coating carbon/carbon-copper composite material of the method for black alkene/carbon/carbon-copper composite material, CN201510679161.2
A kind of preparation method of spherical copper powder surface in situ growing three-dimensional graphene of method, CN201610697806.X- is all made of ball
Grinding process mixes solid-state carbon source PMMA with copper powder by ball-milling technology, and the PMMA thickness for obtaining ball milling copper sheet surface is larger,
Graphene, and residual fraction carbon product can not be translated into during reduction treatment completely, may cause in subsequent system
Its reinforcing effect is influenced on standby block materials, and ball-milling technology cannot make the complete coated high molecular carbon source of Copper Powder Surface, copper powder
Easy-sintering is at block during the high temperature treatment process.
Patent CN201510506051.6- is a kind of to prepare graphene/copper in Copper Powder Surface supported solid carbon source with infusion process
The method of composite material uses dimethylformamide or acetone soln for solvent using PMMA as solid-state carbon source, with ball milling flaking
Copper powder is raw material, obtains graphene coated copper composite powders by the technique that solution impregnates.Since graphene does not moisten with Copper substrate
It is wet, base is seriously undermined due to that cannot be sintered together there are graphene between copper powder particle during subsequent sinter molding
The intensity of body.
Summary of the invention
The purpose of the present invention is: in view of the above-mentioned problems, the present invention is first using polyethylene glycol/polyvinyl alcohol as solid-state carbon source,
Using ethyl alcohol as solvent, using dendroid electrolytic copper powder as raw material, in Copper Powder Surface in-situ preparation stone under the conditions of hydrogen-argon-mixed atmosphere
Black alkene film.Macromolecule may be implemented to the complete cladding of copper powder by solution impregnation technology, therefore copper powder can be prevented in height
It is sintered in warm treatment process blocking.Secondly, copper powder can will be coated on by carrying out ball-milling treatment to graphene coated electrolytic copper powder
Interdendritic graphite alkene ball milling enters inside copper powder, and Copper Powder Surface only has part by graphene coated.This aspect can pass through machine
Tool ball milling realizes that graphene in conjunction with the good interface of Copper substrate, on the other hand solves graphene coated copper powder and is difficult to sinter into
The problem of type.
The technical scheme is that in view of the above-mentioned problems, providing a kind of novel graphene copper-base alloy composite material
Preparation method, it is therefore an objective to have both the graphene Cu-base composites of high-strength plating high conduction performance in preparation.
A kind of preparation method of graphene Cu-base composites based on fabricated in situ is provided, is included the following steps:
Step 1, using polyethylene glycol or polyvinyl alcohol as solid-state polymer carbon source, and solid-state polymer carbon source is dissolved in wine
Essence forms homogeneous mixture solotion；It is preferred that solution temperature is 20~80 DEG C；
Copper powder is sufficiently stirred step 2 in the homogeneous mixture solotion, after filtering by the copper powder in solution and be dry,
It can be coated with the macromolecule layer of polyethylene glycol or polyvinyl alcohol in Copper Powder Surface, the copper powder for being coated with macromolecule layer is obtained, will wrap
The copper powder for being covered with macromolecule layer is placed in heating and calcining in high-temperature heater, and heating and calcining temperature is 500~1050 DEG C, and the time is
0.5~2 hour, the protective gas of heating was the mixed gas of hydrogen and argon gas, the polyethylene glycol or polyvinyl alcohol of Copper Powder Surface
Graphene is converted into protective gas；The copper powder is dendroid copper powder；
The copper powder for being coated with graphene is placed in ball-grinding machine and carries out ball milling by step 3, and the dendroid copper powder passes through ball
It can extend after mill and be deformed into flake copper powder, the graphene wrapped up between the branch fork of dendroid copper powder can be inside flake copper powder；Prolong
Exhibition causes Copper Powder Surface to exist not by graphene coated part.Not there is no good burning between the copper powder of graphene coated part
Mouldability is tied, by the effect of mechanical ball mill, graphene is preferably combined into one with Copper substrate, and it is strong to improve interface cohesion
Degree；
Copper powder after ball milling is prepared into graphene carbon/carbon-copper composite material block material by powder metallurgy forming technique by step 4
Material.
