CN110560698A - preparation method of carbon nano tube reinforced copper-based composite material - Google Patents
preparation method of carbon nano tube reinforced copper-based composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 146
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 146
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 40
- 239000010949 copper Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 52
- 238000000498 ball milling Methods 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011812 mixed powder Substances 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 238000007747 plating Methods 0.000 claims abstract description 14
- 238000007731 hot pressing Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 28
- 229910002804 graphite Inorganic materials 0.000 claims description 19
- 239000010439 graphite Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- 230000009467 reduction Effects 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000004886 process control Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 230000005408 paramagnetism Effects 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 4
- 238000003825 pressing Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 9
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 9
- 230000005415 magnetization Effects 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
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- 238000006243 chemical reaction Methods 0.000 description 4
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 3
- 229910002666 PdCl2 Inorganic materials 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
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- 238000003466 welding Methods 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 2
- 239000011156 metal matrix composite Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
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- B22F1/0003—
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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
- B22F3/02—Compacting only
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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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
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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
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Abstract
the invention discloses a preparation method of a carbon nano tube reinforced copper-based composite material, which comprises the following steps: preparing sheet copper powder, and carrying out nickel plating treatment on the carbon nano tube to obtain a nickel-plated carbon nano tube; mixing the flake copper powder and the nickel-plated carbon nano tube, performing ball milling treatment to obtain mixed powder, and performing rotary orientation treatment on the mixed powder under a magnetic field to obtain a composite powder compact; and pressing and sintering the composite powder to obtain the carbon nano tube reinforced copper-based composite material. The method adopts the steps of preparing flaky copper powder in advance, and simultaneously carrying out nickel plating treatment on the carbon nano tube to increase the paramagnetism of the carbon nano tube; the mixed powder of the flake copper powder and the nickel-plated carbon nano tube is subjected to magnetic field rotation orientation treatment, and the carbon nano tube oriented reinforced copper-based composite material is prepared after hot-pressing sintering, so that the mechanical and physical properties of the material are improved.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a preparation method of a carbon nano tube reinforced copper-based composite material.
background
Metal Matrix Nanocomposites (MMNCs) are a new material consisting of nanoreinforcements added to a metal or alloy matrix by physical or chemical means. Compared with large-size reinforced materials, the nano reinforcement has the advantages of surface effect, small-size effect and macroscopic quantum tunneling effect, and shows unique physical, chemical and mechanical properties. The MMNCs can exert the synergistic effect of each component, has the excellent characteristics of the nano reinforcement and the metal matrix, such as high specific strength, high temperature resistance, corrosion resistance, good electric conduction and heat conduction performance and the like, and is widely applied to the high-technology fields of machinery, electronics, national defense and military industry and the like.
the carbon nanotube is a novel one-dimensional carbon material discovered by Iijima, has the characteristics of extremely small pipe diameter, ultrahigh length-diameter ratio, high axial elastic modulus (more than 1TPa) and high strength (50-200 GPa), and is an ideal composite material reinforcing phase. In view of the unique structure and performance, when the carbon nanotube is used as a reinforcing phase to be compounded with a polymer, ceramic or metal material, the mechanical, electrical, thermal and other properties of the material can be improved under the condition of lower content.
However, the existing prepared carbon nanotube reinforced metal-based composite materials are all isotropic materials in all directions, and in the actual use process of the materials, many materials pay attention to the mechanical or physical properties in a specific direction, such as a bearing beam of a rod-shaped member, a wheel shaft and the like, mainly emphasize the mechanical properties in the length direction, and because the bearing capacity of the materials in other directions is relatively small; also, with respect to the existing carbon nanotube reinforced functional composite material, although the carbon nanotube itself is a good electric and thermal conductor, the electric and thermal conductivity of the whole material is not significantly improved.
disclosure of Invention
the invention aims to provide a preparation method of a carbon nanotube reinforced copper-based composite material, which aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
A preparation method of a carbon nanotube reinforced copper-based composite material comprises the following steps:
Preparing flake copper powder;
Nickel plating the carbon nano tube to obtain a nickel-plated carbon nano tube;
Mixing the flaky copper powder and the nickel-plated carbon nano tube, and performing ball milling treatment to obtain mixed powder;
Carrying out rotary orientation treatment on the mixed powder under a magnetic field to obtain a composite powder compact;
And the composite powder is pressed and sintered to obtain the carbon nano tube directional reinforced copper-based composite material.
preferably, the step of preparing the flake copper powder comprises the following steps:
ball milling the copper powder to obtain sheet copper powder;
Drying and reducing the flaky copper powder to obtain reduced flaky powder;
And screening the particle size of the reduced flaky powder.
