CN112877561B - Graphene-carbon nanotube commonly-reinforced copper-based composite material and preparation method thereof - Google Patents

Graphene-carbon nanotube commonly-reinforced copper-based composite material and preparation method thereof Download PDF

Info

Publication number
CN112877561B
CN112877561B CN202110045837.8A CN202110045837A CN112877561B CN 112877561 B CN112877561 B CN 112877561B CN 202110045837 A CN202110045837 A CN 202110045837A CN 112877561 B CN112877561 B CN 112877561B
Authority
CN
China
Prior art keywords
graphene
carbon nanotube
copper
network
composite material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110045837.8A
Other languages
Chinese (zh)
Other versions
CN112877561A (en
Inventor
杨名
李铁军
刘文祎
王耀奇
侯红亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AVIC Beijing Aeronautical Manufacturing Technology Research Institute
Original Assignee
AVIC Beijing Aeronautical Manufacturing Technology Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by AVIC Beijing Aeronautical Manufacturing Technology Research Institute filed Critical AVIC Beijing Aeronautical Manufacturing Technology Research Institute
Priority to CN202110045837.8A priority Critical patent/CN112877561B/en
Publication of CN112877561A publication Critical patent/CN112877561A/en
Application granted granted Critical
Publication of CN112877561B publication Critical patent/CN112877561B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • 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
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C22C2026/002—Carbon nanotubes

Abstract

The invention relates to the technical field of metal matrix composite materials, and particularly discloses a graphene-carbon nanotube jointly reinforced copper matrix composite material and a preparation method thereof. The copper-based composite material disclosed by the invention contains most of oriented copper-carbon heterogeneous interfaces and pi-pi bonds between graphene and carbon nanotubes, so that the mechanical strength of the composite material can be enhanced through mechanisms such as interface combination, load transfer, pull-out effect and dispersion strengthening, and electrons can be rapidly and directionally transmitted across the copper-carbon heterogeneous interfaces. The preparation method combines the processes of carbon nanotube network construction, graphene-carbon nanotube composite network construction, copper electrodeposition, vacuum hot-pressing sintering, heat treatment and the like, successfully prepares the interpenetrating and oriented network-like composite copper-based composite material, effectively increases the bonding interface of a copper matrix and a conductive network, improves the fine structure of the conductive network, and obviously improves the mechanical strength and the conductivity while reducing the weight.

