CN105619916A - Nano-toughened carbon fiber composite material and preparation method thereof - Google Patents

Nano-toughened carbon fiber composite material and preparation method thereof Download PDF

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CN105619916A
CN105619916A CN201510994172.XA CN201510994172A CN105619916A CN 105619916 A CN105619916 A CN 105619916A CN 201510994172 A CN201510994172 A CN 201510994172A CN 105619916 A CN105619916 A CN 105619916A
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mixed solution
halloysite nanotubes
carbon nanotube
graphene
laminated film
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CN105619916B (en
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隋刚
吴剑桥
郭健
张清杰
李�浩
杨小平
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The invention provides a nano-toughened carbon fiber composite material and a preparation method thereof, and belongs to the technical field of carbon fiber composite materials. The carbon fiber composite material is formed by die-pressing and curing 16-20 layers of prepreg, one layer of activated graphene and halloysite nanotube composite thin film and one layer of activated carbon nanotube and halloysite nanotube composite thin film, wherein the activated graphene and halloysite nanotube composite thin film is prepared from 10%-15% of aminated graphene, 70%-80% of benzyl glycidyl ether and 10%-15% of modified halloysite nanotubes grafted with long-chain polymers, and the activated carbon nanotube and halloysite nanotube composite thin film is prepared from 10%-15% of carbon nanotubes, 70%-80% of benzyl glycidyl ether and 10%-15% of modified halloysite nanotubes grafted with long-chain polymers. According to the nano-toughened carbon fiber composite material and the preparation method thereof, the defects in the prior art are overcome, multi-dimension and multi-scale reinforcing and toughening of the carbon fiber composite material are achieved, and the mechanical property of the carbon fiber composite is greatly improved.

Description

A kind of nanometer increases tough carbon-fibre composite and its preparation method
Technical field:
The present invention relates to carbon-fibre composite technical field, it is specifically related to a kind of Graphene/halloysite nanotubes film and the carbon-fibre composite of carbon nanotube/halloysite nanotubes film coordination plasticizing.
Background technology:
Graphene has carbon atom to become the individual layer two-dimension plane structure of honeycomb crystal lattice by positive hexagon close-packed arrays, has stronger electroconductibility, higher intensity. The original lamella of Graphene because its low apparent activation energy, often can not very well and polymkeric substance infiltration and reach good dispersion, finally cause its composite property strengthened not rise counter falling.
Since Japanese Scientists in 1991 finds carbon nanotube, its preparation method, performance and application are obtained for be studied widely. The caliber of carbon nanotube can reach micron level in 2-20nm, length, and bigger length-to-diameter ratio and specific surface area make it easily reunite, it is very difficult to scatter in the base. Meanwhile, surface inertness makes the interface binding power between itself and matrix more weak, and when being carried, stress can not effectively shift between matrix and carbon nanotube.
The bad dispersibility that interface cohesion is not good and nanoparticle is in resin matrix is the key issue in nanometer fortifying fibre polymer matrix composites all the time. General simple mechanically mixing is difficult to nanoparticle is effectively disperseed in resin matrix.
As a kind of high performance composite, there is the problems such as fragility height, toughness are low in carbon-fibre composite, traditional solution has thermoplastic resin modified, rubber particles modification etc. But, by the traditional method modification such as thermoplastic resin and rubber particles, although the toughness of matrix material can be improved, but a series of problems such as the thermotolerance that can cause matrix material declines, modulus decline. Present invention employs toughening carbon fiber reinforced prepreg between nanoparticle layers and prepare carbon-fibre composite, it is possible to increase substantially the toughness of material, also can improve the modulus of matrix material simultaneously, obtain high performance composite.
Summary of the invention:
The object of the invention is the feature of the carbon-fibre composite toughness deficiency overcoming in prior art, the carbon-fibre composite of a kind of graphene/carbon nano-tube/halloysite nanotubes coordination plasticizing is provided, described carbon-fibre composite by 16��20 layers of prepreg film, 1 layer of active Graphene/halloysite nanotubes laminated film with 1 layer activated carbon nanotube/halloysite nanotubes laminated film molded curing is shaping and becomes; Wherein, described active Graphene/halloysite nanotubes laminated film is by 10��15% amination Graphenes, and the halloysite nanotubes of the benzyl glycidyl ether of 70��80% and 10��15% modified grafting long chain polymers is made; Described activated carbon nanotube/halloysite nanotubes laminated film is made up of the halloysite nanotubes of the carbon nanotube of 10��15% and the benzyl glycidyl ether of 70��80% and 10��15% modified grafting long chain polymers.
Further, the thickness of described carbon-fibre composite is: 2��3mm, described prepreg thickness to be 0.09��0.17mm, active Graphene/halloysite nanotubes laminated film thickness be 50��80 ��m, the thickness of activated carbon nanotube/halloysite nanotubes laminated film be 50��80 ��m.
