CN107893169B

CN107893169B - Preparation method of carbon nanotube and graphene hybrid reinforced metal matrix composite

Info

Publication number: CN107893169B
Application number: CN201711071194.4A
Authority: CN
Inventors: 杜文博; 孟繁婧; 王朝辉; 刘轲; 李淑波; 杜宪; 赵晨辰
Original assignee: Beijing University of Technology
Current assignee: Beijing University of Technology
Priority date: 2017-11-03
Filing date: 2017-11-03
Publication date: 2020-04-24
Anticipated expiration: 2037-11-03
Also published as: CN107893169A

Abstract

A preparation method of a metal matrix composite reinforced by mixing carbon nanotubes and graphene belongs to the field of dispersion of carbon nanotubes and preparation of composites. According to the method, the graphene oxide is added and a series of process flows are carried out, so that the carbon nano tubes are effectively dispersed in the metal matrix, the content of the carbon nano tubes in the composite material is increased, and the oxidation of the metal matrix is reduced. The method mainly comprises the following implementation steps: (1) preparing a carbon nano tube graphene dispersion liquid; (2) and (3) preparing the carbon nano tube graphene metal matrix composite. The method has the advantages of good dispersion effect, easy operation, short process flow, less introduction of new impurities, small environmental pollution and the like.

Description

Preparation method of carbon nanotube and graphene hybrid reinforced metal matrix composite

Technical Field

The invention belongs to the field of dispersion of carbon nanotubes and preparation of composite materials, and particularly relates to a preparation method of a metal-based composite material reinforced by mixing carbon nanotubes and graphene.

Background

Since 1991, Carbon Nanotubes (CNTs) were discovered by doctor saikoku (s.ijima) of japan electronics, they have been widely used in various industries such as materials science because of their excellent mechanical, thermal, and electrical properties. The carbon nanotube is a seamless and hollow tube body rolled by a graphene sheet formed by carbon atoms, is a one-dimensional carbon material, has extremely high axial strength, has the axial Young modulus close to 2Tpa, has the tensile strength as high as 100GPa, and is 100 times that of steel. In addition, the high elastic modulus, the large specific surface area, the good high-temperature stability, the good antifriction and wear resistance, the high thermal conductivity and the like of the composite material can be used as an ideal reinforcing phase of a matrix nano composite material such as ceramic polymer, metal and the like with high strength and stability.

Although carbon nanotubes have many excellent characteristics and special functions, they have a high aspect ratio, a large specific surface area and a high surface energy, and they spontaneously agglomerate in order to reduce the free energy. The spontaneous agglomeration tendency prevents the carbon nano tube from being dispersed in a matrix, and influences the exertion of excellent mechanical property, thermal property and electrical property of a single carbon nano tube, thereby influencing the performance of the carbon nano tube composite material.

The dispersion method is divided into physical and chemical methods before adding the carbon nanotubes to the matrix of the composite material, however, the physical method is not stable, and is often used as an auxiliary dispersion method, such as "A new technique for dispersion of carbon nanotubes in a metal media" (Xiaoshu Zeng. materials Science and Engineering, (2010) 5335-5340), the ball milling of the carbon nanotubes is performed, and the experimental results show that the carbon nanotube aggregates are opened to some extent under the impact of ball milling, and can be better dispersed without oxidation, the dispersion method of modified carbon nanotubes in a modified carbon nanotube with a hydrophobic addition is performed by using a covalent bond modification method such as "CHEN FEN CHEN FEN CHEN that the dispersion method of carbon nanotube modification method is effective to modify covalent bond modification method to modify the carbon nanotube dispersion method to modify the carbon nanotube modification method to prepare a carbon nanotube dispersion method includes a carbon nanotube dispersion method of chemically modified carbon nanotube dispersion method including the hydrophobic modification method of covalent bond modification.

But the physical method has poor dispersion effect, and the unique structure of the carbon nano tube can be damaged by mechanical external force; although the covalent bond modification method can disperse the carbon nanotubes to a certain degree, the carbon nanotube dispersion is realized by directly introducing functional groups on the sidewall or the top of the carbon tube, which changes the structure of the carbon tube and influences the exertion of the unique performance of the carbon tube. When the carbon nano tube is dispersed by the non-covalent bond modification method, the carbon nano tube is mainly adsorbed by physics, and the covalent bond is not generated, so the structure of the carbon nano tube is not damaged. The non-covalent bond dispersant is mainly ionic, has a hydrophilic group and a lipophilic group, and achieves dispersion through association between hydrophobic chains and separation due to charge repulsion between ionic head groups and hydration, which allows the surfactant to disperse carbon nanotubes excellently in water but has a slightly poor dispersion effect in organic solvents such as alcohols. In the preparation process of active metal composite materials such as magnesium and the like, organic solvents such as absolute ethyl alcohol and the like are often used as solvents for reducing oxidation, however, the dispersion of the carbon nano tube in the metal matrix is influenced, and the content of the carbon nano tube in the metal matrix is limited; if the carbon nanotubes and the metal powder are mixed with a solvent such as water during the preparation process, the metal powder is severely oxidized. It is therefore necessary to find new methods by which carbon nanotubes can be dispersed in a metal matrix.