Description

Graphene-carbon nanotube commonly-reinforced copper-based composite material and preparation method thereof
Technical Field
The invention relates to the technical field of metal matrix composite materials, in particular to a graphene-carbon nanotube jointly reinforced copper matrix composite material and a preparation method thereof.
Background
Copper and copper alloy have the characteristics of electric conductivity, heat conductivity, corrosion resistance, good plasticity and the like, are important basic materials for national defense and military industry development and national economy construction, and are widely applied to various fields of national defense industry such as electronic information, aerospace and the like. With the development of material science and modern industry, higher requirements are put on the performance of copper, and the copper-based composite material is possible to meet the requirements. In the copper-based composite material, the improvement of mechanical strength and the improvement of electrical conductivity are a pair of outstanding contradictions, and the two are difficult to be synergistically improved.
At present, four methods are mainly used for improving the mechanical strength or the electrical conductivity of a copper-based composite material, one method is to manufacture high-purity copper and single crystal copper, reduce impurities and defects in the pure copper and improve the electrical conductivity, but the method has the defects that the electrical conductivity is close to the physical upper limit, the optimization space is very limited, the tensile strength of the material is reduced, and the technical difficulty and the production cost are high; secondly, the mechanical strength of the material is improved by adopting an alloying method, but the mechanical strength is improved by the method, the conductivity is reduced at the same time, particularly under the condition that the conductivity is generally lower than that of copper, the conductivity of the copper alloy is increased firstly and then reduced along with the increase of the content of alloy elements, and the conductivity is difficult to exceed that of copper; thirdly, ceramic particles and/or carbon fibers are used for preparing the composite material, so that the mechanical property of the material is improved, but the method has no improvement effect on the conductivity, and the conductivity is reduced; fourthly, the particle-reinforced copper-based composite material is prepared by compounding nano materials, the currently most commonly used reinforcements are carbon nanotubes and graphene, the two reinforcements can be added independently or in a mixed manner, and the preparation method of the corresponding composite material comprises ball milling, interface modification, electrodeposition and the like. The copper-based composite material reinforced by the nano material has great potential for improving the performance, but the effect is mainly focused on the increase of the mechanical strength, the conductivity is still difficult to exceed that of copper, and the weight reduction effect is limited. The reasons for this phenomenon are mainly three: the composite quantity of the reinforcement is low, the reinforcement is not uniformly oriented and distributed in the copper matrix, and the specific surface area of the reinforcement is large and the reinforcement is easy to agglomerate to form defects. At present, methods such as grafting functional groups, positive and negative electric attraction, introduction of interface compounds and the like are adopted to solve the agglomeration problem, and the methods have good effects on enhancing interface combination and increasing mechanical strength, but hinder electron transmission on a graphene-copper interface, have different reductions in conductivity compared with copper, and have no obvious effect on weight reduction.
In summary, the existing composite methods have disadvantages, and most of the methods can effectively improve the mechanical strength of the copper-based composite material, but can cause the reduction of the electrical conductivity, and cannot realize the synergistic improvement of the mechanical strength and the electrical conductivity of the copper-based composite material while reducing the weight.
Disclosure of Invention
First, technical problem to be solved
The invention mainly solves the technical problem of providing a graphene-carbon nanotube commonly reinforced copper-based composite material and a preparation method thereof, so as to realize the synergistic improvement of mechanical strength and electrical conductivity of the copper-based composite material while reducing weight.
Second, technical scheme
In a first aspect, the invention provides a graphene-carbon nanotube co-reinforced copper-based composite material, which comprises a copper matrix, and graphene and carbon nanotubes which are distributed in the copper matrix in an oriented manner, wherein a network structure of the carbon nanotubes forms a basic skeleton of graphene dispersion composite, and pi-pi bonds are formed between the graphene and the carbon nanotubes.
In a preferred embodiment, the mass ratio of the graphene to the carbon nanotubes in the copper-based composite material is 1:1-1: 20. Still further preferably, the mass ratio of graphene to carbon nanotubes in the copper-based composite material is 1: 10.
As a preferred embodiment, the compounding amount of the graphene and the carbon nanotubes in the copper-based composite material is 8-40 wt%. Still more preferably, the compounding amount of the graphene and the carbon nanotubes in the copper-based composite material is 8-10 wt%.
In a second aspect, the invention provides a preparation method of a graphene-carbon nanotube jointly reinforced copper-based composite material, which comprises the following steps:
(1) preparing an oriented carbon nanotube network by a floating catalysis method;
