CN115255020A - Preparation method of carbon nanotube/copper composite wire - Google Patents
Preparation method of carbon nanotube/copper composite wire Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 141
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000010949 copper Substances 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 79
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011889 copper foil Substances 0.000 claims abstract description 50
- 238000007731 hot pressing Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000001652 electrophoretic deposition Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 12
- 238000000137 annealing Methods 0.000 claims abstract description 10
- ZZCONUBOESKGOK-UHFFFAOYSA-N aluminum;trinitrate;hydrate Chemical compound O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZZCONUBOESKGOK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 6
- 239000010935 stainless steel Substances 0.000 claims abstract description 6
- 238000005242 forging Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001962 electrophoresis Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 3
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- 230000000694 effects Effects 0.000 abstract description 7
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- 238000004663 powder metallurgy Methods 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 3
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- 238000012545 processing Methods 0.000 abstract description 2
- 238000000967 suction filtration Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 239000011156 metal matrix composite Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
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- 238000011161 development Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
- C25D13/16—Wires; Strips; Foils
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- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
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- Conductive Materials (AREA)
Abstract
The invention discloses a preparation method of a carbon nano tube/copper composite wire material, belonging to the field of material processing. Adding acidified CNTs into absolute ethyl alcohol for ultrasonic dispersion, then adding aluminum nitrate hydrate for continuous ultrasonic dispersion, and fully dispersing the CNTs and the aluminum nitrate hydrate; carrying out electrophoretic deposition by taking a copper foil as a cathode and a stainless steel plate as an anode to obtain the copper foil deposited with the CNTs; repeatedly folding and hot-pressing the copper foil for multiple times to prepare a CNTs/Cu composite blank, and then die-forging the composite blank into a composite bar; and finally, annealing the drawn wire to obtain the CNTs/Cu composite wire. The method avoids the situation that the compounding effect is poor due to the agglomeration of the CNTs, and simultaneously solves the problem that the electrical conductivity is reduced due to the increase of the mechanical property in the preparation of the CNTs reinforced copper-based composite wire material by the powder metallurgy process.
Description
Technical Field
The invention relates to a preparation method of a carbon nano tube/copper composite wire material, belonging to the technical field of material processing.
Background
CNTs have attracted a great deal of attention since their discovery in 1991 due to their excellent mechanical properties, electrical properties and physicochemical properties; CNTs are a nano-scale tubular structure material composed of carbon atoms, and have a very large length-diameter ratio which can reach 1.32 multiplied by 1081 is one of the materials with the largest aspect ratio known at present; due to the special structure of the CNTs on the nanometer scale, the CNTs become an ideal reinforcing material. At present, the composite material reinforced by using the CNTs is successfully applied to the fields of automobiles, aerospace, industrial machinery and the like. Therefore, related research on CNTs is a research hotspot. So far, due to the special structure and excellent performance of CNTs, CNTs are a common reinforcement of metal matrix composites.
In the research of metal matrix composite materials, a great deal of research shows that the performance of reinforced metal matrix composite materials is greatly improved by compounding CNTs into metal materials such as magnesium, aluminum, titanium, copper and the like. The copper-based composite material has good electrical conductivity, high wear resistance, high corrosion resistance and the like, and is particularly suitable for being applied to the field of electricity, so the CNTs/Cu composite wire has wide application prospect. Although conventional fiber reinforcement can increase the strength of the material, it tends to reduce its electrical conductivity. Therefore, the development of copper-based composite materials with excellent conductivity and high strength is one of the problems that needs to be solved at present.
