CN101069928A - Method for preparing copper-base composite particles of internal carbon-inlaid nano pipe - Google Patents
Method for preparing copper-base composite particles of internal carbon-inlaid nano pipe Download PDFInfo
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Abstract
The present invention relates to a preparation method of carbon nano tube intercalated copper base composite granules. Said method includes the following steps: making 0.1g of carbon nano tube treated by mixed acid be dissolved in gelatin solution, then placing the above-mentioned material into a water bath and utilizing ultrasonic wave to disperse the mixed solution to obtain uniformly-dispersed carbon nano tube gelatin solution; then placing said carbon nano tube gelatin solution into a drying box, fully-drying, then taking out and grinding; making the carbon nano tube fine powder covered with gelatin be dissolved in deionzed water, at the same time adding polyethylene glycol, then successively adding copper sulphate solution and glucose solution; making the obtained mixed solution undergo the process of ultrasonic treatment, then transferring said mixed solution into a constant-temperature water-bath tank, heating, continuously stirring to make full reaction; using centrifugal machine to wash and separate out precipitate, drying said precipitate in a vacuum drying box, placing the above-mentioned product into a resistance furnace, making reaction under the condition of hydrogen gas atmosphere and a certain temperature, then naturally cooling so as to obtain the invented product.
Description
Technical field
The present invention relates to a kind of preparation method of copper-base composite particles of internal carbon-inlaid nano pipe.
Background technology
The conduction of CNT excellence, heat conduction and high specific strength, low-density and low thermal coefficient of expansion make it not only at the enhancing body as macromolecular material, and have all demonstrated huge application potential as metal-base composites enhancing body aspect.Yet for the polymer composite system, the research of carbon nano-tube reinforced metal-matrix composite material faces bigger difficulty.Compare with traditional material with carbon element, CNT not only exists similarly and the matrix wellability is poor, occur problems such as poly-partially easily, but also because size is little, more difficult realization is single to be disperseed.Directly adopt traditional powder metallurgic method or pressure sintering, fusion casting, be difficult to avoid a difficult problem that is separated and reunites.For solid phase mixing, the difference of size and proportion will cause the CNT reunion and gather partially being difficult to avoid.During sinter molding, because the plastic flow of both relatively poor compatibilities and copper causes more serious gathering partially.Mix for liquid phase, liquid copper and carbon strengthen body be difficult to each other wetting, can reacting generating compound yet, easilier cause CNT to gather partially even problem such as come-up.When utilizing traditional carbon fibres to strengthen metal-base composites, need usually carbon fiber is carried out the coating preliminary treatment, then by powder metallurgic method or technological formings such as pressure sintering, fusion casting.Yet, this method is also inapplicable for CNT, because the CNT diameter only is a nanoscale, carries out the metal level plating on its surface and is difficult to reach even, fine and close, and that large-scale plating more cannot say for sure to demonstrate,prove clad is continuous and fine and close, and agglomeration still can't be avoided; People also expect to improve performance of composites by advanced person's moulding process in addition, and as using plasma flame sintering process, though can improve density, CNT still is difficult to even distribution.These difficulties are greatly restricting the research and development of carbon nano-tube reinforced metal-matrix composite material.Therefore it is just significant to research and develop new complex technique route.
Summary of the invention
The technical problem to be solved in the present invention is, is difficult to a compound difficult problem at existing CNT and metal, proposes a kind of preparation method of copper-base composite particles of internal carbon-inlaid nano pipe, and CNT is inlayed in particle, is network and distributes, and form chemical bonding with copper; Being embedded into CNT in the particle can avoid CNT to reunite, strengthen strong bonded with matrix, greatly improve its flowability and compressibility, the difficulty of processing and forming is reduced, for the technology difficult problem of this class material of preparation of solving present existence provides a valid approach, also provide useful enlightenment simultaneously for the preparation of other class nano composite material.