(2) dispersing and compounding graphene in the oriented carbon nanotube network to form a graphene-carbon nanotube composite network;
(3) depositing copper on the graphene-carbon nanotube composite network by adopting an electrochemical method to obtain a deposition body;
(4) and carrying out vacuum hot-pressing sintering on the deposited body after compression molding, and then carrying out heat treatment in an inert gas environment to obtain the graphene-carbon nanotube jointly reinforced copper-based composite material.
As a preferred embodiment, in step (1), the preparation parameters of the floating catalysis method are as follows: the injection rate is 0.1-20mL/h, the carrier gas is pure hydrogen or hydrogen-argon mixed gas (the mixing volume ratio is 10:1-1:10), the total flow of the carrier gas is 600-. Still more preferably, the preparation parameters of the floating catalyst method are: the injection rate is 1.0mL/h, the carrier gas is pure hydrogen, the total flow of the carrier gas is 1000sccm, the synthesis temperature is 1170 ℃, and the synthesis speed is 2.5 m/min.
As a preferred embodiment, in the step (2), the graphene is prepared by a plasma enhanced synthesis method, the graphene is scattered from the outlet of the reactor to the oriented carbon nanotube network due to gravity, and the content of the graphene in the graphene-carbon nanotube composite network is controlled according to the difference of scattering time. The carbon source in the plasma enhanced synthesis method is ethanol, the injection speed is 0.1-10mL/h, and the vacuum degree of a plasma generator is 10-4-10-6Pa, argon as the glow generating gas and 5-40W of power. More preferably, the carbon source in the plasma enhanced synthesis method is ethanol, the injection speed is 0.5mL/h, the vacuum degree of a plasma generator is 2.5 multiplied by 10-5Pa, the glow-generating gas is argon, and the power is 23W.
As a preferred embodiment, in the step (2), the mass ratio of graphene to carbon nanotubes in the graphene-carbon nanotube composite network is 1:1 to 1: 20. Still further preferably, the mass ratio of graphene to carbon nanotubes in the graphene-carbon nanotube composite network is 1: 10.
As a preferred embodiment, in the step (3), the electrochemical method may adopt a two-electrode method or a three-electrode method. In the two-electrode method, the graphene-carbon nanotube composite network is used as a working electrode, and a copper wire is used as an anode; constant-current deposition is adopted, the voltage is 5-36V, the current is 2mA, and the deposition time is 10-600 s. Still more preferably, in the two-electrode method, the voltage is 24V, the current is 2mA, and the deposition time is 300 s. In a three-electrode processIn the method, a graphene-carbon nanotube composite network is used as a working electrode, a copper wire is used as an anode, and Cu/CuSO is added4The electrode is used as a reference electrode; constant voltage deposition is adopted, the voltage is 24V, the current is 0.05-6mA, and the deposition time is 10-600 s. Still more preferably, in the three-electrode method, the voltage is 24V, the current is 2mA, and the deposition time is 300 s.
In a preferred embodiment, in step (3), the deposition solution in the electrochemical method is CuSO4·5H2O、H2SO4(98%) and polyoxyethylene octylphenol ether-10, wherein CuSO4·5H2O concentration is 50-300g/L, H2SO4(98%) concentration is 5-20mL/L, and polyoxyethylene octyl phenol ether-10 concentration is 0.2-5 mL/L. Even more preferably, the deposition solution has CuSO4·5H2The concentration of O is 170g/L, H2SO4The concentration of (98%) was 11mL/L, and the concentration of polyoxyethylene octylphenol ether-10 was 1 mL/L.
In a preferred embodiment, in the step (4), the vacuum degree of the vacuum hot-pressing sintering is 1-20Pa, the sintering temperature is 700-1200 ℃, the sintering pressure is 50-300MPa, and the sintering time is 0.5-2 h. Still more preferably, the vacuum degree of the vacuum hot-pressing sintering is 5Pa, the sintering temperature is 1200 ℃, the sintering pressure is 200MPa, and the sintering time is 2 h.
As a preferred embodiment, in the step (4), the heat treatment is carried out under an argon atmosphere, the heat treatment temperature is 200-400 ℃, and the treatment time is 30-240 min. Still more preferably, the heat treatment temperature is 200 ℃ and the treatment time is 30 min.
As a preferred embodiment, the preparation method of the graphene-carbon nanotube co-reinforced copper-based composite material provided by the invention comprises the following steps:
(1) preparation of oriented carbon nanotube networks
Preparing an oriented carbon nanotube network by adopting a floating catalysis method, wherein the preparation parameters are as follows: the liquid injection rate is 0.1-20mL/h, the carrier gas is pure hydrogen or a hydrogen-argon mixed gas, the total flow of the carrier gas is 600-;
(2) compounding graphene in carbon nanotube networks
Dispersing and compounding graphene in the oriented carbon nanotube network to form a graphene-carbon nanotube composite network; the graphene is prepared by adopting a plasma enhanced synthesis method, ethanol is selected as a carbon source, the injection speed is 0.1-10mL/h, and the vacuum degree of a plasma generator is 10-4-10-6Pa, using argon as a glow-generating gas, wherein the power is 5-40W, and the graphene is scattered into an oriented carbon nanotube network from the outlet of the reactor due to gravity, and the mass ratio of the graphene to the carbon nanotubes is 1:1-1: 20;
(3) deposition of copper on composite networks
Depositing copper on the graphene-carbon nanotube composite network by adopting an electrochemical method to obtain a deposition body; the electrochemical method adopts a two-electrode method or a three-electrode method, wherein a graphene-carbon nanotube composite network is used as a working electrode in the two-electrode method, a copper wire is used as an anode, constant-current deposition is adopted, the voltage is 5-36V, the current is 2mA, and the deposition time is 10-600 s; in the three-electrode method, the graphene-carbon nanotube composite network is used as a working electrode, the copper wire is used as an anode, and Cu/CuSO is added4The electrode is used as a reference electrode, constant voltage deposition is adopted, the voltage is 24V, the current is 0.05-6mA, and the deposition time is 10-600 s; the deposition solution is CuSO4·5H2O, concentrated H2SO4And a mixed aqueous solution of polyoxyethylene octylphenol ether-10, CuSO4·5H2O concentration is 50-300g/L, and H concentration is high2SO4The concentration of the polyoxyethylene octyl phenol ether is 5-20mL/L, and the concentration of the polyoxyethylene octyl phenol ether-10 is 0.2-5 mL/L;
(4) preparation of copper-based composite material
Putting the sediment body into a mould for compression molding, and then performing vacuum hot-pressing sintering, wherein the vacuum degree of the vacuum hot-pressing sintering is 1-20Pa, the sintering temperature is 700-1200 ℃, the sintering pressure is 50-300MPa, and the sintering time is 0.5-2 h; and then carrying out heat treatment in an argon environment at the temperature of 200-400 ℃ for 30-240min to obtain the graphene-carbon nanotube commonly-reinforced copper-based composite material.
Third, beneficial effect
The invention provides a graphene-carbon nanotube commonly reinforced copper-based composite material, which comprises a majority of oriented copper-carbon heterogeneous interfaces and pi-pi bonds between graphene and carbon nanotubes, can enhance the mechanical strength of the composite material through mechanisms such as interface combination, load transfer, pull-out effect and dispersion strengthening, and can enable electrons to rapidly and directionally transmit across the copper-carbon heterogeneous interfaces. Experiments prove that the tensile strength of the graphene-carbon nanotube jointly reinforced copper-based composite material is not lower than 334.0MPa and can reach 402.6 MPa; the conductivity is not lower than 11.5% IACS, and can reach 101.38% IACS at most.
As mentioned above, the composite method in the prior art can mostly effectively improve the mechanical strength of the copper-based composite material, but causes the decrease of the electrical conductivity, which is caused by three reasons, on one hand, the composite amount of the adopted reinforcement (graphene, carbon nanotube or the mixture of the two) in the copper matrix is less, generally less than 1.5 wt%, while the composite amount required for theoretically calculating the optimal performance of the composite material is 40-50 wt% (o.hjorstam, p.isberg, S).
Figure BDA0002897251230000051
et al.Can we achieve ultra-low resistivity in carbon nanotube-based metal composites？[J]Appl.phys.a,2004,78: 1175-; on the other hand, the reinforcements are dispersed and distributed in the copper matrix and are not oriented, the load transmission capacity and the electron transmission capacity of the graphene and the carbon nano tube are anisotropic, and the dispersion distribution proves that the mechanical property can be effectively enhanced, but the excellent electron transmission capacity of the graphene or the carbon nano tube is difficult to utilize; thirdly, the graphene and the carbon nano tube belong to nano materials, the specific surface area is large, the interface wettability with copper is poor, the agglomeration of the reinforcing phase is difficult to avoid in the preparation process, the agglomeration of the reinforcing phase is equivalent to the defect in the composite material, and the performance of the composite material can be seriously influenced.
Aiming at the problems, the invention provides a preparation method of a copper-based composite material, which can simultaneously solve the problems of low composite quantity of a reinforcement, difficult orientation of the reinforcement and agglomeration in the preparation process, and the performance of the composite material can achieve the synergistic improvement of mechanical strength and electrical conductivity under certain weight reduction. The method adopts an oriented carbon nanotube network as a basic framework, firstly graphene is dispersed and compounded in the oriented carbon nanotube network, then copper is deposited on the framework compounded with the graphene by an electrodeposition method, then the obtained composite blank is compacted by a die, then vacuum hot-pressed and sintered, and finally the graphene-carbon nanotube jointly reinforced copper-based composite material is obtained by heat treatment.
The method of the invention firstly provides a three-dimensional interpenetrating orientation network preparation process route, combines the processes of carbon nanotube network construction, graphene-carbon nanotube composite network construction, copper electrodeposition, vacuum hot-pressing sintering, heat treatment and the like, successfully prepares the interpenetrating and oriented network-like composite copper-based composite material, realizes the tight connection of the reinforcement and the copper matrix interface, and obviously improves the mechanical strength and the conductivity while reducing the weight. The method is based on the graphene composite carbon nanotube oriented network, effectively increases the bonding interface of copper and the network, improves the fine structure of the conductive network, and lays a technical foundation for preparing a high-performance copper-based composite material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the embodiments of the present invention will be briefly described below. It is obvious that the drawings described below are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is a schematic diagram of a preparation method of a graphene-carbon nanotube co-reinforced copper-based composite material provided by the invention.
Fig. 2 is an SEM photograph of the graphene-carbon nanotube composite network prepared in the example of the present invention.
Fig. 3 is a raman spectrum of the graphene-carbon nanotube composite network prepared in the embodiment of the present invention.
Fig. 4 is a sample photograph of the graphene-carbon nanotube co-reinforced copper-based composite material prepared in the embodiment of the present invention.
Detailed Description
Embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. The following detailed description of the embodiments and the accompanying drawings are used to illustrate the technical solutions of the present invention, but are not used to limit the scope of the present invention, i.e., the present invention is not limited to the embodiments described in the embodiments. Any modification, replacement or improvement of the raw materials and means is covered without departing from the spirit of the present invention.
It should be noted that the embodiments of the present invention and features of the embodiments may be combined with each other without conflict. The raw materials, instruments and equipment used in the following examples and experimental examples are commercially available.
Example 1
The graphene-carbon nanotube jointly reinforced copper-based composite material in the embodiment comprises a copper matrix, and graphene and carbon nanotubes which are distributed in the copper matrix in an oriented manner, wherein a network structure of the carbon nanotubes forms a basic skeleton of graphene dispersion composite, and pi-pi bonds are formed between the graphene and the carbon nanotubes.
In this embodiment, the preparation method of the graphene-carbon nanotube jointly reinforced copper-based composite material (shown in fig. 1) includes the following steps:
(1) preparation of oriented carbon nanotube networks
Preparing an oriented carbon nanotube network by adopting a floating catalysis method, wherein the preparation parameters are as follows: the injection rate is 1.0mL/h, the carrier gas is pure hydrogen, the total flow of the carrier gas is 1000sccm, the synthesis temperature is 1170 ℃, and the synthesis speed is 2.5 m/min;
(2) compounding graphene in carbon nanotube networks
Dispersing and compounding graphene in the oriented carbon nanotube network to form a graphene-carbon nanotube composite network (shown in fig. 2 and 3); the graphene is prepared by adopting a plasma enhanced synthesis method, ethanol is selected as a carbon source, the injection speed is 0.5mL/h, and the vacuum degree of a plasma generator is 2.5 multiplied by 10-5Pa, using argon as a glow gas, ensuring that the power is 23W, scattering graphene into an oriented carbon nanotube network from the outlet of the reactor due to gravity, wherein the mass ratio of the graphene to the carbon nanotubes is 1: 10;
(3) deposition of copper on composite networks
Depositing copper on the graphene-carbon nanotube composite network by adopting a three-electrode method to obtain a deposition body; in the three-electrode method, the graphene-carbon nanotube composite network is used as a working electrode, the copper wire is used as an anode, and the Cu/CuSO4The electrode is used as a reference electrode, constant voltage deposition is adopted, the voltage is 24V, the current is 2mA, and the deposition time is 300 s; the deposition solution is CuSO4·5H2O、H2SO4(98%) mixed aqueous solution with polyoxyethylene octylphenol ether-10, CuSO4·5H2The concentration of O is 170g/L, H2SO4(98%) concentration is 11mL/L, and polyoxyethylene octyl phenol ether-10 concentration is 1 mL/L;
(4) preparation of copper-based composite material
Putting the sediment into a mold for compression molding, and then putting the mould into a vacuum hot pressing furnace for sintering, wherein the vacuum degree is 5Pa, the sintering temperature is 1200 ℃, the sintering pressure is 200MPa, and the sintering time is 2h, so as to obtain a composite material; and (3) placing the composite material in argon gas for heat treatment at 200 ℃ for 30min to obtain the graphene-carbon nanotube jointly reinforced copper-based composite material (shown in figure 4).
Example 2
The graphene-carbon nanotube jointly reinforced copper-based composite material in the embodiment comprises a copper matrix, and graphene and carbon nanotubes which are distributed in the copper matrix in an oriented manner, wherein a network structure of the carbon nanotubes forms a basic skeleton of graphene dispersion composite, and pi-pi bonds are formed between the graphene and the carbon nanotubes.
The preparation method of the graphene-carbon nanotube jointly reinforced copper-based composite material in the embodiment comprises the following steps:
(1) preparation of oriented carbon nanotube networks
Preparing an oriented carbon nanotube network by adopting a floating catalysis method, wherein the preparation parameters are as follows: the injection rate is 20mL/h, the carrier gas is hydrogen-argon mixed gas (volume ratio is 1:10), the total flow of the carrier gas is 600sccm, the synthesis temperature is 1170 ℃, and the synthesis speed is 2.5 m/min;
(2) compounding graphene in carbon nanotube networks
Mixing graphene oxideThe graphene and the carbon nanotube are dispersed and compounded in the oriented carbon nanotube network to form a graphene-carbon nanotube composite network; the graphene is prepared by adopting a plasma enhanced synthesis method, ethanol is selected as a carbon source, the injection speed is 0.1mL/h, and the vacuum degree of a plasma generator is 10-6Pa, using argon as a glow gas, ensuring the power to be 40W, scattering graphene into an oriented carbon nanotube network from the outlet of the reactor due to gravity, wherein the mass ratio of the graphene to the carbon nanotubes is 1: 1;
(3) deposition of copper on composite networks
