CN111151765B - Preparation method of three-dimensional structure nano carbon material reinforced copper-based composite material - Google Patents

Preparation method of three-dimensional structure nano carbon material reinforced copper-based composite material Download PDF

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CN111151765B
CN111151765B CN202010067371.7A CN202010067371A CN111151765B CN 111151765 B CN111151765 B CN 111151765B CN 202010067371 A CN202010067371 A CN 202010067371A CN 111151765 B CN111151765 B CN 111151765B
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nano carbon
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CN111151765A (en
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张剑峰
黎栋栋
刘璐
潘晓龙
张于胜
董龙龙
李亮
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Xian Rare Metal Materials Research Institute Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • 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
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • 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
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • 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
    • C22C9/00—Alloys based on copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Abstract

The invention discloses a preparation method of a three-dimensional structure nano carbon material reinforced copper-based composite material, which comprises the following steps: uniformly mixing the pretreated graphene oxide and the pretreated carboxylated carbon nano tube for amidation reaction to obtain a three-dimensional GO-polyamino compound-CNTs nano carbon material, and then dispersing the three-dimensional GO-polyamino compound-CNTs nano carbon material in a solvent containing Cu (Ac) 2 And dropwise adding the aqueous solution of ammonia into a sodium hydroxide solution for reaction to obtain GO-polyamino compound-CNTs/CuO particles with a three-dimensional structure, and then sequentially performing reduction and spark plasma sintering to obtain the nano carbon material reinforced copper-based composite material with the three-dimensional structure. According to the invention, the oxidized graphene and the carboxylated carbon nanotube are connected by adopting the polyamino compound, so that the aggregation of the oxidized graphene is inhibited, the problems of poor dispersion and wettability of the graphene and the carbon nanotube in a copper matrix are solved, the mechanical property of the three-dimensional structure carbon nanomaterial reinforced copper-based composite material is improved, and the method is suitable for practical application.

Description

Preparation method of three-dimensional structure nano carbon material reinforced copper-based composite material
Technical Field
The invention belongs to the technical field of metal matrix composite material preparation, and particularly relates to a preparation method of a three-dimensional structure nano carbon material reinforced copper matrix composite material.
Background
Copper is one of the most important metals in human production and life, has the advantages of good electric and heat conductivity, high corrosion resistance, easy formability and the like, and is widely applied to the fields of energy chemical industry, aerospace, ship manufacturing, electronic industry, transportation and the like. In recent years, with the rapid development of electronics, high-speed rail and printing industries, the demand for copper alloys has been increasing, and accordingly, higher requirements for the performance have been made. In order to meet the actual requirements, the copper alloy is required to have higher strength, hardness and wear resistance while ensuring excellent electric conductivity, heat conductivity and corrosion resistance.
The metal matrix composite material is used as an important branch of advanced composite materials, supports the leap-type development of high and new technology industry and national defense industry in China, and has wide development prospect. The metal matrix composite has superior performance incomparable with a single material, such as designability, structural integration, economic benefit maximization, functional diversity and the like. The high-performance graphene, the carbon nano tube and the derivative thereof and other reinforcements are added into the metal matrix and serve as reinforcing phases to bear the load transmitted by the metal matrix, so that the load borne by the metal matrix is reduced, and therefore, the nano carbon material reinforced metal matrix nano composite material has good mechanical properties, heat conduction and electric conduction properties, wear resistance and other properties, and has attracted extensive research interest in the field of reinforced metal matrix composite materials.
At present, the preparation method of the composite material can be divided into a ball milling method, a semi-powder metallurgy method, a molecular level mixing method, a carbon material in-situ growth method, an electrochemical reduction method and the like according to different dispersion methods of the carbon material. The difficult problems faced by the nanocarbon material reinforced copper-based nanocomposite include four aspects: the dispersion uniformity and the structural integrity of the carbon material in the metal matrix are difficult to meet simultaneously, the carbon material is easy to agglomerate in the preparation process, the wettability of the carbon material to the metal matrix is poor, the preparation method is complicated, and the industrialization is difficult.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a three-dimensional structure nanocarbon material reinforced copper-based composite material, aiming at the defects of the prior art. According to the method, a polyamino compound is adopted to connect graphene oxide with a carboxylated carbon nanotube, a mixed three-dimensional structure formed by the zigzag carboxylated multi-walled carbon nanotube and the graphene oxide is utilized to inhibit the aggregation of the graphene oxide, the problems of dispersion and poor wettability of the graphene and the carbon nanotube in a copper matrix are solved, the mechanical property of the three-dimensional structure carbon nanomaterial reinforced copper-based composite material is improved, and the three-dimensional structure carbon nanomaterial reinforced copper-based composite material with high strength, high electric conductivity, high heat conductivity and low expansion is obtained.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of a three-dimensional structure nano carbon material reinforced copper-based composite material is characterized by comprising the following steps:
step one, synthesis of a three-dimensional structure nano carbon material: respectively pretreating graphene oxide and a carboxylated carbon nanotube, dispersing the pretreated graphene oxide and the pretreated carboxylated carbon nanotube in DMF by ultrasonic waves, uniformly mixing, carrying out amidation reaction by magnetic stirring at room temperature, and sequentially filtering, washing and freeze-drying to obtain a GO-polyamino compound-CNTs nano carbon material with a three-dimensional structure;
the specific process of the graphene oxide pretreatment comprises the following steps: dispersing graphene oxide GO in DMF by ultrasonic, then sequentially adding an activating agent EDC and a stabilizing agent NHS, stirring at room temperature for activation, then sequentially filtering and washing to obtain activated GO, namely f-GO, adding an excessive polyamino compound into the f-GO, performing ultrasonic dispersion, magnetically stirring at room temperature for amidation reaction, and then sequentially filtering and washing to obtain GO-polyamino compound;
the concrete process of the carboxylic carbon nano tube pretreatment comprises the following steps: dispersing carboxylated carbon nanotube CNTs-OOH in DMF by ultrasonic, then sequentially adding activating agent EDC and stabilizing agent NHS, stirring at room temperature for activation, and then sequentially filtering and washing to obtain f-CNTs;
step two, preparing GO-polyamino compound-CNTs/CuO particles with a three-dimensional structure: dispersing the GO-polyamino compound-CNTs nano carbon material with the three-dimensional structure prepared in the step one in Cu-containing nano carbon material by ultrasonic dispersion(Ac) 2 Adding a sodium hydroxide solution dropwise into the ammonia water solution under magnetic stirring for reaction, gradually changing a reaction solution system from light blue to black, and sequentially filtering and washing to obtain GO-polyamino compounds-CNTs/CuO particles with a three-dimensional structure;
step three, preparing the GO-polyamino compound-CNTs/Cu with a three-dimensional structure: flatly laying the three-dimensional GO-polyamino compound-CNTs/CuO particles prepared in the second step in an aluminum oxide ark, and then placing the ark in a tube furnace for reduction to obtain the three-dimensional GO-polyamino compound-CNTs/Cu;
step four, preparing the three-dimensional structure nano carbon material reinforced copper-based composite material: and (3) placing the three-dimensional GO-polyamino compound-CNTs/Cu prepared in the third step into a graphite mould, performing discharge plasma sintering under a vacuum condition, cooling to room temperature, and taking out to obtain the three-dimensional nanocarbon material reinforced copper-based composite material.
