CN115838880B - Preparation method of copper-graphene composite material - Google Patents
Preparation method of copper-graphene composite material Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to the field of high-conductivity metal composite materials, in particular to a preparation method of a copper-graphene composite material, which has the characteristics of high operability, stable product quality, excellent conductivity and low manufacturing cost, and comprises the following steps: (1) producing copper@polymer powder by mechanical alloying; (2) obtaining a high-compactness bar using cold isostatic pressing; (3) Further adopting zone melting to obtain a high-carbon solid solubility and regular porous bar; (4) Through adjustment of a heat treatment mechanism, carbon atoms in the matrix are segregated to the surface of the hole wall to grow graphene in situ; (5) Finally, the high-conductivity material with metallurgical bonding matrix and various specifications is obtained by a hot-pressing continuous rolling mode.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a copper-graphene composite material.
Background
Copper has higher carrier (electron) concentration, graphene has extremely high carrier migration speed, and the copper/graphene composite material formed by effectively combining the copper and the graphene can obtain conductivity superior to that of pure copper and even silver, and the copper/graphene composite material has become an important development field in the industry and the academy and represents the development direction of high-conductivity materials.
At present, the preparation of the copper graphene composite material mainly comprises two technical routes of a material mixing method and a copper foil in-situ growth graphene lamination method. The main technical principle of the mixing method is that copper (particles, blocks and the like) and graphene (or graphene oxide and the like) powder are physically mixed, and then casting, hot isostatic pressing, hot extrusion and the like are adopted to compact and shape the material, so that the mixing method is difficult to achieve a higher conductivity level under the influence of the dispersion uniformity, orientation uniformity and maximum effective addition amount of the graphene in the copper. The method for in-situ growth of the graphene on the copper foil adopts a CVD method, and then the multi-layer graphene copper foil is subjected to hot pressing to realize interlayer metallurgical bonding, so that a high-conductivity material with a certain thickness is obtained; the method has the defects that the growth of copper foil graphene with larger size (generally with the size of below 50 cm) cannot be realized due to the limitation of the CVD technology in the current stage, the oxidation prevention treatment of the copper foil and the graphene needs to be enhanced, the block material is formed in the subsequent hot press forming, and the shape of a target product can be obtained through complex mechanical processing.
Therefore, the technical limitation of the copper graphene composite material at the present stage is improved by comprehensively considering the high conductivity and the manufacturing cost, and the composition is a hot spot for research in the field.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a copper-graphene composite material, and the composite material prepared by the method provided by the invention has better performance.
The invention provides a preparation method of a copper-graphene composite material, which comprises the following steps:
Preparing copper and a polymer into copper-polymer powder by adopting a mechanical alloying method;
carrying out cold isostatic pressing on the copper-polymer powder to obtain a bar;
Carrying out zone smelting on the bar material to obtain a porous bar material;
Carrying out heat treatment on the porous bar material to obtain an intermediate product;
And carrying out hot press molding on the intermediate product to obtain the copper-graphene composite material.
Preferably, the polymer is a polymer containing C, H elements.
Preferably, the polymer is selected from one or more of polyethylene, polystyrene and polymethyl methacrylate.
Preferably, the mass ratio of the polymer to the copper is (0.05% -1%): 1.
Preferably, the mechanical alloying method is ball milling, and the mechanical alloying is carried out in a high-speed ball mill; the time of the mechanical alloying is 5-48 hours.
Preferably, the particle size of the copper-polymer powder is 30 to 50 μm.
Preferably, copper pipe is used to wrap copper-polymer powder in the cold isostatic pressing process, the pressure in the cold isostatic pressing process is 100-250 MPa, and the pressure maintaining time is 5-60 min.
Preferably, the zone melting adopts an electromagnetic induction heating mode; the pulling speed in the zone smelting process is 2-10 mm/min.
Preferably, the temperature of the heat treatment is 750-950 ℃; the heat preservation time of the heat treatment is 1-15 min.
