CN112111665B - Method for preparing carbon modified aluminum alloy composite material by vacuum pressure infiltration method - Google Patents
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Abstract
The invention relates to the technical field of aluminum alloy preparation, and discloses a method for preparing a carbon modified aluminum alloy composite material by a vacuum pressure infiltration method, which comprises the following steps: fully mixing the ceramic particles with a cationic surfactant aqueous solution, and drying to obtain the ceramic particles coated with the cationic surfactant; adding a carbon material and ceramic particles coated with a cationic surfactant into water, carrying out electrostatic self-assembly under stirring, and drying to obtain composite particles; uniformly mixing the composite particles with a foaming agent, and performing hot-pressing sintering to obtain a porous prefabricated body; and melting and impregnating an aluminum alloy ingot into the porous preform in vacuum pressure impregnation equipment, and cooling to obtain the carbon modified aluminum alloy composite material. The method can effectively improve the compatibility between the aluminum alloy and the carbon material, the prefabricated body is not easy to crack in the preparation process, and the aluminum alloy can be fully filled in the pores of the prefabricated body, so that the composite material with better tensile strength and heat-conducting property can be obtained.
Description
Technical Field
The invention relates to the technical field of aluminum alloy preparation, in particular to a method for preparing a carbon modified aluminum alloy composite material by a vacuum pressure infiltration method.
Background
The aluminum alloy composite material consists of two parts, namely a base material (pure aluminum and aluminum alloy) and a reinforcing material (fiber, whisker and particle), and belongs to a light metal matrix composite material due to light weight; the aluminum-based composite material not only has the advantages of low density, good thermal conductivity, strong corrosion resistance and the like of an aluminum matrix, but also maintains some integral performances of the metal-based composite material, such as the advantages of high specific stiffness, good dimensional stability and the like, and becomes the key point of novel material research. The carbon modified aluminum alloy composite material is a general name of composite materials taking carbon materials such as carbon fibers, carbon nanotubes, graphene and the like as reinforcements and aluminum alloy as a matrix, has high tensile strength and electric and heat conducting properties, and is widely applied to the fields of automobiles, electronics, communication and the like as a structure and heat dissipation material. However, due to density differences and the like, the wettability between the carbon material and the aluminum matrix is poor, which seriously hinders the preparation of the composite material and greatly affects the mechanical properties and the heat conductivity of the composite material.
Chinese patent publication No. CN106119587A discloses a method for preparing an aluminum alloy composite material to which carbon nanotubes are effectively added, comprising the following steps: (1) preparing carbon nano tube aluminum-based composite powder: putting the carbon nano tube, the aluminum powder and the foaming agent into a high-energy ball mill according to a certain proportion, uniformly mixing, and cooling to prepare composite powder; (2) preparing a carbon nano tube aluminum-based composite billet: putting the composite powder prepared in the step (1) into a vacuum hot pressing furnace for sintering densification to prepare a composite billet; (3) smelting: and (3) after the pure aluminum ingot is melted, adding the composite billet prepared in the step (2) at a certain temperature, and stirring, preserving heat and casting to obtain the carbon nano tube aluminum alloy composite material. The method has the advantages that the foaming agent is added into the composite powder, the vacuum hot-pressing sintering process is combined, so that particles are fused, the strong mechanical binding force among the particles is eliminated, the severe foaming phenomenon is generated after the composite billet is added with the aluminum liquid, fine particles are formed, and the problem of wettability of the carbon nano tube and the aluminum liquid is solved. However, at the same time, this method also has the following problems: (1) the composite billet formed by hot-pressing and sintering the aluminum and the carbon nano tube has low strength, and the problems of cracking and the like can occur in the stirring and casting process, so that the strength of the finally prepared composite material is influenced; (2) the foaming agent plays a role after being added with the aluminum liquid, a large amount of bubbles can be generated in the aluminum liquid, the aluminum liquid is filled into the composite billet by adopting a stirring casting method, the speed of the aluminum liquid permeating into the composite billet is low, so that pores which are not filled with the aluminum liquid can exist in the finally prepared composite material, and the strength and the heat conductivity of the composite material are influenced; and the carbon material and the aluminum liquid can react after being contacted for a long time to generate Al4C3The thermal conductivity coefficient is small (140W/m.K), so that the interface thermal resistance between the carbon material and the aluminum matrix is large, and the thermal conductivity of the composite material is influenced.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing a carbon-modified aluminum alloy composite material by a vacuum pressure infiltration method. The problem of cracking of the prefabricated body does not exist in the process of preparing the composite material by the method, and the aluminum alloy can be fully filled in the pores of the prefabricated body, so that the composite material with better tensile strength and heat conductivity can be obtained.
