CN116727676A - Preparation method of nitrogen-doped carbon nanotube reinforced high-conductivity copper-based composite material - Google Patents

Preparation method of nitrogen-doped carbon nanotube reinforced high-conductivity copper-based composite material Download PDF

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CN116727676A
CN116727676A CN202310719391.1A CN202310719391A CN116727676A CN 116727676 A CN116727676 A CN 116727676A CN 202310719391 A CN202310719391 A CN 202310719391A CN 116727676 A CN116727676 A CN 116727676A
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陶静梅
孙伟
陈小丰
易健宏
鲍瑞
刘意春
刘亮
李才巨
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Kunming University of Science and Technology
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Abstract

The invention discloses a preparation method of a nitrogen-doped carbon nanotube reinforced high-conductivity copper-based composite material, and belongs to the technical field of metal-based composite materials. The preparation method comprises the following steps: introducing N 2 And Ar mixed gas, performing plasma treatment on CNTs to obtain NCNTs; mixing NCNTs with a copper acetate solution, and obtaining NCNTs/CuO powder by a molecular-grade blending method; carrying out reduction annealing treatment on the NCNTs/CuO powder to obtain NCNTs/Cu composite powder; ball milling and drying are carried out on the NCNTs/Cu composite powder, and then reduction annealing is carried out to obtain NCNTs/Cu composite powder; finally warpAnd sintering the spark plasma to obtain the nitrogen-doped carbon nano tube composite reinforced copper-based material. According to the invention, on the premise of not damaging the CNTs structure, the nitrogen-containing functional groups are introduced into the CNTs surface, so that the dispersion uniformity of the CNTs in the copper matrix and the interface bonding strength between the CNTs and the copper matrix are improved. Meanwhile, the introduction of the nitrogen-containing functional group can effectively improve the interfacial electron transport capacity of the copper-based composite material, so that the copper-based composite material with excellent mechanical and conductive properties is prepared.

Description

Preparation method of nitrogen-doped carbon nanotube reinforced high-conductivity copper-based composite material
Technical Field
The invention belongs to the technical field of preparation of metal matrix composite materials, and particularly relates to a preparation method of a nitrogen-doped carbon nanotube reinforced high-conductivity copper matrix composite material.
Background
Carbon nanotubes, CNTs for short, are considered one of the ideal reinforcements for composite materials due to their excellent mechanical, electrical and thermal properties. Copper-based composite materials are widely used in the fields of electronic devices, integrated circuit heat dissipation plates, automobile rotors and the like due to their good electric conduction, heat conduction and corrosion resistance. In the research of CNTs/Cu composite materials, how to develop the advantages of CNTs and Cu, and the preparation of CNTs/Cu composite materials with excellent mechanical and electrical properties has become a research hotspot in the field.
Currently, the application of CNTs in Cu-based composites faces the following challenges: firstly, CNTs are easy to agglomerate under the action of Van der Waals force due to huge length-diameter ratio and high specific surface area, so that the CNTs are difficult to disperse in a metal matrix; the interface wettability between two CNTs and the Cu matrix is poor, the interface bonding mode is mainly mechanical embedding, and the physical bonding mode leads to weaker interface bonding strength of the CNTs/Cu composite material. By utilizing the chemical bridging action of oxygen generated by acidifying CNTs, the wettability between CNTs and Cu can be improved, and the interface combination of CNTs and Cu can be enhanced, but the existence of oxygen-containing functional groups can greatly reduce the conductivity of CNTs/Cu composite materials. Therefore, there is a need to provide a viable strategy to improve CNTs to Cu matrix interface bonding to meet the needs of structural and functional integration.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a nitrogen-doped carbon nano tube reinforced high-conductivity copper-based composite material.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the nitrogen-doped carbon nanotube reinforced high-conductivity copper-based composite material comprises the following steps:
(1) Introducing N 2 Carrying out plasma treatment on the carbon nano tube by using the mixed gas of Ar, and cooling to room temperature in a protective atmosphere after the plasma treatment is finished to obtain the nitrogen-doped carbon nano tube;
(2) Performing ultrasonic dispersion on the nitrogen-doped carbon nano tube in water, then adding the carbon nano tube into a copper acetate solution, and preparing NCNTs/CuO composite powder by a molecular-level blending method;
(3) Carrying out reduction annealing treatment on NCNTs/CuO composite powder, wherein the reduction atmosphere is N 2 And H 2 Obtaining NCNTs/Cu composite powder;
(4) Ball milling and drying NCNTs/Cu composite powder, and then carrying out reduction annealing treatment in the reducing atmosphere of N 2 And H 2 Obtaining NCNTs/Cu composite powder;
(5) And (3) sintering the NCNTs/Cu composite powder by discharge plasma to obtain the nitrogen-doped carbon nano tube composite reinforced copper-based block material.
