CN115255020B - A method for preparing carbon nanotube/copper composite wire - Google Patents
A method for preparing carbon nanotube/copper composite wire Download PDFInfo
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- CN115255020B CN115255020B CN202210839080.4A CN202210839080A CN115255020B CN 115255020 B CN115255020 B CN 115255020B CN 202210839080 A CN202210839080 A CN 202210839080A CN 115255020 B CN115255020 B CN 115255020B
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 138
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000010949 copper Substances 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 84
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 24
- 239000011889 copper foil Substances 0.000 claims abstract description 50
- 238000007731 hot pressing Methods 0.000 claims abstract description 34
- 238000000137 annealing Methods 0.000 claims abstract description 15
- 238000001652 electrophoretic deposition Methods 0.000 claims abstract description 15
- 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 9
- 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 abstract description 8
- 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
- 238000001962 electrophoresis Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000020477 pH reduction Effects 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 22
- 238000002360 preparation method Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004663 powder metallurgy Methods 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 238000000967 suction filtration Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011156 metal matrix composite Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 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
- 230000003014 reinforcing effect Effects 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
Classifications
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a preparation method of a carbon nano tube/copper composite wire, belonging to the field of material processing. Adding acidified CNTs into absolute ethyl alcohol for ultrasonic dispersion, and then adding hydrated aluminum nitrate for continuous ultrasonic dispersion to fully disperse the CNTs and the hydrated aluminum nitrate; performing electrophoretic deposition by taking a copper foil as a cathode and a stainless steel plate as an anode to obtain a copper foil deposited with CNTs; repeatedly folding and hot-pressing the copper foil for a plurality of times to prepare a CNTs/Cu composite blank, and then die-forging the composite blank into a composite bar; and then putting the CNTs/Cu composite bar into a drawing device for drawing to prepare a CNTs/Cu composite wire, and finally annealing the drawn wire to obtain the CNTs/Cu composite wire. The method of the invention avoids the situation of poor composite effect caused by the agglomeration of CNTs, and solves the problems of the increase of mechanical property and the decrease of conductivity existing in the preparation of CNTs reinforced copper-based composite wire material by a powder metallurgy process.
Description
Technical Field
The invention relates to a preparation method of a carbon nano tube/copper composite wire, belonging to the technical field of material processing.
Background
CNTs have attracted considerable attention since their discovery in 1991 due to their excellent mechanical, electrical and physicochemical properties; CNTs are nano-scale tubular structural materials composed of carbon atoms, have extremely large length-diameter ratio, the length-diameter ratio can reach 1.32X10 8:1, and are one of the materials with the largest length-diameter ratio known at present; CNTs are ideal reinforcing materials due to their special structure on the nanometer scale. The composite materials reinforced by CNTs are successfully applied to the fields of automobiles, aerospace, industrial machinery and the like. Thus, related research on CNTs is a research hotspot. So far, CNTs are common reinforcements for metal matrix composites due to their special structure and excellent properties.
In the research of metal matrix composites, a great deal of research has shown that CNTs are compounded into metal materials such as magnesium, aluminum, titanium, copper and the like, and the performance of the reinforced metal matrix composites is greatly improved. The copper-based composite material has good conductivity, high wear resistance, high corrosion resistance and other performances, and is particularly suitable for being applied to the electrical field, so that the CNTs/Cu composite wire material has wide application prospect. While conventional fiber reinforcements can increase the strength of a material, they tend to decrease its electrical conductivity. Therefore, developing a copper-based composite material having excellent conductivity and high strength is one of the problems currently in need of solving.