Further, the ply stacking-sequence of described carbon-fibre composite is respectively from top to bottom: 8��10 layers of prepreg, 1 layer of active Graphene/halloysite nanotubes laminated film and 1 layer of activated carbon nanotube/halloysite nanotubes laminated film and 8��10 layers of prepreg.
Simultaneously, the present invention also provides the preparation method of a kind of carbon-fibre composite, described carbon-fibre composite adopts compression molding preparation, specifically the carbon fiber prepreg of 0.09��0.17mm, active Graphene/halloysite nanotubes laminated film and activated carbon nanotube/halloysite nanotubes laminated film are placed in compression molding instrument, it is cured shaping according to the curing process of carbon fiber prepreg, finally it is pressed into the unidirectional composite material laminated wood that thickness is 2��3mm.
Wherein, the preparation method of active Graphene/halloysite nanotubes laminated film comprises the steps:
A) adding in hydrochloric acid soln by halloysite nanotubes, take off a layer turbid solution, adding distil water centrifugal treating, taking precipitate is dried, and grinding, obtains powder I;
B) adding sodium chloride solution in powder I, stir, distilled water centrifugal treating, dry under 105 DEG C of conditions, grinding, obtains powder II;
C) adding cetyl trimethylammonium bromide in powder II, 60 DEG C of oil baths are stirred, and ethanol is centrifugal, 90 DEG C of oven dry, and grinding, obtains the halloysite nanotubes of modified grafting long chain polymer;
D) amination Graphene is mixed in benzyl glycidyl ether, mechanical stirring, obtain mixed solution I;
E) mixed solution I is added in ball mill, under nitrogen protection ball milling, obtain mixed solution II;
Oil bath when f) mixed solution II being placed in 150 �� 5 DEG C, then normal temperature leaves standstill, and obtains active Graphene mixed solution;
G) in active Graphene mixed solution, add the halloysite nanotubes of modified grafting long chain polymer, obtain mixed solution III;
H) completely mixing after mixed solution III is heated to 90 �� 5 DEG C, and when 90 �� 5 DEG C mechanical stirring, obtain mixed solution IV;
I) by mixed solution IV supersound process under 60W ultrasonic power, the active Graphene halloysite nanotubes mixed solution that normal temperature obtains after leaving standstill;
J) by activity Graphene/halloysite nanotubes mixed solution film, then normal temperature leaves standstill, and obtains Graphene/halloysite nanotubes laminated film.
The preparation method of described activated carbon nanotube/halloysite nanotubes laminated film comprises the steps:
A) amination carbon nanotube is joined in benzyl glycidyl ether, stir, obtain mixed solution 1.;
B) 1. mixed solution is added in ball mill, under nitrogen protection ball milling, obtain mixed solution 2.;
C) by the mixed solution 2. oil bath when 150 �� 5 DEG C, then normal temperature leaves standstill, and obtains activated carbon nanotube mixed solution;
D) being added in activated carbon nanotube mixed solution by the halloysite nanotubes finished product of modified grafting long chain polymer, and be heated to 90 �� 5 DEG C, 3. the mechanical stirring when 90 �� 5 DEG C, obtain mixed solution;
3. e) mixed solution be placed under 60W ultrasonic power supersound process, and then normal temperature leaves standstill, the activated carbon nanotube/halloysite nanotubes mixed solution obtained;
F) activated carbon nanotube/halloysite nanotubes mixed solution being carried out film on tetrafluoroethylene flat board, normal temperature leaves standstill, and obtains carbon nanotube/halloysite nanotubes laminated film.
Further, the condition of described ball milling is: rotational speed of ball-mill 200��500r/min, needs interval 5min, the ball milling time 0.5��4h after continuous ball milling 10min.
The method of film of the present invention comprises: use glass stick film, with rejection film machine film, uses film applicator film.
Useful effect:
Its one:
The deficiency overcome in prior art of the present invention, by the combination treatment of active Graphene/halloysite nanotubes, the combination treatment of activated carbon nanotube/halloysite nanotubes, realize matrix material various dimensions, the activeness and quietness of many yardsticks, by the data of embodiment 1��4 it may be seen that substantially increase the mechanical property of matrix material.
First, amination Graphene, by amination Graphene is carried out pre-treatment, is reacted by the present invention with benzyl glycidyl ether, obtains active Graphene through wet ball grinding process. Secondly, by amination carbon nanotube is carried out pre-treatment, amination carbon nanotube is reacted with benzyl glycidyl ether, activated carbon nanotube is obtained through wet ball grinding process, finally, the present invention, by halloysite nanotubes is carried out pre-treatment, by the halloysite nanotubes of purchase and concentration hydrochloric acid reaction, leaves standstill. Outwelling supernatant liquor, distilled water centrifugal treating, to PH=6, is dried, grinding. Then adding sodium chloride solution reaction, distilled water centrifugal treating, until not chloride ion-containing, is dried, grinding. Last same cetyl trimethylammonium bromide, ethanol is centrifugal, dries, and grinding obtains the halloysite nanotubes of modified grafting long chain polymer.
