CN100528419C - Method for in situ preparing carbon nano-tube reinforced metal-matrix composite material from supercritical fluid - Google Patents
Method for in situ preparing carbon nano-tube reinforced metal-matrix composite material from supercritical fluid Download PDFInfo
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- CN100528419C CN100528419C CNB2008100330097A CN200810033009A CN100528419C CN 100528419 C CN100528419 C CN 100528419C CN B2008100330097 A CNB2008100330097 A CN B2008100330097A CN 200810033009 A CN200810033009 A CN 200810033009A CN 100528419 C CN100528419 C CN 100528419C
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Abstract
The invention discloses a method to prepare a carbon nano-tube reinforced metal matrix composite material of a supercritical fluid in situ, which adds carbon source materials, catalyst and metal powder into a reaction container to enable the carbon source materials to form supercritical fluid under the temperature of 400 DEG C to 600 DEG C and under the condition of 5 MPa to 20 MPa through heating and increasing pressure. Besides, carbon nano-tube is generated on the metal powder surface in situ to obtain the compound powder of carbon nano-tube and metal, and then a powder metallurgy method is used for preparing the carbon nano-tube reinforced metal matrix composite material. The method provided by the invention can cause the carbon nano-tube to scatter evenly in the metal matrix composite material which is friendly to environment, easy and high efficient and applicable to batch production.
Description
Technical field
The present invention relates to a kind of preparation method of technical field of composite materials, specifically is the method that a kind of supercritical fluid in-situ preparing CNT strengthens metal-base composites.
Background technology
CNT has performances such as less density and excellent mechanics, electricity, calorifics, is hardening constituent desirable in the metal-base composites.But owing to there is very strong Van der Waals force between the CNT, very easily produces and reunite, cause CNT in composite, to be difficult to evenly disperse; This reason just, the carbon nano-tube reinforced metal-matrix composite material of conventional methods such as powder metallurgy, stirring casting, pressureless penetration preparation, its performance gets a desired effect far away.On the other hand, the compound difficult problem that as if can solve the CNT dispersion of original position, this comprises two aspects: one, original position generates metal under the condition that CNT exists, as methods such as electro-deposition, chemical depositions; They are two years old, original position generates CNT under the condition that metal exists, for example, find through literature search prior art, Chinese invention patent " the vapour deposition reaction in-situ prepares the method for carbon nanotube enhanced aluminium-based composite material " (publication number CN 1730688A), method in-situ preparing CNT on metal dust that this patent adopts chemical vapour deposition (CVD) utilizes powder metallurgy process to prepare carbon nanotube enhanced aluminium-based composite material again.This patent has solved the scattering problem of CNT in metal-base composites preferably, but equipment requires height and complex process, is difficult to large-scale application.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of simple, efficient, the supercritical fluid in-situ preparing CNT with scale application potential strengthens the method for metal-base composites.The present invention significantly promotes original position to generate the speed and the purity of CNT by the peculiar property of supercritical fluid, obtains the metal-base composites that even carbon nanotube is disperseed.
The present invention is achieved by the following technical solutions, the present invention adopts supercritical fluid technique to generate CNT at the metal dust surface in situ, after obtaining the composite powder of CNT and metal, adopt the PM technique densification to obtain the carbon nano-tube reinforced metal composite again.
The inventive method may further comprise the steps:
(1) mixture with carbon source material, catalyst and metal dust joins in the reaction vessel, the mol ratio of wherein said carbon source material and metal dust is 0.1-3.0, the mol ratio of described catalyst and metal dust is 0.01-0.1, make temperature, pressure reach 400 ℃-600 ℃ and 5MPa-20MPa respectively by the heating pressurization, make described carbon source material be in the supercritical fluid state and generate CNT in metal dust surface in situ reaction, separate solid content after question response is finished and carry out drying, promptly obtain the composite powder of CNT and metal;
(2) previous step gained composite powder is cold-pressed into block;
(3) again previous step gained block is carried out densification and obtain carbon nano-tube reinforced metal-matrix composite material.
Described densification is meant under 350 ℃-550 ℃, 1000MPa-1500MPa and carries out hot-pressing processing.
Key step of the present invention is carried out in heat-resisting withstand voltage reactor, with one to multiple kind of compound in hydrocarbon, alcohol, ether, ketone, aldehyde, the phenol as carbon source material, with transition metal and alloy thereof or compound is catalyst, the catalyse pyrolysis reaction takes place under the condition of critical-temperature that surpasses described carbon source material and critical pressure, generates CNT in the powder surface original position of metal such as aluminium, copper, magnesium, titanium and alloy thereof.
The present invention makes carbon source material form supercritical fluid by the heating pressurization, and the reaction of formation of CNT is carried out under the supercritical fluid state.So-called supercritical fluid is meant that gas-liquid two-phase character is very approaching in supercritical fluid at critical-temperature and the fluid more than the critical pressure, to such an extent as to can't differentiate.The present invention promotes the generating rate and the productive rate of CNT by supercritical fluid extraordinary diffusion and solvability, thereby improves the content of in-situ carbon nanotube in the metal-base composites.
Compared with prior art, the present invention has the following advantages: supercritical fluid is a kind of new technology of environmental protection, fast in order to the reaction condition gentleness, the speed that generate CNT, and apparatus and process is simple and easy to do, therefore method of the present invention is applicable to that preparation CNT original position in enormous quantities strengthens metal-base composites, and CNT is uniformly dispersed in the gained composite, content can regulate and control in the scope of 0.1%-10%.
The specific embodiment
Below in conjunction with embodiment the present invention is elaborated, these embodiment are to be prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention are not limited to following embodiment.
Among the present invention, described metal dust is the one to multiple kind in aluminium, copper, magnesium, titanium and the alloy powder thereof.The metal dust that adopts in following examples is 400 orders, and wherein embodiment 1 and embodiment 2 are pure aluminium powder, and embodiment 3 is pure magnesium powder, and embodiment 4 is 2024 Al alloy powders, and embodiment 5 is pure aluminium powder and the pure magnesium powder mixed-powder with 20: 1 ratios.Adopt iron pentacarbonyl as catalyst in following examples, toluene and ethanol are as carbon source material, and wherein the critical-temperature of toluene and critical pressure are respectively 319 ℃, 4.1MPa, and the critical-temperature of ethanol and critical pressure are respectively 243 ℃, 6.4MPa.
Below five embodiment in heat-resisting withstand voltage reaction vessel, carry out, toluene, ethanol, iron pentacarbonyl and aluminium powder are joined in the reaction vessel, wherein, the mol ratio that toluene and ethanol are added up with metal dust is 0.1-3.0, and the mol ratio of iron pentacarbonyl and metal dust is 0.01-0.1.Make temperature, pressure reach 400 ℃-600 ℃ and 5MPa-20Mpa respectively by the heating pressurization, make toluene, ethanol under the supercritical fluid state, react 1h, stop heating then, the reaction vessel of opening after the room temperature to be cooled separates solid content and is drying to obtain CNT and composite metal powder; Earlier the gained composite powder is cold-pressed into block, under 350 ℃-550 ℃, 1000MPa-1500Mpa, carries out hot-pressing densification then and handle.
Characterize the pattern and the microstructure of CNT in the gained composite with SEM and transmission electron microscope, determine the multi-walled carbon nano-tubes that is that all embodiment obtain, caliber is distributed between the 10nm-60nm.Adopt weight method to calculate the mass content of CNT in the gained composite, gained data and related process parameter are listed in table 1.
The mass content and the process conditions of CNT among the table 1. part embodiment
Annotate: a, b, c are respectively toluene, ethanol, the iron pentacarbonyl mol ratio with respect to metal dust.
Claims (5)
1, a kind of supercritical fluid in-situ preparing CNT strengthens the method for metal-base composites, it is characterized in that, adopt supercritical fluid technique to generate CNT at the metal dust surface in situ, after obtaining the composite powder of CNT and metal, adopt the PM technique densification to obtain the carbon nano-tube reinforced metal composite again, specifically may further comprise the steps:
(1) with carbon source material, the mixture of catalyst and metal dust joins in the reaction vessel, the mol ratio of carbon source material and metal dust is 0.1-3.0, catalyst is transition metal and alloy or compound, the mol ratio of catalyst and metal dust is 0.01-0.1, make temperature by the heating pressurization, pressure reaches 400 ℃-600 ℃ and 5MPa-20MPa respectively, make carbon source material be in the supercritical fluid state and generate CNT in metal dust surface in situ reaction, separate solid content after question response is finished and carry out drying, promptly obtain the composite powder of CNT and metal;
(2) previous step gained composite powder is cold-pressed into block;
(3) again previous step gained block is carried out densification and obtain carbon nano-tube reinforced metal-matrix composite material.
2, supercritical fluid in-situ preparing CNT according to claim 1 strengthens the method for metal-base composites, it is characterized in that described carbon source material is selected from the one to multiple kind in hydrocarbon, alcohol, ether, ketone, aldehyde or the phenol.
3, supercritical fluid in-situ preparing CNT according to claim 1 strengthens the method for metal-base composites, it is characterized in that described metal dust is the one to multiple kind in aluminium, copper, magnesium, titanium and the alloy powder thereof.
4, supercritical fluid in-situ preparing CNT according to claim 3 strengthens the method for metal-base composites, it is characterized in that described metal dust is aluminium powder or Al alloy powder.
5, supercritical fluid in-situ preparing CNT according to claim 1 strengthens the method for metal-base composites, it is characterized in that described densification is meant under 350 ℃-550 ℃, 1000MPa-1500MPa and carries out hot-pressing processing.
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| CNB2008100330097A CN100528419C (en) | 2008-01-24 | 2008-01-24 | Method for in situ preparing carbon nano-tube reinforced metal-matrix composite material from supercritical fluid |
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| CNB2008100330097A CN100528419C (en) | 2008-01-24 | 2008-01-24 | Method for in situ preparing carbon nano-tube reinforced metal-matrix composite material from supercritical fluid |
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| CN101234427A CN101234427A (en) | 2008-08-06 |
| CN100528419C true CN100528419C (en) | 2009-08-19 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101818274A (en) * | 2010-04-17 | 2010-09-01 | 上海交通大学 | Preparation method of nanometer carbon-reinforced metal base composite material |
| 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 |
| CN103128284B (en) * | 2013-03-15 | 2014-11-05 | 南昌航空大学 | Reinforced method of carbon nanotubes (CNTs) of laser-induced composite fused deposition gradient content for copper matrix composite materials |
| CN116002666B (en) * | 2023-01-05 | 2024-06-11 | 青岛科技大学 | Continuous production device and method for in-situ preparation and dispersion integration of carbon nanotubes |
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Non-Patent Citations (4)
| Title |
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| 催化剂结构与形态对碳纳米管生长的影响. 雷中兴，刘静，王建波，李轩科，汪厚植.新型炭材料，第18卷第4期. 2003 |
| 催化剂结构与形态对碳纳米管生长的影响. 雷中兴，刘静，王建波，李轩科，汪厚植.新型炭材料，第18卷第4期. 2003 * |
| 超临界流体技术在介孔材料制备中的应用. 陈蓓怡，于文利，赵亚平.化工进展，第24卷第5期. 2005 |
| 超临界流体技术在介孔材料制备中的应用. 陈蓓怡，于文利，赵亚平.化工进展，第24卷第5期. 2005 * |
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