In the process of preparing the carbon nano tube reinforced metal matrix composite material, the problems of agglomeration of CNTs, hindered interface combination of CNTs reinforcement and a metal matrix, damage of CNTs structure in the dispersing and hot pressing processes and the like are inevitably encountered. In recent years, a great deal of research and reports have shown that the strength of the metal-based material can be greatly improved by adopting a powder metallurgy process to prepare the CNTs/Cu composite material, but the conductivity of the metal-based material is reduced, for example, wang Yan in the preparation and performance research of the carbon nano tube/copper composite material, the conductivity of the carbon nano tube/copper composite material is reduced along with the increase of the CNTs content. Therefore, the carbon nano tube/copper composite material prepared by the powder metallurgy process is not suitable for manufacturing wires. Therefore, the development of a novel preparation method for preparing the carbon nano tube reinforced copper-based composite wire by electrophoretic deposition is significant.
Disclosure of Invention
In order to solve the above-mentioned problems, the present invention provides a method for preparing a carbon nanotube/copper composite wire material having both excellent strength and conductivity, comprising the steps of dispersing CNTs by electrophoretic deposition, repeatedly folding and hot-pressing for a plurality of times to prepare drawn blanks, and drawing and annealing to obtain the CNTs/Cu composite wire material, comprising the steps of:
(1) Adding acidified CNTs into absolute ethyl alcohol for ultrasonic dispersion, then adding hydrated aluminum nitrate for continuous ultrasonic dispersion, so that CNTs and the hydrated aluminum nitrate are fully dispersed, and a uniformly dispersed electrophoresis liquid is prepared; al 3+ in the electrophoretic liquid easily attracts hydroxyl, carboxyl and other groups, so that CNTs are easier to move towards a cathode along with Al 3+, and the electrophoretic deposition efficiency is improved.
(2) Performing electrophoretic deposition by taking a copper foil as a cathode and a stainless steel plate as an anode to obtain a copper foil deposited with CNTs; the CNTs are effectively and uniformly deposited on the surface of the copper foil, so that 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 CNTs and Cu are compounded in the next hot pressing step.
(3) Folding the copper foil obtained in the step (2) for a plurality of times, then carrying out hot pressing, repeating the steps of folding and hot pressing for a plurality of times, fully combining CNTs and copper to prepare a CNTs/Cu composite blank, and die-forging the composite blank into a CNTs/Cu composite bar; as 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 off, more fresh copper foil surfaces are exposed to be fully compounded with CNTs, and the interface bonding effect of the obtained composite material is better, so that the conductivity and the tensile strength of the composite material are improved.
(4) Putting the CNTs/Cu composite bar 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 liquid in the step (1) 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 25-70 KHz.
Preferably, in the step (2) of the invention, the interval between the anodes is 3cm, the direct current voltage is kept at 30V, and the deposition is carried out for 30min.
Preferably, the hot pressing temperature is 300-500 ℃, the hot pressing pressure is 80-100 t, the repeated hot pressing times are 3-5 times, the heat preservation time is 2-4 h, and then the furnace cooling is carried out.
Preferably, the annealing treatment temperature in the step (4) is 200-400 ℃ for 1-3 hours.
Preferably, in the step (4) of the invention, the diameter of the solid round bar is 5mm, and the diameter of the wire is 2mm.
The invention utilizes the electrophoretic deposition mode to deposit CNTs, thereby achieving the purpose of uniformly dispersing the CNTs on the surface of the copper foil, and further solving the problem that the CNTs reinforced metal-based composite wire prepared by adopting the powder metallurgy process only improves the mechanical property unilaterally and reduces the conductivity; in addition, in the preparation process, the material is maintained for a certain time under a certain pressure, and then hot pressing is carried out, so that air can be effectively extruded in the process, the generation of oxide films 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 CNTs on the copper foil in an electrophoretic deposition mode, avoids poor composite effect caused by agglomeration of the CNTs, and realizes effective combination of the copper foil and the CNTs.
(2) According to the invention, CNTs are better contacted with fresh metal through repeated folding and hot pressing, so that oxygen at a bonding interface is effectively eliminated, and a high interface bonding rate is obtained, thereby solving the problems that the strength is unilaterally improved and the conductivity is reduced when the carbon nano tube reinforced metal matrix composite material is prepared by adopting a powder metallurgy process.