During the process of preparing the carbon nano tube reinforced metal matrix composite, the problems of CNTs agglomeration, hindered combination of a CNTs reinforcement body and a metal matrix interface, damage of a CNTs structure in the dispersion and hot pressing process and the like are often inevitable. In recent years, a great deal of research and reports show that the strength of the metal-based material can be greatly improved by preparing the CNTs/Cu composite material by using a powder metallurgy process, but the conductivity of the metal-based material is reduced, for example, the conductivity of the carbon nanotube/copper composite material obtained by Wangbei in the preparation and performance research of the carbon nanotube/copper composite material is reduced along with the increase of the content of the CNTs. Therefore, the carbon nanotube/copper composite material prepared by the powder metallurgy process is not suitable for being applied to the manufacturing of wires. Therefore, the development of a novel preparation method for preparing the carbon nano tube reinforced copper-based composite wire material by electrophoretic deposition has great significance.
Disclosure of Invention
In order to solve the above mentioned problems, the present invention aims to provide a method for preparing a carbon nanotube/copper composite wire with excellent strength and conductivity, which comprises the following steps:
(1) Adding the acidified CNTs into absolute ethyl alcohol for ultrasonic dispersion, then adding aluminum nitrate hydrate for continuous ultrasonic dispersion, and fully dispersing the CNTs and the aluminum nitrate hydrate to prepare uniformly dispersed electrophoretic fluid; al in electrophoretic fluids3+Easily attract hydroxyl, carboxyl and other groups, and enable CNTs to be more easily matched with Al3+Move to the cathode and improve the electrophoretic deposition efficiency.
(2) Carrying out electrophoretic deposition by taking a copper foil as a cathode and a stainless steel plate as an anode to obtain the copper foil deposited with the CNTs; the CNTs are effectively and uniformly deposited on the surface of the copper foil, stress and defects caused by uneven distribution of the CNTs are effectively avoided, the strength of the CNTs/Cu composite material is improved, and the compounding of the CNTs and Cu in the next hot pressing process is facilitated.
(3) Folding the copper foil obtained in the step (2) for multiple times, then carrying out hot pressing, repeating the steps of folding and hot pressing for multiple times, fully combining the CNTs and the copper to prepare a CNTs/Cu composite blank, and carrying out die forging on the composite blank to obtain a CNTs/Cu composite bar; because the surface area of the copper foil is increased during hot pressing, the oxide film which is not cleaned in the step (1) is torn and cracked, more fresh copper foil surfaces are exposed and fully compounded with the CNTs, the interface bonding effect of the obtained composite material is better, and the conductivity and the tensile strength of the composite material are improved.
(4) And (3) placing the CNTs/Cu composite rod obtained in the step (3) into a drawing device for drawing to prepare a CNTs/Cu composite wire, annealing the drawn wire, and then cooling along with a furnace to obtain the CNTs/Cu composite wire.
Preferably, the concentration of CNTs in the electrophoresis solution in the step (1) of the invention is 0.01-0.03 g/L, and the concentration of hydrated aluminum nitrate is 0.02-0.06 g/L.
Preferably, the ultrasonic frequency range in step (1) of the present invention is 25 to 70KHz.
Preferably, in step (2) of the present invention, the distance between the anode and the cathode is 3cm, the dc voltage is maintained at 30V, and the deposition is performed for 30min.
Preferably, the hot pressing temperature is 300-500 ℃, the hot pressing pressure is 80-100 t, the hot pressing is repeated for 3-5 times, the heat preservation time is 2-4 h, and then the furnace cooling is carried out.
Preferably, the temperature range of the heat treatment in the step (4) of the invention is 200-400 ℃ and the time is 1-3 h.
Preferably, the diameter of the solid round bar in the step (4) of the present invention is 5mm, and the diameter of the wire is 2 mm.
According to the invention, CNTs are deposited in an electrophoretic deposition mode, so that the purpose of uniformly dispersing the CNTs on the surface of a copper foil is achieved, and the problem that the electrical conductivity is reduced because the mechanical property is only improved unilaterally when the CNTs reinforced metal matrix composite wire prepared by adopting a powder metallurgy process is solved; in addition, in the preparation process, the material is firstly kept under a certain pressure for a certain time and then is subjected to hot pressing, so that air can be effectively extruded in the process, the generation of an oxide film and defects is avoided, and the CNTs/Cu composite wire with improved strength and conductivity is obtained.