According to the method, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) are adopted to activate graphene oxide, and then excessive polyamino compound is adopted to modify the activated graphene oxide so as to enable NH at one end of the polyamino compound 2 Performing amidation reaction on the functional group and carboxyl in activated graphene oxide to obtain a GO-polyamino compound, filtering and washing to remove unreacted polyamino compound, and adding a carboxyl carbon nanotube activated by EDC and NHS to enable NH at the other end of the polyamino compound in the GO-polyamino compound 2 And performing amidation reaction on the functional groups and carboxyl groups in the carboxyl carbon nano tubes activated by EDC and NHS to generate a GO-polyamino compound-CNTs nano carbon material with a three-dimensional structure, dropwise adding a sodium hydroxide solution, controlling the nucleation rate of CuO on the surface of the nano carbon material with the three-dimensional structure, preparing the nano carbon material coated with copper oxide and with the three-dimensional structure, and sequentially performing reduction and discharge plasma sintering (SPS sintering) to obtain the reinforced copper-based composite material with the nano carbon material with the three-dimensional structure.
At present, the main preparation methods of the carbon material reinforced metal matrix composite materials such as graphene are a ball milling method, a wet stirring method, an electrodeposition method and a molecular level method. Compared with the prior art, the invention synthesizes the carbon nano material reinforced copper-based composite material with the three-dimensional structure through a molecular level method, so that the GO and the CNTs are connected through a chemical bond, a mixed three-dimensional structure is formed by the zigzag carboxylated multi-walled carbon nano tube and the graphene oxide, the aggregation of the graphene oxide is inhibited, the CNTs in the three-dimensional structure are used as an expansion coordination arm, the drawing and bridging effect is realized in the stretching deformation process, the problems of dispersion and poor wettability of the graphene and the carbon nano tube in a copper matrix are solved, the synergistic effect of the graphene and the carbon nano tube reinforced copper-based composite material is utilized on the basis of keeping the advantages of the electrical property and the thermal property of copper, the mechanical property of the carbon nano material reinforced copper-based composite material with the three-dimensional structure is improved, the problem of toughness and mismatch of the traditional metal-based composite material is solved, and finally the copper-based composite material with high strength, high electric conductivity, high heat conductivity and low expansion is obtained, and the requirement of practical application is met.
The preparation method of the three-dimensional structure nanocarbon material reinforced copper-based composite material is characterized in that in the first step, the mass ratio of the graphene oxide to the carboxylated carbon nanotubes is (1-3): 1.
the preparation method of the three-dimensional structure nano carbon material reinforced copper-based composite material is characterized in that in the first step, the polyamino compound is polyether amine D400. The polyether amine D400 is used as a linear chain polymer, both ends of a linear chain of the polyether amine D400 contain amino groups, carboxyl groups in graphene oxide can be subjected to amidation reaction with the amino groups after being activated by EDC and NHS, and when the polyether amine D400 is excessive, one end of the amino groups at both ends of the linear chain of the polyether amine D400 is ensured to be reacted with the carboxyl groups in the graphene oxide, and the other end of the amino groups is connected with a carboxylated carbon nanotube through a chemical bond, so that the agglomeration of the graphene oxide is effectively inhibited.
The preparation method of the three-dimensional structure nano carbon material reinforced copper-based composite material is characterized in that the concentration of the sodium hydroxide solution in the second step is 4mol/L.
The preparation method of the three-dimensional structure nanocarbon material reinforced copper-based composite material is characterized in that in the third step, the reducing atmosphere adopted by the reduction is a mixed atmosphere of argon and hydrogen, or a mixed atmosphere of nitrogen and hydrogen, and the reduction temperature is 400-500 ℃.
The preparation method of the three-dimensional structure nano carbon material reinforced copper-based composite material is characterized in that the specific process of spark plasma sintering in the fourth step is as follows: heating to 600-750 deg.c at 50-100 deg.c/min and maintaining at 40-50 MPa sintering pressure for 5-10 min.
The room temperature in the invention is 25-35 ℃.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the three-dimensional structure carbon nano-material reinforced copper-based composite material is synthesized by a molecular level method, the mixed three-dimensional structure formed by the zigzag carboxylated multi-walled carbon nano-tube and the graphene oxide is utilized to inhibit the aggregation of the graphene oxide, and CNTs in the three-dimensional structure are used as an expansion coordination arm, so that the drawing bridging effect is achieved in the stretching deformation process, the problems of dispersion and poor wettability of the graphene and the carbon nano-tube in a copper matrix are solved, the mechanical property of the three-dimensional structure carbon nano-material reinforced copper-based composite material is improved by utilizing the synergistic effect of the graphene and the carbon nano-tube reinforced copper-based composite material on the basis of keeping the advantages of the electrical property and the thermal property of copper, the problem of toughness mismatch of the traditional metal-based composite material is solved, and the three-dimensional structure carbon nano-material reinforced copper-based composite material with high strength, high electric conductivity, high heat conductivity and low expansion is finally obtained, and the requirement of practical application is met.
2. According to the invention, the chemical bond connection of the graphene oxide and the carboxylated carbon nanotube is realized by modifying the graphene oxide and the carboxylated carbon nanotube through a chemical bond, the nano carbon material with a three-dimensional structure is constructed, the carbon nanotube is used as an expansion coordination arm to prop open the sheet graphene, so that the agglomeration of the graphene is inhibited, meanwhile, the synthesized nano carbon material with the three-dimensional structure has a large specific surface area, and is beneficial to metal ion adsorption, in the molecular level synthesis process, copper oxide particles preferentially nucleate on the surface of the three-dimensional structure material, so that the uniform distribution of the graphene and the carbon nanotube in a copper matrix is ensured, and the structure of the nano carbon material with the three-dimensional structure coated by CuO particles is formed.
3. According to the invention, the graphene oxide and the carboxylated carbon nanotube are connected by adopting the polyamino compound, and as the graphene oxide and the carboxylated carbon nanotube contain oxygen-containing functional groups, cu-O bonds are formed at the interface of the Cu matrix and the nano carbon material in the subsequent discharge plasma sintering process, the interface binding force is improved, and the improvement of the mechanical property of the three-dimensional nano carbon material reinforced copper-based composite material is facilitated.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a flow chart of the manufacturing process of the present invention.
FIG. 2 is a temperature profile of the spark plasma sintering process of example 1 of the present invention.
FIG. 3a is an SEM image of the three-dimensional structure GO-D400-CNTs/CuO particles prepared in example 1 of the present invention.
FIG. 3b is an SEM image of the three-dimensional structure GO-D400-CNTs/CuO particles in the box of FIG. 3 a.
FIG. 3c is the XRD pattern of the three-dimensional GO-D400-CNTs/CuO particles prepared in example 1 of the present invention.
FIG. 4a is SEM image of the three-dimensional structure GO-D400-CNTs/Cu prepared by the example 1 of the invention.
FIG. 4b XRD pattern of GO-D400-CNTs/Cu with three-dimensional structure prepared in example 1 of the present invention.
FIG. 5 is a photo of a polished and etched light mirror of the three-dimensional nanocarbon material reinforced copper-based composite material prepared in example 1 of the present invention.
Detailed Description
As shown in fig. 1, the preparation process of the three-dimensional structure nano carbon material reinforced copper-based composite material of the present invention includes two parts, namely synthesis of the three-dimensional structure nano carbon material and preparation of the three-dimensional structure nano carbon material reinforced copper-based composite material: (1) synthesis of three-dimensional structure nano carbon material: activating graphene oxide GO by EDC and NHS, filtering and washing in sequence to obtain f-GO, adding excessive polyamino compound into the f-GO, and carrying out amidation by magnetic stirring at room temperatureReacting, and sequentially filtering and washing to obtain a GO-polyamino compound; activating carboxylated carbon nano-tubes CNTs-OOH by EDC and NHS, sequentially filtering and washing to obtain f-CNTs, ultrasonically dispersing and ultrasonically mixing GO-polyamino compounds and f-CNTs, magnetically stirring at room temperature to perform amidation reaction, and sequentially filtering, washing and freeze-drying to obtain a GO-polyamino compound-CNTs nano-carbon material (namely 3D GO-polyamino compound-CNTs) with a three-dimensional structure; (2) The three-dimensional structure nano carbon material reinforced copper-based composite material comprises the following components: ultrasonically dispersing a GO-polyamino compound-CNTs nano carbon material with a three-dimensional structure in a material containing Cu (Ac) 2 And (2) dropwise adding a sodium hydroxide solution into the ammonia water solution for reaction through a peristaltic pump, sequentially filtering and washing to obtain three-dimensional GO-polyamino compound-CNTs/CuO particles (namely 3D GO-polyamino compound-CNTs/CuO), reducing to obtain three-dimensional GO-polyamino compound-CNTs/Cu (namely 3D GO-polyamino compound-CNTs/Cu), and sintering through SPS to obtain the three-dimensional nano carbon material reinforced copper-based composite material.