The specific technical scheme of the invention is as follows:
a method for preparing a carbon modified aluminum alloy composite material by a vacuum pressure infiltration method comprises the following steps:
(1) fully mixing the ceramic particles with a cationic surfactant aqueous solution, and drying to obtain the ceramic particles coated with the cationic surfactant;
(2) adding a carbon material and ceramic particles coated with a cationic surfactant into water, carrying out electrostatic self-assembly under stirring, and drying to obtain composite particles;
(3) uniformly mixing the composite particles with a foaming agent, and performing hot-pressing sintering to obtain a porous prefabricated body;
(4) and melting and impregnating an aluminum alloy ingot into the porous preform in vacuum pressure impregnation equipment, and cooling to obtain the carbon modified aluminum alloy composite material.
According to the invention, the ceramic particles and the carbon material are mixed to prepare the porous preform, and the characteristics of high compression resistance and high shear strength of the ceramic material are utilized, so that the strength of the preform can be improved, and the preform is prevented from cracking in the subsequent aluminum liquid infiltration process, and thus the carbon material and the ceramic particles are more uniformly distributed in the composite material, and the tensile strength and the heat conductivity of the composite material are improved. Meanwhile, the cationic surfactant is coated outside the ceramic particles, so that the surfaces of the ceramic particles are charged with positive charges, and the ceramic particles are effectively combined with the carbon materials with the negative charges on the surfaces through electrostatic attraction, so that the strength of the prefabricated body can be further improved, and the prefabricated body is prevented from deforming and collapsing in the vacuum pressure infiltration process.
In addition, the invention can prevent the wettability between the preform and the aluminum alloy melt from being improved and improve the interface combination between the preform and the aluminum alloy melt by adding the foaming agent into the preform, wherein the foaming agent plays a role in the hot-pressing sintering process to form pores in the preform and then infiltrating the aluminum alloy melt into the pores through the vacuum pressure infiltration method, thereby improving the wettability between the preform and the aluminum alloy meltHigh tensile strength and heat conductivity of the composite material. Compared with the patent with the publication number of CN106119587A, the foaming agent plays a role in hot-pressing sintering, and the vacuum pressure infiltration method is adopted to accelerate the process of infiltrating the aluminum alloy melt into the porous preform, so that the finally prepared composite material can be prevented from having pores which are not filled with the aluminum alloy, the tensile strength and the heat conductivity of the composite material can be improved, and the generation of Al by the reaction of a carbon material and the aluminum liquid can be reduced4C3Thereby reducing the interface thermal resistance and improving the heat-conducting property of the composite material.
Preferably, in the step (2), the carbon material is at least one of carbon nanotube, graphene, fullerene, nano carbon black, nano graphite and short carbon fiber; the short carbon fiber has a length of 30-50 μm and a diameter of 4-7 μm.
Preferably, in the step (1), the ceramic particles are at least one of nano aluminum oxide, nano sodium silicate, nano feldspar and nano quartz stone.
Preferably, in the step (1), the cationic surfactant is at least one of a fatty amine, a polyoxyethylene fatty amine, a quaternary ammonium salt, and a polyoxyethylene quaternary ammonium salt.
Preferably, in the step (1), the mass fraction of the aqueous cationic surfactant solution is 5 to 50 wt.%.
Preferably, the amount of the ceramic particles used in step (1) is 5 to 10wt.% of the amount of the carbon material used in step (2).
Preferably, in the step (3), the amount of the foaming agent is 1 to 5wt.% of the amount of the composite particles.
Preferably, in the step (3), the foaming agent is at least one of calcium carbonate, magnesium carbonate and sodium bicarbonate.
Preferably, in the step (3), the temperature of the hot-pressing sintering is 1500-2000 ℃.
Preferably, in the step (3), the pressure of the hot-pressing sintering is 5-10 MPa.
Preferably, in the step (4), the pressure for impregnation is 1 to 5 Mpa.
Preferably, the short carbon fiber comprises a core and a skin layer wrapped outside the core; the core is carbon and the skin is a carbon/aluminum composite material.
The short carbon fiber is designed into a sheath-core structure, and the carbon core part can improve the carbon content in the short carbon fiber, so that the reinforcing effect of the short carbon fiber on the composite material can be better exerted; the aluminum/carbon composite skin layer acts as a transition layer between the carbon core part and the aluminum matrix, so that the compatibility between the short carbon fibers and the aluminum matrix can be improved, the interface bonding between the short carbon fibers and the aluminum matrix is improved, the load can be effectively transmitted from the aluminum matrix to the carbon fibers, the two are prevented from being peeled off when being pulled, the tensile property of the composite material is improved, the interface bonding is improved, and the interface thermal resistance can be reduced, so that the heat conduction property of the composite material is improved.