(3) The invention effectively utilizes the excellent performance of CNTs, realizes the direct compounding of metal base and CNTs through a multi-time hot pressing process, effectively avoids the generation of defects such as oxide inclusion, holes and the like, obtains the metal base composite material with conductivity and strength improved simultaneously, and can obtain the CNTs/Cu composite wire material with excellent strength and conductivity by drawing the composite material with excellent strength and conductivity into wires and annealing the wires.
Drawings
FIG. 1 is a schematic illustration of a process flow of the present invention;
FIG. 2 is a SEM image of the fracture of the composite blank obtained in example 1;
FIG. 3 is a SEM image of the fracture of a composite blank obtained in example 2;
Fig. 4 is a SEM image of the fracture of the composite blank obtained in example 3.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific embodiments, but the scope of the invention is not limited to the description;
The materials used in the experiment in the embodiment of the invention are high-purity copper foil, the thickness is 0.2mm, the length is 20mm, the width is 20mm, and in the actual process, the size of the copper foil is determined according to the requirement.
Example 1
The preparation method of the carbon nano tube/copper composite wire material specifically comprises the following steps:
(1) Preparing a copper foil: the surface treatment is carried out on the copper foil, the dilute hydrochloric acid is used for cleaning the copper foil, the surface oxide layer and oil stains are removed, and the surface of the copper foil is polished, so that the copper foil is smooth and flat; the high-purity copper foil is selected in the embodiment, and the specification is 0.2mm thick, 20mm wide and 20mm long.
(2) Acidification of CNTs: mixing 25ml of concentrated sulfuric acid and 75ml of concentrated nitric acid, adding 1g of original CNTs, carrying out ultrasonic vibration for 5 hours under the water bath condition of 60 ℃, pouring the mixed acid liquor into distilled water, diluting and carrying out suction filtration, continuing to mix the CNTs obtained by suction filtration with distilled water, stirring, then carrying out washing and suction filtration, repeating the process until the solution becomes neutral, and finally drying the CNTs in a vacuum oven for standby to obtain the functional CNTs.
(3) 0.01G of the carbon nano tube after acid washing is weighed, dissolved by 1000ml of ethanol and dispersed for 3 hours by ultrasonic, the ultrasonic frequency is 25KHz, then 0.02g of aluminum nitrate hydrate is taken, and the uniform dispersion electrophoresis liquid is prepared by ultrasonic dispersion for 1 hour.
(4) And (3) electrophoretic deposition: and (3) taking the copper foil as a cathode and a stainless steel plate as an anode, performing electrophoretic deposition under a certain voltage to obtain the copper foil deposited with CNTs, keeping the interval between the cathode and the anode to be 3cm, and performing electrophoretic deposition for 30min by using a voltage of 30V.
(5) Vacuum hot pressing: folding the copper foil in the step (4) for 2 times, then placing the copper foil into a vacuum hot press, setting proper temperature and pressure for pressing, repeating the folding and hot pressing of the step 3, and fully combining CNTs and copper to prepare a CNTs/Cu composite blank; the hot pressing temperature is 300 ℃, the hot pressing pressure is 80t, and the hot pressing time is 2h each time.
(6) Putting the CNTs/Cu composite blank in the step (5) into a die to prepare a CNTs/Cu composite bar with the diameter of 5mm, 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, annealing at the temperature of 200 ℃ for 1h, and then cooling along with the furnace.
Performance test: and (3) conducting conductivity and mechanical property tests on the prepared wire, and comparing the conductivity and tensile property with those of pure copper.
The conductivity of the pure copper foil is measured to be 95% IACS, the conductivity of the annealed CNTs/Cu composite wire is measured to be 96.9% IACS, and the conductivity is improved by 2% compared with that of the pure copper.
The tensile strength of the pure copper is 183MPa, and the tensile strength of the CNTs/Cu composite wire is 196MPa, which is improved by 7.1% compared with the pure copper.