Technical solution of the present invention is that the step of described preparation copper-base composite particles of internal carbon-inlaid nano pipe method is:
1) be that the pure concentrated sulfuric acid of analysis of 96%-98% and the pure red fuming nitric acid (RFNA) mixed liquor of analysis that concentration is 65%-70% add hot reflux 1.8-2.2 hour with diameter range under 100 ℃ in the CNT concentration of 10-40 nanometer, sediment after the filtration is that the analysis pure hydrochloric acid of 35%-40% was at 100 ℃ of following backflow 1.8-2.2 hours with concentration again, use deionized water rinsing at last, make filtrate pH value to neutrality, oven dry grind the CNT handled through nitration mixture; The volume ratio of the described concentrated sulfuric acid and red fuming nitric acid (RFNA) is 3: 0.9-1.1;
2) the described CNT of handling through nitration mixture of 0.1g is dissolved in the 10ml-100ml gelatin solution, gelatin solution concentration is 0.01g/ml-0.15g/ml, be placed on 30-80 ℃ of water-bath then, ultrasonic dispersion mixed solution 2.8 hours-3.2 hours makes super homodisperse carbon nanotubes gelatin solution;
3) described carbon nanotubes gelatin solution is placed drying box,, get gelatin coated carbon nanotube fine powder in 30-120 ℃ of baking taking-up after 2-6 hour down;
4) the described gelatin coated carbon nanotube fine powder of 0.1 gram is dissolved in the 20-160ml deionized water, the polyethylene glycol that adds 2-20ml, 0.01g/ml-0.15g/ml simultaneously, add the copper-bath of 10ml-100ml, 0.1M-1.2M and the glucose solution of 10ml-100ml, 0.1M-1.2M more successively, get mixed solution;
5) with the ultrasonic processing of described mixed solution after 1-3 hour, transfer in the thermostat water bath 20-90 ℃ of heating and stirred simultaneously 1-4 hour, utilize the centrifuge washing to isolate sediment then, and dry in vacuum drying chamber, solid product;
6) above-mentioned solid product is put in the resistance furnace, 200～700 ℃ were reacted 1～4 hour down in nitrogen atmosphere, and cooling naturally promptly obtains composite particles then.
Described CNT can be the CNT of single wall or many walls.
The present invention can make spherical composite particles, and CNT inlays in particle.At first utilize described mixed acid solution that CNT is carried out purification process, on the one hand can remove impurity, can make carbon nano tube surface have hydroxyl (OH) and carboxyl (functional group such as COOH) on the other hand.On this basis, adopt gelatin that CNT is carried out further functionalization, its surperficial functional group can be used as the effect of a ligand and catches copper ion after the functionalization, and the CNT of having caught copper ion can singly be dispersed in the copper solution.The copper ion of diverse location is grown up by reduction, nucleation, merging on the different subsequently CNTs or on the same pipe, forms particle, and CNT is inlayed therein.In chemistry and heat treatment process subsequently, remove impurity and anion, next in nitrogen atmosphere, the oxide of copper is reduced into copper.The carbon nanotubes copper-base composite particles size that is obtained by the inventive method is even, adjustable, the purity height, and CNT is uniformly dispersed in particle, and network-like attitude, as shown in Figure 1 and Figure 2.This composite particles can be used as powder stock and prepares high performance Cu-base composites and face coat, has considerable economic and far-reaching social benefit.
Description of drawings
Fig. 1 is the scanning electron micrograph of gained composite particles;
Fig. 2 is the transmission electron micrograph of gained composite particles.
The specific embodiment
Embodiment 1: the step of preparation copper-base composite particles of internal carbon-inlaid nano pipe method is:
1) be that 98% the pure concentrated sulfuric acid of analysis and concentration are that 67% the pure red fuming nitric acid (RFNA) mixed liquor of analysis adds hot reflux 2 hours under 100 ℃ with diameter range in the CNT concentration of 10-40 nanometer, sediment after the filtration is that 37% analysis pure hydrochloric acid refluxed 2 hours down at 100 ℃ with concentration again, use deionized water rinsing at last, make filtrate pH value to neutrality, oven dry grind the CNT handled through nitration mixture, stand-by; The volume ratio of the described concentrated sulfuric acid and red fuming nitric acid (RFNA) is 3: 1;
2) the described CNT of handling through nitration mixture of 0.1g is dissolved in the 55ml gelatin solution, gelatin solution concentration is 0.08g/ml, is placed on 60 ℃ of-80 ℃ of water-baths then, and ultrasonic dispersion mixed solution made super homodisperse carbon nanotubes gelatin solution in 3 hours;
3) described carbon nanotubes gelatin solution is placed drying box,, get gelatin coated carbon nanotube fine powder in 808 ℃ of baking taking-ups after 4 hours down;
4) the described gelatin coated carbon nanotube fine powder of 0.1 gram is dissolved in the 90ml deionized water, adds the polyethylene glycol of 11ml, 0.08g/ml simultaneously, add the copper-bath of 55ml, 0.65M and the glucose solution of 55ml, 0.65M more successively, get mixed solution;
5) with the ultrasonic processing of described mixed solution after 2 hours, transfer in the thermostat water bath 90 ℃ of heating and stirred simultaneously 3 hours, utilize the centrifuge washing to isolate sediment then, and dry in vacuum drying chamber, solid product;
6) above-mentioned solid product is put in the resistance furnace, 700 ℃ were reacted 3 hours down in nitrogen atmosphere, and cooling naturally promptly obtains the composite particles that average diameter is 90 nanometers then.