The method of the invention carries out nitrogen doping treatment on the surface of the carbon nano tube on the premise of ensuring the structural integrity of the carbon nano tube. The carbon nano tube after nitrogen doping treatment can not only improve the self dispersibility, but also can improve the wettability between Cu and the nitrogen doped nano tube due to the change of the surface property when being combined with Cu-based materials, so that the nitrogen doped nano tube is uniformly dispersed in a Cu matrix, and the interface bonding strength of CNTs and the Cu matrix is improved.
The invention uniformly disperses the carbon nano tubes on the quartz plate, ensures that the carbon nano tubes are uniformly tiled and fluffy, and then places the quartz plate dispersed with the carbon nano tubes into a plasma treatment device for plasma treatment.
As a preferred embodiment of the present invention, the carbon nanotubes have a purity of 98%, an outer diameter of 20-50nm, and a length of 10-50. Mu.m.
As a preferred embodiment of the present invention, in the step (1), the plasma treatment power is 150 to 250W, N 2 The flow rate is 60-90 sccm, and the Ar flow rate is 10-40 sccm.
The invention regulates and controls the content of the nitrogen-containing functional groups on the surface of the carbon nano tube through plasma treatment, realizes the regulation and control of the performance of the nitrogen-doped carbon nano tube, and further strengthens the interface binding force with the copper-based material. Meanwhile, the nitrogen doping treatment can reduce the back scattering of the Cu matrix around the carbon nano tube, thereby being beneficial to the transfer of electrons on the interface of the carbon nano tube and the Cu matrix and obtaining the nitrogen doped carbon nano tube composite reinforced copper-based material with excellent mechanical property and electrical property.
The nitrogen doped carbon nanotubes are called NCNTs for short; the NCNTs/CuO composite powder is nitrogen-doped carbon nano tube/CuO composite powder; the NCNTs/Cu composite powder is nitrogen-doped carbon nano tube/Cu composite powder.
As a preferred embodiment of the present invention, the molecular-stage blending method comprises the steps of: adding the nitrogen doped carbon nano tube into copper acetate solution, stirring, adding sodium hydroxide solution, heating, finally adding glucose solution for reaction, washing and drying after the reaction is finished to obtain NCNTs/CuO composite powder.
As a preferred embodiment of the invention, the volume fraction of Cu in the NCNTs/Cu composite powder is 97.5-99.5%, and the volume fraction of the nitrogen-doped carbon nano tube is 0.5-2.5%.
As a preferred embodiment of the present invention, the molar ratio of copper acetate, sodium hydroxide and glucose is 0.2:7:2.
as a preferred embodiment of the present invention, in the step (3), the temperature of the reduction annealing is 250 to 350℃for 4 to 7 hours.
As a preferred embodiment of the invention, in the step (4), the ball milling time is 2-3 hours, and the rotating speed is 250-350r/min; the temperature of the reduction annealing is 200-300 ℃ and the time is 3-6 hours.
As a preferred embodiment of the invention, the temperature rising rate of spark plasma sintering is 120-200 ℃/min, the temperature is 600-900 ℃, and the heat preservation time is 5-20min.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts the processes of plasma treatment, molecular level blending, plasma sintering and the like, regulates and controls the content of functional groups on the surface of the nitrogen-doped carbon nano tube on the basis of not changing the structure of the carbon nano tube, not only enhances the dispersibility of the carbon nano tube, but also enhances the interface bonding strength with a Cu matrix, and the obtained nitrogen-doped carbon nano tube composite enhanced copper-based material not only has excellent mechanical properties, but also has good electrical properties.
