CN114000003A - Preparation method of graphene/carbon dot synergistically-reinforced copper-based composite material - Google Patents
Preparation method of graphene/carbon dot synergistically-reinforced copper-based composite material Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 158
- 239000002131 composite material Substances 0.000 title claims abstract description 144
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 56
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 104
- 238000005245 sintering Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000013329 compounding Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 239000011449 brick Substances 0.000 claims description 7
- 239000013590 bulk material Substances 0.000 claims description 7
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 230000002195 synergetic effect Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001238 wet grinding Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 238000002490 spark plasma sintering Methods 0.000 claims description 6
- 238000004729 solvothermal method Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000002787 reinforcement Effects 0.000 abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
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- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
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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
-
- 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
- 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
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- 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
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
- 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
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
-
- 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
-
- 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
- B22F9/16—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
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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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
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
-
- 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 invention discloses a preparation method of a reduced graphene oxide/carbon dot-copper composite material, belonging to the technical field of composite material preparation; firstly, compounding graphene oxide and carbon dots with copper powder by using a molecular-level blending method and a ball milling method, then mixing the two powders by ball milling, and finally sintering to obtain an RGO/CPD-Cu block material; compared with pure copper and composite materials containing single reinforcement, the composite material obtained by the invention has improved comprehensive properties.
Description
Technical Field
The invention belongs to the technical field of composite material preparation and powder metallurgy, and particularly relates to a preparation method of a graphene/carbon dot synergistically enhanced copper-based composite material.
Background
In the research of copper-based composites, the addition of a reinforcing phase leads to some performance improvement, but often the improvement comes at the expense of other performance, such as the improvement of the strength of the composite accompanied by the reduction of the conductivity or elongation, and the like. Therefore, in recent years, synergistic strengthening becomes a new research hotspot for copper-based composite materials. Synergistic strengthening, i.e., the addition of two or more reinforcing phases to the matrix, results in a composite having superior properties to composites containing only a single reinforcing phase.
The carbon nanomaterial is considered to be an ideal reinforcement of the metal matrix composite due to its own properties, wherein the graphene oxide surface contains more functional groups than the graphene surface, which is more beneficial to the interface bonding of carbon and copper, but the dispersibility needs to be improved due to its inherent size and physical properties. And the other carbon nano material carbon dots have small size, are easily soluble in water and organic solvents, have rich functional groups on the surface and can improve the dispersibility of the reinforcement. In addition, the research shows that the addition of the carbon dots into the copper matrix can keep the conductivity of the composite material not to be reduced or even improved, and has a certain toughening effect.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a synergistically enhanced copper-based composite material, which comprises the steps of utilizing two different reinforcements, namely reduced graphene oxide and carbon dots, mixing the powder obtained by the two different preparation methods, namely molecular-level blending and ball milling, to obtain composite powder with two reinforcements and copper powder of two sizes uniformly distributed, and reducing and sintering the composite powder to obtain the composite material with high density and good electrical and mechanical properties;
