CN104629069B - A kind of preparation of insulating barrier enveloped carbon nanometer tube orientation absorption carbon fiber prepreg - Google Patents
A kind of preparation of insulating barrier enveloped carbon nanometer tube orientation absorption carbon fiber prepreg Download PDFInfo
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Abstract
The invention belongs to field of composite material preparation, more particularly to a kind of preparation method of insulating barrier enveloped carbon nanometer tube orientation absorption carbon fiber/epoxy resin prepreg, to interlayer multi-scale enhancement carbon fibre composite.The present invention includes following technical step.Step I：CNT is added in preferred insulating coating material, uniform powder mixture is obtained through ball milling；Step II：Mixture obtained by step I stirs in deionized water, and heating obtains the CNT of insulating barrier cladding；Step III：The CNT that insulating barrier is coated uniformly is sprayed on the copper coin of connection positive pole, and carbon fiber prepreg is connected into negative pole, and applying voltage makes CNT is vertical orientated to be adsorbed onto prepreg surface, and control carbon nanotube adsorption thickness degree is at 20 ~ 80 μm.Present invention process is easy, and CNT is vertical orientated on prepreg surface, is remarkably improved the bending strength, compressive strength and interlaminar fracture toughness of composite, it is easy to the popularization and application in actual production.
Description
Technical field
The invention belongs to the preparation field of carbon fibre composite, more particularly to a kind of insulating barrier enveloped carbon nanometer tube orientation
Adsorb the preparation method of carbon fiber/epoxy resin prepreg.
Background technology
Carbon fiber enhancement resin base composite material has specific strength height, specific modulus height, endurance, corrosion-resistant and size steady
A series of fixed high excellent properties, are widely used in Aeronautics and Astronautics, automobile, the energy and sports equipment field, particularly aviation,
The application of space industry is growing day by day.But carbon fiber surface inertia is big, active function can roll into a ball few, the bad adhesion with matrix, multiple
There is substantial amounts of defect in condensation material interface.Moreover, the excellent mechanical performances of carbon fibre composite all concentrate on the axle along fiber
To the humidification perpendicular to machine direction is weaker, causes the interlayer poor mechanical property of composite, it is impossible to farthest full
Demand of the sufficient Aeronautics and Astronautics field for material property.
Since CNT is found and is prepared on a large scale, with its nanometer grade diameter, high length-diameter ratio, as advanced multiple
The preferable reinforcement of condensation material.It is current to improve the heat that composite horizontal mechanical performance has become research using CNT
Point, some researchers are successfully prepared the carbon fibre composite of CNT multi-scale enhancement, and to the property of composite
It can change and be analyzed, result of study shows that the CNT existed perpendicular to machine direction has higher humidification.
Preparing the method for vertical orientated CNT enhancing carbon fibre composite at present mainly has two kinds：A kind of method is to make carbon nanometer
Pipe is grown directly upon carbon fiber surface, such as Hu Zhihui（Patent publication No. CN102351166 A）Carbon fiber is activated
Processing, makes catalyst be attached to carbon fiber surface, so as to grow array-like CNT in carbon fiber surface, although this is combined
The boundary strength of material is improved, but this method has been damaged to the tensile strength of carbon fiber in itself, and process conditions are multiple
It is miscellaneous, also it is merely resting on laboratory stage；Another method is to use chemical vapor deposition（CVD）Technology prepares the carbon of array arrangement
Nanotube, such as Cui Shen（Patent publication No. CN101348901 A）Invent by the use of hexamethylene as carbon source, with CVD system
Standby array carbon nano tube, is added to the interlayer of composite, passes through molding, autoclave or resin transfer moulding（RTM）Work
Skill prepares the composite with " sandwich " sandwich, and this method mechanical property horizontal to composite has changed
Kind, but have the disadvantage that the array arrangement CNT prepared is limited by masterplate, thus area very little, temperature needed for CVD needs height
In 600 DEG C, complex process, cost is high, it is difficult to realize large-scale application.
To solve the deficiency of existing vertical orientated preparation method of carbon nano-tube, the interlayer power of composite is more effectively improved
Learn performance, the CNT that insulating barrier is coated is placed in company by the present invention using electric charge identical charges repel each other the physical characteristic that there is a natural attraction between the sexes
Connect on the copper coin of positive pole, carbon fiber/epoxy resin prepreg connection negative electrode.Apply after voltage, CNT can be made vertically to take
To prepreg surface is adsorbed onto, it is in array-like arrangement on prepreg surface.Can be obviously improved composite bending, compression with
Interlaminar fracture toughness.
