CN115747594A - Method for modifying carbon nano tube reinforced magnesium matrix composite material by using mace structure - Google Patents
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Abstract
A method for reinforcing magnesium-based composite material by modified carbon nano tube with mace structure comprises forming pits on the surface of carbon nano tube, and implanting zinc oxide into the pits to obtain modified carbon nano tube with mace structure. Then, uniformly dispersing the carbon nano tube with the wolf tooth stick structure and the magnesium alloy powder in ethanol; filtering and vacuum drying to obtain a carbon nanotube-magnesium alloy powder mixture; and finally, pressing, sintering and extruding to obtain the modified carbon nano tube reinforced magnesium matrix composite material with the wolf tooth rod structure. The method has the advantages of simple operation, low cost, uniform dispersion of the modified carbon nano tubes with the wolf tooth bar structure in the magnesium alloy, good bonding quality with a magnesium matrix interface, remarkable grain refinement, excellent comprehensive mechanical properties of the composite material and larger application prospect.
Description
Technical Field
The invention belongs to the field of metal material preparation, and particularly relates to a preparation method of a magnesium-based composite material.
Background
In recent years, with the rapid development of fields such as automobiles, electronics, aerospace and the like, higher requirements are being made on properties such as strength and plasticity of a magnesium-based composite material. Magnesium-based composite materials have advantages of specific stiffness/specific strength, low density, environmental friendliness, etc., and have received wide attention from the industry. Theoretically, carbon Nanotubes (CNTs) have excellent mechanical properties, with an elastic modulus of up to 1TPa, and a strength 100 times that of steel, and are considered as ideal reinforcements for preparing high-performance mg-based composites. However, the carbon nanotube and the magnesium alloy have poor wettability, weak interface bonding, and easy agglomeration, which results in poor strengthening effect.
Disclosure of Invention
The invention aims to provide a preparation method of a mace structure modified carbon nanotube reinforced magnesium matrix composite. The modified carbon nano tube with the wolf tooth stick structure is formed by digging some pit defects on the surface of the carbon nano tube and implanting zinc oxide nano particles into the pit defects, and the modified carbon nano tube is added into a magnesium alloy matrix, so that the interface bonding quality of the carbon nano tube and the magnesium matrix can be effectively improved, and meanwhile, the crystal grain structure is refined, and the magnesium-based composite material with excellent mechanical property is obtained.
The invention is realized by the following technical scheme.
The invention discloses a method for reinforcing a magnesium-based composite material by using modified carbon nano tubes with a wolf tooth rod structure.
(1) Wolf tooth stick structure modified carbon nano tube.
1) Pits are formed on the surface of the carbon nano tube.
a) And (3) low-temperature reaction: graphitized carbon nanotubes, sodium nitrate, 98% concentrated sulfuric acid and potassium permanganate are mixed according to the mass ratio of 1:0.5-1.0:40-55: 3-5; firstly, adding the prepared graphitized carbon nano tube, sodium nitrate and concentrated sulfuric acid into a beaker, uniformly mixing, and then placing the mixture in a freezer for low-temperature reaction at the temperature of 0-4 ℃ for 10-30min; and then under the stirring condition of 5-10rpm, gradually adding the prepared potassium permanganate into the mixed solution of the reaction solution, and continuing stirring for 2-5h.
b) And (3) medium-temperature reaction: and (b) removing the mixture obtained in the step a) from the freezer, placing the mixture into a water bath kettle at 35-40 ℃, gradually adding distilled water into the reaction liquid under the stirring condition of 5-10rpm after the reaction liquid becomes viscous, wherein the adding amount of the distilled water is 100-500% of the volume of the reaction liquid, each adding amount is 1/10 of the total adding amount, the adding time interval of the water is 2min, and then, continuously stirring at 5-10rpm for 0.5-1h.
c) High-temperature reaction: and c) raising the temperature of the water bath kettle in the step b) to 90-100 ℃, keeping stirring during the temperature raising, adding distilled water into the reaction liquid after the temperature raising is finished, wherein the adding amount of the distilled water is 100-400% of the volume of the reaction liquid, and continuously stirring at 5-10rpm for 0.5-1h.
