CN111057899A - Graphene/silicon carbide reinforced copper-based composite material and preparation method thereof - Google Patents

Graphene/silicon carbide reinforced copper-based composite material and preparation method thereof Download PDF

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CN111057899A
CN111057899A CN201911338642.1A CN201911338642A CN111057899A CN 111057899 A CN111057899 A CN 111057899A CN 201911338642 A CN201911338642 A CN 201911338642A CN 111057899 A CN111057899 A CN 111057899A
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graphene
copper
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silicon carbide
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CN111057899B (en
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汪全芳
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Hunan Carbon Material Technology Co ltd
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Anhui Yuewei Technology Co Ltd
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    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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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
    • B22F3/02—Compacting only
    • 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
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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
    • B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
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    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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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    • 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
    • B22F2009/042—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling using a particular milling fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Abstract

The invention provides a graphene/silicon carbide reinforced copper-based composite material and a preparation method thereof, relating to the technical field of copper-based composite materials, wherein the graphene/silicon carbide reinforced copper-based composite material comprises the following components in percentage by weight: 0.3-0.8 wt% of graphene, SiC: 0.2 to 0.6 wt%, Ni: 0.02-0.2 wt% and the balance copper; the preparation method comprises the following steps: (1) mixing; (2) carrying out ultrasonic dispersion on graphene, adding mixed powder and stearic acid, carrying out ultrasonic dispersion, and mixing and stirring; (3) ball milling; (4) drying; removing stearic acid; (5) prepressing and forming, and loading into a graphite mold; (6) vacuum hot pressing: the hot pressing temperature is 840-860 ℃, the hot pressing pressure is 40-50MPa, and the hot pressing time is 100-130 min; (7) hot rolling; heating to 360-400 ℃, cooling to 160-180 ℃ after heat preservation, and air cooling. The raw materials are reasonably selected and proportioned, and the optimized preparation process is combined, so that the prepared composite material has the advantages of good conductivity, high strength, high hardness, good toughness and excellent wear resistance.

Description

Graphene/silicon carbide reinforced copper-based composite material and preparation method thereof
Technical Field
The invention relates to the technical field of copper-based composite materials, in particular to a graphene/silicon carbide reinforced copper-based composite material and a preparation method thereof.
Background
Graphene is a two-dimensional material with a thickness of only a single atomic layer, formed by carbon atoms passing through sp2The hybrid orbitals, which were first successfully separated in 2004 by physicists of the university of manchester, uk in experiments using mechanically applied techniques, were considered as the basic modules constituting graphite materials of all other dimensions (wrapped in fullerenes, rolled into carbon nanotubes, packed into graphite). Graphene is only 0.35nm thick, the thinnest two-dimensional material in the world. At the same time, the stable regular hexagonal lattice structure allows it to possess many unique properties, such as: the carrier mobility reaches 15000-2V · s, over 10 times that of commercial silicon wafers; the thermal conductivity reaches 5000W/(m.K), which is 3 times of that of diamond; the tensile strength reaches about 130GPa, which is the highest of the currently known materials; has room temperature quantum Hall effect. The graphene has the advantages of large specific surface area, low cost and the like, so that the graphene is very suitable for development of high-performance composite materials.
Copper has good electrical and thermal conductivity, but has low strength, which cannot meet the requirements of industrial production, so adding a proper reinforcement into copper to improve the strength without reducing the electrical and thermal conductivity becomes a key problem to be solved. Although the traditional carbon fiber reinforced copper-based composite material has high electric conductivity, heat conductivity and wear resistance, the mechanical property is poor; carbon nanotubes have a better reinforcing effect than carbon fibers, but are difficult to prepare; the application of these two composites is greatly limited. The development of novel composite materials and the improvement of the comprehensive performance of the copper-based composite materials become problems to be solved urgently. Research in recent years shows that the mechanical property and the conductivity of the composite material can be remarkably improved by adding a small amount of graphene into a copper matrix, so that the graphene is taken as an ideal reinforcement of the copper-based composite material and is a research hotspot in recent years.
At present, the preparation methods related to graphene reinforced copper-based composite materials mainly comprise a powder metallurgy method, a hydrothermal method, a chemical deposition method, an in-situ growth method and the like, but due to the fact that graphene is large in specific surface area and easy to agglomerate, the comprehensive performance of the prepared graphene copper-based composite materials is not high.