Contrasting existing CNT strengthens the preparation method of carbon fibre composite, and the technology of the present invention is easy to operate, can
Significantly improve the compressive strength, bending strength and interlaminar fracture toughness of carbon fibre composite, it is easy to promoted in actual production
Using.
The content of the invention
It is an object of the invention to provide a kind of orientation absorption carbon fiber/epoxy resin preimpregnation of insulating barrier enveloped carbon nanometer tube
The preparation method of material, particular technique content is as follows：
A kind of preparation method of insulating barrier enveloped carbon nanometer tube orientation absorption carbon fiber/epoxy resin prepreg, its feature
It is, including following components and step：Component 1：Multi-walled carbon nanotube, includes the common multi-walled carbon nanotube of surface free processing
With the multi-walled carbon nanotube of surface grafting amino.The multi-walled carbon nanotube of surface grafting amino can be by functionalized multi-wall carbonnanotubes
Obtained through chloride and amidized chemical treatment, the technique belongs to the known mature technology of this area；Component 2：It is preferred that nothing
Machine insulating coating material, including aluminium isopropoxide or sodium metaaluminate；Component 3：Carbon fiber/epoxy resin unidirectional pre-immersion material；Step I：
Component 1 is added in component 2, ball-milling treatment 1 ~ 3 hour, obtain uniform powder mixture, wherein component 2 and component 1
Mass ratio is 10:1~20:1, the draw ratio of CNT is controlled between 50 ~ 300 after ball milling；Step II：By powder obtained by step I
Last shape mixture stirs in deionized water, is then heated to 250 DEG C, hydrolysis obtain insulating barrier cladding CNT its
In, the mass ratio of wherein deionized water and component 2 is 5:1~10:1；Step III：The CNT grinding that insulating barrier is coated,
It is even to be sprayed on the copper coin of connection positive pole, the carbon fiber/epoxy resin prepreg for being cut into certain size is connected into negative pole, applied
Voltage, it is 10 ~ 25 kV/cm to control electric-field intensity, makes CNT is vertical orientated to be adsorbed onto prepreg surface, in prepreg table
Face is in array-like arrangement, and it is 15 ~ 45 min to control the Electrostatic Absorption time, and the carbon for obtaining adsorption different content CNT is fine
Dimension/epoxy prepreg, the thickness of carbon nanotube adsorption layer is 20 ~ 80 μm.
Carbon fiber/epoxy resin prepreg is remarkably improved carbon after the orientation absorption of insulating barrier enveloped carbon nanometer tube
Bending, compressive strength and the interlaminar fracture toughness of fibrous composite.Meanwhile, the addition of CNT does not influence composite
Processing technology, the CNT being orientated perpendicular to carbon fiber direction is controllable in the content of composite interlayer, can be effectively improved boundary
Face performance.The technical operation is easy, it is easy to the popularization and application in actual production.
Following invention effect can be obtained by above-mentioned technology contents：Carbon fiber/epoxy resin prepreg is by insulation
After layer enveloped carbon nanometer tube orientation absorption, carbon fiber composite layer plywood is pressed into, bending, compressive strength lifting amplitude >=
10%th, interlaminar fracture toughness lifting amplitude >=20%.
Embodiment
By following examples, the present invention is described in detail.
In each embodiment, carbon fibre composite bending property is tested according to ASTM D 7264, using three-point bending
Pattern.Carbon fibre composite compressive strength is tested according to GB/T 1448-2005, measurement direction and carbon in composite
The direction of fiber is in 90 °.The interlaminar fracture toughness G of carbon fibre compositeICAnd GIICRespectively according to HB 7402-1996 and HB
7403-1996 is tested.
