CN100482453C - Preparation method of reinforced polymer base composite material for high volume fraction carbon nano-pipe - Google Patents
Preparation method of reinforced polymer base composite material for high volume fraction carbon nano-pipe Download PDFInfo
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- CN100482453C CN100482453C CNB2005100614729A CN200510061472A CN100482453C CN 100482453 C CN100482453 C CN 100482453C CN B2005100614729 A CNB2005100614729 A CN B2005100614729A CN 200510061472 A CN200510061472 A CN 200510061472A CN 100482453 C CN100482453 C CN 100482453C
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Abstract
A high-volume-fraction carbon nanotube reinforced polymer-based composition used as high performance structure material and functional material is prepared through spreading layers on prefabricated CNT layer by layer and liquid-phase moulding, such as pressure casting (RTM) and resin film fusion osmosis/impregnation (RFI).
Description
Technical field
The present invention relates to a kind of preparation method of reinforced polymer base composite material for high volume fraction carbon nano-pipe.
Background technology
The carbon fiber enhancement resin base structural composite material is strong with its lightweight, height ratio, height ratio mould and strong material-performance designability be in the various fields that comprises sophisticated industries such as electronics, space flight, the aviation application of succeeding, and is bringing into play irreplaceable effect in national economy and national defense construction kind.Properties of carbon is one of key factor of decision composite property quality.CNT (CNT) is with the incomparable high-modulus of its great draw ratio (greater than 100), existing traditional fibre, high strength (it is 100 times of steel that theoretical strength can reach 1.0TPa), high-elongation, and excellent heat-resisting and chemical resistance, and be considered to ultimate carbon fiber, be that the ideal of high performance structures composite of future generation and multifunctional material strengthens body.And the continuous progress of CNT synthetic technology, the improving constantly and the progressively reduction of price of production efficiency is for broad scale research with use CNT material guarantee is provided.
Over past ten years; launched a large amount of research around the CNT/ polymer matrix composite both at home and abroad, research contents relates to the synthetic and growth mechanism of CNT, the finishing of CNT and functionalized; the preparation of CNT/ polymer composites and sign etc. are very active subject crossing fields.Yet people still are in initial period to the research that CNT strengthens resin-based structural composite material (CRPSC).A basic problem is that the present method that effectively prepares CRPSC that still lacks can not make the high-performance CRPSC that conforms with instructions for use.
The preparation of CRPSC at present is that the preparation method according to particle-filled polymer carries out substantially, promptly earlier CNT is carried out surface modification and functionalized, then adopts the method for solution or melt blending and polymer compound.The ubiquitous problem of this method is: (1) CNT is independence and being evenly dispersed in the matrix fully; (2) the shared volume fraction low (being generally less than 5vt%) of CNT in the composite can't effectively be carried; (3) CNT random orientation in matrix can't be in the high-performance of carrying direction performance CNT.The main cause that causes these problems to occur can be summed up as the surface inertness, dimensional effect of CNT and be easy to convergence because of what Van der Waals force strong between pipe had.The existence of these problems not only makes the performance advantage of CNT be difficult to embody, and can not obtain to satisfy the material of instructions for use.So new method and the technical foundation thereof of exploration and development preparation CRPSC are imperative.
Summary of the invention
In order to overcome existing carbon nano-tube/polymer based composites preparation technology's drawback, the object of the present invention is to provide a kind of preparation method of reinforced polymer base composite material for high volume fraction carbon nano-pipe.
The technical solution adopted for the present invention to solve the technical problems is that the step of this method is as follows:
1) by the ply sequence of setting, stack CNT precast body, the phase that is enhanced preform;
2) by liquid phase molding technological forming, promptly get reinforced polymer base composite material for high volume fraction carbon nano-pipe.
The CNT precast body that described CNT precast body is single wall or many walls, modification or unmodified CNT precast body.
Described liquid phase moulding technology is extrusion process or resin molding infiltration process.
The beneficial effect that the present invention has is: the CNT/ polymer composites that is made by the present invention has that CNT is evenly distributed, the excellent properties of CNT volume fraction height (can reach more than 50%), CNT can be given full play to.The high-performance composite materials that the present invention makes can be used as structural material and functional material, have broad application prospects.