d) And (3) terminating the reaction: adding H with the concentration of 30 percent and the volume of 5 to 20 percent of the reaction liquid into the reaction liquid obtained in the step c) 2 O 2 While continuing to stir until the reaction is complete.
e) Filtering and drying: adding distilled water into the reaction liquid obtained in the step d), wherein the adding amount of the distilled water is 300-800% of the volume of the reaction liquid, standing, pouring out the supernatant until the pH value of the solution is 6-7, and continuously washing, filtering and drying by using the distilled water to obtain the carbon nanotube powder with pits on the surface.
2) And the zinc oxide is implanted into the pits.
a) Mixing carbon nano tubes with pits on the surface, zinc nitrate hexahydrate and distilled water according to the mass ratio of 1:0.1-0.5:1000-5000 of the mixture is added into a beaker for ultrasonic dispersion to form uniformly dispersed carbon nanotube-zinc nitrate mixed solution.
b) Gradually dripping 5-30% of the volume of the reaction solution and 1-3mol/L aqueous ammonia solution into the mixed solution of the carbon nano tube and the zinc nitrate at the titration rate of 1-5mL/min, simultaneously carrying out mechanical stirring at the rate of 20-80rpm, and standing for 0.5-1h after dripping to obtain a precipitate.
c) Filtering the precipitate obtained in the step b), and drying at 60-80 ℃ for 2-4h to obtain the precursor of the modified carbon nano tube with the wolfsbane stick structure.
d) Sintering the precursor obtained in the step d) for 1-3h at 500-700 ℃ under the protection of argon to obtain the modified carbon nanotube with the wolf tooth stick structure.
(2) And (3) preparing the magnesium alloy composite material.
1) Dispersing carbon nanotubes with a wolf tooth stick structure: mixing the modified carbon nano tube with the wolf tooth stick structure and ethanol according to the weight ratio of 1-5g: mixing at a ratio of 200-1000mL, and ultrasonically dispersing for 0.5-1h under the power condition of 500-1000W to obtain uniformly dispersed mixed liquor.
2) The carbon nano tube with the wolf tooth stick structure and the magnesium alloy powder form uniform dispersion: adding magnesium alloy powder with the granularity of 200-400 meshes into the obtained mixed solution according to the proportion that the weight percentage of the carbon nano tube with the mace structure is 1-5%, mechanically stirring for 0.5-1h to obtain carbon nano tube-magnesium alloy powder mixed slurry with uniform dispersion, and finally filtering and vacuum drying at 60 ℃ for 1-2h to obtain the carbon nano tube-magnesium alloy powder mixture.
3) Pressing and forming: adding the carbon nano tube-magnesium alloy powder mixture into a die with the diameter of 30-40mm, and carrying out cold press forming at room temperature to obtain a composite material green compact, wherein the pressure is 50-200MPa.
4) Sintering and forming: sintering the composite material green body obtained in the step 3) for 2-3h at 600-650 ℃ under the protection of argon to obtain the sintered composite material.
5) Extrusion molding: and (3) extruding and forming the sintered composite material obtained in the step 4) under the conditions that the extrusion speed is 1-5mm/min and the extrusion temperature is 400-550 ℃ to obtain the mace structure modified carbon nanotube reinforced magnesium-based composite material.
The method has the advantages of simple operation, low cost, uniform dispersion of the modified carbon nano tube with the wolf tooth rod structure in the magnesium alloy, good bonding quality with a magnesium matrix interface, remarkable grain refinement, excellent comprehensive mechanical property of the composite material and larger application prospect.
Drawings
FIG. 1 is a schematic diagram of modified carbon nanotubes with mace structure prepared by the present invention and their application in magnesium matrix.
FIG. 2 is a TEM (transmission electron microscope) morphology of modified carbon nanotubes with mace structures prepared by the invention.
FIG. 3 is HRTEM (high resolution transmission electron microscope) morphology of modified carbon nanotubes with mace structure prepared by the invention.