Preferably, the hot press molding method is hot rolling, and the speed of the hot rolling is 3-20 mm/min.
The invention follows the segregation growth mechanism of graphene on the metal surface, and realizes the capability of growing graphene in a metal material matrix for the first time by optimizing a solid carbon source, regulating and controlling copper crystal grains and a graphene growth interface, and combines the intrinsic properties of copper/graphene with high conductivity to realize an innovative and applicable scheme.
Compared with the existing copper/graphene composite material technology, the graphene in the invention is self-grown on the regular gas hole wall in the copper matrix in situ, so that the quality fluctuation of the graphene raw material and the difficulty of the dispersion uniformity of the graphene in the copper aggregate in the mixing method are avoided, and the generated graphene has good consistency and good bonding property with copper. The graphene is realized by segregation growth of carbon atoms in the matrix, and the process has physical isolation capability to ambient air and moisture, so that the problem that copper foil and graphene are easy to oxidize in a CVD method is avoided, and the difficulty in storage and transportation is eliminated. The polymer solid carbon source is adopted, the cost is obviously lower than that of a CVD method which takes H 2 and CH 4 as gaseous carbon sources, and the popularization and the application with high cost performance are easier to realize. The regional smelting process is adopted for many times in the process procedure, the intrinsic characteristics of metallurgical impurity removal and realization of large-size copper grains are achieved, and adverse effects of scattering and diffusion in the electron transmission process are reduced by the material, so that the conductivity level is further improved. The material hot rolling forming process can adopt rollers with different cross section shapes, has strong process control capability, and can directly form wires and strips with different specification requirements.
The invention can realize the manufacture of the high-conductivity material, has the advantages of strong forming capability, low process cost and high manufacturing efficiency, and is beneficial to promoting the industrial scale application of the high-conductivity material. The high-conductivity material product obtained by the invention is suitable for application scenes such as power transmission loss reduction, electromechanical product energy efficiency improvement and the like, and has wide market prospect.
Drawings
Fig. 1 is a process flow diagram of preparing a copper-graphene composite material according to an embodiment of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a copper-graphene composite material, which comprises the following steps:
Preparing copper and a polymer into copper-polymer powder by adopting a mechanical alloying method;
carrying out cold isostatic pressing on the copper-polymer powder to obtain a bar;
Carrying out zone smelting on the bar material to obtain a porous bar material;
Carrying out heat treatment on the porous bar material to obtain an intermediate product;
And carrying out hot press molding on the intermediate product to obtain the copper-graphene composite material.
In the present invention, the preparation method of the copper-polymer powder preferably includes:
Mechanically alloying copper and polymer to obtain copper-polymer powder.
In the present invention, the copper material is preferably copper powder; the copper powder is preferably spherical particles obtained by an atomization method or particles obtained by a crushing method and dendrite particles; the particle size of the copper powder is preferably 5 to 80. Mu.m, more preferably 10 to 70. Mu.m, still more preferably 20 to 60. Mu.m, and most preferably 30 to 50. Mu.m.
In the present invention, oxidation is preferably removed by reduction with heated H 2 before use of the copper powder.
In the present invention, the polymer is preferably a polymer powder containing C, H elements, more preferably one or a mixture of Polyethylene (PE), polystyrene (PS), polymethyl methacrylate (PMMA) and other organic substances with high C, H element content in a solid state at normal temperature.
In the present invention, the polymer is preferably dried with hot air before use.
In the invention, the mass ratio of the polymer to the copper is preferably (0.05% -1%): 1, more preferably (0.1% -0.5%): 1, most preferably 0.3%:1.
In the present invention, the method of mechanical alloying is preferably ball milling, preferably mechanical alloying is performed in a high-speed ball mill; the time for the mechanical alloying is preferably 5 to 48 hours, more preferably 10 to 36 hours, still more preferably 20 to 30 hours, most preferably 25 hours.
