CN103626997A - High-interface-bonding-firmness carbon fiber/carbon nanotube composite material and preparation technique thereof - Google Patents
High-interface-bonding-firmness carbon fiber/carbon nanotube composite material and preparation technique thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of nano materials, and particularly relates to a high-interface-bonding-firmness carbon fiber/carbon nanotube composite material and a preparation technique thereof. The preparation technique comprises the following steps: carrying out carboxylation and acyl-chlorination on purified carbon nanotubes and dried carbon fibers, introducing diamines or polyamines with characteristic structure so as to connect abundant diamines or polyamines onto the surfaces of the carbon nanotubes and carbon fibers, carrying out addition reaction on the carbon nanotubes and a bismaleimide resin to obtain a carbon-nanotube-containing bismaleimide resin linear block polymer, and compounding the block polymer used as a base with the carbon fibers in a certain mode to finally form a multidimensional hybrid composite material structure connected by covalent bonds. The strength and toughness of the carbon nanotubes are utilized to strengthen the bismaleimide and enhance the bonding strength with the carbon fiber base surface, thereby enhancing the overall performance of the carbon fiber/carbon nanotube/bismaleimide resin multidimensional hybrid composite material.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of interface bond firmly carbon fiber/carbon nano tube compound material and preparation technology thereof.
Background technology
Matrix material is the important component part of field of new, compares with traditional material, and it is strong that matrix material has designability, and specific tenacity, specific modulus are high, and fatigue crack-resistant performance is good, a series of high-performances such as structure-function integration.Matrix material, as being difficult to alternative functional materials and structured material, is development modern industry, national defence and scientific and technical indispensable base mateiral, is also the important substance basis that new technology revolution is rely and developed, and has become the important leading material of field of new.
The evolution of advanced composite material matrix resin from epoxy resin, thermoplastic resin, isocyanate resin (CE) to bimaleimide resin (BMI), polyimide resin (PI).
Bismaleimides (BMI) is to take the bifunctional compound that maleimide (MI) is active end group.Bismaleimides (BMI) resin has the anti-fatigue performance under better thermostability, dimensional stability and high humid and warm environment than epoxy resin, there is good Molecular Structure Design, simultaneously radiation hardness, low temperature resistant and building-up properties, flame retardant resistance, electrical insulating property are also relatively good, condition of cure is similar to epoxy-resin systems, is difficult for producing pore during moulding.As composite matrix resin, in recent years, paid attention to widely, be widely used in the high-tech areas such as aerospace, mechano-electronic, printed circuit board (PCB).But the bismaleimides solidification value after curing cross-linked is high, and cured article cross-linking density is higher, toughness is not enough, and fragility is larger, has limited its range of application.Therefore, need in actual applications it to carry out modification.
Since carbon nanotube (CNTs) was found by Japanese scientist from 1991, with its distinctive mechanical property, electric property, thermal property and chemical property, caused countries in the world chemistry, physics, the personage's of material educational circles very big concern, in scientific basic research and applied research, gained great popularity.Although carbon nanotube has potential application prospect in preparing light weight, high strength composite, it really be come true, also have many problems to need to solve.The surface of carbon nanotube can be higher, easily reunites, and it is difficult in polymkeric substance dispersed.How dispersed carbon nanotube and strengthen carbon nanotube and body material interface between keying action, be the key that improves matrix material properties.The excellent properties of carbon-fibre composite has obtained widespread use in every profession and trade.The comparable Carbon Fiber/Epoxy Composite of working temperature of carbon fiber/bismaleimides (BMI) matrix material improves more than 50 degrees Celsius, and this matrix material that aerospace industry is used is very important.Can utilize carbon fiber and the carbon nanotube mechanical property modified bismaleimide resin of excellence separately, prepare carbon fiber/carbon nanotube/bimaleimide resin multi-dimensional hybrid composite, the prospect that can predict hybrid composite material of carbon fibers/carbon nanotubes/bismaleimide resin will be boundless.