Chinese patent with application number 201610659237.X discloses a graphene/copper composite material, a preparation method and application thereof, wherein the graphene/copper composite material comprises the following components in percentage by weight: the preparation method for preparing the graphene/copper composite material comprises four steps of weighing, preparation of powder suspension, preparation of composite powder, cold press molding and hot press sintering, wherein the four steps comprise the step of preparing the composite powder, the step of carrying out the cold press molding and the step of carrying out the hot press sintering, the performance of the prepared composite material is excellent, but in the preparation process, the step of reducing the graphene oxide into the graphene is carried out, the step of carrying out the cold press molding and the step of carrying out the hot press sintering, the actual working procedures are complex, and the production cost is high. Meanwhile, the graphene/copper composite material prepared by the method still has limited improvement in strength, toughness, wear resistance and the like, and further optimization is needed.
Disclosure of Invention
The invention aims to provide a graphene/silicon carbide reinforced copper-based composite material and a preparation method thereof, wherein the raw materials are reasonably selected and proportioned, and an optimized preparation process is combined, so that the prepared composite material is good in conductivity, high in strength, high in hardness, good in toughness and excellent in wear resistance.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the graphene/silicon carbide reinforced copper-based composite material comprises the following components in percentage by weight: 0.3-0.8 wt% of graphene, SiC: 0.2 to 0.6 wt%, Ni: 0.02-0.2 wt% and the balance of copper.
Preferably, the graphene/silicon carbide reinforced copper-based composite material comprises the following components in percentage by weight: 0.45-0.7 wt% of graphene, SiC: 0.4 to 0.55 wt%, Ni: 0.05 to 0.12 weight percent of copper and the balance of copper.
Further preferably, the graphene/silicon carbide reinforced copper-based composite material contains the following components in percentage by weight: 0.65 wt% of graphene, SiC: 0.5 wt%, Ni: 0.11 wt% and the balance copper; or comprises the following components in percentage by weight: 0.6 wt% of graphene, SiC: 0.45 wt%, Ni: 0.08 wt% and the balance copper.
The preparation method of the graphene/silicon carbide reinforced copper-based composite material comprises the following steps:
(1) pretreating the original copper powder; premixing the treated copper powder, superfine silicon carbide powder and nickel powder in a high-speed mixer for 8-10h to obtain mixed powder;
(2) placing graphene in absolute ethyl alcohol, performing ultrasonic dispersion for 50-70min, adding stearic acid with the mass of 0.8-1 wt% of the mixed powder and the mixed powder, performing ultrasonic dispersion for 20-30min at 45-50 ℃, and mixing and stirring for 10-15min to obtain a composite powder suspension;
(3) placing the composite powder suspension in a ball milling tank, vacuumizing, introducing high-purity argon for protection, and then carrying out ball milling;
(4) placing the slurry obtained after ball milling in an evaporation kettle, drying the slurry to be in a semi-dry state under stirring, and then transferring the slurry to a vacuum oven for full drying treatment to obtain mixed powder; keeping the mixed powder at the temperature of 255-;
(5) filling the copper-based mixed powder into a steel die, performing pre-pressing forming under the pressure of 100-160MPa, and then filling a pressed blank into a high-strength graphite die;
(6) carrying out vacuum hot pressing in a vacuum hot pressing furnace: the vacuum degree reaches 2-3 multiplied by 10-3Heating after Pa, wherein the hot pressing temperature is 840-860 ℃, the hot pressing pressure is 40-50MPa, and the hot pressing time is 100-130 min; after sintering, cooling the composite material blank to room temperature along with the furnace;
(7) carrying out hot rolling on the prepared composite material blank at the temperature of 710-730 ℃; after finishing hot rolling, heating to 400 ℃ at 360 ℃, preserving the heat for 60-90min, cooling to 180 ℃, and then air-cooling to room temperature.
Preferably, in the step (1), the pretreatment method of the raw copper powder comprises the following steps: putting the original copper powder in 5mol/L acetic acid solution and carrying out ultrasonic treatment for 20 min; cleaning with distilled water, sequentially adding into ethanol and propanol, ultrasonic treating for 25min, filtering, and vacuum drying.