Preferably, the diameter of the core part is 3-5 μm, and the thickness of the skin layer is 1-2 μm; the preparation method of the short carbon fiber comprises the following steps:
(A) spinning: carrying out melt spinning on the asphalt to prepare carbon fiber precursor;
(B) pre-oxidation: pre-oxidizing carbon fiber precursors at 200-400 ℃ in an air atmosphere;
(C) dipping: immersing carbon fiber precursors into a mixed solution of aluminum sol and molten asphalt, and immersing for 30-40 min to obtain carbon fibers coated with the aluminum sol and the molten asphalt; the mass ratio of the aluminum sol to the molten asphalt is 1: 3-5;
(D) pre-oxidation: pre-oxidizing the carbon fiber subjected to the dipping treatment at 200-400 ℃ in an air atmosphere;
(E) carbonizing: carbonizing the carbon fiber subjected to preoxidation treatment at 800-1200 ℃ in a nitrogen atmosphere;
(F) electrolysis: laying the carbonized carbon fiber on the bottom of an electrolytic tank as a cathode, taking a carbon material as an anode and taking molten cryolite as electrolyte to carry out electrolysis; after the electrolysis is finished, taking out the carbon fiber, and cooling to obtain the carbon fiber with the skin-core structure;
(G) cutting: and cutting the skin-core structure carbon fiber in the radial direction to obtain the short carbon fiber.
The invention is achieved by impregnation andthe electrolytic process realizes the coating of the carbon/aluminum composite material outside the carbon core, and the specific mechanism is as follows: pre-oxidizing (stabilizing) carbon fiber precursor, and coating a mixed layer of alumina sol and molten asphalt outside the precursor by a dip coating method; in the subsequent pre-oxidation process, the asphalt in the outer mixed layer undergoes a series of complex reactions and is converted into a pyridine ring trapezoidal structure with thermal stability and semiconductor resistance, and meanwhile, the outer aluminum sol is dried and cured; after the carbonization treatment, the outer alumina is converted to aluminum by electrolysis. The specific process of electrolysis is as follows: during electrolysis, the alumina of the outer layer of the carbon fiber and the AlF in the molten cryolite6 3-Reaction to Al2OF6 2-，Al2OF6 2-Entering into electrolyte to form pores outside the carbon fiber, AlF6 3-And reducing the cathode into aluminum, filling the aluminum liquid into pores of the outer layer of the carbon fiber, and cooling to obtain the carbon fiber with the core part of carbon and the skin layer of aluminum/carbon composite material. During electrolysis, carbon dioxide is generated at the anode, and whether the electrolysis is finished can be judged according to whether bubbles emerge from the anode.
The reason why the aluminum sol is adopted instead of the simple aluminum in the step (B) is that the simple aluminum has a low melting point (660 ℃), and flows away due to melting during carbonization, and aluminum in the aluminum sol exists in the form of aluminum oxide, the melting point of the aluminum oxide reaches 2054 ℃, and the aluminum oxide can still exist stably during high-temperature carbonization. In addition, the porosity of the aluminum sol enables the aluminum sol to form a porous framework in the skin layer, so that the contact area of aluminum and the carbon material in the skin layer is increased, and the compatibility between the short carbon fibers and the aluminum matrix in the composite material is better improved.
Preferably, the skin layer comprises an inner layer, a middle layer and an outer layer, wherein the aluminum content of the inner layer is increased from inside to outside; the diameter of the core part is 2-4 mu m, and the thicknesses of the inner layer, the middle layer and the outer layer are all 0.5-1 mu m; the preparation method of the short carbon fiber comprises the following steps:
(a) spinning: carrying out melt spinning on the asphalt to prepare carbon fiber precursor;
(b) pre-oxidation: pre-oxidizing carbon fiber precursors at 200-400 ℃ in an air atmosphere;
(c) coating an inner layer: immersing carbon fiber precursors into a mixed solution of aluminum sol and molten asphalt, wherein the mass ratio of the aluminum sol to the molten asphalt is 1: 4.5-6.5, and immersing for 18-23 min; pre-oxidizing the carbon fiber subjected to the dipping treatment at 200-400 ℃ in an air atmosphere to obtain carbon fiber coated with an inner layer;
(d) coating the middle layer and the outer layer: changing the mass ratio of the alumina sol to the molten asphalt in the step (c) to 1: 2-4.5 and 1: 1-2, repeating the step (c), and sequentially coating the middle layer and the outer layer;
(e) carbonizing: carbonizing the carbon fiber coated with the outer layer at 800-1200 ℃ in a nitrogen atmosphere;
(f) electrolysis: laying the carbonized carbon fiber on the bottom of an electrolytic tank as a cathode, taking a carbon material as an anode and taking molten cryolite as electrolyte to carry out electrolysis; after the electrolysis is finished, taking out the carbon fiber, and cooling to obtain the carbon fiber with the skin-core structure;
(g) cutting: and cutting the skin-core structure carbon fiber in the radial direction to obtain the short carbon fiber.
By repeating the steps of dipping and pre-oxidation, three layers of aluminum/carbon composite materials are wrapped outside the carbon core part, and the aluminum content from the inner layer to the outer layer is sequentially increased, the compatibility among the core part, the skin layer and the aluminum matrix can be further improved through the gradient transition, the interface bonding between the short carbon fiber and the aluminum matrix is improved, and the tensile strength and the thermal conductivity of the composite material are improved.