Liquid active Graphene, by above-mentioned three kinds of preprocessing process, is carried out mixing process by the present invention with modified halloysite nanotubes, obtains active Graphene/halloysite nanotubes mixed solution. With conventional coating method, activity Graphene/halloysite nanotubes mixed solution is carried out film afterwards. Carry out mixing process with modified halloysite nanotubes by liquid active carbon nanotube, obtain activated carbon nanotube/halloysite nanotubes mixed solution. With conventional coating method, carbon nanotube/halloysite nanotubes mixed solution is carried out film afterwards. Finally being layered between prepreg by two layers of nano composite membrane compression molding prepares composite laminated plate, and wherein, described conventional coating method comprises uses glass stick film, with rejection film machine film, with existing coating methods such as film applicator films.
Its two:
The present invention has prepared the nano composite membrane that two kinds are applied to interlayer toughened. The halloysite nanotubes added in the preparation process of composite membrane can improve the dispersion in resin matrix of Graphene and carbon nanotube. In the process of composite membrane interlayer toughened prepreg, the matrix of composite membrane is studied, have employed the orientation technology of nanoparticle so that Graphene and carbon nanotube well can disperse in composite membrane. Meanwhile, composite membrane matrix is being carried out resin control technique so that two layers of different composite film are adding between prepreg, and the composite material interface place prepared can not be separated, and has good consistency with prepreg matrix. Composite membrane prepared by the method can reach 6 months storage period, is applicable to scientific research and industrial production. Send elsewhere and bright improve Graphene and the problem of carbon nanotube dispersed difference, increased substantially composite material interface performance. Apply the present invention to business-like 977-2/HTS prepreg and prepare laminated wood, obtain composite laminated plate interlaminar shear strength, flexural strength, modulus in flexure and laminated wood I type fracture toughness property and more only adopt one layer of composite film material to compare all raisings more than 20%.
The inventive method is simple, and raw materials cost is low, and the carbon-fibre composite toughness of preparation is significantly increased, and has good market outlook.
Embodiment:
By following examples, the present invention is described in detail. Non-specified otherwise, the reagent in embodiment is analytical pure, wherein:
The Graphene of surface grafting quadrol, the carbon nanotube of surface grafting diethyl toluene diamine are bought by Nanjing Xian Feng nano material Science and Technology Ltd.;
Halloysite nanotubes is bought by Qingdao, Shandong Yuan Xin nanosecond science and technology company limited.
Carbon fiber prepreg is provided by Cytec company of the U.S., trade mark 977-2/HTS.
Embodiment 1
For an active Graphene halloysite nanotubes composite membrane for prepreg interlayer toughened, described composite membrane is composited according to following step by Graphene, halloysite nanotubes, and concrete preparation method is as follows:
A) halloysite nanotubes 10g and concentration 1mol/L hydrochloric acid 300ml will be bought and react 24h, leave standstill 1 day. Outwelling supernatant liquor, distilled water centrifugal treating is to PH=6.0, and dries when being in 60 DEG C, and grinding, obtains powder I.
B) adding the 1mol/L sodium chloride solution of 300ml in powder I, stir 48h, then by distilled water centrifugal treating until not chloride ion-containing (checking with Silver Nitrate), dry under 105 DEG C of conditions, grinding, obtains powder II.
C) getting 5g powder II and add 250ml, 0.014mol/L cetyl trimethylammonium bromide, 12h is stirred in 60 DEG C of oil baths, and ethanol is centrifugal, 90 DEG C of oven dry, and grinding, obtains the halloysite nanotubes of modified grafting long chain polymer.
D) get amination Graphene 1g, and mix with 8g benzyl glycidyl ether, mechanical stirring 3h, obtain mixed solution I.
E) adding in planetary ball mill by mixed solution I, under nitrogen protection ball milling 1h, rotational speed of ball-mill is 300r/min, obtains mixed solution II.
Oil bath 1h when f) mixed solution II being placed in 150 DEG C, normal temperature leaves standstill 24h subsequently, obtains active Graphene mixed solution.
G) halloysite nanotubes getting the modified grafting long chain polymer of 1g adds in active Graphene mixed solution, obtains mixed solution III. Completely mixing after mixed solution III is heated to 90 DEG C, and when 90 DEG C mechanical stirring, obtain mixed solution IV.
H) mixed solution IV be placed under 60W ultrasonic power supersound process 2h, and normal temperature leaves standstill 4h afterwards, the active Graphene halloysite nanotubes mixed solution obtained.
I) activity Graphene halloysite nanotubes mixed solution being carried out film on tetrafluoroethylene flat board, coating thickness is 80 ��m, and normal temperature leaves standstill, and obtains Graphene halloysite nanotubes laminated film.