Summary of the invention
The object of the present invention is to provide a kind of good dispersity, the interface firmly preparation method of hybrid composite material of carbon fibers/carbon nanotubes/bismaleimide resin that bonds.
The preparation method of the hybrid composite material of carbon fibers/carbon nanotubes/bismaleimide resin that the present invention proposes, by carbon nano tube surface purifying, to the carbon nano tube surface of purifying, carry out carboxylated, after chloride, introducing has the diamine of feature structure, obtain the graft type carbon nanotube that surface has active amino, on surface, have on the graft type carbon nanotube of quantitative active amino and carry out with bimaleimide resin the hybrid composite that Michael addition reaction generates the linear block polymer of carbon fiber-containing and carbon nanotube again, carbon fiber and carbon nano tube surface will be wound with a large amount of polymkeric substance.
Its concrete steps are as follows:
(1) take 1g～1 * 10
2the carbon nanotube that g is dry and 10g～1 * 10
3g organic acid mixes, in 10～150kHz ultrasonic wave or 10r/min～10
6under the rotating speed of r/min, process 1～100 hour, be then heated to 10～200 ℃, react 1～60 hour, with microfiltration membrane suction filtration, repetitive scrubbing is to neutral, and at 20～180 ℃ of temperature, vacuum-drying is 1～60 hour, obtains the carbon nanotube of purifying;
(2) by 1～1 * 10
2the carbon fiber that g is dry, step obtain purifying carbon nano-tube 1g～1 * 10 in (1)
2g respectively with acid with strong oxidizing property 1～1 * 10
4mL mixes, under 1～150kHz ultrasonic wave, process 1～100 hour, then be heated to 15～150 ℃, stirring back flow reaction 1～100 hour, ultramicropore filter membrane suction filtration, it is neutral that repetitive scrubbing to solution is, and at 15～250 ℃ of temperature, vacuum-drying is 1～60 hour, obtains respectively carbon fiber and the carbon nanotube of acidifying;
(3) add carbon fiber and carbon nanotube 1g～1 * 10 of step (2) gained acidifying
2g respectively with acylating reagent 1～1 * 10
4mL, after 0.5～15 hour, is heated to 15～250 ℃ with 1～150kHz ultrasonication, stirring back flow reaction 1～100 hour, and suction filtration repetitive scrubbing are removed acylating reagent, obtain respectively carbon fiber and the carbon nanotube of acylations;
(4) add step (3) gained acidylate carbon fiber and carbon nanotube 1g～1 * 10
2g respectively with diamine or polyamine 10g～1 * 10
4g, with 1～150kHz ultrasonication 1～120 hour, then at 15～250 ℃ of temperature, react 1～100 hour suction filtration repetitive scrubbing, at 20～200 ℃ of temperature, vacuum-drying is 1～60 hour, obtains respectively surface with graft type carbon fiber and the carbon nanotube of active amino;
(5) add step (4) gained surface with the carbon nanotube 1～1 * 10 of active amino
2g and bismaleimides 10～1 * 10
4g, is warming up to after resin matrix melting, and dispersed with stirring bubble removing evenly and under vacuum condition carries out Michael addition reaction simultaneously, obtains the bimaleimide resin linear block polymer that contains carbon nanotube;
(6) add the resulting bimaleimide resin linear block polymer that contains carbon nanotube of step (5) as matrix, and step (4) is resulting with amino graft type carbon fiber reaction, froth in vacuum, obtains carbon fiber-containing/carbon nanotube/span and carrys out amide resins hybrid composite.
In the present invention, carbon nanotube described in step (1) is any single wall of preparing, double-walled or the multi-walled carbon nano-tubes in arc-over, chemical gaseous phase deposition, template, sun power method and laser evaporation method.
In the present invention, organic acid described in step (1) is the nitric acid of 1～50% weight acid concentration, any or its mixed solution in the hydrochloric acid of the sulfuric acid of 1～60% weight acid concentration or 1～60% weight acid concentration.