Preferably, in the step (F) or (g), the mass ratio of the cathode to the molten cryolite is 1: 2-2.5.
Preferably, in the step (C) or the step (C), the immersion time is 30 to 40 min.
Preferably, in the step (B) or the step (D) or the step (B) or the step (c), the pre-oxidation time is 30-40 min.
Preferably, in the step (E) or the step (E), the carbonization time is 3-6 h.
Preferably, in the step (F) or the step (F), the voltage of the electrolysis is 3.5 to 4.5V.
Compared with the prior art, the invention has the following advantages:
(1) the strength of the porous preform in the preparation process is high, the problems of cracking and the like can not occur in the process of impregnating the aluminum alloy melt, and the finally prepared composite material has high tensile strength and heat conductivity;
(2) the foaming agent, the hot-pressing sintering and the vacuum pressure infiltration method are combined, so that the wettability between the aluminum alloy melt and the carbon material can be improved, the aluminum alloy melt and the carbon material are better combined, and the tensile strength and the heat conductivity of the composite material are improved;
(3) the short carbon fiber with the sheath-core structure can improve the compatibility between the carbon material and the aluminum matrix, and further improve the tensile strength and the heat-conducting property of the composite material.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A method for preparing a carbon-modified aluminum alloy composite material by a vacuum pressure infiltration method comprises the following steps (shown in figure 1):
(1) fully mixing ceramic particles with 5-50 wt.% of cationic surfactant aqueous solution, and drying to obtain ceramic particles coated with cationic surfactant; the ceramic particles are at least one of nano aluminum oxide, nano sodium silicate, nano feldspar and nano quartz stone; the cationic surfactant is at least one of fatty amine, polyoxyethylene fatty amine, quaternary ammonium salt and polyoxyethylene quaternary ammonium salt;
(2) adding a carbon material and ceramic particles coated with a cationic surfactant into water, carrying out electrostatic self-assembly under stirring, and drying to obtain composite particles; the carbon material is at least one of carbon nano tube, graphene, fullerene, nano carbon black, nano graphite and short carbon fiber; the length of the short carbon fiber is 30-50 mu m, and the diameter of the short carbon fiber is 4-7 mu m; the using amount of the ceramic particles in the step (1) is 5-10 wt% of the using amount of the carbon material in the step (2);
(3) uniformly mixing the composite particles with a foaming agent, and performing hot-pressing sintering at 1500-2000 ℃ and 5-10 MPa to obtain a porous preform; the foaming agent is at least one of calcium carbonate, magnesium carbonate and sodium bicarbonate; the amount of the foaming agent is 1-5 wt% of the amount of the composite particles;
(4) and melting an aluminum alloy ingot in vacuum pressure infiltration equipment, infiltrating the aluminum alloy ingot into the porous preform under the pressure of 1-5 Mpa, and cooling to obtain the carbon modified aluminum alloy composite material.
Optionally, in the step (2), the carbon material is short carbon fiber with the length of 30-50 μm and the diameter of 4-7 μm; the short carbon fiber comprises a core and a skin layer wrapped outside the core; the core part is carbon, and the diameter is 3-5 mu m; the skin layer is made of carbon/aluminum composite material and has a thickness of 1-2 μm. The preparation method of the short carbon fiber comprises the following steps:
(A) spinning: carrying out melt spinning on the asphalt to prepare carbon fiber precursor;
(B) pre-oxidation: pre-oxidizing carbon fiber precursors at 200-400 ℃ in an air atmosphere for 30-40 min;
(C) dipping: immersing carbon fiber precursors into a mixed solution of aluminum sol and molten asphalt, and immersing for 30-40 min to obtain carbon fibers coated with the aluminum sol and the molten asphalt; the mass ratio of the aluminum sol to the molten asphalt is 1: 3-5;
(D) pre-oxidation: pre-oxidizing the carbon fiber subjected to the dipping treatment for 30-40 min at 200-400 ℃ in an air atmosphere;
(E) carbonizing: carbonizing the carbon fiber subjected to preoxidation treatment for 3-6 hours at 800-1200 ℃ in a nitrogen atmosphere;
(F) electrolysis: laying the carbonized carbon fibers at the bottom of an electrolytic tank as a cathode, wherein the mass ratio of the cathode to the molten cryolite is 1: 2-2.5, the carbon material is used as an anode, the molten cryolite is used as electrolyte, and electrolysis is carried out at the voltage of 3.5-4.5V; after no bubble emerges from the anode, taking out the carbon fiber, and cooling to obtain the carbon fiber with the skin-core structure;
(G) cutting: and cutting the skin-core structure carbon fiber in the radial direction to obtain the short carbon fiber.
