CN104846231A - Preparation method of copper-based graphene composite blocky material - Google Patents
Preparation method of copper-based graphene composite blocky material Download PDFInfo
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Abstract
The invention provides a preparation method of a copper-based graphene composite blocky material. The preparation method comprises carrying out in-situ mixing on a copper salt solution, reducing sugar, alkali and graphene as raw materials by a solution method so that graphene is uniformly dispersed in the copper solution, reducing copper into cuprous oxide by a hydrothermal reduction method, carrying out in-situ deposition on cuprous oxide particles on the graphene surface, reducing the cuprous oxide particles into copper particles by hydrogen, and carrying out discharge plasma sintering to obtain the copper-based graphene composite blocky material. The copper-based graphene composite blocky material has good graphene dispersibility, good adhesion of a copper base and a graphene reinforcing phase, high tensile strength and compressive strength, and good thermal conductivity.
Description
Technical field
The present invention relates to Cu-base composites technical field, particularly relate to a kind of preparation method of copper-base graphite alkene composite block material.
Background technology
Copper is the good conductor of heat, and its thermal conductivity is 401W/mK, is only second to silver, is applied to field of electronics more.But along with developing rapidly of modern industrial technology, the design of plant and instrument and component is compacter, especially electric and electronic field, appliance electronic component towards gentlier, thinner, less future development, large energy density and little heat-dissipating space, heat conductivility for material is had higher requirement, and the single metallic substance of tradition can not meet design requirement, and the metal-base composites having both metallic matrix and reinforcing component excellent properties receives extensive concern.
Graphene is a kind of novel material with individual layer sheet structure be made up of carbon atom, is thin, the hardest nano material in known world.The thermal conductivity of Graphene is up to 5300W/mK, and higher than carbon nanotube and diamond, intensity can reach 130GPa, and Young's modulus is up to 1TPa, and specific surface area is 2630m
2g
-1, be that phase filled by desirable matrix material.
At present, the research of graphene composite material mainly concentrates on polymer-based carbon graphene composite material field, and less for the research of metal matrix graphene composite material.This is mainly because the research of metal matrix graphene composite material is faced with technical barrier: the bonding force of Graphene and metallic matrix is weak; In addition, the technical barrier also existed is: Graphene is easily reunited in metallic matrix, and this two large technical barrier causes the metal matrix Graphene block materials of preparation at present cannot obtain the excellent properties of expection.
The current method improving metal and Graphene bonding force mainly contains two kinds: a kind of method is at metallic particles such as graphenic surface plating nickel, copper, silver.But this method relates to plating or plating process more, process is complicated, and employs poisonous and harmful pharmaceutical chemicals to some extent, is unfavorable for environmental protection and safety.Another kind method adds functional group at graphenic surface to carry out surface modification.But this method is owing to changing the surface tissue of Graphene, thus can weaken the performance of Graphene.
Summary of the invention
For the above-mentioned state of the art, the present invention aims to provide a kind of preparation method of copper-base graphite alkene composite block material, in the copper-base graphite alkene block composite material utilizing the method obtained, graphene dispersion is good, between Copper substrate and Graphene wild phase, there is good bonding force, and there is good thermal conductivity.
In order to realize above-mentioned technical purpose, the present inventor finds after great many of experiments, with copper salt solution, reducing sugar, alkali and Graphene are raw material, adopt the mixing of solution method original position, graphene uniform is made to be dispersed in Copper substrate, then be Red copper oxide by hydrothermal reduction method by copper reduction, pass through hydrogen reducing Red copper oxide particle again to copper particle, finally by discharge plasma sintering, obtain copper-base graphite alkene composite block material, this composite block material not only has good thermal conductivity, and there is higher tensile strength and compressive strength, show that wherein copper base and Graphene wild phase have good bonding force.