FIG. 4 is a microstructure diagram of an AZ91 base alloy material.
Fig. 5 is a microstructure diagram of an AZ91 magnesium-based composite material with 3.0wt.% of modified carbon nanotubes of a mace structure prepared by the present invention.
Detailed Description
The invention will be further illustrated by the following examples.
Example 1.
(1) The wolf tooth stick structure modifies the carbon nanotube.
1) Pits are formed on the surface of the carbon nano tube.
a) And (3) low-temperature reaction: 1g of graphitized carbon nanotube, 0.5g of sodium nitrate and 25mL of 98% concentrated sulfuric acid are added into a beaker to be mixed, and the mixture is placed in a freezer, the reaction temperature is 0 ℃, and the mixture is fully stirred for 20 min. 4g of potassium permanganate (KMnO) are gradually added with mechanical stirring (speed 10 rpm) 4 ) After that, stirring was continued for 2 hours.
b) And (3) medium-temperature reaction: and (2) moving the mixture obtained in the step 1) out of the freezer, placing the mixture into a water bath kettle at 35 ℃, mechanically stirring (at the speed of 10 rpm) after the reaction solution becomes viscous, and simultaneously, gradually adding 100mL of distilled water into the reaction solution (in order to prevent the solution from boiling due to overheating, the adding amount of the distilled water is 10mL each time, and the adding time interval of the distilled water is 2 min), and then continuing stirring for 0.5h under the condition of the same stirring speed.
c) High-temperature reaction: and (3) raising the temperature of the water bath kettle in the step 2) to 90 ℃, keeping stirring during the temperature raising, adding 150mL of distilled water into the reaction liquid after the temperature raising is finished, and continuously stirring for 0.5h (the stirring speed is constant).
d) And (3) terminating the reaction: 15 mL of H was added to the reaction solution obtained in step 3) 2 O 2 (30%) while stirring was continued for 10min to terminate the reaction.
e) And (3) filtering and drying: adding 1000mL of distilled water into the reaction solution obtained in the step 4), standing, pouring out the supernatant until the solution has an acidic pH of 7, washing with distilled water continuously, filtering, and drying to obtain carbon nanotube powder with pits on the surface.
2) And zinc oxide is implanted into the pits.
a) 1g of carbon nano tube with a pit on the surface is added into 1000mL of distilled water, and is subjected to ultrasonic dispersion to form a mixed solution, and 0.2g of zinc nitrate hexahydrate is added at the same time, and is subjected to ultrasonic dispersion to form a carbon nano tube-zinc nitrate mixed solution.
b) Gradually dripping 50mL of 2mol/L ammonia water solution into the carbon nano tube-zinc nitrate mixed solution, wherein the titration rate is 1mL/min, simultaneously carrying out mechanical stirring at the speed of 50rpm, and obtaining a precipitate after the net value is 0.5h after the dripping is finished.
c) And filtering the precipitate, and drying at 60 ℃ for 2h to obtain the precursor of the modified carbon nanotube with the wolfsbane stick structure.
d) And sintering the precursor for 2h at 650 ℃ under the protection of argon to obtain the modified carbon nanotube with the wolf tooth rod structure.
(2) And (3) preparing the magnesium alloy composite material.
1) Dispersing carbon nano tubes with wolf tooth stick structures: adding 1g of mace structure modified carbon nano tube into 1000mL of ethanol, and performing ultrasonic dispersion for 0.5h under the condition of 500W of power to obtain uniformly dispersed mixed solution.
2) Uniformly dispersing carbon nano tubes with wolf tooth rod structures and magnesium alloy powder: adding 99g of magnesium alloy powder (with the granularity of 300 meshes) into the mixed solution, mechanically stirring for 0.5h to obtain carbon nanotube-magnesium alloy powder mixed slurry with uniform dispersion, and finally filtering and vacuum drying (drying for 1h at 60 ℃) to obtain a carbon nanotube-magnesium alloy powder mixture.