Embodiment 1
Component 1：The nanometer company production of section's epoch, purity in TNM3 multi-walled carbon nanotubes, Chengdu>95%, CNT external diameter
For 10 ~ 30nm, 10 μm of average length；Component 2：Aluminium isopropoxide, purity >=99%, the production of Shanghai Chemical Co., Ltd. of Xinchen；Component
3：Homemade Toray T700-12K carbon fibers/glycidyl amine epoxy resin of 4,4 ' MDA four it is unidirectional
Prepreg, contained curing agent is 4,4 ' diamino diphenyl sulfones, and prepreg thickness is 0.15mm, and surface density is 220g/m2.Step
I：TNM3 multi-walled carbon nanotubes are added in aluminium isopropoxide, ball-milling treatment 1 hour obtains uniform powder mixture, wherein
The mass ratio of aluminium isopropoxide and CNT is 10:1, the draw ratio of CNT is 300 after ball milling.Step II：By step I institutes
Obtain powder mixture to stir in deionized water, be then heated to 250 DEG C, hydrolysis obtains the carbon nanometer of insulating barrier cladding
Pipe, the wherein mass ratio of deionized water and aluminium isopropoxide are 5:1.Step III：The CNT grinding that insulating barrier is coated, uniformly
On the copper coin for being sprayed at connection positive pole, the carbon fiber/epoxy resin prepreg for being cut into certain size is connected into negative pole, applies electricity
Pressure, it is 10kV/cm to control electric-field intensity, makes CNT is vertical orientated to be adsorbed onto prepreg surface, is in battle array on prepreg surface
Column-shaped is arranged, and it is 15min to control the Electrostatic Absorption time, and CNT is in carbon fiber/epoxy resin prepreg surface absorbed layer
Thickness is 20 μm.
Use die pressing that carbon fiber prepreg is pressed into unidirectional composite material laminate of the thickness for 2mm, hot press pressure
Power is 10MPa, fiber volume fraction 65%.Not in prepreg adsorption CNT, T700 carbon fibre composites are unidirectional
The bending strength of plate is 1480MPa, and 90 ° of compressive strengths are 225MPa, GICAnd GIICRespectively 0.25kJ/m2With 4.53 kJ/
m2.After the orientation absorption CNT of prepreg surface, the bending strength of T700 carbon fibre composite one-way slabs is
1630MPa, 90 ° of compressive strengths are 248MPa, GICAnd GIICRespectively 0.31kJ/m2With 5.45 kJ/m2。
Embodiment 2
Component 1：The nanometer company production of section's epoch, purity in TNM3 multi-walled carbon nanotubes, Chengdu>95%, CNT external diameter
For 10 ~ 30nm, 10 μm of average length；Component 2：Sodium metaaluminate, purity >=99%, the production of Guangzhou Qing Sheng Chemical Co., Ltd.s；Component
3：Homemade Toray T700-12K carbon fibers/glycidyl amine epoxy resin of 4,4 ' MDA four it is unidirectional
Prepreg, contained curing agent is 4,4 ' diamino diphenyl sulfones, and prepreg thickness is 0.15mm, and surface density is 220g/m2.Step
I：TNM3 multi-walled carbon nanotubes are added in aluminium isopropoxide, ball-milling treatment 2 hours obtains uniform powder mixture, wherein
The mass ratio of aluminium isopropoxide and CNT is 15:1, the draw ratio of CNT is 150 after ball milling.Step II：By step I institutes
Obtain powder mixture to stir in deionized water, be then heated to 250 DEG C, hydrolysis obtains the carbon nanometer of insulating barrier cladding
Pipe, the wherein mass ratio of deionized water and aluminium isopropoxide are 7.5:1.Step III：The CNT grinding that insulating barrier is coated,
It is even to be sprayed on the copper coin of connection positive pole, the carbon fiber/epoxy resin prepreg for being cut into certain size is connected into negative pole, applied
Voltage, it is 15kV/cm to control electric-field intensity, makes CNT is vertical orientated to be adsorbed onto prepreg surface, is on prepreg surface
Array-like is arranged, and it is 30min to control the Electrostatic Absorption time, and CNT is in carbon fiber/epoxy resin prepreg surface absorbed layer
Thickness be 50 μm.