Further, the mass fraction of the polyethylene glycol in homogeneous mixture solotion or polyvinyl alcohol is 1.0%~25%.
Further, the partial size of the dendroid copper powder is 80~1000 mesh.
Further, the rotational speed of ball-mill of ball-grinding machine is 60~350 revs/min, and ratio of grinding media to material is 5:1~40~1.
Further, the powder metallurgy forming technique is cold-rolled sintered technique, repressing and re-sintering technique, hot-pressing sintering technique
Or discharge plasma sintering process.
Further, the partial size of the dendroid copper powder is 500~1000 mesh.
Further, the rotational speed of ball-mill of ball-grinding machine is 250 revs/min, and ratio of grinding media to material is 5:1~40~1.
Further, the mass fraction of the polyethylene glycol in homogeneous mixture solotion or polyvinyl alcohol is 10%.
The invention has the advantages that the 1, present invention is solid-state carbon source in electrolytic copper powder surface in situ synthetic graphite using macromolecule
Alkene, it is evenly dispersed in copper powder to realize graphene, saves graphene raw material cost.2, the present invention is impregnated by solution and is wrapped
Coating process prepares graphene coated copper composite powders, and copper powder can be effectively prevented and sinter into during high temperature chemical vapor deposition
Block.3, the present invention can will be coated on graphene ball between copper powder branch by carrying out ball-milling treatment to graphene coated electrolytic copper powder
Mill enters inside copper powder, and Copper Powder Surface only has part by graphene coated, and graphene copper composite powders have good sinter into
Type, and good interface cohesion is formed under mechanical ball mill effect between graphene and Copper substrate.
Detailed description of the invention
Fig. 1 is electrolytic copper powder raw material scanned photograph in embodiment 1；
Fig. 2 is coated with polyethylene glycol electrolytic copper powder scanned photograph in embodiment 1；
Fig. 3 is that process for preparing graphenes by chemical vapour deposition coats electrolytic copper powder scanned photograph in embodiment 1；
Fig. 4 is that preparing graphene through chemical vapor deposition coats copper powder Raman spectrogram in embodiment 1；
Fig. 5 is graphene copper composite powders scanned photograph after ball milling in embodiment 1；
Fig. 6 is that non-ball-milling powder prepares graphene Cu-base composites stretching fracture in embodiment 1；
Fig. 7 is that ball-milling powder prepares graphene Cu-base composites stretching fracture in embodiment 1.
Specific embodiment
The present invention is described in further details below.
Embodiment 1
A kind of preparation method of graphene Cu-base composites based on fabricated in situ is provided, is included the following steps:
Step 1, using polyethylene glycol as solid-state polymer carbon source, and solid-state polymer carbon source is dissolved in alcohol and is formed uniformly
Mixed solution；Solution temperature is 50 DEG C；In the mixed solution, the mass fraction of polyethylene glycol is 3.5%, is stirred solution
Make mixed solution uniform at least 0.5 hour.
200 mesh electrolytic copper powders are sufficiently stirred at least 0.5 hour step 2 in the homogeneous mixture solotion, will be in solution
Copper powder filtering and it is dry after, the macromolecule layer of polyethylene glycol or polyvinyl alcohol can be coated in Copper Powder Surface, be coated with
The copper powder of macromolecule layer；The copper powder for being coated with macromolecule layer is placed in heating and calcining in high-temperature heater, heating and calcining temperature is
800 DEG C, the time is 1 hour, and the protective gas of heating is the mixed gas of hydrogen and argon gas, and hydrogen-argon-mixed ratio is 1:4, gas
Body flow is 500sccm.The polyethylene glycol of Copper Powder Surface is converted into graphene in protective gas.
The copper powder for being coated with graphene is placed in ball-grinding machine and carries out ball milling by step 3, and 300 revs/min of rotational speed of ball-mill,
Ball-milling Time at least 1 hour, graphene copper composite powders are obtained, the dendroid copper powder can extend after ball milling is deformed into piece
Shape copper powder, the graphene that the branch of dendroid copper powder wraps up between pitching can be inside flake copper powders；Extension causes Copper Powder Surface to exist
Not by graphene coated part.Not there is no good sinter molding between the copper powder of graphene coated part, by machinery
The effect of ball milling, graphene are preferably combined into one with Copper substrate, improve interface bond strength；
Copper powder after ball milling is prepared into graphene carbon/carbon-copper composite material block material by powder metallurgy forming technique by step 4
Material.
Fig. 1 is electrolytic copper powder raw material.It can see that from Fig. 2, may make that polyethylene glycol is good by solution dipping method
It is coated on Copper Powder Surface.Fig. 3 and Fig. 4 shows that it is complete to be transformed into graphene for polyethylene glycol after chemical vapor deposition process is handled
It is whole to be coated on Copper Powder Surface.Fig. 5 shows that after ball-milling technology is handled, copper powder becomes sheet, copper interdendritic graphite alkene from dendroid
Enter inside copper particle through ball milling, Copper Powder Surface graphene fragmentation and discontinuously arranged.Fig. 6 is compound with non-Graphite alkene copper
Powder is that raw material prepares composite material block stretching fracture photo, and composite material stretches special in typical grain boundary fracture as the result is shown
Sign, this shows that continuously distributed graphene seriously hinders sinter molding between copper particle, and composite material block is preferentially in coated graphite alkene
Copper granular boundary at disconnect.Fig. 7 is that composite material block tension test is prepared by raw material of Graphite alkene copper composite powders
Fracture photo afterwards.Composite material stretching fracture is made of a large amount of dimples, and composite material has good plasticity, after this shows ball milling
Composite granule has good sinter molding, which prepares composite material and have both high intensity and plasticity.
Claims (8)
1. a kind of preparation method of the graphene Cu-base composites based on fabricated in situ, includes the following steps:
Step 1, using polyethylene glycol or polyvinyl alcohol as solid-state polymer carbon source, and solid-state polymer carbon source is dissolved in alcohol shape
At homogeneous mixture solotion；It is preferred that solution temperature is 20~80 DEG C；
Copper powder is sufficiently stirred step 2 in the homogeneous mixture solotion, after filtering by the copper powder in solution and is dry, in copper
Powder surface can be coated with the macromolecule layer of polyethylene glycol or polyvinyl alcohol, obtain the copper powder for being coated with macromolecule layer, will be coated with
The copper powder of macromolecule layer is placed in heating and calcining in high-temperature heater, and heating and calcining temperature is 500~1050 DEG C, and the time is 0.5~2
Hour, the protective gas of heating is the mixed gas of hydrogen and argon gas, and the polyethylene glycol or polyvinyl alcohol of Copper Powder Surface are being protected
Graphene is converted into gas；The copper powder is dendroid copper powder；
The copper powder for being coated with graphene is placed in ball-grinding machine and carries out ball milling by step 3, and the dendroid copper powder is after ball milling
It can extend and be deformed into flake copper powder, the graphene wrapped up between the branch fork of dendroid copper powder can be inside flake copper powder；Extension is made
Exist at Copper Powder Surface not by graphene coated part.Not there is no good sinter between the copper powder of graphene coated part
Type, by the effect of mechanical ball mill, graphene is preferably combined into one with Copper substrate, improves interface bond strength；
Copper powder after ball milling is prepared into graphene carbon/carbon-copper composite material block materials by powder metallurgy forming technique by step 4.
2. a kind of preparation method of the graphene Cu-base composites based on fabricated in situ as described in claim 1, feature
Be: the mass fraction of polyethylene glycol or polyvinyl alcohol in homogeneous mixture solotion is 1.0%~25%.
3. a kind of preparation method of the graphene Cu-base composites based on fabricated in situ as described in claim 1, feature
Be: the partial size of the dendroid copper powder is 80~1000 mesh.
4. a kind of preparation method of the graphene Cu-base composites based on fabricated in situ as described in claim 1, feature
Be: the rotational speed of ball-mill of ball-grinding machine is 60~350 revs/min, and ratio of grinding media to material is 5:1~40~1.
5. a kind of preparation method of the graphene Cu-base composites based on fabricated in situ as described in claim 1, feature
Be: the powder metallurgy forming technique is cold-rolled sintered technique, repressing and re-sintering technique, hot-pressing sintering technique or plasma discharging
Sintering process.