3) Pressing and forming: adding the carbon nano tube-magnesium alloy powder mixture into a die with the diameter of 38mm, and carrying out cold press forming at room temperature to obtain a composite material green compact, wherein the pressure is 150MPa.
4) Sintering and forming: sintering the composite material green body obtained in the step 3) for 2 hours at 650 ℃ under the protection of argon to obtain a sintered composite material.
5) Extrusion molding: and (3) extruding and forming the sintered composite material obtained in the step 4) at the extrusion rate of 2mm/min and the extrusion temperature of 400 ℃ to obtain the AZ91 magnesium-based composite material with the content of the modified carbon nanotube with the wolf tooth rod structure of 1.0 wt.%. The composite material is tested for mechanical properties, the tensile strength of the composite material reaches 250-280MPa, the elongation reaches 10.1-12.3%, and the hardness is 80.1-91.4HV, so that the composite material has good mechanical properties.
Example 2.
(1) Wolf tooth stick structure modified carbon nano tube.
1) Pits are formed on the surface of the carbon nano tube.
a) And (3) low-temperature reaction: 1g of graphitized carbon nanotube, 0.5g of sodium nitrate and 25mL of 98% concentrated sulfuric acid are added into a beaker to be mixed, and the mixture is placed in a freezer, the reaction temperature is 0 ℃, and the mixture is fully stirred for 20 min. 4g of potassium permanganate (KMnO) are gradually added with mechanical stirring (speed 10 rpm) 4 ) After that, stirring was continued for 2 hours.
b) And (3) medium-temperature reaction: and (b) moving the mixture obtained in the step a) out of the freezer, placing the mixture into a water bath kettle at 35 ℃, mechanically stirring (at the speed of 10 rpm) after the reaction solution becomes viscous, and simultaneously, gradually adding 100mL of distilled water into the reaction solution (in order to prevent the solution from boiling due to overheating, the adding amount of the distilled water is 10mL each time, and the adding time interval of the distilled water is 2 min), and then continuing stirring for 0.5h under the condition of the same stirring speed.
c) High-temperature reaction: and (c) raising the temperature of the water bath kettle in the step b) to 90 ℃, keeping stirring during the temperature raising, adding 150mL of distilled water into the reaction liquid after the temperature raising is finished, and continuously stirring for 0.5h (the stirring speed is constant).
d) And (3) terminating the reaction: 15 mL of H was added to the reaction mixture obtained in step c) 2 O 2 (30%) while stirring was continued for 10min to terminate the reaction.
e) Filtering and drying: adding 1000mL of distilled water into the reaction liquid obtained in the step d), standing, pouring out the supernatant until the solution has an acidic pH of 7, washing with distilled water continuously, filtering, and drying to obtain carbon nanotube powder with pits on the surface.
2) And zinc oxide is implanted into the pits.
a) 1g of carbon nano tube with a pit on the surface is added into 1000mL of distilled water, and is subjected to ultrasonic dispersion to form a mixed solution, and 0.2g of zinc nitrate hexahydrate is added at the same time, and is subjected to ultrasonic dispersion to form a carbon nano tube-zinc nitrate mixed solution.
b) And gradually dripping 50mL of 2mol/L ammonia water solution into the mixed solution of the carbon nano tube and the zinc nitrate at the titration speed of 1mL/min, simultaneously mechanically stirring at the speed of 50rpm, and obtaining a precipitate after the net value is 0.5h after the dripping.
c) And filtering the precipitate, and drying at 60 ℃ for 2h to obtain the precursor of the modified carbon nanotube with the mace structure.
d) And sintering the precursor for 2h at 650 ℃ under the protection of argon to obtain the modified carbon nanotube with the wolf tooth stick structure.
(2) Preparing the magnesium alloy composite material.
1) Dispersing carbon nanotubes with a wolf tooth stick structure: dispersing carbon nano tubes with wolf tooth stick structures: adding 2g of mace structure modified carbon nanotubes into 1500mL of ethanol, and performing ultrasonic dispersion for 0.5h under the power condition of 500W to obtain a uniformly dispersed mixed solution.
