CN111719311A - Modified carbon fiber, modified carbon fiber reinforced epoxy resin composite material and preparation method thereof - Google Patents
Modified carbon fiber, modified carbon fiber reinforced epoxy resin composite material and preparation method thereof Download PDFInfo
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Abstract
The application relates to a modified carbon fiber, a method for preparing the modified carbon fiber, a modified carbon fiber reinforced epoxy resin composite material with interface self-repairing performance and a method for preparing the modified carbon fiber reinforced epoxy resin composite material. The modified carbon fiber reinforced epoxy resin composite material has the advantages of simple and convenient repair conditions, easy realization, low repair cost, capability of repairing for multiple times and the like, and can effectively prolong the service life of the carbon fiber reinforced epoxy resin composite material.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a modified carbon fiber, a method for preparing the modified carbon fiber, a modified carbon fiber reinforced epoxy resin composite material with interface self-repairing performance and a method for preparing the modified carbon fiber reinforced epoxy resin composite material.
Background
The carbon fiber reinforced epoxy resin composite material has the advantages of high specific strength, fatigue resistance, high specific modulus, chemical corrosion resistance, strong designability, small thermal expansion coefficient, stable structure size and the like. As a novel high-performance composite material, the carbon fiber reinforced epoxy resin composite material can meet the strict requirements of special fields on weight, strength, rigidity, fatigue resistance, dimensional stability and the like. At present, carbon fiber reinforced epoxy resin composite materials are widely applied to the fields of aerospace, automobiles, traffic, energy sources, buildings, medical appliances, electronic and electric appliances and the like. As a two-phase composite, there are a large number and area of interfacial phases between the carbon fibers and the epoxy resin. The interface phase is directly related to the transmission and diffusion of internal stress, electricity, magnetism, heat and the like of the material, and plays an important and even decisive role in the overall performance of the composite material.
In the long-term service process, the carbon fiber reinforced epoxy resin composite material is influenced by service conditions and is easy to be damaged in different forms such as internal delamination and the like. These failures mostly originate from microcracks generated at the interface structure of the materials. The growth, expansion and fusion of the interface microcracks can cause the reduction of the mechanical, electric conduction, heat conduction, electromagnetic shielding and other properties of the composite material, and further influence the service life of the composite material. Therefore, the repair of the interfacial microcracks and the inhibition of the growth of the microcracks become problems to be solved urgently in the application process of the composite material.
In recent years, researchers at home and abroad have conducted researches on repairing microcracks on carbon fiber composite material interfaces from different angles. Chinese patent application publication No. CN103113745A discloses introducing gold nanoparticles into a carbon fiber/polyethersulfone composite interface, and repairing the composite interface by using the plasmon resonance effect of the gold nanoparticles. However, the repairing method is driven by light with specific wavelength and light intensity, and obviously has no effect on repairing interfacial microcracks in the large-size composite material. However, domestic research on repairing microcracks at the interface of the carbon fiber composite material is rarely reported.
Disclosure of Invention
The present application aims to provide a modified carbon fiber which can be used for preparing a carbon fiber reinforced epoxy resin with an interface self-repairing performance, thereby solving the technical problems.
It is also an object of the present application to provide a process for preparing a modified carbon fiber as described above.
The application also aims to provide a modified carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance.
It is also an object of the present application to provide a method for preparing a modified carbon fiber reinforced epoxy resin composite as described above.
Specifically, the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance is prepared by introducing thermally reversible Diels-Alder covalent bonds into an interface region of the carbon fiber reinforced epoxy resin composite material by a carbon fiber surface modification method. The method takes dopamine, polyethyleneimine, furoyl chloride and bismaleimide as raw materials to prepare the carbon fiber grafted with bismaleimide ring, then compounds the carbon fiber with 2-furancarboxamide and epoxy resin to prepare the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance, and realizes the self-repairing of the interface microcracks through a two-step heating process. The invention aims to solve the problem that the material performance is reduced and even fails due to the microcrack expansion of the interface of the traditional carbon fiber reinforced epoxy resin matrix composite material, has the advantages of simple and convenient repairing conditions, easy realization, lower repairing cost, capability of repairing for multiple times and the like, and can effectively prolong the service life of the carbon fiber reinforced epoxy resin matrix composite material.