the preparation method of the graphene/carbon dot synergistic reinforced copper-based composite material is characterized by comprising the following steps:
s1: preparation of reduced graphene oxide-copper (RGO-Cu) composite powder: compounding 10-1000g of copper acetate monohydrate (CuAc) solution with 0.1-5.0% of reduced graphene oxide by a molecular level blending method, and obtaining RGO-Cu powder through the steps of washing, vacuum filtration, drying and reduction;
s2: preparation of carbon dot-copper (CPD-Cu) composite powder: preparing a CPD solution, purifying, freeze-drying to obtain solid CPD, compounding 10-1000g of copper powder and 0.1-5.0% of CPD by a ball milling method, and drying and reducing to obtain CPD-Cu powder;
s3: preparation of reduced graphene oxide/carbon dot-copper (RGO/CPD-Cu) composite powder: fully mixing the RGO-Cu composite powder and the CPD-Cu composite powder according to a proportion, and reducing to obtain RGO/CPD-Cu composite powder;
s4: and (3) sintering: sintering the RGO/CPD-Cu composite powder obtained in S3, and reducing to obtain an RGO/CPD-Cu block material;
preferably, the molecular-grade blending method in S1 is to fully mix RGO with 500ml of 0.156M copper acetate solution, put the mixed solution in a water bath kettle at 60-80 ℃ and stir and heat the mixed solution until the temperature of the solution is stable, add 30ml of 4M NaOH solution and continue to stir and heat for 5-15min, add 15ml of 2M glucose solution and stir and heat the mixed solution until the mixed solution turns brick red, and stop the process;
preferably, the volume fraction of RGO in the RGO-Cu composite powder in S1 is 0.75-3.00 vol.%, and the volume fraction of CPD in the CPD-Cu composite powder in S2 is 0.75-3.00 vol.%;
preferably, the reduction in S1, S2 and S3 is carried out by placing the powder in a vacuum tube furnace, and reducing the powder for 240-480min at 350 ℃ in a reducing atmosphere, wherein the reducing atmosphere can be one of hydrogen, carbon monoxide and ammonia gas mixed with an inert gas in a certain proportion, and the inert gas is nitrogen or argon;
preferably, the CPD solution used in S2 is prepared by hydrothermal and solvothermal methods, wherein the reaction temperature of hydrothermal and solvothermal methods is generally 150-200 ℃, and the CPD solution contains a carbon source and a certain amount of a compound containing a nitrogen source or a compound capable of providing both a carbon source and a nitrogen source; the CPD solution is purified by one of centrifugation, dialysis and silica gel column chromatography; the ball milling adopts a high-energy ball mill, the mass ratio of ball materials is 10:1, the ball milling medium is stainless steel balls, and the ball milling process is alcohol wet milling at 100-200rpm for 8-13 h;
preferably, the RGO-Cu composite powder and the CPD-Cu composite powder with the same volume fraction in S3 are ball-milled for 1-3h at a ratio of 1:1 to 1:6 to prepare RGO/CPD-Cu composite powder;
preferably, in the step S4, sintering may be performed under vacuum by using a sintering method such as spark plasma sintering and hot press sintering, wherein the sintering temperature is 550-800 ℃.
The invention has the beneficial effects that:
(1) the density and the conductivity of the RGO/CPD-Cu composite material prepared by the invention are maintained at the same level or slightly improved compared with pure copper, the distribution of the reinforcement is more uniform, and the mechanical property of the composite material is effectively improved;
(2) the RGO/CPD-Cu composite material prepared by the invention reduces the cost and weakens or even overcomes the contradiction between the strength and the toughness as well as between the strength and the electrical conductivity of the composite material on the basis of achieving better performance.
Drawings
FIG. 1 is a graph showing a comparison of mechanical properties of an RGO/CPD-Cu composite prepared in example 1, a pure copper sample prepared by the same process as the composite, and a bulk material prepared by sintering the composite powder obtained in step (1) and step (2) of example 1 through the same sintering process as the composite;
FIG. 2 is a gold phase diagram of the RGO/CPD-Cu composite in example 1;
FIG. 3 is a microscopic morphology of the RGO/CPD-Cu composite powder in example 2;
FIG. 4 is a stress-strain curve of a pure copper sample prepared by the same process and a composite material obtained by each example;
FIG. 5 is a process flow diagram of the preparation method of the present invention.