That is, the technical solution adopted in the present invention is: a kind of preparation method of copper-base graphite alkene composite block material, comprises the steps:
(1) in mantoquita ethanolic soln, add appropriate Graphene, the aqueous solution of reducing sugar and alkaline matter, mix and be placed in reactor, hydrothermal reduction reaction is carried out in isoperibol, copper reduction is made to be Red copper oxide, then reaction product is filtered, through washing, vacuum-drying, obtain Red copper oxide Graphene composite powder;
(2) the Red copper oxide Graphene composite powder that hydrogen gas reduction step (1) is obtained, Red copper oxide is wherein reduced to copper, obtains copper-base graphite alkene composite granule;
(3) the copper-base graphite alkene composite granule that step (2) is obtained is put into graphite jig; discharge plasma sintering stove is put into after pre-molding; in vacuum or protective atmosphere, carry out discharge plasma sintering shaping, obtain copper-base graphite alkene composite block material.
Described mantoquita is not limit, and can be selected from copper nitrate, copper acetate, copper vitriol etc.
Described reducing sugar is not limit, and can be selected from one or more the mixing in glucose, lactose, maltose, fructose, semi-lactosi etc.
Described alkaline matter is not limit, and can be selected from one or more the mixing in sodium hydroxide, potassium hydroxide, ammoniacal liquor etc.
In described copper-base graphite alkene composite block material, the mass percent of Graphene is preferably 0.01% ~ 10%, and surplus is copper.
In described step (1), the quality of Graphene and the mass ratio of copper are 1:9999 ~ 10:90.In order to improve the thermal conductivity of Graphene composite block material further, the quality of Graphene and the mass ratio of copper are more preferably 5:9955 ~ 5:95.
In described step (1), Graphene is preferably dimensioned to be 5 ~ 15 μm, and thickness is preferably 0.4 ~ 6nm.
In described step (1), temperature of reaction is preferably 60 ~ 120 DEG C.
In described step (1), the reaction times is preferably 2 ~ 4h.
In described step (1), in described washing process, according to pure deionized water wash reaction product, the dispersiveness of destructible Graphene, according to straight alcohol solution washing reaction product, reaction product pattern and character is easily caused to change, for this reason, as preferably, adopt the mixing liquid washing reaction product of alcohol and deionized water.Further preferably, in described mixing liquid, the volume ratio of alcohol and deionized water is 2:1 ~ 1:2.
In described step (2), reduction temperature is preferably 100 ~ 500 DEG C.
In described step (2), the recovery time is preferably 2 ~ 10 hours.
In described step (3), preload pressure is preferably 5 ~ 20MPa.
In described step (3), when adopt carry out in a vacuum discharge plasma sintering shaping time, vacuum tightness is preferably 10
-4pa ~ 10
-1pa.
In described step (3), in SPS sintering process, temperature rise rate is preferably 50 DEG C/min ~ 500 DEG C/min, and sintering temperature is preferably 400 ~ 1000 DEG C, and multiple pressure pressure is preferably 10MPa ~ 100MPa, and soaking time is preferably 1 ~ 120min.
In described step (3), the time is pressed to be preferably 4 ~ 10min again.
In sum, compared with prior art, the invention has the advantages that:
(1) the inventive method efficiently avoid Graphene reunion on the one hand, not only has good thermal conductivity on the other hand, and improves the bonding force of Graphene and Copper substrate, thus have higher tensile strength and compressive strength, trace it to its cause as follows:
The present invention adopts solution method original position to mix powder, makes graphene uniform be dispersed in Copper substrate; Then hydrothermal reduction method is utilized to be Red copper oxide by copper reduction, in this process, the reaction that part copper is reduced to Red copper oxide occurs in graphenic surface, namely the cuprous particle in-situ of partial oxidation is deposited on graphenic surface, obtain the Graphene of Red copper oxide particle and surface attachment Red copper oxide particle, this not only efficiently avoid Graphene and reunites, and graphenic surface in-situ preparation Red copper oxide, produce carbon-oxygen bond, thus improve the bonding force of Graphene and surface copper particle; Finally by hydrogen reducing Red copper oxide particle, obtain the Graphene of copper particle-matrix and surface attachment copper particle, due to graphenic surface attachment copper particle, substantially increase the bonding force of Graphene wild phase and Copper substrate.
(2) the present invention adopts discharge plasma sintering technique to sinter copper-base graphite alkene composite granule.