In order to solve the above technical problem, the present application provides the following technical solutions.
In a first aspect, the present application provides a method of making a modified carbon fiber, characterized in that the method comprises the steps of:
s1: soaking carbon fibers in a first mixed solution at room temperature for 18-30 hours, and drying to obtain amino-functionalized carbon fibers, wherein the first mixed solution is obtained by mixing a buffer solution, dopamine and polyethyleneimine;
s2: soaking the amino functionalized carbon fiber in a second mixed solution in advance, then dropwise adding an anhydrous solution of diene containing acyl chloride groups into the second mixed solution, continuously reacting for 6-12 hours at the temperature of 30-60 ℃, and drying to obtain the diene grafted carbon fiber, wherein the second mixed solution is obtained by mixing an anhydrous solvent, an acid-binding agent and a catalyst;
s3: and stirring and reacting the carbon fiber of the grafted diene body and a solution of a dienophile containing two double bonds in a good solvent at the temperature of 50-70 ℃ for 4-8 hours to obtain the modified carbon fiber of the grafted dienophile.
In one embodiment of the first aspect, in step S1, the pH of the buffer solution is 7.5 to 9.5, preferably 8.5;
the buffer solution can be prepared by trihydroxymethyl aminomethane-hydrochloric acid buffer pair, glycine-sodium hydroxide buffer pair, borax-sodium hydroxide buffer pair or boric acid-borax buffer pair;
the number average molecular weight of the polyethyleneimine is 600-10000;
the mass ratio of the dopamine to the polyethyleneimine to the buffer solution is 1: (0.25-4): (400-600).
In one embodiment of the first aspect, in step S2, the anhydrous solvent should be a good solvent of diene containing acid chloride group, preferably a mixed solution of one or more of anhydrous dichloromethane, anhydrous dichloroethane, anhydrous chloroform and anhydrous carbon dichloride;
the acid-binding agent is one or more of triethylamine, sodium bicarbonate, sodium carbonate, sodium hydroxide, carbonate, phosphate, acetate and the like;
the catalyst is one of N, N' -dimethylformamide or pyridine;
the diene body containing acyl chloride group is one or more of furan acyl chloride or acyl chloride containing a butadiene structure, the furan acyl chloride is preferably 2-furoyl chloride, 2-furan acetyl chloride and the like, and the acyl chloride containing the butadiene structure can be 3, 5-di-dilute acyl chloride or 4, 6-di-dilute acyl chloride.
In one embodiment of the first aspect, the anhydrous solvent, the acid-binding agent, and the catalyst are mixed in a mass ratio of 100: (30-50): (0.5 to 1).
In one embodiment of the first aspect, the dienophile containing two double bonds is one or a mixture of bismaleimide compounds, preferably 1, 4-bismaleimidobutane, 1, 2-bismaleimidoethane, 1, 6-bismaleimidohexane, N' - (4, 4-methylenediphenyl) bismaleimide, or unsaturated double bond compounds, such as 1, 4-pentadiene, 1, 5-hexadiene, etc.; the mass fraction of the dienophile containing two double bonds in the solution is 20-40%.
In a second aspect, the present application provides a modified fiber grafted with a dienophile prepared by the method of the first aspect.
In a third aspect, the present application provides a method of preparing a modified carbon fiber reinforced epoxy resin composite, characterized in that the method comprises the steps of:
(1) mixing diene containing amido or diene containing epoxy and epoxy resin according to the proportion of (5-30): mixing according to the mass ratio of 100 to obtain an epoxy resin mixed solution;
(2) and (2) precuring the modified fiber grafted with the dienophile according to the second aspect and the epoxy resin mixed solution obtained in the step (1), and then curing to obtain the modified carbon fiber reinforced epoxy resin composite material.
In one embodiment of the third aspect, in step (1), the diene compound containing a monoamine group is one or more of 2-furanmethylamine, 2-furanethylamine, 2-furanpropylamine, 2, 4-pentadiene-1-amine, and 1, 3-butadiene-1-amine. The diene containing epoxy groups is one or more of glycidyl furfuryl ether and 2-epoxy methyl furan. In one embodiment of the third aspect, the pre-curing temperature is 50 to 70 ℃ and the pre-curing time is 4 to 8 hours.