Preferably, the copper powder ball milling step is as follows:
Putting the atomized spherical copper powder with the particle size of 45-109 mu m into a ball milling tank, and adding absolute ethyl alcohol as a process control agent for ball milling;
The ball-to-material ratio in the ball milling process is 10: 1, the ball milling speed is 250rpm, and the ball milling time is 10 h.
Preferably, the step of drying and reducing comprises: carrying out vacuum drying on the flake copper powder obtained after ball milling at 60 ℃ for 12 h;
Reducing the dried flake copper powder in a tubular reduction furnace by using hydrogen;
The reduction temperature is 400 ℃, and the reduction time is 3 h.
Preferably, the particle size screening has the following target particle size:
Sieving to obtain flake powder with particle size of 48-75 μm.
Preferably, the step of subjecting the mixed powder to a rotational orientation treatment under a magnetic field comprises:
filling the mixed powder into a graphite die;
Placing the graphite mould filled with the mixed powder in an external magnetic field for rotation treatment;
And in the rotating treatment process, the radial direction of the graphite mold is kept the same as the direction of the magnetic field.
Preferably, in the rotating treatment process, the die head of the graphite die is gradually compacted until the graphite die is completely compacted and then taken out of the magnetic field;
an aligned composite powder compact was obtained.
Preferably, in the rotating treatment process, the strength of the external magnetic field is 0.5-2.0T, the rotating speed of the graphite mold is 5-10rpm, and the rotating time is 10-15 min.
Preferably, the composite powder compact sintering adopts vacuum hot-pressing sintering, the sintering temperature is 700 ℃, the sintering time is 1h, the sintering pressure is 30MPa, and the vacuum degree is maintained at 1 x 10-2Pa or less.
compared with the prior art, the invention has the beneficial effects that:
the invention adopts the pre-prepared flake copper powder, which is beneficial to the dispersion of the carbon nano tube; meanwhile, the carbon nano tube is subjected to nickel plating treatment, so that the paramagnetism of the carbon nano tube is increased; the mixed powder of the flake copper powder and the nickel-plated carbon nano tube is subjected to magnetic field rotation orientation treatment, and the carbon nano tube reinforced copper-based composite material is prepared after hot-pressing sintering. The plated nickel layer improves the paramagnetism of the carbon nano tube, and the directional arrangement is realized in the magnetic field of the nickel-plated carbon nano tube. The irregular carbon nano-tube magnetized in the magnetic field treatment process is equivalent to a magnetic needle in the magnetic field, and the end part of the irregular carbon nano-tube is high in coupling magnetization intensity and is subjected to large magnetic force; the magnetization intensity of the middle position is weak, and the magnetic force is small, so that the mutual magnetic adsorption between the carbon nano tubes can be reduced, the original agglomerated carbon nano tubes can be pulled apart, the performance of the carbon nano tubes can be more effectively exerted, and the mechanical and physical properties of the material are improved.
Drawings
FIG. 1 is a schematic view of magnetic field orientation treatment in example 1 of the present invention;
FIG. 2 is a diagram showing the carbon nanotubes aligned in the composite material after the magnetic field alignment treatment in example 1 of the present invention;
FIG. 3 is a graph showing tensile strengths before and after magnetic field treatment in example 1 of the present invention;
FIG. 4 is a diagram showing the carbon nanotubes aligned in the composite material after the magnetic field alignment treatment in example 2 of the present invention;
FIG. 5 is a graph showing tensile strengths before and after magnetic field treatment in example 2 of the present invention.
Detailed Description
In order to enhance the understanding of the present invention, the present invention will be further described with reference to the following examples, which are only for the purpose of illustrating the present invention and are not to be construed as limiting the scope of the present invention.
The embodiment of the invention provides a preparation method of a carbon nano tube reinforced copper-based composite material, which comprises the following steps:
preparing flake copper powder;
Nickel plating the carbon nano tube to obtain a nickel-plated carbon nano tube;
Performing ball milling treatment on the flaky copper powder and the nickel-plated carbon nano tube to obtain mixed powder;
Carrying out rotary orientation treatment on the mixed powder under a magnetic field to obtain a composite powder compact;
And pressing and sintering the composite powder to obtain the carbon nano tube reinforced copper-based composite material.