Optionally, in the step (2), the carbon material is short carbon fiber with the length of 30-50 μm and the diameter of 4-7 μm; the short carbon fiber comprises a core and a skin layer wrapped outside the core; the core part is carbon, and the diameter is 2-4 mu m; the cortex is a carbon/aluminum composite material and comprises an inner layer, a middle layer and an outer layer, wherein the aluminum content of the inner layer, the aluminum content of the middle layer and the aluminum content of the outer layer are sequentially increased from inside to outside, and the thicknesses of the inner layer, the middle layer and the outer layer are all 0.5-1 mu m. The preparation method of the short carbon fiber comprises the following steps:
(a) spinning: carrying out melt spinning on the asphalt to prepare carbon fiber precursor;
(b) pre-oxidation: pre-oxidizing carbon fiber precursors at 200-400 ℃ in an air atmosphere for 30-40 min;
(c) coating an inner layer: immersing carbon fiber precursors into a mixed solution of aluminum sol and molten asphalt, wherein the mass ratio of the aluminum sol to the molten asphalt is 1: 4.5-6.5, and immersing for 18-23 min; pre-oxidizing the carbon fiber subjected to the dipping treatment at 200-400 ℃ for 30-40 min in an air atmosphere to obtain carbon fiber coated with an inner layer;
(d) coating the middle layer and the outer layer: changing the mass ratio of the alumina sol to the molten asphalt in the step (c) to 1: 2-4.5 and 1: 1-2, repeating the step (c), and sequentially coating the middle layer and the outer layer;
(e) carbonizing: carbonizing the carbon fiber coated with the outer layer for 3-6 hours at 800-1200 ℃ in a nitrogen atmosphere;
(f) electrolysis: laying the carbonized carbon fiber at the bottom of an electrolytic tank as a cathode, taking a carbon material as an anode, taking the mass ratio of the cathode to the molten cryolite as 1: 2-2.5, taking the molten cryolite as an electrolyte, and electrolyzing at the voltage of 3.5-4.5V; after no bubble emerges from the anode, taking out the carbon fiber, and cooling to obtain the carbon fiber with the skin-core structure;
(g) cutting: and cutting the skin-core structure carbon fiber in the radial direction to obtain the short carbon fiber.
Example 1
A method for preparing a carbon modified aluminum alloy composite material by a vacuum pressure infiltration method comprises the following steps:
(1) fully mixing nano aluminum oxide particles with 30 wt.% aqueous solution of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, and drying to obtain ceramic particles coated with a cationic surfactant;
(2) adding carbon nanotubes and ceramic particles coated with cationic surfactant into water, carrying out electrostatic self-assembly under stirring, and drying to obtain composite particles; the amount of the ceramic particles in the step (1) is 8 wt.% of the amount of the carbon material in the step (2);
(3) after the composite particles and calcium carbonate are uniformly mixed, carrying out hot-pressing sintering at 1800 ℃ under 10MPa to obtain a porous prefabricated body; the amount of the foaming agent is 3 wt.% of the amount of the composite particles;
(4) and melting a 6061 aluminum alloy ingot in a vacuum pressure impregnation device, impregnating the 6061 aluminum alloy ingot into the porous preform under 4Mpa, and cooling to obtain the carbon modified aluminum alloy composite material.
Example 2
The preparation was carried out by following the procedure of example 1, and the difference from example 1 is that the carbon material in step (2) is carbon black.
Example 3
The preparation was carried out by following the procedure of example 1, and the difference from example 1 is that the carbon material in step (2) is nanographite.
Example 4
The preparation was carried out according to the procedure of example 1, except that the carbon material in step (2) was graphene.
Example 5
The carbon material obtained by the procedure of example 1 was a short carbon fiber having a length of 40 μm and a diameter of 5.5 μm in step (2), and was prepared by the following method:
A) spinning: carrying out melt spinning on the asphalt to prepare carbon fiber precursor;
B) pre-oxidation: pre-oxidizing carbon fiber precursors for 35min at 300 ℃ in an air atmosphere;
C) carbonizing: carbonizing the carbon fiber subjected to preoxidation treatment for 5 hours at 1000 ℃ in a nitrogen atmosphere;
D) cutting: the sheath-core carbon fiber was cut in the radial direction to obtain a short carbon fiber having a length of 40 μm.
Example 6
Prepared according to the procedure of example 1, except that the ceramic particles in step (1) are sodium carbonate, which is the difference from example 1.
Example 7
Prepared according to the procedure of example 1, except that the ceramic particles in step (1) are feldspar, as the difference from example 1.
Example 8
The preparation was carried out by following the procedure of example 1, except that the ceramic particles in step (1) were quartz.
Example 9
The preparation was carried out by following the procedure of example 1, differing from example 1 in that the hot press sintering temperature in step (3) was 1600 ℃.
Example 10
The preparation was carried out by following the procedure of example 1, differing from example 1 in that the hot press sintering temperature in step (3) was 1700 ℃.
Example 11
The preparation was carried out by following the procedure of example 1, differing from example 1 in that the hot press sintering temperature in step (3) was 1900 ℃.
Example 12
Prepared by following the procedure of example 1, differing from example 1 in that the infiltration pressure in step (4) is 2 MPa.