6. a kind of preparation method of the graphene Cu-base composites based on fabricated in situ as described in claim 1, feature
Be: the partial size of the dendroid copper powder is 500~1000 mesh.
7. a kind of preparation method of the graphene Cu-base composites based on fabricated in situ as described in claim 1, feature
Be: the rotational speed of ball-mill of ball-grinding machine is 250 revs/min, and ratio of grinding media to material is 5:1~40~1.
8. a kind of preparation method of the graphene Cu-base composites based on fabricated in situ as described in claim 1, feature
Be: the mass fraction of polyethylene glycol or polyvinyl alcohol in homogeneous mixture solotion is 10%.
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Cited By (7)
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| CN110666159A (en) * | 2019-09-30 | 2020-01-10 | 上海元颉新材料科技有限公司 | Composite copper powder for acid degreasing process and preparation method and application thereof |
| CN110923662A (en) * | 2019-10-30 | 2020-03-27 | 北京碳垣新材料科技有限公司 | Preparation method of graphene-metal composite material |
| CN111408714A (en) * | 2020-04-29 | 2020-07-14 | 西安稀有金属材料研究院有限公司 | Preparation method of graphene reinforced copper-based composite material with dual-scale structure and in-situ growth |
| CN113073227A (en) * | 2021-03-25 | 2021-07-06 | 南昌工程学院 | Preparation method of high-conductivity deformed Cu-Fe series in-situ composite material |
| CN113913640A (en) * | 2021-09-17 | 2022-01-11 | 河海大学 | Copper alloy composite material and preparation method and application thereof |
| CN117463999A (en) * | 2023-12-28 | 2024-01-30 | 天津大学 | Copper-based conductive composite material and preparation method and application thereof |
| CN117680676A (en) * | 2024-02-02 | 2024-03-12 | 深圳市绚图新材科技有限公司 | Preparation method of antioxidant high-conductivity graphene-copper composite powder |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110666159A (en) * | 2019-09-30 | 2020-01-10 | 上海元颉新材料科技有限公司 | Composite copper powder for acid degreasing process and preparation method and application thereof |
| CN110666159B (en) * | 2019-09-30 | 2022-04-01 | 元颉新材料科技(浙江)有限公司 | Composite copper powder for acid degreasing process and preparation method and application thereof |
| CN110923662A (en) * | 2019-10-30 | 2020-03-27 | 北京碳垣新材料科技有限公司 | Preparation method of graphene-metal composite material |
| CN110923662B (en) * | 2019-10-30 | 2021-09-17 | 北京碳垣新材料科技有限公司 | Preparation method of graphene-metal composite material |
| CN111408714A (en) * | 2020-04-29 | 2020-07-14 | 西安稀有金属材料研究院有限公司 | Preparation method of graphene reinforced copper-based composite material with dual-scale structure and in-situ growth |
| CN111408714B (en) * | 2020-04-29 | 2022-04-01 | 西安稀有金属材料研究院有限公司 | Preparation method of graphene reinforced copper-based composite material with dual-scale structure and in-situ growth |
| CN113073227A (en) * | 2021-03-25 | 2021-07-06 | 南昌工程学院 | Preparation method of high-conductivity deformed Cu-Fe series in-situ composite material |
| CN113073227B (en) * | 2021-03-25 | 2022-02-01 | 南昌工程学院 | Preparation method of high-conductivity deformed Cu-Fe series in-situ composite material |
| CN113913640A (en) * | 2021-09-17 | 2022-01-11 | 河海大学 | Copper alloy composite material and preparation method and application thereof |
| CN117463999A (en) * | 2023-12-28 | 2024-01-30 | 天津大学 | Copper-based conductive composite material and preparation method and application thereof |
| CN117463999B (en) * | 2023-12-28 | 2024-03-22 | 天津大学 | Copper-based conductive composite material and preparation method and application thereof |
| CN117680676A (en) * | 2024-02-02 | 2024-03-12 | 深圳市绚图新材科技有限公司 | Preparation method of antioxidant high-conductivity graphene-copper composite powder |
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Application publication date: 20190816 |