In the present invention, acid with strong oxidizing property described in step (2) be in 0.5～75% weight acid concentration nitric acid, 3～100% weight acid concentration sulfuric acid, 1/100～100/1 mol ratio potassium permanganate and sulfuric acid mixed solution, 1/100～100/1 mol ratio nitric acid and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and nitric acid mixing solutions, 1/100～100/1 mol ratio hydrogen peroxide and sulfuric acid mixture liquid, 1/100～100/1 mol ratio hydrogen peroxide and hydrochloric acid mixed solution any.
In the present invention, acyl chlorinating agent described in step (3) be in thionyl chloride, phosphorus trichloride or phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide or thionyl bromide any.
In the present invention, diamine described in step (4) be quadrol, polyethyene diamine, hexanediamine, Ursol D, mphenylenediamine, m-xylene diamine, diaminodiphenyl-methane, the Meng alkane diamines, divinyl propylamine, diaminodiphenyl-methane, chlorination hexanediamine, chlorination nonamethylene diamine, chlorination decamethylene diamine, 12 carbon diamines or 13 carbon diamines in any; Described polyamine be in fourth triamine, Dyhard RU 100, adipic dihydrazide, tetraethylene pentamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines or six ethene seven amine any.
In the present invention, in step (2), the quantitative analysis of carboxyl-content in the carbon nanotube of acidifying and carbon fiber, can adopt TGA, XPS or nuclear magnetic resonance method.
In the present invention, the surface obtaining described in step (4) is with graft type carbon nanotube and the carbon fiber of active amino, and its amino is diamine or polyamine.
In the present invention, bismaleimides described in step (5) adopt ditane type bismaleimides, diphenyl ether type bismaleimides, alkyl type bismaleimides, to penylene type bismaleimides, a penylene type bismaleimides or connect arbitrary in hexichol type bismaleimides in.
In the present invention, the linear block polymer of the carbon nanotube obtaining described in step (5), is the linear block polymer of carbon nanotube that is connected to the block polymer of bismaleimides on amidized carbon nanotube.
In the present invention, carbon fiber described in step (6) is any in unidirectional macrofiber or random staple fibre.
Preparation method provided by the invention is simple, gained be the carbon fiber multi-dimensional hybrid mixture that surface is connected to bismaleimides/carbon nanotube.The amino of carbon nano tube surface is by producing Michael addition reaction with bimaleimide resin, make carbon nanotube become a part for bismaleimide resin system, again by reacting with the carbon fiber of surface amination, froth in vacuum, obtains carbon fiber-containing/carbon nanotube/span and carrys out amide resins multi-dimensional hybrid composite.Due to the effect of carbon nano-tube modification bimaleimide resin, increased the boundary strength between matrix resin and carbon cloth, make matrix material there is good interlaminar shear strength.
The present invention introduces diamine or the polyamine with feature structure at carbon nanotube and carbon fiber surface, utilize this structure and bismaleimides to carry out Michael addition reaction, carbon nanotube and carbon fiber surface will be wound with a large amount of polymkeric substance, because polymkeric substance has the characteristic of avidity and carbon nanotube itself to matrix resin, thereby improve the shortcoming of the interlaminar shear strength deficiency etc. of carbon fiber, this multi-dimensional hybrid mixture has the multiple performances such as interface bonding is firm, strength and toughness is good, easily solidify, and the comprehensive mechanical property of matrix material is obviously carried.
Embodiment
The following examples are to further illustrate of the present invention.
Embodiment 1:
Take the standby multi-walled carbon nano-tubes of chemical gaseous phase deposition legal system (OD<8nm) and carbon fiber is initial raw material, multi-walled carbon nano-tubes is through purifying, respectively carbon nanotube and carbon fiber are carried out to acidifying, chloride, after amination, carbon nanotube and a penylene bismaleimides are carried out to Michael addition reaction, obtain surface and be connected to a multi-walled carbon nano-tubes for penylene bismaleimides, again that itself and amidized carbon cloth is compound in a certain way, obtain carbon fiber-containing/carbon nanotube/span and carry out amide resins multi-dimensional hybrid composite.
Step (1): in the mono-neck round-bottomed flask of the 250mL that agitator is housed, add the multi-walled carbon nano-tubes raw material of 1.1g drying and 100mL, 30% salpeter solution, under 100kHz ultrasonic wave, process 20 hours, then be heated to 30 ℃, reacting 40 hours, is the poly-inclined to one side tetrafluoroethylene microfiltration membrane suction filtration of 0.8 μ m with aperture, with deionized water wash 4-10 time to neutrality, at 30 ℃, vacuum-drying, after 48 hours, obtains the multi-walled carbon nano-tubes of purifying;
Step (2): in two mono-neck round-bottomed flasks of 250mL that agitator has been housed, one of them enters carbon nanometer tube material 1g and the 100mL of the purifying obtaining in step (1), 50% weight concentration concentrated nitric acid, another adds carbon fiber 20g and the 100mL of drying, the 50% weight concentration vitriol oil, two flasks are processed through following the same terms: add through 1 hour post-heating to 50 ℃ of 80kHz ultrasonication, stir and reflux down and react 15 hours, with aperture, be the poly-inclined to one side tetrafluoroethylene ultra-filtration membrane suction filtrations of 1.2 μ m, with deionized water repetitive scrubbing 3-10 time to neutral, 100 ℃ of vacuum-dryings are after 48 hours, obtain respectively multi-walled carbon nano-tubes and the carbon fiber of carboxylic acid,
Step (3): in two 250mL tri-neck round-bottomed flasks that agitator has been housed, one of them adds carbon nanotube 1g and the thionyl chloride 10g of step (2) gained acidifying, another adds carbon fiber 20g and the thionyl chloride 100g of acidifying, two flasks are processed through following the same terms: use 100Hz ultrasonication after 3 hours, be heated to 100 ℃, stir and reflux down and react 80 hours, suction filtration repetitive scrubbing are removed thionyl chloride, obtain respectively multi-walled carbon nano-tubes and the carbon fiber of chloride;
Step (4): in two 250mL tri-neck round-bottomed flasks that agitator has been housed, one of them adds carbon nanotube 1g and the diaminodiphenyl-methane 10g of step (3) gained acidylate, another adds carbon fiber 20g and the diaminodiphenyl-methane 100g of acidylate, two flasks are processed through following the same terms: use 120kHz ultrasonication after 2 hours, at 200 ℃, stirring reaction is 1 hour, suction filtration is removed unreacted reactant and byproduct of reaction, repeatedly use after deionized water wash 3-10 time, 80 ℃ of vacuum-drying 24 hours, obtain respectively surface with amino multi-walled carbon nano-tubes and carbon fiber,
Step (5): in the 250mL tri-neck round-bottomed flasks of agitator are housed, add the amidized carbon nanotube 1g of step (4) and a penylene bismaleimides 20g, heat and stir, by 60kHz ultrasonication after 2 hours, at 240 ℃, react 12 hours, obtain surface and be connected to a multi-walled carbon nano-tubes for penylene bismaleimides;
Step (6): get multi-walled carbon nano-tubes mixture 20g and the amidized carbon fiber 20g of step (4) that surface is connected to a penylene bismaleimides compound in a certain way, de-bubble under vacuum condition, obtains carbon fiber-containing/carbon nanotube/span and carrys out amide resins multi-dimensional hybrid composite.
In step (2), in the carbon nanotube of acidifying and carbon fiber, the quantitative analysis of carboxyl-content adopts TGA method, show that multi-wall carbon nano-tube tube-surface carboxyl-content is 5.0%, and after processing, multi-wall carbon nano-tube tube-surface amido content is 5.0%.
Embodiment 2:
The standby double-walled carbon nano-tube of sun power legal system (OD<8nm) of take is initial raw material, double-walled carbon nano-tube is through purifying, respectively carbon nanotube and carbon fiber are carried out to acidifying, chloride, after amination, carbon nanotube and diphenyl ether type bismaleimides are carried out to Michael addition reaction, obtain the double-walled carbon nano-tube that surface is connected to diphenyl ether type bismaleimides, again that itself and amidized carbon fiber is compound in a certain way, obtain carbon fiber-containing/carbon nanotube/span and carry out amide resins multi-dimensional hybrid composite.