In the invention, the cold isostatic pressing can realize a compact and homogenized rod-shaped copper/polymer mixed material, and a bar with high compactness is obtained.
In the present invention, the cold isostatic pressing is preferably further comprising:
Sieving the copper-polymer powder, removing broken polymer fine powder by sieving, and taking the copper-polymer powder remained on a screen for standby, wherein the powder is copper-polymer particles with good mechanical alloying effect; the particle size of the remaining copper-polymer powder is preferably 30 to 50. Mu.m, more preferably 35 to 45. Mu.m, most preferably 40. Mu.m.
In the invention, a copper pipe with an opening at the upper end and a closed lower end is preferably selected in the cold isostatic pressing process, the copper pipe is placed in a steel mould, copper-polymer particles obtained by screening are filled into the copper pipe, static pressure is applied from top to bottom by a pressure head at normal temperature, and the pressure is maintained for a period of time, so that the integral densification of the particles in the pipe is realized.
In the present invention, the pressure during the cold isostatic pressing is preferably 100 to 250MPa, more preferably 150 to 200MPa; the pressure holding time is preferably 5 to 60 minutes, more preferably 10 to 30 minutes, and most preferably 20 minutes. In the invention, the reasonable cold isostatic pressing process is beneficial to minimizing gaps generated by loose loading of particles, so as to realize the densification of materials in the copper pipe; preferably, the process of sectionally filling particles and repeatedly cold isostatic pressing can be adopted to promote the uniform densification of the materials in the copper pipe.
The invention does not make limiting requirements on the selection of the length, diameter, wall thickness and other dimensions of the copper pipe, and is suitable for facilitating the development of the front and back working procedures.
In the invention, after the cold pressing treatment is finished, the obtained densification tube cladding is preferably taken out of the steel die, and the upper opening of the copper tube is sealed by adopting modes such as welding, hot melting and the like.
According to the invention, the zone melting process can realize the regulation and control of the temperature field and the temperature gradient in the melting process, and the porous copper bar with higher C atom solid solubility and regular directional distribution of pores is obtained.
In the invention, the zone melting preferably adopts an electromagnetic induction heating mode; the "tube-wrapped" bar thus obtained is preferably pulled vertically downwards, preferably at a speed of 2 to 10mm/min, more preferably 3 to 8mm/min, most preferably 4 to 6mm/min. In the invention, in the zone smelting process, the copper rod and the coil heated by electromagnetic induction are relatively and vertically applied, thereby not only playing the role of smelting the copper rod, but also realizing the role of regulating and controlling the solidification temperature field; when the bar is positioned in the coil area, the copper pipe and the metal components in the pipe are melted by heat, and the melting point of the copper is obviously higher than that of the polymer, so that the polymer is decomposed into H, C and other elements at the temperature far higher than the melting point; h atoms in the melt are polymerized into H 2 molecules, and are further combined into air holes and grow; the C atoms obtained by pyrolysis are dispersed in the micro-zone melt and are dissolved in the matrix along with the solidification of copper, so that the C atoms become a carbon source for promoting the segregation growth of graphene in the later stage; the bar moves downwards relative to the electromagnetic coil, equivalently, the molten zone moves upwards, and the copper liquid separated from the molten zone is quickly solidified, so that a dynamic temperature gradient is formed, copper grains grow directionally, and H 2 pores which are continuously polymerized and grown are influenced to be distributed in a regular and directional manner in the copper matrix.
In the invention, the zone smelting is preferably performed in a sealed hearth, and the introducing pressure of Ar 2,Ar2 after the hearth is vacuumized in the zone smelting process is preferably 0.5-2 MPa, more preferably 1-1.5 MPa; plays a role in preventing the melt from oxidizing and pressing H 2 from overflowing the surface of the copper bar.