For carbon nanotube/halloysite nanotubes composite membrane of prepreg interlayer toughened, described composite membrane is composited according to following step by carbon nanotube, halloysite nanotubes, and concrete preparation method is as follows:
A) get amination carbon nanotube 1g, and mix with 8g benzyl glycidyl ether, mechanical stirring 2h, obtain mixed solution I.
B) adding in planetary ball mill by mixed solution I, under nitrogen protection ball milling 4h, rotational speed of ball-mill is 300r/min, obtains mixed solution II.
Oil bath 1h when c) mixed solution II being placed in 150 DEG C, normal temperature leaves standstill 24h subsequently, obtains activated carbon nanotube mixed solution.
D) the halloysite nanotubes finished product getting the modified grafting long chain polymer of 1g joins in 9g activated carbon nanotube mixed solution, fully mixes, and mixed solution is heated to 90 DEG C, and the mechanical stirring when 90 DEG C, obtains mixed solution III.
E) mixed solution III be placed under 60W ultrasonic power supersound process 3h, and normal temperature leaves standstill 4h afterwards, the activated carbon obtained nanotube/halloysite nanotubes mixed solution.
F) activated carbon nanotube/halloysite nanotubes mixed solution being carried out film on tetrafluoroethylene flat board, coating thickness is 80 ��m, and normal temperature leaves standstill, and obtains graphene carbon nanotube composite film.
A kind of high-modulus high tenacity macromolecular material, adopt compression molding that the carbon fiber prepreg film of 16 layers of 0.13mm, 1 layer of active Graphene/halloysite nanotubes laminated film and 1 layer of activated carbon nanotube/halloysite nanotubes laminated film are pressed into the unidirectional composite material laminated wood that thickness is 2mm, wherein, ply stacking-sequence is from top to bottom: 8 layers of carbon fiber prepreg, 1 layer of active Graphene/halloysite nanotubes laminated film, 1 layer of activated carbon nanotube/halloysite nanotubes laminated film is finally 8 layers of carbon fiber prepreg. Above-mentioned prepreg is placed in mould after completing by laying, it may also be useful to compression molding instrument is cured shaping according to the original curing process of carbon fiber prepreg, obtains the carbon-fibre composite of graphene/carbon nano-tube/halloysite nanotubes coordination plasticizing.
Comparative example 1: a kind of carbon fiber prepreg material, adopt compression molding that active to the carbon fiber prepreg of 16 layers of 0.13mm and 1 layer Graphene halloysite nanotubes laminated film is pressed into the unidirectional composite material laminated wood that thickness is 2mm, wherein, ply stacking-sequence is from top to bottom: 8 layers of carbon fiber prepreg film, 1 layer of active Graphene halloysite nanotubes laminated film is finally 8 layers of carbon fiber prepreg film. Above-mentioned prepreg is placed in mould after completing by laying, it may also be useful to compression molding instrument is cured shaping according to the original curing process of carbon fiber prepreg, obtains carbon-fibre composite I.
Comparative example 2: a kind of carbon fiber prepreg material, adopt compression molding that the carbon fiber prepreg of 16 layers of 0.13mm and 1 layer of activated carbon nanotube/halloysite nanotubes laminated film are pressed into the unidirectional composite material laminated wood that thickness is 2mm, wherein, ply stacking-sequence is from top to bottom: 8 layers of carbon fiber prepreg, 1 layer of active stone carbon nanotube/halloysite nanotubes laminated film is finally 8 layers of carbon fiber prepreg film. Above-mentioned prepreg is placed in mould after completing by laying, it may also be useful to compression molding instrument is cured shaping according to the original curing process of carbon fiber prepreg, obtains carbon-fibre composite II.
Embodiment 2
For active Graphene/halloysite nanotubes composite membrane of prepreg interlayer toughened, described composite membrane is composited according to following step by Graphene, halloysite nanotubes, and concrete preparation method is as follows:
K) halloysite nanotubes 10g and concentration 1mol/L hydrochloric acid 300ml will be bought and react 24h, leave standstill 1 day. Outwelling supernatant liquor, distilled water centrifugal treating is to PH=6.0, and dries when being in 60 DEG C, and grinding, obtains powder I.
L) adding the 1mol/L sodium chloride solution of 300ml in powder I, stir 48h, then by distilled water centrifugal treating until not chloride ion-containing (checking with Silver Nitrate), dry under 105 DEG C of conditions, grinding, obtains powder II.
M) getting 5g powder II and add 250ml, 0.014mol/L cetyl trimethylammonium bromide, 12h is stirred in 60 DEG C of oil baths, and ethanol is centrifugal, 90 DEG C of oven dry, and grinding, obtains the halloysite nanotubes of modified grafting long chain polymer.
N) get amination Graphene 1.5g, and mix with 7g benzyl glycidyl ether, mechanical stirring 2h, obtain mixed solution I.