(2) The preparation method is simple and easy to implement, and can be widely applied to the compounding of other metal-based materials and carbon nanotubes.
Drawings
Fig. 1 is a process flow diagram of a method for preparing a nitrogen-doped carbon nanotube-reinforced highly conductive copper-based composite material according to the present invention.
FIG. 2 is a TEM image of nitrogen-doped carbon nanotubes or untreated carbon nanotubes prepared in example 1, comparative example 1 of the present invention, wherein (a) is a TEM image of untreated carbon nanotubes prepared in comparative example 1; (b) A TEM image of the nitrogen doped carbon nanotubes prepared in example 1.
FIG. 3 is an X-ray photoelectron spectrum of a nitrogen-doped carbon nanotube prepared in example 1 of the present invention.
Fig. 4 is a graph showing engineering stress-strain curves obtained by tensile test of the materials prepared in examples 1, 2, 3 and comparative examples 1 and 5 according to the present invention.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Example 1
The preparation method of the nitrogen-doped carbon nanotube reinforced high-conductivity copper-based composite material specifically comprises the following steps:
(1) Uniformly dispersing 100mg of carbon nanotubes on a quartz plate through a screen, and ensuring that the carbon nanotubes are uniformly tiled and fluffy; the purity of the carbon nano tube is 98%, the outer diameter is 20-50nm, and the length is 10-50 mu m.
(2) Putting a quartz plate fully paved with carbon nano into a tubular furnace with a plasma generator, approaching a plasma emission source, and introducing 90sccm N 2 And 10sccm of high purity Ar, then treating CNTs with 250W plasma for 25min, opening a furnace cover after the treatment is completed, and cooling to room temperature in a protective atmosphere to obtain NCNTs.
(3) 36mgNCNTs are subjected to ultrasonic dispersion in 50ml of water for 1 hour, then added into 0.2ml of copper acetate solution for stirring, 7mol of sodium hydroxide solution is added for heating, and finally 2mol of glucose solution is added for reaction, and after the reaction is finished, the NCNTs/CuO composite powder is obtained through washing and drying.
(4) Placing NCNTs/CuO composite powder in a tubular furnace for heating and reducing at 350deg.C for 5 hr at a heating rate of 10deg.C/min under N 2 And H 2 The total flow of gas was 200sccm, where N 2 And H is 2 The flow ratio is 10:1, and the composite powder is obtained.
(5) Ball milling the composite powder for 2 hours at a ball-material ratio of 10:1 and a rotating speed of 250r/min, suction filtering, drying, and finally carrying out heating reduction treatment in a tube furnace at 250 ℃ for 5 hours at a heating rate of 10 ℃/min under a reducing atmosphere of N 2 And H 2 The total flow of gas was 200sccm, where N 2 And H is 2 The flow ratio is 10:1, and NCNTs/Cu composite powder is obtained;
(6) And (3) performing SPS sintering on the NCNTs/Cu composite powder, wherein the heating rate is 100 ℃/min, the sintering temperature is 700 ℃, and the heat preservation time is 10min, so as to obtain the nitrogen-doped carbon nano tube composite reinforced copper-based material.
Detecting the nitrogen-doped carbon nanotube obtained in the step (2), namely an NCNTs sample, wherein the microscopic morphology of the NCNTs sample is shown in fig. 2, a graph (a) is the morphology of the carbon nanotube photographed by the HRTEM, and a graph (b) is the morphology of the carbon nanotube photographed by the HRTEM, and the surface of the carbon nanotube after being treated by a plasma process is in a bamboo joint shape along the tube wall, which is completely different from the tubular shape of the carbon nanotube.
Analysis of test results of XPS, TEM and the like of the graph (2) and the graph (3) shows that after the CNTs are bombarded by plasma, nitrogen-containing functional groups are successfully introduced into the surface of the CNTs, and the CNTs are compounded with pure Cu to prepare the nitrogen-doped carbon nano tube composite reinforced copper-based material.