Preferably, in the step (1), the particle size of the original copper powder is 1-5 μm; the granularity of the superfine silicon carbide powder is 20-50 nm; the particle size of the nickel powder is 10-20 μm.
Preferably, in the step (3), the ball milling time is 5-6.5h, the rotation speed is 300-: 1; the positive and negative rotation alternation time is 20-25min, and the acceleration time and the deceleration time are both 15 s.
Preferably, in the step (6), the heating rate is 11-13 ℃/min.
Preferably, in the step (7), the deformation of the rolled piece is 7-9%.
The invention has the beneficial effects that:
according to the invention, the graphene and the silicon carbide are used for reinforcing the copper together, the silicon carbide has a good reinforcing effect on the copper, so that the strength, toughness and wear resistance of the copper-based composite material are effectively improved, and a proper amount of nickel is added, so that the comprehensive performance is better. When the composite material is prepared, stearic acid is added into the mixed powder, and graphene agglomeration can be effectively prevented, so that the composite powder has good dispersibility, and the prepared composite material has excellent comprehensive performance.
Parameters are reasonably set during vacuum hot pressing and sintering, so that the composite material obtained by sintering has fine matrix grains, high microhardness and high yield strength. On the basis of sintering, the composite material is subjected to hot rolling treatment, the grains of the rolled composite material are obviously elongated along the rolling direction, and under subsequent heat treatment, the tissues are recovered and recrystallized, so that the uniformity of the composite material is obviously improved, the compactness of the composite material is further improved, the grains of a matrix are more refined, and the stability and the mechanical property of the composite material are effectively improved.
When the graphene/silicon carbide reinforced copper-based composite material is prepared, raw materials are reasonably selected and proportioned, and an optimized preparation process is combined, so that the prepared composite material is good in conductivity, high in strength, high in hardness, good in toughness, excellent in wear resistance and good in use prospect. Meanwhile, the preparation process is simple, easy to operate and beneficial to controlling the production cost.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the graphene/silicon carbide reinforced copper-based composite material comprises the following components in percentage by weight: 0.5 wt% of graphene, SiC: 0.6 wt%, Ni: 0.1 wt% and the balance copper.
The preparation method of the graphene/silicon carbide reinforced copper-based composite material comprises the following steps:
(1) the method for pretreating the original copper powder comprises the following steps: putting the original copper powder in 5mol/L acetic acid solution and carrying out ultrasonic treatment for 20 min; cleaning with distilled water, sequentially placing in ethanol and propanol, ultrasonic treating for 25min, filtering, and vacuum drying;
pre-mixing the pretreated copper powder, superfine silicon carbide powder and nickel powder in a high-speed mixer for 10 hours to obtain mixed powder;
the granularity of the original copper powder is 1-5 mu m; the granularity of the superfine silicon carbide powder is 20-50 nm; the particle size of the nickel powder is 10-20 μm.
(2) And (2) placing the graphene in absolute ethyl alcohol for ultrasonic dispersion for 60min, adding the mixed powder and stearic acid accounting for 1 wt% of the mixed powder, performing ultrasonic dispersion for 20min at 50 ℃, and mixing and stirring for 15min to obtain a composite powder suspension.
(3) Placing the composite powder suspension in a ball milling tank, vacuumizing, introducing high-purity argon for protection, and then carrying out ball milling; wherein the ball milling time is 6.5h, the rotating speed is 300r/min, the ball-material ratio is 9: 1; the forward and reverse rotation alternation time is 25min, and the acceleration time and the deceleration time are both 15 s.
(4) Placing the slurry obtained after ball milling in an evaporation kettle, drying the slurry to be in a semi-dry state under stirring, and then transferring the slurry to a vacuum oven for full drying treatment to obtain mixed powder; and (3) preserving the temperature of the mixed powder at 265 ℃ for 1.5h to remove stearic acid, thus obtaining the copper-based mixed powder.
(5) And filling the copper-based mixed powder into a steel die, prepressing and forming under the pressure of 130MPa, and filling a pressed compact into a high-strength graphite die.