Example 1
The embodiment comprises the following steps:
step one, synthesis of a three-dimensional structure nano carbon material: dispersing 0.0600g of graphene oxide GO in 200mL of DMF (dimethylformamide) by ultrasonic for 3h, then sequentially adding 0.5000g of activating agent EDC and 0.1200g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding a PBS buffer solution of 2- (N-morpholino) ethanesulfonic acid with the pH =6.0, stirring at room temperature for activating for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, centrifuging at the rotating speed of 10000rad/min for 30min to obtain activated GO, namely f-GO, adding 6mL of polyetheramine D400 into the f-GO, performing ultrasonic for 1h, adjusting the pH of the solution after ultrasonic to 7.4 by dropwise adding ammonia water with the mass concentration of 25%, performing amidation reaction for 12h by magnetic stirring at room temperature, and sequentially filtering and washing to remove redundant DMF and polyetheramine D400 to obtain GO-D400;
dispersing 0.0300g of carboxylated carbon nanotube CNTs-OOH in 100mL of DMF by ultrasonic for 3h, then sequentially adding 0.2500g of activating agent EDC and 0.060g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding PBS buffer solution of 2- (N-morpholino) ethanesulfonic acid with the pH =6.0, stirring at room temperature for activation for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, and centrifuging at the rotating speed of 10000rad/min for 30min to obtain f-CNTs;
dispersing the GO-D400 in 200mL of DMF by ultrasonic, then slowly dripping the f-CNTs, regulating the PH to 7.4 by dripping ammonia water with the mass concentration of 25%, carrying out amidation reaction for 12h by magnetic stirring at room temperature, and then sequentially carrying out filtration, washing and freeze drying to obtain a GO-D400-CNTs nano carbon material with a three-dimensional structure;
step two, preparing GO-D400-CNTs/CuO particles with a three-dimensional structure: weighing 140.6250g of Cu (Ac) 2 ·H 2 O was dissolved in 250mL of 25% by mass aqueous ammonia to obtain a solution containing Cu (Ac) 2 0.09g of the three-dimensional GO-D400-CNTs nanocarbon material prepared in the first step is dispersed in the solution containing Cu (Ac) through ultrasound for 4h 2 Adding 500mL of 4mol/L sodium hydroxide solution dropwise into the ammonia water solution under magnetic stirring by a peristaltic pump to react for 20h, changing the reaction solution system from light blue to black gradually, continuing to stir for 4h by magnetic stirring, and sequentially filtering and washing with ethanol to remove impurity ions (Na) adsorbed on the particle surface + 、OH - ) Drying in a vacuum drying oven at 60 deg.C for 12h to obtain GO-D400-CNTs/CuO particles with three-dimensional structure;
step three, preparing the GO-D400-CNTs/Cu with the three-dimensional structure: flatly laying the GO-D400-CNTs/CuO particles with the three-dimensional structure prepared in the step two in an aluminum oxide ark, and then putting the ark in a tube furnace for reduction to obtain GO-D400-CNTs/Cu with the three-dimensional structure; the atmosphere adopted in the reduction process is mixed gas of argon and hydrogen with the hydrogen volume content of 8%, the introduction flow rate of the mixed gas of argon and hydrogen is 1.5L/min, the reduction temperature is 400 ℃, and the time is 240min;
step four, preparing the three-dimensional structure nano carbon material reinforced copper-based composite material: 44.50g of the three-dimensional structure GO-D400-CNTs/Cu prepared in the third step are placed in a graphite mold, and the vacuum degree is lower than 1 multiplied by 10 -3 Performing discharge plasma sintering under the condition of Pa, cooling to room temperature, and taking out to obtain the three-dimensional nano carbon material reinforced copper baseA composite material; the specific process of spark plasma sintering is as follows: heating to 400 deg.C at a rate of 50 deg.C/min under 40MPa sintering pressure, maintaining for 5min, heating to 750 deg.C, and maintaining for 10min, wherein the heating and maintaining processes are shown in FIG. 2.
Polishing and corroding the three-dimensional structure nano carbon material reinforced copper-based composite material prepared in the embodiment, then sequentially cleaning the composite material by using distilled water and absolute ethyl alcohol, and then carrying out metallographic observation, wherein the polishing solution used for polishing and corroding is 5g of FeCl 3 20mL of dilute hydrochloric acid solution with the mass concentration of 35 percent and 70mL of anhydrous ethanol, and the polishing and corrosion time is 2 s-3 s.
Through detection, the tensile yield strength of the three-dimensional structure nano carbon material reinforced copper-based composite material prepared by the embodiment is 445.93MPa, the tensile breaking tensile strength is 370.50MPa, the reduction of area is 26.25%, and the elongation after breaking is 8.67%; after rolling at room temperature (deformation amount is 50%), the yield strength is 484.47MPa, the tensile strength is 516.44MPa, the reduction of area is 22.25%, and the elongation after fracture is 7.49%.
Fig. 3a is an SEM image of GO-D400-CNTs/CuO prepared in this embodiment, fig. 3b is an SEM image of GO-D400-CNTs/CuO particles in a box of fig. 3a, and it can be seen from fig. 3a and fig. 3b that GO-D400-CNTs/CuO particles prepared in this embodiment are formed by coating GO-CNTs with nanosheet CuO particles, and do not contain GO or CNTs that are not coated, which illustrates that the method of the present invention achieves uniform dispersion of nanocarbon materials GO or CNTs in a copper-based material.
Fig. 3c is an XRD spectrum of GO-D400-CNTs/CuO particles prepared in this example, and it can be seen from fig. 3c that the main component of GO-D400-CNTs/CuO particles is a CuO phase, and as GO-D400-CNTs/CuO particles contain fewer nanocarbon materials GO and CNTs, XRD peaks of GO or CNTs do not appear.
FIG. 4a is SEM image of GO-D400-CNTs/Cu prepared in this example, and from FIG. 4a, it can be seen that the GO-D400-CNTs/Cu prepared in this example has unchanged particle structure framework but smoother surface.
FIG. 4b shows the XRD spectrum of GO-D400-CNTs/Cu prepared in this example, and it can be seen from FIG. 4b that the main component of GO-D400-CNTs/Cu obtained after reduction only contains a Cu phase.
Fig. 5 is a photo-mirror picture of the three-dimensional structure nanocarbon material reinforced copper-based composite material prepared in this embodiment after polishing and corrosion, and it can be seen from fig. 5 that the structure of the three-dimensional structure nanocarbon material reinforced copper-based composite material prepared in this embodiment is composed of nano-crystalline grains, and the structure is compact without obvious holes, which indicates that the three-dimensional structure nanocarbon material reinforced copper-based composite material with compact structure is obtained by using the plasma sintering process of the present invention.