Discharge plasma sintering is in the mould by the materials such as powder loading graphite such as metal being made, utilize upper and lower stamping and powered electrode that specific sintering power supply and pressing pressure are put on sintered powder, complete a kind of powder metallurgy sintered technology newly producing high performance material through discharge activation, thermoplastic deformation and cooling.Discharge plasma sintering has the advantages that to sinter in pressure process, and the pressurization in the plasma body that pulsed current produces and sintering process is conducive to reducing the sintering temperature of powder.The feature of low voltage, high electric current simultaneously, can make powder Fast Sintering fine and close.This unique sintering method effectively can reduce the sintering temperature of copper-base graphite alkene matrix material, avoids Graphene performance to be damaged, obtains high-performance copper graphene composite material.
(3) the present invention adopts Graphene as raw material, and with graphene oxide as compared with raw material, material performance of the present invention is good;
(4) the present invention adopts reducing sugar as reductive agent, compared with the reductive agents such as hydrazine hydrate, to human body and environmentally friendly, and safety and environmental protection.
(5), in the present invention, Graphene content adjustable, can control the distribution of Graphene in this matrix material by adjustment Graphene content, and then available energy anisotropy copper-base graphite alkene composite block material.Research finds, low levels Graphene trends towards stochastic distribution, and high-content Graphene trends towards distribution of orientations.Further, when in copper-base graphite alkene composite block material, when Graphene mass percentage is 0.05% ~ 5%, thermal conductivity and intensity are apparently higher than Copper substrate itself.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern analysis of Red copper oxide graphene composite powder before and after hydrogen reducing that the embodiment of the present invention 1 obtains;
Fig. 2 is the outward appearance photo of the copper-base graphite alkene composite block material that the embodiment of the present invention 1 obtains;
Fig. 3 is the Raman pattern analysis results figure of the copper-base graphite alkene composite block material that the embodiment of the present invention 1 obtains.
Embodiment
Below with reference to drawings and Examples, the present invention will be further described, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and do not play any restriction effect to it.
Embodiment 1:
In the present embodiment, the preparation method of copper-base graphite alkene composite block material is as follows:
(1) be that 99.8wt% takes cupric nitrate according to copper content, prepare cupric nitrate ethanolic soln.
(2) in cupric nitrate ethanolic soln, add Graphene, the quality of Graphene and the mass ratio of copper are 2:998, ultrasonic agitation 1h; Add the glucose solution that concentration is 0.6M again, ultrasonic agitation 0.5h; Then ultrasonic agitation limit in limit adds the sodium hydroxide solution of concentration 0.6M, obtains mixing solutions.
Mixing solutions is placed in reactor, hydrothermal reduction 2h in 80 DEG C of baking ovens; Filter gained reaction product, the mixing liquid of recycling deionized water and ethanol washs, and in this mixing liquid, the volume ratio of alcohol and deionized water is 2:1, and then vacuum 60 DEG C of dryings, obtain powdered product.
This powdered product is carried out XRD test, and as shown in Figure 1, its main diffraction peak, from Red copper oxide, shows that copper is reduced to Red copper oxide, and obtained powdered product main body is Red copper oxide Graphene composite powder in the reaction of this hydrothermal reduction to result.
(3) the Red copper oxide Graphene composite powder that step (2) is obtained is put into tube furnace, pass into hydrogen, reduce to this Red copper oxide Graphene composite powder under 400 DEG C of conditions, the recovery time is 2h, obtains reduzate.
This reduzate is carried out XRD test, and its result as shown in Figure 1, obtains diffraction peak and is copper diffraction peak, shows that in this process, Red copper oxide is reduced to copper, and this reduzate is copper-base graphite alkene composite powder.
(4) the copper-base graphite alkene composite powder taking a certain amount of step (3) obtained puts into Φ 20 mould pre-molding, preload pressure 5MPa; Matrix material after precompressed is put into discharge plasma sintering stove together with mould and carries out vacuum discharge plasma agglomeration, vacuum tightness is 10
-2pa.This discharge plasma sintering process is: temperature rise rate is 100 DEG C/min, and sintering pressure is 40MPa, and sintering temperature is 800 DEG C, and at sintering temperature insulation 10min, multiple pressure pressure is 50MPa, presses the time to be 7min again.Obtaining diameter after sintering is Φ 20, and thickness is the copper-base graphite alkene composite block material of 5mm.
Fig. 2 is the exterior appearance figure of above-mentioned obtained copper-base graphite alkene composite block material, shows this block materials homogeneous microstructure fine and close, has bright metalluster.Archimedes' principle is utilized to record the density of this block materials for 8.605g/cm
3, that is, this block materials has very high density.