Use die pressing that carbon fiber prepreg is pressed into unidirectional composite material laminate of the thickness for 2mm, hot press pressure
Power is 10MPa, fiber volume fraction 65%.Not in prepreg adsorption CNT, T700 carbon fibre composites are unidirectional
The bending strength of plate is 1480MPa, and 90 ° of compressive strengths are 225MPa, GICAnd GIICRespectively 0.25kJ/m2With 4.53 kJ/
m2.After the orientation absorption CNT of prepreg surface, the bending strength of T700 carbon fibre composite one-way slabs is
1650MPa, 90 ° of compressive strengths are 255MPa, GICAnd GIICRespectively 0.31kJ/m2With 5.51 kJ/m2。
Embodiment 3
Component 1：The nanometer company production of section's epoch, purity in TNM3 multi-walled carbon nanotubes, Chengdu>95%, CNT external diameter
For 10 ~ 30nm, 10 μm of average length；Component 2：Aluminium isopropoxide, purity >=99%, the production of Shanghai Chemical Co., Ltd. of Xinchen；Component
3：Homemade Toray T700-12K carbon fibers/glycidyl amine epoxy resin of 4,4 ' MDA four it is unidirectional
Prepreg, contained curing agent is 4,4 ' diamino diphenyl sulfones, and prepreg thickness is 0.15mm, and surface density is 220g/m2.Step
I：TNM3 multi-walled carbon nanotubes are added in aluminium isopropoxide, ball-milling treatment 3 hours obtains uniform powder mixture, wherein
The mass ratio of aluminium isopropoxide and CNT is 20:1, the draw ratio of CNT is 50 after ball milling.Step II：By step I institutes
Obtain powder mixture to stir in deionized water, be then heated to 250 DEG C, hydrolysis obtains the carbon nanometer of insulating barrier cladding
Pipe, the wherein mass ratio of deionized water and aluminium isopropoxide are 10:1.Step III：The CNT grinding that insulating barrier is coated,
It is even to be sprayed on the copper coin of connection positive pole, the carbon fiber/epoxy resin prepreg for being cut into certain size is connected into negative pole, applied
Voltage, it is 25kV/cm to control electric-field intensity, makes CNT is vertical orientated to be adsorbed onto prepreg surface, is on prepreg surface
Array-like is arranged, and it is 45min to control the Electrostatic Absorption time, and CNT is in carbon fiber/epoxy resin prepreg surface absorbed layer
Thickness be 80 μm.
Use die pressing that carbon fiber prepreg is pressed into unidirectional composite material laminate of the thickness for 2mm, hot press pressure
Power is 10MPa, fiber volume fraction 65%.Not in prepreg adsorption CNT, T700 carbon fibre composites are unidirectional
The bending strength of plate is 1480MPa, and 90 ° of compressive strengths are 225MPa, GICAnd GIICRespectively 0.25kJ/m2With 4.53 kJ/
m2.After the orientation absorption CNT of prepreg surface, the bending strength of T700 carbon fibre composite one-way slabs is
1705MPa, 90 ° of compressive strengths are 265MPa, GICAnd GIICRespectively 0.33kJ/m2With 5.58 kJ/m2。
Embodiment 4
Component 1：The multi-walled carbon nanotube of ethylenediamine surface grafting, using section's epoch nanometer company production in Chengdu
TNMC3 functionalized multi-wall carbonnanotubes are obtained through chloride, amination processing, and the surface grafting rate of amino is 2.5wt%, and carbon is received
Mitron external diameter is 10 ~ 30nm, 5 μm of average length；Component 2：Sodium metaaluminate, purity >=99%, the life of Guangzhou Qing Sheng Chemical Co., Ltd.s
Production；Component 3：The homemade Toray T700-12K carbon fibers/glycidyl amine epoxy resin of 4,4 ' MDA four
Unidirectional pre-immersion material, contained curing agent be 4,4 ' diamino diphenyl sulfones, prepreg thickness be 0.15mm, surface density is 220g/
m2.Step I：TNM3 multi-walled carbon nanotubes are added in aluminium isopropoxide, ball-milling treatment 1 hour obtains uniform powder-mixed
The mass ratio of thing, wherein aluminium isopropoxide and CNT is 10:1, the draw ratio of CNT is 300 after ball milling.Step II：Will
Powder mixture obtained by step I stirs in deionized water, is then heated to 250 DEG C, hydrolysis obtains insulating barrier cladding
CNT, wherein the mass ratio of deionized water and aluminium isopropoxide be 5:1.Step III：The CNT that insulating barrier is coated
On grinding, the copper coin for being uniformly sprayed at connection positive pole, the carbon fiber/epoxy resin prepreg for being cut into certain size is connected negative
Pole, applies voltage, and it is 10kV/cm to control electric-field intensity, makes CNT is vertical orientated to be adsorbed onto prepreg surface, in prepreg
Surface is in array-like arrangement, and it is 15min to control the Electrostatic Absorption time, and CNT is on carbon fiber/epoxy resin prepreg surface
The thickness of adsorption layer is 20 μm.