Comparative example 1
This comparative example comprises the following steps:
step one, preparing copper oxide: weighing 140.6250g of Cu (Ac) 2 ·H 2 O was dissolved in 250mL of 25% by mass aqueous ammonia to obtain a solution containing Cu (Ac) 2 Then adding 500mL of 4mol/L sodium hydroxide solution dropwise under magnetic stirring to react for 20h, changing the reaction solution system from light blue to black gradually, continuing to stir magnetically for 4h, and then sequentially filtering and washing with ethanol to remove impurity ions (Na) adsorbed on the particle surface + 、OH - ) Drying the CuO particles in a vacuum drying oven at 60 ℃ for 12 hours to obtain CuO particles;
step three, preparing Cu: flatly laying the CuO particles prepared in the step two in an aluminum oxide ark, and then placing the ark in a tubular furnace for reduction to obtain Cu; the atmosphere adopted in the reduction process is argon-hydrogen mixed gas with the hydrogen volume content of 8 percent, the introduction flow of the argon-hydrogen mixed gas is 1.5L/min, the reduction temperature is 400 ℃, and the time is 240min;
step four, preparing the three-dimensional structure nano carbon material reinforced copper-based composite material: 44.50g of Cu obtained in step three were placed in a graphite mold and the degree of vacuum was less than 1X 10 -3 Carrying out discharge plasma sintering under the condition of Pa, cooling to room temperature, and taking out to obtain a copper-based composite material; the specific process of spark plasma sintering is as follows: heating to 400 ℃ at the speed of 50 ℃/min under the sintering pressure of 40MPa, preserving heat for 5min, and continuously heating to 750 ℃ and preserving heat for 10min.
Through detection, the tensile yield strength of the copper-based composite material prepared by the comparative example is 317.29MPa, the tensile strength is 318.59MPa, the reduction of area is 13.78%, and the elongation after fracture is 10.8%.
Comparing the copper-based composite material prepared in the embodiment 1 and the copper-based composite material prepared in the comparative example 1, it can be seen that the yield strength of the copper-based composite material prepared by using the three-dimensional GO-D400-CNTs nanocarbon material as the reinforcing phase is increased by 128.64MPa, and the tensile strength is increased by 51.91MPa, which indicates that the carbon nanotubes in the three-dimensional carbon nanomaterial reinforced copper-based composite material prepared in the embodiment have a drawing bridging effect when being stretched and deformed, have a coordination and reinforcement effect, and can remarkably improve the strength while maintaining good plasticity.
Example 2
The embodiment comprises the following steps:
step one, synthesis of a three-dimensional structure nano carbon material: dispersing 0.0450g of graphene oxide GO in 150mL of DMF (dimethylformamide) by ultrasonic for 3h, then sequentially adding 0.3750g of activating agent EDC and 0.0900g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding PBS buffer solution of 2- (N-morpholino) ethanesulfonic acid with the pH =6.0, stirring at room temperature for activation for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, centrifuging at the rotating speed of 10000rad/min for 30min to obtain activated GO, namely f-GO, adding 4.5mL of polyetheramine D400 into f-GO, performing ultrasonic for 1h, adjusting the pH of the solution after ultrasonic to 7.4 by dropwise adding ammonia water with the mass concentration of 25%, magnetically stirring at room temperature for amidation reaction for 12h, and sequentially filtering and washing to remove redundant DMF and polyetheramine D400 to obtain GO-D400;
dispersing 0.0450g of carboxylated carbon nanotube CNTs-OOH in 150mL of DMF by ultrasonic for 3h, then sequentially adding 0.3750g of activating agent EDC and 0.0900g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding 2- (N-morpholino) ethanesulfonic acid PBS buffer solution with the pH =6.0, stirring at room temperature for activating for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, and centrifuging for 30min at the rotating speed of 10000rad/min to obtain f-CNTs;
dispersing the GO-D400 in 150mL of DMF by ultrasonic, then slowly dripping the f-CNTs, regulating the PH to 7.4 by dripping ammonia water with the mass concentration of 25%, carrying out amidation reaction for 12 hours by magnetic stirring at room temperature, and then sequentially carrying out filtering, washing and freeze drying to obtain a GO-D400-CNTs nano carbon material with a three-dimensional structure;
step two, preparing GO-D400-CNTs/CuO particles with a three-dimensional structure: 140.6250g of Cu (Ac) were weighed out 2 ·H 2 O was dissolved in 250mL of 25% by mass aqueous ammonia to obtain a solution containing Cu (Ac) 2 0.09g of the GO-D400-CNTs nanocarbon material with the three-dimensional structure prepared in the step one is dispersed in the solution containing Cu (Ac) by ultrasonic treatment for 4h 2 Adding 500mL of 4mol/L sodium hydroxide solution dropwise into the ammonia water solution under magnetic stirring by a peristaltic pump to react for 20h, changing the reaction solution system from light blue to black gradually, continuing to stir magnetically for 4h, and sequentially filtering and washing with ethanol to remove impurity ions (Na) adsorbed on the particle surface + 、OH - ) Drying in a vacuum drying oven at 60 deg.C for 12h to obtain GO-D400-CNTs/CuO particles with three-dimensional structure;
step three, preparing GO-D400-CNTs/Cu with a three-dimensional structure: flatly laying the GO-D400-CNTs/CuO particles with the three-dimensional structure prepared in the step two in an aluminum oxide ark, and then putting the ark in a tube furnace for reduction to obtain GO-D400-CNTs/Cu with the three-dimensional structure; the atmosphere adopted in the reduction process is mixed gas of argon and hydrogen with the hydrogen volume content of 8%, the introduction flow rate of the mixed gas of argon and hydrogen is 1.5L/min, the reduction temperature is 400 ℃, and the time is 240min;
step four, preparing the three-dimensional structure nano carbon material reinforced copper-based composite material: placing 44.20g of the three-dimensional structure GO-D400-CNTs/Cu prepared in the third step into a graphite mold, and keeping the vacuum degree lower than 1 multiplied by 10 -3 Performing spark plasma sintering under Pa, cooling to room temperature, and collectingObtaining the three-dimensional structure nano carbon material reinforced copper-based composite material; the specific process of spark plasma sintering is as follows: heating to 400 ℃ at the speed of 50 ℃/min under the sintering pressure of 40MPa, preserving heat for 5min, and continuously heating to 750 ℃ and preserving heat for 10min.
Example 3
The embodiment comprises the following steps:
step one, synthesizing a three-dimensional structure nano carbon material: dispersing 0.0750g of graphene oxide GO in 300mL of DMF (dimethylformamide) by ultrasonic for 3h, then sequentially adding 0.6250g of activating agent EDC and 0.1500g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding 2- (N-morpholino) ethanesulfonic acid PBS buffer solution with the pH =6.0, stirring at room temperature for activating for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, centrifuging at the rotating speed of 10000rad/min for 30min to obtain activated GO, namely f-GO, adding 7.5mL of polyetheramine D400 into the f-GO for ultrasonic 1h, adjusting the pH of the solution after ultrasonic to 7.4 by dropwise adding ammonia water with the mass concentration of 25%, magnetically stirring at room temperature for amidation reaction for 12h, and sequentially filtering and washing to remove redundant DMF and polyetheramine D400 to obtain GO-D400;
dispersing 0.0250g of carboxylated carbon nanotube CNTs-OOH in 100mL of DMF (dimethyl formamide) through ultrasonic treatment for 3h, then sequentially adding 0.2080g of activating agent EDC and 0.0500g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding PBS buffer solution of 2- (N-morpholino) ethanesulfonic acid with the pH =6.0, stirring at room temperature for activation for 30min, sequentially filtering and washing to remove redundant EDC and NHS, and centrifuging at the rotating speed of 10000rad/min for 30min to obtain f-CNTs;
dispersing the GO-D400 in 200mL of DMF by ultrasonic, then slowly dripping the f-CNTs, regulating the PH to 7.4 by dripping ammonia water with the mass concentration of 25%, carrying out amidation reaction for 12 hours by magnetic stirring at room temperature, and then sequentially carrying out filtering, washing and freeze drying to obtain a GO-D400-CNTs nano carbon material with a three-dimensional structure;
step two, preparing GO-D400-CNTs/CuO particles with a three-dimensional structure: 156.2500g of Cu (Ac) was weighed 2 ·H 2 O was dissolved in 300mL of 25% by mass aqueous ammonia to obtain a solution containing Cu (Ac) 2 0.10 of ammonia aqueous solution of (2)g, dispersing the three-dimensional GO-D400-CNTs nano carbon material prepared in the step one in the Cu (Ac) through ultrasonic for 4h 2 Then 550mL of 4mol/L sodium hydroxide solution is added dropwise into the ammonia water solution under magnetic stirring by a peristaltic pump to react for 20 hours, the reaction solution system is gradually changed from light blue to black, then the magnetic stirring is continued for 4 hours, and impurity ions (Na) adsorbed on the surfaces of the particles are removed by filtering and washing by ethanol in sequence + 、OH - ) Drying the mixture in a vacuum drying oven at 60 ℃ for 12 hours to obtain GO-D400-CNTs/CuO particles with a three-dimensional structure;
step three, preparing the GO-D400-CNTs/Cu with the three-dimensional structure: flatly laying the GO-D400-CNTs/CuO particles with the three-dimensional structure prepared in the step two in an aluminum oxide ark, and then putting the ark in a tube furnace for reduction to obtain GO-D400-CNTs/Cu with the three-dimensional structure; the atmosphere adopted in the reduction process is argon and hydrogen mixed gas with the hydrogen volume content of 8 percent, the introduction flow rate of the argon and hydrogen mixed gas is 1.5L/min, the reduction temperature is 400 ℃, and the time is 240min;
step four, preparing the three-dimensional structure nano carbon material reinforced copper-based composite material: 49.30g of three-dimensional GO-D400-CNTs/Cu prepared in the third step is placed in a graphite mold, and the vacuum degree is lower than 1 multiplied by 10 -3 Carrying out spark plasma sintering under the condition of Pa, cooling to room temperature, and taking out to obtain the three-dimensional structure nano carbon material reinforced copper-based composite material; the specific process of spark plasma sintering is as follows: heating to 400 ℃ at the speed of 50 ℃/min under the sintering pressure of 40MPa, preserving heat for 5min, and continuously heating to 750 ℃ and preserving heat for 10min.
Example 4
Step one, synthesis of a three-dimensional structure nano carbon material: dispersing 0.0600g of graphene oxide GO in 200mL of DMF (dimethylformamide) by ultrasonic for 3h, then sequentially adding 0.5000g of activating agent EDC and 0.1200g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding a PBS buffer solution of 2- (N-morpholino) ethanesulfonic acid with the pH =6.0, stirring at room temperature for activating for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, centrifuging at the rotating speed of 10000rad/min for 30min to obtain activated GO, namely f-GO, adding 6mL of polyetheramine D400 into the f-GO, performing ultrasonic 1h, adjusting the pH of the solution after ultrasonic to 7.4 by dropwise adding ammonia water with the mass concentration of 25%, magnetically stirring at room temperature for amidation reaction for 12h, and sequentially filtering and washing to remove redundant DMF and polyetheramine D400 to obtain GO-D400;
dispersing 0.0300g of carboxylated carbon nanotube CNTs-OOH in 100mL of DMF by ultrasonic for 3h, then sequentially adding 0.2500g of activating agent EDC and 0.060g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding 2- (N-morpholino) ethanesulfonic acid PBS buffer solution with the pH =6.0, stirring at room temperature for activating for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, and centrifuging for 30min at the rotating speed of 10000rad/min to obtain f-CNTs;
dispersing the GO-D400 in 200mL of DMF by ultrasonic, then slowly dripping the f-CNTs, regulating the PH to 7.4 by dripping ammonia water with the mass concentration of 25%, carrying out amidation reaction for 12h by magnetic stirring at room temperature, and then sequentially carrying out filtration, washing and freeze drying to obtain a GO-D400-CNTs nano carbon material with a three-dimensional structure;
step two, preparing GO-D400-CNTs/CuO particles with a three-dimensional structure: 140.6250g of Cu (Ac) were weighed out 2 ·H 2 O was dissolved in 250mL of 25% by mass aqueous ammonia to obtain a solution containing Cu (Ac) 2 0.09g of the three-dimensional GO-D400-CNTs nanocarbon material prepared in the first step is dispersed in the solution containing Cu (Ac) through ultrasound for 4h 2 Adding 500mL of 4mol/L sodium hydroxide solution dropwise into the ammonia water solution under magnetic stirring by a peristaltic pump to react for 20h, changing the reaction solution system from light blue to black gradually, continuing to stir magnetically for 4h, and sequentially filtering and washing with ethanol to remove impurity ions (Na) adsorbed on the particle surface + 、OH - ) Drying the mixture in a vacuum drying oven at 60 ℃ for 12 hours to obtain GO-D400-CNTs/CuO particles with a three-dimensional structure;
step three, preparing the GO-D400-CNTs/Cu with the three-dimensional structure: flatly laying the GO-D400-CNTs/CuO particles with the three-dimensional structure prepared in the step two in an aluminum oxide ark, and then putting the ark in a tube furnace for reduction to obtain GO-D400-CNTs/Cu with the three-dimensional structure; the atmosphere adopted in the reduction process is a mixed gas of nitrogen and hydrogen with the hydrogen volume content of 8 percent, the introduction flow rate of the mixed gas of nitrogen and hydrogen is 1.5L/min, the reduction temperature is 450 ℃, and the time is 240min;
step four, preparing the three-dimensional structure nano carbon material reinforced copper-based composite material: 44.50g of three-dimensional GO-D400-CNTs/Cu prepared in the third step are placed in a graphite die, and the vacuum degree is lower than 1 multiplied by 10 -3 Performing discharge plasma sintering under the condition of Pa, cooling to room temperature, and taking out to obtain the three-dimensional structure nano carbon material reinforced copper-based composite material; the specific process of spark plasma sintering is as follows: heating to 400 ℃ at the speed of 100 ℃/min under the sintering pressure of 50MPa, preserving heat for 5min, and continuously heating to 600 ℃ and preserving heat for 5min.