The invention has the beneficial effects that:
(1) The process method is simple, easy to operate and low in cost; the invention achieves the effect of uniformly dispersing the CNTs on the copper foil in an electrophoretic deposition mode, avoids the poor compounding effect caused by the agglomeration of the CNTs, and realizes the effective combination of the copper foil and the CNTs.
(2) According to the invention, through multiple times of folding and hot pressing, the CNTs are better contacted with fresh metal, the oxygen on the bonding interface is effectively removed, and the high interface bonding rate is obtained, so that the problem that the single-aspect strength is improved and the conductivity is reduced when the carbon nano tube reinforced metal matrix composite material is prepared by adopting a powder metallurgy process is solved.
(3) According to the invention, the excellent performance of the CNTs is effectively utilized, the direct compounding of the metal matrix and the CNTs is realized through a multiple hot pressing process, the defects of oxide inclusions, holes and the like are effectively avoided, the metal matrix composite material with improved conductivity and strength is obtained, the composite material with excellent strength and conductivity is drawn into wires, and the CNTs/Cu composite wire with excellent strength and conductivity can be obtained through annealing.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention;
FIG. 2 is a SEM image of a fracture of the composite ingot obtained in example 1;
FIG. 3 is a SEM image of a fracture of the composite billet obtained in example 2;
fig. 4 is a SEM image of a fracture of the composite ingot obtained in example 3.
Detailed Description
The invention will be described in further detail with reference to the following figures and specific examples, without limiting the scope of the invention;
the material used in the experiment in the embodiment of the invention is high-purity copper foil with the thickness of 0.2mm, the length of 20mm and the width of 20mm, and the size of the copper foil is determined according to the requirement in the actual process.
Example 1
A preparation method of a carbon nanotube/copper composite wire material specifically comprises the following steps:
(1) Preparation of copper foil: performing surface treatment on the copper foil, cleaning the copper foil by using dilute hydrochloric acid, removing a surface oxidation layer and oil stains, and polishing the surface of the copper foil to ensure that the copper foil is smooth and flat; the present example selects high purity copper foil with a thickness of 0.2mm, a width of 20mm and a length of 20mm.
(2) Acidification of CNTs: mixing 25ml of concentrated sulfuric acid and 75ml of concentrated nitric acid, adding 1g of the original CNTs, carrying out ultrasonic oscillation for 5 hours under the condition of a water bath at 60 ℃, pouring the mixed acid solution into distilled water, diluting and carrying out suction filtration, then continuously mixing the CNTs obtained by suction filtration with the distilled water, stirring, cleaning and carrying out suction filtration, repeating the process until the solution becomes neutral, and finally drying the CNTs in a vacuum oven for later use to obtain the functionalized CNTs.
(3) Weighing 0.01 g of carbon nano tube after acid washing, dissolving the carbon nano tube by 1000 ml of ethanol, performing ultrasonic dispersion for 3 hours at the ultrasonic frequency of 25 KHz, then taking 0.02g of aluminum nitrate hydrate, and performing ultrasonic dispersion for 1 hour to prepare uniformly dispersed electrophoresis liquid.
(4) Electrophoretic deposition: taking a copper foil as a cathode and a stainless steel plate as an anode, carrying out electrophoretic deposition under a certain voltage to obtain the copper foil deposited with the CNTs, keeping the distance between the cathode and the anode to be 3cm, and carrying out electrophoretic deposition for 30min by using a voltage of 30V.
(5) Vacuum hot pressing: folding the copper foil obtained in the step (4) for 2 times, then placing the copper foil into a vacuum hot press, setting proper temperature and pressure for pressing, and repeating the folding and hot pressing of the step (3) to fully combine the CNTs and the copper to prepare a CNTs/Cu composite blank; the hot pressing temperature is 300 ℃, the hot pressing pressure is 80 t, and the hot pressing time is 2h.