Fig. 2 is an SEM image of a fracture of the composite blank obtained in example 1, and it can be seen from the image that there is a remarkable ductile pit at the fracture of the blank, and the blank is de-bonded, and after the blank is die-forged into a bar, the CNTs/Cu composite wire is obtained by drawing and annealing, and at this time, the strength and conductivity of the CNTs/Cu composite wire are improved compared with pure copper.
Example 2
The preparation method of the carbon nano tube/copper composite wire material specifically comprises the following steps:
(1) Preparing a copper foil: the surface treatment is carried out on the copper foil, the dilute hydrochloric acid is used for cleaning the copper foil, the surface oxide layer and oil stains are removed, and the surface of the copper foil is polished, so that the copper foil is smooth and flat; the high-purity copper foil is selected in the embodiment, and the specification is 0.2mm thick, 20mm wide and 20mm long.
(2) Acidification of CNTs: mixing 25ml of concentrated sulfuric acid and 75ml of concentrated nitric acid, adding 1g of original CNTs, carrying out ultrasonic vibration for 5 hours under the water bath condition of 60 ℃, pouring the mixed acid liquor into distilled water, diluting and carrying out suction filtration, continuing to mix the CNTs obtained by suction filtration with distilled water, stirring, then carrying out washing and suction filtration, repeating the process until the solution becomes neutral, and finally drying the CNTs in a vacuum oven for standby to obtain the functional CNTs.
(3) 0.02G of the carbon nano tube after acid washing is weighed, dissolved by 1000ml of ethanol and dispersed for 3 hours by ultrasonic, the ultrasonic frequency is 50KHz, then 0.04g of aluminum nitrate hydrate is taken, and the uniform dispersion electrophoresis liquid is prepared by ultrasonic dispersion for 1 hour.
(4) And (3) electrophoretic deposition: performing electrophoretic deposition under a certain voltage by taking a copper foil as a cathode and a stainless steel plate as an anode to obtain a copper foil deposited with CNTs; the cathode-anode spacing was maintained at 3cm and the deposition was performed for 30min using a voltage of 30V.
(5) Vacuum hot pressing: folding the copper foil in the step (4) for 2 times, then placing the copper foil into a vacuum hot press, and carrying out hot pressing at the hot pressing temperature of 400 ℃ and the hot pressing pressure of 90t for 3 hours each time, and repeatedly carrying out folding and hot pressing for 4 times to fully combine CNTs and copper to prepare the CNTs/Cu composite blank.
(6) Putting the CNTs/Cu composite blank in the step (5) into a die to prepare a CNTs/Cu composite bar with the length of 5mm, putting the bar-shaped material into a drawing device for drawing to prepare a CNTs/Cu composite wire with the length of 2mm, putting the drawn wire into an annealing furnace for annealing at 300 ℃ for 2 hours, and then cooling along with the furnace.
Performance test: and (3) conducting conductivity and mechanical property tests on the prepared wire, and comparing the conductivity and tensile property with those of pure copper.
The conductivity of the high-purity copper foil is measured to be 95% IACS, the conductivity of the annealed CNTs/Cu composite wire is measured to be 98.1% IACS, and the conductivity is improved by 3.2% compared with that of pure copper.
The tensile strength of the pure copper is 183MPa, and the tensile strength of the CNTs/Cu composite wire is 213MPa, which is improved by 16.4% compared with the pure copper.
Fig. 3 is an SEM image of the fracture of the composite blank obtained in example 2, and it can be seen from the image that the number of the ductile pits at the fracture is further increased relative to that in example 1, a significant bridging phenomenon occurs, a debonding phenomenon is not significant, and the strength and the conductivity of the finally obtained CNTs/Cu composite wire are significantly improved relative to that in example 1.