The mechanical property test result shows that the tensile strength of the nitrogen-doped carbon nano tube composite reinforced copper-based material is 290MPa, the breaking elongation is 16%, and compared with pure copper (tensile strength 224 MPa), the tensile strength is obviously improved, and the interface combination of the nitrogen-doped carbon nano tube and a Cu matrix is obviously improved due to the introduction of the nitrogen-containing functional group, so that the load transfer capability of the nitrogen-doped carbon nano tube composite reinforced copper-based material is obviously exerted. Simultaneously, the nitrogen doping treatment reduces the back scattering of Cu matrix around the nitrogen doped carbon nano tube, so that the nitrogen doped carbon nano tube composite reinforced copper-based material maintains excellent conductivity while the mechanical property is improved, and the conductivity is 94.3 percent IACS.
Example 2
The preparation method of the nitrogen-doped carbon nanotube reinforced high-conductivity copper-based composite material specifically comprises the following steps:
(1) Uniformly dispersing 100mg of carbon nanotubes on a quartz plate through a screen, and ensuring that the carbon nanotubes are uniformly tiled and fluffy; the purity of the carbon nano tube is 98%, the outer diameter is 20-50nm, and the length is 10-50 mu m.
(2) Putting a quartz plate fully paved with carbon nano into a tubular furnace with a plasma generator, approaching a plasma emission source, and introducing 70sccm N 2 And 30sccm of high purity Ar, then treating CNTs with 250W plasma for 25min, opening a furnace cover after the treatment is completed, and cooling to room temperature in a protective atmosphere to obtain NCNTs.
(3) 36mgNCNTs are subjected to ultrasonic dispersion in 50ml of water for 1 hour, then added into 0.2ml of copper acetate solution for stirring, 7mol of sodium hydroxide solution is added for heating, and finally 2mol of glucose solution is added for reaction, and after the reaction is finished, the NCNTs/CuO composite powder is obtained through washing and drying.
(4) Placing NCNTs/CuO composite powder in a tubular furnace for heating and reducing at 350deg.C for 5 hr at a heating rate of 10deg.C/min under N 2 And H 2 The total flow of gas was 200sccm, where N 2 And H is 2 The flow ratio is 10:1, and the composite powder is obtained.
(5) Ball milling the composite powder for 2 hours at a ball-material ratio of 10:1 and a rotating speed of 250r/min, suction filtering, drying, and finally carrying out heating reduction treatment in a tube furnace at 250 ℃ for 5 hours at a heating rate of 10 ℃/min under a reducing atmosphere of N 2 And H 2 The total flow of gas was 200sccm, where N 2 And H is 2 The flow ratio is 10:1, and NCNTs/Cu composite powder is obtained;
(6) And (3) performing SPS sintering on the NCNTs/Cu composite powder, wherein the heating rate is 100 ℃/min, the sintering temperature is 700 ℃, and the heat preservation time is 10min, so as to obtain the nitrogen-doped carbon nano tube composite reinforced copper-based material.
The obtained nitrogen-doped carbon nano tube composite reinforced copper-based material has the tensile strength of 282MPa, the breaking elongation of 23% and the conductivity of 94.5% IACS.
Analysis of test results of figures (2) and (3) on XPS, TEM and the like shows that the nitrogen-containing functional groups are successfully introduced into the surfaces of CNTs through plasma nitrogen doping treatment, NCNTs/Cu composite materials are prepared after the CNTs and copper powder are compounded, and mechanical property test results show that the strength of the nitrogen-doped carbon nano tube composite reinforced copper-based material is remarkably improved compared with that of pure copper prepared by the same method, good plasticity is maintained, and meanwhile, the carbon nano tube composite reinforced copper-based material has conductivity equivalent to that of pure copper prepared by the same method.
Example 3
The preparation method of the nitrogen-doped carbon nanotube reinforced high-conductivity copper-based composite material specifically comprises the following steps:
(1) Uniformly dispersing 100mg of carbon nanotubes on a quartz plate through a screen, and ensuring that the carbon nanotubes are uniformly tiled and fluffy; the purity of the carbon nano tube is 98%, the outer diameter is 20-50nm, and the length is 10-50 mu m.