Raman atlas analysis is carried out to above-mentioned obtained copper Graphene composite block material, result as shown in Figure 3, display detects obvious Graphene Characteristic Raman peak, and there is no considerable change with the Raman trace analysis of Graphene raw material, illustrate that Graphene is not reunited in preparation process, structure is not damaged.
The tensile strength test results display of above-mentioned obtained copper-base graphite alkene composite block material, its tensile strength is 350MPa, improves 20% than the in kind obtained tensile strength of not adding the pure copper material of Graphene.
The compressive strength test result display of above-mentioned obtained copper-base graphite alkene composite block material, its compressive strength 480MPa is 1.5 times that do not add the compressive strength of the pure copper material of Graphene that in kind obtain.
The heat conduction result display of above-mentioned obtained copper-base graphite alkene composite block material, it is 432K/ (mK) perpendicular to in-plane thermal conductivity, exceeds 15% than the in kind obtained pure copper material not adding Graphene.In-plane and be 0.9 perpendicular to thermal conductivity ratio on in-plane.
Embodiment 2:
The preparation method providing a kind of copper-base graphite alkene composite block material in the present embodiment is as follows:
(1) be that 99wt% takes copper sulfate according to copper content, prepare copper sulfate ethanolic soln.
(2) in copper sulfate ethanolic soln, add Graphene, the quality of Graphene and the mass ratio of copper are 1:99, ultrasonic agitation 2h; Add the glucose solution that concentration is 0.5M again, ultrasonic agitation 1h; Then ultrasonic agitation limit in limit adds the potassium hydroxide solution stirring of concentration 0.5M, obtains mixing solutions.
Mixing solutions is placed in reactor, hydrothermal reduction 4h in 80 DEG C of baking ovens; Filter gained reaction product, the mixing liquid of recycling deionized water and ethanol washs, and in this mixing liquid, the volume ratio of deionized water and alcohol is 1:1, and then vacuum 80 DEG C of dryings, obtain powdered product.
Described in similar embodiment 1, this powdered product is carried out XRD test, display main diffraction peak, from Red copper oxide, shows that copper is reduced to Red copper oxide, and obtained powdered product main body is Red copper oxide Graphene composite powder in the reaction of this hydrothermal reduction.
(3) the Red copper oxide Graphene composite powder that step (2) is obtained is put into tube furnace, pass into hydrogen, reduce to this Red copper oxide Graphene composite powder under 300 DEG C of conditions, the recovery time is 2h, obtains reduzate.
Described in similar embodiment 1, this reduzate is carried out XRD test, display diffraction peak is copper diffraction peak, and show that in this process, Red copper oxide is reduced to copper, this reduzate is copper-base graphite alkene composite powder.
(4) the copper-base graphite alkene composite powder taking a certain amount of step (3) obtained puts into Φ 20 mould pre-molding, preload pressure 10MPa; Matrix material after precompressed is put into discharge plasma sintering stove together with mould and carries out vacuum discharge plasma agglomeration, vacuum tightness is 10
-2pa.This discharge plasma sintering process is: temperature rise rate is 80 DEG C/min, and sintering pressure is 40MPa, and sintering temperature is 600 DEG C, and at sintering temperature insulation 5min, multiple pressure pressure is 60MPa, presses the time to be 5min again.Obtaining diameter after sintering is Φ 20, and thickness is the copper-base graphite alkene composite block material of 5mm.
The homogeneous microstructure of above-mentioned obtained copper-base graphite alkene composite block material is fine and close, has bright metalluster, has high density.
Similar embodiment 1, Raman atlas analysis is carried out to above-mentioned obtained copper Graphene composite block material, result display detects obvious Graphene Characteristic Raman peak, and there is no considerable change with the Raman trace analysis of Graphene raw material, illustrate that Graphene is not reunited in preparation process, structure is not damaged.
The compressive strength test result display of above-mentioned obtained copper-base graphite alkene composite block material, its compressive strength is greater than 600MPa, is the twice of not adding the compressive strength of the pure copper material of Graphene in kind obtained.