Use die pressing that carbon fiber prepreg is pressed into unidirectional composite material laminate of the thickness for 2mm, hot press pressure
Power is 10MPa, fiber volume fraction 65%.Not in prepreg adsorption CNT, T700 carbon fibre composites are unidirectional
The bending strength of plate is 1480MPa, and 90 ° of compressive strengths are 225MPa, GICAnd GIICRespectively 0.25kJ/m2With 4.53 kJ/
m2.After the orientation absorption CNT of prepreg surface, the bending strength of T700 carbon fibre composite one-way slabs is
1680MPa, 90 ° of compressive strengths are 260MPa, GICAnd GIICRespectively 0.32kJ/m2With 5.52 kJ/m2。
Embodiment 5
Component 1：The multi-walled carbon nanotube of ethylenediamine surface grafting, using section's epoch nanometer company production in Chengdu
TNMC3 functionalized multi-wall carbonnanotubes are obtained through chloride, amination processing, and the surface grafting rate of amino is 2.5wt%, and carbon is received
Mitron external diameter is 10 ~ 30nm, 5 μm of average length；Component 2：Aluminium isopropoxide, purity >=99%, the life of Shanghai Chemical Co., Ltd. of Xinchen
Production；Component 3：The homemade Toray T700-12K carbon fibers/glycidyl amine epoxy resin of 4,4 ' MDA four
Unidirectional pre-immersion material, contained curing agent be 4,4 ' diamino diphenyl sulfones, prepreg thickness be 0.15mm, surface density is 220g/
m2.Step I：TNM3 multi-walled carbon nanotubes are added in aluminium isopropoxide, ball-milling treatment 2 hours obtains uniform powder-mixed
The mass ratio of thing, wherein aluminium isopropoxide and CNT is 15:1, the draw ratio of CNT is 150 after ball milling.Step II：Will
Powder mixture obtained by step I stirs in deionized water, is then heated to 250 DEG C, hydrolysis obtains insulating barrier cladding
CNT, wherein the mass ratio of deionized water and aluminium isopropoxide be 7.5:1.Step III：The carbon nanometer that insulating barrier is coated
Pipe is ground, on the copper coin for being uniformly sprayed at connection positive pole, and the carbon fiber/epoxy resin prepreg for being cut into certain size is connected
Negative pole, applies voltage, and it is 15kV/cm to control electric-field intensity, makes CNT is vertical orientated to be adsorbed onto prepreg surface, in preimpregnation
Material surface is in array-like arrangement, and it is 30min to control the Electrostatic Absorption time, and CNT is in carbon fiber/epoxy resin prepreg table
The thickness of face adsorption layer is 50 μm.
Use die pressing that carbon fiber prepreg is pressed into unidirectional composite material laminate of the thickness for 2mm, hot press pressure
Power is 10MPa, fiber volume fraction 65%.Not in prepreg adsorption CNT, T700 carbon fibre composites are unidirectional
The bending strength of plate is 1480MPa, and 90 ° of compressive strengths are 225MPa, GICAnd GIICRespectively 0.25kJ/m2With 4.53 kJ/
m2.After the orientation absorption CNT of prepreg surface, the bending strength of T700 carbon fibre composite one-way slabs is
1720MPa, 90 ° of compressive strengths are 268MPa, GICAnd GIICRespectively 0.35kJ/m2With 5.75 kJ/m2。
Embodiment 6
Component 1：The multi-walled carbon nanotube of ethylenediamine surface grafting, using section's epoch nanometer company production in Chengdu
TNMC3 functionalized multi-wall carbonnanotubes are obtained through chloride, amination processing, and the surface grafting rate of amino is 2.5wt%, and carbon is received
Mitron external diameter is 10 ~ 30nm, 5 μm of average length；Component 2：Sodium metaaluminate, purity >=99%, the life of Guangzhou Qing Sheng Chemical Co., Ltd.s
Production；Component 3：The homemade Toray T700-12K carbon fibers/glycidyl amine epoxy resin of 4,4 ' MDA four
Unidirectional pre-immersion material, contained curing agent be 4,4 ' diamino diphenyl sulfones, prepreg thickness be 0.15mm, surface density is 220g/
m2.Step I：TNM3 multi-walled carbon nanotubes are added in aluminium isopropoxide, ball-milling treatment 3 hours obtains uniform powder-mixed
The mass ratio of thing, wherein aluminium isopropoxide and CNT is 20:1, the draw ratio of CNT is 50 after ball milling.Step II：Will
Powder mixture obtained by step I stirs in deionized water, is then heated to 250 DEG C, hydrolysis obtains insulating barrier cladding
CNT, wherein the mass ratio of deionized water and aluminium isopropoxide be 10:1.Step III：The CNT that insulating barrier is coated
On grinding, the copper coin for being uniformly sprayed at connection positive pole, the carbon fiber/epoxy resin prepreg for being cut into certain size is connected negative
Pole, applies voltage, and it is 25kV/cm to control electric-field intensity, makes CNT is vertical orientated to be adsorbed onto prepreg surface, in prepreg
Surface is in array-like arrangement, and it is 45min to control the Electrostatic Absorption time, and CNT is on carbon fiber/epoxy resin prepreg surface
The thickness of adsorption layer is 80 μm.
