CN108642882A - A kind of method of carbon fiber surface modification - Google Patents
A kind of method of carbon fiber surface modification Download PDFInfo
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- CN108642882A CN108642882A CN201810435940.1A CN201810435940A CN108642882A CN 108642882 A CN108642882 A CN 108642882A CN 201810435940 A CN201810435940 A CN 201810435940A CN 108642882 A CN108642882 A CN 108642882A
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
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- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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- D06M2101/40—Fibres of carbon
Abstract
The present invention relates to a kind of method of carbon fiber surface modification, the carbon fiber that surface is coated to thermosetting resin sizing agent carries out Low Temperature Heat Treatment so that the carbon fiber surface that surface coats thermosetting resin sizing agent is rich in carboxyl；Carboxyl and the ratio of surface C C key molar contents are 2~30%；Low Temperature Heat Treatment refers to 0.5~15min of heat preservation at 250~350 DEG C；Low Temperature Heat Treatment is carried out in oxidizing atmosphere；Oxidizing atmosphere is the mixed-gas environment of oxidizing gas environment or oxidizing gas and inert gas, and the volume ratio of oxidizing gas is more than or equal to 5% in mixed-gas environment.The method of modifying of the present invention, heat treatment temperature is low, energy consumption is small, high treating effect, processing rear surface is obtained rich in the carboxyl that can be reacted with thermoplastic resin matrix, be conducive to carbon fiber and the chemical bonding of thermoplastic resin matrix, greatly improve the interface performance of carbon fiber and thermoplastic matrix, great application prospect.
Description
Technical field
The invention belongs to carbon fiber modifying fields, are related to a kind of method of carbon fiber surface modification.
Background technology
Due to fibre reinforced thermoplastic resin (CFRTP) based composites have be molded it is fast, recyclable, easy repair, at
This low, resistance to limiting fatigue has excellent performance the advantage simple with prepreg storage condition, in aerospace, automobile and Leisure Sport
Equal fields are widely applied.The fast development of High performance plastic resin in recent years also accelerates CFRTP based composites
Development.
Compared to carbon fiber-reinforced thermosetting resin composite materials, the occupation rate of market of CFRTP based composites is also suitable
Low, this is primarily due to carbon fiber material used in thermoplas tic resin composite and more limits to.Carbon fiber-reinforced thermosetting at present
Resin composite materials are mostly epoxy resin sizing agent, but the carbon fiber coated with this kind of thermosetting resin carries out thermoplastic resin increasing
It is had the following problems when strong：
(1) carbon fiber and most of thermoplastic resin poor compatibilities or incompatible.Epoxy resin sizing agent is not hot with these
Thermoplastic polymer chemically reacts, and causes its composite material interlayer shear strength low；
(2) forming temperature of thermosetting epoxy resin sizing agent is less than 250 DEG C, the epoxy resin sizing agent meeting more than 250 DEG C
Degradation generates gas, forms tiny micropore in composite material surface, composite molding is caused to fail；
(3) it is used for a long time at high temperature after being coated with the carbon fiber progress thermoplastic resin enhancing of epoxy resin sizing agent,
Interface often will produce gap and layering, cause composite material interface performance to decline serious.
At present carbon fiber is carried out thermoplastic resin to enhance feasible method being to the carbon fiber coated with thermosetting resin
Destarch.The method of destarch has solvent method and ablation, the former needs a large amount of solvents, the latter to will produce a large amount of tar, not only pollute
Environment, and carbon fiber after starching is gone to will produce a large amount of lousiness, fracture of wire, to reduce the quality of carbon fiber.In addition, desizing
Pyroprocess can make to remove by the oxygen-containing functional group that anodic oxidation means obtain on carbon fiber, be unfavorable for carbon fiber and resin base
The infiltration of body and interface cohesion.The fundamental solution for solving carbon fiber for thermoplastic resin is the compatible of change carbon fiber sizing agent
Property, keep it compatible with thermoplastic resin.