In the present invention, the heat treatment is preferably performed in a vacuum annealing furnace; the temperature of the heat treatment is preferably 750-950 ℃, more preferably 800-900 ℃, and most preferably 950 ℃; the heat-preserving time of the heat treatment is preferably 1 to 15min, more preferably 5 to 10min; the cooling mode after the heat treatment and heat preservation is finished is preferably air cooling.
According to the invention, through the regulation and control of a heat treatment mechanism, C atoms in a copper matrix are segregated to the surface of an air hole, and grow into graphene; preferably, placing the carbon-rich regular porous copper obtained by smelting the area in a vacuum annealing furnace for heat treatment, quickly heating to a fixed temperature of between 750 and 950 ℃, keeping the temperature for 1 to 15 minutes at a constant temperature, enabling C atoms existing at crystal grains or crystal boundaries of a copper matrix to segregate to the surfaces of H 2 holes, growing into high-quality few-layer or single-layer graphene crystals under the 'etching' effect and copper catalytic capability of H 2 in the holes, and then taking out a copper bar for quick cooling; the process follows a graphene segregation growth mechanism, the surface of the air hole in the matrix is an interface for graphene growth, and regular, long continuous and directional air holes guide the uniform distribution of graphene in the copper rod.
In the present invention, the graphene composite material is preferably densified and formed into a target shape by hot press molding, and hot press molding may be performed by hot rolling, hot isostatic pressing, or the like. The purpose of the hot pressing process is to flatten the air holes and realize the compaction of the material under the diffusion action of copper atoms; when the porous bar is formed by hot rolling, the porous bar can be rolled into a copper graphene composite material with a round, square or other long continuous cross section and good metallurgical bonding by changing rollers with different shapes.
In the present invention, the temperature of the hot-rolled molding is preferably 750 to 1050 ℃, more preferably 800 to 1000 ℃, and most preferably 900 ℃; the pressure is preferably 20 to 50MPa, more preferably 30 to 40MPa, most preferably 35MPa; the speed is preferably 2 to 15mm/min, more preferably 5 to 10mm/min, most preferably 6 to 8mm/min. In the present invention, the speed of the hot rolling is preferably 3 to 20mm/min, more preferably 5 to 10mm/min.
In the present invention, the temperature of the hot isostatic pressing is preferably 700 to 900 ℃, more preferably 750 to 850 ℃, and most preferably 800 ℃; the pressure is preferably 50 to 100MPa, more preferably 60 to 90MPa, most preferably 70 to 80MPa; the time is preferably 30 to 120 minutes, more preferably 50 to 100 minutes, and most preferably 60 to 80 minutes.
The invention provides a manufacturing technology capable of realizing copper graphene composite materials, which has the technical route and key working procedures shown in figure 1 and mainly comprises mechanical alloying of copper powder and solid polymer, realization of cold isostatic pressing of densified bar-shaped mixture, realization of regional smelting of porous carbon-containing copper bars, element bias heat treatment of obtaining graphene in a matrix and hot press forming technology for densification forming of copper graphene materials; preferably comprises:
(1) Manufacturing copper@polymer powder by adopting mechanical alloying;
(2) Obtaining a high-compactness bar by using cold isostatic pressing;
(3) Further adopting zone melting to obtain a high-carbon solid solubility and regular porous bar;
(4) Through heat treatment regulation and control, carbon atoms in the matrix are segregated to the surface of the hole wall, so that graphene grows in situ;
(5) Finally, the high-conductivity material with metallurgical bonding matrix and various specifications is obtained by a hot-pressing continuous rolling mode.
The method preferably specifically comprises the following steps:
1. Mechanical alloying: copper @ polymer powder was achieved.
1.1, The copper powder and the polymer powder containing C, H elements are matched according to a proportion, and are put into a high-speed ball mill for mechanical alloying. Copper powder can be spherical particles obtained by an atomization method, or particles or dendrite particles obtained by a crushing method, the particle size is 5-80 mu m, and oxidation is removed by adopting methods such as heating H 2 reduction before use; the polymer powder can be solid Polystyrene (PS), polymethyl methacrylate (PMMA), PE (polyethylene) and other organic matters or mixtures with high C, H element content at normal temperature, and is dried by hot air before use; the weight percentage of the polymer and copper powder is 0.05-1%; the mechanical alloying time is 5-48 hours.
1.2 Sieving the powder after high-speed ball milling mechanical alloying, sieving out broken polymer fine powder and particles with overlarge and undersize particle sizes, and taking copper@polymer particles with the particle size range of 30-50 microns for standby.
2 Cold isostatic pressing: a dense and homogenized rod-shaped copper/polymer hybrid material is achieved.
2.1, Taking a copper pipe with an open upper end and a closed lower end, placing the copper pipe in a steel mould, filling the screened copper@polymer particles into the copper pipe, applying static pressure from top to bottom by a pressure head at normal temperature, and maintaining the pressure for a period of time to realize the integral densification of the particles in the pipe. The reasonable cold isostatic pressing process is favorable for minimizing gaps generated by loose loading of particles and realizing the densification of materials in the copper pipe. In particular, the process of sectionally filling particles and repeatedly cold isostatic pressing can be adopted, so that the uniformity of the density of the materials in the copper pipe is improved.
The selection of the length, diameter, wall thickness and other dimensions of the copper pipe is not limited, so that the post-process zone melting and hot pressing are convenient to develop.
2.2, Taking out the densification tube wrapping material from the steel die, and sealing the upper opening of the copper tube by adopting modes of welding, hot melting and the like.
3. Zone melting: through regulating and controlling the temperature field and the temperature gradient in the copper melting-condensing process, the excessive solid solution of C atoms in the matrix and the regular directional growth of pores are realized, namely the carbon-rich regular porous copper.
3.1 Zone melting is performed by adopting an electromagnetic induction heating mode aiming at a 'tube cladding' rod-shaped material obtained by cold isostatic pressing. In the zone melting process, the bar is pulled vertically downwards, and the pulling speed can be 2mm/min to 10mm/min.
3.2 In the regional smelting process, the coil heated by electromagnetic induction is vertically applied relative to the copper rod, so that the effect of melting the copper rod is achieved, and the effect of regulating and controlling the solidification temperature field is also achieved.
When the bar is in the coil area, the copper pipe and the metal component in the pipe are melted by heating, and the polymer is decomposed into H, C and other elements by heating. H atoms are polymerized into H 2 molecules, and are further combined into air holes and grow; the polymer is subjected to a heating temperature far above the melting point, and the cracked C atoms can be dispersed in the micro-zone melt and are dissolved in the matrix along with the solidification of copper, so that the polymer becomes a carbon source for the late segregation growth of graphene.
The bar moves downwards relative to the electromagnetic coil, equivalently, the molten zone moves upwards, and the copper liquid separated from the molten zone is quickly solidified, so that a dynamic temperature gradient is formed, copper grains grow directionally, and H 2 pores which are continuously polymerized and grown are influenced to be distributed in a regular and directional manner in the copper matrix.
3.3 Zone melting process is carried out in a sealed hearth, ar 2 is introduced after the hearth is vacuumized, the pressure is 0.5-2 MPa, and the functions of preventing melt oxidation and pressing H 2 from overflowing the surface of the copper rod are achieved.
4. Segregation growth: through the regulation and control of the heat treatment mechanism, C atoms in the copper matrix are segregated to the surface of the air hole, and are nucleated and grown into graphene.
And (3) placing the carbon-rich regular porous copper obtained by smelting the area into a vacuum annealing furnace for heat treatment, quickly heating to a fixed temperature of 750-950 ℃, keeping the constant temperature for 1-15 min, enabling C atoms existing at crystal grains or crystal boundaries of a copper matrix to segregate to the surfaces of H 2 air holes, growing into high-quality few-layer or single-layer graphene crystals under the 'etching' effect and copper catalytic capability of H 2 in the holes, and then taking out the copper rod for quick cooling.
The process follows a graphene segregation growth mechanism, the surface of the air hole in the matrix is an interface for graphene growth, and regular, long continuous and directional air holes guide the uniform distribution of graphene in the copper rod.
5. Hot press molding: and (3) densifying and forming the copper graphene composite material through hot press forming.
The porous copper bar with the segregated graphene grown is subjected to hot press forming, the material can be densified by adopting hot continuous rolling or hot isostatic pressing and other modes, the pressure and time parameters can be controlled, and the process flattens the air holes and realizes the densification of the material under the diffusion action of copper atoms. When the porous bar is formed by hot rolling, the porous bar can be rolled into a copper graphene composite material with a round, square or other long continuous cross section and good metallurgical bonding by changing rollers with different shapes.
In the invention, graphene grows on the regular gas hole wall in the copper matrix in situ, so that the quality fluctuation of the graphene raw material and the difficulty of the dispersion uniformity of the graphene in the copper aggregate in the mixing method are avoided, and the generated graphene has good consistency and good combination with copper. The graphene is realized by segregation growth of carbon atoms in the matrix, the process has physical isolation to ambient air and moisture, the problem of easy oxidization of copper foil graphene by a CVD method is avoided, and the difficulties of storage and transportation are eliminated. The polymer solid carbon source is adopted, the cost is obviously lower than that of a CVD method which takes H 2 and CH 4 as gaseous carbon sources, and the popularization and the application with high cost performance are easier to realize. The regional smelting process is adopted for many times in the process procedure, the intrinsic characteristics of metallurgical impurity removal and realization of large-size copper grains are achieved, and adverse effects of scattering and diffusion in the electron transmission process are reduced by the material, so that the conductivity level is further improved. The material hot rolling forming process can adopt rollers with different cross section shapes, has strong process control capability, and can directly form wires and strips with different specification requirements.
Example 1
The preparation method of the copper-graphene composite material comprises the following steps:
Firstly, weighing spherical copper powder and polyethylene powder according to the mass ratio of polyethylene to copper powder of 0.25%; after simply mixing the powder, putting the powder into a high-speed ball mill for mechanical alloying, and setting the high-speed ball milling at 800r/min for 12 hours; the mechanically alloyed copper@polyethylene powder is sieved by a multi-stage screen, and the powder with the particle size of 30-50 mu m is reserved for standby.
Selecting a copper pipe with the outer diameter of 20mm and the inner diameter of 16mm and the lower end sealed, loosely filling the copper@polyethylene powder obtained by screening into the copper pipe, and placing the copper pipe in a steel mould which is conformal with the copper pipe. Applying 180MPa pressure from the open end of the copper pipe at normal temperature, and maintaining the pressure for 20 minutes; and sealing the upper end of the copper pipe by adopting a welding mode.
Step three, vertically penetrating the copper pipe through an electromagnetic induction coil of the zone melting furnace and clamping and fixing the copper pipe; vacuumizing a regional smelting hearth, filling Ar 2, and keeping Ar 2 pressure at 1.5MPa in the regional smelting process; and starting electromagnetic induction heating current, keeping the copper pipe to move downwards at the speed of 5mm/min, and realizing the bottom-up melting-solidification process of copper@polyethylene powder in the copper pipe and the pipe, so that the copper rod obtains high C solid solubility and a regular porous structure.
And fourthly, placing the copper bar after zone-melting smelting in a vacuum heat treatment furnace, heating to 900 ℃, preserving heat for 10 minutes, taking out the copper bar, and naturally cooling in air to enable C atoms dissolved in a copper matrix to segregate to pore interface nucleation and grow into graphene.
And fifthly, hot-pressing and tandem rolling the copper bar after heat treatment, wherein the rolling temperature is 950 ℃, the rolling pressure is 25MPa, the rolling speed is 15mm/min, the air holes are closed, the Cu atoms at the two sides of the interface of the original air holes are mutually diffused to realize grain fusion, and the graphene is dispersed in the copper matrix.
Copper grains and graphene of the copper-graphene composite material prepared in example 1 show orientation consistency, and metallographic observation can find that the size of the copper grains reaches the centimeter level, and the conductivity of the obtained material is 105% IACS according to a conductivity measurement van der Waals method test of a T/CSTM00591-2022 graphene-copper film material.
Example 2
The preparation method of the copper-graphene composite material comprises the following steps:
Mixing the mass ratio of polyethylene to polystyrene and the like with dendrite copper powder, wherein the total addition amount of the polyethylene and the polystyrene is 0.3% of the mass of the copper powder; after simply mixing the powder, putting the powder into a high-speed ball mill for mechanical alloying, and setting the high-speed ball milling at 600r/min for 24 hours; the mechanically alloyed copper@polymer powder is sieved by a multi-stage screen, and the powder with the particle size of 30-50 mu m is reserved for standby.
Selecting a copper pipe with the outer diameter of 20mm and the inner diameter of 16mm and a sealed lower end, loosely filling the screened copper@polymer powder into the copper pipe, and placing the copper pipe in a steel mould which is conformal with the copper pipe; applying 150MPa pressure from the open end of the copper pipe at normal temperature, and maintaining the pressure for 20 minutes; and sealing the upper end of the copper pipe by adopting a welding mode.
Step three, vertically penetrating the copper pipe through an electromagnetic induction coil of the zone melting furnace and clamping and fixing the copper pipe; vacuumizing a regional smelting hearth, filling Ar 2, and keeping Ar 2 pressure at 1.5MPa in the regional smelting process; and starting electromagnetic induction heating current, keeping the copper pipe to move downwards at the speed of 3mm/min, and realizing the melting-solidifying process of the copper pipe and copper@polymer powder in the copper pipe from bottom to top, so that the copper rod obtains high C solid solubility and a regular porous structure.
And fourthly, placing the copper bar after zone-melting smelting in a vacuum heat treatment furnace, heating to 780 ℃, preserving heat for 8 minutes, taking out the copper bar, and naturally cooling in air to enable C atoms dissolved in a copper matrix to segregate to pore interface nucleation and grow into graphene.
And fifthly, hot-pressing and tandem rolling the copper bar after heat treatment, wherein the rolling temperature is 900 ℃, the rolling pressure is 30MPa, the rolling speed is 6mm/min, the air holes are closed, the Cu atoms at the two sides of the interface of the original air holes are mutually diffused to realize grain fusion, and the graphene is dispersed in the copper matrix.
The copper crystal grains and graphene of the copper-graphene composite material prepared in example 2 show orientation consistency, the size of the copper crystal grains along the radial direction of a copper rod reaches the centimeter level, and the conductivity of the composite material is 102% IACS.
Example 3
The preparation method of the copper-graphene composite material comprises the following steps:
Firstly, weighing spherical copper powder and methyl methacrylate particles according to the mass ratio of polymethyl methacrylate to copper powder of 0.8%; after the materials are simply mixed, the materials are put into a high-speed ball mill for mechanical alloying, and the high-speed ball milling is carried out for 36 hours under the condition of setting 600 r/min; the mechanically alloyed copper@polymethyl methacrylate powder is sieved by a multi-stage screen, and the powder with the particle size of 30-50 mu m is reserved for standby.
Selecting a copper pipe with the outer diameter of 20mm and the inner diameter of 16mm and a sealed lower end, loosely filling the copper@polymethyl methacrylate powder obtained by screening into the copper pipe, and placing the copper pipe in a steel mould which is conformal with the copper pipe; applying 200MPa pressure from the open end of the copper pipe at normal temperature, and maintaining the pressure for 30 minutes; and sealing the upper end of the copper pipe by adopting a welding mode.
Step three, vertically penetrating the copper pipe through an electromagnetic induction coil of the zone melting furnace and clamping and fixing the copper pipe; vacuumizing a regional smelting hearth, filling Ar 2, and keeping Ar 2 pressure at 1.5MPa in the regional smelting process; and starting electromagnetic induction heating current, keeping the copper pipe to move downwards at the speed of 3mm/min, and realizing the bottom-up melting-solidification process of copper@polymethyl methacrylate powder in the copper pipe and the copper pipe, so that the copper rod obtains high C solid solubility and a regular porous structure.
And fourthly, placing the copper bar after zone-melting smelting in a vacuum heat treatment furnace, heating to 850 ℃, preserving heat for 10 minutes, taking out the copper bar, and naturally cooling in air to enable C atoms dissolved in a copper matrix to segregate to pore interface nucleation and grow into graphene.
And fifthly, hot-pressing and tandem rolling the copper bar after heat treatment, wherein the rolling temperature is 850 ℃, the rolling pressure is 50MPa, the rolling speed is 5mm/min, the air holes are closed, the Cu atoms at the two sides of the interface of the original air holes are mutually diffused to realize grain fusion, and the graphene is dispersed in the copper matrix.
The copper crystal grains and graphene of the copper-graphene composite material prepared in the embodiment 3 show orientation consistency, the size of the copper crystal grains along the radial direction of a copper rod reaches the centimeter level, and the conductivity of the composite material is 101% IACS.
The key of the invention is that the adopted process route combination mode; adopting PS, PE, PMMA and other polymers as solid carbon sources and adopting a mechanical alloying combination method with copper powder; a method for realizing bar densification by adopting cold isostatic pressing; in particular to a process method for manufacturing regular porous and high C atom solid solubility by adopting zone melting and polymer thermal decomposition; and a method for growing graphene on the Cu surface by segregation through heat treatment regulation and control is realized.
While the application has been described and illustrated with reference to specific embodiments thereof, the description and illustration is not intended to limit the application. It will be apparent to those skilled in the art that various changes may be made in this particular situation, material, composition of matter, substance, method or process without departing from the true spirit and scope of the application as defined by the following claims, so as to adapt the objective, spirit and scope of the application. All such modifications are intended to be within the scope of this appended claims. Although the methods disclosed herein have been described with reference to particular operations being performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form an equivalent method without departing from the teachings of the present disclosure. Thus, unless specifically indicated herein, the order and grouping of operations is not a limitation of the present application.
Claims (5)
1. A method for preparing a copper-graphene composite material, comprising:
Preparing copper and a polymer into copper-polymer powder by adopting a mechanical alloying method;
The polymer is selected from one or more of polyethylene, polystyrene and polymethyl methacrylate, and the mass ratio of the polymer to copper is (0.05% -1%): 1, a step of;
carrying out cold isostatic pressing on the copper-polymer powder to obtain a bar;
Carrying out zone smelting on the bar material to obtain a porous bar material;
The zone smelting adopts an electromagnetic induction heating mode, and the pulling speed in the zone smelting process is 2-10 mm/min;
Carrying out heat treatment on the porous bar material to obtain an intermediate product;
the temperature of the heat treatment is 750-950 ℃, and the heat preservation time of the heat treatment is 1-15 min;
And carrying out hot press molding on the intermediate product to obtain the copper-graphene composite material.
2. The method of claim 1, wherein the method of mechanical alloying is ball milling, and the mechanical alloying is performed in a high-speed ball mill; the time of the mechanical alloying is 5-48 hours.
3. The method according to claim 1, wherein the particle size of the copper-polymer powder is 30-50 μm.
4. The method according to claim 1, wherein copper pipe is used to encapsulate the copper-polymer powder during cold isostatic pressing, the pressure applied during cold isostatic pressing is 100-250 MPa, and the dwell time is 5-60 min.
5. The method according to claim 1, wherein the hot press forming method is hot rolling, and the speed of the hot rolling is 3-20 mm/min.
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