CN101818274A - Preparation method of nanometer carbon-reinforced metal base composite material - Google Patents
Preparation method of nanometer carbon-reinforced metal base composite material Download PDFInfo
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Abstract
The invention provides a preparation method of a nanometer carbon-reinforced metal base composite material, belonging to the technical field of a composite material. Based on the dehalogenation of lewis acid-catalyzed halohydrocarbon, a nanometer carbon reinforcement body is generated at the surface of base metal powder, and nanometer metal powder is induced into the surface of the base metal power, thereby promoting the nanometer carbon reinforcement body to be formed into nucleus, and inducing and adjusting the growth status of the nanometer carbon reinforcement body. The preparation method is simple and effective, and is suitable for quantity production; and the nanometer carbon reinforcement body comprises nanometer ball, carbon nanometer piece, carbon nanometer fiber and carbon nanometer pipe, etc.
Description
Technical field
That the present invention relates to is a kind of preparation method of technical field of composite materials, specifically is a kind of preparation method of nanometer carbon-reinforced metal base composite material.
Background technology
With Nano carbon balls, carbon nanosheet, carbon nanofiber, carbon nanotube is that the novel carbon nanomaterial of representative has excellent mechanical property and physical property, with serve as the nanometer carbon-reinforced metal base composite material that strengthens body, not only can be as the structured material of high-strength light, but also can be used as the functional materials of conduction, heat conduction, wear-resisting, vibration damping, therefore become the Recent study hot of research and development.But have very strong Van der Waals force between the body because nano-sized carbon strengthens, very easily produce and reunite, cause nano-sized carbon be difficult in serve as homodisperse in the metal-base composites of enhancing body.This reason just, the nanometer carbon-reinforced metal base composite material of traditional methods such as powder metallurgy, stirring casting, pressureless penetration preparation, its performance gets a desired effect far away.On the other hand, original position is compound can solve the homodisperse difficult problem of nano-sized carbon preferably.
Find through retrieval the prior art document, Chinese invention patent " the vapour deposition reaction in prepares the method for carbon nanotube enhanced aluminium-based composite material " (publication number CN 1730688A), this technology adopt the electroless plating precipitator method to generate Ni (OH) on the metal-powder surface earlier
2, obtain metal nano Ni catalyzer through high-temperature calcination, hydrogen reducing then; Chinese invention patent " supercutical fluid in-situ preparing carbon nanotube strengthens the method for metal-base composites " (publication number CN 101234427), this technology generates the nanometer Fe catalyzer by the pyrolytic decomposition of pentacarbonyl iron on the metal-powder surface.Above technology is by generating metallic catalyst, and then generate nano-sized carbon by the cracking of carbon source molecule high-temperature catalytic in matrix metal powder surface original position and strengthen body, adopt powder metallurgy process that the gained composite powder is made the block matrix material then, solved the dispersion difficult problem of nano-sized carbon in metal-base composites preferably.But the common problem is that the Pintsch process that (1) relies on the carbon source molecule provides the carbon atom that generates nano-sized carbon enhancing body, temperature of reaction height; (2) rely on chemical reaction and generate metallic catalyst on the metal-powder surface, catalyst particle size is dispersed big, the form that nano-sized carbon strengthens body be difficult to control and formation efficiency lower.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of nanometer carbon-reinforced metal base composite material is provided.The present invention utilizes the dehalogenation reaction original position of halohydrocarbon to generate nano-sized carbon enhancing body, and pass through to introduce nano metal powder on the surface of matrix metal powder, promote nano-sized carbon to strengthen bodily form nuclear, induce and regulate and control its growthhabit, thereby obtain nano-sized carbon and strengthen the homodisperse composite powder of body, adopt powder metallurgical technique then, the gained composite powder is made closely knit nanometer carbon-reinforced metal base composite material.
The present invention is achieved by the following technical solutions:
The present invention is based on the halohydrocarbon dehalogenation reaction of Louis acid catalysis, surface in situ at the matrix metal powder generates nano-sized carbon enhancing body, and by the nano metal powder of introducing at the matrix metal powder surface, promote nano-sized carbon to strengthen bodily form nuclear, induce and regulate and control its growthhabit.The present invention can prepare nano-sized carbon and strengthen the equally distributed composite powder of body, and then obtains closely knit nanometer carbon-reinforced metal base composite material by densification.
The present invention includes following steps:
(1) at first makes matrix metal powder and nano metal powder uniform mixing in organic solvent, obtain the dispersion liquid of metal-powder and organic solvent by ultra-sonic dispersion;
(2) dispersion liquid, Lewis acid and the halohydrocarbon with above metal-powder and organic solvent joins in the reaction vessel, heating and pressurizing is reacted 0.5-5h under 250-450 ℃ and 5-20MPa condition, isolate solid substance after cooling and wash drying, promptly obtain the composite powder that nano-sized carbon strengthens body and metal;
(3) composite powder to above nano-sized carbon enhancing body and metal carries out densification, obtains closely knit nanometer carbon-reinforced metal base composite material.
Described matrix metal powder is the one to multiple kind in Al, Cu, Mg, Ti and the powdered alloy thereof.
Described nano metal powder is the one to multiple kind among Al, Cu, Mg, Ti, Fe, Co, the Ni, and powder diameter is 10-100nm.
Described organic solvent is methyl alcohol, ethanol, benzene, toluene and composition thereof.The amount of organic solvent is used to regulate and control reaction pressure with the size variation of reaction vessel.Organic solvent, halohydrocarbon and lewis acid catalyst all gasify under preferred temperature of reaction or distillation is gaseous phase, thereby constitute the reaction system of a homogeneous, help generating homodisperse nano-sized carbon in matrix metal powder surface original position and strengthen body.
Described Lewis acid is a metal halide, is selected from AlCl
3, FeCl
3, FeCl
2, CuCl
2, MgCl
2, ZnCl
2, SnCl
2In a kind of to multiple.
Described halohydrocarbon is the one to multiple kind in methyl halide, halo ethane and the vinyl halides, as CCl
4, CBr
4, C
2Cl
6, C
2Br
6, C
2Cl
4And C
2Br
4In one to multiple kind.。
The mol ratio of nano metal powder and halohydrocarbon is 0.01-0.2, and the mol ratio of Lewis acid and halohydrocarbon is 0.05-0.5, and the mol ratio of halohydrocarbon and matrix metal powder is 0.001-0.1.
Described densification is cold-pressed into block for the composite powder that earlier nano-sized carbon is strengthened body and metal, and then carries out thermal distortion processing such as hot pressing, hot isostatic pressing, hot extrusion, hot rolling.
The generation that strengthens body in nano-sized carbon of the present invention can be divided into forming core and grow up two stages.Introduce nano-metal particle with high reaction activity at the matrix metal powder surface, as Al, Mg, Cu, Fe, Co, Ni etc., can be used as efficient reductive agent and remove halogen atom in the halohydrocarbon, the carbon laydown that is generated is on the nano-metal particle surface, form the carbon-coated nano metallic particles, can be used as nano-sized carbon and strengthen the core that body is further grown up, play a significant role for the form of inducing and regulate and control nano-sized carbon to strengthen body.
Nano-sized carbon strengthen body according to nano-metal particle surface forming core after, its process of further growing up is based on the dehalogenation reaction of halohydrocarbon equally, but is not the dehalogenation reaction under the nano metal effect, but the dehalogenation reaction under the lewis acid catalyst effect.
Strengthen the forming core of body and growth process as can be known from nano-sized carbon, nano metal powder is most crucial for the dispersing uniformity that the in-situ authigenic nano-sized carbon strengthens body at the uniform distribution of base metal surface.In the method for the invention, make nano metal powder and matrix metal powder uniform mixing in organic solvent by ultra-sonic dispersion, because nano metal powder has high specific area and high surface energy, tend to be adsorbed on the surface of matrix metal powder, thereby realize that nano metal powder is in the equally distributed purpose of base metal surface.
As everyone knows, nano-metal particle has vital role for the form of inducing gained nano-sized carbon product.In existent method, rely on matrix metal powder surface reaction in mostly and generate nano-metal particle, its size-grade distribution is wide and be difficult to control, is not easy to the form that the gained nano-sized carbon strengthens body.In the method for the invention, nano metal powder system directly introduces from the external world, and strictness limits its size-grade distribution as required, therefore can regulate and control the form that the gained nano-sized carbon strengthens body effectively.
Carry out morphology observation with scanning electronic microscope and transmission electron microscope, confirm that the present invention can generate nano-sized carbon such as Nano carbon balls, carbon nanosheet, carbon nanofiber, carbon nanotube and strengthen body in matrix metal powder surface original position, and distribute very evenly.
The original position that nano-sized carbon of the present invention strengthens body generates the reduction dehalogenation reaction that is based on halohydrocarbon, rather than the Pintsch process of carbon source molecule, so reaction conditions is comparatively gentle; The nano-metal particle of directly introducing from the external world is examined the center as promoting nano-sized carbon to strengthen the bodily form, and strictness limits its size-grade distribution as required, therefore can effectively induce and regulate and control the form that the gained nano-sized carbon strengthens body.As seen, method mild condition of the present invention, simple and easy to do is applicable to in-situ preparing nanometer carbon-reinforced metal base composite material in enormous quantities, and the gained nano-sized carbon strengthens, and body is uniformly dispersed, form is controlled, and content can regulation and control arbitrarily in the scope of 0.1%-10%.
Description of drawings
Fig. 1 principle of work synoptic diagram of the present invention;
Fig. 2 carbon nano electronic microscope of the present invention scanned photograph.
Embodiment
Below in conjunction with accompanying drawing embodiment of the present invention is further described: following examples are being to implement under the prerequisite with the technical solution of the present invention; provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
In following examples, the matrix metal powder that is adopted is the 300-400 order, and wherein embodiment 1 is a pure aluminium powder, and embodiment 2 is a pure copper powder, and embodiment 3 is 2024 Al alloy powders.Adopt nanometer aluminium powder, nano-nickel powder and nanometer iron powder as forming core promotor respectively among three embodiment, particle diameter is the 10-100 nanometer.All embodiment all carry out in the heat-resistant pressure vessel of 450ml, as shown in Figure 1.Specific implementation process is as follows:
(1) at first makes matrix metal powder and nano metal powder uniform mixing in organic solvent, obtain the dispersion liquid of metal-powder and organic solvent by ultra-sonic dispersion;
(2) dispersion liquid, Lewis acid and the halohydrocarbon etc. with above metal-powder and organic solvent join in the reaction vessel, heating and pressurizing is reacted 0.5-5h under 250-450 ℃ and 5-20MPa condition, isolate solid substance after cooling and wash drying, promptly obtain the composite powder that nano-sized carbon strengthens body and metal;
(3) elder generation is cold-pressed into block with the composite powder that above nano-sized carbon strengthens body and metal, and then carries out thermal distortions processing such as hot pressing, hot isostatic pressing, hot extrusion, hot rolling, can obtain closely knit nanometer carbon-reinforced metal base composite material.
In following examples, the mol ratio of nano metal powder and halohydrocarbon is 0.01-0.2, and the mol ratio of Lewis acid and halohydrocarbon is 0.05-0.5, and the mol ratio of halohydrocarbon and matrix metal powder is 0.001-0.1.Can calculate the mass content that nano-sized carbon in the gained matrix material strengthens body according to the mol ratio that adds halohydrocarbon and matrix metal powder, gained data and related process parameter are listed in table 1.With the pattern and the microtexture of carbon nanotube in scanning electronic microscope and the transmission electron microscope sign gained matrix material, determine to comprise Nano carbon balls, carbon nanosheet, carbon nanofiber, carbon nanotube etc. in the gained nano-sized carbon enhancing body.
Embodiment 1: 0.02g nanometer aluminium powder and 50g aluminum substrate powder are successively joined in the 120ml benzene, and ultrasonic 0.5h obtains containing the benzene dispersion liquid of aluminum substrate powder and nanometer aluminium powder, then together with 0.16g FeCl
3With 2.4g C
2Cl
6Join together in the 450ml reaction vessel, react 5h under heating and pressurizing to 300 ℃ and the 5MPa condition, isolate solid substance after cooling and wash drying, promptly obtain the 0.5wt% nano-sized carbon and strengthen aluminium-based powder composite.Sem observation shows, contains a large amount of carbon nanotubes in the generated in-situ nano-sized carbon enhancing body, as shown in Figure 2.
Embodiment 2: 0.05g nano-nickel powder and 50g copper matrix powder are successively joined in the 150ml toluene, and ultrasonic 0.5h obtains containing the toluene dispersion liquid of copper matrix powder and nano-nickel powder, then together with 0.2g AlCl
3With 2ml C
2Cl
4Join together in the 450ml reaction vessel, react 3h under heating and pressurizing to 350 ℃ and the 9MPa condition, isolate solid substance after cooling and wash drying, promptly obtain the 1wt% nano-sized carbon and strengthen copper base composite powder.
Embodiment 3: 0.2g nanometer iron powder and 50g 2024 alloy matrix aluminum powder are joined in the 200ml methyl alcohol, and ultrasonic 0.5h obtains the methyl alcohol dispersion liquid of 2024 alloy matrix aluminum powder and nanometer iron powder, then together with 1.6g FeCl
3With 10ml C
2Cl
4Join together in the 450ml reaction vessel, react 0.5h under heating and pressurizing to 400 ℃ and the 18MPa condition, isolate solid substance after cooling and wash drying, promptly obtain the 5wt% nano-sized carbon and strengthen 2024 aluminium alloy compound powder.
The processing condition of table 1. part embodiment and the nano-sized carbon that generates strengthen the mass content of body
| The embodiment numbering | Organic solvent | The matrix metal powder | Nano metal powder | The halohydrocarbon carbon source | Lewis acid catalyst | The temperature/pressure soaking time | The mass content of nano-sized carbon |
| ??1 | Benzene 120ml | Aluminium 50g | Aluminium 0.02g | ??C 2Cl 6??2.4g | ??FeCl 3??0.16g | ??300℃/5.5MPa??5h | ??0.5％ |
| ??2 | Toluene 150ml | Copper 50g | Nickel 0.05g | ??C 2Cl 4??2ml | ??AlCl 3??0.2g | ??350℃/9MPa??3h | ??1％ |
| ??3 | Methyl alcohol 200ml | 2024 aluminium 50g | Iron 0.2g | ??C 2Cl 4??10ml | ??FeCl 3??1.6g | ??400℃/20MPa??0.5h | ??5％ |
Claims (10)
1. the preparation method of a nanometer carbon-reinforced metal base composite material, it is characterized in that, the halohydrocarbon dehalogenation reaction based on Louis acid catalysis, surface in situ at the matrix metal powder generates nano-sized carbon enhancing body, and by the nano metal powder of introducing at the matrix metal powder surface, promote nano-sized carbon to strengthen bodily form nuclear, induce and regulate and control its growthhabit.
2. the preparation method of nanometer carbon-reinforced metal base composite material according to claim 1 is characterized in that, may further comprise the steps:
(1) at first makes matrix metal powder and nano metal powder uniform mixing in organic solvent, obtain the dispersion liquid of metal-powder and organic solvent by ultra-sonic dispersion;
(2) dispersion liquid, Lewis acid and the halohydrocarbon etc. with above metal-powder and organic solvent join in the reaction vessel, heating and pressurizing is reacted 0.5-5h under 250-450 ℃ and 5-20MPa condition, isolate solid substance after cooling and wash drying, promptly obtain the composite powder that nano-sized carbon strengthens body and metal;
(3) composite powder to above nano-sized carbon enhancing body and metal carries out densification, obtains closely knit nanometer carbon-reinforced metal base composite material.
3. according to the preparation method of claim 1 or 2 described nanometer carbon-reinforced metal base composite materials, it is characterized in that described matrix metal powder is the one to multiple kind in Al, Cu, Mg, Ti and the powdered alloy thereof.
4. according to the preparation method of claim 1 or 2 described nanometer carbon-reinforced metal base composite materials, it is characterized in that described nano metal powder is the one to multiple kind among Al, Cu, Mg, Ti, Fe, Co, the Ni, powder diameter is 10-100nm.
5. the preparation method of nanometer carbon-reinforced metal base composite material according to claim 1 is characterized in that, described organic solvent is methyl alcohol, ethanol, benzene, toluene and composition thereof.
6. according to the preparation method of claim 1 or 2 described nanometer carbon-reinforced metal base composite materials, it is characterized in that described halohydrocarbon is the one to multiple kind in methyl halide, halo ethane and the vinyl halides.
7. the preparation method of nanometer carbon-reinforced metal base composite material according to claim 6 is characterized in that, described halohydrocarbon is CCl
4, CBr
4, C
2Cl
6, C
2Br
6, C
2Cl
4And C
2Br
4In one to multiple kind.
8. according to the preparation method of claim 1 or 2 described nanometer carbon-reinforced metal base composite materials, it is characterized in that described Lewis acid is AlCl
3, FeCl
3, FeCl
2, CuCl
2, MgCl
2, ZnCl
2, SnCl
2In a kind of to multiple metal halide.
9. according to the preparation method of claim 1 or 2 described nanometer carbon-reinforced metal base composite materials, it is characterized in that, the mol ratio of described nano metal powder and described halohydrocarbon is 0.01-0.2, the mol ratio of described Lewis acid and described halohydrocarbon is 0.05-0.5, and the mol ratio of described halohydrocarbon and described matrix metal powder is 0.001-0.1.
10. the preparation method of nanometer carbon-reinforced metal base composite material according to claim 2, it is characterized in that, described densification is cold-pressed into block for the composite powder that earlier nano-sized carbon is strengthened body and metal, and then carries out hot pressing, hot isostatic pressing, hot extrusion or hot rolling thermal distortion processing.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002652A (en) * | 2010-12-08 | 2011-04-06 | 上海交通大学 | Carbon nano tube reinforced metal matrix composite material and in-situ preparation method thereof |
| CN103911566A (en) * | 2014-03-11 | 2014-07-09 | 上海交通大学 | Powder metallurgy preparation method of carbon nanotube reinforced aluminium alloy composite material |
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| CN1532144A (en) * | 2003-03-26 | 2004-09-29 | ������������ʽ���� | Method for preparing nano carbon material |
| CN1974083A (en) * | 2006-11-01 | 2007-06-06 | 大连理工大学 | Prepn process and application of metal-carbon nanometer composite material |
| CN101234427A (en) * | 2008-01-24 | 2008-08-06 | 上海交通大学 | Method for in situ preparing carbon nano-tube reinforced metal-matrix composite material from supercritical fluid |
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2010
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| CN1386722A (en) * | 2002-04-05 | 2002-12-25 | 北京化工大学 | Process for preparing nano metal particles/carbon composite material |
| CN1532144A (en) * | 2003-03-26 | 2004-09-29 | ������������ʽ���� | Method for preparing nano carbon material |
| CN1974083A (en) * | 2006-11-01 | 2007-06-06 | 大连理工大学 | Prepn process and application of metal-carbon nanometer composite material |
| CN101234427A (en) * | 2008-01-24 | 2008-08-06 | 上海交通大学 | Method for in situ preparing carbon nano-tube reinforced metal-matrix composite material from supercritical fluid |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002652A (en) * | 2010-12-08 | 2011-04-06 | 上海交通大学 | Carbon nano tube reinforced metal matrix composite material and in-situ preparation method thereof |
| CN102002652B (en) * | 2010-12-08 | 2012-06-27 | 上海交通大学 | Carbon nano tube reinforced metal matrix composite material and in-situ preparation method thereof |
| CN103911566A (en) * | 2014-03-11 | 2014-07-09 | 上海交通大学 | Powder metallurgy preparation method of carbon nanotube reinforced aluminium alloy composite material |
| CN103911566B (en) * | 2014-03-11 | 2016-06-01 | 上海交通大学 | The method for preparing powder metallurgy of a kind of carbon nano tube reinforced aluminum alloy composite material |
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Application publication date: 20100901 |