2) The carbon nano tube with the wolf tooth stick structure and the magnesium alloy powder form uniform dispersion: adding 99g of magnesium alloy powder (with the granularity of 300 meshes) into the mixed solution, mechanically stirring for 0.5h to obtain carbon nanotube-magnesium alloy powder mixed slurry with uniform dispersion, and finally filtering and vacuum drying (drying for 1h at 60 ℃) to obtain a carbon nanotube-magnesium alloy powder mixture.
3) Pressing and forming: adding the carbon nano tube-magnesium alloy powder mixture into a die with the diameter of 38mm, and carrying out cold press forming at room temperature to obtain a composite material green compact, wherein the pressure is 150MPa.
4) Sintering and forming: sintering the composite material green blank obtained in the step 3) for 2h at 650 ℃ under the protection of argon to obtain the sintered composite material.
5) And (3) extrusion forming: and (3) extruding and forming the sintered composite material obtained in the step 4) at the extrusion rate of 2mm/min and the extrusion temperature of 400 ℃ to obtain the AZ91 magnesium-based composite material with the content of the modified carbon nanotube with the wolf tooth rod structure of 2.0 wt.%. The composite material is tested for mechanical properties, the tensile strength of the composite material reaches 300-340MPa, the elongation reaches 12.5-13.6%, and the hardness is 90.6-101.7HV, so that the composite material is excellent in mechanical properties.
Example 3.
(1) Wolf tooth stick structure modified carbon nano tube.
1) Pits are formed on the surface of the carbon nano tube.
a) And (3) low-temperature reaction: 1g of graphitized carbon nanotube, 0.5g of sodium nitrate and 25mL of 98% concentrated sulfuric acid are added into a beaker to be mixed, and the mixture is placed in a freezer, the reaction temperature is 0 ℃, and the mixture is fully stirred for 20 min. 4g of potassium permanganate (KMnO) are gradually added with mechanical stirring (speed 10 rpm) 4 ) After that, stirring was continued for 2 hours.
b) And (3) medium-temperature reaction: and (b) moving the mixture obtained in the step a) out of the freezer, putting the mixture into a 35 ℃ water bath kettle, mechanically stirring (at the speed of 10 rpm) after the reaction solution becomes viscous, gradually adding 100mL of distilled water into the reaction solution (in order to prevent the solution from boiling due to overheating, the adding amount of the distilled water is 10mL each time, and the adding time interval of the distilled water is 2 min), and then continuously stirring for 0.5h under the condition of the same stirring speed.
c) High-temperature reaction: and (c) raising the temperature of the water bath kettle in the step b) to 90 ℃, keeping stirring during the temperature raising, and after the temperature raising is finished, adding 150mL of distilled water into the reaction liquid and continuously stirring for 0.5h (the stirring speed is unchanged).
d) And (3) reaction termination: 15 mL of H was added to the reaction mixture obtained in step c) 2 O 2 (30%) while stirring was continued for 10min to terminate the reaction.
e) Filtering and drying: adding 1000mL of distilled water into the reaction liquid obtained in the step d), standing, pouring out the supernatant until the solution is acidic pH7, washing with distilled water continuously, filtering, and drying to obtain carbon nanotube powder with pits on the surface.
2) And the zinc oxide is implanted into the pits.
a) 1g of carbon nano tube with a pit on the surface is added into 1000mL of distilled water, and is subjected to ultrasonic dispersion to form a mixed solution, and 0.2g of zinc nitrate hexahydrate is added at the same time, and is subjected to ultrasonic dispersion to form a carbon nano tube-zinc nitrate mixed solution.
b) And gradually dripping 50mL of 2mol/L ammonia water solution into the mixed solution of the carbon nano tube and the zinc nitrate at the titration speed of 1mL/min, simultaneously mechanically stirring at the speed of 50rpm, and obtaining a precipitate after the net value is 0.5h after the dripping.
c) And filtering the precipitate, and drying at 60 ℃ for 2h to obtain the precursor of the modified carbon nanotube with the wolfsbane stick structure.
d) And sintering the precursor for 2h at 650 ℃ under the protection of argon to obtain the modified carbon nanotube with the wolf tooth stick structure.