Disclosure of Invention

The invention mainly aims to solve the problem that the effect of dispersing carbon nanotubes in a metal matrix is poor by the conventional method, and develops a method which can not damage the structure of the carbon nanotubes, can not introduce a large amount of other substances, can well disperse the carbon nanotubes in the metal matrix, can reduce the oxidation of the metal matrix and can improve the content of the carbon nanotubes in a metal composite material. The method reduces the oxidation of the metal matrix when the carbon nano tube is added, and effectively disperses the carbon nano tube while improving the content, thereby improving the performance of the carbon nano tube metal matrix composite material.

A preparation method of a metal matrix composite reinforced by mixing carbon nanotubes and graphene is realized by the following technical scheme. The method comprises the following steps:

(1) preparing a carbon nano tube graphene dispersion liquid; (2) and (3) preparing the carbon nano tube graphene metal matrix composite.

The method comprises the following specific steps:

(1) preparation of carbon nanotube graphene dispersion liquid

Weighing a certain mass of graphene oxide and carbon nanotubes, adding the graphene oxide and the carbon nanotubes into an inorganic solvent, uniformly mixing, preferably, the mass ratio of the graphene oxide to the carbon nanotubes is (0.1-10): 1, and preferably, the solvent is deionized water.

The mixture was sonicated at room temperature with mechanical stirring. The ultrasonic stirring time is preferably 20-120 min.

The carbon nanotubes used in the method can be single-walled carbon nanotubes, multi-walled carbon nanotubes or a combination of two kinds of carbon nanotubes with different contents, and the purity of the carbon nanotubes is preferably not less than 95.0 wt.%. The used graphene oxide is preferably 5-10 mu m in lamellar spacing and 1-2 nm in thickness.

And drying the carbon nano tube graphene oxide dispersion liquid, wherein the preferable drying temperature is 80-200 ℃, and the preferable drying time is 7-24 h. And reducing the dried powder under the protection of inert gas at the reduction temperature of 300-700 ℃ for 2-8 h to obtain the carbon nano tube graphene mixed powder.

Adding the carbon nanotube graphene mixed powder into an organic solvent, and carrying out ultrasonic treatment at room temperature while mechanically stirring; and preferably, the ultrasonic stirring time is 20-120 min, so that the carbon nano tube graphene dispersion liquid can be obtained.

The organic solvent is preferably selected from acetone, ethanol, methanol, etc.

(2) Preparation of carbon nano tube graphene metal-based composite material

Weighing metal matrix powder with required mass, preferably 50-1000 meshes in particle size, adding the metal matrix powder into the carbon nanotube graphene dispersion liquid prepared in the step (1), stirring for 15-120 min, and placing the stirred mixture into a vacuum drying oven for vacuum drying, preferably at the drying temperature of 60-120 ℃ for 60-180 min;

and carrying out extrusion forming on the dried mixed powder, wherein the extrusion ratio is 10-25. The extrusion temperature is preferably 300 to 450 ℃.

The inert gas is used only for protection and does not participate in the reaction, and is preferably argon or the like.

The method can adjust the dispersion content of the carbon nano tube in the metal matrix according to the requirement, namely, the dispersion content of the carbon nano tube in the metal matrix can be improved and can at least reach the content of 7wt percent or even higher.

The dispersion method of the invention has the following advantages: the whole preparation process is simple, the flow is short, and the problems of poor dispersibility and low content of the carbon nano tube in the metal matrix and easy oxidation of the metal matrix in the process of mixing the carbon nano tube can be solved. The graphene oxide promotes the dispersion of the carbon nanotubes, is not limited to be realized in inorganic solvents such as water and the like, can also play a role in an organic solvent, so that metal powder and the carbon nanotubes can be mixed in the organic solvent, the oxidation caused by the contact of the graphene oxide with water and air is reduced, a brand new, convenient and effective process method is provided for improving the dispersion of the carbon nanotubes in a metal matrix, reducing the oxidation of the metal matrix and improving the content of the carbon nanotubes in a composite material, and the composite material has a wide prospect.

