CN108642882B - Method for modifying surface of carbon fiber - Google Patents
Method for modifying surface of carbon fiber Download PDFInfo
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- CN108642882B CN108642882B CN201810435940.1A CN201810435940A CN108642882B CN 108642882 B CN108642882 B CN 108642882B CN 201810435940 A CN201810435940 A CN 201810435940A CN 108642882 B CN108642882 B CN 108642882B
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Abstract
The invention relates to a method for modifying the surface of carbon fiber, which comprises the following steps of carrying out low-temperature heat treatment on the carbon fiber coated with a thermosetting resin sizing agent on the surface to ensure that the surface of the carbon fiber coated with the thermosetting resin sizing agent is rich in carboxyl; the ratio of the molar content of carboxyl to the molar content of C-C bonds on the surface is 2-30%; the low-temperature heat treatment refers to heat preservation for 0.5-15 min at 250-350 ℃; the low-temperature heat treatment is carried out in an oxidizing atmosphere; the oxidizing atmosphere is an oxidizing gas atmosphere or a mixed gas atmosphere of an oxidizing gas and an inert gas, and the volume ratio of the oxidizing gas in the mixed gas atmosphere is 5% or more. The modification method disclosed by the invention is low in heat treatment temperature, low in energy consumption and good in treatment effect, the surface of the treated carbon fiber is rich in carboxyl capable of reacting with the thermoplastic resin matrix, the chemical bonding of the carbon fiber and the thermoplastic resin matrix is facilitated, the interface performance of the carbon fiber and the thermoplastic matrix is greatly improved, and the application prospect is wide.
Description
Technical Field
The invention belongs to the field of carbon fiber modification, and relates to a method for modifying the surface of carbon fiber.
Background
The carbon fiber reinforced thermoplastic resin (CFRTP) -based composite material has the advantages of quick forming, recoverability, easiness in repair, low cost, excellent extreme fatigue resistance and simple storage condition of the prepreg, and is widely applied to the fields of aerospace, automobiles, sports and leisure and the like. The rapid development of high-performance thermoplastic resins in recent years has also accelerated the development of CFRTP-based composites.
The market share of CFRTP based composites is still rather low compared to carbon fiber reinforced thermoset resin composites, mainly because of the limited carbon fiber raw materials used for thermoplastic resin composites. Most of the existing carbon fiber reinforced thermosetting resin composite materials are epoxy resin sizing agents, but the following problems exist when the carbon fibers coated with the thermosetting resin are reinforced by the thermoplastic resin:
(1) carbon fibers are poorly compatible or incompatible with most thermoplastic resins. Epoxy resin sizing agents do not chemically react with these thermoplastic polymers, resulting in low interlaminar shear strength of their composites;
(2) the molding temperature of the thermosetting epoxy resin sizing agent is lower than 250 ℃, the epoxy resin sizing agent can be degraded to generate gas when the temperature is higher than 250 ℃, and fine micropores are formed on the surface of the composite material, so that the molding failure of the composite material is caused;
(3) after the carbon fiber coated with the epoxy resin sizing agent is reinforced by the thermoplastic resin, the carbon fiber is used at high temperature for a long time, and gaps and delamination are often generated on the interface, so that the interface performance of the composite material is seriously reduced.
A currently available solution for thermoplastic resin reinforcement of carbon fibers is to desize carbon fibers coated with a thermosetting resin. The desizing method comprises a solvent method and an ablation method, wherein the former method needs a large amount of solvent, the latter method can generate a large amount of tar, so that the environment is polluted, and the carbon fiber after desizing can generate a large amount of broken filaments and broken filaments, so that the quality of the carbon fiber is reduced. In addition, the high temperature process of desizing can remove oxygen-containing functional groups on the carbon fibers obtained by means of anodic oxidation, which is not favorable for wetting and interface bonding of the carbon fibers and the resin matrix. The fundamental way to solve the problem of the carbon fiber for the thermoplastic resin is to change the compatibility of the carbon fiber sizing agent so as to ensure that the carbon fiber sizing agent is compatible with the thermoplastic resin.
Yi et al (Composites: Part a,2016,87, 212-one 219) used a modified thermoplastic phenoxy resin as a sizing agent to perform secondary sizing on commercial carbon fibers, and the interlaminar shear strength of the treated carbon fiber reinforced nylon 6 composite material was improved by 20.4%, indicating that ester groups contained in the sizing agent were subjected to transesterification with a thermoplastic matrix to form a new chemical bonding effect, thereby improving the interfacial properties of the carbon fibers and the thermoplastic resin. But the method carries out sizing on the carbon fiber twice, the sizing amount is up to 5.2-7.5%, the bundling property among carbon fiber tows is greatly increased, and the wetting property between the carbon fiber tows and a thermoplastic resin matrix is not facilitated; and secondly, the thermoplastic sizing agent has low reactivity of reactive groups and weak interfacial bonding force with carbon fibers, so that the thermoplastic sizing agent has small improvement on the interfacial properties of the carbon fiber reinforced thermoplastic resin.
Ma et al (Applied surface science:2016,379, 199-. This indicates that the vacuum heat treatment causes a decrease in the number of reactive groups on the carbon fibers, and is even less favorable for interfacial bonding with the thermoplastic resin matrix having low reactivity.
The application of oxidative heat treatment to carbon fibers that have not been sized to reinforce thermosetting or thermoplastic resins is well studied.
Li Zeying (Changsha, Master thesis of southern China, 2014) adopts air of 400-600 ℃ to oxidize the desized carbon fiber for 15min, so that oxygen-containing functional groups on the surface of the carbon fiber are improved, the wettability of the carbon fiber with the reinforced thermosetting resin is improved, the improvement of the interface performance is facilitated, but the method is high in heat treatment temperature, large in energy consumption and harsh in conditions. The oxidation of the carbon fiber surface simultaneously promotes the cracking of the oxygen-containing functional groups, which causes the method to be long in time consumption, low in efficiency and limited in the increase of the amount of the oxygen-containing functional groups on the surface.
Huttinger et al (Journal of applied polymer science:1994,51,737-742) treated unsized fibers 100s with 0.75% ozone at 100 ℃ gave more carboxyl groups on the carbon fiber surface and indicated that the increase in interfacial shear strength of carbon fiber reinforced thermoplastic resin after ozone oxidation was mainly due to chemical bonding between the carboxyl groups on the carbon fiber surface and the matrix. But the ozone oxidation reaction is severe, the carbon fiber is seriously damaged, the tensile strength of the carbon fiber is reduced, the stability is difficult to control, the repeatability is poor, and the operation elasticity is narrow.
In addition, the surface of the carbon fiber coated with the thermosetting epoxy resin sizing agent has a large amount of hydroxyl and methylene, the processing temperature of the thermoplastic resin is higher than 250 ℃, and if the carbon fiber and the thermoplastic resin are directly processed and molded, unstable groups and carbon chains on the surface of the carbon fiber can be decomposed to generate a large amount of gas, so that the interface adhesive force is greatly reduced.
Therefore, it is very significant to develop a method for surface-modifying the carbon fiber coated with thermosetting epoxy resin sizing agent to improve the compatibility with thermoplastic resin.
Disclosure of Invention
The invention aims to solve the problems in the prior art, provides a method for modifying the surface of carbon fibers, and particularly provides a method for modifying the surface of carbon fibers for a reinforced thermoplastic resin composite material, in particular to a method for modifying the surface of carbon fibers coated with a thermosetting resin sizing agent, which carries out low-temperature oxidation treatment on the carbon fibers coated with the thermosetting resin sizing agent to ensure that the surfaces of the carbon fibers are rich in carboxyl groups, improves the interface bonding force between the carbon fibers and the thermosetting resin sizing agent coated on the surfaces, and improves the compatibility of the carbon fibers and a thermoplastic resin matrix. The surface of the treated carbon fiber is rich in carboxyl, and has chemical bonding effect with a thermoplastic resin matrix, so that the interface performance of the thermoplastic resin can be effectively enhanced.
The product obtained by modifying the carbon fiber is mainly used for reinforcing the thermoplastic resin material. The invention carries out low-temperature oxidation treatment on the carbon fiber coated with the thermosetting resin sizing agent, the methylene and the hydroxyl on the surface are oxidized into carboxyl which can react with a thermoplastic resin matrix which is subsequently treated, the interface bonding effect between the treated carbon fiber and the thermoplastic matrix which is subsequently treated is improved, in addition, the carboxyl generated by the surface oxidation of the thermosetting sizing agent can also be dehydrogenated with the original oxygen-containing group on the surface of the carbon fiber to form crosslinking, and the interface effect between the carbon fiber and the thermosetting sizing agent is enhanced, thereby enhancing the interface and the mechanical property of the integral composite material.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for modifying the surface of carbon fiber comprises the following steps of carrying out low-temperature heat treatment on the carbon fiber coated with a thermosetting resin sizing agent on the surface to ensure that the surface of the carbon fiber coated with the thermosetting resin sizing agent is rich in carboxyl; the ratio of the molar content of carboxyl to the molar content of C-C bonds on the surface is 2-30%;
the low-temperature heat treatment refers to heat preservation at 250-350 ℃ for 0.5-15 min.
As a preferred technical scheme:
the method for modifying the surface of the carbon fiber is characterized in that the carbon fiber is more than one of polyacrylonitrile-based carbon fiber, petroleum asphalt-based carbon fiber, coal asphalt-based carbon fiber, viscose-based carbon fiber, phenolic-based carbon fiber, vapor-grown carbon fiber, bacterial cellulose-based carbon fiber, cellulose-based carbon fiber and lignin-based carbon fiber.
In the method for modifying the surface of the carbon fiber, the thermosetting resin sizing agent is one or more of epoxy resin and derivatives thereof, unsaturated polyester resin, polyurethane resin, phenolic resin, melamine formaldehyde resin, furan resin, polybutadiene resin and organic silicon resin. The scope of the invention is not limited thereto, and other sizing agents having similar properties may be used in the invention.
A method for surface modification of carbon fiber as described above, said low temperature heat treatment being carried out in an oxidizing atmosphere; the oxidizing atmosphere is oxidizing gas environment or mixed gas environment of oxidizing gas and inert gas, and the volume ratio of the oxidizing gas in the mixed gas environment is more than or equal to 5%.
In the method for modifying the surface of the carbon fiber, the oxidizing gas is one or more of nitrogen dioxide, chlorine, sulfur dioxide, sulfur trioxide, air and oxygen.
In the method for modifying the surface of the carbon fiber, the inert gas is nitrogen, argon, helium, neon, krypton, xenon or radon. The inert gas of the present invention is not limited thereto, and other gases having similar properties may be applied to the present invention.
The method for modifying the surface of the carbon fiber is characterized in that the carboxyl is a carboxyl group and/or a macromolecule and/or particle grafted by the reaction of the carboxyl. The carboxyl group of the present invention is not limited to a carboxyl group, and other polymers and/or particles grafted by reaction with a carboxyl group can be applied to the present invention.
In the method for modifying the surface of the carbon fiber, the polymer is more than one of polyurethane, polyamide, polyanhydride and polyester; the particles are more than one of nano graphene and carbon nano tubes. The scope of the present invention is not limited thereto, and other polymers and/or particles having similar properties may be applied to the present invention.
The invention mechanism is as follows:
different from the thermal aging of single thermosetting resin in the air, the thermal treatment temperature of the carbon fiber coated with the thermosetting resin sizing agent on the surface is 250-350 ℃. The thermal oxidation of the carbon fiber coated with the thermosetting resin sizing agent on the surface has the following characteristics:
(1) in order to meet the requirement of improving the interface performance of the reinforced thermoplastic resin, enough carboxyl groups need to be enriched on the surface of the carbon fiber, and the surface of the carbon fiber coated with the thermosetting resin sizing agent is subjected to thermal oxidation treatment, so that on one hand, unstable groups such as methylene, hydroxyl and the like of the thermosetting resin sizing agent are promoted to be oxidized into carboxyl, and on the other hand, the original oxygen-containing functional groups on the carbon fiber and the shrinkage dehydration or oxidative dehydrogenation effect of the thermosetting sizing agent are promoted, so that the carboxyl groups newly generated by the thermal oxidation treatment of the carbon fiber are consumed. The temperature is lower than 250 ℃, the oxidation activation energy of methylene or hydroxyl on the surface of the thermosetting resin is high, so that the oxidation rate is low, and the rate of newly generated carboxyl is lower than the consumption rate of carboxyl caused by the reaction between the carbon fiber and the sizing agent, so that the surface of the carbon fiber cannot be enriched with enough carboxyl groups. Therefore, the heat treatment temperature of the invention is more than 250 ℃, so that the requirement of enriching a large amount of carboxyl on the surface of the carbon fiber after thermal oxidation treatment can be met, and the improvement of the interface performance of the reinforced thermoplastic resin is facilitated.
(2) Through thermal oxidation treatment of the carbon fiber coated with the thermosetting resin sizing agent on the surface, the thermal stability of the carbon fiber is improved, and the phenomenon that a large amount of gas is generated on the surface of a composite material to form tiny micropores due to degradation of an unstable group or a carbon chain at the interface of the carbon fiber and the resin when the thermoplastic resin is subjected to high-temperature processing molding at the temperature of more than 250 ℃ is avoided, so that the interface and the overall mechanical property of the composite material are reduced. If the heat treatment temperature of the invention is lower than 250 ℃, some groups or carbon chains which are unstable in the molding temperature of the thermoplastic resin matrix cannot be decomposed and volatilized in advance through the thermal oxidation treatment process, so that the subsequent combination of the composite material interface is not facilitated.
(3) The surface treatment technique of carbon fiber is matched with the existing production line of carbon fiber, so that a large amount of carboxyl is generated in a short time (no more than half an hour). If the heat treatment temperature is lower than 250 ℃, the oxidation activation energy of methylene or hydroxyl on the carbon fiber coated with the thermosetting resin sizing agent on the surface is high, so that the oxidation rate is low, and the on-line production requirement of the carbon fiber cannot be met.
(4) When the heat treatment temperature reaches 350 ℃, the thermal decomposition rate of carboxyl and the rate of oxidizing newly generated carboxyl are balanced, if the heat treatment temperature exceeds 350 ℃, the degradation rate of oxidizing methylene and hydroxyl on the carbon fiber coated with the thermosetting resin sizing agent on the surface into carboxyl is greatly improved, the thermal decomposition rate of carboxyl exceeds the generation rate of carboxyl, the amount of carboxyl consumed by degradation is more than that of carboxyl generated by thermal oxidation, the amount of carboxyl on the surface of the carbon fiber is reduced, and the improvement of the interface performance of the subsequent reinforced thermoplastic resin is not facilitated.
Has the advantages that:
(1) the method for modifying the surface of the carbon fiber directly improves the carbon fiber widely used for compounding thermosetting resin, on one hand, avoids the damage of the desizing process to the carbon fiber, and reduces the pollution of the desizing process to the environment; on the other hand, the method protects the oxygen-containing functional groups on the carbon fibers, which are obtained by the anodic oxidation means, and avoids the removal of a large amount of oxygen-containing functional groups caused by the high-temperature desizing process, thereby being beneficial to the infiltration and interface combination of the carbon fibers and the subsequent thermoplastic resin matrix;
(2) the method for modifying the surface of the carbon fiber avoids the problem that the secondary sizing causes the sizing layer on the surface of the carbon fiber to be greatly thickened, is beneficial to improving the wettability of the carbon fiber and the thermoplastic resin, and improves the interface bonding force of the carbon fiber and the thermoplastic resin;
(3) according to the method for modifying the surface of the carbon fiber, the surface of the carbon fiber is coated with the thermosetting resin sizing agent, compared with the thermoplastic sizing agent, the thermosetting sizing agent has more reactive groups and high activity on the surface, so that the interface bonding between the carbon fiber and the thermosetting sizing agent is higher than that of the thermoplastic sizing agent;
(4) the method for modifying the surface of the carbon fiber has low heat treatment temperature and low energy consumption, can achieve the same effect as the reported carbon fiber which is not subjected to high-temperature treatment after the carbon fiber coated with the thermosetting resin sizing agent is subjected to oxidation treatment, obtains carboxyl groups which are rich in reaction with a thermoplastic resin matrix on the surface, is beneficial to chemical bonding of the surface of the carbon fiber and the thermoplastic resin matrix, realizes great improvement of the interface performance of the carbon fiber reinforced thermoplastic matrix coated with the thermosetting resin sizing agent on the surface, and has great application prospect.
Drawings
FIG. 1 is an XPS surface chemical composition and structure map of carbon fibers coated with epoxy resin sizing agent after low temperature oxidation treatment in example 1;
FIG. 2 is an XPS surface chemical composition and structure map of carbon fibers having surfaces coated with an epoxy sizing agent after a high temperature desizing treatment in comparative example 1;
FIG. 3 is an XPS surface chemistry and structure map of untreated carbon fibers with surface coated epoxy sizing;
fig. 4 is a comparison graph of the interlaminar shear strength at 280 ℃ of the carbon fiber/nylon 66 composite material with the surface coated with the epoxy resin sizing agent after the low-temperature oxidation treatment, the carbon fiber/nylon 66 composite material with the surface coated with the epoxy resin sizing agent without the treatment, and the carbon fiber/nylon 66 composite material with the surface coated with the epoxy resin sizing agent after the high-temperature desizing treatment.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A method for modifying the surface of carbon fiber features that the polyacrylonitrile-based carbon fiber whose surface is coated with epoxy resin sizing agent is thermally insulated at 280 deg.C for 10min in oxidizing atmosphere, which is air environment.
The prepared carbon fiber with the surface coated with the epoxy resin sizing agent is rich in carboxyl on the surface, the ratio of the carboxyl to the C-C bond molar content on the surface is 8.62%, and the XPS surface chemical composition and the structural map of the carbon fiber obtained after the treatment are shown in figure 1.
And (3) maintaining the carbon fiber and the nylon 66 film obtained after the treatment for 40min at 280 ℃ and 6.6MPa by a laminating method to prepare the carbon fiber reinforced nylon 66 unidirectional composite laminated board, and testing the interlaminar shear strength (ILSS) data by taking JC/T773-one 2010 as a standard to obtain the ILSS of the carbon fiber/nylon 66 subjected to low-temperature oxidation treatment at 70.78 MPa.
Comparative example 1
A carbon fiber treatment method comprises the steps of carrying out high-temperature desizing treatment on polyacrylonitrile-based carbon fibers coated with epoxy resin sizing agents, and then maintaining the polyacrylonitrile-based carbon fibers and a nylon 66 film for 40min at 280 ℃ and 6.6MPa through a lamination method to prepare the carbon fiber reinforced nylon 66 unidirectional composite material laminated plate.
The platen interlaminar shear strength (ILSS) data was tested using JC/T773-.
The polyacrylonitrile-based carbon fiber with the surface coated with the epoxy resin sizing agent and the nylon 66 film which are not subjected to any treatment are prepared into the carbon fiber reinforced nylon 66 unidirectional composite material laminated board under the same conditions, and then the ILSS of the carbon fiber/nylon 66 which is not subjected to any treatment is measured to be 15.32MPa, and the XPS surface chemical composition and the structure map of the carbon fiber which is not subjected to any treatment are shown in figure 3.
Analysis of FIGS. 1, 2 and 3 combined shows that peaks 284.7 and 285.6ev represent sp
2And sp
3The peak of 286.5 to 286.7ev represents a hydroxyl group or an ether bond C-OH&Peaks at C-O-C, 287.5eV represent C ═ O bonds in the carbonyl or quinone structure, and peaks at 288.8-289.2eV represent carboxyl or ester groups COOH&COO,291.2-291.4ev, represents a pi-pi bond. Analysis of the above figures revealed that the untreated carbon fiber (carbon fiber in fig. 3) having a surface coated with a thermosetting resin sizing agent had a large amount of hydroxyl groups and an extremely small amount of carboxyl groups, wherein the proportion of the hydroxyl groups to the C — C bonds was 70.8%, and the carboxyl groups were only 1.85%; the oxygen-containing groups on the surface of the carbon fiber (the carbon fiber in figure 2) subjected to high-temperature desizing treatment are greatly reduced, wherein the hydroxyl groups are reduced to 35.1 percent, and the carboxyl groups are almost unchanged; the proportion of carboxyl groups on the surface of the carbon fiber (the carbon fiber in figure 1) subjected to low-temperature oxidation treatment is greatly improved to 8.62%, so that the modification method disclosed by the application can be found out that the functional groups on the surface of the carbon fiber are changed, and the surface of the carbon fiber is rich in carboxyl groups.
The interlaminar shear strength (ILSS) data of the carbon fiber/nylon 66 subjected to low-temperature oxidation treatment, the carbon fiber/nylon 66 subjected to high-temperature desizing treatment and the carbon fiber/nylon 66 not subjected to treatment are shown in fig. 4, and it can be seen from fig. 4 that the interlaminar shear strength of the laminated composite board is remarkably improved by the carbon fiber surface modification method, that is, the interface bonding force between the carbon fiber and the thermoplastic matrix is improved.
Example 2
A method for modifying the surface of carbon fibre features that the petroleum asphalt-base carbon fibre whose surface is coated with the sizing agent of lactone-modified epoxy resin is thermally insulated at 250 deg.C for 0.5min in oxidizing atmosphere, which is nitrogen dioxide environment.
The prepared carbon fiber surface of the sizing agent with the surface coated with the epoxy resin derivative is rich in carboxyl, and the ratio of the carboxyl to the C-C bond molar content on the surface is 9.45%.
Example 3
A method for modifying the surface of carbon fibre features that the carbon fibre coated with unsaturated vinyl polyester resin sizing agent is thermally insulated at 350 deg.C for 15min in the oxidizing atmosphere of chlorine gas.
The prepared carbon fiber surface coated with the vinyl unsaturated polyester resin sizing agent is rich in carboxyl, and the ratio of the carboxyl to the molar content of C-C bonds on the surface is 25.51 percent.
Example 4
A method for modifying the surface of carbon fiber features that the viscose-based carbon fiber whose surface is coated by phenolic resin sizing agent is thermally insulated at 300 deg.C in the oxidizing atmosphere of sulfur dioxide for 5 min.
The prepared carbon fiber surface coated with the phenolic resin sizing agent is rich in carboxyl, and the ratio of the carboxyl to the C-C bond molar content on the surface is 2.00%.
Example 5
A method for modifying the surface of carbon fiber features that the phenolic carbon fiber whose surface is coated with the sizing agent of melamine-formaldehyde resin is thermally insulated at 280 deg.C for 1min in the oxidizing atmosphere of sulfur trioxide.
The prepared carbon fiber surface coated with the melamine formaldehyde resin sizing agent is rich in carboxyl, and the ratio of the carboxyl to the C-C bond molar content on the surface is 4.84%.
Example 6
A method for modifying the surface of carbon fibre features that the carbon fibre whose surface is coated with furan resin sizing agent is thermally insulated at 320 deg.C for 8min in oxidizing atmosphere, which is oxygen atmosphere.
The prepared carbon fiber surface of the surface-coated furan resin sizing agent is rich in carboxyl, and the ratio of the carboxyl to the C-C bond molar content on the surface is 6.12%.
Example 7
A method for modifying the surface of carbon fiber comprises the step of preserving the temperature of bacterial cellulose-based carbon fiber coated with polybutadiene resin sizing agent at 310 ℃ for 3min in oxidizing atmosphere, wherein the oxidizing atmosphere is mixed gas environment of nitrogen dioxide and nitrogen, and the volume ratio of the nitrogen dioxide in the mixed gas environment is 5%.
The prepared carbon fiber surface coated with the polybutadiene resin sizing agent is rich in carboxyl, and the ratio of the carboxyl to the C-C bond molar content on the surface is 30.00%.
Example 8
A method for modifying the surface of carbon fiber comprises the step of preserving the heat of cellulose-based carbon fiber coated with an organic silicon resin sizing agent at 340 ℃ for 9min in an oxidizing atmosphere, wherein the oxidizing atmosphere is a mixed gas environment of chlorine and argon, and the volume ratio of the chlorine in the mixed gas environment is 10%.
The prepared carbon fiber with the surface coated with the organic silicon resin sizing agent is rich in carboxyl on the surface, and the ratio of the carboxyl to the C-C bond mole content on the surface is 13.62%.
Example 9
A method for modifying the surface of carbon fiber is characterized in that lignin-based carbon fiber coated with polyurethane resin sizing agent on the surface is subjected to heat preservation for 6min at 290 ℃ in oxidizing atmosphere, wherein the oxidizing atmosphere is a mixed gas environment of sulfur trioxide and nitrogen, and the volume ratio of the sulfur trioxide in the mixed gas environment is 20%.
The prepared carbon fiber surface coated with the polyurethane resin sizing agent is rich in carboxyl, and the ratio of the carboxyl to the C-C bond molar content on the surface is 23.00%.
Example 10
A method for modifying the surface of carbon fiber is characterized in that lignin-based carbon fiber coated with epoxy resin/unsaturated polyester resin sizing agent (the mass ratio is 1:1) on the surface is subjected to heat preservation for 0.8min at 260 ℃ in an oxidizing atmosphere, wherein the oxidizing atmosphere is a mixed gas environment of sulfur dioxide and neon, and the volume ratio of the sulfur dioxide in the mixed gas environment is 50%.
The prepared carbon fiber surface coated with the epoxy resin/unsaturated polyester resin sizing agent is rich in carboxyl, and the ratio of the carboxyl to the C-C bond molar content on the surface is 16.33%.
Example 11
A method for modifying the surface of carbon fiber is characterized in that polyacrylonitrile-based carbon fiber coated with melamine formaldehyde resin/furan resin sizing agent (mass ratio of 1:2) at the surface is subjected to heat preservation for 5min at the temperature of 270 ℃ in oxidizing atmosphere, wherein the oxidizing atmosphere is nitrogen dioxide/chlorine gas (volume ratio of 1: 1).
The prepared carbon fiber surface coated with the melamine formaldehyde resin/furan resin sizing agent is rich in carboxyl, and the ratio of the carboxyl to the C-C bond molar content on the surface is 5.68%.
Example 12
A method for modifying the surface of carbon fiber comprises the step of preserving the temperature of vapor-grown carbon fiber coated with polybutadiene resin/organic silicon resin sizing agent (mass ratio is 2:9) for 12min at 290 ℃ in an oxidizing atmosphere, wherein the oxidizing atmosphere is a mixed gas environment of nitrogen dioxide, chlorine and helium, the volume ratio of the chlorine in the mixed gas environment is 5%, and the volume ratio of the nitrogen dioxide is 15%.
The prepared carbon fiber surface coated with the polybutadiene resin/organic silicon resin sizing agent is rich in carboxyl, and the ratio of the carboxyl to the molar content of C-C bonds on the surface is 19.64%.
Example 13
A method for modifying the surface of carbon fiber is characterized in that polyacrylonitrile-based carbon fiber coated with unsaturated polyester resin/organic silicon resin sizing agent (mass ratio is 1:1) on the surface is subjected to heat preservation for 1min at 255 ℃ in oxidizing atmosphere, wherein the oxidizing atmosphere is mixed gas environment of chlorine and krypton, and the volume ratio of the chlorine in the mixed gas environment is 6%.
The prepared carbon fiber surface coated with the unsaturated polyester resin/organic silicon resin sizing agent is rich in carboxyl, and the ratio of the carboxyl to the molar content of C-C bonds on the surface is 14.41 percent.
Example 14
A method for modifying the surface of carbon fiber comprises the step of preserving the temperature of viscose-based carbon fiber coated with a phenolic resin/melamine formaldehyde resin sizing agent (mass ratio is 2:3) at 345 ℃ for 14min in an oxidizing atmosphere, wherein the oxidizing atmosphere is a mixed gas environment of nitrogen dioxide and xenon, and the volume ratio of the nitrogen dioxide in the mixed gas environment is 70%.
The prepared carbon fiber surface coated with the phenolic resin/melamine formaldehyde resin sizing agent is rich in carboxyl, and the ratio of the carboxyl to the C-C bond molar content on the surface is 6.41%.
Example 15
A method for modifying the surface of carbon fiber is characterized in that phenolic carbon fiber coated with furan resin/organic silicon resin sizing agent (mass ratio is 1:3) on the surface is subjected to heat preservation for 7min at 305 ℃ in oxidizing atmosphere, wherein the oxidizing atmosphere is a mixed gas environment of sulfur dioxide, chlorine and radon, the volume ratio of chlorine in the mixed gas environment is 15%, and the volume ratio of sulfur dioxide is 25%.
The prepared carbon fiber surface of the surface-coated furan resin/organic silicon resin sizing agent is rich in carboxyl, and the ratio of the carboxyl to the molar content of C-C bonds on the surface is 11.58%.
Example 16
A method for modifying the surface of carbon fiber comprises the step of preserving the temperature of bacterial cellulose-based carbon fiber coated with polybutadiene resin/phenolic resin sizing agent (mass ratio is 3:1) at 255 ℃ for 4min in oxidizing atmosphere, wherein the oxidizing atmosphere is a mixed gas environment of sulfur trioxide, oxygen and radon gas, the volume ratio of the sulfur trioxide in the mixed gas environment is 2%, and the volume ratio of the oxygen is 4%.
The prepared carbon fiber surface coated with the polybutadiene resin/phenolic resin sizing agent is rich in carboxyl, and the ratio of the carboxyl to the molar content of C-C bonds on the surface is 21.70%.
Claims (7)
1. A method for modifying the surface of carbon fiber is characterized by comprising the following steps: carrying out low-temperature heat treatment on the carbon fiber coated with the thermosetting resin sizing agent on the surface to ensure that the surface of the carbon fiber coated with the thermosetting resin sizing agent is rich in carboxyl; the ratio of the molar content of carboxyl to the molar content of C-C bonds on the surface is 2-30%;
the low-temperature heat treatment refers to heat preservation for 0.5-15 min at 250-350 ℃;
the thermosetting resin sizing agent comprises more than one of epoxy resin and derivatives thereof, unsaturated polyester resin, polyurethane resin, phenolic resin, melamine formaldehyde resin, furan resin, polybutadiene resin and organic silicon resin.
2. The method of claim 1, wherein the carbon fiber is one or more of polyacrylonitrile-based carbon fiber, petroleum pitch-based carbon fiber, coal pitch-based carbon fiber, viscose-based carbon fiber, phenolic-based carbon fiber, vapor-grown carbon fiber, bacterial cellulose-based carbon fiber, and lignin-based carbon fiber.
3. The method for surface modification of carbon fiber according to claim 1, wherein the low-temperature heat treatment is carried out in an oxidizing atmosphere; the oxidizing atmosphere is oxidizing gas environment or mixed gas environment of oxidizing gas and inert gas, and the volume ratio of the oxidizing gas in the mixed gas environment is more than or equal to 5%.
4. The method of claim 3, wherein the oxidizing gas is one or more of nitrogen dioxide, chlorine, sulfur dioxide, sulfur trioxide, air, and oxygen.
5. The method of claim 3, wherein the inert gas is nitrogen, argon, helium, neon, krypton, xenon, or radon.
6. The method for surface modification of carbon fiber according to claim 1, wherein the carboxyl group is a carboxyl group and/or a polymer and/or a particle grafted by reaction with the carboxyl group.
7. The method for surface modification of carbon fiber according to claim 6, wherein the polymer is one or more of polyurethane, polyamide, polyanhydride and polyester; the particles are more than one of nano graphene and carbon nano tubes.
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| CN110219168B (en) * | 2019-07-05 | 2021-12-31 | 聊城大学 | Carbon fiber surface modification method |
| CN110607693A (en) * | 2019-09-25 | 2019-12-24 | 安徽旭升新材料有限公司 | Method for modifying carbon fiber in carbon fiber PA66 thermoplastic composite material |
| CN110747647A (en) * | 2019-11-07 | 2020-02-04 | 武汉纺织大学 | Antibacterial carbon fiber sizing agent emulsion and preparation method and application thereof |
| CN113278173B (en) * | 2021-07-07 | 2022-07-26 | 中科英华长春高技术有限公司 | Application of lignin-based sizing agent in epoxy acrylate composite material |
| CN113529242A (en) * | 2021-07-29 | 2021-10-22 | 吉祥三宝高科纺织有限公司 | Method for preparing anti-cutting gloves by using carbon fiber composite material |
| CN115262278B (en) | 2022-08-01 | 2023-06-16 | 浙江科技学院 | Preparation method of high-uniformity double-layer gradient pore carbon paper base paper |
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