Example 5
Step one, synthesis of a three-dimensional structure nano carbon material: dispersing 0.0600g of graphene oxide GO in 200mL of DMF (dimethylformamide) by ultrasonic for 3h, then sequentially adding 0.5000g of activating agent EDC and 0.1200g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding a PBS buffer solution of 2- (N-morpholino) ethanesulfonic acid with the pH =6.0, stirring at room temperature for activating for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, centrifuging at the rotating speed of 10000rad/min for 30min to obtain activated GO, namely f-GO, adding 6mL of polyetheramine D400 into the f-GO, performing ultrasonic 1h, adjusting the pH of the solution after ultrasonic to 7.4 by dropwise adding ammonia water with the mass concentration of 25%, magnetically stirring at room temperature for amidation reaction for 12h, and sequentially filtering and washing to remove redundant DMF and polyetheramine D400 to obtain GO-D400;
dispersing 0.0300g of carboxylated carbon nanotube CNTs-OOH in 100mL of DMF by ultrasonic for 3h, then sequentially adding 0.2500g of activating agent EDC and 0.060g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding 2- (N-morpholino) ethanesulfonic acid PBS buffer solution with the pH =6.0, stirring at room temperature for activating for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, and centrifuging for 30min at the rotating speed of 10000rad/min to obtain f-CNTs;
dispersing the GO-D400 in 200mL of DMF by ultrasonic, then slowly dripping the f-CNTs, regulating the PH to 7.4 by dripping ammonia water with the mass concentration of 25%, carrying out amidation reaction for 12h by magnetic stirring at room temperature, and then sequentially carrying out filtration, washing and freeze drying to obtain a GO-D400-CNTs nano carbon material with a three-dimensional structure;
step two, preparing GO-D400-CNTs/CuO particles with a three-dimensional structure: 140.6250g of Cu (Ac) were weighed out 2 ·H 2 O was dissolved in 250mL of 25% by mass aqueous ammonia to obtain a solution containing Cu (Ac) 2 0.09g of the three-dimensional GO-D400-CNTs nanocarbon material prepared in the first step is dispersed in the solution containing Cu (Ac) through ultrasound for 4h 2 Adding 500mL of 4mol/L sodium hydroxide solution dropwise into the ammonia water solution under magnetic stirring by a peristaltic pump to react for 20h, changing the reaction solution system from light blue to black gradually, continuing to stir for 4h by magnetic stirring, and sequentially filtering and washing with ethanol to remove impurity ions (Na) adsorbed on the particle surface + 、OH - ) Drying the mixture in a vacuum drying oven at 60 ℃ for 12 hours to obtain GO-D400-CNTs/CuO particles with a three-dimensional structure;
step three, preparing the GO-D400-CNTs/Cu with the three-dimensional structure: flatly laying the GO-D400-CNTs/CuO particles with the three-dimensional structure prepared in the step two in an aluminum oxide ark, and then putting the ark in a tube furnace for reduction to obtain GO-D400-CNTs/Cu with the three-dimensional structure; the atmosphere adopted in the reduction process is a mixed gas of nitrogen and hydrogen with the hydrogen volume content of 8%, the introduction flow rate of the mixed gas of nitrogen and hydrogen is 1.5L/min, the reduction temperature is 500 ℃, and the time is 240min;
step four, preparing the three-dimensional structure nano carbon material reinforced copper-based composite material: 44.50g of three-dimensional GO-D400-CNTs/Cu prepared in the third step are placed in a graphite die, and the vacuum degree is lower than 1 multiplied by 10 -3 Performing discharge plasma sintering under the condition of Pa, cooling to room temperature, and taking out to obtain the three-dimensional structure nano carbon material reinforced copper-based composite material; the specific process of spark plasma sintering is as follows: heating to 400 ℃ at the speed of 100 ℃/min under the sintering pressure of 50MPa, preserving heat for 5min, and continuously heating to 650 ℃ and preserving heat for 5min.
Example 6
Step one, synthesis of a three-dimensional structure nano carbon material: dispersing 0.0600g of graphene oxide GO in 200mL of DMF (dimethylformamide) by ultrasonic for 3h, then sequentially adding 0.5000g of activating agent EDC and 0.1200g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding a PBS buffer solution of 2- (N-morpholino) ethanesulfonic acid with the pH =6.0, stirring at room temperature for activating for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, centrifuging at the rotating speed of 10000rad/min for 30min to obtain activated GO, namely f-GO, adding 6mL of polyetheramine D400 into the f-GO, performing ultrasonic 1h, adjusting the pH of the solution after ultrasonic to 7.4 by dropwise adding ammonia water with the mass concentration of 25%, magnetically stirring at room temperature for amidation reaction for 12h, and sequentially filtering and washing to remove redundant DMF and polyetheramine D400 to obtain GO-D400;
dispersing 0.0300g of carboxylated carbon nanotube CNTs-OOH in 100mL of DMF by ultrasonic for 3h, then sequentially adding 0.2500g of activating agent EDC and 0.060g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding 2- (N-morpholino) ethanesulfonic acid PBS buffer solution with the pH =6.0, stirring at room temperature for activating for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, and centrifuging for 30min at the rotating speed of 10000rad/min to obtain f-CNTs;
dispersing the GO-D400 in 200mL of DMF by ultrasonic, then slowly dripping the f-CNTs, regulating the PH to 7.4 by dripping ammonia water with the mass concentration of 25%, carrying out amidation reaction for 12h by magnetic stirring at room temperature, and then sequentially carrying out filtration, washing and freeze drying to obtain a GO-D400-CNTs nano carbon material with a three-dimensional structure;
step two, preparing GO-D400-CNTs/CuO particles with a three-dimensional structure: 140.6250g of Cu (Ac) were weighed out 2 ·H 2 O was dissolved in 250mL of 25% by mass aqueous ammonia to obtain a solution containing Cu (Ac) 2 0.09g of the GO-D400-CNTs nanocarbon material with the three-dimensional structure prepared in the step one is dispersed in the solution containing Cu (Ac) by ultrasonic treatment for 4h 2 Adding 500mL of 4mol/L sodium hydroxide solution dropwise into the ammonia water solution under magnetic stirring by a peristaltic pump to react for 20h, changing the reaction solution system from light blue to black gradually, continuing to stir magnetically for 4h, and sequentially filtering and washing with ethanol to remove impurity ions (Na) adsorbed on the particle surface + 、OH - ) Drying in a vacuum drying oven at 60 deg.C for 12h to obtain GO-D400-CNTs/CuO particles with three-dimensional structure；
Step three, preparing the GO-D400-CNTs/Cu with the three-dimensional structure: flatly laying the GO-D400-CNTs/CuO particles with the three-dimensional structure prepared in the step two in an aluminum oxide ark, and then putting the ark in a tube furnace for reduction to obtain GO-D400-CNTs/Cu with the three-dimensional structure; the atmosphere adopted in the reduction process is a mixed gas of nitrogen and hydrogen with the hydrogen volume content of 8 percent, the introduction flow rate of the mixed gas of nitrogen and hydrogen is 1.5L/min, the reduction temperature is 450 ℃, and the time is 240min;
step four, preparing the three-dimensional structure nano carbon material reinforced copper-based composite material: 44.50g of the three-dimensional structure GO-D400-CNTs/Cu prepared in the third step are placed in a graphite mold, and the vacuum degree is lower than 1 multiplied by 10 -3 Performing discharge plasma sintering under the condition of Pa, cooling to room temperature, and taking out to obtain the three-dimensional structure nano carbon material reinforced copper-based composite material; the specific process of spark plasma sintering is as follows: heating to 400 ℃ at the speed of 50 ℃/min under the sintering pressure of 40MPa, preserving heat for 5min, and continuously heating to 700 ℃ and preserving heat for 10min.