The above embodiment adopts the pre-prepared flake copper powder, which is beneficial to the dispersion of the carbon nanotubes; meanwhile, the carbon nano tube is subjected to nickel plating treatment, so that the paramagnetism of the carbon nano tube is increased; and carrying out countercurrent rotation orientation treatment on the mixed powder in a magnetic field, and carrying out hot-pressing sintering to prepare the carbon nano tube reinforced copper-based composite material. The plated nickel layer improves the paramagnetism of the carbon nano tube, and the directional arrangement is realized in the magnetic field of the nickel-plated carbon nano tube. The irregular carbon nano-tube magnetized in the magnetic field treatment process is equivalent to a magnetic needle in the magnetic field, and the end part of the irregular carbon nano-tube is high in coupling magnetization intensity and is subjected to large magnetic force; the magnetization intensity of the middle position is weak, and the magnetic force is small, so that the mutual magnetic adsorption between the carbon nano tubes can be reduced, the original agglomerated carbon nano tubes can be pulled apart, and the performance of the carbon nano tubes can be more effectively exerted.
In the implementation, the carbon nano tubes can be directionally arranged in the matrix along the axial direction, so that the mechanical and physical properties of the composite material along the axial arrangement direction of the carbon nano tubes are obviously improved; the axial direction of the carbon nano tube is parallel to the required electric conduction or heat conduction direction, which is equivalent to introducing a convenient channel for electric conduction or heat conduction, and the electric conductivity or the heat conductivity in the direction can be obviously improved, thereby achieving the purpose of directionally enhancing the electric conduction or the heat conduction.
in one embodiment, the preparation process of the flake copper powder comprises the steps of putting atomized spherical copper powder with the particle size of 45-109 microns into a ball milling tank, and adding absolute ethyl alcohol as a process control agent to avoid the excessive cold welding phenomenon of the copper powder in the ball milling process, wherein the ball-to-material ratio is 10: 1, ball milling at the rotation speed of 250rpm for 10h to obtain copper powder with different sheet diameter sizes, and vacuum drying the copper powder at 60 ℃ for 12h after ball milling. Then, reducing the dried powder in a tubular reduction furnace by using hydrogen, wherein the reduction temperature is 400 ℃, and the reduction time is 3 h; and screening the reduced flaky powder by using a 200-mesh 300-mesh sieve to obtain flaky powder with the particle size of 48-75 mu m to obtain the final flaky copper powder.
In the embodiment, the matrix metal powder is prepared into flaky particles in a mechanical ball milling mode, the flaky particles with high content are beneficial to dispersing the carbon nanotubes, and meanwhile, the collision and the shearing in the mechanical ball milling process can effectively overcome the van der Waals force among the carbon nanotubes, so that the carbon nanotubes are more uniformly dispersed in the metal matrix, the surface energy of the carbon nanotubes is reduced, and the agglomeration of the carbon nanotubes is hindered; avoiding agglomeration in the mixing process, thereby improving the performance of the composite material.
In one embodiment, the nickel plating process for carbon nanotubes comprises the following steps:
putting carbon nano-tubes with moderate length, specifically 10-30 μm and 10-20 nm of tube diameter into proper amount of deionized waterand (3) carrying out ultrasonic treatment in water for 30min to improve the dispersibility of the carbon nano tube in the solution. Then, SnCl was used2·2H2Hydrochloric acid solution of O (SnCl)2·2H2O10 g/L + HCl 40mL/L), followed by ultrasonic oscillation for 30min, followed by filtering the mixed solution and rinsing it to neutrality with deionized water.
Using PdCl2Hydrochloric acid solution (PdCl)20.5g/L + HCl 25mL/L) is activated, ultrasonic vibration is assisted for 30min, and then the mixed solution is filtered and washed to be neutral by deionized water.
Sequentially adding NiSO4Solution (20g/L), C6H5Na3O7·2H2O solution (10g/L), NaH2PO2·H2o solution (30g/L) is added into the activated carbon nano tube solution, and NH is used3·H2Adjusting the pH value of the mixed solution by using the O solution, performing ultrasonic treatment for 30min at the reaction temperature of 35 +/-3 ℃ and the pH value of 8.5-9.5, filtering the mixed solution, and washing the mixed solution to be neutral by using deionized water. And finally, drying the carbon nano tube subjected to chemical nickel plating for 24 hours in vacuum at the drying temperature of 60 ℃ to obtain nickel-plated carbon nano tube powder.
in one embodiment, the flake copper powder and the nickel-plated carbon nanotube are placed in a ball milling tank and ball milled for 4 hours at a ball milling rotation speed of 150rpm to obtain the nickel-carbon nanotube/copper composite powder, and then the mixed powder is obtained.
According to the embodiment of the invention, firstly, after the carbon nano tubes are sensitized and activated, the agglomeration of the carbon nano tubes is prevented, and the dispersibility of the carbon nano tubes is improved; meanwhile, the high-content flaky powder particles are beneficial to dispersing the carbon nano tubes, and the collision and shearing in the mechanical ball milling process can effectively overcome the van der Waals force among the carbon nano tubes, so that the carbon nano tubes are more uniformly dispersed in the metal matrix. The surface of the carbon nano tube is plated with a film with a certain thickness by using the technical means of chemical plating and the like, so that the surface energy of the carbon nano tube is reduced, and the agglomeration of the carbon nano tube is hindered; on the other hand, the surface damage of the carbon nano tube in the ball milling process can be prevented, and most importantly: the film can form a reaction bonding interface with the substrate in the high-temperature sintering process of the material, so that the interface bonding strength between the carbon nano tube and the substrate material is improved, and the strength of the composite material is further improved. Meanwhile, the plated nickel layer improves the paramagnetism of the carbon nano tube, and the nickel-plated carbon nano tube can be directionally arranged in a smaller magnetic field. The irregular carbon nano-tube magnetized in the magnetic field treatment process is equivalent to a magnetic needle in the magnetic field, and the end part of the irregular carbon nano-tube is high in coupling magnetization intensity and is subjected to large magnetic force; the magnetization intensity of the middle position is weak, and the magnetic force is small, so that the mutual magnetic adsorption between the carbon nano tubes can be reduced, the original agglomerated carbon nano tubes can be pulled apart, and the performance of the carbon nano tubes can be more effectively exerted.
In one embodiment, the step of subjecting the mixed powder to a rotational orientation treatment under a magnetic field comprises:
Filling the mixed powder into a graphite die;
placing the graphite mould filled with the mixed powder in an external magnetic field for rotation treatment;
And in the rotating treatment process, the radial direction of the graphite mold is kept the same as the direction of the magnetic field.
Specifically, as shown in fig. 1, the mixed powder, i.e., the nickel-carbon nanotube/copper composite powder mixed to obtain a loose state, is loaded into a graphite mold, and at this time, the carbon nanotubes on the surface layer of the mixed powder are only subjected to a small pressure and are in a 'free movement' state; placing the mold in an external strong magnetic field with the strength of 0.5-2.0T, rotating the mold at the speed of 5-10rpm for 10-15min, always keeping the radial direction of the mold the same as the direction of the magnetic field, and deflecting the carbon nano tube on the surface layer to the direction of the magnetic field under the action of the strong magnetic field. The carbon nano-tube in the inner layer is gradually increased in pressure and friction along with the increase of the depth, so that the carbon nano-tube in the deep layer can only slightly rotate or can not rotate. In order to make all the carbon nanotubes be directionally arranged, the radial direction of the die and the direction of the magnetic field are always kept the same in the magnetic field, the die is rotated, the surface layer of the composite powder flows downwards due to gravity, the subsurface layer is exposed and changed into a new surface layer, and the carbon nanotubes in the new surface layer begin to deflect under the action of the magnetic field. At this time, the graphite in the original surface layer is buried in the mixed powder in a certain orientation; the carbon nano tubes can be distributed in the mixed powder along the direction of the magnetic field through multiple rotations; and gradually compacting the die head to control the powder flowability in the rotation process of the die, and taking out the die from the magnetic field after the die is completely compacted to obtain the directionally arranged composite powder compact. The obtained transverse green compact was processed as shown in fig. 1 (c). By the same method, if the radial direction of the die is always kept perpendicular to the direction of the magnetic field during the magnetization process, the directionally arranged transverse composite powder compact can be obtained, and the obtained longitudinal compact process is shown in fig. 1 (d).
in one embodiment, the composite powder compact sintering process is to perform hot-pressing sintering on the nickel-carbon nanotube/copper composite powder subjected to magnetic field treatment, wherein the sintering temperature is 700 ℃, the sintering time is 1h, the sintering pressure is 30MPa, and the vacuum degree is kept at 1 × 10-2pa or less, and obtaining the composite material.
According to the embodiment of the invention, the carbon nanotubes in the carbon nanotube reinforced copper-based composite material prepared by magnetic field treatment are uniformly dispersed and directionally arranged, and compared with the carbon nanotubes which are not subjected to magnetic field orientation treatment under the same condition, the electrical property and the mechanical property of the composite material in the magnetic field direction are improved by the magnetic field orientation treatment.
The following is a detailed description by way of specific examples:
Example 1:
A preparation method of a carbon nanotube reinforced copper-based composite material comprises the following steps:
preparing flake copper powder, putting atomized spherical copper powder with the particle size of 45-109 mu m into a ball milling tank, and adding absolute ethyl alcohol as a process control agent to avoid the excessive cold welding phenomenon of the copper powder in the ball milling process, wherein the ball-to-material ratio is 10: 1, ball milling at the rotation speed of 250rpm for 10h to obtain copper powder with different sheet diameter sizes, and vacuum drying the copper powder at 60 ℃ for 12h after ball milling. Then, reducing the dried powder in a tubular reduction furnace by using hydrogen, wherein the reduction temperature is 400 ℃, and the reduction time is 3 h; and screening the reduced flaky powder by using a 200-mesh 300-mesh sieve to obtain flaky powder with the particle size of 48-75 mu m to obtain the final flaky copper powder.
sensitization treatment of the carbon nano tube comprises the steps of firstly, putting the carbon nano tube with the length of 10-30 mu m and the tube diameter of 10-20 nm into a proper amount of deionized water for ultrasonic treatment for 30min, and improving the dispersibility of the carbon nano tube in a solution. Then, SnCl was used2·2H2hydrochloric acid solution of O (SnCl)2·2H2o10 g/L + HCl 40mL/L), followed by ultrasonic oscillation for 30min, followed by filtering the mixed solution and rinsing it to neutrality with deionized water.
Activation treatment of carbon nanotubes using PdCl2Hydrochloric acid solution (PdCl)20.5g/L + HCl 25mL/L) is activated, ultrasonic vibration is assisted for 30min, and then the mixed solution is filtered and washed to be neutral by deionized water.
Nickel plating treatment of carbon nanotube, sequentially adding NiSO4solution (20g/L), C6H5Na3O7·2H2O solution (10g/L), NaH2PO2·H2o solution (30g/L) is added into the activated carbon nano tube solution, and NH is used3·H2adjusting the pH value of the mixed solution by using the O solution, performing ultrasonic treatment for 30min at the reaction temperature of 35 +/-3 ℃ and the pH value of 8.5-9.5, filtering the mixed solution, and washing the mixed solution to be neutral by using deionized water. And finally, drying the carbon nano tube subjected to chemical nickel plating in vacuum for 24 hours at the drying temperature of 60 ℃ to obtain nickel-plated carbon nano tube powder.
and (3) carrying out uniform ball milling treatment on the flake copper powder and the nickel-plated carbon nano tube, putting the nickel-plated carbon nano tube powder and the flake copper powder into a ball milling tank, and carrying out ball milling for 4 hours at the ball milling rotating speed of 150rpm to obtain the nickel-carbon nano tube/copper composite powder.
Performing rotational orientation treatment on the carbon nano tube under a magnetic field, namely filling the nickel-carbon nano tube/copper composite powder in a loose state into a graphite mold, putting the mold into an external strong magnetic field with the strength of 0.5T, rotating the mold at the speed of 10rpm for 10min, and always keeping the radial direction of the mold to be the same as the direction of the magnetic field so that the carbon nano tube is distributed in the mixed powder along the direction of the magnetic field; and gradually compacting the die head to control the powder fluidity in the rotation process of the die, and taking out the die from the magnetic field after the die is completely compacted to obtain the composite powder pressed compact with the directionally arranged carbon nano tubes.
Sintering the mixed powder, and performing hot-pressing sintering on the nickel-carbon nano-phase/copper composite powder subjected to magnetic field treatment, wherein the sintering temperature is 700 ℃, the sintering time is 1h, the sintering pressure is 30MPa, and the vacuum degree is kept at 1 x 10-2And Pa below, obtaining the carbon nano tube oriented reinforced metal matrix composite material sample.
as shown in fig. 2, the morphology of the carbon nanotubes aligned in the composite material after the magnetic field alignment treatment is shown, and it can be seen from the figure that the carbon nanotubes aligned in the copper matrix after the magnetic field treatment. As shown in the tensile strength chart before and after the magnetic field treatment in FIG. 3, it can be seen that the magnetic field orientation treatment improves the tensile strength of the material under the same conditions, and the tensile strength is improved from 287MPa to 293 MPa. The prepared 0.5 vol.% graphene-reinforced copper-based composite material has the conductivity of 71.8% IACS, and after the copper-based composite material is subjected to orientation treatment by a 0.5T magnetic field, the conductivity along the direction of the magnetic field is 72.5% IACS, and the conductivity of the material is improved by the orientation treatment by the magnetic field.
Example 2:
a preparation method of a carbon nanotube reinforced copper-based composite material comprises the following steps:
Preparing flake copper powder, putting atomized spherical copper powder with the particle size of 45-109 mu m into a ball milling tank, and adding absolute ethyl alcohol as a process control agent to avoid the excessive cold welding phenomenon of the copper powder in the ball milling process, wherein the ball-to-material ratio is 10: 1, ball milling at the rotation speed of 250rpm for 10h to obtain copper powder with different sheet diameter sizes, and vacuum drying the copper powder at 60 ℃ for 12h after ball milling. Then, reducing the dried powder in a tubular reduction furnace by using hydrogen, wherein the reduction temperature is 400 ℃, and the reduction time is 3 h; and screening the reduced flaky powder by using a 200-mesh 300-mesh sieve to obtain flaky powder with the particle size of 48-75 mu m to obtain the final flaky copper powder.
sensitizing the carbon nano-tube, firstly, putting the carbon nano-tube with the length of 10-30 mu m and the tube diameter of 10-20 nm into a proper amount of deionized water for ultrasonic treatment for 30min to improve the dissolution of the carbon nano-tubeDispersibility in liquids. Then, SnCl was used2·2H2hydrochloric acid solution of O (SnCl)2·2H2O10 g/L + HCl 40mL/L), followed by ultrasonic oscillation for 30min, followed by filtering the mixed solution and rinsing it to neutrality with deionized water.
Activation treatment of carbon nanotubes using PdCl2hydrochloric acid solution (PdCl)20.5g/L + HCl 25mL/L) is activated, ultrasonic vibration is assisted for 30min, and then the mixed solution is filtered and washed to be neutral by deionized water.
nickel plating treatment of carbon nanotube, sequentially adding NiSO4solution (20g/L), C6H5Na3O7·2H2O solution (10g/L), NaH2PO2·H2O solution (30g/L) is added into the activated carbon nano tube solution, and NH is used3·H2Adjusting the pH value of the mixed solution by using the O solution, performing ultrasonic treatment for 30min at the reaction temperature of 35 +/-3 ℃ and the pH value of 8.5-9.5, filtering the mixed solution, and washing the mixed solution to be neutral by using deionized water. And finally, drying the carbon nano tube subjected to chemical nickel plating in vacuum for 24 hours at the drying temperature of 60 ℃ to obtain nickel-plated carbon nano tube powder.
And (3) carrying out uniform ball milling treatment on the flake copper powder and the nickel-plated carbon nano tube, putting the nickel-plated carbon nano tube powder and the flake copper powder into a ball milling tank, and carrying out ball milling for 4 hours at the ball milling rotating speed of 150rpm to obtain the nickel-carbon nano tube/copper composite powder.
Performing rotational orientation treatment on the carbon nano tube under a magnetic field, namely filling the nickel-carbon nano tube/copper composite powder in a loose state into a graphite mold, putting the mold into an external strong magnetic field with the strength of 2.0T, rotating the mold at the speed of 5rpm for 15min, and always keeping the radial direction of the mold to be the same as the direction of the magnetic field so that the carbon nano tube is distributed in the mixed powder along the direction of the magnetic field; and gradually compacting the die head to control the powder fluidity in the rotation process of the die, and taking out the die from the magnetic field after the die is completely compacted to obtain the composite powder pressed compact with the directionally arranged carbon nano tubes.
sintering the mixed powder, and treating the nickel-carbon nano powder after magnetic field treatmenthot-pressing and sintering the rice phase/copper composite powder at 700 ℃ for 1h under 30MPa with the vacuum degree of 1 × 10-2And Pa below, obtaining the carbon nano tube oriented reinforced metal matrix composite material sample.
as shown in fig. 4, the morphology of the carbon nanotubes aligned in the composite material after the magnetic field alignment treatment is shown, and it can be seen from the figure that the carbon nanotubes aligned in the copper matrix after the magnetic field treatment. As shown in the tensile strength chart before and after the magnetic field treatment in FIG. 5, it can be seen that the magnetic field orientation treatment improves the tensile strength of the material under the same conditions, and the tensile strength is improved from 288MPa to 322 MPa. The prepared 0.5 vol.% graphene-reinforced copper-based composite material has the conductivity of 71.8% IACS, and after 2.0T magnetic field orientation treatment, the conductivity along the magnetic field direction is 76.8% IACS, and the magnetic field orientation treatment improves the conductivity of the material.
the foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A preparation method of a carbon nanotube reinforced copper-based composite material is characterized by comprising the following steps:
preparing flake copper powder;
Nickel plating the carbon nano tube to obtain a nickel-plated carbon nano tube;
Mixing the flaky copper powder and the nickel-plated carbon nano tube, and performing ball milling treatment to obtain mixed powder;
carrying out rotary orientation treatment on the mixed powder under a magnetic field to obtain a composite powder compact;
and the composite powder is pressed and sintered to obtain the carbon nano tube directional reinforced copper-based composite material.
2. The method for preparing the carbon nanotube reinforced copper-based composite material according to claim 1, wherein the step of preparing the flake copper powder comprises the following steps:
ball milling the copper powder to obtain sheet copper powder;
drying and reducing the flaky copper powder to obtain reduced flaky powder;
And screening the particle size of the reduced flaky powder.
3. the method for preparing the carbon nanotube reinforced copper-based composite material according to claim 2, wherein the copper powder ball milling comprises the following steps:
Putting the atomized spherical copper powder with the particle size of 45-109 mu m into a ball milling tank, and adding absolute ethyl alcohol as a process control agent for ball milling;
the ball-to-material ratio in the ball milling process is 10: 1, the ball milling speed is 250rpm, and the ball milling time is 10 h.
4. the method for preparing a carbon nanotube reinforced copper-based composite material according to claim 2, wherein the drying and reducing steps comprise: carrying out vacuum drying on the flake copper powder obtained after ball milling at 60 ℃ for 12 h;
Reducing the dried flake copper powder in a tubular reduction furnace by using hydrogen;
The reduction temperature is 400 ℃, and the reduction time is 3 h.
5. the method for preparing the carbon nanotube reinforced copper-based composite material according to claim 2, wherein the particle size screening is performed on the following target particle sizes:
Sieving to obtain flake powder with particle size of 48-75 μm.
6. The method for preparing a carbon nanotube reinforced copper-based composite material according to claim 1, wherein the step of subjecting the mixed powder to a rotational orientation treatment under a magnetic field comprises:
Filling the mixed powder into a graphite die;
Placing the graphite mould filled with the mixed powder in an external magnetic field for rotation treatment;
And in the rotating treatment process, the radial direction of the graphite mold is kept the same as the direction of the magnetic field.
7. The method for preparing the carbon nanotube reinforced copper-based composite material according to claim 6, wherein in the rotating process, a die head of a graphite die is gradually compacted until the graphite die is taken out of a magnetic field after being completely compacted;
An aligned composite powder compact was obtained.
8. The method for preparing the carbon nanotube reinforced copper-based composite material according to claim 6, wherein in the rotating treatment process, the intensity of the external magnetic field is 0.5-2.0T, the rotating speed of the graphite mold is 5-10rpm, and the rotating time is 10-15 min.
9. The method for preparing the carbon nanotube reinforced copper-based composite material according to claim 1, wherein the green compact sintering of the composite powder is vacuum hot-pressing sintering, the sintering temperature is 700 ℃, the sintering time is 1h, the sintering pressure is 30MPa, and the vacuum degree is maintained at 1 x 10-2pa or less.
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