In a third aspect, the present application provides a modified carbon fiber reinforced epoxy resin composite prepared by the method as described in the third aspect.
In an embodiment of the third aspect, the modified carbon fiber reinforced epoxy resin composite material has an interface self-repair performance, and the self-repair method is performed according to the following steps: firstly, the prepared modified carbon fiber reinforced epoxy resin composite material is heated for 1-3 hours at the temperature of 100-120 ℃, and then heated for 1-3 hours at the temperature of 50-70 ℃.
Compared with the prior art, the method has the beneficial effects that the thermally reversible Diels-Alder covalent bond is introduced into the carbon fiber reinforced epoxy resin interface through the surface codeposition and chemical grafting modification method. After the composite material is in service for a long time, the disconnection and reconstruction of the thermal reversible covalent bond in the interface area can be realized through two heating processes, so that the carbon fiber reinforced epoxy resin interface can be accurately repaired, and the method is suitable for repairing the carbon fiber reinforced epoxy resin matrix composite material with a complex structure. The repair temperature required by the repair method provided by the invention is 120 ℃ at most, the repair condition is simple and convenient, the repair is easy to realize, the repair cost is low, the preparation method and the repair method of the composite material provided by the invention can realize multiple accurate repairs of the carbon fiber reinforced epoxy resin composite material, and the interface repair efficiency is up to 70%. In addition, the preparation method provided by the invention can also improve the interface adhesion performance of the carbon fiber reinforced epoxy resin composite material.
Drawings
The present application may be better understood by describing embodiments thereof in conjunction with the following drawings, in which:
fig. 1 is a surface element test result of the carbon fiber grafted with maleimide rings prepared in example 1 based on the present invention and the carbon fiber of comparative example 1, and specifically shows XPS broad spectrum and O1s peak spectrum of different carbon fibers. In fig. 1, a and b represent undrawn carbon fibers; c and d represent carbon fibers grafted with maleimide rings.
Fig. 2 is an initial interfacial shear strength test curve and an interfacial shear strength test curve after two self-repairs of the carbon fiber reinforced epoxy resin composite material with the interfacial self-repair performance prepared in example 1 and the carbon fiber reinforced epoxy resin composite material in comparative example 1. In fig. 2, a denotes a modified carbon fiber-reinforced epoxy resin composite material of example 1, and b denotes a composite material according to comparative example 1.
Fig. 3 is a schematic diagram of a thermally reversible Diels-Alder covalent bond structure in an interface region of a carbon fiber reinforced epoxy resin composite material with an interface self-repairing performance prepared based on embodiment 1 of the present invention.
Detailed Description
Unless otherwise defined, technical or scientific terms used herein in the specification and claims should have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All numerical values recited herein as between the lowest value and the highest value are intended to mean all values between the lowest value and the highest value in increments of one unit when there is more than two units difference between the lowest value and the highest value.
In the following detailed description of the embodiments of the present invention, reference is made to the accompanying drawings, which are included to provide a further understanding of the invention, and in which is shown by way of illustration specific embodiments in which the invention may be practiced.
As described above, it is difficult for the carbon fiber reinforced epoxy resin material in the related art to achieve self-repair cracks. Therefore, the present application aims at providing a grafted dienophile modified carbon fiber, which can form a thermo-reversible Diels-Alder covalent bond with an amino modified epoxy resin, thereby providing a modified carbon fiber reinforced epoxy resin composite material with an interface self-repairing property.
In a preferred embodiment, the application provides a preparation method of a carbon fiber reinforced epoxy resin composite material with an interface self-repairing performance, which is specifically prepared according to the following steps:
the method comprises the following steps: preparing a buffer solution with the mass fraction of 1.2 per mill, and adjusting the pH value to 7.5-9.5;
step two: mixing dopamine, polyethyleneimine and the buffer solution prepared in the first step according to a certain proportion to obtain a mixed solution;
step three: and (4) adding the carbon fibers into the mixed solution prepared in the step two, and soaking for 18-30 hours at room temperature. The carbon fibers are then removed and cleaned. Drying the cleaned carbon fiber to obtain the amino functionalized carbon fiber;
step four: and (2) soaking the amino functionalized carbon fiber prepared in the third step into a mixed solution composed of an anhydrous solvent, an acid-binding agent and a catalyst according to a certain mass ratio, dropwise adding a solution which is prepared from a diene containing acyl chloride groups and the anhydrous solvent and has a mass fraction of 30-50%, heating to 30-60 ℃, and allowing the reaction to continue for 6-12 hours. After the reaction is finished, taking out the carbon fiber, cleaning, and then heating and drying to obtain the carbon fiber grafted with the diene;
step five: and (3) placing the carbon fiber grafted with the diene in the step four into a reaction kettle filled with a solution of dienophile with two double bonds and a certain concentration, heating and stirring. Taking out the carbon fibers, washing the carbon fibers by using a good solvent of the dienophile, and then heating and drying the carbon fibers to obtain the carbon fibers grafted with the dienophile;
step six: and (2) mixing the diene containing amino or the diene containing epoxy and epoxy resin according to the ratio of (5-30): mixing according to the mass ratio of 100, and uniformly stirring;
step seven: compounding the carbon fiber grafted with the diene prepared in the fifth step with the resin mixed solution prepared in the sixth step, then pre-curing at a certain temperature, curing according to a resin curing process, and curing to obtain the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance.
Examples
The present application is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
The preparation method of the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance comprises the following steps:
the method comprises the following steps: preparing 1.2 per mill aqueous solution of tris (hydroxymethyl) aminomethane by mass fraction, and adjusting the pH value to 8.5 by using hydrochloric acid solution;
step two: mixing dopamine, polyethyleneimine with the number average molecular weight of 600 and the solution with the pH value of 8.5 prepared in the step one according to the mass ratio of 1:0.25:400 to obtain a mixed solution;
step three: adding carbon fibers to the mixed solution prepared in the second step, and soaking at room temperature for 18 hours. The carbon fibers are then removed and cleaned. Drying the cleaned carbon fiber to obtain the amino functionalized carbon fiber;
step four: soaking the amino functionalized carbon fiber prepared in the third step into a mixed solution of anhydrous dichloromethane, triethylamine and N, N' -dimethylformamide according to the mass ratio of 100:30:0.5, dropwise adding a solution with the mass fraction of 30% prepared from 2-furoyl chloride and the anhydrous dichloromethane, and heating to 30 ℃ to enable the reaction to continue for 6 hours. After the reaction is finished, taking out the carbon fiber, cleaning, and then heating and drying to obtain the carbon fiber grafted with the diene;
step five: and (3) placing the carbon fiber grafted with the diene in the step four into a reaction kettle containing 20 mass percent of acetonitrile solution of 1, 4-bismaleimide butane, heating to 50 ℃, and stirring for 4 hours. Taking out the carbon fiber, washing with acetonitrile, and then heating and drying to obtain the carbon fiber grafted with the maleimide ring;
step six: mixing 2-furanmethanamine and epoxy resin according to the weight ratio of 5: mixing according to the mass ratio of 100, and uniformly stirring;
step seven: compounding the carbon fiber grafted with the maleimide ring prepared in the fifth step with the resin mixed solution prepared in the sixth step, then pre-curing for 5 hours at 50 ℃, curing according to a resin curing process, and obtaining the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance after curing.
The self-repairing of the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance prepared in the embodiment is carried out according to the following steps: the composite material thus prepared was first heated at 100 ℃ for 1 hour and then at 50 ℃ for 1 hour.
Example 2
The preparation method of the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance comprises the following steps:
the method comprises the following steps: preparing 1.2 per mill of sodium hydroxide solution by mass fraction, and adjusting the pH value to 7.5 by using glycine;
step two: mixing dopamine, polyethyleneimine with the number average molecular weight of 1000 and the solution with the pH value of 7.5 prepared in the step one according to the mass ratio of 1:2:400 to obtain a mixed solution;
step three: adding carbon fibers to the mixed solution prepared in the second step, and soaking at room temperature for 21 hours. The carbon fibers are then removed and cleaned. Drying the cleaned carbon fiber to obtain the amino functionalized carbon fiber;
step four: soaking the amino functionalized carbon fiber prepared in the third step into a mixed solution of anhydrous dichloroethane, sodium bicarbonate and N, N' -dimethylformamide according to the mass ratio of 100:40:0.5, dropwise adding a solution of 40% by mass of 2-furanacetyl chloride and the anhydrous dichloroethane, heating to 40 ℃, and allowing the reaction to continue for 8 hours. After the reaction is finished, taking out the carbon fiber, cleaning, and then heating and drying to obtain the carbon fiber grafted with the furan ring;
step five: and (3) placing the carbon fiber grafted with the furan ring in the step four into a reaction kettle containing 20 mass percent of acetonitrile solution of 1, 6-bismaleimide butane, heating to 60 ℃, and stirring for 6 hours. Taking out the carbon fiber, washing with acetonitrile, and then heating and drying to obtain the carbon fiber grafted with the maleimide ring;
step six: mixing 2-furan ethylamine with epoxy resin according to the weight ratio of 13: mixing according to the mass ratio of 100, and uniformly stirring;
step seven: compounding the carbon fiber grafted with the maleimide ring prepared in the fifth step with the resin mixed solution prepared in the sixth step, then pre-curing for 6 hours at 60 ℃, curing according to a resin curing process, and obtaining the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance after curing.
The self-repairing of the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance prepared in the embodiment is carried out according to the following steps: the composite material thus prepared was first heated at 100 ℃ for 2 hours and then at 50 ℃ for 3 hours.
Example 3
The preparation method of the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance comprises the following steps:
the method comprises the following steps: preparing 1.2 per mill of sodium hydroxide solution by mass fraction, and adjusting the pH value to 8.5 by using borax;
step two: mixing dopamine, polyethyleneimine with the number average molecular weight of 5000 and the solution with the pH value of 8.5 prepared in the step one according to the mass ratio of 1:3:500 to obtain a mixed solution;
step three: adding carbon fibers to the mixed solution prepared in the second step, and soaking at room temperature for 24 hours. The carbon fibers are then removed and cleaned. Drying the cleaned carbon fiber to obtain the amino functionalized carbon fiber;
step four: and (2) soaking the amino functionalized carbon fiber prepared in the third step into a mixed solution of anhydrous chloroform, sodium carbonate and pyridine according to the mass ratio of 100:40:1, dropwise adding a solution with the mass fraction of 40% prepared from 3, 5-dichlormethane and anhydrous chloroform, heating to 50 ℃, and allowing the reaction to continue for 10 hours. After the reaction is finished, taking out the carbon fiber, cleaning, and then heating and drying to obtain the carbon fiber grafted with the diene;
step five: and (3) placing the carbon fiber grafted with the diene in the step four into a reaction kettle containing 20 mass percent of 1, 4-pentadiene n-hexane solution, heating to 60 ℃, and stirring for 6 hours. Taking out the carbon fibers, cleaning the carbon fibers with n-hexane, and then heating and drying the carbon fibers to obtain the carbon fibers grafted with the dienophile;
step six: reacting 2, 4-pentadien-1-amine with an epoxy resin according to a 21: mixing according to the mass ratio of 100, and uniformly stirring;
step seven: compounding the carbon fiber grafted with the dienophile prepared in the fifth step with the resin mixed solution prepared in the sixth step, then pre-curing for 8 hours at 60 ℃, curing according to a resin curing process, and obtaining the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance after curing.
The self-repairing of the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance prepared in the embodiment is carried out according to the following steps: the composite material thus prepared was first heated at 110 ℃ for 3 hours and then at 60 ℃ for 3 hours.
Example 4
The preparation method of the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance comprises the following steps:
the method comprises the following steps: preparing a borax solution with the mass fraction of 1.2 per mill, and adjusting the pH value to 9.5 by using boric acid;
step two: mixing dopamine, polyethyleneimine with the number average molecular weight of 10000 and the solution with the pH value of 9.5 prepared in the step one according to the mass ratio of 1:4:600 to obtain a mixed solution;
step three: adding carbon fibers to the mixed solution prepared in the second step, and soaking at room temperature for 30 hours. The carbon fibers are then removed and cleaned. Drying the cleaned carbon fiber to obtain the amino functionalized carbon fiber;
step four: soaking the amino functionalized carbon fiber prepared in the third step into a mixed solution of anhydrous carbon dichloride, sodium hydroxide and pyridine according to the mass ratio of 100:50:1, dropwise adding a solution with the mass fraction of 50% prepared from 4, 6-dichlorine and the anhydrous carbon dichloride, heating to 60 ℃, and keeping the reaction for 12 hours. After the reaction is finished, taking out the carbon fiber, cleaning, and then heating and drying to obtain the carbon fiber grafted with the diene;
step five: and (3) placing the carbon fiber grafted with the diene in the step four into a reaction kettle filled with 40 mass percent of 1, 5-hexadiene normal hexane solution, heating to 70 ℃, and stirring for 8 hours. Taking out the carbon fibers, cleaning the carbon fibers with n-hexane, and then heating and drying the carbon fibers to obtain the carbon fibers grafted with the dienophile;
step six: mixing glycidyl furfuryl ether with epoxy resin according to a ratio of 30: mixing according to the mass ratio of 100, and uniformly stirring;
step seven: compounding the carbon fiber grafted with the dienophile prepared in the fifth step with the resin mixed solution prepared in the sixth step, then pre-curing for 8 hours at 70 ℃, curing according to a resin curing process, and obtaining the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance after curing.
The self-repairing of the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance prepared in the embodiment is carried out according to the following steps: the composite material thus prepared was first heated at 120 ℃ for 3 hours and then at 70 ℃ for 3 hours.
Comparative example 1
Comparative example 1 the preparation method was as follows:
the carbon fiber used in comparative example 1 was a carbon fiber which had not been modified by the modification method in steps one to five of the examples. Mixing carbon fibers with 2-furanmethanamine and epoxy resin according to the weight ratio of 5: the mixed resin mixed liquor with the mass ratio of 100 is compounded, and then is pre-cured for 5 hours at the temperature of 50 ℃, and then is cured according to the resin curing process.
The self-repairing of the carbon fiber reinforced epoxy resin composite material prepared in the comparative example 1 is carried out according to the following steps: the composite material thus prepared was first heated at 100 ℃ for 1 hour and then at 50 ℃ for 1 hour.
The surface elements of the maleimide ring-grafted carbon fiber prepared in example 1 and the carbon fiber of comparative example 1 were analyzed using an X-ray photoelectron spectrometer model 1/AXIS UltraDLD from Shimadzu-Kratos, Japan, and the results are shown in FIG. 1 and Table 1. The interfacial shear strength of the carbon fiber reinforced epoxy resin composite materials with interfacial self-repairing performance of examples 1 to 4 and the carbon fiber reinforced epoxy resin composite material of comparative example 1 was measured by a micro-droplet method, and the result is shown in table 2, and the load-displacement curves of example 1 and comparative example 1 are shown in fig. 2, where the test apparatus is a fiber composite material interfacial performance evaluation device manufactured by beijing rich marcotechnik inc. The interfacial repair efficiency is defined as the ratio of the interfacial shear strength after repair to the initial interfacial shear strength multiplied by 100%, and the repair efficiency is shown in table 2.
Tables 1 and 2 are as follows.
Table 1 carbon fibers prepared in example 1 and carbon fiber surface element and functional group contents of comparative example
TABLE 2 interfacial shear strength and self-healing efficiency for the examples and comparative examples
As can be seen from fig. 1 and table 1, the maleimide ring-grafted carbon fiber of example 1 has more nitrogen elements than the unmodified carbon fiber surface of comparative example 1, and the oxygen-containing functional group C ═ O content is significantly increased, indicating that the maleimide ring is successfully grafted to the carbon fiber surface. As can be seen from fig. 2 and table 2, the carbon fiber reinforced epoxy resin composite material with the interface self-repairing performance prepared in embodiments 1 to 4 still has strong interface shear strength after repair, and shows high-efficiency self-repairing performance and multiple self-repairing behaviors. The initial interfacial shear strength of the carbon fiber reinforced epoxy resin composite material with the interfacial self-repairing performance prepared in the embodiments 1-4 is improved by about 51% compared with that of the carbon fiber reinforced epoxy resin composite material prepared in the comparative example 1, which shows that the preparation method provided by the invention can effectively improve the interfacial adhesion performance of the carbon fiber reinforced epoxy resin composite material.
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (10)
1. A method of making a modified carbon fiber, comprising the steps of:
s1: soaking carbon fibers in a first mixed solution at room temperature for 18-30 hours, and drying to obtain amino-functionalized carbon fibers, wherein the first mixed solution is obtained by mixing a buffer solution, dopamine and polyethyleneimine;
s2: soaking the amino functionalized carbon fiber in a second mixed solution in advance, then dropwise adding an anhydrous solution of diene containing acyl chloride groups into the second mixed solution, continuously reacting for 6-12 hours at the temperature of 30-60 ℃, and drying to obtain the diene grafted carbon fiber, wherein the second mixed solution is obtained by mixing an anhydrous solvent, an acid-binding agent and a catalyst;
s3: and stirring and reacting the carbon fiber of the grafted diene body and a solution of a dienophile containing two double bonds in a good solvent at the temperature of 50-70 ℃ for 4-8 hours to obtain the modified carbon fiber of the grafted dienophile.
2. The method of claim 1, wherein in step S1, the pH of the buffer solution is 7.5 to 9.5, preferably 8.5;
the buffer solution is prepared from a trihydroxymethyl aminomethane-hydrochloric acid buffer pair, a glycine-sodium hydroxide buffer pair, a borax-sodium hydroxide buffer pair or a boric acid-borax buffer pair;
the number average molecular weight of the polyethyleneimine is 600-10000;
the mass ratio of the dopamine to the polyethyleneimine to the buffer solution is 1: (0.25-4): (400-600).
3. The method according to claim 1, wherein in step S2, the anhydrous solvent is a good solvent of diene containing acyl chloride group, preferably a mixed solution of one or more of anhydrous dichloromethane, anhydrous dichloroethane, anhydrous chloroform and anhydrous carbon dichloride;
the acid-binding agent is one or more of triethylamine, sodium bicarbonate, sodium carbonate, sodium hydroxide, carbonate, phosphate, acetate and the like;
the catalyst is one of N, N' -dimethylformamide or pyridine;
the diene body containing acyl chloride groups is one or a mixture of more of furan acyl chloride or acyl chloride containing a butadiene structure, and the furan acyl chloride is preferably 2-furoyl chloride or 2-furylacetyl chloride; the acyl chloride containing the butanediyl structure is preferably 3, 5-dichlorine chloride or 4, 6-dichlorine chloride;
the mixing mass ratio of the anhydrous solvent, the acid binding agent and the catalyst is preferably 100: (30-50): (0.5 to 1).
4. The method of claim 1, wherein the dienophile containing two double bonds is one or a mixture of bismaleimides or unsaturated double bond compounds, preferably 1, 2-bismaleimidoethane, 1, 4-bismaleimidobutane, 1, 6-bismaleimidohexane, or N, N' - (4, 4-methylenediphenyl) bismaleimide; the unsaturated double bond compound is preferably 1, 4-pentadiene or 1, 5-hexadiene; the mass fraction of the dienophile containing two double bonds in the solution is 20-40%.
5. A modified fiber grafted dienophile prepared by the process of any of claims 1-4.
6. A method for preparing a modified carbon fiber reinforced epoxy resin composite material, characterized in that the method comprises the following steps:
(1) mixing diene containing amido or diene containing epoxy and epoxy resin according to the proportion of (5-30): mixing according to the mass ratio of 100 to obtain an epoxy resin mixed solution;
(2) precuring the modified fiber of the grafted dienophile of claim 5 and the epoxy resin mixed solution obtained in step (1), and then curing to obtain the modified carbon fiber reinforced epoxy resin composite material.
7. The method of claim 6, wherein in step (1), the diene containing amine group is one or more of 2-furanmethylamine, 2-furanethylamine, 2-furanpropylamine, 2, 4-pentadiene-1-amine, 1, 3-butadiene-1-amine;
the diene containing epoxy groups is one or more of glycidyl furfuryl ether and 2-epoxy methyl furan.
8. The method of claim 6, wherein the pre-cure temperature is 50-70 ℃ and the pre-cure time is 4-8 hours.
9. A modified carbon fiber reinforced epoxy resin composite prepared by the method of any one of claims 6-8.
10. The modified carbon fiber reinforced epoxy resin composite material of claim 9, wherein the modified carbon fiber reinforced epoxy resin composite material has an interface self-repair performance, and the self-repair method comprises the following steps: firstly, the prepared modified carbon fiber reinforced epoxy resin composite material is heated for 1-3 hours at the temperature of 100-120 ℃, and then heated for 1-3 hours at the temperature of 50-70 ℃.
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