The specific embodiment
A kind of preparation method of porous C NT precast body: (applicant has applied for patent of invention in addition, November 7 2005 applying date, application number 200510061453.6)
A) the pore creating material solution that contains adhesive of every gram CNT and 0.1～4ml, wherein the concentration of adhesive is 0.01-20%, mixes, and stirs, grinds, and reaches even mixing;
B) powder that mixes is put into mould, add the pressure of 1～100MPa, be warming up to 50～250 ℃, behind heat-insulation pressure keeping 0.5～12h, naturally cool to normal temperature and release, promptly get prefab of porous carbon nanometer tube with 0.5～5 ℃/minute speed.
Described CNT is the CNT of single wall or many walls, modification or unmodified CNT.
Described adhesive is the natural or synthetic organic polymer of energy wiring solution-forming, is beneficial to mix with even carbon nanotube; Concrete adhesive is: starch, gelatin, polyvinyl alcohol, polymine, polyoxyethylene, polyvinylpyrrolidone, cellulose, polyethylene, polyvinyl chloride, polyvinyl acetate, polyurethane, epoxy resin or bimaleimide resin and combination arbitrarily thereof.
Described pore creating material is the solvent at the energy dissolved adhesive, or also can comprise other composition.Other composition of described pore creating material is the solid that easily distils, and they are KI, dry ice, sulphur, phosphorus, camphor, dinitronaphthalene or naphthalene; Or the solvent of energy dissolved adhesive, they are alcohols or ketone.
One, the raw material of the present invention's employing:
1) porous C NT precast body: CNT can be single wall, Duo Bi, modification or unmodified CNT precast body and their any combination.
2) resin: all resin systems that are applicable to extrusion process or resin molding infiltration process resin, as unsaturated polyester (UP), epoxy resin, properties of diallyl isophathalate (DAIP) resin, bimaleimide resin, cyanate ester resin system or the like and their modified system, and any combination of these resin systems.
Two, preparation method of the present invention:
1) by the ply sequence of setting, stack CNT precast body, the phase that is enhanced preform;
2) strengthen polymer composites by liquid phase molding technological forming CNT, promptly get reinforced polymer base composite material for high volume fraction carbon nano-pipe.
Embodiment 1:
1) with five layers of single wall CNT precast body stack, obtains the CNT preform.Then the CNT preform is put in the mould of extrusion process;
2) epoxy resin/anhydride system (as the TDE85/MNA acid anhydrides) of configuring of die casting at normal temperatures is expelled in the mould;
3) after injection finishes, with the program Solidification of setting: 130 ℃/2h+150 ℃/1h+180 ℃/2h+200 ℃/3h.After finishing, curing naturally cools to normal temperature.From mould, take out sample, promptly obtain the CNT/ epoxy composite material.
Embodiment 2:
1) 2g SWCN (SWNT) is put into 50 ℃ of following ultrasonic concussions of 200ml mixed acid (red fuming nitric acid (RFNA): concentrated sulfuric acid volume ratio is 3: 1) 8 hours.Diluting this system with deionized water, is the miillpore filter vacuum filtration of 0.22 μ m then with the aperture.Deposit is used washed with de-ionized water again, suction filtration again, so repeatedly, to the pH value to cleaning fluid be 5～6, product places vacuum drying oven to dry, and obtains acidifying SWCNTs.
2) preparation method with prefab of porous carbon nanometer tube makes acidifying SWCNTs precast body;
3) with five layers of acidifying single wall CNT precast body stack, obtain the CNT preform.Then the CNT preform is put in the mould of extrusion process;
4) epoxy resin/anhydride system (as the TDE85/MNA acid anhydrides) of configuring of die casting at room temperature;
5) after die casting finishes, with the program Solidification of setting: 130 ℃/2h+150 ℃/1h+180 ℃/2h+200 ℃/3h.After finishing, curing naturally cools to room temperature.From mould, take out sample, promptly obtain the CNT/ epoxy composite material.
Embodiment 3:
1) with acidifying multi-walled carbon nano-tubes (MWNT), thionyl chloride (SOCl
2) and N, dinethylformamide (DMF) is added to (acidifying CNTs:SOCl in the conical flask
2: the DMF proportioning is 200mg:20ml:1ml), ultrasonic dispersion back adds hot reflux 24h at 70 ℃, then is heated to 140 ℃, with most of SOCl in the system
2Steam, vacuum drying obtains chloride MWCNT.Chloride MWCNT is added in the excessive ethylenediamine, and dilute with ethanol 120 ℃ of reactions four days ultrasonic dispersion back again, decompress filter, and the ethylenediamine that flush away is unnecessary, vacuum drying obtains amination MWCNTs.