Detailed Description
For clearly and completely explaining the scheme and the effect of the invention, the following embodiments are used for detailed description;
example 1
A preparation method of a graphene/carbon dot synergistically enhanced copper-based composite material is characterized by comprising the following specific steps:
s1: preparation of reduced graphene oxide-copper (RGO-Cu) composite powder: dissolving 15.6g of copper acetate monohydrate (CuAc) in 500ml of deionized water, adding 0.0167g of graphene oxide, magnetically stirring until the mixture is fully mixed, placing the mixed solution in a water bath kettle at 75 ℃ to heat until the temperature of the solution is stable, adding 30ml of 4M NaOH solution, continuously stirring and heating for 10min, adding 15ml of 2M glucose solution, stirring and heating until the mixture is brick red, and stopping heating; washing, vacuum filtering, drying and the like to obtain GO-Cu2O composite powder, placing the GO-Cu2O composite powder in a vacuum tube furnace, heating to 300 ℃ in a reducing atmosphere of 10% nitrogen-hydrogen mixed gas, and reducing for 300min to obtain RGO-Cu composite powder;
s2: preparation of carbon dot-copper (CPD-Cu) composite powder: dissolving 12g of citric acid in 120ml of deionized water, adding 2ml of ethylenediamine solution, carrying out hydrothermal reaction for 6h at 150 ℃ in a reaction kettle, cooling the reactant, and then centrifuging, dialyzing, and freeze-drying to obtain solid CPD; placing 19.94g of copper powder, 0.06g of CPD, absolute alcohol and 200g of stainless steel ball into a ball milling tank, and wet-milling for 8 hours at 100rpm and 5 hours at 200rpm by a high-energy ball mill; placing the dried powder in a vacuum tube furnace, heating to 300 ℃ in a reducing atmosphere of 10% nitrogen-hydrogen mixed gas, and reducing for 300min to obtain CPD-Cu composite powder;
s3: preparation of reduced graphene oxide/carbon dot-copper (RGO/CPD-Cu) composite powder: ball milling the RGO-Cu composite powder and the CPD-Cu composite powder for 2h at the mass ratio of 1:3 and 100rpm, placing the mixed powder in a vacuum tube furnace, heating to 300 ℃ in the reducing atmosphere of 10% nitrogen-hydrogen mixed gas, and reducing for 300min to obtain RGO/CPD-Cu composite powder;
s4: and (3) sintering: and (2) sintering the RGO/CPD-Cu composite powder obtained in S3 by using SPS, loading the powder into a graphite die with the diameter of 20mm, heating to 650 ℃ under the vacuum condition of 0.01-10Pa and the pressure of 50MPa, preserving the heat for 5min, and cooling to obtain the RGO/CPD-Cu bulk material.
The mechanical properties of the RGO/CPD-Cu composite material prepared in this example, the pure copper sample prepared by the same process as the composite material, and the bulk material prepared by sintering the composite powder obtained in this example S1 and S2 in the same sintering process as the composite material are shown in fig. 1, and it can be seen by comparison that: the tensile strength of the RGO-Cu is improved, the elongation is greatly reduced, the fracture elongation of the CPD-Cu is improved to 42 percent, the strength is slightly reduced, and the strength and the elongation of the RGO/CPD-Cu composite material are improved compared with pure copper;
the density and the conductivity of the RGO/CPD-Cu composite material in the embodiment are shown in Table 1, and both the density and the conductivity are slightly improved;
the gold phase diagram of the RGO/CPD-Cu composite in this example is shown in FIG. 2, from which it can be seen that the grain size is 2-5 μm.
Example 2
A preparation method of a graphene/carbon dot synergistically enhanced copper-based composite material is characterized by comprising the following specific steps:
s1: preparation of reduced graphene oxide-copper (RGO-Cu) composite powder: dissolving 15.6g of copper acetate monohydrate (CuAc) in 500ml of deionized water, adding 0.0167g of graphene oxide, magnetically stirring until the mixture is fully mixed, placing the mixed solution in a water bath kettle at 75 ℃ to heat until the temperature of the solution is stable, adding 30ml of 4M NaOH solution, continuously stirring and heating for 10min, adding 15ml of 2M glucose solution, stirring and heating until the mixture is brick red, and stopping heating; washing, vacuum filtering, drying and the like to obtain GO-Cu2O composite powder, placing the GO-Cu2O composite powder in a vacuum tube furnace, heating to 300 ℃ in a reducing atmosphere of 10% nitrogen-hydrogen mixed gas, and reducing for 300min to obtain RGO-Cu composite powder;
s2: preparation of carbon dot-copper (CPD-Cu) composite powder: 6g of citric acid 1.2ml of ethylenediamine solution, carrying out solvothermal reaction for 20min at 170 ℃ in a crucible, adding 50ml of deionized water after the reactant is cooled, uniformly stirring, and centrifuging, dialyzing and freeze-drying the solution to obtain solid CPD; placing 19.94g of copper powder, 0.06g of CPD, absolute alcohol and 200g of stainless steel ball into a ball milling tank, and wet-milling for 8 hours at 100rpm and 5 hours at 200rpm by a high-energy ball mill; placing the dried powder in a vacuum tube furnace, heating to 300 ℃ in a reducing atmosphere of 10% nitrogen-hydrogen mixed gas, and reducing for 300min to obtain CPD-Cu composite powder;
s3: preparation of reduced graphene oxide/carbon dot-copper (RGO/CPD-Cu) composite powder: ball milling the RGO-Cu composite powder and the CPD-Cu composite powder for 2h at the mass ratio of 1:3 and 100rpm, placing the mixed powder in a vacuum tube furnace, heating to 300 ℃ in the reducing atmosphere of 10% nitrogen-hydrogen mixed gas, and reducing for 300min to obtain RGO/CPD-Cu composite powder;
s4: and (3) sintering: sintering the RGO/CPD-Cu composite powder obtained from S3 by using a hot-pressing sintering furnace, loading the powder into a graphite die with the diameter of 30mm, heating to 600 ℃ under the vacuum condition of 0.01-10Pa and the pressure of 50MPa, preserving heat for 1h, and cooling to obtain the RGO/CPD-Cu block material.
The microstructure of the RGO/CPD-Cu composite powder in this example is shown in FIG. 3, from which it can be seen that the matrix copper has two morphologies, one is cubic granular copper prepared by mixing at S1, and the other is flake copper prepared by ball milling at S2, and the two morphologies are substantially distributed in a ratio of 1: 3;
the compactness and the conductivity of the RGO/CPD-Cu composite material in the embodiment are shown in Table 1, and the conductivity of the composite material is improved by 3.33 percent IACS compared with that of pure copper;
the stress-strain curve of the RGO/CPD-Cu composite in this example is shown in FIG. 4, and the elongation at break of the composite is improved by 135%.
Example 3
A preparation method of a graphene/carbon dot synergistically enhanced copper-based composite material is characterized by comprising the following specific steps:
s1: preparation of reduced graphene oxide-copper (RGO-Cu) composite powder: dissolving 15.6g of copper acetate monohydrate (CuAc) in 500ml of deionized water, adding 0.0084g of graphene oxide, magnetically stirring until the mixture is fully mixed, placing the mixed solution in a water bath kettle at 80 ℃ and heating until the solution temperature is stable, adding 30ml of 4M NaOH solution, continuously stirring and heating for 5min, adding 15ml of 2M glucose solution, stirring and heating until the mixture is brick red, and stopping; washing, vacuum filtering, drying and the like to obtain GO-Cu2O composite powder, placing the GO-Cu2O composite powder in a vacuum tube furnace, heating to 250 ℃ in a reducing atmosphere of 5% nitrogen-hydrogen mixed gas, and reducing for 480min to obtain RGO-Cu composite powder;
s2: preparation of carbon dot-copper (CPD-Cu) composite powder: dissolving 12g of citric acid in 120ml of deionized water, adding 2ml of ethylenediamine solution, carrying out hydrothermal reaction for 6h at 180 ℃ in a reaction kettle, cooling the reactant, and then centrifuging, dialyzing, and freeze-drying to obtain solid CPD; placing 19.97g of copper powder, 0.03g of CPD, absolute alcohol and 200g of stainless steel ball into a ball milling tank, and wet-milling for 8 hours at 100rpm and 5 hours at 200rpm by a high-energy ball mill; placing the dried powder in a vacuum tube furnace, heating to 250 ℃ in a reducing atmosphere of 5% nitrogen-hydrogen mixed gas, and reducing for 480min to obtain CPD-Cu composite powder;
s3: preparation of reduced graphene oxide/carbon dot-copper (RGO/CPD-Cu) composite powder: ball milling the RGO-Cu composite powder and the CPD-Cu composite powder for 2h at the mass ratio of 1:3 and 100rpm, placing the mixed powder in a vacuum tube furnace, heating to 250 ℃ in the reducing atmosphere of 5% of nitrogen-hydrogen mixed gas, and reducing for 480min to obtain RGO/CPD-Cu composite powder;
s4: and (3) sintering: and (2) sintering the RGO/CPD-Cu composite powder obtained in S3 by using SPS, loading the powder into a graphite die with the diameter of 20mm, heating to 550 ℃ under the vacuum condition of 0.01-10Pa and under the pressure of 50MPa, preserving heat for 5min, and cooling to obtain the RGO/CPD-Cu bulk material.
The compactness and the conductivity of the RGO/CPD-Cu composite material in the embodiment are shown in Table 1, and the conductivity of the composite material is improved by 9 percent compared with that of pure copper;
the stress-strain curve of the RGO/CPD-Cu composite material in this example is shown in FIG. 4, the ultimate tensile strength of the composite material is 314MPa, the elongation at break is 51%, and the simultaneous improvement of the strength and the elongation is realized.
Example 4
A preparation method of a graphene/carbon dot synergistically enhanced copper-based composite material is characterized by comprising the following specific steps:
s1: preparation of reduced graphene oxide-copper (RGO-Cu) composite powder: dissolving 15.6g of copper acetate monohydrate (CuAc) in 500ml of deionized water, adding 0.0334g of graphene oxide, magnetically stirring until the mixture is fully mixed, placing the mixed solution in a water bath kettle at 60 ℃ to heat until the solution temperature is stable, adding 30ml of 4M NaOH solution, continuously stirring and heating for 15min, adding 15ml of 2M glucose solution, stirring and heating until the mixture turns brick red, and stopping heating; washing, vacuum filtering, drying and the like to obtain GO-Cu2O composite powder, placing the GO-Cu2O composite powder in a vacuum tube furnace, heating to 300 ℃ in a reducing atmosphere of 10% nitrogen-hydrogen mixed gas, and reducing for 360min to obtain RGO-Cu composite powder;
s2: preparation of carbon dot-copper (CPD-Cu) composite powder: dissolving 12g of citric acid in 120ml of deionized water, adding 2ml of ethylenediamine solution, carrying out hydrothermal reaction for 6h at 150 ℃ in a reaction kettle, cooling the reactant, and carrying out silica gel column chromatography and freeze drying to obtain solid CPD; putting 19.88g of copper powder, 0.12g of CPD, absolute alcohol and 200g of stainless steel ball into a ball milling tank, and wet-milling for 8 hours by a high-energy ball mill at 200 rpm; placing the dried powder in a vacuum tube furnace, heating to 300 ℃ in a reducing atmosphere of 10% nitrogen-hydrogen mixed gas, and reducing for 360min to obtain CPD-Cu composite powder;
s3: preparation of reduced graphene oxide/carbon dot-copper (RGO/CPD-Cu) composite powder: ball milling the RGO-Cu composite powder and the CPD-Cu composite powder for 1h at the mass ratio of 1:1 and 100rpm, placing the mixed powder in a vacuum tube furnace, heating to 300 ℃ in the reducing atmosphere of 10% of nitrogen-hydrogen mixed gas, and reducing for 360min to obtain RGO/CPD-Cu composite powder;
s4: and (3) sintering: and (3) sintering the RGO/CPD-Cu composite powder obtained in the step (3) by using SPS, loading the powder into a graphite die with the diameter of 20mm, heating to 800 ℃ under the vacuum condition of 0.01-10Pa and the pressure of 50MPa, preserving heat for 5min, and cooling to obtain the RGO/CPD-Cu bulk material.
The compactness and the conductivity of the RGO/CPD-Cu composite material in the embodiment are shown in Table 1, and the conductivity of the composite material and the conductivity of pure copper are maintained at the same level;
the stress-strain curve of the RGO/CPD-Cu composite material in this example is shown in FIG. 4, and the ultimate tensile strength of the composite material is 372MPa, which is improved by 36%.
Example 5
A preparation method of a graphene/carbon dot synergistically enhanced copper-based composite material is characterized by comprising the following specific steps:
s1: preparation of reduced graphene oxide-copper (RGO-Cu) composite powder: dissolving 15.6g of copper acetate monohydrate (CuAc) in 500ml of deionized water, adding 0.0167g of graphene oxide, magnetically stirring until the mixture is fully mixed, placing the mixed solution in a water bath kettle at 75 ℃ to heat until the temperature of the solution is stable, adding 30ml of 4M NaOH solution, continuously stirring and heating for 10min, adding 15ml of 2M glucose solution, stirring and heating until the mixture is brick red, and stopping heating; washing, vacuum filtering, drying and the like to obtain GO-Cu2O composite powder, placing the GO-Cu2O composite powder in a vacuum tube furnace, heating to 350 ℃ in a reducing atmosphere of 10% nitrogen-hydrogen mixed gas, and reducing for 240min to obtain RGO-Cu composite powder;
s2: preparation of carbon dot-copper (CPD-Cu) composite powder: 5.4g of p-phenylenediamine is dissolved in 60ml of deionized water, hydrothermal reaction is carried out in a reaction kettle for 24 hours at 200 ℃, and after the reactant is cooled, solid CPD is obtained after centrifugation, dialysis and freeze drying; putting 19.94g of copper powder, 0.06g of CPD, absolute alcohol and 200g of stainless steel ball into a ball milling tank, and wet-milling for 10 hours by a high-energy ball mill at 150 rpm; placing the dried powder in a vacuum tube furnace, heating to 350 ℃ in a reducing atmosphere of 10% nitrogen-hydrogen mixed gas, and reducing for 240min to obtain CPD-Cu composite powder;
s3: preparation of reduced graphene oxide/carbon dot-copper (RGO/CPD-Cu) composite powder: ball milling the RGO-Cu composite powder and the CPD-Cu composite powder for 3h at the mass ratio of 1:6 and 100rpm, placing the mixed powder in a vacuum tube furnace, heating to 350 ℃ in the reducing atmosphere of 10% nitrogen-hydrogen mixed gas, and reducing for 240min to obtain RGO/CPD-Cu composite powder;
s4: and (3) sintering: and (2) sintering the RGO/CPD-Cu composite powder obtained in S3 by using SPS, loading the powder into a graphite die with the diameter of 20mm, heating to 650 ℃ under the vacuum condition of 0.01-10Pa and the pressure of 50MPa, preserving the heat for 5min, and cooling to obtain the RGO/CPD-Cu bulk material.
The compactness and the conductivity of the RGO/CPD-Cu composite material in the embodiment are shown in Table 1, and the conductivity of the composite material and the conductivity of pure copper are maintained at the same level;
in the embodiment, the stress-strain curve of the RGO/CPD-Cu composite material is shown in FIG. 4, the ultimate tensile strength of the composite material is 357MPa, the elongation at break is 21%, and the tensile strength is greatly improved under the condition that the elongation is maintained to be basically at the same level as that of pure copper.
TABLE 1 compactness and conductivity of pure copper samples prepared by the same process and composite materials obtained in each example
| Density (%) | Electrical conductivity (% IACS) | |
| Cu | 98.39±0.77 | 87.62±0.46 |
| Example 1 | 99.04±0.29 | 93.74±0.34 |
| Example 2 | 98.11±0.99 | 90.95±0.31 |
| Example 3 | 99.06±0.56 | 95.15±0.51 |
| Example 4 | 97.14±0.61 | 88.18±0.37 |
| Example 5 | 98.47±0.30 | 88.67±0.36 |
Claims (7)
1. The preparation method of the graphene/carbon dot synergistic reinforced copper-based composite material is characterized by comprising the following steps:
s1: preparation of reduced graphene oxide-copper (RGO-Cu) composite powder: compounding 10-1000g of copper acetate monohydrate (CuAc) solution with 0.1-5.0% of reduced graphene oxide by a molecular level blending method, and obtaining RGO-Cu powder through the steps of washing, vacuum filtration, drying and reduction;
s2: preparation of carbon dot-copper (CPD-Cu) composite powder: preparing a CPD solution, purifying, freeze-drying to obtain solid CPD, compounding 10-1000g of copper powder and 0.1-5.0% of CPD by a ball milling method, and drying and reducing to obtain CPD-Cu powder;
s3: preparation of reduced graphene oxide/carbon dot-copper (RGO/CPD-Cu) composite powder: fully mixing the RGO-Cu composite powder and the CPD-Cu composite powder according to a proportion, and reducing to obtain RGO/CPD-Cu composite powder;
s4: and (3) sintering: and sintering the RGO/CPD-Cu composite powder obtained in S3, and reducing to obtain the RGO/CPD-Cu bulk material.
2. The method for preparing the graphene/carbon dot synergistic reinforced copper-based composite material as claimed in claim 1, wherein the molecular-grade blending method in S1 includes steps of fully mixing RGO with 500ml of 0.156M copper acetate solution, placing the mixed solution in a water bath kettle at 60-80 ℃ and heating with stirring until the solution temperature is stable, adding 30ml of 4M NaOH solution and continuing to heat with stirring for 5-15min, adding 15ml of 2M glucose solution and heating with stirring until the mixture turns brick red.
3. The method for preparing the graphene/carbon dot synergistic reinforced copper-based composite material as claimed in claim 1, wherein the volume fraction of RGO in the RGO-Cu composite powder in S1 is 0.75-3.00 vol.%, and the volume fraction of CPD in the CPD-Cu composite powder in S2 is 0.75-3.00 vol.%.
4. The method as claimed in claim 1, wherein the reduction in S1, S2 and S3 is performed by placing the powder in a vacuum tube furnace, and performing reduction at 250-350 ℃ for 480min in a reducing atmosphere, wherein the reducing atmosphere is a mixture of one of hydrogen, carbon monoxide and ammonia with an inert gas in a certain proportion, and the inert gas is nitrogen or argon.
5. The method for preparing the graphene/carbon point synergistically enhanced copper-based composite material as claimed in claim 1, wherein the CPD solution used in S2 is a compound containing a carbon source and a certain amount of nitrogen source or a compound capable of providing both a carbon source and a nitrogen source, and is prepared by hydrothermal and solvothermal methods, wherein the reaction temperature of hydrothermal and solvothermal methods is generally 150-; the CPD solution is purified by one of centrifugation, dialysis and silica gel column chromatography; the ball milling adopts a high-energy ball mill, the mass ratio of ball materials is 10:1, the ball milling medium is stainless steel balls, and the ball milling process is alcohol wet milling at 100-200rpm for 8-13 h.
6. The method for preparing the graphene/carbon dot synergistic reinforced copper-based composite material according to claim 1, wherein the RGO-Cu composite powder and the CPD-Cu composite powder with the same volume fraction in S3 are ball-milled for 1-3h at a ratio of 1:1 to 1:6 to obtain the RGO/CPD-Cu composite powder.
7. The method as claimed in claim 1, wherein the sintering process in S4, such as spark plasma sintering and hot press sintering, is performed under vacuum at a sintering temperature of 550-800 ℃.
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