Embodiment 2: the step of preparation copper-base composite particles of internal carbon-inlaid nano pipe method is:
1) be that 98% the pure concentrated sulfuric acid of analysis and concentration are that 70% the pure red fuming nitric acid (RFNA) mixed liquor of analysis adds hot reflux 2.2 hours under 100 ℃ with diameter range in the CNT concentration of 10-40 nanometer, sediment after the filtration is that 40% analysis pure hydrochloric acid refluxed 2.2 hours down at 100 ℃ with concentration again, use deionized water rinsing at last, make filtrate pH value to neutrality, oven dry grind the CNT handled through nitration mixture, stand-by; The volume ratio of the described concentrated sulfuric acid and red fuming nitric acid (RFNA) is 3: 1.1;
2) the described CNT of handling through nitration mixture of 0.1g is dissolved in the 100ml gelatin solution, gelatin solution concentration is 0.15g/ml, is placed on 80 ℃ of water-baths then, and ultrasonic dispersion mixed solution made super homodisperse carbon nanotubes gelatin solution in 3.2 hours;
3) described carbon nanotubes gelatin solution is placed drying box,, get gelatin coated carbon nanotube fine powder in 120 ℃ of baking taking-ups after 6 hours down;
4) the described gelatin coated carbon nanotube fine powder of 0.1 gram is dissolved in the 160ml deionized water, adds the polyethylene glycol of 20ml, 0.15g/ml simultaneously, add the copper-bath of 100ml, 1.2M and the glucose solution of 100ml, 1.2M more successively, get mixed solution;
5) with the ultrasonic processing of described mixed solution after 3 hours, transfer in the thermostat water bath 90 ℃ of heating and stirred simultaneously 4 hours, utilize the centrifuge washing to isolate sediment then, and dry in vacuum drying chamber, solid product;
6) above-mentioned solid product is put in the resistance furnace, 700 ℃ were reacted 4 hours down in nitrogen atmosphere, and cooling naturally promptly obtains the composite particles that average diameter is 700 nanometers then.
Embodiment 3: the step of preparation copper-base composite particles of internal carbon-inlaid nano pipe method is:
1) be that 96%% the pure concentrated sulfuric acid of analysis and concentration are that 65% the pure red fuming nitric acid (RFNA) mixed liquor of analysis adds hot reflux 1.8 hours under 100 ℃ with diameter range in the CNT concentration of 10-40 nanometer, sediment after the filtration is that 35% analysis pure hydrochloric acid refluxed 1.8 hours down at 100 ℃ with concentration again, use deionized water rinsing at last, make filtrate pH value to neutrality, oven dry grind the CNT handled through nitration mixture, stand-by; The volume ratio of the described concentrated sulfuric acid and red fuming nitric acid (RFNA) is 3: 0.9;
2) the described CNT of handling through nitration mixture of 0.1g is dissolved in the 10ml gelatin solution, gelatin solution concentration is 0.01g/ml, is placed on 30 ℃ of water-baths then, and ultrasonic dispersion mixed solution made super homodisperse carbon nanotubes gelatin solution in 2.8 hours;
3) described carbon nanotubes gelatin solution is placed drying box,, get gelatin coated carbon nanotube fine powder in 30 ℃ of baking taking-ups after 2 hours down;
4) the described gelatin coated carbon nanotube fine powder of 0.1 gram is dissolved in the 20ml deionized water, adds the polyethylene glycol of 2ml, 0.01g/mlg/ml simultaneously, add the copper-bath of 10ml, 0.1M and the glucose solution of 10ml, 0.1M more successively, get mixed solution;
5) with the ultrasonic processing of described mixed solution after 1 hour, transfer in the thermostat water bath 20 ℃ of heating and stirred simultaneously 1 hour, utilize the centrifuge washing to isolate sediment then, and dry in vacuum drying chamber, solid product;
6) above-mentioned solid product is put in the resistance furnace, 200 ℃ were reacted 1 hour down in nitrogen atmosphere, and cooling naturally promptly obtains the composite particles that average diameter is 1200 nanometers then.