(6) Carrying out vacuum hot pressing in a vacuum hot pressing furnace: the vacuum degree reaches 3 multiplied by 10-3Heating after Pa, wherein the heating rate is 13 ℃/min, the hot-pressing temperature is 840-860 ℃, the hot-pressing pressure is 40-50MPa, and the hot-pressing time is 130 min; after sintering, cooling the composite material blank to room temperature along with the furnace;
(7) hot rolling the prepared composite material blank at 730 ℃, wherein the deformation of a rolled piece is 8.6%; and after hot rolling, heating to 400 ℃, preserving heat for 60min, cooling to 180 ℃, and then cooling to room temperature in air.
Example 2:
the graphene/silicon carbide reinforced copper-based composite material comprises the following components in percentage by weight: 0.45 wt% of graphene, SiC: 0.4 wt%, Ni: 0.05 wt% and the balance copper.
The preparation method of the graphene/silicon carbide reinforced copper-based composite material comprises the following steps:
(1) the method for pretreating the original copper powder comprises the following steps: putting the original copper powder in 5mol/L acetic acid solution and carrying out ultrasonic treatment for 20 min; cleaning with distilled water, sequentially placing in ethanol and propanol, ultrasonic treating for 25min, filtering, and vacuum drying;
pre-mixing the pretreated copper powder, superfine silicon carbide powder and nickel powder in a high-speed mixer for 10 hours to obtain mixed powder;
the granularity of the original copper powder is 1-5 mu m; the granularity of the superfine silicon carbide powder is 20-50 nm; the particle size of the nickel powder is 10-20 μm.
(2) And (2) placing the graphene in absolute ethyl alcohol for ultrasonic dispersion for 70min, adding stearic acid accounting for 0.8 wt% of the mass of the mixed powder and the mixed powder, performing ultrasonic dispersion for 25min at 45 ℃, and mixing and stirring for 12min to obtain a composite powder suspension.
(3) Placing the composite powder suspension in a ball milling tank, vacuumizing, introducing high-purity argon for protection, and then carrying out ball milling; wherein the ball milling time is 5h, the rotating speed is 400r/min, the ball-material ratio is 8: 1; the positive and negative rotation alternation time is 20min, and the acceleration time and the deceleration time are both 15 s.
(4) Placing the slurry obtained after ball milling in an evaporation kettle, drying the slurry to be in a semi-dry state under stirring, and then transferring the slurry to a vacuum oven for full drying treatment to obtain mixed powder; and (3) preserving the temperature of the mixed powder at 255 ℃ for 1.5h to remove stearic acid, thus obtaining the copper-based mixed powder.
(5) And filling the copper-based mixed powder into a steel die, prepressing and forming under the pressure of 100MPa, and filling a pressed blank into a high-strength graphite die.
(6) Carrying out vacuum hot pressing in a vacuum hot pressing furnace: the vacuum degree reaches 2 x 10-3Heating after Pa, wherein the heating rate is 11.5 ℃/min, the hot pressing temperature is 860 ℃, the hot pressing pressure is 50MPa, and the hot pressing time is 120 min; after sintering, cooling the composite material blank to room temperature along with the furnace;
(7) hot rolling the prepared composite material blank at 710 ℃, wherein the deformation of a rolled piece is 7%; and after hot rolling, heating to 360 ℃, preserving heat for 80min, cooling to 160 ℃, and then cooling to room temperature in air.
Example 3:
the graphene/silicon carbide reinforced copper-based composite material comprises the following components in percentage by weight: 0.55 wt% of graphene, SiC: 0.55 wt%, Ni: 0.12 wt% and the balance copper.
The preparation method of the graphene/silicon carbide reinforced copper-based composite material comprises the following steps:
(1) the method for pretreating the original copper powder comprises the following steps: putting the original copper powder in 5mol/L acetic acid solution and carrying out ultrasonic treatment for 20 min; cleaning with distilled water, sequentially placing in ethanol and propanol, ultrasonic treating for 25min, filtering, and vacuum drying;
pre-mixing the pretreated copper powder, superfine silicon carbide powder and nickel powder in a high-speed mixer for 8 hours to obtain mixed powder;
the granularity of the original copper powder is 1-5 mu m; the granularity of the superfine silicon carbide powder is 20-50 nm; the particle size of the nickel powder is 10-20 μm.
(2) And (2) placing the graphene in absolute ethyl alcohol for ultrasonic dispersion for 50min, adding stearic acid accounting for 0.85 wt% of the mass of the mixed powder and the mixed powder, performing ultrasonic dispersion for 30min at 50 ℃, and mixing and stirring for 10min to obtain a composite powder suspension.
(3) Placing the composite powder suspension in a ball milling tank, vacuumizing, introducing high-purity argon for protection, and then carrying out ball milling; wherein the ball milling time is 6h, the rotating speed is 350r/min, the ball-material ratio is 6: 1; the positive and negative rotation alternation time is 22min, and the acceleration time and the deceleration time are both 15 s.
(4) Placing the slurry obtained after ball milling in an evaporation kettle, drying the slurry to be in a semi-dry state under stirring, and then transferring the slurry to a vacuum oven for full drying treatment to obtain mixed powder; and (3) preserving the temperature of the mixed powder at 260 ℃ for 1.5h to remove stearic acid, thus obtaining the copper-based mixed powder.
(5) And filling the copper-based mixed powder into a steel die, prepressing and forming under the pressure of 160MPa, and filling a pressed blank into a high-strength graphite die.
(6) Carrying out vacuum hot pressing in a vacuum hot pressing furnace: the vacuum degree reaches 2 x 10-3Heating after Pa, wherein the heating rate is 11 ℃/min, the hot pressing temperature is 840 ℃, the hot pressing pressure is 40MPa, and the hot pressing time is 100 min; after sintering, cooling the composite material blank to room temperature along with the furnace;
(7) hot rolling the prepared composite material blank at 720 ℃, wherein the deformation of a rolled piece is 7%; and after finishing hot rolling, heating to 380 ℃, preserving heat for 90min, cooling to 170 ℃, and then cooling to room temperature in air.
Example 4:
the graphene/silicon carbide reinforced copper-based composite material comprises the following components in percentage by weight: 0.65 wt% of graphene, SiC: 0.5 wt%, Ni: 0.11 wt% and the balance copper.
The preparation method of the graphene/silicon carbide reinforced copper-based composite material comprises the following steps:
(1) the method for pretreating the original copper powder comprises the following steps: putting the original copper powder in 5mol/L acetic acid solution and carrying out ultrasonic treatment for 20 min; cleaning with distilled water, sequentially placing in ethanol and propanol, ultrasonic treating for 25min, filtering, and vacuum drying;
pre-mixing the pretreated copper powder, superfine silicon carbide powder and nickel powder in a high-speed mixer for 9 hours to obtain mixed powder;
the granularity of the original copper powder is 1-5 mu m; the granularity of the superfine silicon carbide powder is 20-50 nm; the particle size of the nickel powder is 10-20 μm.
(2) And (2) placing the graphene in absolute ethyl alcohol for ultrasonic dispersion for 60min, adding stearic acid accounting for 0.9 wt% of the mass of the mixed powder and the mixed powder, performing ultrasonic dispersion for 23min at 48 ℃, and mixing and stirring for 15min to obtain a composite powder suspension.
(3) Placing the composite powder suspension in a ball milling tank, vacuumizing, introducing high-purity argon for protection, and then carrying out ball milling; wherein the ball milling time is 6h, the rotating speed is 400r/min, the ball-material ratio is 9: 1; the positive and negative rotation alternation time is 20min, and the acceleration time and the deceleration time are both 15 s.
(4) Placing the slurry obtained after ball milling in an evaporation kettle, drying the slurry to be in a semi-dry state under stirring, and then transferring the slurry to a vacuum oven for full drying treatment to obtain mixed powder; and (3) preserving the temperature of the mixed powder at 265 ℃ for 1.5h to remove stearic acid, thus obtaining the copper-based mixed powder.
(5) And filling the copper-based mixed powder into a steel die, prepressing and forming under the pressure of 150MPa, and filling a pressed blank into a high-strength graphite die.
(6) Carrying out vacuum hot pressing in a vacuum hot pressing furnace: the vacuum degree reaches 3 multiplied by 10-3Heating after Pa, wherein the heating rate is 13 ℃/min, the hot pressing temperature is 850 ℃, the hot pressing pressure is 50MPa, and the hot pressing time is 120 min; after sintering, cooling the composite material blank to room temperature along with the furnace;
(7) hot rolling the prepared composite material blank at 730 ℃, wherein the deformation of a rolled piece is 7.5%; and after hot rolling, heating to 400 ℃, preserving heat for 80min, cooling to 170 ℃, and then cooling to room temperature in air.