(2) Putting a quartz plate fully paved with carbon nano into a tubular furnace with a plasma generator, approaching a plasma emission source, and introducing 60sccm N 2 And 40sccm of high purity Ar, then treating CNTs with 250W plasma for 25min, opening a furnace cover after the treatment is completed, and cooling to room temperature in a protective atmosphere to obtain NCNTs.
(3) 36mgNCNTs are subjected to ultrasonic dispersion in 50ml of water for 1 hour, then added into 0.2ml of copper acetate solution for stirring, 7mol of sodium hydroxide solution is added for heating, and finally 2mol of glucose solution is added for reaction, and after the reaction is finished, the NCNTs/CuO composite powder is obtained through washing and drying.
(4) Placing NCNTs/CuO composite powder in a tubular furnace for heating and reducing at 350deg.C for 5 hr at a heating rate of 10deg.C/min under N 2 And H 2 The total flow of gas was 200sccm, where N 2 And H is 2 The flow ratio is 10:1, and the composite powder is obtained.
(5) Ball milling the composite powder for 2 hours at a ball-material ratio of 10:1 and a rotating speed of 250r/min, suction filtering, drying, and finally carrying out heating reduction treatment in a tube furnace at 250 ℃ for 5 hours at a heating rate of 10 ℃/min under a reducing atmosphere of N 2 And H 2 The total flow of gas was 200sccm, where N 2 And H is 2 The flow ratio is 10:1, and NCNTs/Cu composite powder is obtained;
(6) And (3) performing SPS sintering on the NCNTs/Cu composite powder, wherein the heating rate is 100 ℃/min, the sintering temperature is 700 ℃, and the heat preservation time is 10min, so as to obtain the nitrogen-doped carbon nano tube composite reinforced copper-based material.
The obtained nitrogen-doped carbon nano tube composite reinforced copper-based material has the tensile strength of 273MPa, the breaking elongation of 24% and the conductivity of 94.7% IACS.
Analysis of test results of XPS, TEM and the like in the graph (2) and the graph (3) shows that the nitrogen-containing functional groups are successfully introduced into the surfaces of CNTs through the plasma nitrogen doping treatment, and the nitrogen-doped carbon nano tube composite reinforced copper-based material is prepared after the CNTs are compounded with copper powder, and the mechanical property test results show that the nitrogen-doped carbon nano tube composite reinforced copper-based material maintains excellent conductivity while mechanical property is improved.
Example 4
The preparation method of the nitrogen-doped carbon nanotube reinforced high-conductivity copper-based composite material specifically comprises the following steps:
(1) Uniformly dispersing 100mg of carbon nanotubes on a quartz plate through a screen, and ensuring that the carbon nanotubes are uniformly tiled and fluffy; the purity of the carbon nano tube is 98%, the outer diameter is 20-50nm, and the length is 10-50 mu m.
(2) Putting a quartz plate fully paved with carbon nano into a tubular furnace with a plasma generator, approaching a plasma emission source, and introducing 60sccm N 2 And 40sccm of high purity Ar, then treating CNTs with 150W plasma for 25min, opening a furnace cover after the treatment is completed, and cooling to room temperature in a protective atmosphere to obtain NCNTs.
(3) Performing ultrasonic dispersion on 12mgNCNTs in 50ml of water for 1 hour, adding the mixture into 0.2ml of copper acetate solution, stirring, adding 7mol of sodium hydroxide solution, heating, finally adding 2mol of glucose solution for reaction, washing and drying after the reaction is finished to obtain NCNTs/CuO composite powder.
(4) Placing NCNTs/CuO composite powder in a tubular furnace for heating and reducing at 250deg.C for 7 hr at a heating rate of 10deg.C/min under a reducing atmosphere of N 2 And H 2 The total flow of gas was 200sccm, where N 2 And H is 2 The flow ratio is 10:1, and the composite powder is obtained.