Step (1): in the mono-neck round-bottomed flask of the 500mL that magnetic agitation rotor is housed, add 1.1g double-walled carbon nano-tube raw material, the sulfuric acid of 100mL, 50% weight concentration, with 10
3under the rotating speed of r/min, processing 30 hours, be then heated to 150 ℃, react 50 hours, is the poly-inclined to one side tetrafluoroethylene microfiltration membrane suction filtration of 0.8 μ m with aperture, and with deionized water repetitive scrubbing, to neutral, 100 ℃ of vacuum-dryings, after 36 hours, obtain the carbon nanotube of purifying;
Step (2): in two mono-neck round-bottomed flasks of 500mL that magnetic agitation rotor has been housed, one of them adds carbon nanometer tube material 1g and the 200mL of the purifying obtaining in step (1), 85% concentrated sulfuric acid solution, another adds carbon fiber and the 200mL of 100g drying, 85% concentrated sulfuric acid solution, two flasks are processed through following the same terms: with 1 hour post-heating to 100 ℃ of 90kHz ultrasonication, stir and reflux down and react 75 hours, with aperture, be the poly-inclined to one side tetrafluoroethylene ultra-filtration membrane suction filtrations of 1.2 μ m, with deionized water repetitive scrubbing 3-10 time to neutral, 100 ℃ of vacuum-dryings are after 36 hours, obtain respectively carbon nanotube and the carbon fiber of carboxylic acid,
Step (3): in two 500mL tri-neck round-bottomed flasks that magnetic agitation rotor has been housed, one of them adds carbon nanotube 1g and the phosphorus pentachloride 10g of step (2) gained acidifying, another adds carbon fiber 100g and the phosphorus pentachloride 200g of acidifying, two flasks are processed through following the same terms: use 100Hz ultrasonication after 12 hours, be heated to 50 ℃, stir and reflux down and react 58 hours, suction filtration repetitive scrubbing are repeatedly removed phosphorus pentachloride, obtain respectively carbon nanotube and the carbon fiber of chloride;
Step (4): in two 500mL tri-neck round-bottomed flasks that magnetic agitation rotor has been housed, the carbon nanotube 1g and the tetraethylene pentamine 30g that add step (3) gained acidylate, two flasks are processed through following the same terms: use 3kHz ultrasonication after 80 hours, at 200 ℃, react 20 hours, suction filtration is removed unreacted reactant and byproduct of reaction, repeatedly with after deionized water wash, 200 ℃ of vacuum-drying 1 hour, obtains respectively surface with amino carbon nanotube;
Step (5): in the 500mL tri-neck round-bottomed flasks of magnetic agitation rotor are housed, add the amidized carbon nanotube 1g of step (4) and diphenyl ether type bismaleimides 50g, heat and stir, by 100kHz ultrasonication after 1 hour, at 250 ℃, react 12 hours, obtain carbon fiber and double-walled carbon nano-tube mishmash that surface is connected to diphenyl ether type bismaleimides.
Step (6): get in double-walled carbon nano-tube mixture 50g that surface is connected to diphenyl ether type bismaleimides and step (4) amidized carbon fiber 100g compound in a certain way, de-bubble under vacuum condition, obtains carbon fiber-containing/carbon nanotube/span and carrys out amide resins multi-dimensional hybrid composite.
In step (2), in the carbon nanotube of acidifying and carbon fiber, the quantitative analysis of carboxyl-content adopts nuclear magnetic resonance method, show that double-walled carbon nano-tube surface carboxyl-content is 5.5%, and after processing, multi-wall carbon nano-tube tube-surface amido content is 5.5%.
Claims (1)
1. bond firmly carbon fiber/carbon nano tube compound material and a preparation technology thereof of interface, is characterized in that preparation process is as follows:
(1) take 1g～1 * 10
2the carbon nanotube that g is dry and 10g～1 * 10
3g organic acid mixes, in 10～150kHz ultrasonic wave or 10r/min～10
6under the rotating speed of r/min, process 1～100 hour, be then heated to 10～200 ℃, react 1～60 hour, with microfiltration membrane suction filtration, repetitive scrubbing is to neutral, and at 20～180 ℃ of temperature, vacuum-drying is 1～60 hour, obtains the carbon nanotube of purifying;
(2) by 1～1 * 10
2the carbon fiber that g is dry, step obtain purifying carbon nano-tube 1g～1 * 10 in (1)
2g respectively with acid with strong oxidizing property 1～1 * 10
4mL mixes, under 1～150kHz ultrasonic wave, process 1～100 hour, then be heated to 15～150 ℃, stirring back flow reaction 1～100 hour, ultramicropore filter membrane suction filtration, it is neutral that repetitive scrubbing to solution is, and at 15～250 ℃ of temperature, vacuum-drying is 1～60 hour, obtains respectively carbon fiber and the carbon nanotube of acidifying;
(3) add carbon fiber and carbon nanotube 1g～1 * 10 of step (2) gained acidifying
2g respectively with acylating reagent 1～1 * 10
4mL, after 0.5～15 hour, is heated to 15～250 ℃ with 1～150kHz ultrasonication, stirring back flow reaction 1～100 hour, and suction filtration repetitive scrubbing are removed acylating reagent, obtain respectively carbon fiber and the carbon nanotube of acylations;
(4) add step (3) gained acidylate carbon fiber and carbon nanotube 1g～1 * 10
2g respectively with diamine or polyamine 10g～1 * 10
4g, with 1～150kHz ultrasonication 1～120 hour, then at 15～250 ℃ of temperature, react 1～100 hour suction filtration repetitive scrubbing, at 20～200 ℃ of temperature, vacuum-drying is 1～60 hour, obtains respectively surface with graft type carbon fiber and the carbon nanotube of active amino;
(5) add step (4) gained surface with the carbon nanotube 1～1 * 10 of active amino
2g and bismaleimides 10～1 * 10
4g, is warming up to after resin matrix melting, and dispersed with stirring bubble removing evenly and under vacuum condition carries out Michael addition reaction simultaneously, obtains the bimaleimide resin linear block polymer that contains carbon nanotube;
(6) add the resulting bimaleimide resin linear block polymer that contains carbon nanotube of step (5) as matrix, and step (4) is resulting with amino graft type carbon fiber reaction, froth in vacuum, obtains carbon fiber-containing/carbon nanotube/span and carrys out amide resins hybrid composite.
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| CN107706399A (en) * | 2017-11-10 | 2018-02-16 | 哈尔滨万鑫石墨谷科技有限公司 | One-dimensional carbon fiber/carbon nanotube composite, preparation method and the usage |
| CN108868828A (en) * | 2018-07-11 | 2018-11-23 | 河南理工大学 | It is a kind of for being crushed the interface adhesive and preparation method thereof of coal body reinforcing |
| CN111719311A (en) * | 2020-06-23 | 2020-09-29 | 上海交通大学 | Modified carbon fiber, modified carbon fiber reinforced epoxy resin composite material and preparation method thereof |
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| CN107706399A (en) * | 2017-11-10 | 2018-02-16 | 哈尔滨万鑫石墨谷科技有限公司 | One-dimensional carbon fiber/carbon nanotube composite, preparation method and the usage |
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| CN111719311A (en) * | 2020-06-23 | 2020-09-29 | 上海交通大学 | Modified carbon fiber, modified carbon fiber reinforced epoxy resin composite material and preparation method thereof |
| CN111719311B (en) * | 2020-06-23 | 2021-05-11 | 上海交通大学 | Modified carbon fiber, modified carbon fiber reinforced epoxy resin composite material and preparation method thereof |
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Application publication date: 20140312 |