Example 5:
the graphene/silicon carbide reinforced copper-based composite material comprises the following components in percentage by weight: 0.6 wt% of graphene, SiC: 0.45 wt%, Ni: 0.08 wt% and the balance copper.
The preparation method of the graphene/silicon carbide reinforced copper-based composite material comprises the following steps:
(1) the method for pretreating the original copper powder comprises the following steps: putting the original copper powder in 5mol/L acetic acid solution and carrying out ultrasonic treatment for 20 min; cleaning with distilled water, sequentially placing in ethanol and propanol, ultrasonic treating for 25min, filtering, and vacuum drying;
pre-mixing the pretreated copper powder, superfine silicon carbide powder and nickel powder in a high-speed mixer for 8-10h to obtain mixed powder;
the granularity of the original copper powder is 1-5 mu m; the granularity of the superfine silicon carbide powder is 20-50 nm; the particle size of the nickel powder is 10-20 μm.
(2) And (2) placing graphene in absolute ethyl alcohol, performing ultrasonic dispersion for 50-70min, adding stearic acid accounting for 0.8 wt% of the mass of the mixed powder and the mixed powder, performing ultrasonic dispersion for 230min at 45 ℃, and mixing and stirring for 15min to obtain a composite powder suspension.
(3) Placing the composite powder suspension in a ball milling tank, vacuumizing, introducing high-purity argon for protection, and then carrying out ball milling; wherein the ball milling time is 6h, the rotating speed is 350r/min, the ball-material ratio is 7: 1; the forward and reverse rotation alternation time is 25min, and the acceleration time and the deceleration time are both 15 s.
(4) Placing the slurry obtained after ball milling in an evaporation kettle, drying the slurry to be in a semi-dry state under stirring, and then transferring the slurry to a vacuum oven for full drying treatment to obtain mixed powder; and (3) preserving the temperature of the mixed powder at 265 ℃ for 1.5h to remove stearic acid, thus obtaining the copper-based mixed powder.
(5) And filling the copper-based mixed powder into a steel die, prepressing and forming under the pressure of 130MPa, and filling a pressed compact into a high-strength graphite die.
(6) Carrying out vacuum hot pressing in a vacuum hot pressing furnace: the vacuum degree reaches 3 multiplied by 10-3Heating after Pa, wherein the heating rate is 12.5 ℃/min, the hot pressing temperature is 850 ℃, the hot pressing pressure is 50MPa, and the hot pressing time is 100 min; after sintering, cooling the composite material blank to room temperature along with the furnace;
(7) hot rolling the prepared composite material blank at 715 ℃, wherein the deformation of a rolled piece is 7.6%; and after finishing hot rolling, heating to 380 ℃, preserving heat for 70min, cooling to 175 ℃, and then cooling to room temperature in air.
Example 6:
the graphene/silicon carbide reinforced copper-based composite material comprises the following components in percentage by weight: 0.7 wt% of graphene, SiC: 0.5 wt%, Ni: 0.08 wt% and the balance copper.
The preparation method of the graphene/silicon carbide reinforced copper-based composite material is the same as that in example 1.
Example 7:
the graphene/silicon carbide reinforced copper-based composite material comprises the following components in percentage by weight: 0.3 wt% of graphene, SiC: 0.2 wt%, Ni: 0.02 wt% and the balance copper.
The preparation method of the graphene/silicon carbide reinforced copper-based composite material is the same as that in example 1.
Example 8:
the graphene/silicon carbide reinforced copper-based composite material comprises the following components in percentage by weight: 0.8 wt% of graphene, SiC: 0.5 wt%, Ni: 0.2 wt% and the balance copper.
The preparation method of the graphene/silicon carbide reinforced copper-based composite material is the same as that in example 2.
The graphene/silicon carbide reinforced copper-based composite materials of examples 1 to 8 were subjected to performance tests, and the results are shown in table 1.
TABLE 1 Properties of graphene/silicon carbide reinforced copper-based composites
Figure BDA0002331651790000111
As can be seen from Table 1, the graphene/silicon carbide reinforced copper-based composite material prepared by the method has high strength and hardness. Meanwhile, the conductive coating has better conductivity and excellent comprehensive performance.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. The graphene/silicon carbide reinforced copper-based composite material is characterized by comprising the following components in percentage by weight: 0.3-0.8 wt% of graphene, SiC: 0.2 to 0.6 wt%, Ni: 0.02-0.2 wt% and the balance of copper.
2. The graphene/silicon carbide reinforced copper-based composite material according to claim 1, wherein the composite material comprises the following components in percentage by weight: 0.45-0.7 wt% of graphene, SiC: 0.4 to 0.55 wt%, Ni: 0.05 to 0.12 weight percent of copper and the balance of copper.
3. The graphene/silicon carbide reinforced copper-based composite material according to claim 2, wherein the composite material comprises the following components in percentage by weight: 0.65 wt% of graphene, SiC: 0.5 wt%, Ni: 0.11 wt% and the balance copper.
4. The graphene/silicon carbide reinforced copper-based composite material according to claim 2, wherein the composite material comprises the following components in percentage by weight: 0.6 wt% of graphene, SiC: 0.45 wt%, Ni: 0.08 wt% and the balance copper.
5. The method for preparing the graphene/silicon carbide reinforced copper-based composite material according to any one of claims 1 to 4, comprising the steps of:
(1) pretreating the original copper powder; mixing and premixing the treated copper powder, superfine silicon carbide powder and nickel powder in a high-speed mixer for 8-10h to obtain mixed powder;
(2) placing graphene in absolute ethyl alcohol, performing ultrasonic dispersion for 50-70min, adding stearic acid with the mass of 0.8-1 wt% of the mixed powder and the mixed powder, performing ultrasonic dispersion for 20-30min at 45-50 ℃, and mixing and stirring for 10-15min to obtain a composite powder suspension;
(3) placing the composite powder suspension in a ball milling tank, vacuumizing, introducing high-purity argon for protection, and then carrying out ball milling;
(4) placing the slurry obtained after ball milling in an evaporation kettle, drying the slurry to be in a semi-dry state under stirring, and then transferring the slurry to a vacuum oven for full drying treatment to obtain mixed powder; keeping the mixed powder at the temperature of 255-;
(5) filling the copper-based mixed powder into a steel die, performing pre-pressing forming under the pressure of 100-160MPa, and then filling a pressed blank into a high-strength graphite die;
(6) carrying out vacuum hot pressing in a vacuum hot pressing furnace: the vacuum degree reaches 2-3 multiplied by 10-3Heating after Pa, wherein the hot pressing temperature is 840-860 ℃, the hot pressing pressure is 40-50MPa, and the hot pressing time is 100-130 min; after sintering, cooling the composite material blank to room temperature along with the furnace;
(7) carrying out hot rolling on the prepared composite material blank at the temperature of 710-730 ℃; after finishing hot rolling, heating to 400 ℃ at 360 ℃, preserving the heat for 60-90min, cooling to 180 ℃, and then air-cooling to room temperature.
6. The preparation method of the graphene/silicon carbide reinforced copper-based composite material according to claim 5, wherein in the step (1), the pretreatment method of the raw copper powder comprises the following steps: putting the original copper powder in 5mol/L acetic acid solution and carrying out ultrasonic treatment for 20 min; cleaning with distilled water, sequentially adding into ethanol and propanol, ultrasonic treating for 25min, filtering, and vacuum drying.
7. The preparation method of the graphene/silicon carbide reinforced copper-based composite material according to claim 5, wherein in the step (1), the particle size of the raw copper powder is 1-5 μm; the granularity of the superfine silicon carbide powder is 20-50 nm; the particle size of the nickel powder is 10-20 μm.
8. The method for preparing the graphene/silicon carbide reinforced copper-based composite material as claimed in claim 5, wherein in the step (3), the ball milling time is 5-6.5h, the rotation speed is 300-400r/min, and the ball-to-material ratio is 6-9: 1; the positive and negative rotation alternation time is 20-25min, and the acceleration time and the deceleration time are both 15 s.
9. The method for preparing the graphene/silicon carbide reinforced copper-based composite material according to claim 5, wherein in the step (6), the temperature rise rate is 11-13 ℃/min.
10. The preparation method of the graphene/silicon carbide reinforced copper-based composite material according to claim 5, wherein in the step (7), the deformation of a rolled piece is 7-9%.
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