Drawings

Fig. 1 is a photograph of a uniformly dispersed carbon nanotube graphene solution obtained in example 1;

FIG. 2 is a TEM photograph of the dispersed carbon nanotube graphene of example 1, with diffraction spots of the carbon nanotube at the top right corner;

FIG. 3 is a photograph of the extruded rods of the composite powders of examples 1-5;

FIG. 4 is a metallographic photograph of the composite material of example 4;

Detailed Description

The present invention is further illustrated by the following specific examples, which are intended to be merely illustrative of specific embodiments of the present invention and not to limit the scope of the claims.

Example 1

(1) 100mg of graphene oxide and 500mg of carbon nanotubes are weighed and added into 60ml of deionized water, and the mixed solution is subjected to ultrasonic treatment at room temperature for 20min while being subjected to mechanical stirring. And (3) placing the mixed dispersion liquid in a drying oven, wherein the temperature is 200 ℃, and the drying time is 7 hours. And taking out the dried solid, and placing the solid in a tubular furnace for reduction at the temperature of 300 ℃ for 8 hours. The reduced powder was added to 160ml acetone and sonicated at room temperature for 20min with mechanical stirring.

(2) 49.4g of pure magnesium powder is weighed and added into the dispersion liquid obtained in the step (1), and stirred for 40 min. Then placing the mixture in a vacuum drying box, wherein the drying temperature is 70 ℃ and the drying time is 180 min. And (3) carrying out extrusion forming on the dried powder, wherein the extrusion temperature is 350 ℃, and the extrusion ratio is 10.

Example 2

(1) Weighing 700mg of graphene oxide and 100mg of carbon nanotubes, adding the graphene oxide and the carbon nanotubes into 80ml of distilled water, and carrying out ultrasonic treatment on the mixed solution at room temperature for 60min while carrying out mechanical stirring. And (3) placing the mixed dispersion liquid in a drying oven, wherein the temperature is 80 ℃, and the drying time is 24 hours. And taking out the dried solid, and reducing in a tubular furnace at 400 ℃ for 6 hours. Adding the reduced powder into 180ml of absolute ethyl alcohol, and carrying out ultrasonic treatment at room temperature for 60min while carrying out mechanical stirring.

(2) 49.2g of aluminum alloy (1060) powder was weighed out and added to the dispersion liquid obtained in (1), and stirred for 120 min. Then placing the mixture in a vacuum drying box, wherein the drying temperature is 85 ℃ and the time is 120 min. And (3) carrying out extrusion forming on the dried powder, wherein the extrusion temperature is 400 ℃, and the extrusion ratio is 10.

Example 3

(1) 100mg of graphene oxide and 900mg of carbon nanotubes are weighed and added into 100ml of distilled water, and the mixed solution is subjected to ultrasonic treatment at room temperature for 120min while being subjected to mechanical stirring. And (3) placing the mixed dispersion liquid in a drying oven, wherein the temperature is 150 ℃, and the drying time is 12 hours. Taking out the dried solid, and placing the solid in a tubular furnace for reduction at the temperature of 500 ℃ for 5 hours. Adding the reduced powder into 200ml of absolute ethyl alcohol, and carrying out ultrasonic treatment at room temperature for 120min while carrying out mechanical stirring.

(2) 49.0g of titanium alloy (TA22) powder was weighed out and added to the dispersion obtained in (1), and stirred for 90 min. Then placing the mixture in a vacuum drying oven, wherein the drying temperature is 100 ℃ and the drying time is 80 min. And (3) carrying out extrusion forming on the dried powder, wherein the extrusion temperature is 500 ℃, and the extrusion ratio is 16.

Example 4

(1) 10mg of graphene oxide and 100mg of carbon nanotubes are weighed and added into 40ml of deionized water, and the mixed solution is subjected to ultrasonic treatment at room temperature for 20min while being subjected to mechanical stirring. The mixed dispersion was placed in a drying oven at 110 ℃ for 13 hours. And taking out the dried solid, and reducing in a tubular furnace at 600 ℃ for 4 hours. The reduced powder was added to 140ml of methanol and sonicated at room temperature for 20min with mechanical stirring.

(2) 49.9g of magnesium alloy (ZK61) powder was weighed out and added to the dispersion liquid obtained in (1), and stirred for 15 min. Then placing the mixture in a vacuum drying box, wherein the drying temperature is 60 ℃ and the time is 180 min. And (3) carrying out extrusion forming on the dried powder, wherein the extrusion temperature is 300 ℃, and the extrusion ratio is 10.