Example 7
Step one, synthesis of a three-dimensional structure nano carbon material: dispersing 0.0600g of graphene oxide GO in 200mL of DMF (dimethylformamide) by ultrasonic for 3h, then sequentially adding 0.5000g of activating agent EDC and 0.1200g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding a PBS buffer solution of 2- (N-morpholino) ethanesulfonic acid with the pH =6.0, stirring at room temperature for activating for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, centrifuging at the rotating speed of 10000rad/min for 30min to obtain activated GO, namely f-GO, adding 6mL of polyetheramine D400 into the f-GO, performing ultrasonic 1h, adjusting the pH of the solution after ultrasonic to 7.4 by dropwise adding ammonia water with the mass concentration of 25%, magnetically stirring at room temperature for amidation reaction for 12h, and sequentially filtering and washing to remove redundant DMF and polyetheramine D400 to obtain GO-D400;
dispersing 0.0300g of carboxylated carbon nanotube CNTs-OOH in 100mL of DMF by ultrasonic for 3h, then sequentially adding 0.2500g of activating agent EDC and 0.060g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding 2- (N-morpholino) ethanesulfonic acid PBS buffer solution with the pH =6.0, stirring at room temperature for activating for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, and centrifuging for 30min at the rotating speed of 10000rad/min to obtain f-CNTs;
dispersing the GO-D400 in 200mL of DMF by ultrasonic, then slowly dripping the f-CNTs, regulating the PH to 7.4 by dripping ammonia water with the mass concentration of 25%, carrying out amidation reaction for 12 hours by magnetic stirring at room temperature, and then sequentially carrying out filtering, washing and freeze drying to obtain a GO-D400-CNTs nano carbon material with a three-dimensional structure;
step two, preparing GO-D400-CNTs/CuO particles with a three-dimensional structure: weighing 140.6250g of Cu (Ac) 2 ·H 2 O was dissolved in 250mL of 25% by mass aqueous ammonia to obtain a solution containing Cu (Ac) 2 0.09g of the three-dimensional GO-D400-CNTs nanocarbon material prepared in the first step is dispersed in the solution containing Cu (Ac) through ultrasound for 4h 2 Adding 500mL of 4mol/L sodium hydroxide solution dropwise into the ammonia water solution under magnetic stirring by a peristaltic pump to react for 20h, changing the reaction solution system from light blue to black gradually, continuing to stir for 4h by magnetic stirring, and sequentially filtering and washing with ethanol to remove impurity ions (Na) adsorbed on the particle surface + 、OH - ) Drying the mixture in a vacuum drying oven at 60 ℃ for 12 hours to obtain GO-D400-CNTs/CuO particles with a three-dimensional structure;
step three, preparing the GO-D400-CNTs/Cu with the three-dimensional structure: flatly laying the GO-D400-CNTs/CuO particles with the three-dimensional structure prepared in the step two in an aluminum oxide ark, and then putting the ark in a tube furnace for reduction to obtain GO-D400-CNTs/Cu with the three-dimensional structure; the atmosphere adopted in the reduction process is mixed gas of argon and hydrogen with the hydrogen volume content of 8%, the introduction flow rate of the mixed gas of argon and hydrogen is 1.5L/min, the reduction temperature is 450 ℃, and the time is 240min;
step four, preparing the three-dimensional structure nano carbon material reinforced copper-based composite material: 44.50g of three-dimensional GO-D400-CNTs/Cu prepared in the third step are placed in a graphite die, and the vacuum degree is lower than 1 multiplied by 10 -3 Performing discharge plasma sintering under the condition of Pa, cooling to room temperature, and taking out to obtain the three-dimensional structure nano carbon material reinforced copper-based composite material; the discharge plasma sintering methodThe process is as follows: heating to 400 ℃ at the speed of 50 ℃/min under the sintering pressure of 50MPa, preserving heat for 5min, and continuously heating to 750 ℃ and preserving heat for 10min.
Example 8
Step one, synthesis of a three-dimensional structure nano carbon material: dispersing 0.1600g of graphene oxide GO in 200mL of DMF (dimethylformamide) by ultrasonic for 3h, then sequentially adding 1.0080g of activator EDC and 0.1760g of stabilizer NHS, adjusting the pH value to 5.5 by adding 2- (N-morpholino) ethanesulfonic acid PBS buffer solution with the pH =6.0, stirring at room temperature for activation for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, centrifuging at the rotating speed of 10000rad/min for 30min to obtain activated GO, namely f-GO, adding 6mL of polyetheramine D400 into the f-GO, performing ultrasonic for 1h, adjusting the pH of the solution after ultrasonic to 7.4 by dropwise adding ammonia water with the mass concentration of 25%, performing amidation reaction for 12h by magnetic stirring at room temperature, and sequentially filtering and washing to remove redundant DMF and polyetheramine D400 to obtain GO-D400;
dispersing 0.0800g of carboxylated carbon nanotube CNTs-OOH in 100mL of DMF by ultrasonic for 3h, then sequentially adding 0.5000g of activating agent EDC and 0.0840g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding 2- (N-morpholino) ethanesulfonic acid PBS buffer solution with the pH =6.0, stirring at room temperature for activating for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, and centrifuging for 30min at the rotating speed of 10000rad/min to obtain f-CNTs;
dispersing the GO-D400 in 400mL of DMF by ultrasonic, then slowly dripping the f-CNTs, regulating the PH to 7.4 by dripping ammonia water with the mass concentration of 25%, carrying out amidation reaction for 12h by magnetic stirring at room temperature, and then sequentially carrying out filtration, washing and freeze drying to obtain a GO-D400-CNTs nano carbon material with a three-dimensional structure;
step two, preparing GO-D400-CNTs/CuO particles with a three-dimensional structure: weighing 125.6250g of Cu (Ac) 2 ·H 2 O was dissolved in 200mL of 25% by mass aqueous ammonia to obtain a solution containing Cu (Ac) 2 0.24g of the three-dimensional GO-D400-CNTs nanocarbon material prepared in the step one is dispersed in the solution containing Cu (Ac) by ultrasonic treatment for 4h 2 Then passing through a peristaltic pump under magnetic stirringDropwise adding 500mL of 4mol/L sodium hydroxide solution to react for 20h, changing the reaction solution system from light blue to black gradually, continuing to magnetically stir for 4h, and sequentially filtering and washing with ethanol to remove impurity ions (Na) adsorbed on the particle surface + 、OH - ) Drying in a vacuum drying oven at 60 deg.C for 12h to obtain GO-D400-CNTs/CuO particles with three-dimensional structure;
step three, preparing the GO-D400-CNTs/Cu with the three-dimensional structure: flatly laying the three-dimensional GO-D400-CNTs/CuO particles prepared in the second step in an aluminum oxide ark, and then placing the ark in a tube furnace for reduction to obtain the three-dimensional GO-D400-CNTs/Cu; the atmosphere adopted in the reduction process is argon and hydrogen mixed gas with the hydrogen volume content of 8 percent, the introduction flow rate of the argon and hydrogen mixed gas is 1.5L/min, the reduction temperature is 400 ℃, and the time is 240min;
step four, preparing the three-dimensional structure nano carbon material reinforced copper-based composite material: 39.50g of GO-D400-CNTs/Cu with a three-dimensional structure prepared in the third step is placed in a graphite mould, and the vacuum degree is lower than 1 multiplied by 10 -3 Performing discharge plasma sintering under the condition of Pa, cooling to room temperature, and taking out to obtain the three-dimensional structure nano carbon material reinforced copper-based composite material; the specific process of spark plasma sintering is as follows: heating to 400 ℃ at the speed of 50 ℃/min under the sintering pressure of 40MPa, preserving heat for 5min, and continuously heating to 750 ℃ and preserving heat for 10min.
Example 9
The embodiment comprises the following steps:
step one, synthesis of a three-dimensional structure nano carbon material: dispersing 0.0450g of graphene oxide GO in 150mL of DMF (dimethylformamide) by ultrasonic for 3h, then sequentially adding 0.3750g of activating agent EDC and 0.0900g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding 2- (N-morpholino) ethanesulfonic acid PBS buffer solution with the pH =6.0, stirring at room temperature for activating for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, centrifuging at the rotating speed of 10000rad/min for 30min to obtain activated GO, namely f-GO, adding 4.5mL of polyetheramine D400 into the f-GO for ultrasonic 1h, adjusting the pH of the ultrasonic solution to 7.4 by dropwise adding ammonia water with the mass concentration of 25%, magnetically stirring at room temperature for amidation reaction for 12h, and sequentially filtering and washing to remove redundant DMF and polyetheramine D400 to obtain GO-D400;
dispersing 0.0450g of carboxylated carbon nanotube CNTs-OOH in 150mL of DMF by ultrasonic for 3h, then sequentially adding 0.3750g of activating agent EDC and 0.0900g of stabilizing agent NHS, adjusting the pH value to 5.5 by adding 2- (N-morpholino) ethanesulfonic acid PBS buffer solution with the pH =6.0, stirring at room temperature for activating for 30min, then sequentially filtering and washing to remove redundant EDC and NHS, and centrifuging for 30min at the rotating speed of 10000rad/min to obtain f-CNTs;
dispersing the GO-D400 in 150mL of DMF by ultrasonic, then slowly dripping the f-CNTs, regulating the PH to 7.4 by dripping ammonia water with the mass concentration of 25%, carrying out amidation reaction for 12h by magnetic stirring at room temperature, and then sequentially carrying out filtration, washing and freeze drying to obtain a GO-D400-CNTs nano carbon material with a three-dimensional structure;
step two, preparing GO-D400-CNTs/CuO particles with a three-dimensional structure: 140.6250g of Cu (Ac) were weighed out 2 ·H 2 O was dissolved in 250mL of 25% by mass aqueous ammonia to obtain a solution containing Cu (Ac) 2 0.09g of the GO-D400-CNTs nanocarbon material with the three-dimensional structure prepared in the step one is dispersed in the solution containing Cu (Ac) by ultrasonic treatment for 4h 2 Adding 500mL of 4mol/L sodium hydroxide solution dropwise into the ammonia water solution under magnetic stirring by a peristaltic pump to react for 20h, changing the reaction solution system from light blue to black gradually, continuing to stir magnetically for 4h, and sequentially filtering and washing with ethanol to remove impurity ions (Na) adsorbed on the particle surface + 、OH - ) Drying in a vacuum drying oven at 60 deg.C for 12h to obtain GO-D400-CNTs/CuO particles with three-dimensional structure;
step three, preparing the GO-D400-CNTs/Cu with the three-dimensional structure: flatly laying the GO-D400-CNTs/CuO particles with the three-dimensional structure prepared in the step two in an aluminum oxide ark, and then putting the ark in a tube furnace for reduction to obtain GO-D400-CNTs/Cu with the three-dimensional structure; the atmosphere adopted in the reduction process is mixed gas of argon and hydrogen with the hydrogen volume content of 8%, the introduction flow rate of the mixed gas of argon and hydrogen is 1.5L/min, the reduction temperature is 400 ℃, and the time is 240min;
step four, preparing the three-dimensional structure nano carbon material reinforced copper-based composite material: 44.20g of three-dimensional GO-D400-CNTs/Cu prepared in the third step are placed in a graphite die, and the vacuum degree is lower than 1 multiplied by 10 -3 Performing discharge plasma sintering under the condition of Pa, cooling to room temperature, and taking out to obtain the three-dimensional structure nano carbon material reinforced copper-based composite material; the specific process of spark plasma sintering is as follows: heating to 400 ℃ at the speed of 75 ℃/min under the sintering pressure of 45MPa, preserving heat for 5min, and continuously heating to 750 ℃ and preserving heat for 8min.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.

Claims (6)

1. A preparation method of a three-dimensional structure nano carbon material reinforced copper-based composite material is characterized by comprising the following steps:
step one, synthesis of a three-dimensional structure nano carbon material: respectively pretreating graphene oxide and a carboxylated carbon nanotube, dispersing the pretreated graphene oxide and the pretreated carboxylated carbon nanotube in DMF (dimethyl formamide) by ultrasonic waves, uniformly mixing, carrying out an amidation reaction by magnetic stirring at room temperature, and sequentially filtering, washing and freeze-drying to obtain a three-dimensional GO-polyamino compound-CNTs nanocarbon material;
the specific process of the graphene oxide pretreatment is as follows: dispersing graphene oxide GO in DMF by ultrasonic, then sequentially adding an activating agent EDC and a stabilizing agent NHS, stirring at room temperature for activation, then sequentially filtering and washing to obtain activated GO, namely f-GO, adding an excessive polyamino compound into the f-GO, performing ultrasonic dispersion, magnetically stirring at room temperature for amidation reaction, and then sequentially filtering and washing to obtain GO-polyamino compound;
the concrete process of the carboxylated carbon nanotube pretreatment comprises the following steps: dispersing the carboxylated carbon nanotube CNTs-OOH in DMF (dimethyl formamide) by ultrasonic, then sequentially adding an activating agent EDC and a stabilizing agent NHS, stirring at room temperature for activation, and then sequentially filtering and washing to obtain f-CNTs;
step two, preparing GO-polyamino compound-CNTs/CuO particles with a three-dimensional structure: dispersing the GO-polyamino compound-CNTs nano carbon material with the three-dimensional structure prepared in the step one in Cu (Ac) through ultrasonic dispersion 2 Adding a sodium hydroxide solution dropwise into the ammonia water solution under magnetic stirring for reaction, gradually changing a reaction solution system from light blue to black, and sequentially filtering and washing to obtain GO-polyamino compounds-CNTs/CuO particles with a three-dimensional structure;
step three, preparing the GO-polyamino compound-CNTs/Cu with a three-dimensional structure: flatly laying the GO-polyamino compound-CNTs/CuO particles with the three-dimensional structure prepared in the step two in an aluminum oxide ark, and then putting the ark in a tubular furnace for reduction to obtain GO-polyamino compound-CNTs/Cu with the three-dimensional structure;
step four, preparing the three-dimensional structure nano carbon material reinforced copper-based composite material: and (3) placing the three-dimensional structure GO-polyamino compound-CNTs/Cu prepared in the third step into a graphite mold, performing discharge plasma sintering under a vacuum condition, cooling to room temperature, and taking out to obtain the three-dimensional structure nano carbon material reinforced copper-based composite material.
2. The method for preparing the three-dimensional structure nanocarbon material reinforced copper-based composite material according to claim 1, wherein the mass ratio of the graphene oxide to the carboxylated carbon nanotubes in the first step is (1-3): 1.
3. the method for preparing the three-dimensional structure nano carbon material reinforced copper-based composite material as claimed in claim 1, wherein the polyamino compound in the first step is polyetheramine D400.
4. The method as claimed in claim 1, wherein the concentration of the sodium hydroxide solution in step two is 4mol/L.
5. The method for preparing the three-dimensional structure nanocarbon material reinforced copper-based composite material according to claim 1, wherein the reducing atmosphere adopted in the reduction in the step three is a mixed atmosphere of argon and hydrogen, or a mixed atmosphere of nitrogen and hydrogen, and the reducing temperature is 400 ℃ to 500 ℃.
6. The method for preparing the three-dimensional structure nano carbon material reinforced copper-based composite material according to claim 1, wherein the specific process of spark plasma sintering in the fourth step is as follows: heating to 600-750 deg.c at 50-100 deg.c/min and maintaining at 40-50 MPa sintering pressure for 5-10 min.
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CN112267040A (en) * 2020-10-20 2021-01-26 南昌航空大学 Preparation method of graphene-carbon nanotube/copper-based composite material
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JP2014231453A (en) * 2013-05-29 2014-12-11 株式会社船井電機新応用技術研究所 Porous composite carbon material and production method thereof
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US9879141B2 (en) * 2014-12-19 2018-01-30 Tesla Nanocoatings, Inc. Tunable materials
WO2016145201A1 (en) * 2015-03-10 2016-09-15 Massachusetts Institute Of Technology Metal-nanostructure composites
CN105070888B (en) * 2015-07-09 2017-11-14 山东玉皇新能源科技有限公司 Ternary material of CNT graphene complex three-dimensional network structure cladding of coupling and preparation method thereof
CN106189088B (en) * 2016-07-19 2018-07-27 沈阳航空航天大学 A kind of preparation method of carbon nanotube-graphene oxide hybrid reinforced composite material
CN107523381A (en) * 2017-09-30 2017-12-29 陕西科技大学 A kind of preparation method of graphene carbon nanometer tube composite materials load nano copper particle lubriation material
US11332830B2 (en) * 2017-11-15 2022-05-17 Global Graphene Group, Inc. Functionalized graphene-mediated metallization of polymer article
CN108912659B (en) * 2018-06-08 2021-04-06 东南大学 Preparation method of crosslinked three-dimensional carbon nano composite polyurethane material
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