Use die pressing that carbon fiber prepreg is pressed into unidirectional composite material laminate of the thickness for 2mm, hot press pressure
Power is 10MPa, fiber volume fraction 65%.Not in prepreg adsorption CNT, T700 carbon fibre composites are unidirectional
The bending strength of plate is 1480MPa, and 90 ° of compressive strengths are 225MPa, GICAnd GIICRespectively 0.25kJ/m2With 4.53 kJ/
m2.After the orientation absorption CNT of prepreg surface, the bending strength of T700 carbon fibre composite one-way slabs is
1695MPa, 90 ° of compressive strengths are 270MPa, GICAnd GIICRespectively 0.32kJ/m2With 5.66 kJ/m2。
Claims (3)
1. a kind of preparation method of insulating barrier enveloped carbon nanometer tube orientation absorption carbon fiber/epoxy resin prepreg, its feature exists
In, including following components and step：
Component 1：Multi-walled carbon nanotube；
Component 2：Aluminium isopropoxide；
Component 3：Carbon fiber/epoxy resin prepreg；
Step I：Component 1 is added in component 2, ball-milling treatment 1~3 hour obtains uniform powder mixture, wherein component
2 be 10 with the mass ratio of component 1:1~20:1, the draw ratio of CNT is controlled between 50~300 after ball milling；
Step II：Powder mixture obtained by step I is stirred in deionized water, 250 DEG C is then heated to, hydrolyzes
The mass ratio of the CNT coated to insulating barrier, wherein deionized water and component 2 is 5:1~10:1；
Step III：On the CNT grinding that insulating barrier is coated, the copper coin for being uniformly sprayed at connection positive pole, one will be cut into
The carbon fiber/epoxy resin prepreg connection negative pole being sized, applies voltage, it is 10~25kV/cm to control electric-field intensity, makes carbon
Nanotube is vertical orientated to be adsorbed onto prepreg surface, is in array-like arrangement on prepreg surface, and it is 15 to control the Electrostatic Absorption time
~45min, obtains the carbon fiber/epoxy resin prepreg of adsorption different content CNT, carbon nanotube adsorption layer
Thickness is 20~80 μm.
2. a kind of insulating barrier enveloped carbon nanometer tube orientation absorption carbon fiber/epoxy resin prepreg according to claim 1
Preparation method, wherein, multi-walled carbon nanotube described in component 1 include surface free handle common multi-walled carbon nanotube and table
The multi-walled carbon nanotube of face grafted amino group.
3. a kind of insulating barrier enveloped carbon nanometer tube orientation absorption carbon fiber/epoxy resin prepreg according to claim 1
Preparation method, wherein, carbon fiber/epoxy resin prepreg described in component 3 be unidirectional pre-immersion material.
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| CN101823689A (en) * | 2010-02-20 | 2010-09-08 | 哈尔滨工业大学 | Method for preparing porous metal oxide-coated carbon nanotube composite material |
| CN102296461A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Method for improving strength of carbon fiber |
| CN102296456A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Method for enhancing strength carbon fiber |
| CN103015157A (en) * | 2012-12-03 | 2013-04-03 | 天津工业大学 | Method for improving tensile strength of carbon fiber by utilizing graphene |
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| CN101823689A (en) * | 2010-02-20 | 2010-09-08 | 哈尔滨工业大学 | Method for preparing porous metal oxide-coated carbon nanotube composite material |
| CN102296461A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Method for improving strength of carbon fiber |
| CN102296456A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Method for enhancing strength carbon fiber |
| CN103015157A (en) * | 2012-12-03 | 2013-04-03 | 天津工业大学 | Method for improving tensile strength of carbon fiber by utilizing graphene |
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