Example 3
The preparation method of the carbon nano tube/copper composite wire material specifically comprises the following steps:
(1) Preparing a copper foil: the surface treatment is carried out on the copper foil, the dilute hydrochloric acid is used for cleaning the copper foil, the surface oxide layer and oil stains are removed, and the surface of the copper foil is polished, so that the copper foil is smooth and flat; the high-purity copper foil is selected in the embodiment, and the specification is 0.2mm thick, 20mm wide and 20mm long.
(2) Acidification of CNTs: mixing 25ml of concentrated sulfuric acid and 75ml of concentrated nitric acid, adding 1g of original CNTs, carrying out ultrasonic vibration for 5 hours under the water bath condition of 60 ℃, pouring the mixed acid liquor into distilled water, diluting and carrying out suction filtration, continuing to mix the CNTs obtained by suction filtration with distilled water, stirring, then carrying out washing and suction filtration, repeating the process until the solution becomes neutral, and finally drying the CNTs in a vacuum oven for standby to obtain the functional CNTs.
(3) 0.03G of the carbon nano tube after acid washing is weighed, dissolved by 1000ml of ethanol and dispersed for 3 hours by ultrasonic, the ultrasonic frequency is 75KHz, then 0.06g of aluminum nitrate hydrate is taken, and the uniform dispersion electrophoresis liquid is prepared by ultrasonic dispersion for 1 hour.
(4) And (3) electrophoretic deposition: performing electrophoretic deposition under a certain voltage by taking a copper foil as a cathode and a stainless steel plate as an anode to obtain a copper foil deposited with CNTs; the cathode-anode spacing was maintained at 3cm and the deposition was performed for 30min using a voltage of 30V.
(5) Vacuum hot pressing: folding the copper foil 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 ℃, and the hot pressing pressure to be 100t, carrying out hot pressing and heat preservation for 4 hours each time, and repeating the folding and hot pressing for 5 times, so that CNTs and copper are fully combined, and a CNTs/Cu composite blank is manufactured.
(6) Putting the CNTs/Cu composite blank in the step (5) into a die to prepare a CNTs/Cu composite bar with the length of 5mm, putting the bar-shaped material into a drawing device for drawing to prepare a CNTs/Cu composite wire with the length of 2mm, putting the drawn wire into an annealing furnace, annealing for 3 hours at 400 ℃, and then cooling along with the furnace.
Performance test: and (3) conducting conductivity and mechanical property tests on the prepared wire, and comparing the conductivity and tensile property with those of pure copper.
The conductivity of the high-purity copper foil is measured to be 95% IACS, the conductivity of the annealed CNTs/Cu composite wire is measured to be 99% IACS, and the conductivity is improved by 4.2% compared with that of the pure copper.
The tensile strength of the pure copper is 183MPa, the tensile strength of the CNTs/Cu composite wire is 231MPa, and the tensile strength is improved by 26.2 percent compared with that of the pure copper.
Fig. 4 is an SEM image of the fracture of the composite blank obtained in example 3, and it can be seen from the figure that, compared with example 2, the ductile pit at the fracture is further increased, the bridging phenomenon is more obvious, the debonding phenomenon is almost eliminated, and the composite wire material of CNTs/Cu is obtained after die forging, drawing and annealing of the blank, at this time, the strength and the electrical conductivity of the composite wire material are most excellent.
The strength and conductivity of the obtained CNTs/Cu composite wire in the above three examples are improved compared with pure copper, and the strength and conductivity of the obtained CNTs/Cu composite wire are gradually improved from example 1 to example 3, mainly because the higher the hot pressing temperature is, the higher the pressure is, the better the bonding effect of CNTs and copper matrix is, the better the reinforcing effect of CNTs is fully exerted, and the better the bonding effect is, the smaller the contact resistance between CNTs and copper matrix is, which is more favorable for the improvement of conductivity.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210839080.4A CN115255020B (en) | 2022-07-18 | 2022-07-18 | A method for preparing carbon nanotube/copper composite wire |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210839080.4A CN115255020B (en) | 2022-07-18 | 2022-07-18 | A method for preparing carbon nanotube/copper composite wire |
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| Publication Number | Publication Date |
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