2) preparation method with prefab of porous carbon nanometer tube makes amination MWCNTs precast body;
3) with five layers of amination MWCNTs precast body stack, obtain the CNT preform.Then the CNT preform is put in the mould of extrusion process;
4) epoxy resin/anhydride system (as the TDE85/MNA acid anhydrides) of configuring of die casting at room temperature;
5) after die casting finishes, with the program Solidification of setting: 130 ℃/2h+150 ℃/1h+180 ℃/2h+200 ℃/3h.After finishing, curing naturally cools to room temperature.From mould, take out sample, promptly obtain the CNT/ epoxy composite material.
Embodiment 4:
1) with the stack of the precast body of wall CNT more than four layers, obtains the CNT preform.Then the CNT preform is put in the mould of extrusion process;
2) the BMI resin system (as commodity 4503A) that configures of die casting at room temperature;
3) after die casting finishes, with the program Solidification of setting: 130 ℃/2h+150 ℃/1h+180 ℃/2h+200 ℃/12h.After finishing, curing naturally cools to room temperature.From mould, take out sample, promptly obtain the CNT/ Bismaleimide composites.
Embodiment 5:
1) with the stack of the precast body of wall CNT more than four layers, obtains the CNT preform.Then the CNT preform is put in the mould of extrusion process;
2) the DAIP resin system that configures of die casting at room temperature;
3) after die casting finishes, with the program Solidification of setting: 125 ℃/12h+150 ℃/3h+170 ℃/7h.After finishing, curing naturally cools to room temperature.From mould, take out sample, promptly obtain the CNT/DAIP composite.
Embodiment 6:
1) the BMI resin molding is put in the mould of resin molding infiltration process,
2) with the stack of the CNT of wall amination more than three layers precast body, obtain the CNT preform.Then put into the CNT preform in the mould and be placed directly in resin molding above;
3) vacuum bag with the sealing location seals die cavity.Then with baking oven heating, molten resin.Resin solidifies behind the permeable fiber layer under vacuum action, and curing process is 130 ℃/1h+150 ℃/1h+180 ℃/2h+200 ℃/2h+220 ℃/6h.After finishing, curing naturally cools to room temperature.From mould, take out sample, promptly obtain the CNT/ Bismaleimide composites.
Claims (1)
1, the preparation method of reinforced polymer base composite material for high volume fraction carbon nano-pipe is characterized in that the step of this method is as follows:
1) with four layers of multi-walled carbon nano-tubes precast body stack, obtains the CNT preform, then the CNT preform is put in the mould of extrusion process; Wherein, the preparation process of CNT precast body is:
A) the pore creating material solution that contains adhesive of every gram CNT and 0.1～4ml, wherein the concentration of adhesive is 0.01-20%, mixes, and stirs, grinds, and reaches even mixing;
B) powder that mixes is put into mould, add the pressure of 1～100MPa, be warming up to 50～250 ℃, behind heat-insulation pressure keeping 0.5～12h, naturally cool to normal temperature and release, promptly get prefab of porous carbon nanometer tube with 0.5～5 ℃/minute speed;
Described CNT is the CNT of many walls;
2) properties of diallyl isophathalate (DAIP) resin system that configures of die casting at room temperature;
3) after die casting finishes, with the program Solidification of setting: 125 ℃/12h+150 ℃/3h+170 ℃/7h; Naturally cool to room temperature after curing is finished, from mould, take out sample, promptly obtain the CNT/DAIP composite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100614729A CN100482453C (en) | 2005-11-08 | 2005-11-08 | Preparation method of reinforced polymer base composite material for high volume fraction carbon nano-pipe |
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| CNB2005100614729A CN100482453C (en) | 2005-11-08 | 2005-11-08 | Preparation method of reinforced polymer base composite material for high volume fraction carbon nano-pipe |
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| CN1785658A CN1785658A (en) | 2006-06-14 |
| CN100482453C true CN100482453C (en) | 2009-04-29 |
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| CN101284423B (en) * | 2008-05-30 | 2010-06-02 | 沈阳航空工业学院 | Preparation method of carbon nano tube/carbon fiber multi-dimension mixing composite material |
| CN102073198B (en) * | 2010-12-07 | 2013-08-07 | 北京富纳特创新科技有限公司 | Spacer |
| CN102702745B (en) * | 2012-06-15 | 2014-03-19 | 苏州大学 | Preparation method of carbon nanotube/thermosetting resin composite material |
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