CN105441706A - Preparation method for carbon nano tube metal-matrix composite material - Google Patents
Preparation method for carbon nano tube metal-matrix composite material Download PDFInfo
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Abstract
The invention relates to a preparation method for a carbon nano tube metal-matrix composite material. Metal powder is added into a polymer solution for surface coating; then the polymer coated metal powder is added into a carbon nano tube solution, so that the surface of the polymer coated metal powder evenly adsorbs a carbon nano tube, and evenly dispersed carbon nano tube metal composite powder is obtained; then a powder metallurgy method is adopted, and the obtained composite powder is made into a dense carbon nano tube metal-matrix composite material; and the surface of the carbon nano tube is coated with metal gold. Through surface modification of the metal powder and gold plating treatment of the carbon nano tube, the metal powder is easily dispersed in the carbon nano tube solution and evenly adsorbs the carbon nano tube, the evenly dispersed carbon nano tube metal composite powder is obtained, and thus the metal composite material excellent in mechanical performance and elongation at break can be obtained.
Description
Technical field
The present invention relates to a kind of preparation method of metal composite, particularly be a kind of preparation method of carbon nanotube metal based composite materials.
Background technology
Carbon nano-tube reinforced metal-matrix composite material has unique process based prediction model because having the feature of metal and carbon nanotube concurrently, have broad application prospects in fields such as aerospacecraft, precision optical machinery, medical devices, obtain the attention of increasing material scholar in recent years.But form reunion between carbon nanotube due to stronger Van der Waals force or be wound around, add that between carbon nanotube and metal, surface property differences is remarkable, carbon nanotube is caused to be difficult in metallic matrix dispersed, this reason just, carbon nanotube metal based composite materials prepared by the traditional technologys such as powder metallurgy, stirring casting, melt infiltration, its performance gets a desired effect far away.And on the other hand, along with carbon nano tube surface mechanically modifying, chemical modification, the reaching its maturity of mechanical-chemical modification technology, in addition auxiliary with tensio-active agent and ultrasonic disperse, current people can prepare even carbon nanotube dispersion and have carbon nano-tube aqueous solutions or the ethanolic soln of lasting stability.For this reason, a lot of research is in recent years attempted by joining in carbon nano-tube solution by metal-powder, adopts the methods such as ultrasonic disperse, machinery or magnetic agitation to make even carbon nanotube be distributed to the surface of metal-powder.But acquired results is all undesirable, reason is surface properties and the carbon nanotube of metal-powder and solvent is widely different, avidity is poor, the metal-powder joined in carbon nano-tube solution is not only difficult to realize dispersed, but also tends to original balance in destroying carbon nanometer tube solution and carbon nanotube is reunited again.
The literature search of prior art is found, Japanese Patent (JP2007077457-A) " metal matrix カ mono-ボ Application Na ノ チ ュ mono-ブ Complex condensation material and び そ System making method " (metal matrix carbon nano tube compound material and preparation method thereof) adopts polyvinyl alcohol to prepare carbon nano-tube aqueous solutions as dispersion agent, water or ethanol is adopted to prepare metal-powder slip as solvent, then the two mixing is carried out stirring and ultrasonic disperse, drying obtains the composite green compact of carbon nanotube and metal-powder, then obtains fine and close matrix material through hot-pressing processing.The limitation of the method is, although adopt polyvinyl alcohol to contribute to carbon nanotube in aqueous dispersed as dispersion agent, but the nature difference cannot eliminated between carbon nanotube and metal powder surface, avidity between carbon nanotube and metallic surface is poor, at slip, in blended and drying process, carbon nanotube tends to reunite each other, causes carbon nanotube dispersed in the matrix material of gained and uneven.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of preparation method of carbon nanotube metal based composite materials is provided.The present invention utilizes polymkeric substance to carry out surface modification to metal-powder, and surface modification is carried out to carbon nanotube, its surface is made to be coated with gold, enhance the avidity between metal-powder carbon nanotube and interface cohesion effect, enable its surface adsorbing carbon nanotubes from carbon nano-tube solution, thus obtain even carbon nanotube dispersion composite powder, and then powder metallurgical technique is adopted to prepare the method for carbon nanotube metal based composite materials.
The present invention is achieved by the following technical solutions:
Metal-powder first joins in polymers soln and carries out Surface coating by the present invention, then polymer-coated metal powder is joined in carbon nano-tube solution, described carbon nanotube is the carbon nanotube that surface is coated with gold, make polymer-coated metal powder surface uniform adsorption carbon nanotube from carbon nano-tube solution, obtain homodisperse carbon nano tube metal composite powder, and then adopt powder metallurgical technique, gained composite powder is made closely knit carbon nanotube metal based composite materials.The present invention is little to carbon nanotube destructiveness, can keep its excellent specific property, and can regulate and control the mass percent of carbon nanotube in matrix material in the scope of 1 ~ 8wt%.In addition, environmental friendliness of the present invention, has mass-producing application potential.
The present invention includes following steps:
(1) described carbon nanotube is joined in water or organic solvent, preparation carbon nano-tube solution;
(2) described polymkeric substance is joined in water or organic solvent, prepare polymers soln;
(3) Surface coating polymkeric substance: described metal-powder is joined in described polymers soln, namely metal-powder and polymers soln slip is obtained, continue stirring until metal powder surface and form polymeric film, then carry out washing and filtering, namely obtain described polymer-coated metal powder;
(4) surface adsorption carbon nanotube: described polymer-coated metal powder is joined in carbon nano-tube solution, namely metal-powder and carbon nano-tube solution slip is obtained, Keep agitation is until carbon nanotube is adsorbed on the surface of polymer-coated metal powder, then carry out washing and filtering, drying treatment and pyrolysis processing, namely obtain homodisperse carbon nano tube metal composite powder.
(5) adopt powder metallurgical technique, gained carbon nano tube metal composite powder is made closely knit carbon nanotube metal based composite materials, wherein said carbon nanotube is the carbon nanotube that surface is coated with gold.
Described metal-powder is selected from the mixture of a kind of in aluminium, copper, magnesium, titanium, nickel or iron or at least two kinds.The mixture of described mixture such as aluminium and copper, the mixture of aluminium and magnesium, the mixture of aluminium and titanium, the mixture of al and ni, the mixture of aluminium and iron, the mixture of copper and magnesium, the mixture of copper and mickel, the mixture of copper and iron, the mixture of aluminium, copper and magnesium, the mixture of magnesium, titanium and nickel, the mixture of aluminium, copper, magnesium and titanium, the mixture of copper, magnesium, nickel and iron.Described aluminium, copper, magnesium, titanium, nickel or copper, except finger simple substance, also comprise its alloy.
The content of described carbon nano tube surface gold is 1 ~ 3% of content of carbon nanotubes, is less than 1% modified effect poor, is greater than 3%, affects the performance of the effect of carbon nanotube own.
Described organic solvent is selected from the mixture of a kind of in DMF, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO) or at least two kinds, preferred DMF.Described mixture such as dimethyl sulfoxide (DMSO) and N, the mixture of N-N,N-DIMETHYLACETAMIDE, N, the mixture of N-N,N-DIMETHYLACETAMIDE and DMF, dimethyl sulfoxide (DMSO) and N, the mixture of dinethylformamide, the mixture of dimethyl sulfoxide (DMSO), N,N-dimethylacetamide and DMF.
In described carbon nano-tube solution, carbon nanotube accounts for the mass percent concentration of carbon nano-tube solution is 1.2 ~ 5wt%, such as 1.5wt%, 1.8wt%, 2.1wt%, 2.4wt%, 2.8wt%, 3.2wt%, 3.5wt%, 4.2wt%, 4.5wt%, 4.8wt%.
In described carbon nano-tube solution, also include tensio-active agent or/and defoamer.
Described tensio-active agent is selected from a kind of or mixture of at least two kinds in sodium lauryl sulphate, Witco 1298 Soft Acid acid sodium, cetyl trimethylammonium bromide, Triton, chitosan, β-cyclodextrin, glutaraldehyde or biliary salts.The mixture of described mixture such as biliary salts and glutaraldehyde, the mixture of β-cyclodextrin and chitosan, the mixture of Triton and cetyl trimethylammonium bromide, the mixture of Witco 1298 Soft Acid acid sodium and sodium lauryl sulphate, the mixture of biliary salts, glutaraldehyde and β-cyclodextrin, the mixture of chitosan, Triton and cetyl trimethylammonium bromide, the mixture of Witco 1298 Soft Acid acid sodium, sodium lauryl sulphate, biliary salts and β-cyclodextrin.
Described defoamer is selected from the mixture of a kind of in octanol, tributyl phosphate, polydimethylsiloxane or polyethers or at least two kinds.The mixture of described mixture such as polyethers and polydimethylsiloxane, the mixture of tributyl phosphate and octanol, the mixture of polyethers, polydimethylsiloxane and tributyl phosphate, the mixture of octanol, polyethers, polydimethylsiloxane and tributyl phosphate.
In described polymers soln, polymkeric substance accounts for the mass percent concentration of polymers soln is 1 ~ 4wt%, such as 1.3wt%, 1.6wt%, 1.9wt%, 2.3wt%, 2.6wt%, 2.9wt%, 3.5wt%, 3.8wt%, 3.9wt%.
Preferably, the polymkeric substance in described polymers soln is selected from the mixture of a kind of in polyvinyl alcohol, polyoxyethylene glycol, polyvinylpyrrolidone, polyacrylonitrile, polyacrylic acid, polyacrylamide, polymeric amide, polydimethylsiloxane or ethyl cellulose or at least two kinds.The mixture of described mixture such as ethyl cellulose and polydimethylsiloxane, the mixture of polymeric amide and polyacrylamide, the mixture of polyacrylic acid and polyacrylonitrile, the mixture of polyvinylpyrrolidone and polyoxyethylene glycol, polyvinyl alcohol and polyacrylic mixture, the mixture of ethyl cellulose, polydimethylsiloxane, polymeric amide and polyacrylamide, the mixture of polyacrylic acid, polyacrylonitrile, polyvinylpyrrolidone, polyoxyethylene glycol and polyvinyl alcohol.
Polymkeric substance in described polymer overmold carbon nanotube, those skilled in the art can according to the polymkeric substance in the complexity of the embodiment of the determinative of the consistency between polymkeric substance and polymer overmold carbon nanotube voluntarily selective polymer enveloped carbon nanometer tube, and the present invention is not construed as limiting this.Such as, the polymkeric substance the same with in polymers soln can be selected, or select and above-mentioned polymers soln in the good polymkeric substance of polymer compatibility.The selection of polymkeric substance in typical but non-limiting polymer overmold carbon nanotube is consistent with the selection of the polymkeric substance in polymers soln, and in order to save space, the present invention is not at this in repetition, and it is selected as described above.
In described carbon nano tube metal composite powder, it is 1 ~ 8wt% that the mass percent of carbon nanotube can be, such as 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, preferably 1.5 ~ 6.5wt%, further preferred 2 ~ 5wt%.Described carbon nano tube metal composite powder, can repeat Surface coating polymkeric substance and surface adsorption carbon nanotube through step (3) and (4), thus increases the mass percent of carbon nanotube in composite powder.
Described pyrolysis processing is: carry out under the inert atmosphere such as vacuum or argon gas and more than the pyrolysis temperature of polymkeric substance, removes polymkeric substance and other organic impurity.
Described powder metallurgical technique is that described carbon nano tube metal composite powder is cold-pressed into base, and then carries out densification and obtain closely knit carbon nanotube metal based composite materials.
Described densification refers to carries out hot pressing, hot rolling or hot extrusion below the fusing point of metal-powder.
In existing technology, polymkeric substance such as adopting polyvinyl alcohol is had to prepare carbon nano-tube solution as tensio-active agent or dispersion agent, make it the example mixed with metal-powder slip again, as Japanese Patent (JP2007077457-A) " metal matrix カ mono-ボ Application Na ノ チ ュ mono-ブ Complex condensation material and び そ System making method " (metal matrix carbon nano tube compound material and preparation method thereof).Although the polymkeric substance be present in carbon nano-tube solution can improve the dispersiveness of carbon nanotube, but the nature difference do not eliminated between metal powder surface and carbon nanotube, the metal-powder joined in carbon nano-tube solution is still difficult to dispersion and adsorbing carbon nanotubes, and tends to original balance in destroying carbon nanometer tube solution and carbon nanotube is reunited again.
In the method for the invention, adopt polymkeric substance to carry out surface modification to metal-powder, and polymer overmold process is carried out to carbon nanotube or carbon nano tube surface is plated nonmetal silver, thus the dispersiveness improved in a solvent and the affinity to carbon nanotube.Metal-powder is joined in the polymers soln prepared in advance, after ultrasonic disperse, mechanical stirring, magnetic agitation certain hour, one layer of polymeric film can be formed in metallic surface, filter through repetitive scrubbing, remove free polymer molecule, then obtain the metal-powder of polymer overmold.
In the method for the invention, by selecting to carry out modification with the good polymkeric substance of consistency of the polymkeric substance in polymers soln to carbon nanotube, when the metal-powder of polymer overmold modification joins in carbon nano-tube solution, because the consistency between polymkeric substance and polymkeric substance is better, metal powder surface all has good affinity for solvent and carbon nanotube, be easy to dispersed in carbon nano-tube solution and therefrom uniform adsorption carbon nanotube, thus obtain homodisperse carbon nano tube metal composite powder.
Compared with prior art, the present invention has the following advantages: (1) is by carrying out surface modification to metal-powder, improve the affinity of its surface for solvent and carbon nanotube, and polymer overmold process or the process of metallizing silver are carried out to carbon nanotube, thus be easy to dispersed in carbon nano-tube solution and therefrom uniform adsorption carbon nanotube, obtain homodisperse carbon nano tube metal composite powder, thus can excellent in mechanical performance be obtained and the metal composite of elongation at break excellence; (2) nanometer scale is can be controlled at the polymer film thickness that metal powder surface is coated, and the polymkeric substance in polymer overmold carbon nanotube also can control at nano level, if carbon nano tube surface metallizing is silver-colored, the performance of silver alloy powder also can not impact, therefore in carbon nano tube metal composite powder, contained amount of polymers is few, is convenient to be removed by pyrolysis processing; (3) process of Surface coating polymkeric substance and surface adsorption carbon nanotube can be carried out repeatedly repeatedly, therefore, it is possible to prepare the matrix material of high content of carbon nanotubes, its mass percent can obtain in scope at 1 ~ 8wt% and adjust arbitrarily; (4) present invention process is simple, efficient, and energy-saving and environmental protection, have mass-producing application potential.
Embodiment
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
The multi-walled carbon nano-tubes of surface gold-plating (3%) and proper amount of surfactant Sodium dodecylbenzene sulfonate, defoamer polydimethylsiloxane are added in deionized water, ultrasonic disperse 2 hours, then N is added, dinethylformamide regulates carbon nanotube concentration, obtains the carbon nanotube DMF solution of 1.2wt%;
Under 50 DEG C of water bath with thermostatic control heating conditions, be dissolved in by polyacrylonitrile in DMF, mechanical stirring, to dissolving completely, adds DMF and regulates polyvinyl alcohol concentration, obtain the polyacrylonitrile DMF solution of 1wt% after being cooled to room temperature;
Get 10g aluminium powder and copper powder, join in the polyacrylonitrile DMF solution of the 1wt% of 50ml, magnetic agitation 1 hour, then filter repeatedly with deionized water wash, aluminium powder and the copper powder of Surface coating polyacrylonitrile can be obtained;
Coated for above polyacrylonitrile aluminium powder and copper powder are joined in the carbon nanotube DMF solution of the 1.2wt% of 50ml, magnetic agitation becomes limpid to DMF solution by black, show carbon nanotube all by the polyacrylonitrile thin film adsorbs of aluminium powder and Copper Powder Surface, filter repeatedly with deionized water wash, vacuum-drying 12 hours is carried out at 40 DEG C, then vacuum pyrolysis 2 hours at 300 DEG C, remove polyacrylonitrile wherein and surfactant sodium dodecyl base benzene sulfonic acid sodium salt, the organic compositions such as defoamer polydimethylsiloxane, namely carbon nanotube/aluminium/copper composite powder is obtained, wherein the mass percent of carbon nanotube is about 1wt%.
First above carbon nanotube/aluminium/copper composite powder is cold-pressed into base, then vacuum hotpressing 3 hours at 500 DEG C, obtains closely knit carbon nanotube/aluminium/carbon/carbon-copper composite material.