(5) Ball milling the composite powder for 3 hours at a ball-material ratio of 10:1 and a rotating speed of 350r/min, suction filtering, drying, and finally carrying out heating reduction treatment in a tube furnace at 300 ℃ for 3 hours at a heating rate of 10 ℃/min under a reducing atmosphere of N 2 And H 2 The total flow of gas was 200sccm, where N 2 And H is 2 The flow ratio is 10:1, and NCNTs/Cu composite powder is obtained;
(6) And (3) performing SPS sintering on the NCNTs/Cu composite powder, wherein the heating rate is 200 ℃/min, the sintering temperature is 900 ℃, and the heat preservation time is 5min, so as to obtain the nitrogen-doped carbon nano tube composite reinforced copper-based material.
The obtained nitrogen-doped carbon nano tube composite reinforced copper-based material has the tensile strength of 269MPa, the breaking elongation of 28% and the conductivity of 95.2% IACS.
Example 5
The preparation method of the nitrogen-doped carbon nanotube reinforced high-conductivity copper-based composite material specifically comprises the following steps:
(1) Uniformly dispersing 100mg of carbon nanotubes on a quartz plate through a screen, and ensuring that the carbon nanotubes are uniformly tiled and fluffy; the purity of the carbon nano tube is 98%, the outer diameter is 20-50nm, and the length is 10-50 mu m.
(2) Putting a quartz plate fully paved with carbon nano into a tubular furnace with a plasma generator, approaching a plasma emission source, and introducing 60sccm N 2 And 40sccm of high purity Ar, then treating CNTs with 200W plasma for 25min, opening a furnace cover after the treatment is completed, and cooling to room temperature in a protective atmosphere to obtain NCNTs.
(3) 60mgNCNTs are subjected to ultrasonic dispersion in 50ml of water for 1 hour, then added into 0.2ml of copper acetate solution for stirring, 7mol of sodium hydroxide solution is added for heating, and finally 2mol of glucose solution is added for reaction, and after the reaction is finished, the NCNTs/CuO composite powder is obtained through washing and drying.
(4) Placing NCNTs/CuO composite powder in a tubular furnace for heating and reducing at 300 deg.C for 4 hr at a heating rate of 10deg.C/min under a reducing atmosphere of N 2 And H 2 The total flow of gas was 200sccm, where N 2 And H is 2 The flow ratio is 10:1, and the composite powder is obtained.
(5) Ball milling the composite powder for 2 hours at a ball-material ratio of 10:1 and a rotating speed of 300r/min, suction filtering, drying, and finally carrying out heating reduction treatment in a tube furnace at 250 ℃ for 6 hours at a heating rate of 10 ℃/min under a reducing atmosphere of N 2 And H 2 The total flow of gas was 200sccm, where N 2 And H is 2 The flow ratio is 10:1, and NCNTs/Cu composite powder is obtained;
(6) And (3) performing SPS sintering on the NCNTs/Cu composite powder, wherein the heating rate is 150 ℃/min, the sintering temperature is 600 ℃, and the heat preservation time is 20min, so as to obtain the nitrogen-doped carbon nano tube composite reinforced copper-based material.
The obtained nitrogen-doped carbon nano tube composite reinforced copper-based material has the tensile strength of 263MPa, the breaking elongation of 15% and the conductivity of 91.2% IACS.
Comparative example 1
The preparation method of the carbon nano tube composite reinforced copper-based material specifically comprises the following steps:
(1) Performing ultrasonic dispersion on 36mg of carbon nano tubes in 50ml of water for 1 hour, adding the carbon nano tubes into 0.2ml of copper acetate solution, stirring, adding 7mol of sodium hydroxide solution, heating, finally adding 2mol of glucose solution for reaction, washing and drying after the reaction is finished to obtain CNTs/CuO composite powder.
(2) Placing the CNTs/CuO composite powder in a tube furnace for heating and reducing treatment at 350 ℃ for 5 hours, wherein the heating rate is 10 ℃/min, and the reducing atmosphere is N 2 And H 2 The total flow of gas was 200sccm, where N 2 And H is 2 The flow ratio is 10:1, and the composite powder is obtained.