(6) And (3) putting the CNTs/Cu composite blank in the step (5) into a die to prepare a 5mm CNTs/Cu composite bar, putting the bar-shaped material into a drawing device for drawing to prepare a CNTs/Cu composite wire with the diameter of 2mm, putting the drawn wire into an annealing furnace, carrying out heat treatment at 200 ℃ for 1h, and then carrying out furnace cooling.
And (3) performance testing: the prepared wire is tested for conductivity and mechanical property, and is compared with the conductivity and tensile property of pure copper.
The conductivity of the pure copper foil was measured to be 95% IACS, and the conductivity of the heat-treated CNTs/Cu composite wire was 96.9% IACS, which was 2% higher than that of pure copper.
The measured tensile strength of the pure copper is 183MPa, the tensile strength of the finally obtained CNTs/Cu composite wire is 196 MPa, and the tensile strength is improved by 7.1 percent compared with the pure copper.
FIG. 2 is an SEM image of a fracture of the composite billet obtained in example 1, which shows that the fracture of the billet has obvious dimple and the billet is debonded, and after the billet is die-forged into a bar, the CNTs/Cu composite wire is obtained by drawing and annealing, and the strength and the conductivity of the CNTs/Cu composite wire are improved compared with those of pure copper.
Example 2
A preparation method of a carbon nanotube/copper composite wire material specifically comprises the following steps:
(1) Preparation of copper foil: performing surface treatment on the copper foil, cleaning the copper foil by using dilute hydrochloric acid, removing a surface oxidation layer and oil stains, and polishing the surface of the copper foil to ensure that the copper foil is smooth and flat; the present example selects high purity copper foil with a thickness of 0.2mm, a width of 20mm and a length of 20mm.
(2) Acidification of CNTs: mixing 25ml of concentrated sulfuric acid and 75ml of concentrated nitric acid, adding 1g of primary CNTs, carrying out ultrasonic oscillation for 5 hours in a water bath at 60 ℃, pouring the mixed acid liquid into distilled water, diluting and carrying out suction filtration, then continuously mixing the CNTs obtained by suction filtration with the distilled water, stirring, cleaning and carrying out suction filtration, repeating the process until the solution becomes neutral, and finally drying the CNTs in a vacuum oven for later use to obtain the functionalized CNTs.
(3) Weighing 0.02g of carbon nano tube after acid washing, dissolving the carbon nano tube by 1000 ml of ethanol, performing ultrasonic dispersion for 3 hours at the ultrasonic frequency of 50KHz, then taking 0.04g of aluminum nitrate hydrate, and performing ultrasonic dispersion for 1 hour to prepare uniformly dispersed electrophoresis liquid.
(4) Electrophoretic deposition: carrying out electrophoretic deposition under a certain voltage by taking a copper foil as a cathode and a stainless steel plate as an anode to obtain the copper foil deposited with CNTs; the spacing between the cathode and anode was kept at 3cm, and electrophoretic deposition was carried out for 30min at a voltage of 30V.
(5) Vacuum hot pressing: and (5) folding the copper foil obtained in the step (4) for 2 times, then placing the copper foil into a vacuum hot press, carrying out hot pressing at 400 ℃, carrying out hot pressing at 90t, carrying out hot pressing and heat preservation for 3h each time, and repeating the folding and hot pressing for 4 times to fully combine the CNTs and the copper to obtain the CNTs/Cu composite blank.
(6) And (3) putting the CNTs/Cu composite blank in the step (5) into a die to prepare a 5mm CNTs/Cu composite bar, putting the bar-shaped material into a drawing device for drawing to prepare a 2mm CNTs/Cu composite wire, putting the drawn wire into an annealing furnace for heat treatment at 300 ℃ for 2h for annealing treatment, and then cooling along with the furnace.
And (3) performance testing: the prepared wire is tested for conductivity and mechanical property, and is compared with the conductivity and tensile property of pure copper.