O) adding in planetary ball mill by mixed solution I, under nitrogen protection ball milling 0.5h, rotational speed of ball-mill is 200r/min, obtains mixed solution II.
Oil bath 1h when p) mixed solution II being placed in 150 DEG C, normal temperature leaves standstill 5h subsequently, obtains active Graphene mixed solution.
Q) halloysite nanotubes getting the modified grafting long chain polymer of 1.5g adds in the active Graphene mixed solution of above-mentioned 8.5g, obtains mixed solution III. Completely mixing after mixed solution III is heated to 90 DEG C, and when 90 DEG C mechanical stirring, obtain mixed solution IV.
R) mixed solution IV be placed under 60W ultrasonic power supersound process 2h, and normal temperature leaves standstill 4h afterwards, the active Graphene halloysite nanotubes mixed solution obtained.
S) by activity Graphene halloysite nanotubes mixed solution film applicator film, coating thickness is 50 ��m, and normal temperature leaves standstill, and obtains Graphene/halloysite nanotubes laminated film.
For carbon nanotube/halloysite nanotubes composite membrane of prepreg interlayer toughened, described composite membrane is composited according to following step by carbon nanotube, halloysite nanotubes, and concrete preparation method is as follows:
G) get amination carbon nanotube 1.5g, and mix with 7g benzyl glycidyl ether, mechanical stirring 2h, obtain mixed solution I.
H) adding in planetary ball mill by mixed solution I, under nitrogen protection ball milling 0.5h, rotational speed of ball-mill is 200r/min, obtains mixed solution II.
Oil bath 1h when i) mixed solution II being placed in 150 DEG C, normal temperature leaves standstill 5h subsequently, obtains activated carbon nanotube mixed solution.
J) the halloysite nanotubes finished product getting the modified grafting long chain polymer of 1.5g joins in 8.5g activated carbon nanotube mixed solution, fully mixes, and mixed solution is heated to 90 DEG C, and the mechanical stirring when 90 DEG C, obtains mixed solution III.
K) mixed solution III be placed under 60W ultrasonic power supersound process 2h, and normal temperature leaves standstill 1h afterwards, the activated carbon obtained nanotube/halloysite nanotubes mixed solution.
L) by activated carbon nanotube/halloysite nanotubes mixed solution film applicator film, coating thickness is 50 ��m, and normal temperature leaves standstill, and obtains carbon nanotube/halloysite nanotubes laminated film.
A kind of high-modulus high tenacity macromolecular material, adopt compression molding that the carbon fiber prepreg of 16 layers of 0.15mm, 1 layer of active Graphene/halloysite nanotubes laminated film and 1 layer of activated carbon nanotube/halloysite nanotubes laminated film are pressed into the unidirectional composite material laminated wood that thickness is 2.4mm, wherein, ply stacking-sequence is from top to bottom: 8 layers of carbon fiber prepreg, 1 layer of active Graphene/halloysite nanotubes laminated film, 1 layer of activated carbon nanotube/halloysite nanotubes laminated film is finally 8 layers of carbon fiber prepreg. Above-mentioned prepreg is placed in mould after completing by laying, use compression molding instrument to be cured shaping according to the original curing process of carbon fiber prepreg, obtain Graphene/halloysite nanotubes and the carbon-fibre composite of carbon nanotube/halloysite nanotubes coordination plasticizing.
Embodiment 3
For active Graphene/halloysite nanotubes composite membrane of prepreg interlayer toughened, described composite membrane is composited according to following step by Graphene, halloysite nanotubes, and concrete preparation method is as follows:
A) halloysite nanotubes 10g and concentration 1mol/L hydrochloric acid 300ml will be bought and react 24h, leave standstill 1 day. Outwelling supernatant liquor, distilled water centrifugal treating is to PH=6.0, and dries when being in 60 DEG C, and grinding, obtains powder I.
B) adding the 1mol/L sodium chloride solution of 300ml in powder I, stir 48h, then by distilled water centrifugal treating until not chloride ion-containing (checking with Silver Nitrate), dry under 105 DEG C of conditions, grinding, obtains powder II.
C) getting 5g powder II and add 250ml, 0.014mol/L cetyl trimethylammonium bromide, 12h is stirred in 60 DEG C of oil baths, and ethanol is centrifugal, 90 DEG C of oven dry, and grinding, obtains the halloysite nanotubes of modified grafting long chain polymer.
D) get amination Graphene 1.25g, and mix with 7.5g benzyl glycidyl ether, mechanical stirring 2.5h, obtain mixed solution I.
E) adding in planetary ball mill by mixed solution I, under nitrogen protection ball milling 2h, rotational speed of ball-mill is 280r/min, obtains mixed solution II.
Oil bath 1h when f) mixed solution II being placed in 155 DEG C, normal temperature leaves standstill 10h subsequently, obtains active Graphene mixed solution.