(3) Ball milling the composite powder for 2 hours at a ball-material ratio of 10:1 and a rotating speed of 250r/min, suction filtering, drying, and finally carrying out heating reduction treatment in a tube furnace at 250 ℃ for 5 hours at a heating rate of 10 ℃/min under a reducing atmosphere of N 2 And H 2 The total flow of gas was 200sccm, where N 2 And H is 2 The flow ratio is 10:1, and CNTs/Cu composite powder is obtained;
(4) And sintering the CNTs/Cu composite powder through SPS, wherein the heating rate is 100 ℃/min, the sintering temperature is 700 ℃, and the heat preservation time is 10min, so as to obtain the carbon nano tube composite reinforced copper-based material.
The tensile strength of the obtained nanotube composite reinforced copper-based material is 241MPa, the elongation at break is 10%, and the conductivity is 89.3% IACS.
Comparative example 2
The preparation method of the nitrogen-doped carbon nanotube reinforced high-conductivity copper-based composite material in the comparative example is only different from that in the example 1: in the step (2), 100sccm of N is introduced 2 High purity Ar was not introduced.
The obtained nitrogen-doped carbon nano tube composite reinforced copper-based material has the tensile strength of 255MPa, the breaking elongation of 22% and the conductivity of 92.9% IACS.
Due to the presence of a small amount of Ar, N can be promoted 2 Dissociation in the plasma treatment increased the N content of the doped CNTs, and less N content of the doped CNTs without Ar, resulting in inferior performance to the example samples.
Comparative example 3
The preparation method of the nitrogen-doped carbon nanotube reinforced high-conductivity copper-based composite material in the comparative example is only different from that in the example 1: in the step (2), 50sccm of N is introduced 2 And 50sccm of high purity Ar.
The obtained nitrogen-doped carbon nano tube composite reinforced copper-based material has tensile strength of 251MPa, elongation at break of 25% and conductivity of 93.3% IACS.
Because the amount of the introduced Ar is excessive, the Ar is used as a protective gas, the state is very stable, a large amount of Ar exists, and the plasma cannot ionize N 2 Resulting in less N content incorporated into CNTs and less desirable enhancement results, resulting in poorer performance than the example samples.
Comparative example 4
The preparation method of the nitrogen-doped carbon nanotube reinforced high-conductivity copper-based composite material in the comparative example is only different from that in the example 1: in the step (2), 100sccm of high-purity Ar is introduced, and N is not introduced 2 。
The obtained nitrogen-doped carbon nano tube composite reinforced copper-based material has the tensile strength of 245MPa, the breaking elongation of 13% and the conductivity of 89.1% IACS.
Because Ar is only introduced, no N is doped into CNTs due to no nitrogen source, so that the interface bonding strength between the CNTs and a Cu matrix is low, and the mechanical property and the electrical property of the carbon nano tube composite reinforced copper-based material are reduced.
Comparative example 5
The preparation method of the copper-based material comprises the following steps:
(1) 0.2ml of copper acetate solution is stirred uniformly, 7mol of sodium hydroxide solution is added for heating, and finally 2mol of glucose solution is added for reaction, and after the reaction is finished, the CuO powder is washed and dried.
(4) Placing CuO powder into a tube furnace for heating and reducing at 350deg.C for 5 hr at a heating rate of 10deg.C/min under N reducing atmosphere 2 And H 2 The total flow of gas was 200sccm, where N 2 And H is 2 The flow ratio is 10:1, and Cu powder is obtained.
(5) Ball milling Cu powder for 2 hours at a ball-material ratio of 10:1 and a rotating speed of 250r/min, suction filtering, drying, and finally carrying out heating reduction treatment in a tube furnace at 250 ℃ for 5 hours at a heating rate of 10 ℃/min under a reducing atmosphere of N 2 And H 2 The total flow of gas was 200sccm, where N 2 And H is 2 The flow ratio is 10:1, and pure Cu powder is obtained;
(6) And sintering the pure Cu powder by SPS, wherein the heating rate is 100 ℃/min, the sintering temperature is 700 ℃, and the heat preservation time is 10min, so as to obtain the bulk copper-based material.
The tensile strength of the obtained copper-based material is 224MPa, the breaking elongation is 36%, and the conductivity is 95.9% IACS.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (9)

1. The preparation method of the nitrogen-doped carbon nanotube reinforced high-conductivity copper-based composite material is characterized by comprising the following steps of:
(1) Introducing N 2 Carrying out plasma treatment on the carbon nano tube by using the mixed gas of Ar, and cooling to room temperature in a protective atmosphere after the plasma treatment is finished to obtain the nitrogen-doped carbon nano tube;
(2) Performing ultrasonic dispersion on the nitrogen-doped carbon nano tube in water, then adding the carbon nano tube into a copper acetate solution, and preparing NCNTs/CuO composite powder by a molecular-level blending method;
(3) Carrying out reduction annealing treatment on NCNTs/CuO composite powder, wherein the reduction atmosphere is N 2 And H 2 Obtaining NCNTs/Cu composite powder;
(4) Ball milling and drying the composite powder, and then carrying out reduction annealing treatment in the reducing atmosphere of N 2 And H 2 Obtaining NCNTs/Cu composite powder;
(5) And (3) sintering the NCNTs/Cu composite powder by discharge plasma to obtain the nitrogen-doped carbon nano tube reinforced copper-based composite block material.
2. The method for preparing a nitrogen-doped carbon nanotube-reinforced high-conductivity copper-based composite material according to claim 1, wherein the purity of the carbon nanotubes is 98% or more, the outer diameter is 20-50nm, and the length is 10-50 μm.
3. The method for preparing a nitrogen-doped carbon nanotube-reinforced highly conductive copper-based composite material according to claim 1, wherein in the step (1), the plasma treatment power is 150 to 250W, N 2 The flow rate of Ar is 60-90 sccm, and the flow rate of Ar is 10-40 sccm.
4. The method of preparing a nitrogen-doped carbon nanotube-reinforced highly conductive copper-based composite material according to claim 1, wherein in the step (3), the volume fraction of Cu in the NCNTs/Cu composite powder is 97.5% to 99.5%, and the volume fraction of the nitrogen-doped carbon nanotubes is 0.5% to 2.5%.
5. The method for preparing a nitrogen-doped carbon nanotube-reinforced highly conductive copper-based composite material according to claim 1, wherein the molecular-scale blending method comprises the steps of: adding NCNTs into copper acetate solution, stirring, adding sodium hydroxide solution, heating, adding glucose solution, reacting, washing after the reaction is finished, and drying to obtain NCNTs/CuO composite powder.
6. The method for preparing a nitrogen-doped carbon nanotube-reinforced highly conductive copper-based composite material according to claim 1, wherein the molar ratio of copper acetate, sodium hydroxide and glucose is 0.2:7:2.
7. the method for preparing a nitrogen-doped carbon nanotube-reinforced highly conductive copper-based composite material according to claim 1, wherein in the step (3), the reduction annealing temperature is 250-350 ℃ and the time is 4-7 hours.
8. The method for preparing the nitrogen-doped carbon nanotube-reinforced high-conductivity copper-based composite material according to claim 1, wherein in the step (4), the ball milling time is 2-3 hours, and the rotating speed is 250-350r/min; the temperature of the reduction annealing is 200-300 ℃ and the time is 3-6 hours.
9. The method for preparing the nitrogen-doped carbon nanotube-reinforced high-conductivity copper-based composite material according to claim 1, wherein the temperature rise rate of spark plasma sintering is 120-200 ℃/min, the temperature is 600-900 ℃, and the heat preservation time is 5-20min.
CN202310719391.1A 2023-06-16 2023-06-16 Preparation method of nitrogen-doped carbon nanotube reinforced high-conductivity copper-based composite material Pending CN116727676A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117187617A (en) * 2023-09-21 2023-12-08 上海理工大学 High-heat-conductivity composite material and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117187617A (en) * 2023-09-21 2023-12-08 上海理工大学 High-heat-conductivity composite material and preparation method thereof

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