Yi et al. (Composites:Part A, 2016,87,212-219) made using modified thermoplasticity phenol oxygroup resin
For sizing agent, secondary starching is carried out on commercialization carbon fiber, 6 composite material interlayer of carbon fiber reinforced nylon shearing that treated
Intensity improves 20.4%, it is indicated that transesterification has occurred with thermoplastic matrix in the ester group contained in sizing agent, forms new change
Bonding action is learned, to improve the interface performance of carbon fiber and thermoplastic resin.But this method carries out twice carbon fiber
Starching, starching amount are up to 5.2~7.5%, considerably increase the convergence of carbon fiber wire interfascicular, be unfavorable for it is thermoplastic resin-based
Wellability between body；Secondly thermoplasticity sizing agent itself can reactive group activity it is low, the interface binding power between carbon fiber is weak,
It is smaller to the raising of fibre reinforced thermoplastic resin interface performance to result in the thermoplasticity sizing agent.
Ma et al. (Applied surface science:Surface 2016,379,199-205) is coated into thermoset epoxy
The carbon fiber of resin is vacuum-treated 2h at 200 DEG C, and reinforced epoxy composite material interface performance declines, this is because very
Empty heat treated carbon fiber, promotes carbon fiber before being molded with resin matrix, and it is anti-that crosslinking itself has occurred in the sizing agent on carbon fiber
It answers, to reduce carbon fiber and the chemical reaction group in thermosetting resin matrix molding.This illustrates vacuum heating treatment meeting
Promote on carbon fiber can reactive group reduction, be less useful for the thermoplastic resin matrix interface cohesion low with reactivity.
Oxidizing thermal treatment is carried out to unsized carbon fiber, reapplies and is ground in enhancing thermosetting resin or thermoplastic resin
Study carefully quite ripe.
Li Zeying (Changsha, Central South University's Master's thesis, 2014) is using 400~600 DEG C of air to the carbon fiber of desizing
Oxidation processes 15min improves the oxygen-containing functional group of carbon fiber surface, to improve the wellability with enhancing thermosetting resin, profit
It is improved in interface performance, but this method heat treatment temperature is high, energy consumption is big, condition is harsh.Meeting while carbon fiber surface aoxidizes
Promote oxygen-containing functional group to crack, cause this method take that longer, efficiency is low and surface oxygen functional group amount increase it is limited.
Huttinger et al. (Journal of applied polymer science:1994,51,737-742) use
0.75% ozone handles unsized fiber 100s at 100 DEG C, and carbon fiber surface is made to obtain more carboxyl, and points out smelly
The raising of fibre reinforced thermoplastic resin interface shear strength, is mainly due to the carboxyl and base of carbon fiber surface after oxygen oxidation
Chemical bonding effect between body.But ozone oxidation reaction is more violent, major injury carbon fiber itself leads to carbon fiber sheet
The tensile strength of body declines, and secondly stability is difficult to control, and repeatability is poor, and operating flexibility is narrow.
In addition, the carbon fiber surface of surface cladding thermosetting epoxy resin sizing agent has great amount of hydroxy group and methylene, and it is hot
The processing temperature of plastic resin is higher than 250 DEG C, if when directly by the carbon fiber with thermoplastic resin machine-shaping, carbon fiber surface
Unstable group and carbochain on face can decompose generation bulk gas, and interface binding force is caused to substantially reduce.
Therefore, a kind of carbon fiber coating thermosetting epoxy resin sizing agent to surface of exploitation carries out surface modification to improve
The great realistic meaning of method of itself and thermoplastic resin compatibility.
Invention content
The purpose of the present invention is to solve problems of the prior art, provide a kind of side of carbon fiber surface modification
Method is especially to provide a kind of carbon fiber surface modification method of enhancing thermoplas tic resin composite, and specifically surface coats
The surface of the carbon fiber of thermosetting resin sizing agent is modified, and the carbon fiber that thermosetting resin sizing agent is coated to surface carries out low temperature
Oxidation processes make its surface be rich in carboxyl, improve the interface cohesion between carbon fiber and surface coated thermosetting resin sizing agent
Power improves the compatibility of carbon fiber and thermoplastic resin matrix.Treated, and carbon fiber surface is rich in carboxyl, with thermoplastic resin
There are chemical bonding effects for matrix, can effectively enhance thermoplastic resin interface performance.
The present invention is modified rear products obtained therefrom to carbon fiber and is mainly used for enhancing thermoplastic resin material.The present invention is to table
The carbon fiber that bread covers thermosetting resin sizing agent carries out low-temperature oxidation processing, and the methylene on surface and hydroxyl are oxidized to can be with
The carboxyl of thermoplastic resin matrix's reaction of subsequent processing, after improvement processing between carbon fiber and the thermoplastic matrix of subsequent processing
Interface cohesion acts on, and the carboxyl that this thermoset sizing agent surface oxidation generates can also be with the original oxygen-containing group of carbon fiber surface
Dehydrogenation forms crosslinking, enhances the interface interaction between carbon fiber and thermosetting property sizing agent, to enhance the interface of integral composite
And mechanical property.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of method of carbon fiber surface modification, the carbon fiber that surface is coated to thermosetting resin sizing agent carry out Low Temperature Thermal
Processing so that the carbon fiber surface that surface coats thermosetting resin sizing agent is rich in carboxyl；Carboxyl and surface C-C key molar contents
Ratio be 2~30%；
The Low Temperature Heat Treatment refers to 0.5~15min of heat preservation at 250~350 DEG C.
As preferred technical solution：
A kind of method of carbon fiber surface modification as described above, the carbon fiber are polyacrylonitrile-based carbon fibre, oil
Asphalt base carbon fiber, coal tar pitch base carbon fibre, viscose-based carbon fiber, phenolic aldehyde base carbon fibre, gas-phase growth of carbon fibre, bacterial fibers
One or more of plain base carbon fibre, cellulose base carbon fiber and lignin-base carbon fiber.
The ingredient of a kind of method of carbon fiber surface modification as described above, the thermosetting resin sizing agent is asphalt mixtures modified by epoxy resin
Fat and its derivative, polyurethane resin, phenolic resin, melamine resin, furane resins, gather unsaturated polyester resin
One or more of butadiene resin, organic siliconresin.Protection scope of the present invention is not limited to that other properties are similar
Sizing agent be equally applicable to the present invention.
A kind of method of carbon fiber surface modification as described above, the Low Temperature Heat Treatment be in oxidizing atmosphere into
Row；The oxidizing atmosphere is the mixed-gas environment of oxidizing gas environment or oxidizing gas and inert gas, gaseous mixture
The volume ratio of oxidizing gas is more than or equal to 5% in body environment.
A kind of method of carbon fiber surface modification as described above, the oxidizing gas are nitrogen dioxide, chlorine, dioxy
Change one or more of sulphur, sulfur trioxide, air and oxygen.
A kind of method of carbon fiber surface modification as described above, the inert gas be nitrogen, argon gas, helium, neon,
Krypton, xenon and radon gas.The inert gas of the present invention is not limited to that other kin gases are equally applicable to this hair
It is bright.
A kind of method of carbon fiber surface modification as described above, the carboxyl are carboxylic group and/or are reacted with carboxyl
The macromolecule and/or particle of grafting.The carboxyl of the present invention is not limited in carboxylic group, other react the high score of scion grafting with carboxyl
Son and/or particle are applied both to the present invention.
A kind of method of carbon fiber surface modification as described above, the macromolecule be polyurethane, polyamide, polyanhydride and
Polyester more than one；The particle is more than one of nano-graphene and carbon nanotube.Protection scope of the present invention is not
It is only limitted to this, other kin macromolecules and/or particle are equally applicable to the present invention.
Invention mechanism：
Different from the aerial heat ageing of single hot set property resin, the present invention coats thermosetting resin sizing agent to surface
Carbon fiber thermal treatment temperature be 250~350 DEG C.The thermal oxide of the carbon fiber of surface cladding thermosetting resin sizing agent has
Following characteristics：
(1) to meet the requirement for improving enhancing thermoplastic resin interface performance, carbon fiber surface needs to be enriched with enough carboxylics
Base group carries out thermal oxidation to surface cladding thermosetting resin sizing agent carbon fiber, on the one hand can be because promoting thermosetting property tree
The unstable group of fat sizing agent such as methylene and hydroxyl etc. are oxidized to carboxyl, on the other hand can promote original on carbon fiber contain
Oxygen functional group and the de- conjunction of shrink or oxidative dehydrogenation of thermosetting property sizing agent act on, to consume the carbon fiber because of thermal oxidation
And newly-generated carboxylic group.Temperature is less than 250 DEG C, and the methylene on thermosetting resin surface or the oxidation activation energy of hydroxyl are high,
Cause oxidation rate low, therefore the rate of newly-generated carboxyl is less than the speed that carboxyl caused by being reacted between carbon fiber and sizing agent consumes
Rate so that carbon fiber surface can not be enriched with enough carboxylic groups.Therefore the heat treatment temperature of the present invention is more than 250 DEG C, Cai Nengman
The foot carbon fiber is after thermal oxidation, the requirement of a large amount of carboxyls of surface enrichment, is conducive to enhancing thermoplastic resin interface performance
Raising.
(2) by coating the thermal oxidation of thermosetting resin sizing agent carbon fiber to surface, the heat of the carbon fiber is improved
Stability is avoided when subsequently carrying out 250 DEG C or more high temperature process moldings to thermoplastic resin, the interface of the carbon fiber and resin
Tiny micropore is formed in composite material surface because unstable group or carbochain degradation will produce a large amount of gas, reduces composite material
Interface and overall mechanical properties.If the heat treatment temperature of the present invention is less than 250 DEG C, then can not be made by thermal oxidation processes
Some unstable groups in thermoplastic resin matrix's forming temperature or carbochain are decomposed in advance to vapor away, follow-up to be unfavorable for
The combination of composite material interface.
(3) process for treating surface of carbon fiber will match the production line of existing carbon fiber, therefore need in the short time (to be no more than
Half an hour) generate a large amount of carboxyl.If heat treatment temperature is less than 250 DEG C, surface coats on thermosetting resin sizing agent carbon fiber
Methylene or hydroxyl oxidation activation energy it is high, cause oxidation rate low, to cannot be satisfied the online production requirement of carbon fiber.
(4) when heat treatment temperature reaches 350 DEG C, carboxyl rhermal decomposition rate has been reached with the new rate for generating carboxyl of oxidation
It it is more than 350 DEG C to balance, such as heat treatment temperature, surface coats the methylene and hydroxyl oxygen on thermosetting resin sizing agent carbon fiber
The degradation rate for turning to carboxyl greatly improves, and carboxyl rhermal decomposition rate is more than the generating rate of carboxyl, the carboxyl amount for consumption of degrading
More than the carboxyl amount that thermal oxide generates, the amount of carbon fiber surface carboxyl can reduce, be unfavorable for subsequently enhancing thermoplastic resin
Interface performance improve.
Advantageous effect：
(1) method of a kind of carbon fiber surface modification of the invention, it is compound directly against thermosetting resin is widely used in
Carbon fiber be improved, on the one hand avoid the damage that sizing process brings carbon fiber, reduce slurry process to environment
Pollution；On the other hand, original oxygen-containing functional group obtained by anodic oxidation means on carbon fiber is protected, is avoided because of height
Warm desizing processes cause a large amount of oxygen-containing functional group to remove, to the infiltration conducive to carbon fiber and subsequent thermoplastic resin matrix
And interface cohesion；
(2) method of a kind of carbon fiber surface modification of the invention, avoids secondary starching and makes carbon fiber surface starching
The problem of layer is greatly thickened, is conducive to the raising of carbon fiber and thermoplastic resin wellability, and improve carbon fiber and thermoplastic resin
The interface binding power of fat；
(3) a kind of method of carbon fiber surface modification of the invention, carbon fiber surface are coated with thermosetting resin starching
Agent, compared to thermoplasticity sizing agent, thermosetting property sizing agent surface can reactive group it is more and activity is high so that carbon fiber and thermosetting
Property sizing agent between interface cohesion be higher than thermoplasticity sizing agent；
(4) method of a kind of carbon fiber surface modification of the invention, heat treatment temperature is low, energy consumption is small, and heat is coated to surface
After the carbon fiber of thermosetting resin sizing agent carries out oxidation processes, it can reach same with the non-starching carbon fiber of high-temperature process reported
The effect of sample, surface are obtained rich in the carboxylic group that can be reacted with thermoplastic resin matrix, are conducive to carbon fiber surface and thermoplastic
Property resin matrix chemical bonding, realize surface cladding thermosetting resin sizing agent fibre reinforced thermoplastic matrix interface
Performance increases substantially, great application prospect.
Description of the drawings
Fig. 1 is that the XPS for the carbon fiber that low-temperature oxidation handles rear surface coated epoxy resin sizing agent in embodiment 1 comes to the surface
Learn the Nomenclature Composition and Structure of Complexes collection of illustrative plates；
Fig. 2 is the surfaces XPS of the carbon fiber of the high temperature desizing processing rear surface coated epoxy resin sizing agent in comparative example 1
Chemical composition and structure collection of illustrative plates；
Fig. 3 is the XPS surface chemistries composition and knot of the carbon fiber for the surface coated epoxy resin sizing agent being not handled by
Composition is composed；
Fig. 4 be low-temperature oxidation handle rear surface coated epoxy resin sizing agent carbon fiber/nylon 66 composite material, not into
Carbon fiber/the nylon 66 composite material and high temperature desizing processing rear surface cladding of the surface coated epoxy resin sizing agent of row processing
Interlaminar shear strength comparison diagram of the carbon fiber/nylon 66 composite material of epoxy resin sizing agent at 280 DEG C.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of method of carbon fiber surface modification, by the polyacrylonitrile-radical carbon fiber of surface coated epoxy resin resin sizing agent
Dimension keeps the temperature 10min under 280 DEG C of oxidizing atmosphere, and oxidizing atmosphere is air environment.
The carbon fiber surface of coated epoxy resin sizing agent in surface obtained is rich in carboxyl, carboxyl and surface C-C keys mole
The ratio of content is 8.62%, and the XPS surface chemistry the Nomenclature Composition and Structure of Complexes collection of illustrative plates of the carbon fiber obtained after above-mentioned processing is as shown in Figure 1.
The carbon fiber obtained after above-mentioned processing and nylon66 fiber film are maintained into 40min by laminating method at 280 DEG C, 6.6MPa
66 unidirectional composite material laminate of carbon fiber reinforced nylon is prepared, its interlayer shear is strong using JC/T 773-2010 as standard testing
(ILSS) data are spent, the ILSS for measuring carbon fiber/nylon66 fiber of low-temperature oxidation processing is 70.78MPa.
Comparative example 1
A kind of carbon fiber processing method carries out the polyacrylonitrile-based carbon fibre of surface coated epoxy resin resin sizing agent
High temperature desizing is handled, after maintain 40min to prepare carbon fiber at 280 DEG C, 6.6MPa by laminating method with nylon66 fiber film it
Reinforced PA66 unidirectional composite material laminate.
Using JC/T 773-2010 as above-mentioned pressing plate interlaminar shear strength (ILSS) data of standard testing, high temperature desizing is measured
The ILSS of carbon fiber/nylon66 fiber of processing is 46.59MPa, the XPS surface chemistries composition of high temperature desizing treated carbon fiber and
Structure collection of illustrative plates is as shown in Figure 2.
Polyacrylonitrile-based carbon fibre and the nylon66 fiber that will not carry out the surface coated epoxy resin sizing agent of any processing are thin
Carbon fiber reinforced nylon 66 unidirectional composite material laminate is made with identical condition in film, after measure the carbon fiber being not handled by
The ILSS of dimension/nylon66 fiber is 15.32MPa, the XPS surface chemistry the Nomenclature Composition and Structure of Complexes collection of illustrative plates such as Fig. 3 for the carbon fiber being not handled by
It is shown.
Complex chart 1,2 and 3 is analyzed it can be found that the peak of 284.7 and 285.6ev represents sp in figure2And sp3C-C keys,
What the peak of 286.5~286.7ev represented be hydroxyl or ehter bond C-OH＆C-O-C, 287.5ev peak represents is carbonyl or quinone knot
C=O keys on structure, what the peak of 288.8-289.2ev represented is the peak generation of carboxyl or ester group COOH＆COO, 291.2-291.4ev
Table is π-π * keys.Above-mentioned each figure is analyzed it can be found that the surface being not handled by coats the carbon fiber of thermosetting resin sizing agent
Dimension (carbon fiber in Fig. 3) surface has a large amount of hydroxyl and extremely a small amount of carboxyl, the ratio that wherein hydroxyl accounts for C-C keys to be
70.8%, carboxyl is only 1.85%；Carry out high temperature destarch treated carbon fiber (carbon fiber in Fig. 2) oxygen-containing group on surface
It substantially reduces, wherein hydroxyl is reduced to 35.1%, and carboxyl is almost unchanged；Low-temperature oxidation treated the carbon fiber (carbon fiber in Fig. 1
Dimension), the carboxylic group ratio on surface greatly improves, and reaches 8.62%, it is possible thereby to find that the method for modifying of the application changes
The functional group of carbon fiber surface makes its surface be rich in carboxyl.
It carbon fiber/nylon66 fiber of low-temperature oxidation processing, carbon fiber/nylon66 fiber of high temperature desizing processing and is not handled by
Interlaminar shear strength (ILSS) data of carbon fiber/nylon66 fiber as shown in figure 4, by Fig. 4 it can be seen that the carbon fiber of the application
Surface modifying method has been obviously improved the interlaminar shear strength of laminated composite board, that is, improves the boundary of carbon fiber and thermoplastic matrix
Face binding force.
Embodiment 2
Surface is coated the asphalt of lactones modified epoxy sizing agent by a kind of method of carbon fiber surface modification
Base carbon fibre keeps the temperature 0.5min under 250 DEG C of oxidizing atmosphere, and oxidizing atmosphere is nitrogen dioxide environment.
The carbon fiber surface of coated epoxy resin derivative sizing agent in surface obtained is rich in carboxyl, carboxyl and surface C-C
The ratio of key molar content is 9.45%.
Embodiment 3
Surface is coated the coal tar pitch of vinyl unsaturated polyester resin sizing agent by a kind of method of carbon fiber surface modification
Base carbon fibre keeps the temperature 15min under 350 DEG C of oxidizing atmosphere, and oxidizing atmosphere is chlorine gas environment.
The carbon fiber surface of cladding vinyl unsaturated polyester resin sizing agent in surface obtained is rich in carboxyl, carboxyl and table
The ratio of face C-C key molar contents is 25.51%.
Embodiment 4
Surface is coated the viscose-based carbon fiber of phenolic resin sizing agent 300 by a kind of method of carbon fiber surface modification
DEG C oxidizing atmosphere under keep the temperature 5min, oxidizing atmosphere is sulfur dioxide environment.
The carbon fiber surface of cladding phenolic resin sizing agent in surface obtained is rich in carboxyl, carboxyl and surface C-C keys mole
The ratio of content is 2.00%.
Embodiment 5
Surface is coated the phenolic aldehyde base carbon fiber of melamine resin sizing agent by a kind of method of carbon fiber surface modification
Dimension keeps the temperature 1min under 280 DEG C of oxidizing atmosphere, and oxidizing atmosphere is sulfur trioxide environment.
The carbon fiber surface of cladding melamine resin sizing agent in surface obtained is rich in carboxyl, carboxyl and surface C-
The ratio of C key molar contents is 4.84%.
Embodiment 6
A kind of method of carbon fiber surface modification, the gas-phase growth of carbon fibre that surface is coated to furane resins sizing agent exist
8min is kept the temperature under 320 DEG C of oxidizing atmosphere, oxidizing atmosphere is oxygen atmosphere.
The carbon fiber surface of cladding furane resins sizing agent in surface obtained is rich in carboxyl, carboxyl and surface C-C keys mole
The ratio of content is 6.12%.
Embodiment 7
Surface is coated the bacteria cellulose-base carbon of polybutadiene sizing agent by a kind of method of carbon fiber surface modification
Fiber keeps the temperature 3min under 310 DEG C of oxidizing atmosphere, and oxidizing atmosphere is the mixed-gas environment of nitrogen dioxide and nitrogen, is mixed
The volume ratio for closing nitrogen dioxide in gaseous environment is 5%.
The carbon fiber surface of cladding polybutadiene sizing agent in surface obtained is rich in carboxyl, carboxyl and surface C-C keys
The ratio of molar content is 30.00%.
Embodiment 8
A kind of method of carbon fiber surface modification, the cellulose base carbon fiber that surface is coated to organic siliconresin sizing agent exist
9min is kept the temperature under 340 DEG C of oxidizing atmosphere, oxidizing atmosphere is the mixed-gas environment of chlorine and argon gas, mixed-gas environment
The volume ratio of middle chlorine is 10%.
The carbon fiber surface of cladding organic siliconresin sizing agent in surface obtained is rich in carboxyl, and carboxyl rubs with surface C-C keys
The ratio of your content is 13.62%.
Embodiment 9
A kind of method of carbon fiber surface modification, the lignin-base carbon fiber that surface is coated to polyurethane resin sizing agent exist
6min is kept the temperature under 290 DEG C of oxidizing atmosphere, oxidizing atmosphere is the mixed-gas environment of sulfur trioxide and nitrogen, mixed gas
The volume ratio of sulfur trioxide is 20% in environment.
The carbon fiber surface of cladding polyurethane resin sizing agent in surface obtained is rich in carboxyl, and carboxyl rubs with surface C-C keys
The ratio of your content is 23.00%.
Embodiment 10
A kind of method of carbon fiber surface modification, by surface coated epoxy resin/unsaturated polyester resin sizing agent (quality
Than being 1:1) lignin-base carbon fiber keeps the temperature 0.8min under 260 DEG C of oxidizing atmosphere, and oxidizing atmosphere is sulfur dioxide
Volume ratio with the mixed-gas environment of neon, mixed-gas environment sulfur dioxide is 50%.
The carbon fiber surface of surface coated epoxy resin/unsaturated polyester resin sizing agent obtained is rich in carboxyl, carboxyl
Ratio with surface C-C key molar contents is 16.33%.
Embodiment 11
Surface is coated melamine resin/furane resins sizing agent (matter by a kind of method of carbon fiber surface modification
Amount is than being 1:2) polyacrylonitrile-based carbon fibre keeps the temperature 5min under 270 DEG C of oxidizing atmosphere, and oxidizing atmosphere is titanium dioxide
Nitrogen/chlorine gas environment (volume ratio 1:1).
The carbon fiber surface of cladding melamine resin/furane resins sizing agent in surface obtained is rich in carboxyl, carboxylic
Base and the ratio of surface C-C key molar contents are 5.68%.
Embodiment 12
Surface is coated polybutadiene/organic siliconresin sizing agent (quality by a kind of method of carbon fiber surface modification
Than 2:9) gas-phase growth of carbon fibre keeps the temperature 12min under 290 DEG C of oxidizing atmosphere, and oxidizing atmosphere is nitrogen dioxide, chlorine
The mixed-gas environment of gas and helium, the volume ratio of chlorine is 5% in mixed-gas environment, and the volume ratio of nitrogen dioxide is
15%.
The carbon fiber surface of cladding polybutadiene/organic siliconresin sizing agent in surface obtained is rich in carboxyl, carboxyl
Ratio with surface C-C key molar contents is 19.64%.
Embodiment 13
Surface is coated unsaturated polyester resin/organic siliconresin sizing agent (matter by a kind of method of carbon fiber surface modification
Measure ratio 1:1) polyacrylonitrile-based carbon fibre keeps the temperature 1min under 255 DEG C of oxidizing atmosphere, and oxidizing atmosphere is chlorine and krypton
The mixed-gas environment of gas, the volume ratio of chlorine is 6% in mixed-gas environment.
The carbon fiber surface of cladding unsaturated polyester resin/organic siliconresin sizing agent in surface obtained is rich in carboxyl, carboxylic
Base and the ratio of surface C-C key molar contents are 14.41%.
Embodiment 14
Surface is coated phenolic resin/melamine resin sizing agent (matter by a kind of method of carbon fiber surface modification
Measure ratio 2:3) viscose-based carbon fiber keeps the temperature 14min under 345 DEG C of oxidizing atmosphere, and oxidizing atmosphere is nitrogen dioxide and xenon
The mixed-gas environment of gas, the volume ratio of nitrogen dioxide is 70% in mixed-gas environment.
The carbon fiber surface of cladding phenolic resin/melamine resin sizing agent in surface obtained is rich in carboxyl, carboxylic
Base and the ratio of surface C-C key molar contents are 6.41%.
Embodiment 15
Surface is coated furane resins/organic siliconresin sizing agent (mass ratio 1 by a kind of method of carbon fiber surface modification:
3) phenolic aldehyde base carbon fibre keeps the temperature 7min under 305 DEG C of oxidizing atmosphere, and oxidizing atmosphere is sulfur dioxide, chlorine and radon gas
Mixed-gas environment, the volume ratio of chlorine is 15% in mixed-gas environment, and the volume ratio of sulfur dioxide is 25%.
The carbon fiber surface of cladding furane resins/organic siliconresin sizing agent in surface obtained is rich in carboxyl, carboxyl and table
The ratio of face C-C key molar contents is 11.58%.
Embodiment 16
Surface is coated polybutadiene/phenolic resin sizing agent (mass ratio by a kind of method of carbon fiber surface modification
3:1) bacteria cellulose base carbon fibre keeps the temperature 4min under 255 DEG C of oxidizing atmosphere, and oxidizing atmosphere is sulfur trioxide, oxygen
The mixed-gas environment of gas and radon gas, the volume ratio of sulfur trioxide is 2% in mixed-gas environment, and the volume ratio of oxygen is 4%.
The carbon fiber surface of surface obtained cladding polybutadiene/phenolic resin sizing agent is rich in carboxyl, carboxyl with
The ratio of surface C-C key molar contents is 21.70%.
Claims (8)
1. a kind of method of carbon fiber surface modification, it is characterized in that：By surface coat thermosetting resin sizing agent carbon fiber into
Row Low Temperature Heat Treatment so that the carbon fiber surface that surface coats thermosetting resin sizing agent is rich in carboxyl；Carboxyl and surface C-C keys
The ratio of molar content is 2~30%；
The Low Temperature Heat Treatment refers to 0.5~15min of heat preservation at 250~350 DEG C.
2. a kind of method of carbon fiber surface modification according to claim 1, which is characterized in that the carbon fiber is poly- third
Alkene itrile group carbon fiber, petroleum pitch-based carbon fiber, coal tar pitch base carbon fibre, viscose-based carbon fiber, phenolic aldehyde base carbon fibre, gas phase life
One or more of long carbon fiber, bacteria cellulose base carbon fibre, cellulose base carbon fiber and lignin-base carbon fiber.
3. a kind of method of carbon fiber surface modification according to claim 1, which is characterized in that on the thermosetting resin
The ingredient for starching agent is epoxy resin and its derivative, unsaturated polyester resin, polyurethane resin, phenolic resin, melamine first
One or more of urea formaldehyde, furane resins, polybutadiene, organic siliconresin.
4. a kind of method of carbon fiber surface modification according to claim 1, which is characterized in that the Low Temperature Heat Treatment is
It is carried out in oxidizing atmosphere；The oxidizing atmosphere is the mixing of oxidizing gas environment or oxidizing gas and inert gas
Gaseous environment, the volume ratio of oxidizing gas is more than or equal to 5% in mixed-gas environment.
5. a kind of method of carbon fiber surface modification according to claim 4, which is characterized in that the oxidizing gas is
One or more of nitrogen dioxide, chlorine, sulfur dioxide, sulfur trioxide, air and oxygen.
6. a kind of method of carbon fiber surface modification according to claim 4, which is characterized in that the inert gas is nitrogen
Gas, argon gas, helium, neon, Krypton, xenon or radon gas.
7. a kind of method of carbon fiber surface modification according to claim 1, which is characterized in that the carboxyl is carboxyl base
Group and/or macromolecule and/or particle with carboxyl reactive grafting.
8. a kind of method of carbon fiber surface modification according to claim 7, which is characterized in that the macromolecule is poly- ammonia
Ester, polyamide, polyanhydride and polyester more than one；The particle is more than one of nano-graphene and carbon nanotube.
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| CN115262278A (en) * | 2022-08-01 | 2022-11-01 | 浙江科技学院 | Preparation method of high-uniformity double-layer gradient hole carbon paper base paper |
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