G) halloysite nanotubes getting the modified grafting long chain polymer of 1.25g adds in active Graphene mixed solution, obtains mixed solution III. Completely mixing after mixed solution III is heated to 95 DEG C, and when 95 DEG C mechanical stirring, obtain mixed solution IV.
H) mixed solution IV be placed under 60W ultrasonic power supersound process 2h, and normal temperature leaves standstill 4h afterwards, the active Graphene/halloysite nanotubes mixed solution obtained.
I) activity Graphene halloysite nanotubes mixed solution being adopted glass stick coating method film, coating thickness is 60 ��m, and normal temperature leaves standstill, and obtains Graphene/halloysite nanotubes laminated film.
For carbon nanotube/halloysite nanotubes composite membrane of prepreg interlayer toughened, described composite membrane is composited according to following step by carbon nanotube, halloysite nanotubes, and concrete preparation method is as follows:
A) get amination carbon nanotube 1.25g, and mix with 7.5g benzyl glycidyl ether, mechanical stirring 2.5h, obtain mixed solution I.
B) adding in planetary ball mill by mixed solution I, under nitrogen protection ball milling 2h, rotational speed of ball-mill is 280r/min, obtains mixed solution II.
Oil bath 1h when c) mixed solution II being placed in 155 DEG C, normal temperature leaves standstill 10h subsequently, obtains activated carbon nanotube mixed solution.
D) the halloysite nanotubes finished product getting the modified grafting long chain polymer of 1.25g joins in activated carbon nanotube mixed solution, fully mixes, and mixed solution is heated to 95 DEG C, and the mechanical stirring when 95 DEG C, obtains mixed solution III.
E) mixed solution III be placed under 60W ultrasonic power supersound process 2.5h, and normal temperature leaves standstill 2h afterwards, the activated carbon obtained nanotube/halloysite nanotubes mixed solution.
F) activated carbon nanotube/halloysite nanotubes mixed solution being adopted glass stick coating method film, coating thickness is 60 ��m, and normal temperature leaves standstill, and obtains graphene carbon nanotube composite film.
A kind of high-modulus high tenacity macromolecular material, adopt compression molding that the carbon fiber prepreg film of 20 layers of 0.15mm, 1 layer of active Graphene/halloysite nanotubes laminated film and 1 layer of activated carbon nanotube/halloysite nanotubes laminated film are pressed into the unidirectional composite material laminated wood that thickness is 3.0mm, wherein, ply stacking-sequence is from top to bottom: 10 layers of carbon fiber prepreg, 1 layer of active Graphene/halloysite nanotubes laminated film, 1 layer of activated carbon nanotube/halloysite nanotubes laminated film is finally 10 layers of carbon fiber prepreg. Above-mentioned prepreg is placed in mould after completing by laying, use compression molding instrument to be cured shaping according to the original curing process of carbon fiber prepreg, obtain Graphene/halloysite nanotubes and the carbon-fibre composite of carbon nanotube/halloysite nanotubes coordination plasticizing.
Embodiment 4
For active Graphene/halloysite nanotubes composite membrane of prepreg interlayer toughened, described composite membrane is composited according to following step by Graphene, halloysite nanotubes, and concrete preparation method is as follows:
A) halloysite nanotubes 10g and concentration 1mol/L hydrochloric acid 300ml will be bought and react 24h, leave standstill 1 day. Outwelling supernatant liquor, distilled water centrifugal treating is to PH=6.0, and dries when being in 60 DEG C, and grinding, obtains powder I.
B) adding the 1mol/L sodium chloride solution of 300ml in powder I, stir 48h, then by distilled water centrifugal treating until not chloride ion-containing (checking with Silver Nitrate), dry under 105 DEG C of conditions, grinding, obtains powder II.
C) getting 5g powder II and add 250ml, 0.014mol/L cetyl trimethylammonium bromide, 12h is stirred in 60 DEG C of oil baths, and ethanol is centrifugal, 90 DEG C of oven dry, and grinding, obtains the halloysite nanotubes of modified grafting long chain polymer.
D) get amination Graphene 1g, and mix with 7.5g benzyl glycidyl ether, mechanical stirring 2h, obtain mixed solution I.
E) adding in planetary ball mill by mixed solution I, under nitrogen protection ball milling 3h, rotational speed of ball-mill is 240r/min, obtains mixed solution II.
Oil bath 1h when f) mixed solution II being placed in 145 DEG C, normal temperature leaves standstill 20h subsequently, obtains active Graphene mixed solution.
G) halloysite nanotubes getting the modified grafting long chain polymer of 1.5g adds in active Graphene mixed solution, obtains mixed solution III. Completely mixing after mixed solution III is heated to 85 DEG C, and when 85 DEG C mechanical stirring, obtain mixed solution IV.
H) mixed solution IV be placed under 60W ultrasonic power supersound process 2h, and normal temperature leaves standstill 4h afterwards, the active Graphene/halloysite nanotubes mixed solution obtained.