Embodiment 2
The Single Walled Carbon Nanotube and proper amount of surfactant Triton, the defoamer tributyl phosphate that surface are coated with gold (1%) add DMSO, ultrasonic disperse makes the Single Walled Carbon Nanotube of surface gold-plating dispersed for 2 hours, then add DMSO and regulate carbon nanotube concentration, the surface obtaining 3wt% is coated with the Single Walled Carbon Nanotube DMSO solution of gold;
Under 45 DEG C of water bath with thermostatic control heating conditions, be dissolved in by polyvinylpyrrolidone in DMSO, mechanical stirring, to dissolving completely, adds DMSO and regulates polyvinyl alcohol concentration, obtain the DMSO solution of the polyvinylpyrrolidone of 2wt% after being cooled to room temperature;
Get 10g magnesium powder, join in the DMSO solution of the polyvinylpyrrolidone of the 2wt% of 50ml, magnetic agitation 1 hour, then filter repeatedly with deionized water wash, the magnesium powder of Surface coating polyvinylpyrrolidone can be obtained;
The surface that coated for above polyvinylpyrrolidone magnesium powder joins the 3wt% of 50ml is coated with in the Single Walled Carbon Nanotube DMSO solution of argent, magnetic agitation becomes limpid to DMSO by black, show that surface is coated with the Single Walled Carbon Nanotube of argent all by the polyvinylpyrrolidone thin film adsorbs on magnesium powder surface, filter repeatedly with deionized water wash, vacuum-drying 12 hours is carried out at 40 DEG C, then vacuum pyrolysis 2 hours at 300 DEG C, remove polyvinylpyrrolidone wherein and tensio-active agent Triton, the organic compositions such as defoamer tributyl phosphate, namely carbon nano tube/silver composite powder is obtained, wherein the mass percent of carbon nanotube is about 4wt%.
First above carbon nanotube/aluminium composite powder is cold-pressed into base, then at 450 DEG C, vacuum stripping carried out hot extrusion after 2 hours, and extrusion ratio is 20: 1, obtained closely knit carbon nanotube/magnesium base composite material.
Embodiment 3
(2%) double-walled carbon nano-tube of surface gold-plating and proper amount of surfactant SDBS are added N, in N-N,N-DIMETHYLACETAMIDE, ultrasonic disperse 2 hours, then N is added, N-N,N-DIMETHYLACETAMIDE regulates carbon nanotube concentration, obtain the double-walled carbon nano-tube N,N-dimethylacetamide solution that the polyacrylic acid of 5wt% is coated;
Be dissolved in by polyvinylpyrrolidone in N,N-dimethylacetamide, mechanical stirring is to dissolving completely, N is added after being cooled to room temperature, N-N,N-DIMETHYLACETAMIDE regulates polyvinylpyrrolidone concentration, obtains the polyvinylpyrrolidone N,N-dimethylacetamide solution of 4wt%;
Get 10g nickel powder, join in the polyvinylpyrrolidone N,N-dimethylacetamide solution of the 4wt% of 50ml, magnetic agitation 0.5 hour, then filter repeatedly with absolute ethanol washing, the nickel powder that polyvinylpyrrolidone is coated can be obtained;
Coated for above polyvinylpyrrolidone nickel powder is joined the double-walled carbon nano-tube N of the 5wt% of 50ml, in N-dimethylacetamide solution, magnetic agitation is to N, N-dimethylacetamide solution becomes limpid by black, show carbon nanotube all by the polyvinylpyrrolidone thin film adsorbs on nickel powder surface, filter repeatedly with absolute ethanol washing, vacuum-drying 12 hours is carried out at 40 DEG C, then at 500 DEG C, vacuum pyrolysis 2 hours in argon gas atmosphere, remove polyvinylpyrrolidone wherein, the organic compositions such as polyacrylic acid and tensio-active agent SDBS, namely carbon nanotube/nickel composite powder is obtained, wherein the mass percent of carbon nanotube is about 8wt%.
Comparative example 1
Comparative example 1 is one of them embodiment disclosed in CN101818280A.
Add in deionized water by carbon nanotube and proper amount of surfactant SDS, defoamer octanol, ultrasonic disperse makes even carbon nanotube disperse in 2 hours, then adds deionized water and regulates carbon nanotube concentration, obtain the carbon nano-tube aqueous solutions of 0.02wt%;
Under 90 DEG C of water bath with thermostatic control heating conditions, be dissolved in by polyvinyl alcohol in deionized water, mechanical stirring, to dissolving completely, adds deionized water and regulates polyvinyl alcohol concentration, obtain the polyvinyl alcohol water solution of 0.2wt% after being cooled to room temperature;
Get 10g aluminium powder, join in the polyvinyl alcohol water solution of the 0.2wt% of 50ml, magnetic agitation 1 hour, then filter repeatedly with deionized water wash, the aluminium powder of Surface coating polyvinyl alcohol can be obtained;
Coated for above polyvinyl alcohol aluminium powder is joined in the carbon nano-tube aqueous solutions of the 0.02wt% of 50ml, magnetic agitation becomes limpid to the aqueous solution by black, show that carbon nanotube is all adsorbed by the PVA (PVOH) FILM on aluminium powder surface, filter repeatedly with deionized water wash, vacuum-drying 12 hours is carried out at 40 DEG C, then vacuum pyrolysis 2 hours at 300 DEG C, remove polyvinyl alcohol wherein and the organic composition such as surfactant SDS, defoamer octanol, namely obtain carbon nanotube/aluminium composite powder, wherein the mass percent of carbon nanotube is about 0.1wt%.With the surface topography of scanning electronic microscope gained composite powder, distributing very evenly of visible carbon nanotube.
First above carbon nanotube/aluminium composite powder is cold-pressed into base, then vacuum hotpressing 3 hours at 500 DEG C, obtains closely knit carbon nanotube/aluminum composite.
Carry out Mechanics Performance Testing to matrix material described in embodiment 1-3 and comparative example 1, result is as shown in the table:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | |
| Elongation at break % | 98 | 102 | 105 | 75 |
| Tensile strength MPa | 30 | 32 | 31 | 15 |
It should be noted that and understand, when not departing from the spirit and scope of the present invention required by accompanying claim, various amendment and improvement can be made to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not by the restriction of given any specific exemplary teachings.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. the preparation method of a carbon nanotube metal based composite materials, it is characterized in that, first metal-powder is joined in polymers soln and carry out Surface coating, then polymer-coated metal powder is joined in carbon nano-tube solution, make polymer-coated metal powder surface uniform adsorption carbon nanotube, obtain homodisperse carbon nano tube metal composite powder, and then adopt powder metallurgical technique, gained composite powder is made closely knit carbon nanotube metal based composite materials;
Described carbon nanotube is the carbon nanotube that surface is coated with gold.
2. the method for claim 1, is characterized in that, comprises the following steps:
(1) described carbon nanotube is joined in organic solvent, preparation carbon nano-tube solution;
(2) described polymkeric substance is joined in water or organic solvent, prepare polymers soln;
(3) Surface coating polymkeric substance: described metal-powder is joined in described polymers soln, namely metal-powder and polymers soln slip is obtained, continue stirring until metal powder surface and form polymeric film, then carry out washing and filtering, namely obtain described polymer-coated metal powder;
(4) surface adsorption carbon nanotube: described polymer-coated metal powder is joined in carbon nano-tube solution, namely metal-powder and carbon nano-tube solution slip is obtained, Keep agitation is until carbon nanotube is adsorbed on the surface of polymer-coated metal powder, then carry out washing and filtering, drying treatment and pyrolysis processing, namely obtain homodisperse carbon nano tube metal composite powder;
(5) adopt powder metallurgical technique, gained carbon nano tube metal composite powder is made closely knit carbon nanotube metal based composite materials;
Described carbon nanotube is the carbon nanotube that surface is coated with gold.
3. method as claimed in claim 1 or 2, is characterized in that, described metal-powder is selected from the mixture of a kind of in aluminium, copper, magnesium, titanium, nickel or iron or at least two kinds.
4. the method as described in one of claim 1-3, is characterized in that, the content of described carbon nano tube surface gold is 1 ~ 3% of content of carbon nanotubes.
5. the method as described in one of claim 1-4, is characterized in that, described organic solvent is selected from the mixture of a kind of in DMF, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO) or at least two kinds, preferred DMF.
6. the method as described in one of claim 1-5, is characterized in that, in described carbon nano-tube solution, carbon nanotube accounts for the mass percent concentration of carbon nano-tube solution is 1.2 ~ 5wt%;
Preferably, in described carbon nano-tube solution, also include tensio-active agent or/and defoamer;
Preferably, described tensio-active agent is selected from the mixture of a kind of in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, cetyl trimethylammonium bromide, Triton, chitosan, β-cyclodextrin or glutaraldehyde or biliary salts or at least two kinds;
Preferably, described defoamer is selected from the mixture of a kind of in octanol, tributyl phosphate, polydimethylsiloxane or polyethers or at least two kinds.
7. the method as described in one of claim 1-6, is characterized in that, in described polymers soln, polymkeric substance accounts for the mass percent concentration of polymers soln is 1 ~ 4wt%;
Preferably, the polymkeric substance in described polymers soln is selected from the mixture of a kind of in polyvinyl alcohol, polyoxyethylene glycol, polyvinylpyrrolidone, polyacrylonitrile, polyacrylic acid, polyacrylamide, polymeric amide, polydimethylsiloxane or ethyl cellulose or at least two kinds.
8. the method as described in one of claim 1-7, is characterized in that, in described carbon nano tube metal composite powder, the mass percent of carbon nanotube is 1 ~ 8wt%, preferably 1.5 ~ 6.5wt%, further preferred 2 ~ 5wt%.
9. the method as described in one of claim 1-8, is characterized in that, described pyrolysis processing is: carry out under the inert atmosphere such as vacuum or argon gas and more than the pyrolysis temperature of polymkeric substance.
10. the method as described in one of claim 1-9, is characterized in that, described powder metallurgical technique, is described carbon nano tube metal composite powder is cold-pressed into base, and then carries out densification and obtain closely knit carbon nanotube metal based composite materials; Described densification refers to carries out hot pressing, hot rolling or hot extrusion below the fusing point of metal-powder.
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| CN106676305A (en) * | 2017-01-12 | 2017-05-17 | 苏州思创源博电子科技有限公司 | Preparation method for carbon nano tube titanium matrix composite material |
| CN108793926A (en) * | 2018-07-11 | 2018-11-13 | 俞小峰 | A kind of preparation method of permanent seal cooling aluminosilicate fiberboard |
| CN109502570A (en) * | 2018-12-14 | 2019-03-22 | 郑州大学 | Conductive big strain carbon nano-tube coextruded film, preparation method and test method |
| CN109536761A (en) * | 2018-12-03 | 2019-03-29 | 山东科技大学 | A kind of carbon nanotube/metal-base composites and preparation method thereof |
| CN110387281A (en) * | 2019-06-26 | 2019-10-29 | 包头协同纳米新材科技有限公司 | Carbon nanotube/zero dimensional nanometer materials composite material and its preparation method and application |
| WO2019245000A1 (en) * | 2018-06-21 | 2019-12-26 | 日立金属株式会社 | Aluminum-based composite material |
| CN111979437A (en) * | 2020-07-14 | 2020-11-24 | 深圳烯湾科技有限公司 | Metal/carbon nano tube composite material and preparation method thereof |
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| CN106676305A (en) * | 2017-01-12 | 2017-05-17 | 苏州思创源博电子科技有限公司 | Preparation method for carbon nano tube titanium matrix composite material |
| WO2019245000A1 (en) * | 2018-06-21 | 2019-12-26 | 日立金属株式会社 | Aluminum-based composite material |
| CN108793926A (en) * | 2018-07-11 | 2018-11-13 | 俞小峰 | A kind of preparation method of permanent seal cooling aluminosilicate fiberboard |
| CN109536761A (en) * | 2018-12-03 | 2019-03-29 | 山东科技大学 | A kind of carbon nanotube/metal-base composites and preparation method thereof |
| CN109502570A (en) * | 2018-12-14 | 2019-03-22 | 郑州大学 | Conductive big strain carbon nano-tube coextruded film, preparation method and test method |
| CN110387281A (en) * | 2019-06-26 | 2019-10-29 | 包头协同纳米新材科技有限公司 | Carbon nanotube/zero dimensional nanometer materials composite material and its preparation method and application |
| CN111979437A (en) * | 2020-07-14 | 2020-11-24 | 深圳烯湾科技有限公司 | Metal/carbon nano tube composite material and preparation method thereof |
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