(2) And (3) preparing the magnesium alloy composite material.
1) Dispersing carbon nano tubes with wolf tooth stick structures: adding 3g of mace-structured modified carbon nanotubes into 2000mL of ethanol, and performing ultrasonic dispersion for 0.5h under the power condition of 500W to obtain a uniformly dispersed mixed solution.
2) The carbon nano tube with the wolf tooth stick structure and the magnesium alloy powder form uniform dispersion: adding 99g of magnesium alloy powder (with the granularity of 300 meshes) into the mixed solution, mechanically stirring for 0.5h to obtain carbon nanotube-magnesium alloy powder mixed slurry with uniform dispersion, and finally filtering and vacuum drying (drying for 1h at 60 ℃) to obtain a carbon nanotube-magnesium alloy powder mixture.
3) And (3) press forming: adding the carbon nano tube-magnesium alloy powder mixture into a die with the diameter of 38mm, and carrying out cold press forming at room temperature to obtain a composite material green compact, wherein the pressure is 150MPa.
4) Sintering and forming: sintering the composite material green body obtained in the step 3) for 2 hours at 650 ℃ under the protection of argon to obtain a sintered composite material.
5) And (3) extrusion forming: and (3) extruding and forming the sintered composite material obtained in the step 4) at the extrusion speed of 2mm/min and the extrusion temperature of 400 ℃ to obtain the AZ91 magnesium-based composite material with the content of the modified carbon nano tubes with the wolf tooth rod structure of 3.0 wt.%. The composite material is tested for mechanical properties, the tensile strength of the composite material reaches 350-380MPa, the elongation reaches 12.0-15.1%, the hardness is 110.3-125.6HV, and the composite material is a composite material with excellent mechanical properties.
Fig. 1 is a schematic diagram of a modified carbon nanotube with a mace structure and in a magnesium matrix in an embodiment, and shows that zinc oxide nanoparticles are embedded in the carbon nanotube as mace to form the modified carbon nanotube with a mace structure. When the nano-zinc oxide particles are compounded in the magnesium matrix, slight interface reaction occurs between the nano-zinc oxide particles and the magnesium matrix, so that carbon nano-particles are tightly embedded in the magnesium matrix to form good interface combination, and the comprehensive mechanical property of the composite material is favorably improved.
Fig. 2 and 3 show the microstructure of the modified carbon nanotube with mace structure in the examples, in which more zinc oxide nanoparticles are implanted into the pits of the carbon nanotube to form the carbon nanotube reinforcement with mace structure.
FIG. 5 shows the microstructure of AZ91 Mg-based composite material with 3.0wt.% modified carbon nanotubes prepared under the conditions of example 3. Compared with the structure and the appearance of the AZ91 matrix alloy shown in the figure 4, the crystal grain size of the composite material is obviously thinned, the fine crystal strengthening is obvious, and the mechanical property of the composite material is obviously improved.
Claims (1)
1. A method for modifying carbon nano tube reinforced magnesium matrix composite material by a mace structure is characterized by comprising the following steps:
(1) Modified carbon nanotube of wolf tooth stick structure:
1) Forming pits on the surface of the carbon nanotube:
a) And (3) low-temperature reaction: graphitized carbon nanotubes, sodium nitrate, concentrated sulfuric acid with the concentration of 98% and potassium permanganate are mixed according to the mass ratio of 1:0.5-1.0:40-55: 3-5; firstly, adding the prepared graphitized carbon nano tube, sodium nitrate and concentrated sulfuric acid into a beaker, uniformly mixing, and then placing the mixture in a freezer for low-temperature reaction at the temperature of 0-4 ℃ for 10-30min; then under the stirring condition of 5-10rpm, gradually adding the prepared potassium permanganate into the reaction liquid mixed solution, and continuously stirring for 2-5h;
b) And (3) medium-temperature reaction: moving the mixture obtained in the step a) out of the freezer, putting the mixture into a water bath kettle at 35-40 ℃, gradually adding distilled water into the reaction liquid under the stirring condition of 5-10rpm after the reaction liquid becomes viscous, wherein the adding amount of the distilled water is 100-500% of the volume of the reaction liquid, each adding amount is 1/10 of the total adding amount, the adding time interval of the water is 2min, and then, continuously stirring at 5-10rpm for 0.5-1h;
c) High-temperature reaction: raising the temperature of the water bath kettle in the step b) to 90-100 ℃, keeping stirring during the temperature raising, adding distilled water into the reaction liquid after the temperature raising is finished, wherein the adding amount of the distilled water is 100-300% of the volume of the reaction liquid, and continuously stirring for 0.5-1h at 5-10 rpm;
d) And (3) reaction termination: adding H with the concentration of 30 percent and the volume of 5 to 20 percent of the reaction liquid into the reaction liquid obtained in the step c) 2 O 2 Meanwhile, continuously stirring until the reaction is finished;
e) And (3) filtering and drying: adding distilled water into the reaction liquid obtained in the step d), wherein the adding amount of the distilled water is 300-800% of the volume of the reaction liquid, standing, pouring out the supernatant liquid until the acid pH of the solution is 6-7, and continuously washing, filtering and drying by using the distilled water to obtain carbon nanotube powder with pits on the surface;
2) Zinc oxide implant pits:
a) Mixing carbon nano tubes with pits on the surface, zinc nitrate hexahydrate and distilled water according to the mass ratio of 1:0.1-0.5: adding the mixture into a beaker in a proportion of 1000-5000, and performing ultrasonic dispersion to form uniformly dispersed carbon nanotube-zinc nitrate mixed solution;
b) Gradually dripping 5-30% of the volume of the reaction solution and 1-3mol/L aqueous ammonia solution into the mixed solution of the carbon nano tube and the zinc nitrate at the titration rate of 1-5mL/min, simultaneously carrying out mechanical stirring at the rate of 20-80rpm, and standing for 0.5-1h after dripping to obtain precipitate;
c) Filtering the precipitate obtained in the step b), and drying at 60-80 ℃ for 2-4h to obtain a precursor of the modified carbon nanotube with the mace structure;
d) Sintering the precursor in the step c) for 1-3h at 500-700 ℃ under the protection of argon to obtain the modified carbon nanotube with the wolf tooth rod structure;
(2) Preparing a magnesium alloy composite material:
1) Dispersing carbon nano tubes with wolf tooth stick structures: mixing the modified carbon nano tube with the wolf tooth stick structure and ethanol according to the weight ratio of 1-5g: after mixing at a ratio of 200-1000mL, ultrasonically dispersing for 0.5-1h under the power condition of 500-1000W to obtain uniformly dispersed mixed liquor;
2) The carbon nano tube with the wolf tooth stick structure and the magnesium alloy powder form uniform dispersion: adding magnesium alloy powder with the granularity of 200-400 meshes into the mixed solution obtained in the step 2) according to the proportion that the weight percentage of the carbon nano tube with the wolf tooth stick structure is 1-5%, mechanically stirring for 0.5-1h to obtain carbon nano tube-magnesium alloy powder mixed slurry with uniform dispersion, and finally filtering, and drying in vacuum at 60 ℃ for 1-2h to obtain a carbon nano tube-magnesium alloy powder mixture;
3) Pressing and forming: adding the carbon nano tube-magnesium alloy powder mixture into a die with the diameter of 30-40mm, and carrying out cold pressing forming at room temperature to obtain a composite material green body, wherein the pressure is 50-200MPa;
4) Sintering and forming: sintering the composite material green blank obtained in the step 3) for 2-3h at 600-650 ℃ under the protection of argon to obtain a sintered composite material;
5) Extrusion molding: and (3) extruding and forming the sintered composite material obtained in the step 4) under the conditions that the extrusion speed is 1-5mm/min and the extrusion temperature is 400-550 ℃ to obtain the mace structure modified carbon nanotube reinforced magnesium-based composite material.
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