I) by activity Graphene halloysite nanotubes mixed solution rejection film machine film, coating thickness is 70 ��m, and normal temperature leaves standstill, and obtains Graphene/halloysite nanotubes laminated film.
For carbon nanotube/halloysite nanotubes composite membrane of prepreg interlayer toughened, described composite membrane is composited according to following step by carbon nanotube, halloysite nanotubes, and concrete preparation method is as follows:
A) get amination carbon nanotube 1g, and mix with 7.5g benzyl glycidyl ether, mechanical stirring 2h, obtain mixed solution I.
B) adding in planetary ball mill by mixed solution I, under nitrogen protection ball milling 3h, rotational speed of ball-mill is 240r/min, obtains mixed solution II.
Oil bath 1h when c) mixed solution II being placed in 145 DEG C, normal temperature leaves standstill 20h subsequently, obtains activated carbon nanotube mixed solution.
D) the halloysite nanotubes finished product getting the modified grafting long chain polymer of 1.5g joins in 8.5g activated carbon nanotube mixed solution, fully mixes, and mixed solution is heated to 85 DEG C, and the mechanical stirring when 85 DEG C, obtains mixed solution III.
E) mixed solution III be placed under 60W ultrasonic power supersound process 3h, and normal temperature leaves standstill 2h afterwards, the activated carbon obtained nanotube/halloysite nanotubes mixed solution.
F) by activated carbon nanotube/halloysite nanotubes mixed solution rejection film machine film, coating thickness is 70 ��m, and normal temperature leaves standstill, and obtains carbon nanotube/halloysite nanotubes laminated film.
A kind of high-modulus high tenacity macromolecular material, adopt compression molding that the carbon fiber prepreg film of 18 layers of 0.15mm, 1 layer of active Graphene/halloysite nanotubes laminated film and 1 layer of activated carbon nanotube/halloysite nanotubes laminated film are pressed into the unidirectional composite material laminated wood that thickness is 2.7mm, wherein, ply stacking-sequence is from top to bottom: 9 layers of carbon fiber prepreg, 1 layer of active Graphene/halloysite nanotubes laminated film, 1 layer of activated carbon nanotube/halloysite nanotubes laminated film is finally 9 layers of carbon fiber prepreg. Above-mentioned prepreg is placed in mould after completing by laying, it may also be useful to compression molding instrument is cured shaping according to the original curing process of carbon fiber prepreg, obtains the carbon-fibre composite of graphene/carbon nano-tube/halloysite nanotubes coordination plasticizing.
The performance index of matrix material have been detected by applicant, wherein, the Interlaminar shear strengths (ILSS) of matrix material carries out test according to JC/T773-2010 and obtains, and bending property carries out test according to GB/T1446-1983 and obtains, laminated wood I mode �� fracture toughness (G��c) carry out test according to ASTMD5528 and obtain.
The mechanical property of the Graphene that embodiment 1��4 prepares/halloysite nanotubes film and carbon nanotube/halloysite nanotubes film coordination plasticizing carbon-fibre composite is such as following table:
The mechanical property of the carbon-fibre composite that comparative example 1��2 prepares is such as following table:

Claims (8)

1. one kind nanometer increases tough carbon-fibre composite, it is characterized in that: described carbon-fibre composite by 16��20 layers of prepreg, 1 layer of active Graphene/halloysite nanotubes laminated film with 1 layer activated carbon nanotube/halloysite nanotubes laminated film molded curing is shaping and becomes;
Wherein, described active Graphene/halloysite nanotubes laminated film is by 10��15% amination Graphenes, and the halloysite nanotubes of the benzyl glycidyl ether of 70��80% and 10��15% modified grafting long chain polymers is made; Described activated carbon nanotube/halloysite nanotubes laminated film is made up of the halloysite nanotubes of the carbon nanotube of 10��15% and the benzyl glycidyl ether of 70��80% and 10��15% modified grafting long chain polymers.
2. carbon-fibre composite according to claim 1, it is characterized in that: the thickness of described carbon-fibre composite is: 2��3mm, described active Graphene/halloysite nanotubes laminated film thickness is 50��80 ��m, the thickness of activated carbon nanotube/halloysite nanotubes laminated film is 50��80 ��m.
3. carbon-fibre composite according to claim 1, it is characterized in that: the ply stacking-sequence of described carbon-fibre composite is respectively from top to bottom: 8��10 layers of prepreg, 1 layer of active Graphene/halloysite nanotubes laminated film and 1 layer of activated carbon nanotube/halloysite nanotubes laminated film and 8��10 layers of prepreg.