Example 13
Prepared by following the procedure of example 1, differing from example 1 in that the infiltration pressure in step (4) was 3 MPa.
Example 14
Prepared by following the procedure of example 1, differing from example 1 in that the infiltration pressure in step (3) is 5 MPa.
Example 15
The carbon material prepared by the procedure of example 1 is different from example 1 in that the carbon material in step (2) is short carbon fiber and is prepared by the following method:
(A) spinning: carrying out melt spinning on the asphalt to prepare carbon fiber precursor;
(B) pre-oxidation: pre-oxidizing carbon fiber precursors for 35min at 300 ℃ in an air atmosphere;
(C) dipping: immersing carbon fiber precursors into a mixed solution of aluminum sol and molten asphalt, and immersing for 35min to obtain carbon fibers coated with the aluminum sol and the molten asphalt; the mass ratio of the aluminum sol to the molten asphalt is 1: 4;
(D) pre-oxidation: pre-oxidizing the carbon fiber subjected to the dipping treatment at 300 ℃ for 35min in an air atmosphere;
(E) carbonizing: carbonizing the carbon fiber subjected to preoxidation treatment for 5 hours at 1000 ℃ in a nitrogen atmosphere;
(F) electrolysis: laying the carbonized carbon fiber on the bottom of an electrolytic tank as a cathode, wherein the mass ratio of the cathode to the molten cryolite is 1:2, graphite is used as an anode, the molten cryolite is used as electrolyte, and electrolysis is carried out at a voltage of 4V; after no bubble emerges from the anode, taking out the carbon fiber, and cooling to obtain the carbon fiber with the skin-core structure;
(G) cutting: the sheath-core carbon fiber was cut in the radial direction to obtain a short carbon fiber having a length of 40 μm.
The core diameter of the resulting short carbon fiber was 4 μm and the skin thickness was 1.5. mu.m.
Example 16
The carbon material prepared by the procedure of example 1 is different from example 1 in that the carbon material in step (2) is short carbon fiber and is prepared by the following method:
(a) spinning: carrying out melt spinning on the asphalt to prepare carbon fiber precursor;
(b) pre-oxidation: pre-oxidizing carbon fiber precursors for 35min at 300 ℃ in an air atmosphere;
(c) coating an inner layer: immersing carbon fiber precursors into a mixed solution of aluminum sol and molten asphalt, wherein the mass ratio of the aluminum sol to the molten asphalt is 1:5.5, and immersing for 18 min; pre-oxidizing the carbon fiber subjected to the dipping treatment at 300 ℃ in an air atmosphere for 35min to obtain carbon fiber coated with an inner layer;
(d) coating the middle layer and the outer layer: changing the mass ratio of the aluminum sol to the molten asphalt in the step (c) to 1:3 and 1:1.5, repeating the step (c), and sequentially coating an upper middle layer and an outer layer;
(e) carbonizing: carbonizing the carbon fiber coated with the outer layer for 5 hours at 1000 ℃ in a nitrogen atmosphere;
(f) electrolysis: laying the carbonized carbon fiber at the bottom of an electrolytic tank as a cathode, taking graphite as an anode, taking the mass ratio of the cathode to molten cryolite as 1:2, taking the molten cryolite as electrolyte, and electrolyzing at 4V; after no bubble emerges from the anode, taking out the carbon fiber, and cooling to obtain the carbon fiber with the skin-core structure;
(g) cutting: the sheath-core carbon fiber was cut in the radial direction to obtain a short carbon fiber having a length of 40 μm.
The diameter of the core of the prepared short carbon fiber is 4 μm, and the thicknesses of the inner layer, the middle layer and the outer layer in the skin layer are all 0.5 μm.
Comparative example 1 (cationic surfactant is not coated on the surface of ceramic particles)
A method for preparing a carbon modified aluminum alloy composite material by a vacuum pressure infiltration method comprises the following steps:
(1) adding carbon nano tubes and nano aluminum oxide particles into water, and uniformly mixing to obtain composite particles;
(2) after the composite particles and calcium carbonate are uniformly mixed, carrying out hot-pressing sintering at 1800 ℃ under 10MPa to obtain a porous prefabricated body;
(3) and melting a 6061 aluminum alloy ingot in a vacuum pressure impregnation device, impregnating the 6061 aluminum alloy ingot into the porous preform under 4Mpa, and cooling to obtain the carbon modified aluminum alloy composite material.
Comparative example 2 (foaming agent acting after addition of aluminum alloy melt)
A method for preparing a carbon modified aluminum alloy composite material by a vacuum pressure infiltration method comprises the following steps:
(1) fully mixing nano aluminum oxide particles with 30 wt.% quaternary ammonium salt aqueous solution, and drying to obtain ceramic particles coated with a cationic surfactant;
(2) adding carbon nanotubes and ceramic particles coated with cationic surfactant into water, carrying out electrostatic self-assembly under stirring, and drying to obtain composite particles;
(3) after the composite particles and calcium carbonate are uniformly mixed, carrying out hot-pressing sintering at 500 ℃ and under 10MPa to obtain a prefabricated body;
(4) and melting a 6061 aluminum alloy ingot in vacuum pressure impregnation equipment, impregnating the molten 6061 aluminum alloy ingot into the preform at the temperature of 900 ℃ under the pressure of 4Mpa, and cooling to obtain the carbon-modified aluminum alloy composite material.