Claims (1)
1, a kind of preparation copper-base composite particles of internal carbon-inlaid nano pipe method is characterized in that its step is:
1) be that the pure concentrated sulfuric acid of analysis of 96%-98% and the pure red fuming nitric acid (RFNA) mixed liquor of analysis that concentration is 65%-70% add hot reflux 1.8-2.2 hour with diameter range under 100 ℃ in the CNT concentration of 10-40 nanometer, sediment after the filtration is that the analysis pure hydrochloric acid of 35%-40% was at 100 ℃ of following backflow 1.8-2.2 hours with concentration again, use deionized water rinsing at last, make filtrate pH value to neutrality, oven dry grind the CNT handled through nitration mixture; The volume ratio of the described concentrated sulfuric acid and red fuming nitric acid (RFNA) is 3: 0.9-1.1;
2) the described CNT of handling through nitration mixture of 0.1g is dissolved in the 10ml-100ml gelatin solution, gelatin solution concentration is 0.01g/ml-0.15g/ml, be placed on 30-80 ℃ of water-bath then, ultrasonic dispersion mixed solution 2.8 hours-3.2 hours makes super homodisperse carbon nanotubes gelatin solution;
3) described carbon nanotubes gelatin solution is placed drying box,, get gelatin coated carbon nanotube fine powder in 30-120 ℃ of baking taking-up after 2-6 hour down;
4) the described gelatin coated carbon nanotube fine powder of 0.1 gram is dissolved in the 20-160ml deionized water, the polyethylene glycol that adds 2-20ml, 0.01g/ml-0.15g/ml simultaneously, add the copper-bath of 10ml-100ml, 0.1M-1.2M and the glucose solution of 10ml-100ml, 0.1M-1.2M more successively, get mixed solution;
5) with the ultrasonic processing of described mixed solution after 1-3 hour, transfer in the thermostat water bath 20-90 ℃ of heating and stirred simultaneously 1-4 hour, utilize the centrifuge washing to isolate sediment then, and dry in vacuum drying chamber, solid product;
6) above-mentioned solid product is put in the resistance furnace, 200～700 ℃ were reacted 1～4 hour down in nitrogen atmosphere, and cooling naturally promptly obtains composite particles then.
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| CN102137728A (en) * | 2008-08-29 | 2011-07-27 | 石原产业株式会社 | Metallic copper dispersion, process for producing the metallic copper dispersion, electrode, wiring pattern, and coating film formed using the metallic copper dispersion, decorative article and antimicrobial article with the coating film formed there |
| CN102307826A (en) * | 2009-02-05 | 2012-01-04 | Lg化学株式会社 | Method for preparing carbon particles/copper composite materials |
| CN103170627A (en) * | 2013-03-21 | 2013-06-26 | 南昌航空大学 | Method for gradient and length-diameter ratio CNTs reinforced copper-based composite materials of laser-induction composite melting deposition |
| CN103862062A (en) * | 2014-04-11 | 2014-06-18 | 南京大学 | Composite material of copper nano particles evenly doped with submicron carbon spheres and one-step synthesis method thereof |
| CN107326401A (en) * | 2017-05-22 | 2017-11-07 | 昆明理工大学 | A kind of preparation method of CNTs/Cu composite granules and CNTs/Cu composites |
| CN108269976A (en) * | 2017-12-19 | 2018-07-10 | 中南大学 | Cobalt-based lithium ion battery negative material preparation method |
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| JP4351120B2 (en) * | 2004-08-19 | 2009-10-28 | シナノケンシ株式会社 | Method for producing metal particles |
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| CN102137728A (en) * | 2008-08-29 | 2011-07-27 | 石原产业株式会社 | Metallic copper dispersion, process for producing the metallic copper dispersion, electrode, wiring pattern, and coating film formed using the metallic copper dispersion, decorative article and antimicrobial article with the coating film formed there |
| CN102137728B (en) * | 2008-08-29 | 2013-09-11 | 石原产业株式会社 | Metallic copper dispersion, process for producing the metallic copper dispersion, electrode, wiring pattern, and coating film formed using the metallic copper dispersion, decorative article and antimicrobial article with the coating film formed there |
| CN102307826A (en) * | 2009-02-05 | 2012-01-04 | Lg化学株式会社 | Method for preparing carbon particles/copper composite materials |
| CN102307826B (en) * | 2009-02-05 | 2014-06-11 | Lg化学株式会社 | Method for preparing carbon particles/copper composite materials |
| US9776928B2 (en) | 2009-02-05 | 2017-10-03 | Lg Chem, Ltd. | Method for preparing carbon-based particle/copper composite material |
| CN103170627A (en) * | 2013-03-21 | 2013-06-26 | 南昌航空大学 | Method for gradient and length-diameter ratio CNTs reinforced copper-based composite materials of laser-induction composite melting deposition |
| CN103862062A (en) * | 2014-04-11 | 2014-06-18 | 南京大学 | Composite material of copper nano particles evenly doped with submicron carbon spheres and one-step synthesis method thereof |
| CN107326401A (en) * | 2017-05-22 | 2017-11-07 | 昆明理工大学 | A kind of preparation method of CNTs/Cu composite granules and CNTs/Cu composites |
| CN108269976A (en) * | 2017-12-19 | 2018-07-10 | 中南大学 | Cobalt-based lithium ion battery negative material preparation method |
| CN108281622A (en) * | 2017-12-19 | 2018-07-13 | 湖南艾华集团股份有限公司 | A kind of preparation method of the porous composite negative pole material of transition metal oxide/carbon nanotube |
| CN115007853A (en) * | 2022-05-23 | 2022-09-06 | 福州大学 | Carbon nanotube surface modification method capable of optimizing CNTs/Al composite material interface |
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