The electrical conductivity of the high purity copper foil was measured to be 95% IACS, the electrical conductivity of the CNTs/Cu composite wire after heat treatment was 98.1% IACS, and the electrical conductivity was increased by 3.2% relative to pure copper.
The measured tensile strength of the pure copper is 183MPa, the tensile strength of the finally obtained CNTs/Cu composite wire is 213 MPa, and the tensile strength is improved by 16.4 percent compared with the pure copper.
FIG. 3 is a SEM image of a fracture of the composite billet obtained in example 2, and it can be seen from the SEM image that the number of the dimples at the fracture is further increased compared with the number of the dimples in example 1, obvious bridging phenomenon occurs, debonding phenomenon is not obvious, and the strength and conductivity of the finally obtained CNTs/Cu composite wire are obviously improved compared with example 1.
Example 3
A preparation method of a carbon nanotube/copper composite wire material specifically comprises the following steps:
(1) Preparation of copper foil: performing surface treatment on the copper foil, cleaning the copper foil by using dilute hydrochloric acid, removing a surface oxidation layer and oil stains, and polishing the surface of the copper foil to ensure that the copper foil is smooth and flat; the high-purity copper foil is selected in the embodiment, and the specification is 0.2mm in thickness, 20mm in width and 20mm in length.
(2) Acidification of CNTs: mixing 25ml of concentrated sulfuric acid and 75ml of concentrated nitric acid, adding 1g of primary CNTs, carrying out ultrasonic oscillation for 5 hours in a water bath at 60 ℃, pouring the mixed acid liquid into distilled water, diluting and carrying out suction filtration, then continuously mixing the CNTs obtained by suction filtration with the distilled water, stirring, cleaning and carrying out suction filtration, repeating the process until the solution becomes neutral, and finally drying the CNTs in a vacuum oven for later use to obtain the functionalized CNTs.
(3) Weighing 0.03g of carbon nano tube after acid washing, dissolving the carbon nano tube in 1000 ml of ethanol, performing ultrasonic dispersion for 3 hours at the ultrasonic frequency of 75KHz, then taking 0.06g of aluminum nitrate hydrate, and performing ultrasonic dispersion for 1 hour to prepare the uniformly dispersed electrophoresis solution.
(4) Electrophoretic deposition: carrying out electrophoretic deposition under a certain voltage by taking a copper foil as a cathode and a stainless steel plate as an anode to obtain the copper foil deposited with CNTs; the cathode and anode spacing was maintained at 3cm and electrophoretic deposition was carried out at 30V for 30min.
(5) Vacuum hot pressing: and (5) folding the copper foil obtained in the step (4) for 2 times, then placing the copper foil into a vacuum hot press, setting the hot pressing temperature to be 500 ℃, the hot pressing pressure to be 100t, carrying out hot pressing and heat preservation for 4h each time, and repeatedly carrying out folding and hot pressing for 5 times to fully combine the CNTs and the copper to obtain the CNTs/Cu composite blank.
(6) And (3) putting the CNTs/Cu composite blank in the step (5) into a die to prepare a 5mm CNTs/Cu composite bar, putting the bar-shaped material into a drawing device for drawing to prepare a 2mm CNTs/Cu composite wire, putting the drawn wire into an annealing furnace, carrying out heat treatment at 400 ℃ for 3h, and then cooling along with the furnace.
And (3) performance testing: the prepared wire is tested for conductivity and mechanical property, and is compared with the conductivity and tensile property of pure copper.
The electrical conductivity of the high purity copper foil was measured to be 95% IACS, and the electrical conductivity of the CNTs/Cu composite wire after heat treatment was measured to be 99% IACS, which was an improvement of 4.2% over the pure copper.
The measured tensile strength of the pure copper is 183MPa, the tensile strength of the finally obtained CNTs/Cu composite wire is 231MPa, and the tensile strength is improved by 26.2 percent compared with the pure copper.
FIG. 4 is an SEM image of a fracture of the composite billet obtained in example 3, and it can be seen from the SEM image that compared with example 2, the dimple at the fracture is further increased, the bridging phenomenon is more obvious, and the debonding phenomenon is almost eliminated, and the CNTs/Cu composite wire is obtained by performing die forging, drawing and annealing on the billet, and the strength and the electric conductivity of the composite wire are the most excellent.
The strength and the conductivity of the CNTs/Cu composite wire obtained in the three embodiments are improved compared with those of pure copper, and from embodiment 1 to embodiment 3, the strength and the conductivity of the CNTs/Cu composite wire are gradually improved, mainly because the higher the hot pressing temperature and the higher the pressure are due to different hot pressing parameters, the better the combination effect of the CNTs and a copper matrix is, the better the enhancement effect of the CNTs is fully exerted, and moreover, the better the combination effect is, the smaller the contact resistance between the CNTs and the copper matrix is, and the more the improvement of the conductivity is facilitated.
Claims (8)
1. A preparation method of a carbon nanotube/copper composite wire is characterized by comprising the following steps:
(1) Adding the acidified CNTs into absolute ethyl alcohol for ultrasonic dispersion, then adding aluminum nitrate hydrate for continuous ultrasonic dispersion, and fully dispersing the CNTs and the aluminum nitrate hydrate to prepare uniformly dispersed electrophoretic solution;
(2) Carrying out electrophoretic deposition by taking a copper foil as a cathode and a stainless steel plate as an anode to obtain the copper foil deposited with the CNTs;
(3) Folding the copper foil obtained in the step (2) for multiple times, then carrying out hot pressing, repeating the steps of folding and hot pressing for multiple times, fully combining the CNTs and the copper to prepare a CNTs/Cu composite blank, and then carrying out die forging on the composite blank to prepare a CNTs/Cu composite bar;
(4) And (3) placing the CNTs/Cu composite rod obtained in the step (3) into a drawing device for drawing to prepare a CNTs/Cu composite wire, annealing the drawn wire, and then cooling along with a furnace to finally obtain the CNTs/Cu composite wire.
2. The method for preparing the carbon nanotube/copper composite wire according to claim 1, wherein: the CNTs in the step (1) are acidified by the following steps: mixing concentrated sulfuric acid and concentrated nitric acid according to the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid being 3, adding 1g of carbon nano tube into each 100 ml of acid solution, placing the raw CNTs in a water bath kettle at 60 ℃, pouring the mixed acid solution into distilled water after ultrasonic oscillation for 5 hours, diluting and filtering, continuously mixing the CNTs obtained by filtering with the distilled water, stirring, cleaning and filtering, repeating the process until the solution becomes neutral, and finally drying the CNTs in a vacuum oven for later use to obtain the functionalized CNTs.
3. The method for preparing a carbon nanotube/copper composite wire according to claim 1 or 2, wherein: in the electrophoresis solution in the step (1), the concentration of CNTs is 0.01-0.03 g/L, and the concentration of hydrated aluminum nitrate is 0.02-0.06 g/L.
4. The method for preparing the carbon nanotube/copper composite wire according to claim 3, wherein: the ultrasonic frequency range in the step (1) is 25-70 KHz.
5. The method for preparing the carbon nanotube/copper composite wire according to claim 4, wherein: in the step (2), the distance between the cathode and the anode is 3cm, the direct current voltage is kept at 30V, and the deposition is carried out for 30min.
6. The method for preparing the carbon nanotube/copper composite wire according to claim 5, wherein: the hot pressing temperature is 300-500 ℃, the hot pressing pressure is 80-100 t, the hot pressing times are 3-5 times, the heat preservation time is 2-4 h, and then the furnace cooling is carried out.
7. The method for preparing the carbon nanotube/copper composite wire according to claim 6, wherein: the heat treatment temperature range is 200-400 ℃ and the time is 1-3 h.
8. The method for preparing the carbon nanotube/copper composite wire according to claim 7, wherein: in the step (4), the diameter of the solid round bar is 5mm, and the diameter of the wire is 2 mm.
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