4. the preparation method of a carbon-fibre composite, it is characterized in that: described carbon-fibre composite adopts compression molding preparation, specifically the carbon fiber prepreg of 0.09��0.17mm, 50��80 ��m of active Graphene/halloysite nanotubes laminated films and 50��80 ��m of activated carbon nanotube/halloysite nanotubes laminated film layings are placed in compression molding instrument, it is cured shaping according to the curing process of carbon fiber prepreg, finally it is pressed into the unidirectional composite material laminated wood that thickness is 2��3mm.
5. the preparation method of carbon-fibre composite according to claim 4, it is characterised in that: the preparation method of described active Graphene/halloysite nanotubes laminated film comprises the steps:
A) adding in hydrochloric acid soln by halloysite nanotubes, take off a layer turbid solution, adding distil water centrifugal treating, taking precipitate is dried, and grinding, obtains powder I;
B) adding sodium chloride solution in powder I, stir, distilled water centrifugal treating, dry under 105 DEG C of conditions, grinding, obtains powder II;
C) adding cetyl trimethylammonium bromide in powder II, 60 DEG C of oil baths are stirred, and ethanol is centrifugal, 90 DEG C of oven dry, and grinding, obtains the halloysite nanotubes of modified grafting long chain polymer;
D) amination Graphene is mixed in benzyl glycidyl ether, mechanical stirring, obtain mixed solution I;
E) mixed solution I is added in ball mill, under nitrogen protection ball milling, obtain mixed solution II;
Oil bath when f) mixed solution II being placed in 150 �� 5 DEG C, then normal temperature leaves standstill, and obtains active Graphene mixed solution;
G) in active Graphene mixed solution, add the halloysite nanotubes of modified grafting long chain polymer, obtain mixed solution III;
H) completely mixing after mixed solution III is heated to 90 �� 5 DEG C, and when 90 �� 5 DEG C mechanical stirring, obtain mixed solution IV;
I) by mixed solution IV supersound process under 60W ultrasonic power, active Graphene/halloysite nanotubes mixed solution that normal temperature obtains after leaving standstill;
J) by activity Graphene/halloysite nanotubes mixed solution film, then normal temperature leaves standstill, and obtains Graphene/halloysite nanotubes laminated film.
6. the preparation method of carbon-fibre composite according to claim 4, it is characterised in that: the preparation method of described activated carbon nanotube/halloysite nanotubes laminated film comprises the steps:
A) amination carbon nanotube is joined in benzyl glycidyl ether, stir, obtain mixed solution 1.;
B) 1. mixed solution is added in ball mill, under nitrogen protection ball milling, obtain mixed solution 2.;
C) by the mixed solution 2. oil bath when 150 �� 5 DEG C, then normal temperature leaves standstill, and obtains activated carbon nanotube mixed solution;
D) being added in activated carbon nanotube mixed solution by the halloysite nanotubes finished product of modified grafting long chain polymer, and be heated to 90 �� 5 DEG C, 3. the mechanical stirring when 90 �� 5 DEG C, obtain mixed solution;
3. e) mixed solution be placed under 60W ultrasonic power supersound process, and then normal temperature leaves standstill, the activated carbon nanotube/halloysite nanotubes mixed solution obtained;
F) by activated carbon nanotube/halloysite nanotubes mixed solution film, then normal temperature leaves standstill, and obtains carbon nanotube/halloysite nanotubes laminated film.
7. the preparation method of a kind of carbon-fibre composite according to claim 5 or 6, it is characterised in that, the condition of described ball milling is: rotational speed of ball-mill 200��500r/min, needs interval 5min, the ball milling time 0.5��4h after continuous ball milling 10min.
8. the preparation method of a kind of carbon-fibre composite according to claim 5 or 6, it is characterised in that, the method for described film comprises: use glass stick film, with rejection film machine film, uses film applicator film.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107200491A (en) * 2017-05-31 2017-09-26 福建江夏学院 Concrete toughness reinforcing modified galapectite and preparation method thereof
CN107416816A (en) * 2017-08-15 2017-12-01 湖南七纬科技有限公司 A kind of multifilament toughened graphite alkene and preparation method thereof
CN107509380A (en) * 2017-09-13 2017-12-22 苏州南尔材料科技有限公司 A kind of preparation method of environmental-protecting electromagnetic shielding composite

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CN104553177A (en) * 2014-12-15 2015-04-29 中航复合材料有限责任公司 Flame-retardant modified carbon fiber prepreg and composite material product

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CN104553177A (en) * 2014-12-15 2015-04-29 中航复合材料有限责任公司 Flame-retardant modified carbon fiber prepreg and composite material product

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107200491A (en) * 2017-05-31 2017-09-26 福建江夏学院 Concrete toughness reinforcing modified galapectite and preparation method thereof
CN107416816A (en) * 2017-08-15 2017-12-01 湖南七纬科技有限公司 A kind of multifilament toughened graphite alkene and preparation method thereof
CN107509380A (en) * 2017-09-13 2017-12-22 苏州南尔材料科技有限公司 A kind of preparation method of environmental-protecting electromagnetic shielding composite

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