Similar embodiment 1, the heat conduction result display of above-mentioned obtained copper-base graphite alkene composite block material, its in-plane thermal conductivity is 427K/ (mK), exceeds 13% than the in kind obtained pure copper material not adding Graphene.In-plane and be 1.5 perpendicular to thermal conductivity ratio on in-plane.
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all make in spirit of the present invention any amendment, supplement or similar fashion substitute etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for copper-base graphite alkene composite block material, is characterized in that: comprise the steps:
(1) in mantoquita ethanolic soln, add appropriate Graphene, the aqueous solution of reducing sugar and alkaline matter, mix and be placed in reactor, hydrothermal reduction reaction is there is in isoperibol, copper reduction is made to be Red copper oxide, then by reaction product filtration, washing, vacuum-drying, Red copper oxide Graphene composite powder is obtained;
(2) the Red copper oxide Graphene composite powder that hydrogen gas reduction step (1) is obtained, Red copper oxide is wherein reduced to copper, obtains copper-base graphite alkene composite granule;
(3) the copper-base graphite alkene composite granule that step (2) is obtained is put into graphite jig; discharge plasma sintering stove is put into after pre-molding; in vacuum or protective atmosphere, carry out discharge plasma sintering shaping, obtain copper-base graphite alkene composite block material.
2. the preparation method of copper-base graphite alkene composite block material as claimed in claim 1, is characterized in that: described mantoquita is selected from one or more the mixture in copper nitrate, copper acetate, copper vitriol.
3. the preparation method of copper-base graphite alkene composite block material as claimed in claim 1, is characterized in that: described reducing sugar is selected from one or more the mixture in glucose, lactose, maltose, fructose, semi-lactosi.
4. the preparation method of copper-base graphite alkene composite block material as claimed in claim 1, is characterized in that: described alkaline matter is selected from one or more the mixture in sodium hydroxide, potassium hydroxide, ammoniacal liquor.
5. the preparation method of the copper-base graphite alkene composite block material as described in claim arbitrary in Claims 1-4, it is characterized in that: in described step (1), the quality of Graphene and the mass ratio of copper are 1:9999 ~ 10:90, more preferably 5:9995 ~ 5:95.
6. the preparation method of the copper-base graphite alkene composite block material as described in claim arbitrary in Claims 1-4, is characterized in that: in described step (1), and hydrothermal temperature is 60 ~ 120 DEG C; As preferably, the reaction times is 2 ~ 4h.
7. the preparation method of the copper-base graphite alkene composite block material as described in claim arbitrary in Claims 1-4, it is characterized in that: in described step (1), in described washing process, adopt the mixing liquid washing reaction product of alcohol and deionized water, in described mixing liquid, the volume ratio of alcohol and deionized water is 2:1 ~ 1:2.
8. the preparation method of the copper-base graphite alkene composite block material as described in claim arbitrary in Claims 1-4, is characterized in that: in described step (2), and reduction temperature is 100 ~ 500 DEG C; As preferably, the recovery time is 2 ~ 10 hours.
9. the preparation method of the copper-base graphite alkene composite block material as described in claim arbitrary in Claims 1-4, is characterized in that: in described step (3), and preload pressure is 5 ~ 20Mpa.
10. the preparation method of the copper-base graphite alkene composite block material as described in claim arbitrary in Claims 1-4, it is characterized in that: in described step (3), in SPS sintering process, temperature rise rate is 50 DEG C/min ~ 500 DEG C/min, sintering temperature is 400 ~ 1000 DEG C, multiple pressure pressure is 10MPa ~ 100MPa, and soaking time is 1 ~ 120min.
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| CN113061768B (en) * | 2021-03-22 | 2023-08-25 | 中南大学 | Preparation method of dispersion strengthening copper-based composite material |
| WO2023040087A1 (en) * | 2021-09-17 | 2023-03-23 | 中国科学院深圳先进技术研究院 | Graphene-copper matrix composite material, and preparation method therefor and use thereof |
| CN114000003A (en) * | 2021-10-22 | 2022-02-01 | 昆明理工大学 | Preparation method of graphene/carbon dot synergistically-reinforced copper-based composite material |
| CN114855020A (en) * | 2022-05-18 | 2022-08-05 | 深圳市明鑫工业材料有限公司 | Preparation process of oxygen-free copper-based high-strength composite material |
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