Example 5

(1) 100mg of graphene oxide and 10mg of carbon nanotubes are weighed and added into 50ml of pure water, and the mixed solution is subjected to ultrasonic treatment at room temperature for 90min while being subjected to mechanical stirring. And (3) placing the mixed dispersion liquid in a drying oven, wherein the temperature is 170 ℃, and the drying time is 10 hours. And taking out the dried solid, and reducing in a tubular furnace at 700 ℃ for 2 hours. Adding the reduced powder into 150ml of absolute ethyl alcohol, and carrying out ultrasonic treatment at room temperature for 20min while carrying out mechanical stirring.

(2) 49.9g of magnesium alloy (AZ91) powder was weighed out and added to the dispersion liquid obtained in (1), and stirred for 60 min. Then placing the mixture in a vacuum drying box, wherein the drying temperature is 120 ℃ and the drying time is 90 min. And extruding and molding the dried powder at 325 ℃ and an extrusion ratio of 25.

Although preferred embodiments have been depicted and described in detail herein, it will be apparent to those skilled in the relevant art that various modifications, additions, substitutions and the like can be made without departing from the spirit of the invention and these are therefore considered to be within the scope of the invention as defined in the following claims.

Claims

1. A preparation method of a carbon nanotube and graphene hybrid reinforced metal matrix composite is characterized by comprising the following steps:

(1) preparing a carbon nano tube graphene dispersion liquid; (2) preparing a carbon nano tube graphene metal matrix composite;

the method comprises the following specific steps:

(1) preparation of carbon nanotube graphene dispersion liquid

Weighing a certain mass of graphene oxide and carbon nanotubes, adding the graphene oxide and the carbon nanotubes into an inorganic solvent, and uniformly mixing; drying the obtained carbon nanotube graphene oxide dispersion liquid, and reducing the dried powder under the protection of inert gas at the reduction temperature of 300-700 ℃ for 2-8 h to obtain carbon nanotube graphene mixed powder; adding the carbon nanotube graphene mixed powder into an organic solvent, and carrying out ultrasonic treatment at room temperature while mechanically stirring;

(2) preparation of carbon nano tube graphene metal-based composite material

Weighing metal matrix powder with required mass, adding the metal matrix powder into the carbon nano tube graphene dispersion liquid prepared in the step (1), stirring, and placing the stirred mixture into a vacuum drying oven for vacuum drying; and carrying out extrusion forming on the dried mixed powder.

2. The method for preparing the carbon nanotube and graphene hybrid reinforced metal matrix composite material according to claim 1, wherein the mass ratio of the graphene oxide to the carbon nanotube is (0.1-10): 1, and the inorganic solvent is deionized water.

3. The preparation method of the carbon nanotube and graphene hybrid reinforced metal matrix composite material according to claim 1, wherein the step (1) of uniformly mixing is that the mixed solution is subjected to ultrasonic treatment at room temperature, and simultaneously mechanical stirring is carried out, wherein the ultrasonic stirring time is 20-120 min; and drying the carbon nano tube graphene oxide dispersion liquid at the drying temperature of 80-200 ℃ for 7-24 h.

4. The method for preparing the carbon nanotube and graphene hybrid reinforced metal matrix composite according to claim 1, wherein the carbon nanotubes are single-walled carbon nanotubes, multi-walled carbon nanotubes or a combination of two kinds of carbon nanotubes with different contents, and the purity of the carbon nanotubes is not less than 95.0 wt.%; the graphene oxide used has a lamellar spacing of 5-10 μm and a thickness of 1-2 nm.

5. The method for preparing the carbon nanotube and graphene hybrid reinforced metal matrix composite according to claim 1, wherein the dried powder is reduced under the protection of inert gas, wherein the reduction temperature is 300-700 ℃ and the reduction time is 2-8 h.

6. The method for preparing the carbon nanotube and graphene hybrid reinforced metal matrix composite according to claim 1, wherein the carbon nanotube and graphene mixed powder is added into an organic solvent, ultrasonic stirring is performed at room temperature and mechanical stirring is performed simultaneously, the ultrasonic stirring time is 20-120 min, and the organic solvent is selected from acetone, ethanol and methanol.

7. The method for preparing the carbon nanotube and graphene hybrid reinforced metal matrix composite material according to claim 1, wherein the vacuum drying temperature in the step (2) is 60-120 ℃, and the drying time is 60-180 min.

8. The method for preparing a carbon nanotube and graphene hybrid reinforced metal matrix composite according to claim 1, wherein the dried mixed powder is extruded and molded at an extrusion ratio of 10-25 and an extrusion temperature of 300-450 ℃.

9. The carbon nanotube and graphene hybrid reinforced metal matrix composite prepared according to the method of any one of claims 1 to 8.