The heat conductivity of the carbon-modified aluminum alloy composite materials prepared in examples 1 to 16 and comparative examples 1 to 2 was tested, and the test results are shown in table 1.
TABLE 1 thermal conductivity and mechanical Properties of the products of examples 1-16 and comparative examples 1-2
Example 1 on the basis of comparative example 1, the thermal conductivity and tensile strength of the composite material obtained by coating the ceramic particles with the cationic surfactant and then mixing the coated ceramic particles with the carbon nanotubes were significantly increased because: the positive charges are carried on the surface of the ceramic particles by coating the cationic surfactant outside the ceramic particles, and the positive charges can be effectively combined with the carbon material with the negative charges on the surface through electrostatic attraction, so that the strength of a prefabricated body is improved, the prefabricated body is prevented from cracking in the subsequent aluminum liquid infiltration process, the carbon material and the ceramic particles are distributed in the composite material more uniformly, and the tensile strength and the heat conductivity of the composite material can be improved.
Example 1 differs from comparative example 2 in that in example 1, the foaming agent functions during the hot press sintering, whereas in comparative example 2, the foaming agent functions after the aluminum alloy melt is added, and the thermal conductivity and tensile strength of the composite material prepared in example 1 are significantly greater because: the foaming agent plays a role when being added into the aluminum alloy melt, and can generate a large amount of bubbles in the melt, so that the melt cannot be fully filled into the pores of the prefabricated body, and the tensile strength and the heat conductivity of the composite material are influenced.
In examples 2 to 14, on the basis of example 1, one of the type of the carbon material, the type of the ceramic particles, the hot-pressing sintering temperature, and the infiltration pressure is changed, and as a result of comparing the test results of the composite materials prepared in examples 1 to 14, it is found that the thermal conductivity coefficient of the aluminum alloy obtained by using the process parameters in example 1 can reach 0.95, the tensile strength can reach 705MPa, and the results are all superior to those of other examples. Thus, the recipe and process parameters of example 1 can be selected as the optimal choice.
Example 15 based on example 5, the short carbon fiber with a sheath-core structure was used to produce a composite material with significantly increased thermal conductivity and tensile strength due to the following reasons: the aluminum/carbon composite skin layer acts as a transition layer between the carbon core part and the aluminum matrix, so that the compatibility between the short carbon fibers and the aluminum matrix can be improved, the interface bonding between the short carbon fibers and the aluminum matrix is improved, the load can be effectively transmitted from the aluminum matrix to the carbon fibers, the two are prevented from being peeled off when being pulled, the tensile property of the composite material is improved, the interface bonding is improved, and the interface thermal resistance can be reduced, so that the heat conduction property of the composite material is improved.
Example 16 the skin layer is designed to be three layers on the basis of example 15, the aluminum content is increased from inside to outside, and the tensile strength and the thermal conductivity of the prepared composite material are obviously increased because: the compatibility among the core part, the skin layer and the aluminum matrix can be further improved through the gradient transition of the aluminum content among the core part, the skin layer inner layer, the middle layer, the outer layer and the aluminum matrix, and the interface combination between the short carbon fiber and the aluminum matrix is improved, so that the tensile strength and the thermal conductivity of the composite material are improved.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for preparing a carbon-modified aluminum alloy composite material by a vacuum pressure infiltration method is characterized by comprising the following steps:
(1) fully mixing the ceramic particles with a cationic surfactant aqueous solution, and drying to obtain the ceramic particles coated with the cationic surfactant;
(2) adding a carbon material and ceramic particles coated with a cationic surfactant into water, carrying out electrostatic self-assembly under stirring, and drying to obtain composite particles;
(3) uniformly mixing the composite particles with a foaming agent, and performing hot-pressing sintering at 1500-2000 ℃ to obtain a porous preform;
(4) and melting and impregnating an aluminum alloy ingot into the porous preform in vacuum pressure impregnation equipment, and cooling to obtain the carbon modified aluminum alloy composite material.
2. The method for preparing a carbon-modified aluminum alloy composite material by vacuum pressure infiltration according to claim 1, wherein in the step (2), the carbon material is at least one of carbon nanotube, graphene, fullerene, nano carbon black, nano graphite and short carbon fiber; the short carbon fiber has a length of 30-50 μm and a diameter of 4-7 μm.
3. The method of claim 1, wherein the carbon-modified aluminum alloy composite is prepared by a vacuum pressure infiltration method, and the method comprises the following steps:
in the step (1), the ceramic particles are at least one of nano aluminum oxide, nano sodium silicate, nano feldspar and nano quartz stone; and/or
In the step (3), the foaming agent is at least one of calcium carbonate, magnesium carbonate and sodium bicarbonate.
4. The method of claim 1, wherein the carbon-modified aluminum alloy composite is prepared by a vacuum pressure infiltration method, and the method comprises the following steps:
in the step (1), the cationic surfactant is at least one of fatty amine, polyoxyethylene fatty amine, quaternary ammonium salt and polyoxyethylene quaternary ammonium salt; and/or
In the step (1), the mass fraction of the cationic surfactant aqueous solution is 5-50 wt.%.
5. The method of claim 1, wherein the carbon-modified aluminum alloy composite is prepared by a vacuum pressure infiltration method, and the method comprises the following steps:
the using amount of the ceramic particles in the step (2) is 5-10 wt.% of the using amount of the carbon material in the step (1); and/or
In the step (3), the amount of the foaming agent is 1-5 wt% of the amount of the composite particles.
6. The method for preparing the carbon-modified aluminum alloy composite material by the vacuum pressure infiltration method according to claim 1, wherein in the step (3), the pressure of the hot-pressing sintering is 5-10 MPa.
7. The method for preparing the carbon-modified aluminum alloy composite material by the vacuum pressure infiltration method according to claim 1, wherein in the step (4), the infiltration pressure is 1-5 Mpa.
8. The method for preparing a carbon-modified aluminum alloy composite material by vacuum pressure infiltration according to claim 2, wherein the short carbon fiber comprises a core part and a skin layer wrapping the core part; the core is carbon and the skin is a carbon/aluminum composite material.
9. The method for preparing a carbon-modified aluminum alloy composite material by vacuum pressure infiltration according to claim 8, wherein the diameter of the core part is 3 to 5 μm, and the thickness of the skin layer is 1 to 2 μm; the preparation method of the short carbon fiber comprises the following steps:
(A) spinning: carrying out melt spinning on the asphalt to prepare carbon fiber precursor;
(B) pre-oxidation: pre-oxidizing carbon fiber precursors at 200-400 ℃ in an air atmosphere;
(C) dipping: immersing carbon fiber precursors into a mixed solution of aluminum sol and molten asphalt, and immersing for 30-40 min to obtain carbon fibers coated with the aluminum sol and the molten asphalt; the mass ratio of the aluminum sol to the molten asphalt is 1: 3-5;
(D) pre-oxidation: pre-oxidizing the carbon fiber subjected to the dipping treatment at 200-400 ℃ in an air atmosphere;
(E) carbonizing: carbonizing the carbon fiber subjected to preoxidation treatment at 800-1200 ℃ in a nitrogen atmosphere;
(F) electrolysis: laying the carbonized carbon fiber on the bottom of an electrolytic tank as a cathode, taking a carbon material as an anode and taking molten cryolite as electrolyte to carry out electrolysis; after the electrolysis is finished, taking out the carbon fiber, and cooling to obtain the carbon fiber with the skin-core structure;
(G) cutting: and cutting the skin-core structure carbon fiber in the radial direction to obtain the short carbon fiber.
10. The method for preparing a carbon-modified aluminum alloy composite material by the vacuum pressure infiltration method according to claim 8, wherein the skin layer comprises an inner layer, a middle layer and an outer layer, the aluminum content of which is increased from inside to outside; the diameter of the core part is 2-4 mu m, and the thicknesses of the inner layer, the middle layer and the outer layer are all 0.5-1 mu m; the preparation method of the short carbon fiber comprises the following steps:
(a) spinning: carrying out melt spinning on the asphalt to prepare carbon fiber precursor;
(b) pre-oxidation: pre-oxidizing carbon fiber precursors at 200-400 ℃ in an air atmosphere;
(c) coating an inner layer: immersing carbon fiber precursors into a mixed solution of aluminum sol and molten asphalt, wherein the mass ratio of the aluminum sol to the molten asphalt is 1: 4.5-6.5, and immersing for 18-23 min; pre-oxidizing the carbon fiber subjected to the dipping treatment at 200-400 ℃ in an air atmosphere to obtain carbon fiber coated with an inner layer;
(d) coating the middle layer and the outer layer: changing the mass ratio of the alumina sol to the molten asphalt in the step (c) to 1: 2-4.5 and 1: 1-2, repeating the step (c), and sequentially coating the middle layer and the outer layer;
(e) carbonizing: carbonizing the carbon fiber coated with the outer layer at 800-1200 ℃ in a nitrogen atmosphere;
(f) electrolysis: laying the carbonized carbon fiber on the bottom of an electrolytic tank as a cathode, taking a carbon material as an anode and taking molten cryolite as electrolyte to carry out electrolysis; after the electrolysis is finished, taking out the carbon fiber, and cooling to obtain the carbon fiber with the skin-core structure;
(g) cutting: and cutting the skin-core structure carbon fiber in the radial direction to obtain the short carbon fiber.
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