CN116083746A - Preparation method of intra-crystal aluminum-oxygen-carbon dispersion strengthening carbon nano tube/aluminum-based composite material - Google Patents
Preparation method of intra-crystal aluminum-oxygen-carbon dispersion strengthening carbon nano tube/aluminum-based composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 103
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 102
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000002131 composite material Substances 0.000 title claims abstract description 90
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 85
- -1 aluminum-oxygen-carbon Chemical compound 0.000 title claims abstract description 23
- 239000013078 crystal Substances 0.000 title claims abstract description 22
- 239000006185 dispersion Substances 0.000 title claims abstract description 22
- 238000005728 strengthening Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 35
- 239000011159 matrix material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims description 37
- 239000000843 powder Substances 0.000 claims description 28
- 238000000498 ball milling Methods 0.000 claims description 16
- 238000001192 hot extrusion Methods 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000875 high-speed ball milling Methods 0.000 claims description 10
- 238000005238 degreasing Methods 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 5
- 239000011246 composite particle Substances 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- WDEOTCWPXLWTRP-UHFFFAOYSA-N [C+4].[O-2].[Al+3] Chemical compound [C+4].[O-2].[Al+3] WDEOTCWPXLWTRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 229910001175 oxide dispersion-strengthened alloy Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 238000011065 in-situ storage Methods 0.000 abstract description 10
- 230000001105 regulatory effect Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 239000011156 metal matrix composite Substances 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract 1
- 230000002787 reinforcement Effects 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010008 shearing Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
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- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/002—Carbon nanotubes
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Abstract
The invention relates to a preparation method of an intra-crystal aluminum-oxygen-carbon dispersion strengthening carbon nano tube/aluminum matrix composite material, belonging to the field of metal matrix composite materials. By regulating the length of the carbon nano tube and the sintering temperature of the carbon nano tube/aluminum composite ingot blank, the carbon nano tube is induced to generate in-situ expansion reaction with the aluminum matrix and the in-situ self-generated aluminum oxide film, so that the aluminum-based composite material with the intra-crystal aluminum-oxygen-carbon phase diffusion reinforcement is obtained. Through in-situ reaction, the mode-increasing effect of the carbon nano tube can be enlarged through volume expansion, and meanwhile, the dislocation movement in the crystal can be coordinated, so that the inversion problem of strength and plasticity can be better relieved.
Description
Technical Field
The invention belongs to the field of metal matrix composite materials, and particularly relates to a preparation method of an intra-crystal aluminum-oxygen-carbon dispersion strengthening carbon nano tube/aluminum matrix composite material.
Background
The metal matrix composite material has the characteristics of high elastic modulus, low density, high strength and the like, and has very wide application in the aerospace field. Carbon nanotube/aluminum-based composites are typically represented by a new generation of nano-metal-based composites, and have been attracting attention in recent years. However, the carbon nanotube/aluminum matrix composite materials still have the problems of difficult dispersion and limited carbon nanotube content. Even in some uniformly dispersed carbon nanotube/aluminum matrix composite systems, there are significant elastic modulus-plastic inversion and strength-plastic inversion problems, i.e., the plasticity decreases dramatically with increasing reinforcing phase content.
In the current research, carbon nanotubes are substantially distributed at grain boundaries of an aluminum matrix, and such distribution tends to generate stress concentration at the interface during deformation, thereby resulting in a decrease in plasticity. If the modulus is increased by simply increasing the carbon nanotube content, the modulus is significantly limited by the carbon nanotube dispersion technique. In addition, when the damage of the carbon nanotube structure is serious, the carbon nanotube structure is extremely liable to react with the aluminum matrix at high temperature to form brittle and deliquescent Al 4 C 3 Intermetallic compounds affect the application of the material.
Therefore, the invention provides the nano aluminum-based composite material with better strong plasticity, which is prepared by controlling sintering conditions to enable the carbon nano tube and the aluminum oxide film generated on the surface of the aluminum powder in situ to react in situ to generate the nano aluminum-oxygen carbon phase distributed in a dispersed manner in the crystal. Firstly, pre-mixing a carbon nano tube and aluminum powder by high-speed shearing, enabling the length of the carbon nano tube to be reduced to be within 200nm, simultaneously uniformly coating the carbon nano tube and the aluminum powder on the surface of the aluminum powder, then preparing CNT/aluminum sheet composite powder by low-speed ball milling, introducing a layer of nano aluminum oxide film by in-situ oxidation, and finally enabling CNTs, an Al matrix and nano aluminum oxide to perform in-situ reaction by regulating sintering conditions and regulating sintering conditions, thereby obtaining a nano aluminum-oxygen-carbon equal reinforcing phase with high content and in-crystal distribution. The reaction is controlled to expand the mode-increasing effect of the carbon nano tube through volume expansion, and coordinate the dislocation movement in the crystal, so that the inversion problem of strength and plasticity is better relieved.
Disclosure of Invention
The invention aims to provide a preparation method of an intra-crystal alumina-carbon dispersion strengthening carbon nano tube/aluminum matrix composite material, which is characterized in that a sintering process of a carbon nano tube/aluminum composite ingot blank is regulated and controlled by controlling a high-speed shearing and premixing process of the carbon nano tube and aluminum powder, and an in-situ expansion reaction is induced between the carbon nano tube and an aluminum matrix and an in-situ authigenic alumina film, so that the high-content intra-crystal dispersion alumina-carbon dispersion strengthening aluminum matrix composite material is obtained, the elastic modulus and the strength of the composite material can be improved, and meanwhile, the good plasticity is maintained.
The aim of the invention can be achieved by the following scheme:
the invention provides a preparation method of an intra-crystal aluminum-oxygen-carbon dispersion strengthening carbon nano tube/aluminum-based composite material, which comprises the following steps:
(1) Premixing carbon nano tube and spherical aluminum powder, and performing low-speed ball milling to obtain carbon nano tube/aluminum sheet composite powder;
(2) Degreasing the carbon nano tube/aluminum sheet composite powder in a vacuum environment, and then oxidizing;
(3) Performing high-speed ball milling on the oxidized carbon nano tube/aluminum sheet composite powder to obtain carbon nano tube/aluminum composite particles;
(4) Cold pressing the carbon nano tube/aluminum composite particles into blocks, and then sintering to obtain a composite ingot blank;
(5) And carrying out hot extrusion treatment on the composite ingot blank to obtain the intra-crystal aluminum-oxygen-carbon dispersion strengthening carbon nano tube/aluminum-based composite material.
Preferably, in the step (1), the content of the carbon nanotubes in the carbon nanotube/aluminum flake composite powder is 0.1 to 3wt.%. The carbon nanotubes include one or more of single-walled carbon nanotubes and multi-walled carbon nanotubes. The average grain diameter of the spherical aluminum powder is 10-100 mu m, and the spherical aluminum powder comprises one or more of pure aluminum and aluminum alloy.
Preferably, in step (1), the premixing process is as follows: the rotating speed is 1800-2000 rpm, and the time is 15-45min. The premixing is high-speed shearing premixing, so that the length of the Carbon Nanotubes (CNTs) is shortened to be within 200nm, and the CNTs are better and more uniformly dispersed on the surface of the aluminum spheres, and if the length is too long, the CNTs are not easy to enter the crystal even if the CNTs react later.
Preferably, in the step (1), the low-speed ball milling process is as follows: the rotating speed is 100-150 rpm, and the time is 6-16h; the thickness of the obtained aluminum sheet is 100-500nm. The ball milling must be performed by premixing spherical aluminum powder and CNTs and then grinding the mixture into aluminum flakes by a low-speed ball milling process, because the direct dispersion of CNTs on the surface of the aluminum flakes cannot be realized by directly mixing the flaky aluminum powder with the carbon nanotubes. To prevent aluminum flakes from welding, stearic acid is added in an amount of 1-2wt% based on the mass of the carbon nanotube/aluminum flake composite powder during ball milling.
Preferably, in step (2), the degreasing process: and (3) performing in a vacuum furnace at 350-450 ℃, preserving heat for 2-4 hours, and removing stearic acid.
Preferably, in step (2), the oxidation treatment is oxidizing the surface of the aluminum sheet in an aerobic environment, preferably in dry air; the temperature of the oxidation treatment is 20-40 ℃, the humidity is less than 10%, and the oxidation time is 20-30h. Oxidizing the surface of the aluminum sheet in air to generate a layer of amorphous aluminum oxide film; the thickness of the aluminum oxide film is 5-10nm, and the content of the aluminum oxide film can be adjusted by adjusting the thickness of the aluminum sheet.
Preferably, in the step (3), the high-speed ball milling process is as follows: the rotating speed is 250-350 rpm, and the time is 1-3 hours.
Preferably, in the step (4), the cold pressing process is one of mould pressing and cold isostatic pressing, and the density of the obtained block is not less than 80%.
Preferably, in the step (4), the sintering treatment temperature is 560-580 ℃ and the sintering time is 2-4h. The temperature is too high, the size of the generated phase increases, and the strengthening effect becomes weak. The sintering treatment is performed under a protective atmosphere or vacuum.
Preferably, in the step (5), the hot extrusion treatment temperature is 400-500 ℃, and the extrusion ratio is 25-100. The hot extrusion can further improve the compactness and enable more nano-phases to enter the crystal along with the extrusion rheological process.
Preferably, in the step (5), the content of carbon nanotubes in the obtained intra-crystalline dispersed alumina-carbon/aluminum composite material is 0.1-3wt.%, and the balance is the matrix.
Preferably, the alumina-carbon phase (Al in the intra-crystal alumina-carbon dispersion strengthening aluminum-based composite material prepared in the step (5) 4 O 4 C) The size is smaller than 100nm, and the particles are uniformly and diffusely distributed in the interior of the crystal grains and well combined with an aluminum matrix interface. The volume fraction of the nano reinforcing phase content in the composite material is greatly increased compared with the content of the added carbon nano tube, the maximum can reach more than 10 times, and the elastic modulus and the strength of the composite material are greatly improved while the excellent plasticity is still maintained.
Compared with the prior art, the invention has the following beneficial effects:
(1) The main reinforcing phase in the carbon nano tube/aluminum composite material prepared by the invention is an aluminum-oxygen-carbon phase, the size is smaller than 100nm, the reinforcing phase is uniformly and dispersedly distributed in the interior of crystal grains, and the reinforcing phase is well combined with an aluminum matrix interface.
(2) The density of the alumina-carbon phase in the composite material is only 2.68g/cm 3 The carbon nanotubes were added in an amount of 1wt% (1.35 vol%) and if fully reacted with the in situ autogenous alumina phase, an alumina-carbon phase content of about 13.6wt% (14 vol%) could be produced, achieving enhanced phase content multiplication. The nanometer alumina-carbon phase dispersed in the crystal can greatly improve the elastic modulus and strength of the composite material and maintain excellent plasticity.
(3) The generated aluminum oxide carbon and Al 4 C 3 Compared with the prior art, the composite material has smaller size, better hydrolysis resistance and corrosion resistance, and can improve the corrosion resistance of the composite material.
(4) The introduced oxygen content can be regulated by controlling the ball milling atmosphere, the thickness of the aluminum sheet and other methods, so that the reaction degree of the carbon nano tube and the alumina can be regulated, and the content of the generated phase can be regulated.
(5) The method can introduce the high-volume dispersed nano reinforcing phase by dispersing a small amount of CNTs, has simple technology and is suitable for macro preparation.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 shows TEM structures of carbon nanotube/pure aluminum composite materials with different sintering temperatures; comparative example 2 where a-b is 510 ℃/2h, comparative example 3,e-f where c-d is 540 ℃/2h, example 1 where 570 ℃/2 h.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The following examples, which are presented to provide those of ordinary skill in the art with a detailed description of the invention and to provide a further understanding of the invention, are presented in terms of implementation and operation. It should be noted that the protection scope of the present invention is not limited to the following embodiments, and several adjustments and improvements made on the premise of the inventive concept are all within the protection scope of the present invention.
Example 1
Performing high-speed shearing premixing (rotation speed 1800 rpm/min, time 20 min) on 99.5wt.% pure aluminum spherical powder with 30 micrometers and 0.5wt.% multiwall carbon nano tube (with the tube diameter of 15nm and the length of 1-5 micrometers), performing low-speed ball milling at 135rpm/6h to obtain CNT/Al flaky composite powder with uniformly dispersed CNTs and the thickness of 400-500nm, performing vacuum degreasing treatment for 400-2 h, oxidizing in a drying oven for 24h, estimating the content of an introduced aluminum oxide film to be 2-4 vol% according to the thickness of the aluminum sheet, and performing high-speed ball milling at 270rpm/1h to obtain the carbon nano tube/aluminum composite powder; putting the ingot into a mold cylinder, cold-pressing the ingot into a round ingot with the diameter of 40mm at room temperature, and then sintering the round ingot in a vacuum sintering furnace, wherein the sintering process is 570 ℃/2h, so as to obtain a composite ingot blank; and carrying out hot extrusion treatment (420 ℃ and extrusion ratio of 25) on the composite ingot blank to obtain the aluminum-oxygen-carbon dispersion-strengthened aluminum-based composite material. The tissue was observed by TEM as shown in fig. 1 e-f. The reinforcing phase in the carbon nano tube/aluminum composite material matrix with the sintering process of 570 ℃/2h is mainly Al 4 O 4 Phase C, which has an average length of 53nm, has a volume dispersion of up to 5.6vol%. The tensile mechanical property and the elastic modulus of the material are tested, and the tensile property is as follows: the yield strength is 263MPa, the tensile strength is 326MPa, the elongation is 16.1 percent, and the elastic modulus is 80.2GPa.
Example 2
Performing high-speed shearing premixing (rotation speed 1800 rpm for 20 min) on 6061 spherical powder with 30 micrometers and 1.5wt.% carbon nano tubes (with the tube diameter of 15nm and the length of 1-5 micrometers), performing low-speed ball milling at 135rpm/12h to obtain CNT/Al flaky composite powder with uniformly dispersed CNTs and the thickness of about 100-200nm, performing vacuum degreasing treatment for 400-2 h, oxidizing for 24h in a drying box, estimating the content of an introduced alumina film to be 5-10 vol% according to the thickness of an aluminum sheet, and performing high-speed ball milling at 270rpm/1h to obtain the carbon nano tube/aluminum composite powder; putting the ingot into a mold cylinder, cold pressing a round ingot with the diameter of 40mm at room temperature, and then putting the round ingot into a vacuum sintering furnace for sintering, wherein the sintering process is 570 ℃/2h, so as to obtain a composite ingot blank; and carrying out hot extrusion treatment (the extrusion ratio is 25) on the composite ingot blank to obtain the aluminum-oxygen-carbon dispersion-strengthened aluminum-based composite material. Observing the structure by using TEM, wherein the main reinforcing phase in the carbon nano tube/6061 composite material matrix with the sintering process of 570 ℃/2h is Al 4 O 4 And C phase. The tensile mechanical property and the elastic modulus of the material are tested, and the tensile property is as follows: the yield strength is 361MPa, the tensile strength is 436MPa, the elongation is 12.6 percent, and the elastic modulus is 85.3GPa.
Comparative example 1
The pure aluminum spherical powder is subjected to low-speed ball milling, vacuum degreasing, oxidation and high-speed ball milling treatment, and the specific process is the same as that of the embodiment 1, so that aluminum powder is obtained; carrying out cold pressing and sintering treatment on aluminum powder, wherein the sintering process is 570 ℃/2 hours, and obtaining an ingot blank; and carrying out hot extrusion treatment on the ingot blank to obtain the pure aluminum material. The tensile mechanical property and the elastic modulus of the material are tested, and the tensile property is as follows: the yield strength is 175.4MPa, the tensile strength is 238.0MPa, and the elongation is 16.9%. The elastic modulus was 75.1GPa.
Comparative example 2
The pure aluminum spherical powder and 0.5wt.% carbon nanotubes were subjected to high-speed shearing premixing and variable-speed ball milling treatment, and carbon nanotube/aluminum composite powder was obtained in the same manner as in example 1; cold pressing and sintering the mixture for 510 ℃ per 2 hours to obtain a composite ingot blank; and carrying out hot extrusion treatment on the composite ingot blank to obtain the carbon nano tube/aluminum composite material. The tissue was observed by TEM as shown in fig. 1 a-b. From the graph, the carbon nanotubes in the carbon nanotube/aluminum composite matrix with the sintering process of 510 ℃/2h are still carbon nanotubes, the average length is 66nm, and the volume fraction is 0.73vol%. The tensile mechanical property and the elastic modulus of the material are tested, and the tensile property is as follows: the yield strength is 204MPa, the tensile strength is 267MPa, and the elongation is 14.8%. The elastic modulus was 77.4GPa.
Comparative example 3
The pure aluminum spherical powder and 0.5wt.% carbon nano tube are subjected to high-speed shearing pre-mixing, low-speed ball milling, vacuum degreasing, oxidation and high-speed ball milling treatment, and the carbon nano tube/aluminum composite powder is obtained in the same way as in the example 1; carrying out cold pressing and sintering treatment on the alloy, wherein the sintering process is 540 ℃/2 hours, and obtaining a composite ingot blank; and carrying out hot extrusion treatment on the composite ingot blank to obtain the carbon nano tube/aluminum composite material. The tissue was observed by TEM as shown in fig. 1 c-d. From the graph, CNTs in the carbon nanotube/aluminum composite matrix with the sintering process of 540 ℃/2h are converted into Al 4 C 3 The average length was 92nm and the volume fraction was 2.8vol%. The tensile mechanical property and the elastic modulus of the material are tested, and the tensile property is as follows: the yield strength is 226.6MPa, the tensile strength is 275.6MPa, and the elongation is 14.0%. The elastic modulus was 78.9GPa.
Comparative example 4
The 6061 spherical powder and 1.5wt.% carbon nano tube are subjected to high-speed shearing pre-mixing, low-speed ball milling, vacuum degreasing, oxidation and high-speed ball milling treatment, and the specific process is the same as that of the example 2, so as to obtain carbon nano tube/aluminum composite powder; cold pressing and sintering the mixture for 510 ℃ per 2 hours to obtain a composite ingot blank; and carrying out hot extrusion treatment on the composite ingot blank to obtain the carbon nano tube/6061 composite material. The carbon nanotubes in the carbon nanotube/6061 composite matrix with the sintering process of 510 ℃/2h are still carbon nanotubes. The tensile mechanical property and the elastic modulus of the material are tested, and the tensile property is as follows: the yield strength was 382MPa, the tensile strength was 453MPa, the elongation was 11.3% and the elastic modulus was 81.1GPa.
Comparative example 5
High 6061 spherical powder and 1.5wt.% carbon nanotubesThe specific process is the same as that of example 2, and carbon nano tube/aluminum composite powder is obtained; carrying out cold pressing and sintering treatment on the alloy, wherein the sintering process is 540 ℃/2 hours, and obtaining a composite ingot blank; and carrying out hot extrusion treatment on the composite ingot blank to obtain the carbon nano tube/6061 composite material. Observing the structure by using TEM, wherein CNTs in the carbon nano tube/6061 composite material matrix with the sintering process of 540 ℃/2h are converted into Al 4 C 3 . The tensile mechanical property and the elastic modulus of the material are tested, and the tensile property is as follows: the yield strength is 360MPa, the tensile strength is 421MPa, the elongation is 11.7%, and the elastic modulus is 82.8GPa.
Comparative example 6
The 6061 spherical powder and 1.5wt.% carbon nano tube are subjected to high-speed shearing pre-mixing, low-speed ball milling, vacuum degreasing, oxidation and high-speed ball milling treatment, and the specific process is the same as that of the example 2, so as to obtain carbon nano tube/aluminum composite powder; cold pressing and sintering the mixture for 600 ℃/2h to obtain a composite ingot blank; and carrying out hot extrusion treatment on the composite ingot blank to obtain the carbon nano tube/6061 composite material. Observing the structure by using TEM, wherein the nano reinforcing phase in the carbon nano tube/6061 composite material matrix with the sintering process of 600 ℃/2h is mainly Al 4 O 4 Phase C, size exceeding 150nm. The tensile mechanical property and the elastic modulus of the material are tested, and the tensile property is as follows: the yield strength is 354MPa, the tensile strength is 406MPa, and the elongation is 12%. The elastic modulus was 85.3GPa.
The performance test data for the CNT/Al, CNT/6061 composites, pure aluminum prepared in each example, comparative example are shown in the following table:
the foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (10)
1. The preparation method of the intra-crystal aluminum-oxygen-carbon dispersion strengthening carbon nano tube/aluminum-based composite material is characterized by comprising the following steps of:
(1) Premixing carbon nano tube and spherical aluminum powder, and performing low-speed ball milling to obtain carbon nano tube/aluminum sheet composite powder;
(2) Degreasing the carbon nano tube/aluminum sheet composite powder in a vacuum environment, and then oxidizing;
(3) Performing high-speed ball milling on the oxidized carbon nano tube/aluminum sheet composite powder to obtain carbon nano tube/aluminum composite particles;
(4) Cold pressing the carbon nano tube/aluminum composite particles into blocks, and then sintering to obtain a composite ingot blank;
(5) And carrying out hot extrusion treatment on the composite ingot blank to obtain the intra-crystal dispersion aluminum-oxygen-carbon/aluminum composite material.
2. The method for producing an intra-crystalline alumina-carbon dispersion strengthened carbon nanotube/aluminum-based composite material according to claim 1, wherein in the step (1), the carbon nanotube is contained in the carbon nanotube/aluminum sheet composite powder in an amount of 0.1 to 3wt.%.
3. The method of preparing an intra-crystalline alumina-carbon dispersion strengthened carbon nanotube/aluminum matrix composite according to claim 1, wherein in step (1), the carbon nanotubes comprise one or more of single-walled carbon nanotubes and multi-walled carbon nanotubes; the average grain diameter of the spherical aluminum powder is 10-100 mu m, and the spherical aluminum powder comprises one or more of pure aluminum powder and aluminum alloy powder.
4. The method for preparing an intra-crystalline aluminum-oxygen-carbon dispersion strengthened carbon nanotube/aluminum-based composite material according to claim 1, wherein in the step (1), the premixing process is as follows: the rotating speed is 1800-2000 rpm, and the time is 15-45min.
5. The method for preparing an intra-crystalline aluminum-oxygen-carbon dispersion strengthened carbon nanotube/aluminum-based composite material according to claim 1, wherein in the step (1), the low-speed ball milling process is as follows: the rotating speed is 100-150 rpm, and the time is 6-16h; the thickness of the obtained aluminum sheet is 100-500nm.
6. The method for producing an intra-crystalline aluminum-oxygen-carbon dispersion-strengthened carbon nanotube/aluminum-based composite material according to claim 1, wherein in the step (2), the oxidation treatment is oxidizing the surface of an aluminum sheet in an aerobic atmosphere; the temperature of the oxidation treatment is 20-40 ℃, the humidity is less than 10%, and the oxidation time is 20-30h.
7. The method for preparing an intra-crystalline aluminum-oxygen-carbon dispersion strengthened carbon nanotube/aluminum-based composite material according to claim 1, wherein in the step (3), the high-speed ball milling process is as follows: the rotating speed is 250-350 rpm, and the time is 1-3 hours.
8. The method for preparing an intra-crystalline aluminum-oxygen-carbon dispersion strengthened carbon nanotube/aluminum-based composite material according to claim 1, wherein in the step (4), the sintering treatment temperature is 560-580 ℃, and the sintering time is 2-4h.
9. The method for producing an intra-crystalline carbon-aluminum oxide dispersion strengthened carbon nanotube/aluminum-based composite material according to claim 1, wherein in the step (5), the hot extrusion treatment temperature is 400 to 500 ℃, and the extrusion ratio is 25 to 100.
10. The method for preparing an intra-crystalline aluminum-oxygen-carbon dispersion-strengthened carbon nanotube/aluminum-based composite material according to claim 1, wherein the size of the aluminum-oxygen-carbon phase in the intra-crystalline aluminum-oxygen-carbon dispersion-strengthened carbon nanotube/aluminum-based composite material prepared in the step (5) is less than 100nm, and the aluminum-oxygen-carbon phase is uniformly dispersed in the interior of crystal grains.
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