Depositing copper on the graphene-carbon nanotube composite network by adopting a two-electrode method to obtain a deposition body; in the two-electrode method, a graphene-carbon nanotube composite network is used as a working electrode, a copper wire is used as an anode, constant-current deposition is adopted, the voltage is 18V, the current is 2mA, and the deposition time is 600 s; the deposition solution is CuSO4·5H2O、H2SO4(98%) mixed aqueous solution with polyoxyethylene octylphenol ether-10, CuSO4·5H2O concentration of 300g/L, H2SO4(98%) the concentration is 20mL/L, and the concentration of polyoxyethylene octyl phenol ether-10 is 0.5 mL/L;
(4) preparation of copper-based composite material
Putting the sediment into a mold for compression molding, and then putting the mould into a vacuum hot pressing furnace for sintering, wherein the vacuum degree is 5Pa, the sintering temperature is 1200 ℃, the sintering pressure is 300MPa, and the sintering time is 2h, so as to obtain a composite material; and (3) placing the composite material in argon gas for heat treatment at the temperature of 200 ℃ for 30min to obtain the graphene-carbon nanotube jointly reinforced copper-based composite material.
Example 3
The graphene-carbon nanotube jointly reinforced copper-based composite material in the embodiment comprises a copper matrix, and graphene and carbon nanotubes which are distributed in the copper matrix in an oriented manner, wherein a network structure of the carbon nanotubes forms a basic skeleton of graphene dispersion composite, and pi-pi bonds are formed between the graphene and the carbon nanotubes.
The preparation method of the graphene-carbon nanotube jointly reinforced copper-based composite material in the embodiment comprises the following steps:
(1) preparation of oriented carbon nanotube networks
Preparing an oriented carbon nanotube network by adopting a floating catalysis method, wherein the preparation parameters are as follows: the liquid injection rate is 0.7mL/h, the carrier gas is pure hydrogen, the total flow of the carrier gas is 1000sccm, the synthesis temperature is 1170 ℃, and the synthesis speed is 2.5 m/min;
(2) compounding graphene in carbon nanotube networks
Dispersing and compounding graphene in the oriented carbon nanotube network to form a graphene-carbon nanotube composite network; the graphene is prepared by adopting a plasma enhanced synthesis method, ethanol is selected as a carbon source, the injection speed is 2mL/h, and the vacuum degree of a plasma generator is 2.5 multiplied by 10-5Pa, using argon as a glow gas, and dispersing graphene into an oriented carbon nanotube network from an outlet of the reactor due to gravity, wherein the mass ratio of the graphene to the carbon nanotubes is 1:3, and the power is 33W;
(3) deposition of copper on composite networks
Depositing copper on the graphene-carbon nanotube composite network by adopting a three-electrode method to obtain a deposition body; in the three-electrode method, the graphene-carbon nanotube composite network is used as a working electrode, the copper wire is used as an anode, and the Cu/CuSO4The electrode is used as a reference electrode, constant voltage deposition is adopted, the voltage is 24V, the current is 6mA, and the deposition time is 600 s; the deposition solution is CuSO4·5H2O、H2SO4(98%) mixed aqueous solution with polyoxyethylene octylphenol ether-10, CuSO4·5H2O concentration of 200g/L, H2SO4(98%) the concentration is 20mL/L, and the concentration of polyoxyethylene octyl phenol ether-10 is 0.2 mL/L;
(4) preparation of copper-based composite material
Putting the sediment into a mold for compression molding, and then putting the mould into a vacuum hot pressing furnace for sintering, wherein the vacuum degree is 5Pa, the sintering temperature is 1200 ℃, the sintering pressure is 300MPa, and the sintering time is 2h, so as to obtain a composite material; and (3) placing the composite material in argon gas for heat treatment at the temperature of 200 ℃ for 60min to obtain the graphene-carbon nanotube jointly reinforced copper-based composite material.
Examples of the experiments
In this experimental example, the graphene-carbon nanotube co-reinforced copper-based composite material prepared in examples 1 to 3 was subjected to density, tensile strength, and conductivity tests, and the test results are shown in table 1 below. Wherein, the density test method refers to the measurement of the density, the oil content and the aperture ratio of the permeable sintered metal material (excluding cemented carbide) of the GB/T5163-2006 sintered metal material; tensile strength test methods see GB/T228.1-2010 metallic material tensile test part 1: room temperature test method; the conductivity test method is disclosed in GB/T27671-2011 copper section for conducting.
TABLE 1 Co-reinforcement of properties of copper-based composites by graphene-carbon nanotubes
Figure BDA0002897251230000101
As can be seen from Table 1, the tensile strength of the graphene-carbon nanotube co-reinforced copper-based composite material prepared in the embodiments 1 to 3 of the present invention is not lower than 334.0MPa, and can reach as high as 402.6MPa, and the electrical conductivity is not lower than 11.5% IACS, and can reach as high as 101.38% IACS.
The above embodiments can show that, in order to achieve the synergistic improvement of mechanical strength and electrical properties while reducing the weight of the copper-based composite material, the invention provides a novel copper-based composite material and a preparation method thereof, which solve the disadvantages of the existing composite method and provide a way for improving the comprehensive properties of the copper-based composite material.
The above description is only an example of the present invention, and does not limit the protection scope of the present invention. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the technical spirit of the invention. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (5)

1. A graphene-carbon nanotube jointly reinforced copper-based composite material is characterized in that: the composite material comprises a copper matrix, graphene and carbon nano tubes which are oriented and distributed in the copper matrix, wherein a basic skeleton of graphene dispersion composite is formed by a network structure of the carbon nano tubes, and pi-pi bonds are formed between the graphene and the carbon nano tubes;
the preparation method of the graphene-carbon nanotube commonly reinforced copper-based composite material comprises the following steps:
(1) preparing an oriented carbon nanotube network by a floating catalysis method;
(2) dispersing and compounding graphene in the oriented carbon nanotube network to form a graphene-carbon nanotube composite network;
(3) depositing copper on the graphene-carbon nanotube composite network by adopting an electrochemical method to obtain a deposition body;
(4) carrying out vacuum hot-pressing sintering on the deposited body after compression molding, and then carrying out heat treatment in an inert gas environment to obtain the graphene-carbon nanotube jointly reinforced copper-based composite material;
in the step (1), the preparation parameters of the floating catalysis method are as follows: the liquid injection rate is 0.1-20mL/h, the carrier gas is pure hydrogen or a hydrogen-argon mixed gas, the total flow of the carrier gas is 600-;
in the step (2), the graphene is prepared by adopting a plasma enhanced synthesis method, and is scattered into an oriented carbon nanotube network from an outlet of a reactor due to gravity; the carbon source in the plasma enhanced synthesis method is ethanol, the injection speed is 0.1-10mL/h, and the vacuum degree of a plasma generator is 10-4-10-6Pa, argon is used as glow generating gas, and the power is 5-40W;
in the step (3), the electrochemical method adopts a two-electrode method or a three-electrode method, wherein in the two-electrode method, the graphene-carbon nanotube composite network is used as a working electrode, a copper wire is used as an anode, and the constant-current deposition is adopted, wherein the voltage is 5-36V, the current is 2mA, and the deposition time is 10-600 s; in the three-electrode method, the graphene-carbon nanotube composite network is used as a working electrode, the copper wire is used as an anode, and the Cu/CuSO4The electrode is used as a reference electrode, constant voltage deposition is adopted, the voltage is 24V, the current is 0.05-6mA, and the deposition time is 10-600 s;
in the step (4), the heat treatment is performed in an argon environment, the heat treatment temperature is 200-400 ℃, and the treatment time is 30-240 min.
2. The graphene-carbon nanotube co-reinforced copper-based composite material according to claim 1, wherein: the mass ratio of the graphene to the carbon nano tube in the copper-based composite material is 1:1-1:20, and the compounding amount of the graphene and the carbon nano tube is 8-40 wt%.
3. A method for preparing the graphene-carbon nanotube co-reinforced copper-based composite material according to claim 1 or 2, wherein: the method comprises the following steps:
(1) preparing an oriented carbon nanotube network by a floating catalysis method;
(2) dispersing and compounding graphene in the oriented carbon nanotube network to form a graphene-carbon nanotube composite network;
(3) depositing copper on the graphene-carbon nanotube composite network by adopting an electrochemical method to obtain a deposition body;
(4) carrying out vacuum hot-pressing sintering on the deposited body after compression molding, and then carrying out heat treatment in an inert gas environment to obtain the graphene-carbon nanotube jointly reinforced copper-based composite material;
in the step (1), the preparation parameters of the floating catalysis method are as follows: the liquid injection rate is 0.1-20mL/h, the carrier gas is pure hydrogen or a hydrogen-argon mixed gas, the total flow of the carrier gas is 600-;
in the step (2), the graphene is prepared by adopting a plasma enhanced synthesis method, and is scattered into an oriented carbon nanotube network from an outlet of a reactor due to gravity; the carbon source in the plasma enhanced synthesis method is ethanol, the injection speed is 0.1-10mL/h, and the vacuum degree of a plasma generator is 10-4-10-6Pa, argon is used as glow generating gas, and the power is 5-40W;
in the step (3), the electrochemical method adopts a two-electrode method or a three-electrode method, wherein in the two-electrode method, the graphene-carbon nanotube composite network is used as a working electrode, a copper wire is used as an anode, and the constant-current deposition is adopted, wherein the voltage is 5-36V, the current is 2mA, and the deposition time is 10-600 s; in the three-electrode method, the graphene-carbon nano tube composite network is used as a working electrode, the copper wire is used as an anode, and Cu is used for the judgment of the temperature of the CuCuSO4The electrode is used as a reference electrode, constant voltage deposition is adopted, the voltage is 24V, the current is 0.05-6mA, and the deposition time is 10-600 s;
in the step (4), the heat treatment is performed in an argon environment, the heat treatment temperature is 200-400 ℃, and the treatment time is 30-240 min.
4. The production method according to claim 3, characterized in that: in the step (3), the deposition solution in the electrochemical method is CuSO4·5H2O, concentrated H2SO4And polyoxyethylene octylphenol ether-10, wherein CuSO4·5H2O concentration is 50-300g/L, and H concentration is high2SO4The concentration of the polyoxyethylene octyl phenol ether is 5-20mL/L, and the concentration of the polyoxyethylene octyl phenol ether-10 is 0.2-5 mL/L.
5. The production method according to claim 3, characterized in that: in the step (4), the vacuum degree of the vacuum hot-pressing sintering is 1-20Pa, the sintering temperature is 700-1200 ℃, the sintering pressure is 50-300MPa, and the sintering time is 0.5-2 h.
CN202110045837.8A 2021-01-14 2021-01-14 Graphene-carbon nanotube commonly-reinforced copper-based composite material and preparation method thereof Active CN112877561B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110045837.8A CN112877561B (en) 2021-01-14 2021-01-14 Graphene-carbon nanotube commonly-reinforced copper-based composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110045837.8A CN112877561B (en) 2021-01-14 2021-01-14 Graphene-carbon nanotube commonly-reinforced copper-based composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112877561A CN112877561A (en) 2021-06-01
CN112877561B true CN112877561B (en) 2022-01-21

Family

ID=76045856

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110045837.8A Active CN112877561B (en) 2021-01-14 2021-01-14 Graphene-carbon nanotube commonly-reinforced copper-based composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112877561B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113549430A (en) * 2021-08-13 2021-10-26 广西师范大学 Preparation method of carbon nanotube/copper composite heat conduction material for constructing delocalized conjugated pi-bond

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102528038A (en) * 2011-12-31 2012-07-04 浙江工业大学 Preparation method of copper/carbon nanotube composite superhydrophobic material
CN103773985A (en) * 2014-02-26 2014-05-07 哈尔滨工业大学 Efficient in-situ preparation method of graphene reinforced copper-based composite material
US20160137504A1 (en) * 2013-07-22 2016-05-19 National Institute Of Advanced Industrial Science And Technology Cnt metal composite material, and method for producing same
CN106947435A (en) * 2016-01-07 2017-07-14 中国科学院苏州纳米技术与纳米仿生研究所 High heat conducting nano carbon composite and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102528038A (en) * 2011-12-31 2012-07-04 浙江工业大学 Preparation method of copper/carbon nanotube composite superhydrophobic material
US20160137504A1 (en) * 2013-07-22 2016-05-19 National Institute Of Advanced Industrial Science And Technology Cnt metal composite material, and method for producing same
CN103773985A (en) * 2014-02-26 2014-05-07 哈尔滨工业大学 Efficient in-situ preparation method of graphene reinforced copper-based composite material
CN106947435A (en) * 2016-01-07 2017-07-14 中国科学院苏州纳米技术与纳米仿生研究所 High heat conducting nano carbon composite and preparation method thereof

Also Published As

Publication number Publication date
CN112877561A (en) 2021-06-01

Similar Documents

Publication Publication Date Title
CN108573763B (en) Preparation method of wire and cable conductor, graphene-coated metal powder and conductor
CN109207834B (en) Modified MXenes powder and preparation method and application thereof
CN109554565A (en) A kind of interface optimization method of carbon nanotube enhanced aluminium-based composite material
CN104700961A (en) Graphene/silver composite material and preparation method thereof
CN102719693A (en) Graphene and carbon nanotube mixed enhanced metal-matrix composite material and preparation method thereof
CN110983211A (en) Preparation method of carbon nano tube reinforced copper-based composite material
CN111979438A (en) Method for improving interface bonding strength of graphene copper-based composite material
CN112877561B (en) Graphene-carbon nanotube commonly-reinforced copper-based composite material and preparation method thereof
CN111996418B (en) Three-dimensional carbon nano-phase composite reinforced aluminum-based material and preparation method thereof
US20220042195A1 (en) Method for preparing copper-based graphene/aluminum composite wire with high electrical conductivity
Zhao et al. Enhancing the mechanical–electrical property simultaneously in pure copper composites by using carbonized polymer dots
CN109554564B (en) Preparation method of amorphous alloy particle and carbon nano tube reinforced aluminum matrix composite material
CN112877562B (en) Boron-doped graphene reinforced copper-based composite material and preparation method thereof
CN109321794B (en) Al2Ca particle and carbon nano tube hybrid reinforced ultralight magnesium lithium-based composite material and preparation method thereof
CN114807656B (en) Preparation method of nanoscale carbon material reinforced metal matrix composite material and product thereof
JP2552679B2 (en) Method for manufacturing high hardness composite copper alloy
CN111321314B (en) Preparation method of graphene reinforced aluminum matrix composite with strong interface bonding strength
CN113005320B (en) Method for preparing carbon nanotube/copper composite material through interface regulation
CN109321793B (en) Al2Y particle and carbon nano tube hybrid reinforced ultra-light magnesium lithium-based composite material and preparation method thereof
Li et al. Fabrication of Cu-GO layered composites with enhanced thermal conductivity by ultrasonic spraying and electrodeposition
CN114752898A (en) Preparation method of aluminum metal composite material with vertically grown graphene
CN108326311A (en) A kind of continuously extruded preparation method of graphene aluminium alloy conductor
CN111041542B (en) Composite metal wire with composite electroplated nano carbon metal film and preparation method thereof
KR20140074045A (en) Method of manufacturing metal-carbon composite with excellent mechanical property
CN110899717A (en) Al (aluminum)2O3-CNTs/Cu composite material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant