CN113308899A - Carbon fiber after surface sizing and preparation method and application thereof - Google Patents

Carbon fiber after surface sizing and preparation method and application thereof Download PDF

Info

Publication number
CN113308899A
CN113308899A CN202110576285.3A CN202110576285A CN113308899A CN 113308899 A CN113308899 A CN 113308899A CN 202110576285 A CN202110576285 A CN 202110576285A CN 113308899 A CN113308899 A CN 113308899A
Authority
CN
China
Prior art keywords
carbon fiber
hydroxyl
substance
sizing agent
alcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110576285.3A
Other languages
Chinese (zh)
Other versions
CN113308899B (en
Inventor
吕永根
姚莉丽
张晨阳
杨树磊
杨常玲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Donghua University
Original Assignee
Donghua University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Donghua University filed Critical Donghua University
Priority to CN202110576285.3A priority Critical patent/CN113308899B/en
Publication of CN113308899A publication Critical patent/CN113308899A/en
Application granted granted Critical
Publication of CN113308899B publication Critical patent/CN113308899B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • 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
    • D06M15/507—Polyesters
    • D06M15/51—Unsaturated polymerisable polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention relates to a carbon fiber after surface sizing, a preparation method and application thereof, wherein the preparation method comprises the following steps: dipping the carbon fiber without the sizing agent in a mixed solution of a substance A and alcohol, and reacting for 0.5-15 min at the polymerization temperature of 200-280 ℃; in the mixed solution of the substance A and the alcohol, the molar ratio of the substance A to the alcohol is 1: 1-1: 5; the substance A is unsaturated dibasic acid/anhydride or substance containing unsaturated acid/anhydride; the polyester sizing agent with a hyperbranched structure rich in hydroxyl groups is formed on the surface of the prepared carbon fiber after surface sizing; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 40-100%. The method of the invention directly adopts the monomer to form the polymeric coating on the surface of the carbon fiber, and the formed sizing agent has more active groups which can react with the surface of the carbon fiber or a matrix, so that the interface combination between the carbon fiber/the sizing agent/the matrix is improved, and the interface strength is improved.

Description

Carbon fiber after surface sizing and preparation method and application thereof
Technical Field
The invention belongs to the technical field of carbon fiber surface modification, and relates to a carbon fiber subjected to surface sizing and a preparation method thereof.
Background
The carbon fiber reinforced thermoplastic resin (CFRTP) -based composite material has the advantages of being recyclable, fast in molding, easy to repair, low in cost, excellent in extreme fatigue resistance and simple in prepreg storage conditions, and is widely applied to the fields of automobiles, aerospace, 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. However, the market share of CFRTP-based composites is still rather low compared to carbon fiber reinforced thermosetting resin composites, which is mainly directly related to the limitation of carbon fiber raw materials used in thermoplastic resin composites.
Most of the surfaces of the commercial carbon fibers are coated with epoxy resin sizing agents, which are suitable for thermosetting epoxy resin matrixes. The carbon fibers sized by the sizing agent are used for reinforcing thermoplastic resin matrixes, but the mechanical property of the sizing carbon fiber reinforced thermoplastic resin composite material is poor, because on one hand, epoxy groups on the surface of the epoxy resin sizing agent are incompatible with most thermoplastic matrixes and further lack of effective chemical bonding with the thermoplastic matrixes, so that the interlaminar shear strength of the composite material is low; on the other hand, the heat-resistant temperature of the thermosetting epoxy resin sizing agent is generally lower than the processing temperature of the plastic resin, so that in the process of processing and forming carbon fibers and the thermoplastic resin after sizing by the sizing agent, an unstable group of the epoxy resin sizing agent and a skeleton carbon chain of the sizing agent are cracked to generate a large amount of gas, a large amount of fine micropores are formed in the composite material, the composite material cannot be formed or the interface adhesive force is low, and the comprehensive mechanical property of the composite material is poor.
To avoid such problems, some researchers desize epoxy-coated carbon fibers. The desizing method comprises an ablation method and a solvent method, wherein the former method can generate a large amount of tar, the latter method needs a large amount of solvent, which not only pollutes the environment, but also the carbon fiber after desizing can generate a large amount of broken filaments and broken filaments in the subsequent processing process, thereby greatly reducing the quality of the carbon fiber. In addition, desizing at temperatures of 500 ℃ and higher can remove a large number of oxygen-containing functional groups from the carbon fibers, which is not favorable for wetting and interfacial bonding of the carbon fibers with 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.
Therefore, researchers at home and abroad have been working on developing a sizing agent suitable for a thermoplastic resin. Document 1(Composites: Part a,2016,87,212-219) uses a cyclohexane-cyclohexanol and tetrahydrofuran solution of a modified thermoplastic phenoxy resin to perform secondary sizing on commercial carbon fibers, and the interlaminar shear strength of the sized carbon fiber reinforced nylon 6 composite material is improved by 20.4%. The interfacial properties of the composite are improved to a lesser extent, which may be related to the poor compatibility of the sizing agent itself with the matrix.
In document 2(Applied Surface Science:2016,382, 144-. Document 3(Polymer Bulletin:1992,29,259-264) synthesized a compound containing acrylic acid and isocyanate, which was dissolved in a methylene chloride solvent to prepare a sizing agent, and the interfacial shear strength of the carbon fiber reinforced acrylic resin after sizing was increased by 131%. Document 4(Materials and Design:2015,88, 810-. The interface performance of the thermoplastic resin reinforced by the carbon fiber treated by the sizing agent is improved greatly, but the sizing agent uses organic solvent in the sizing process, has high toxicity and is difficult to recover, and inevitably causes the problems of environmental pollution and high cost; secondly, they also have the disadvantages that the sizing process time is too long to match with a carbon fiber continuous production line, and the on-line production requirement of the carbon fiber is difficult to meet.
In addition, the researchers developed sizing agents containing nanoparticles such as graphene oxide, carbon nanotubes and metal oxide, which have also proved to be an effective method for improving the interfacial properties of sized carbon fiber reinforced thermoplastic resins. However, the sizing agent also has the problems of environmental pollution, high cost, long sizing process time and the like, and is not beneficial to industrial large-scale use.
Therefore, the development of the carbon fiber sizing method which is environment-friendly, low in cost, short in sizing time and capable of improving the interface performance of the carbon fiber reinforced thermoplastic resin matrix is of practical significance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a carbon fiber after surface sizing as well as a preparation method and application thereof. The sizing agent is chemically grafted on the surface of the carbon fiber, so that the interface bonding force between the carbon fiber and the carbon fiber is enhanced, the compatibility between the carbon fiber and the thermoplastic resin matrix can be improved, and further, the chemical bonding effect is generated between the carbon fiber and the thermoplastic resin matrix, so that the interface and the mechanical property of the integral composite material are enhanced.
In order to achieve the purpose, the invention adopts the following scheme:
a surface-sized carbon fiber, wherein a polyester sizing agent with a hyperbranched structure rich in hydroxyl groups is formed on the surface of the carbon fiber;
the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 40-100%. The reaction of the invention has two types, one is esterification reaction of anhydride and hydroxyl, and the other is addition reaction of hydroxyl and double bond in the substance A. Both reactions consume hydroxyl in the system to cause the reduction of hydroxyl, and because the activity of double bonds in the unsaturated substance A is greatly enhanced by carboxyl and carbonyl, the addition reaction rate is faster than that of esterification reaction, and the content of hydroxyl is greatly reduced, but the content of hydroxyl needs to be controlled to be more than 40 percent, because the excessively low content of hydroxyl also means the excessive progress of the addition reaction, the branching points of the system are too much, the hydrogen bonding effect in molecules is too strong, partial groups are embedded in the molecules of the sizing agent, and the interaction between the groups on carbon fibers or a substrate is not facilitated, so that the interface bonding force between the carbon fibers and the sizing agent is reduced. Meanwhile, the ratio is controlled to be lower than 100 percent because the existence of a large amount of hydroxyl groups means that the degree of esterification and addition reaction is very low, the polymerization degree of a system is too low, even the system exists in the form of a liquid film, the bundling function of a sizing agent cannot be met, especially, the molecules with too low polymerization degree have low strength, become a weak point during interfacial force transmission when the composite material bears load, and are preferentially damaged, so that interlayer slippage and debonding between the carbon fiber and the resin interface are caused, and the composite material is damaged integrally.
As a preferred technical scheme:
the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl groups accounts for 1.0-2.5% of the mass of the carbon fiber after surface sizing. The content of sizing agent is too low, be unfavorable for the inside single carbon fiber of tow to be connected each other, can not satisfy fibrous function of bundling promptly, this will lead to the fact in the follow-up course of working of fibre, the fibre produces broken filament easily even fracture, cracked monofilament easily floats to in the air, in case inhale nasal cavity or mouth, can influence people's health, still can cause the destruction to surrounding environment, in case get into equipment, these electrically conductive carbon fibers just can initiate the equipment short circuit, light then interrupt production, heavy then cause the incident. The content of the sizing agent is too high and is not suitable, the sizing agent is limited by the oxygen-containing group of the carbon fiber, and only a small amount of groups per se and a small amount of sizing agent can interact through hydroxyl bonds or chemical bonds, so that the interface bonding force between the carbon fiber and the sizing agent is enhanced, and the stress transfer between the resin and the fiber is better carried out. However, too much sizing agent cannot participate in the formation of the interfacial region between the carbon fibers and the sizing agent, but exists between the bulk and the fibers and the resin, and cannot continue to play a role of reinforcing the interface, and an excessively high sizing amount causes unnecessary waste and increases in cost.
In the carbon fiber after surface sizing, more than one of covalent bond and hydrogen bond is formed between the active group on the carbon fiber and the polyester sizing agent with the hyperbranched structure rich in hydroxyl. The surface of the carbon fiber is provided with hydroxyl, carboxyl, ester group and other groups, wherein the carboxyl has higher activity and can form a covalent bond through esterification reaction with hydroxyl of a hyperbranched structure rich in hydroxyl, and the hydroxyl on the carbon fiber can form a hydrogen bond with the hydroxyl or the ester group on the polyester sizing agent of the hyperbranched structure, so that the interface bonding force between the carbon fiber and the sizing agent is enhanced, and the stress transfer between resin and fiber is better carried out.
The invention also provides a preparation method of the carbon fiber after surface sizing, which is characterized in that the carbon fiber without the sizing agent is soaked in the mixed solution of the substance A and the alcohol, and then the online polymerization reaction is carried out for 0.5-15 min at the temperature of 200-280 ℃ (the sizing time of the industrial carbon fiber cannot be too long, otherwise the filament winding speed needs to be reduced, thus the production efficiency is reduced); the surface treatment technology of the carbon fiber needs to be matched with the existing production line of the carbon fiber, so that the polymerization reaction between sizing agent molecules needs to be realized in a short time.
If the polymerization temperature of the carbon fiber surface sizing agent is lower than 200 ℃, the degree of converting carboxylic acid into anhydride is low, which is not beneficial to the esterification reaction of anhydride and hydroxyl, and the addition reaction of the hydroxyl and double bonds in the substance A is hardly generated below 200 ℃, so that the polymerization degree of the sizing agent is very low, even the sizing agent exists in a liquid film form, the bundling function of the sizing agent cannot be met, and in addition, the molecules with too low polymerization degree have low strength, which can become a weak point during interface stress transmission when the composite material bears load, and are preferentially damaged, thereby causing interlayer slippage and debonding between the carbon fiber and the resin interface, and further damaging the composite material integrally. If the polymerization temperature of the sizing agent exceeds 280 ℃, the addition reaction speed is too high, so that too many branch points of a system are caused, the hydrogen bond action in molecules is too strong, part of groups are embedded in the sizing agent molecules and are not beneficial to the interaction of the groups on carbon fibers or a matrix, and the interface bonding force between the carbon fibers and the sizing agent and between the sizing agent and the carbon fibers is reduced.
In the mixed solution of the substance A and the alcohol, the molar ratio of the substance A to the alcohol is 1: 1-1: 5;
the substance A is a substance containing unsaturated acid anhydride or unsaturated dibasic acid (such as unsaturated dibasic acid, unsaturated acid anhydride, and macromolecule and/or particle grafted by reacting with acid anhydride, wherein the macromolecule is more than one of polyurethane, polyamide and polyester, and the particle is more than one of nano graphene and carbon nano tube);
the alcohol is one or more of ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, 2-methyl-1, 3-propanediol, 1, 6-hexanediol, pentaerythritol, sorbitol, neopentyl glycol, glycerol, trimethylolpropane, 3-methyl-1, 5-pentanediol, 1, 4-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol and ethylene oxide polymer.
The carbon fiber can be one of polyacrylonitrile-based carbon fiber, petroleum pitch-based carbon fiber, coal pitch-based carbon fiber, viscose-based carbon fiber, phenolic-based carbon fiber, vapor-phase growth carbon fiber, bacterial cellulose-based carbon fiber, cellulose-based carbon fiber and lignin-based carbon fiber which are directly obtained by high-temperature carbonization, can also be more than one carbon fiber subjected to surface oxidation through anodic oxidation or other modes, can also be more than one carbon fiber subjected to sizing and high-temperature treatment to remove sizing agent, and can also be more than one carbon fiber subjected to surface oxidation after the sizing agent is removed.
As a preferred technical scheme:
in the method for preparing the carbon fiber after surface sizing, the unsaturated dibasic acid is more than one of maleic acid, itaconic acid, maleic acid derivatives and itaconic acid derivatives; the unsaturated anhydride is more than one of maleic anhydride, itaconic anhydride, maleic anhydride derivatives and itaconic anhydride derivatives.
In the method for preparing the carbon fiber after surface sizing, in the mixed solution of the substance A and the alcohol, the total mass concentration of the substance A and the alcohol is 2.5-12.5%, and the solvent is more than one of water and toluene; water is preferred.
The preparation method of the carbon fiber after surface sizing has the dipping temperature of room temperature (20-25 ℃) and the time of 0.5-15 min. The surface of the fiber is completely immersed during impregnation.
According to the preparation method of the carbon fiber after surface sizing, the problem that a large amount of monomers are taken away due to evaporation of the solvent in the high-temperature polymerization process of the monomers is avoided, so that the solvent is sufficiently removed at a low temperature before polymerization reaction, the temperature for removing the solvent (namely, the drying temperature) is 80-150 ℃, and the time is generally 0.5-15 min.
In the method for preparing the carbon fiber after surface sizing, the total content of the substance A and the alcohol on the carbon fiber accounts for 1.5-3.5% of the mass ratio of the carbon fiber during polymerization reaction.
The invention also provides an application of the carbon fiber after surface sizing, which is characterized in that the carbon fiber after surface sizing and a nylon film with the thickness of 10-100 mu m (preferably 50-80 mu m) are subjected to hot-press bonding to prepare a nylon film and carbon fiber composite material with the weight ratio of 8: 2-3: 7 (preferably 5: 5-3: 7) under the conditions of the temperature of 200-300 ℃ (preferably 260-280 ℃), the pressure of 4-7 MPa (preferably 5-7 MPa) and the time of 15-45 min (preferably 20-40 min), and the interlayer shear strength (ILSS) of the composite material is tested by taking JC/T773-.
The principle of the invention is as follows:
the raw material A selected in the invention is unsaturated dibasic acid or a substance containing unsaturated anhydride, and alcohol is also added, so that the raw material is easy to obtain, the cost is low, the molar ratio of the substance A to the alcohol is controlled to be 1: 1-1: 5, and the polymerization reaction temperature is 200-280 ℃; since unsaturated dibasic acids themselves dehydrate at 130 ° to form unsaturated anhydrides, the groups that react with alcohols in the present invention are mainly anhydrides of unsaturated anhydrides, and the reactions include the following two: the first reaction is the process of generating ester by the esterification reaction of the anhydride in the unsaturated anhydride and the hydroxyl of alcohol; the second reaction is the process of the addition reaction of the double bond in the unsaturated anhydride and the hydroxyl group of the alcohol to form ether bond. Under the condition that the molar ratio of the substance A to the alcohol is 1: 1-1: 5, the polyester which is the product of the first reaction is terminated by excessive hydroxyl, the product can perform addition reaction through the hydroxyl and double bonds of the product, and the product can also perform addition reaction with the hydroxyl on the excessive alcohol, so that a structure of the polyester rich in the hydroxyl is formed.
However, in the prior art, the carbon fiber surface sizing agent generally selects alcohol with the functionality of 2, the proportion of the dibasic acid to the alcohol is close to 1:1, and the temperature is controlled below 120 ℃, so that the second reaction is avoided as much as possible. Therefore, the product of the reaction in the prior art is a linear high polymer molecular chain structure, and the structural substance is used as a sizing agent of the carbon fiber, so that the fiber can be endowed with a better coating effect, namely, the sizing convergence can be satisfied; however, linear molecules are easy to curl, and oxygen-containing groups are easy to wrap inside the molecules, so that the surface energy of the molecules is reduced, the infiltration of a matrix on the surface of the sized carbon fiber is not facilitated, the interaction between sizing agent molecules and the matrix molecules is also not facilitated, the interface bonding force is weak, and the interface strength is reduced.
Secondly, it is reported in the literature that starting materials of unsaturated anhydride and glycidol are used, a two-step temperature treatment is carried out by using an anhydride to alcohol ratio of less than 1, and a catalyst ZnCl is added2And organic solvents (e.g., benzene) from the preparation of self-crosslinking gums; in this process, the two-step temperature treatment means: firstly, the low-temperature treatment is carried out at 80 ℃ for 2h to generate a first reaction to form a linear oligomer molecular chain structure, and then the high-temperature curing is carried out to form a cross-linking structure for the preparation of the adhesive. The preparation process of the glue needs two steps, in order to ensure that two reactions can not be carried out simultaneously, the temperature of the first step is set to be lower, so that the first reaction can only be carried out in the first step, the obtained product of the first step is liquid, the liquid can be used as the glue, when the glue is used by a customer, the second step of temperature rise treatment is carried out on site, solidification is carried out, and the bonding of site materials is realized. The two-step glue preparation process, particularly the first step, has low temperature and low reaction rate, the reaction time is as long as several hours, and the process cannot be matched with the online production of carbon fibers, so the process cannot be applied to carbon fiber sizing agents.
However, in the present invention, the esterification reaction of the first is disturbed to a lesser extent, since an excess of alcohol, and the occurrence of the second reaction, increases the steric hindrance of the group; the second reaction, namely the addition reaction of double bonds and hydroxyl groups, is mainly used, and more branch points rich in hydroxyl groups are generated on the molecules to form the polyester with the hyperbranched structure.
The substance with the structure is used as a sizing agent, the substance is not easy to curl like linear molecules, oxygen-containing groups are wrapped in the molecules, the groups on the hyperbranched structure molecules are more exposed, and can be easily interacted with carbon fibers or matrix molecules through hydrogen bonds or covalent bonds, so that the interface bonding force is increased, and in addition, the molecules are rich in hydroxyl groups, so that the compatibility of the carbon fibers and the matrix is favorably improved, and the interface strength is improved.
In addition, the invention adopts unsaturated acid and alcohol as monomers, the first is esterification gradual polymerization, the reaction rate is slower, the second reaction is faster because of the high activity of the double bond of the raw materials, and therefore, the rate of the whole reaction is determined by the first reaction. The degree of polymerization in the stepwise polymerization principle is proportional to the degree of reaction and inversely proportional to the water content of the system. The specific surface area of the carbon fiber is large, so that moisture can be timely discharged at a high temperature, the reaction degree is improved, and the reaction degree of the system can also be improved by increasing the temperature. Therefore, high-temperature reaction can be used, full conversion of functional groups can be realized in a short time to realize polymerization, and meanwhile, the selection of the sizing concentration can realize the sizing amount of industrial application, so that the requirements of online sizing production of carbon fibers for 1-3 min are met, and the method has great industrial application prospect.
The invention adopts water-soluble small molecular monomer as the sizing agent raw material, can directly dissolve in water without using organic solvent, and then forms a high molecular structure by temperature treatment and polymerization after sizing, but most of the prior art adopts organic solvent because the raw material of the sizing agent is oligomer or high polymer, thus the requirements of the sizing agent on molecular weight and strength per se can be met, but the water solubility is low, so the organic solvent is needed to be used for dissolving, and carbon fiber is soaked and sized after being prepared into solution.
Advantageous effects
(1) According to the preparation method of the carbon fiber surface sizing agent, the monomers are directly adopted to form the polymerization coating on the carbon fiber surface, so that molecules of the sizing agent are grafted to the carbon fiber surface, and the chemical bonding between the carbon fiber and the sizing agent is promoted, so that the interface bonding force of the carbon fiber and the sizing agent is improved, and the integral mechanical property of the composite material is further improved;
(2) the preparation method of the carbon fiber surface sizing agent has short sizing process time, can be matched with a carbon fiber continuous production line, and meets the online production requirement of carbon fibers.
(3) Compared with a thermoplastic sizing agent, the thermosetting sizing agent formed on the surface of the carbon fiber has more active groups capable of reacting with the surface of the carbon fiber, 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 preparation method of the carbon fiber surface sizing agent is environment-friendly, low in cost and excellent in compatibility with a resin matrix, can achieve the same effect as the reported sized carbon fiber after the carbon fiber obtained by high-temperature carbonization is treated, has rich acid anhydride groups capable of reacting 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 reinforced thermoplastic matrix, and has great application prospect.
Drawings
FIG. 1 is an XPS spectrum of the surface chemical composition of the sized carbon fibers of example 1;
FIG. 2 is a surface chemical composition XPS spectrum of untreated and unsized carbon fiber of comparative example 1;
FIG. 3 is a graph comparing the interlaminar shear strength of the sized carbon fiber/nylon 66 composite prepared in example 1 and the untreated and unsized carbon fiber/nylon 66 composite prepared in comparative example 1.
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.
The carbon fiber sources used in the present invention are shown in table 1.
TABLE 1
Figure BDA0003084453970000061
Figure BDA0003084453970000071
Example 1
A preparation method of carbon fiber after surface sizing comprises the following specific steps:
(1) preparing raw materials;
alcohol: glycerol;
substance A: maleic acid;
carbon fiber without sizing agent: polyacrylonitrile-based carbon fibers;
water;
(2) soaking carbon fiber without sizing agent in mixed solution of substance A and alcohol (the solvent of the mixed solution is water) at 25 deg.C for 15 min; then taking out and fully removing water, wherein the temperature (namely drying temperature) for removing water is 130 ℃, the time is 15min, and then carrying out polymerization reaction for 15min at the polymerization temperature of 280 ℃;
in the mixed solution of the substance A and the alcohol, the molar ratio of the substance A to the alcohol is 1: 2; the total mass concentration of the substance A and the alcohol is 5.5 percent;
during the polymerization reaction, the total content of substance a and alcohol on the carbon fiber was 1.5% by mass of the carbon fiber.
In the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 75.4 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1 percent of the mass of the carbon fiber.
The application comprises the following steps: the carbon fiber after surface sizing and a nylon membrane with the thickness of 50 mu m are subjected to hot-press bonding to prepare the nylon membrane-carbon fiber composite material with the weight ratio of 4:6 under the conditions of the temperature of 280 ℃, the pressure of 6.6MPa and the time of 40min, and the interlayer shear strength (ILSS) of the composite material is tested by taking JC/T773-one 2010 as a standard, and the test result is 66.4 MPa.
Comparative example 1
A preparation method of a nylon membrane and carbon fiber composite material is basically the same as that of example 1, except that carbon fibers used when the nylon membrane with the thickness of 50 μm is compounded are non-sized polyacrylonitrile-based carbon fibers;
as shown in FIG. 3, the interlaminar shear strength (ILSS) of the resulting nylon film and carbon fiber composite was 46.6 MPa.
Compared with the embodiment 1, the interlaminar shear strength of the comparative example 1 is far lower than that of the embodiment 1, because the surface of the carbon fiber after sizing is rich in hydroxyl groups, and the molecular structure of the sizing agent is a hyperbranched structure, the hydroxyl groups are not easily coated by molecular chains and are more easily exposed, and the original active carboxyl groups on the carbon fiber act to form esterified covalent bonds, so that the interface bonding force between the carbon fiber and the sizing agent is enhanced, and the stress transfer between the resin and the fiber is better carried out; an XPS spectrum of the surface chemical composition of the non-sized polyacrylonitrile-based carbon fiber is shown in FIG. 2, and an XPS spectrum of the surface chemical composition of the sized polyacrylonitrile-based carbon fiber is shown in FIG. 1; the analysis of the combined graphs 1 and 2 shows that the peaks at 284.6 ev and 285.1ev represent sp respectively2And sp3286.1ev represents a hydroxyl group or an ether bond C-OH&The peak of 286.9ev represents the anhydride group O ═ C-O-C ═ O, the peak of 288.3-289.7 ev represents the carboxyl group or the ester group COOH or COO, and the peak of 290.3-292.7 ev represents the pi-pi bond. Analysis of the above graphs revealed that the molar ratio of hydroxyl groups to carbon-carbon bonds on the surface of the carbon fiber that had not been sized was 31.6%, while the molar ratio of hydroxyl groups to carbon-carbon bonds on the surface of the carbon fiber that had been sized was 75.4%. It can be seen that the carbon fiber surface after surface sizing in the present invention is rich in hydroxyl groups.
Example 2
A preparation method of carbon fiber after surface sizing comprises the following specific steps:
(1) preparing raw materials;
alcohol: glycerol;
substance A: maleic acid;
carbon fiber without sizing agent: petroleum pitch-based carbon fibers;
water;
(2) soaking carbon fiber without sizing agent in mixed solution of substance A and alcohol (the solvent of the mixed solution is water) at 20 deg.C for 5 min; then taking out and fully removing water, wherein the temperature (namely drying temperature) for removing water is 100 ℃, the time is 5min, and then carrying out polymerization reaction for 5min at the polymerization temperature of 220 ℃;
in the mixed solution of the substance A and the alcohol, the molar ratio of the substance A to the alcohol is 1: 3; the total mass concentration of the substance A and the alcohol is 2.5 percent;
during the polymerization reaction, the total content of substance a and alcohol on the carbon fiber was 1.6% by mass of the carbon fiber.
In the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 60 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.1 percent of the mass of the carbon fiber.
The application comprises the following steps: the carbon fiber after surface sizing and a nylon membrane with the thickness of 80 mu m are prepared into a nylon membrane and carbon fiber composite material with the weight ratio of 2:8 by adopting a hot-pressing adhesion process under the conditions of the temperature of 250 ℃, the pressure of 4.5MPa and the time of 20min, and the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-.
Example 3
A preparation method of carbon fiber after surface sizing comprises the following specific steps:
(1) preparing raw materials;
alcohol: diethylene glycol;
substance A: itaconic acid;
carbon fiber without sizing agent: coal tar pitch-based carbon fibers;
water;
(2) soaking carbon fiber without sizing agent in mixed solution of substance A and alcohol (the solvent of the mixed solution is water) at 22 deg.C for 10 min; then taking out and fully removing water, wherein the temperature (namely drying temperature) for removing water is 110 ℃, the time is 10min, and then carrying out polymerization reaction for 8min when the polymerization temperature is 270 ℃;
in the mixed solution of the substance A and the alcohol, the molar ratio of the substance A to the alcohol is 1: 1; the total mass concentration of the substance A and the alcohol is 6 percent;
during the polymerization reaction, the total content of substance a and alcohol on the carbon fiber was 1.7% by mass of the carbon fiber.
In the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 80 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.2 percent of the mass of the carbon fiber.
The application comprises the following steps: the carbon fiber after surface sizing and a nylon membrane with the thickness of 70 mu m are subjected to hot-press bonding to prepare a nylon membrane-carbon fiber composite material with the weight ratio of 5:5 under the conditions of the temperature of 240 ℃, the pressure of 5.5MPa and the time of 35min, and the interlayer shear strength (ILSS) of the composite material is tested by taking JC/T773-one 2010 as a standard, wherein the test result is 85 MPa.
Example 4
A preparation method of carbon fiber after surface sizing comprises the following specific steps:
(1) preparing raw materials;
alcohol: polyethylene glycol 600;
substance A: maleic anhydride;
carbon fiber without sizing agent: viscose-based carbon fibers;
water;
(2) soaking carbon fiber without sizing agent in mixed solution of substance A and alcohol (the solvent of the mixed solution is water) at 21 deg.C for 0.5 min; then taking out and fully removing water, wherein the temperature (namely drying temperature) for removing water is 120 ℃, the time is 6min, and then carrying out polymerization reaction for 6min at the polymerization temperature of 260 ℃;
in the mixed solution of the substance A and the alcohol, the molar ratio of the substance A to the alcohol is 1: 2; the total mass concentration of the substance A and the alcohol is 3.3 percent;
during the polymerization reaction, the total content of substance a and alcohol on the carbon fiber was 2.3% by mass of the carbon fiber.
In the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 100 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.6 percent of the mass of the carbon fiber.
The application comprises the following steps: the carbon fiber after surface sizing and a nylon film with the thickness of 60 mu m are subjected to hot-press bonding to prepare the nylon film and carbon fiber composite material with the weight ratio of 3:7 under the conditions of the temperature of 260 ℃, the pressure of 6MPa and the time of 40min, and the interlayer shear strength (ILSS) of the composite material is tested by taking JC/T773-one 2010 as a standard, and the test result is 100 MPa.
Example 5
A preparation method of carbon fiber after surface sizing comprises the following specific steps:
(1) preparing raw materials;
alcohol: polyethylene glycol 1000;
substance A: itaconic anhydride;
carbon fiber without sizing agent: phenolic-based carbon fibers;
water;
(2) soaking carbon fiber without sizing agent in mixed solution of substance A and alcohol (the solvent of the mixed solution is water) at 23 deg.C for 3 min; then taking out and fully removing water, wherein the temperature (namely drying temperature) for removing water is 150 ℃, the time is 0.5min, and then carrying out polymerization reaction for 3min at the polymerization temperature of 200 ℃;
in the mixed solution of the substance A and the alcohol, the molar ratio of the substance A to the alcohol is 1: 5; the total mass concentration of the substance A and the alcohol is 10 percent;
during the polymerization reaction, the total content of substance a and alcohol on the carbon fiber was 2.9% by mass of the carbon fiber.
In the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 50 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 2 percent of the mass of the carbon fiber.
The application comprises the following steps: the carbon fiber after surface sizing and a nylon film with the thickness of 40 mu m are subjected to hot-press bonding to prepare the nylon film and carbon fiber composite material with the weight ratio of 7:3 under the conditions of the temperature of 270 ℃, the pressure of 7MPa and the time of 25min, and the interlayer shear strength (ILSS) of the composite material is tested by taking JC/T773-one 2010 as a standard, and the test result is 55 MPa.
Example 6
A preparation method of carbon fiber after surface sizing comprises the following specific steps:
(1) preparing raw materials;
alcohol: tetraethylene glycol;
substance A: maleic anhydride;
carbon fiber without sizing agent: vapor-grown carbon fibers;
water;
(2) soaking carbon fiber without sizing agent in mixed solution of substance A and alcohol (the solvent of the mixed solution is water) at 24 deg.C for 13 min; then taking out and fully removing water, wherein the temperature (namely drying temperature) for removing water is 140 ℃, the time is 13min, and then carrying out polymerization reaction for 0.5min at the polymerization temperature of 220 ℃;
in the mixed solution of the substance A and the alcohol, the molar ratio of the substance A to the alcohol is 1: 4; the total mass concentration of the substance A and the alcohol is 11 percent;
during the polymerization reaction, the total content of substance a and alcohol on the carbon fiber was 3.1% by mass of the carbon fiber.
In the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 40 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 2.2 percent of the mass of the carbon fiber.
The application comprises the following steps: the carbon fiber after surface sizing and a nylon film with the thickness of 30 mu m are subjected to hot-press bonding to prepare the nylon film and carbon fiber composite material with the weight ratio of 8:2 under the conditions of the temperature of 200 ℃, the pressure of 5MPa and the time of 45min, and the interlayer shear strength (ILSS) of the composite material is tested by taking JC/T773-one 2010 as a standard, and the test result is 50 MPa.
Example 7
A preparation method of carbon fiber after surface sizing comprises the following specific steps:
(1) preparing raw materials;
alcohol: polyethylene glycol 400;
substance A: itaconic anhydride;
carbon fiber without sizing agent: cellulose-based carbon fibers;
water;
(2) soaking carbon fiber without sizing agent in mixed solution of substance A and alcohol (the solvent of the mixed solution is water) at 25 deg.C for 8 min; then taking out and fully removing water, wherein the temperature (namely drying temperature) for removing water is 90 ℃, the time is 9min, and then carrying out polymerization reaction for 4min at the polymerization temperature of 250 ℃;
in the mixed solution of the substance A and the alcohol, the molar ratio of the substance A to the alcohol is 1: 2; the total mass concentration of the substance A and the alcohol is 12.5 percent;
during the polymerization reaction, the total content of substance a and alcohol on the carbon fiber was 3.5% by mass of the carbon fiber.
In the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 70%; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 2.5 percent of the mass of the carbon fiber.
The application comprises the following steps: the carbon fiber after surface sizing and a nylon film with the thickness of 100 mu m are subjected to hot-press bonding to prepare the nylon film and carbon fiber composite material with the weight ratio of 6:4 under the conditions of the temperature of 300 ℃, the pressure of 4MPa and the time of 30min, and the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-one 2010 as a standard, and the test result is 69.5 MPa.
Example 8
A preparation method of carbon fiber after surface sizing comprises the following specific steps:
(1) preparing raw materials;
alcohol: 1, 4-butanediol;
substance A: maleic acid;
carbon fiber without sizing agent: lignin-based carbon fibers;
water;
(2) soaking carbon fiber without sizing agent in mixed solution of substance A and alcohol (the solvent of the mixed solution is water) at 20 deg.C for 12 min; then taking out and fully removing water, wherein the temperature (namely drying temperature) for removing water is 130 ℃, the time is 13min, and then carrying out polymerization reaction for 10min at the polymerization temperature of 240 ℃;
in the mixed solution of the substance A and the alcohol, the molar ratio of the substance A to the alcohol is 1: 3; the total mass concentration of the substance A and the alcohol is 7.5 percent;
during the polymerization reaction, the total content of substance a and alcohol on the carbon fiber was 2.1% by mass of the carbon fiber.
In the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 55 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.5 percent of the mass of the carbon fiber.
The application comprises the following steps: the carbon fiber after surface sizing and a nylon film with the thickness of 10 mu m are prepared into a nylon film and carbon fiber composite material with the weight ratio of 4:6 by adopting a hot-pressing adhesion process under the conditions of the temperature of 230 ℃, the pressure of 5MPa and the time of 15min, and the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-one 2010 as a standard, and the test result is 64.9 MPa.
Example 9
A preparation method of carbon fiber after surface sizing comprises the following specific steps:
(1) preparing raw materials;
alcohol: ethylene glycol;
substance A: 2, 3-dimethylmaleic acid;
carbon fiber without sizing agent: polyacrylonitrile-based carbon fibers;
water;
(2) soaking carbon fiber without sizing agent in mixed solution of substance A and alcohol (the solvent of the mixed solution is water) at 23 deg.C for 0.5 min; then taking out and fully removing the toluene, wherein the temperature (namely drying temperature) for removing the toluene is 80 ℃, the time is 15min, and then carrying out polymerization reaction for 15min at the polymerization temperature of 200 ℃;
in the mixed solution of the substance A and the alcohol, the molar ratio of the substance A to the alcohol is 1: 4; the total mass concentration of the substance A and the alcohol is 5.5 percent;
during the polymerization reaction, the total content of substance a and alcohol on the carbon fiber was 1.5% by mass of the carbon fiber.
In the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 40 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1 percent of the mass of the carbon fiber.
The application comprises the following steps: the carbon fiber after surface sizing and a nylon film with the thickness of 10 mu m are prepared into a nylon film and carbon fiber composite material with the weight ratio of 8:2 by adopting a hot-pressing adhesion process under the conditions of the temperature of 200 ℃, the pressure of 7MPa and the time of 45min, and the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-one 2010 as a standard, and the test result is 58.5 MPa.
Example 10
A preparation method of carbon fiber after surface sizing comprises the following specific steps:
(1) preparing raw materials;
alcohol: propylene glycol;
substance A: dimethyl itaconic acid;
carbon fiber without sizing agent: petroleum pitch-based carbon fibers;
the mass ratio is 1:1, a mixed solution of toluene and water;
(2) soaking carbon fiber without sizing agent in mixed solution of substance A and alcohol (the solvent of the mixed solution is mixed solution of toluene and water) at 25 deg.C for 15 min; then taking out the mixture, fully removing the mixed solution of toluene and water at the temperature of 150 ℃ (namely drying temperature) for 0.5min, and carrying out polymerization reaction at the polymerization temperature of 280 ℃ for 0.5 min;
in the mixed solution of the substance A and the alcohol, the molar ratio of the substance A to the alcohol is 1: 5; the total mass concentration of the substance A and the alcohol is 12.5 percent;
during the polymerization reaction, the total content of substance a and alcohol on the carbon fiber was 3.5% by mass of the carbon fiber.
In the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 100 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 2.5 percent of the mass of the carbon fiber.
The application comprises the following steps: the carbon fiber after surface sizing and a nylon film with the thickness of 100 mu m are prepared into a nylon film and carbon fiber composite material with the weight ratio of 3:7 by adopting a hot-pressing adhesion process under the conditions of the temperature of 300 ℃, the pressure of 4MPa and the time of 15min, and the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-one 2010 as a standard, and the test result is 90 MPa.
Example 11
A method for preparing carbon fiber after surface sizing, which is basically the same as example 1, except that a substance a is 2, 3-dichloromaleic anhydride, alcohol is 1, 3-propanediol, and carbon fiber without sizing agent is polyacrylonitrile-based carbon fiber;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 65.3 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.1 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 60.2 MPa.
Example 12
A method for preparing carbon fiber after surface sizing, which is basically the same as example 1, except that a substance a is dimethyl itaconic acid, alcohol is 1, 2-butanediol, and carbon fiber without sizing agent is petroleum pitch-based carbon fiber;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 69.2%; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.1 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 62.4 MPa.
Example 13
A method for preparing carbon fiber after surface sizing, which is basically the same as example 1, except that a substance A is a mixture of maleic acid and itaconic acid in a mass ratio of 1:1, alcohol is 1, 3-butanediol, and carbon fiber without sizing agent is coal pitch-based carbon fiber;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 71.2 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.1 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 65.7 MPa.
Example 14
A method for preparing carbon fibers after surface sizing, which is basically the same as that in example 1, except that a substance a is a mixture of maleic anhydride and itaconic anhydride in a mass ratio of 1:1, an alcohol is 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, and carbon fibers without a sizing agent are viscose-based carbon fibers;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 75.4 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.1 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 66.4 MPa.
Example 15
A method for preparing carbon fiber after surface sizing, which is basically the same as that in example 1, except that a substance a is polyurethane grafted with itaconic anhydride (the mass ratio of the grafted polyurethane to the itaconic anhydride is 4.2), alcohol is 2-methyl-1, 3-propanediol, and carbon fiber without sizing agent is phenolic-based carbon fiber;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 56.3 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.3 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 60.3 MPa.
Example 16
A method for preparing carbon fiber after surface sizing, which is basically the same as example 1, except that the substance a is polyamide grafted with itaconic anhydride (the mass ratio of the grafted polyamide to the itaconic anhydride is 2.2), the alcohol is 1, 6-hexanediol, and the carbon fiber without the sizing agent is vapor grown carbon fiber;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 63.5 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.4 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 76.5 MPa.
Example 17
A method for preparing carbon fiber after surface sizing, which is basically the same as that in example 1, except that a substance a is polyester grafted with itaconic anhydride (the mass ratio of the grafted polyester to the itaconic anhydride is 2.2), alcohol is pentaerythritol, and carbon fiber without sizing agent is bacterial cellulose-based carbon fiber;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich refers to that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 77.4 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.4 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 78.4 MPa.
Example 18
A method for preparing carbon fiber after surface sizing, which is basically the same as example 1, except that a substance a is a carbon fiber having a mass ratio of 1:1 (a) a mixture of itaconic anhydride grafted polyurethane (mass ratio of grafted polyurethane to itaconic anhydride of 4.2) and itaconic anhydride grafted polyester (mass ratio of grafted polyester to itaconic anhydride of 2.2), the alcohol being sorbitol, the carbon fibers without sizing being cellulose-based carbon fibers;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 80.4 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.4 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 85.5 MPa.
Example 19
A preparation method of carbon fiber after surface sizing, which is basically the same as that in example 1, except that a substance a is nanographene grafted with itaconic anhydride (the mass ratio of the grafted nanographene to the itaconic anhydride is 0.1%), alcohol is neopentyl glycol, and carbon fiber without a sizing agent is lignin-based carbon fiber;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 67.4 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.3 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 65.2 MPa.
Example 20
A method for preparing carbon fiber after surface sizing, which is basically the same as example 1, except that a substance a is carbon nanotubes grafted with itaconic anhydride (the mass ratio of the grafted carbon nanotubes to the itaconic anhydride is 0.1%), alcohol is trimethylolpropane, and carbon fiber without sizing agent is lignin-based carbon fiber;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 75.2 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.3 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 66.4 MPa.
Example 21
A method for preparing carbon fiber after surface sizing, which is basically the same as that in example 1, except that a substance a is a mixture of nano graphene grafted with itaconic anhydride (the mass ratio of the grafted nano graphene to the itaconic anhydride is 0.1%) and carbon nanotube grafted with itaconic anhydride (the mass ratio of the grafted carbon nanotube to the itaconic anhydride is 0.1%) in a mass ratio of 1:1, an alcohol is 3-methyl-1, 5-pentanediol, and carbon fiber without a sizing agent is cellulose-based carbon fiber;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 70.3 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.3 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material was prepared under the same process and process parameters as in example 1, and the interlaminar shear strength (ILSS) of the composite material was tested using JC/T773-2010 as a standard, and the test result was 67.3 MPa.
Example 22
A method for preparing carbon fiber after surface sizing, which is basically the same as example 1, except that a substance a is polyurethane grafted with maleic anhydride (the mass ratio of the grafted polyurethane to the maleic anhydride is 4.8), alcohol is 1, 4-cyclohexanedimethanol, and carbon fiber without sizing agent is bacterial cellulose-based carbon fiber;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 58.2 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.4 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 66.9 MPa.
Example 23
A method for preparing carbon fiber after surface sizing, which is basically the same as example 1, except that the substance a is polyamide grafted with maleic anhydride (the mass ratio of the grafted polyamide to the maleic anhydride is 2.5), the alcohol is 1, 3-cyclohexanedimethanol, and the carbon fiber without the sizing agent is vapor grown carbon fiber;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 64.6 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.4 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 70.4 MPa.
Example 24
A method for preparing carbon fiber after surface sizing, which is basically the same as example 1, except that a substance a is polyester grafted with maleic anhydride (the mass ratio of the grafted polyester to the maleic anhydride is 2.5), alcohol is dipropylene glycol, and carbon fiber without sizing agent is phenolic-based carbon fiber;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 75.4 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.4 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 77.4 MPa.
Example 25
A method for preparing carbon fiber after surface sizing, which is basically the same as example 1, except that a substance a is polyurethane grafted with maleic anhydride (the mass ratio of the grafted polyurethane to the maleic anhydride is 4.8), alcohol is triethylene glycol, and carbon fiber without sizing agent is viscose-based carbon fiber;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 66.3 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.4 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 66.3 MPa.
Example 26
A method for preparing carbon fiber after surface sizing, which is basically the same as example 1, except that a substance a is polyamide grafted with maleic anhydride, alcohol is ethylene oxide polymer, and carbon fiber without sizing agent is coal pitch-based carbon fiber;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich refers to that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 77.4 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.4 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 62.7 MPa.
Example 27
A preparation method of carbon fiber after surface sizing, which is basically the same as example 1, except that a substance A is nano graphene grafted with maleic anhydride, alcohol is a mixture of triethylene glycol and tetraethylene glycol in a mass ratio of 1:1, and carbon fiber without sizing agent is petroleum asphalt-based carbon fiber;
in the prepared carbon fiber after surface sizing, polyester sizing agent with hyperbranched structure rich in hydroxyl is formed on the surface of the carbon fiber; the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 66.5 percent; the amount of the polyester sizing agent with the hyperbranched structure rich in hydroxyl accounts for 1.3 percent of the mass of the carbon fiber; the nylon film and carbon fiber composite material is prepared under the same process and process parameters as the example 1, the interlaminar shear strength (ILSS) of the composite material is tested by taking JC/T773-2010 as a standard, and the test result is 65.3 MPa.

Claims (10)

1. A carbon fiber after surface sizing is characterized in that: forming a polyester sizing agent with a hyperbranched structure rich in hydroxyl on the surface of the carbon fiber;
the hydroxyl-rich carbon fiber means that the molar content ratio of hydroxyl on the surface of the carbon fiber to carbon-carbon bond is 40-100%.
2. The surface-sized carbon fiber according to claim 1, wherein the amount of the polyester sizing agent having a hyperbranched structure rich in hydroxyl groups is 1.0 to 2.5% by mass of the carbon fiber.
3. The surface-sized carbon fiber according to claim 1, wherein the active groups on the carbon fiber form one or more of covalent bonds, hydrogen bonds and intermolecular forces with the polyester sizing agent having a hyperbranched structure rich in hydroxyl groups.
4. The method for producing surface-sized carbon fibers according to any one of claims 1 to 3, wherein: soaking carbon fibers without a sizing agent in a mixed solution of a substance A and alcohol, and performing polymerization reaction for 0.5-15 min at the temperature of 200-280 ℃;
in the mixed solution of the substance A and the alcohol, the molar ratio of the substance A to the alcohol is 1: 1-1: 5;
the substance A is a substance containing unsaturated anhydride or unsaturated dibasic acid;
the alcohol is one or more of ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, 2-methyl-1, 3-propanediol, 1, 6-hexanediol, pentaerythritol, sorbitol, neopentyl glycol, glycerol, trimethylolpropane, 3-methyl-1, 5-pentanediol, 1, 4-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol and ethylene oxide polymer.
5. The method of claim 4, wherein the unsaturated dibasic acid is one or more of maleic acid, itaconic acid, maleic acid derivatives, and itaconic acid derivatives; the unsaturated anhydride is more than one of maleic anhydride, itaconic anhydride, maleic anhydride derivatives and itaconic anhydride derivatives.
6. The method for producing surface-sized carbon fibers according to claim 4, wherein the total mass concentration of the substance A and the alcohol in the mixed solution of the substance A and the alcohol is 2.5 to 12.5%, and the solvent is one or more of water and toluene.
7. The method for preparing surface-sized carbon fiber according to claim 4, wherein the impregnation temperature is 20 to 25 ℃ and the time is 0.5 to 15 min.
8. The method for producing surface-sized carbon fiber according to claim 6, wherein the solvent is sufficiently removed before the polymerization reaction, and the temperature of the solvent removal is 80 to 150 ℃.
9. The method for producing surface-sized carbon fibers according to claim 6, wherein the total content of the substance A and the alcohol on the carbon fibers is 1.5 to 3.5% by mass of the carbon fibers during the polymerization reaction.
10. Use of a surface-sized carbon fibre according to any one of claims 1 to 3, characterized in that: the carbon fiber after surface sizing and a nylon film with the thickness of 10-100 mu m are subjected to hot-pressing adhesion to prepare a nylon film and carbon fiber composite material with the weight ratio of 8: 2-3: 7 under the conditions of the temperature of 200-300 ℃, the pressure of 4-7 MPa and the time of 15-45 min, and the interlayer shear strength (ILSS) of the composite material is tested by taking JC/T773-Bush 2010 as a standard, wherein the test result is 50-100 MPa.
CN202110576285.3A 2021-05-26 2021-05-26 Carbon fiber after surface sizing and preparation method and application thereof Active CN113308899B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110576285.3A CN113308899B (en) 2021-05-26 2021-05-26 Carbon fiber after surface sizing and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110576285.3A CN113308899B (en) 2021-05-26 2021-05-26 Carbon fiber after surface sizing and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113308899A true CN113308899A (en) 2021-08-27
CN113308899B CN113308899B (en) 2022-05-06

Family

ID=77375015

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110576285.3A Active CN113308899B (en) 2021-05-26 2021-05-26 Carbon fiber after surface sizing and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113308899B (en)

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1701148A (en) * 2001-05-25 2005-11-23 三菱丽阳株式会社 Sizing agent for carbon fiber, aqueous dispersion thereof, carbon fiber treated by sizing, sheet-form object comprising the carbon fiber, and carbon fiber-reinforced composite material
CN101001915A (en) * 2004-06-08 2007-07-18 兰爱克谢斯德国有限责任公司 Molding compounds based on a thermoplastic polyester having improved flowability
CN101381457A (en) * 2007-09-05 2009-03-11 中国科学院成都有机化学有限公司 Preparation method of aqueous hyperbranched intermediate and water soluble hyperbranched propenoic acid resin
CN101415748A (en) * 2006-03-30 2009-04-22 东丽株式会社 Dendritic polyester, method for producing the same, and thermoplastic resin composition
JP2011162647A (en) * 2010-02-09 2011-08-25 Toray Ind Inc Multi-branched polyester and composition thereof
CN102822278A (en) * 2010-03-23 2012-12-12 巴斯夫欧洲公司 Polyarylene ethers with improved flowability
CN102906145A (en) * 2010-05-27 2013-01-30 巴斯夫欧洲公司 Oil-absorbing polyurethane sponges with good mechanical properties
CN103842415A (en) * 2011-11-28 2014-06-04 赢创德固赛有限公司 Pseudothermoplastic, self-crosslinking composites
CN104011288A (en) * 2011-12-27 2014-08-27 东丽株式会社 Carbon fiber coated with sizing agent, process for producing carbon fiber coated with sizing agent, prepreg, and carbon fiber reinforced composite material
CN105646860A (en) * 2016-01-25 2016-06-08 四川美至科技有限公司 Sizing agent containing terminal carboxyl unsaturated polyester and preparation technology thereof
CN107531969A (en) * 2015-04-22 2018-01-02 英力士苯领集团股份公司 Translucent fibre composite comprising chemical modification of polymer
CN108484891A (en) * 2018-03-12 2018-09-04 吉林乾仁新材料有限公司 The preparation of self assembly self-emulsifying self-stabilization polyester-type high-performance fiber interface modification auxiliary agent and product and application
CN110128034A (en) * 2019-02-12 2019-08-16 吉林化工学院 It nano-oxide fabricated in situ and is applied in polyester-type carbon fiber sizing agent and basalt fibre/glass fiber infiltration agent
US20210071356A1 (en) * 2018-02-21 2021-03-11 Teijin Limited Sizing agent composition, method for producing carbon fibers, and carbon fibers each having sizing agent applied thereonto

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1701148A (en) * 2001-05-25 2005-11-23 三菱丽阳株式会社 Sizing agent for carbon fiber, aqueous dispersion thereof, carbon fiber treated by sizing, sheet-form object comprising the carbon fiber, and carbon fiber-reinforced composite material
CN101001915A (en) * 2004-06-08 2007-07-18 兰爱克谢斯德国有限责任公司 Molding compounds based on a thermoplastic polyester having improved flowability
CN101415748A (en) * 2006-03-30 2009-04-22 东丽株式会社 Dendritic polyester, method for producing the same, and thermoplastic resin composition
CN101381457A (en) * 2007-09-05 2009-03-11 中国科学院成都有机化学有限公司 Preparation method of aqueous hyperbranched intermediate and water soluble hyperbranched propenoic acid resin
JP2011162647A (en) * 2010-02-09 2011-08-25 Toray Ind Inc Multi-branched polyester and composition thereof
CN102822278A (en) * 2010-03-23 2012-12-12 巴斯夫欧洲公司 Polyarylene ethers with improved flowability
CN102906145A (en) * 2010-05-27 2013-01-30 巴斯夫欧洲公司 Oil-absorbing polyurethane sponges with good mechanical properties
CN103842415A (en) * 2011-11-28 2014-06-04 赢创德固赛有限公司 Pseudothermoplastic, self-crosslinking composites
CN104011288A (en) * 2011-12-27 2014-08-27 东丽株式会社 Carbon fiber coated with sizing agent, process for producing carbon fiber coated with sizing agent, prepreg, and carbon fiber reinforced composite material
CN107531969A (en) * 2015-04-22 2018-01-02 英力士苯领集团股份公司 Translucent fibre composite comprising chemical modification of polymer
CN105646860A (en) * 2016-01-25 2016-06-08 四川美至科技有限公司 Sizing agent containing terminal carboxyl unsaturated polyester and preparation technology thereof
US20210071356A1 (en) * 2018-02-21 2021-03-11 Teijin Limited Sizing agent composition, method for producing carbon fibers, and carbon fibers each having sizing agent applied thereonto
CN108484891A (en) * 2018-03-12 2018-09-04 吉林乾仁新材料有限公司 The preparation of self assembly self-emulsifying self-stabilization polyester-type high-performance fiber interface modification auxiliary agent and product and application
CN110128034A (en) * 2019-02-12 2019-08-16 吉林化工学院 It nano-oxide fabricated in situ and is applied in polyester-type carbon fiber sizing agent and basalt fibre/glass fiber infiltration agent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LINA YANG等: "Grafting of a novel hyperbranched polymer onto carbon fiber for interfacial enhancement of carbon fiber reinforced epoxy composites", 《MATERIALS & DESIGN》 *

Also Published As

Publication number Publication date
CN113308899B (en) 2022-05-06

Similar Documents

Publication Publication Date Title
CN108642882B (en) Method for modifying surface of carbon fiber
CN111690158B (en) Method for optimizing interface of basalt fiber reinforced resin matrix composite material
CN103665769B (en) The preparation method of the multiple dimensioned fiber prepreg material of nano-micrometre
CN111101371B (en) High-performance carbon nanotube/carbon composite fiber and rapid preparation method thereof
CN108976711A (en) Carbon nanotube-carbon fiber mixing reinforced epoxy composite material preparation method
CN105671937A (en) Modification method of ramie fibers using as environment-friendly composite material reinforcement
CN104277421A (en) Preparation method of multicomponent-modified carbon-fiber-reinforced epoxy resin composite material
CN108035143B (en) Method for simultaneously improving interface strength and toughness of carbon fiber epoxy composite material
CN111410759B (en) CF/PEEK composite material with excellent high-temperature mechanical property and preparation method thereof
CN101314664A (en) Preparation method for rare earth modified carbon nano-tube/epoxy resin composite material
CN107761375B (en) Method for grafting branched molecular tannic acid on surface of carbon fiber
CN110435239B (en) Multi-scale toughened epoxy resin-based carbon fiber composite material and preparation method thereof
CN111005229B (en) Carbon fiber sizing agent and preparation method thereof
CN106750064A (en) A kind of preparation method of phenolic resin renewable at room temperature and its recovery process and application
CN111572115B (en) CF/PEEK composite material with high fatigue strength and preparation method thereof
CN111410758B (en) High-impact interface modified CF/PEEK composite material and preparation method thereof
CN107880494A (en) A kind of carbon fibre initial rinse fabric and preparation method thereof and metal fiber composite
CN104194263A (en) Nanocrystalline cellulose (NCC) composite waterborne epoxy resin and preparation method thereof
CN113308899B (en) Carbon fiber after surface sizing and preparation method and application thereof
CN108503865B (en) Preparation method of carbon fiber reinforced nylon composite material
CN111393689B (en) CF/PPS composite material with high impact toughness and preparation method thereof
Lyu et al. Improving the interfacial adhesion between recycled carbon fibres and polyphenylene sulphide by bio-inspired dopamine for advanced composites manufacturing
CN118290782B (en) Fibrilia reinforced light resin composite material and preparation method thereof
CN111533931B (en) CF/PEEK composite material with full transverse crystal structure and preparation method thereof
CN118457012A (en) Graphene/carbon nanomaterial modified carbon fiber battery felt process

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant