CN111534050B - Carbon fiber composite material with multi-scale high-temperature-resistant interface structure and preparation method thereof - Google Patents
Carbon fiber composite material with multi-scale high-temperature-resistant interface structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a carbon fiber composite material with a multi-scale high-temperature-resistant interface structure and a preparation method thereof. The surface activity of the carbon fiber is improved by one-step anodic oxidation rapid treatment based on the principle of large-current electrolysis, nano particles are rapidly and efficiently deposited on the surface of the anodic oxidation carbon fiber by utilizing ultrasonic-assisted constant-voltage directional electrophoretic deposition, and a high-temperature-resistant polymer layer is further coated on the surface of the carbon fiber on the basis, so that a multi-scale high-temperature-resistant interface based on the characteristics of sand-cement compounded by the nano particles and the high-temperature-resistant polymer is constructed. Through the synergistic effect of the nano particles and the high-temperature-resistant polymer, the mechanical combination and chemical bonding capability of an interface region are effectively improved, and the temperature-resistant grade of the carbon fiber composite material interface is remarkably improved, so that the integral high-temperature-resistant performance of the composite material is improved, and the composite material can be applied to the application fields of high-performance composite materials such as aerospace, rail transit and the like.
Description
Technical Field
The invention relates to the field of carbon fiber resin matrix composite materials, and mainly relates to a carbon fiber composite material with a multi-scale high-temperature-resistant interface structure and a preparation method thereof.
Background
With the development of aerospace, wind energy and automobile industries, the application of carbon fiber reinforced polymer matrix composite materials under extreme conditions becomes a target after pursuing light weight and high strength requirements. There are many examples of high temperature application scenarios in aerospace and other areas: such as advanced fan case structures, liquid fuel housings, engine exhaust structures, engine nacelles, etc., which tend to have short lifetimes due to thermo-mechanical stress loading and environmental degradation, there is an increasing demand for high temperature resistant carbon fiber reinforced composites. At present, the high temperature resistance level of a resin matrix and a carbon fiber reinforcement can meet the requirement, but due to the specific surface inertia of carbon fibers, the unmodified commercial carbon fibers and the resin matrix are weaker in combination and low in temperature resistance level, so that the carbon fiber composite material has lower interface bonding strength in a high-temperature environment, and the application of the composite material in the high-temperature environment is limited.
Generally, the mechanical property influencing factors of the composite material comprise a matrix, a reinforcement and an interface formed between the matrix and the reinforcement, wherein the interface of the composite material is a bridge for stress transmission between resin and fibers, and is of great importance for the overall performance of the composite material. Due to the surface inertness of the unmodified commercial carbon fiber and the low heat resistance level of the sizing agent, the interface bonding between the unmodified commercial carbon fiber and resin is poor, and the temperature resistance is poor, so that the interface bonding strength between the unmodified commercial carbon fiber and the resin and the temperature resistance of the interface can be improved through the surface modification of the fiber, and the high temperature resistance of the composite material is improved. At present, a great deal of carbon fiber surface modification research mainly focuses on chemical etching of the carbon fiber surface and reinforcing of a nano material, and the interface shear strength of the composite material is improved by increasing the covalent bond action between the carbon fiber surface and a resin matrix and hindering the expansion of interface cracks. At present, the main methods for modifying the surface of the carbon fiber include coating method, chemical grafting, chemical vapor deposition, supermolecular self-assembly, electrochemical deposition and the like. However, in the face of increasing carbon fiber batch application scenes, chemical grafting, vapor deposition, supermolecule self-assembly and the like all have the defect of difficult scale. Chinese patent (CN105239357A) discloses a method for chemically grafting graphene oxide on the surface of carbon fiber, which introduces functional groups to solve the problem of surface inertia of carbon fiber and improve the shearing strength of a carbon fiber/epoxy resin interface, however, the carbon fiber surface treatment method of concentrated acid oxidation and surface ammoniation has great damage to the performance of a carbon fiber body, and does not conform to the development direction of green chemistry due to the large use of strong acid; chinese patent (CN107629224A) discloses a preparation method of a carbon nanotube sizing agent modified carbon fiber reinforced epoxy resin matrix composite, wherein the introduction of carbon nanotubes can effectively improve the bridging effect of an interface, but the carbon nanotubes are easy to agglomerate, and the untreated carbon tubes and a resin matrix have poor interface effect and are easy to cause stress concentration. In recent years, many scholars have reported progress in the study of fiber modification such as supramolecular self-assembly and chemical vapor deposition, but the results have been limited to laboratory level.
The electrophoretic deposition of the nanoparticles on the surface of the fiber is an efficient surface modification method, but in the conventional preparation process, the electrophoretic deposition time needs to be prolonged in order to deposit more nanoparticles on the surface of the fiber, however, as the time increases, the thermal effect of the water electrolysis reaction also increases, so that the temperature of the electrolyte increases, and the dispersion of the nanoparticles is affected. Meanwhile, bubbles are generated at the electrode due to the electrolysis of water, and the bubbles attached to the surface of the fiber seriously affect the uniform deposition of the nano particles on the carbon fiber. Hajizadeh et al (Hajizadeh A, Aliafkhazraei M, Hasanpoor M, et al, company of Electrophoretic Deposition Kinetics of Graphene Oxide in Organic and Aqueous Solutions [ J ]. Ceramics International,2018.) analyzed the dynamics of carbon fiber surface Electrophoretic Deposition of Graphene, and found that the bonding between Graphene and fiber was mainly due to the accumulation of Graphene sheets on the fiber surface driven by an electric field and lacked effective chemical bonding. This is mainly due to the chemical inertness of the fiber surface.
At present, researches for improving the interfacial properties of carbon fiber composites through carbon fiber surface modification are concentrated on the researches on the interfacial properties at normal temperature, but the researches on the interfacial properties of the composites in a high-temperature environment are only reported. The influence of temperature on the interface performance of the carbon fiber/epoxy resin composite material is researched by Chenghainexia and Sunbao (Chenghainexia, Sunbao, temperature on the interface performance of the carbon fiber/epoxy resin composite material [ J ]. university of east China: Nature science edition, 2016,042(003): 318-. Thomason and L.Yang (Thomason J L, Yang L.temperature dependency of the interfacial shear stress in glass-fiber multipropylene Composites [ J ]. Composites Science and Technology,2011,71(13): 1600-) 1605.) the Raghava model was used to analyze the relationship between the interfacial radial thermal residual stress and the thermal expansion coefficient tree, fiber volume content, test temperature, etc., and the glass transition temperature of the interfacial phase was found to be an important influencing factor, but no effective solution was proposed. Generally, for the research on the high temperature modification resistance of the carbon fiber composite material interface, the following technical problems mainly exist at present: 1. the bonding force between the nano particles and the surface of the carbon fiber is weak, the operation of introducing the nano particles into the surface of the carbon fiber is uncontrollable, the strength of the carbon fiber is damaged, and the coating is not uniform easily; 2. the normal temperature interface performance of the carbon fiber composite material can be effectively improved through carbon fiber surface modification, but the synchronous improvement of the normal temperature performance and the high temperature performance of the carbon fiber composite material interface is difficult to realize, and 3, an effective high temperature resistant continuous phase is not formed in the composite material interface area, so that the high temperature resistance of the composite material is low. Therefore, it is desirable to develop a method for preparing a carbon fiber composite material having a multi-scale high temperature resistant interface structure.
Disclosure of Invention
According to the invention, the nano particles are efficiently deposited on the surface of the carbon fiber by combining an anodic oxidation and ultrasonic-assisted electrophoretic deposition method, then the high-temperature-resistant polymer is coated on the surface of the carbon fiber, and a multi-scale high-temperature continuous interface formed by the nano particles/the polymer is successfully constructed on the surface of the fiber, so that the high-temperature-resistant performance of the interface of the composite material is remarkably improved.
In order to achieve the purpose, the invention provides a carbon fiber composite material with a multi-scale high-temperature-resistant interface structure and a preparation method thereof, and the specific technical content is as follows:
firstly, taking an ammonium salt aqueous solution with the mass concentration of 5-10% as an electrolyte and graphite as a plate cathode, carrying out one-step anodic oxidation rapid treatment on the degumming carbon fiber based on a large-current electrolysis principle, and ultrasonically washing the treated degumming carbon fiber by deionized water to remove the residual electrolyte on the surface of the carbon fiber to obtain the anodic oxidation carbon fiber; secondly, taking the uniformly dispersed nano particle aqueous solution as electrolyte, graphite as a plate cathode, taking the anodized carbon fiber obtained in the first step as an anode, and quantitatively and controllably depositing nano particles on the surface of the anodized carbon fiber by using an ultrasonic-assisted constant-pressure directional electrophoresis method to obtain the carbon fiber with the nano particles deposited on the surface, wherein the mass ratio of the carbon fiber to the nano particles is controlled to be 100:0.1-2 by adjusting the mass ratio of the water solvent to the nano particles in the nano particle aqueous solution; thirdly, dipping the carbon fiber with the surface deposited with the nano particles obtained in the second step in a high-temperature-resistant polymer solution for 30-60s, and controlling the mass ratio of the carbon fiber to the high-temperature-resistant polymer to be 100:1-1.5 by adjusting the mass ratio of the solvent to the high-temperature-resistant polymer in the solution to obtain the carbon fiber coated with the high-temperature-resistant polymer; and fourthly, preparing the carbon fiber composite material with the multi-scale high-temperature-resistant interface structure with the sand-cement characteristic by taking the high-temperature-resistant polymer carbon fiber coated on the surface obtained in the third step as a reinforcement and taking a high-temperature-resistant resin system as a matrix material.
Wherein the ammonium salt aqueous solution is one or more of ammonium bicarbonate, ammonium acetate, ammonium carbonate, ammonium sulfate or ammonium phosphate, and the mass concentration of the ammonium salt aqueous solution is 5-10%; the structure of the nanoparticle can be of multiple dimensions, including but not limited to one of zero-dimensional aminated silica microspheres, one-dimensional carboxylated carbon nanotubes, aminated carbon nanotubes, nanofibers, two-dimensional carboxylated graphene oxide and the like; the high-temperature resistant polymer is a high-temperature resistant polymer with adhesion capacity, and comprises but is not limited to one of low molecular weight polyetherimide, low molecular weight imide or low molecular weight polyamic acid, wherein the low molecular weight index average molecular weight is 4000-8000g/mol, and the solvent of the high-temperature resistant polymer is one or more of N, N-dimethylformamide, N-methylpyrrolidone, trichloromethane or acetone; the main resin of the high-temperature resistant resin system is one or more of bismaleimide resin, polyfunctional alicyclic epoxy resin or linear novolac epoxy resin, the curing agent of the high-temperature resistant resin system is one or more of acid anhydride curing agents, the accelerator of the high-temperature resistant resin system is one of imidazole derivatives, the mass part ratio of the main resin, the curing agent and the accelerator is 100:50-90:0.6-2, and the accelerator is one of the imidazole derivatives.
The invention also aims to provide a specific preparation method of the carbon fiber reinforced composite material. The method comprises the following specific steps:
(1) carbon fiber surface modification:
anodic oxidation treatment: adding ammonium salt into deionized water, stirring and dissolving at normal temperature to prepare an ammonium salt aqueous solution with the mass concentration of 5-10%, taking the ammonium salt aqueous solution as an electrolyte and a graphite plate as a cathode plate, and carrying out one-step anodic oxidation rapid treatment on the degumming carbon fiber, wherein the water bath temperature is set to be 25-35 ℃, and the current density is 0.8-1.5mA/cm2And (3) anodizing for 30-60s, and washing the treated degumming carbon fiber with deionized water to remove the residual electrolyte on the surface of the carbon fiber to obtain the anodized carbon fiber.
Deposition of nano particles: adding nanoparticles into deionized water, carrying out ice bath intermittent ultrasonic dispersion by using a cell disruptor, wherein the ultrasonic dispersion time is 30-60min to obtain a uniformly dispersed nanoparticle aqueous solution with the concentration of 0.5-1.0mg/ml, then quantitatively and controllably depositing the nanoparticles on the surface of the anodized carbon fiber obtained in the step (i) by using the uniformly dispersed nanoparticle aqueous solution as an electrolyte and adopting an ultrasonic-assisted constant-pressure directional electrophoresis method, wherein the electrophoretic deposition voltage is set to 10-25V, the deposition time is 5-10min, the ultrasonic power of an electrolyte water bath is 50-100W, the temperature is 20-30 ℃, and then drying the fiber in a forced air oven at 80-100 ℃ for 12-18h to obtain the surface-deposited nanoparticle carbon fiber.
High temperature resistant polymer coating: adding a high-temperature-resistant polymer into a solvent, heating, stirring and dissolving to obtain a high-temperature-resistant polymer solution with the mass concentration of 1% -1.5%, naturally cooling the high-temperature-resistant polymer solution to room temperature, immersing the surface-deposited nano particle carbon fiber obtained in the step II into the high-temperature-resistant polymer solution, performing low-power ultrasound with the ultrasonic power of 30-50W for 30-60s, and finally drying the fiber in a blast oven at the temperature of 80-100 ℃ for 12-24h to obtain the high-temperature-resistant polymer-coated carbon fiber.
(2) Preparation of the high-temperature resistant resin system:
mechanically stirring and mixing the main resin, the curing agent and the accelerator according to the proportion, wherein the mixing conditions are as follows: the oil bath temperature is 40-60 ℃, the stirring speed is 400-.
(3) Preparing a composite material:
and (2) impregnating and compounding the carbon fiber coated with the high-temperature-resistant polymer on the surface prepared in the step (1) and the high-temperature-resistant resin system prepared in the step (2), curing for 1-2h at 80-100 ℃, curing for 1-2h at 120-190 ℃ and curing for 2-3h at 160-190 ℃ by adopting a gradient heating curing mode, and then cooling to room temperature to obtain the carbon fiber composite material with the multi-scale high-temperature-resistant interface structure.
The invention has the following effects: 1) the surface of the carbon fiber is subjected to accurate anodic oxidation, so that the surface activity of the degumming carbon fiber is improved, the binding force between the deposited nanoparticles at the later stage and the surface of the degumming carbon fiber is enhanced, and the body strength of the carbon fiber is not influenced; 2) by adopting an ultrasonic-assisted constant-pressure directional electrophoretic deposition technology, adverse effects of bubbles generated by water electrolysis on nano particle deposition are eliminated in time, and meanwhile, the nano particle is subjected to low-temperature constant-temperature treatment (20-30 ℃), so that nano particle agglomeration and deposition caused by temperature rise in the electrolysis process are avoided, and the nano particles are efficiently, controllably and uniformly distributed on the carbon fibers; 3) the method has the advantages that the high-temperature-resistant polymer is coated on the carbon fiber with the nano particles deposited on the surface by ultrasonic impregnation, so that the high-temperature-resistant polymer is fully impregnated and permeated into gaps of the nano particles, a nano particle layer structure is stabilized, a good multi-scale high-temperature-resistant interface with a bonding effect similar to sand-cement is formed between the high-temperature-resistant polymer and the nano particles, the roughness and the chemical activity of the surface of the carbon fiber are obviously improved, the physical/chemical synchronous modification of the interface performance is realized, the synergistic effect of mechanical bonding and chemical bonding between the carbon fiber and a resin matrix is improved, the effective modulus transition of an interface phase is realized, the expansion of cracks on the surface of the fiber can be inhibited, the stress is uniformly transferred between the carbon fiber and the resin matrix, and the interface bonding strength of the composite material is improved; 4) the nano particles on the surface of the carbon fiber and the high-temperature resistant polymer have excellent heat resistance, and are mutually diffused and reacted with the resin matrix in the material forming process to form a continuous phase high-temperature resistant interface layer with modulus transition effect, so that the prepared carbon fiber resin matrix composite material has excellent heat resistance.
Drawings
Fig. 1 is an electron micrograph of the surface of carbon fiber after ultrasonic-assisted electrophoretic deposition of carboxylated graphene oxide: (a) carrying out anodic oxidation, (b) not carrying out anodic oxidation; the method is used for comparing the influence of the presence or absence of anodic oxidation on the surface appearance of the carbon fiber after the electrophoretic deposition of the carboxylated graphene oxide on the surface of the carbon fiber;
FIG. 2 is an electron microscope photograph of the surface of carbon fiber after electrophoretic deposition of aminated graphene oxide: (a) assisted ultrasound, (b) no assisted ultrasound; the method is used for comparing the influence of the existence of ultrasonic assistance on the surface appearance of the carbon fiber after the amination graphene oxide is electrophoretically deposited on the surface of the carbon fiber.
The specific implementation mode is as follows:
the invention will be better understood from the following examples. However, the content described in the embodiment is only for illustrating the present invention, and should not limit the present invention described in the claims.
In the examples, the interlaminar shear strength test of the carbon fiber resin-based composite material at different temperatures was carried out on a universal material testing machine equipped with a high-low temperature test chamber according to the test method of the interlaminar shear strength of JCT 773-2010.
Example 1
The ammonium salt aqueous solution is ammonium bicarbonate aqueous solution, the nano particles are carboxylated graphene oxide, the high-temperature-resistant polymer is low-molecular-weight polyether imide, and the solvent of the high-temperature-resistant polymer solution is N-methyl pyrrolidone; triglycidyl para-aminophenol is adopted as main resin of the high-temperature resistant resin system, methyl nadic anhydride is adopted as curing agent of the high-temperature resistant resin system, 2-ethyl-4-methylimidazole (2E4MI) is adopted as accelerator of the high-temperature resistant resin system, and the mass part ratio of the main resin, the curing agent and the accelerator is 100:50: 2; the carbon fiber is Dongli T800HB-12k degumming carbon fiber. The preparation process comprises the following steps:
1) carbon fiber surface modification:
anodic oxidation treatment: adding ammonium bicarbonate into deionized water, stirring at normal temperature for dissolving to obtain ammonium bicarbonate aqueous solution with mass concentration of 6%, taking the ammonium bicarbonate aqueous solution as electrolyte, taking a graphite plate as a negative plate, and carrying out one-step anodic oxidation rapid treatment on the degumming carbon fiber, wherein the water bath temperature is set to be 25 ℃, and the current density is 0.8mA/cm2The anodic oxidation time is 60s, and the treated degumming carbon fiber is washed by deionized water to remove the electrolyte remained on the surface of the carbon fiber, so as to obtain the anodic oxidation carbon fiber;
deposition of nano particles: adding carboxylated graphene oxide into deionized water, wherein the concentration is 0.5mg/ml, performing intermittent ultrasonic dispersion by using a cell disruptor for 30min, then quantitatively and controllably depositing nanoparticles on the surface of the anodized carbon fiber obtained in the step (i) by using an ultrasonic-assisted constant-pressure directional electrophoresis method by using a uniformly dispersed carboxylated graphene oxide aqueous solution as an electrolyte, wherein the electrophoretic deposition voltage is set to 10V, the deposition time is 5min, the ultrasonic power of an electrolyte water bath is 50W, the temperature is 20 ℃, and then drying the fiber in a blast oven at 80 ℃ for 12h to obtain the carbon fiber with nanoparticles deposited on the surface;
high temperature resistant polymer coating: adding low molecular weight polyether imide into N-methyl pyrrolidone, heating, stirring and dissolving to prepare a high temperature resistant polymer solution with the mass concentration of 1%, naturally cooling the high temperature resistant polymer solution to room temperature, immersing the surface deposited nano particle carbon fiber obtained in the step two in the high temperature resistant polymer solution, performing ultrasonic power of 40W for 60s, and finally drying the fiber in a forced air oven at 100 ℃ for 12h to obtain the high temperature resistant polymer coated carbon fiber;
2) preparation of the high-temperature resistant resin system: triglycidyl p-aminophenol, methyl nadic anhydride and 2-ethyl-4-methylimidazole (2E4MI) are mixed by mechanical stirring according to the proportion: the oil bath temperature is 40 ℃, the stirring speed is 400r/min, and the stirring time is 40min, so as to obtain a high-temperature resistant resin system;
3) preparing a composite material: and (2) dipping and compounding the carbon fiber coated with the high-temperature-resistant polymer on the surface prepared in the step (1) and the high-temperature-resistant resin system prepared in the step (2), adopting a curing mode of gradient temperature rise, wherein the curing system is 80 ℃/1h +130 ℃/1.5h +180 ℃/3h, and then cooling to room temperature to obtain the carbon fiber composite material with the multi-scale high-temperature-resistant interface structure. And (5) polishing and flattening the sample according to the corresponding national standard requirements after the sample is completely cured, and testing.
The interlaminar shear strength data for the composite is shown in table 1.
Comparative example 1
The carbon fibers were not subjected to the one-step anodization rapid treatment prior to the ultrasonic-assisted electrophoretic deposition, and other conditions were consistent with those of example 1. As can be seen from fig. 1, the deposition effect of the nano particles on the surface of the carbon fiber is obviously reduced without the one-step anodization, which indicates that the surface activity of the carbon fiber can be effectively improved and the modification effect of the electrophoretic deposition can be improved by the anodization.
Example 2
The ammonium salt aqueous solution adopts ammonium phosphate aqueous solution, the nano particles adopt carboxylated carbon nano tubes, the high-temperature resistant polymer adopts polyamide acid, and the solvent of the high-temperature resistant polymer solution adopts N, N-dimethylformamide; the main resin of the high-temperature resistant resin system adopts triglycidyl-p-aminophenol, the curing agent of the high-temperature resistant resin system adopts methyl tetrahydrophthalic anhydride, and the accelerator of the high-temperature resistant resin system adopts 2-methylimidazole, wherein the mass part ratio of the main resin, the curing agent and the accelerator is 100:80: 1.5; the carbon fiber is Dongli T800HB-12K degumming carbon fiber. The preparation process comprises the following steps:
1) carbon fiber surface modification:
anodic oxidation treatment: adding ammonium phosphate into deionized water, stirring and dissolving at normal temperature to prepare an ammonium phosphate aqueous solution with the mass concentration of 8%, taking the ammonium phosphate aqueous solution as an electrolyte, taking a graphite plate as a negative plate, and carrying out one-step anodic oxidation rapid treatment on the degumming carbon fiber, wherein the water bath temperature is set to be 30 ℃, and the current density is 1.0mA/cm2The anodizing time is 45s, and the treated degumming carbon fiber is washed by deionized water to remove the electrolyte remained on the surface of the carbon fiber, so that the anodized carbon fiber is obtained;
deposition of nano particles: adding a carboxylated carbon nanotube into deionized water, wherein the concentration is 0.8mg/ml, carrying out intermittent ultrasonic dispersion by using a cell disruptor for 45min, then quantitatively and controllably depositing nanoparticles on the surface of the anodized carbon fiber obtained in the step one by using an ultrasonic-assisted constant-pressure directional electrophoresis method by using a uniformly dispersed nanoparticle aqueous solution as an electrolyte, wherein the electrophoretic deposition voltage is set to 18V, the deposition time is 8min, the ultrasonic power of an electrolyte water bath is 80W, the temperature is 25 ℃, and then drying the fiber in a 90 ℃ forced air oven for 15h to obtain the surface-deposited nanoparticle carbon fiber;
high temperature resistant polymer coating: adding a high-temperature-resistant polymer into a solvent, heating, stirring and dissolving to prepare a high-temperature-resistant polymer solution with the mass concentration of 1.2%, naturally cooling the high-temperature-resistant polymer solution to room temperature, immersing the surface-deposited nano particle carbon fiber obtained in the step two into the high-temperature-resistant polymer solution for 50s at an ultrasonic power of 30W, and finally drying the fiber in a 90 ℃ blast oven for 20h to obtain the high-temperature-resistant polymer-coated carbon fiber;
2) preparation of the high-temperature resistant resin system: mechanically stirring and mixing triglycidyl p-aminophenol, methyl tetrahydrophthalic anhydride and 2-methylimidazole according to the proportion, wherein the mixing conditions are as follows: the oil bath temperature is 50 ℃, the stirring speed is 600r/min, and the stirring time is 30min, so as to obtain a high-temperature resistant resin system;
3) preparing a composite material: and (2) dipping and compounding the carbon fiber coated with the high-temperature-resistant polymer on the surface prepared in the step (1) and the high-temperature-resistant resin system prepared in the step (2), adopting a curing mode of gradient temperature rise, wherein the curing system is 90 ℃/1h +120 ℃/1h +160 ℃/2.5h, and then cooling to room temperature to obtain the carbon fiber composite material with the multi-scale high-temperature-resistant interface structure. And (5) polishing and flattening the sample according to the corresponding national standard requirements after the sample is completely cured, and testing.
The interlaminar shear strength data for the composite is shown in table 1.
Comparative example 2
After the deposition of the carboxylated carbon nanotubes, the polyamic acid solution is not applied. Other conditions were consistent with the procedure and example 2. As can be seen from the data in Table 1, the interlaminar shear strength of the composite material is significantly reduced without coating the high temperature resistant polymer, i.e., the interfacial properties of the composite material can be significantly improved by the synergistic effect of the nanoparticles and the polymer.
Example 3
The ammonium salt aqueous solution is ammonium carbonate aqueous solution, the nano particles are aminated graphene oxide, the high-temperature-resistant polymer is aminated polyimide, and the solvent of the high-temperature-resistant polymer solution is N, N-dimethylformamide; the main resin of the high-temperature resistant resin system is bismaleimide resin, the curing agent of the high-temperature resistant resin system is methylhexahydrophthalic anhydride, and the accelerator of the high-temperature resistant resin system is 2-ethyl-4-methylimidazole (2E4MI), wherein the mass part ratio of the main resin, the curing agent and the accelerator is 100:90: 0.6; the carbon fiber is Dongli T800HB-12K degumming carbon fiber. The preparation process comprises the following steps:
1) carbon fiber surface modification:
anodic oxidation treatment: adding ammonium carbonate into deionized water, stirring and dissolving at normal temperature to prepare an ammonium carbonate aqueous solution with the mass concentration of 10%, taking the ammonium carbonate aqueous solution as an electrolyte and a graphite plate as a cathode plate, and carrying out one-step anodic oxidation rapid treatment on the degumming carbon fiber, wherein the water bath temperature is set to be 35 ℃, and the current density is 1.5mA/cm2The anodic oxidation time is 30s, and the treated degumming carbon fiber is washed by deionized water to remove the electrolyte remained on the surface of the carbon fiber, so as to obtain the anodic oxidation carbon fiber;
deposition of nano particles: adding aminated graphene oxide into deionized water, wherein the concentration is 1.0mg/ml, performing intermittent ultrasonic dispersion by using a cell disruptor for 60min, quantitatively and controllably depositing nanoparticles on the surface of the anodized carbon fiber obtained in the step one by using an ultrasonic-assisted constant-pressure directional electrophoresis method by using a uniformly dispersed nanoparticle aqueous solution as an electrolyte, wherein the electrophoretic deposition voltage is set to be 25V, the deposition time is 10min, the ultrasonic power of an electrolyte water bath is 100W, the temperature is 30 ℃, and then drying the fiber in a 100 ℃ blast oven for 18h to obtain the surface-deposited nanoparticle carbon fiber;
high temperature resistant polymer coating: adding a high-temperature-resistant polymer into a solvent, heating, stirring and dissolving to prepare a high-temperature-resistant polymer solution with the mass concentration of 1.5%, naturally cooling the high-temperature-resistant polymer solution to room temperature, immersing the surface-deposited nano particle carbon fiber obtained in the step (II) into the high-temperature-resistant polymer solution for 30s at an ultrasonic power of 50W, and finally drying the fiber in a 100 ℃ blast oven for 24h to obtain the surface-coated high-temperature-resistant polymer carbon fiber;
2) preparation of the high-temperature resistant resin system: the bismaleimide resin, the methylhexahydrophthalic anhydride and the 2-ethyl-4-methylimidazole (2E4MI) are mechanically stirred and mixed according to the proportion, and the mixing conditions are as follows: the oil bath temperature is 60 ℃, the stirring speed is 800r/min, and the stirring time is 20min, so as to obtain a high-temperature resistant resin system;
3) preparing a composite material: and (2) dipping and compounding the carbon fiber coated with the high-temperature-resistant polymer on the surface prepared in the step (1) and the high-temperature-resistant resin system prepared in the step (2), adopting a curing mode of gradient temperature rise, wherein the curing system is 90 ℃/1h +120 ℃/2h +160 ℃/3h, and then cooling to room temperature to obtain the carbon fiber composite material with the multi-scale high-temperature-resistant interface structure. And (5) polishing and flattening the sample according to the corresponding national standard requirements after the sample is completely cured, and testing.
The interlaminar shear strength data for the composite is shown in table 1.
Comparative example 3
Auxiliary ultrasound was not added during the electrophoretic deposition, and other conditions were the same as those in example 3. As can be seen from FIG. 2, the deposition effect is better after the auxiliary ultrasound, which shows that the influence of bubbles generated by water decomposition can be timely eliminated by the additional auxiliary ultrasound in the electrophoretic deposition process, and the dispersion of the nanoparticles is improved, thereby enhancing the deposition effect.
TABLE 1 interlaminar shear strength (MPa) for each set of samples in examples and comparative examples
Claims (5)
1. A preparation method of a carbon fiber composite material with a multi-scale high-temperature-resistant interface structure is characterized by comprising the following steps: firstly, taking an ammonium salt aqueous solution with the mass concentration of 5-10% as an electrolyte and a graphite plate as a cathode, carrying out one-step anodic oxidation rapid treatment on the non-adhesive carbon fiber based on a large-current electrolysis principle, and then ultrasonically washing with deionized water to remove the residual electrolyte on the surface of the carbon fiber to obtain the anodic oxidation carbon fiber; secondly, taking the uniformly dispersed nano particle aqueous solution as electrolyte, taking a graphite plate as a cathode, taking the anodized carbon fiber obtained in the first step as an anode, and quantitatively and controllably depositing nano particles on the surface of the anodized carbon fiber by using an ultrasonic-assisted constant-pressure directional electrophoresis method to obtain the carbon fiber with the nano particles deposited on the surface, wherein the mass ratio of the carbon fiber to the nano particles is controlled to be 100:0.1-2 by adjusting the mass ratio of the water solvent to the nano particles in the nano particle aqueous solution; thirdly, dipping the carbon fiber with the surface deposited with the nano particles obtained in the second step in a high-temperature-resistant polymer solution for 30-60s, and controlling the mass ratio of the carbon fiber to the high-temperature-resistant polymer to be 100:1-1.5 by adjusting the mass ratio of the solvent to the high-temperature-resistant polymer in the solution to obtain the carbon fiber with the surface coated with the high-temperature-resistant polymer; fourthly, preparing the carbon fiber composite material with the sand-cement multi-scale characteristic high-temperature resistant interface structure by taking the high-temperature polymer carbon fiber coated on the surface obtained in the third step as a reinforcement and taking a high-temperature resistant resin system as a matrix material;
the nano particles are one of carboxylated graphene oxide, carboxylated carbon nano tubes or aminated graphene oxide;
the high-temperature resistant polymer is one of low-molecular-weight polyimide, low-molecular-weight polyetherimide or low-molecular-weight polyamidic acid.
2. The method for preparing the carbon fiber composite material with the multi-scale high-temperature resistant interface structure according to claim 1, wherein the ammonium salt aqueous solution is one or more of ammonium bicarbonate, ammonium acetate, ammonium carbonate, ammonium sulfate or ammonium phosphate, and the mass concentration of the ammonium salt aqueous solution is 5-10%.
3. The method as claimed in claim 1, wherein the low-molecular-weight-index-average molecular weight of the high-temperature-resistant polymer is 4000-8000g/mol, and the solvent of the high-temperature-resistant polymer solution is one or more of N, N-dimethylformamide, N-methylpyrrolidone, chloroform, and acetone.
4. The preparation method of the carbon fiber composite material with the multi-scale high-temperature-resistant interface structure according to claim 1, characterized in that the main body resin of the high-temperature-resistant resin system is one or more of polyfunctional alicyclic epoxy resin or linear novolac epoxy resin, the curing agent of the high-temperature-resistant resin system is one or more of anhydride curing agents, the accelerator of the high-temperature-resistant resin system is one of imidazole derivatives, and the mass part ratio of the main body resin, the curing agent and the accelerator is 100:50-90: 0.6-2.
5. The preparation method of the carbon fiber composite material with the multi-scale high-temperature resistant interface structure according to claim 1, characterized by comprising the following steps:
(1) carbon fiber surface modification:
anodic oxidation treatment: adding ammonium salt into deionized water, stirring and dissolving at normal temperature to prepare an ammonium salt aqueous solution with the mass concentration of 5-10%, taking the ammonium salt aqueous solution as an electrolyte and a graphite plate as a cathode plate, and carrying out one-step anodic oxidation rapid treatment on the non-glue carbon fiber, wherein the water bath temperature is set to be 25-35 ℃, and the current density is 0.8-1.5mA/cm2The anodic oxidation time is 30-60s, and the treated non-glue carbon fiber is washed by deionized water to remove the residual electrolyte on the surface of the carbon fiber, so as to obtain the anodic oxidation carbon fiber;
deposition of nano particles: adding nanoparticles into deionized water, performing ice bath intermittent ultrasonic dispersion by using a cell disruptor for 30-60min to obtain a uniformly dispersed nanoparticle aqueous solution with the concentration of 0.5-1.0mg/ml, then quantitatively and controllably depositing the nanoparticles on the surface of the anodized carbon fiber obtained in the step (i) by using the uniformly dispersed nanoparticle aqueous solution as an electrolyte and adopting an ultrasonic-assisted constant-pressure directional electrophoresis method, wherein the electrophoretic deposition voltage is set to 10-25V, the deposition time is 5-10min, the ultrasonic power of an electrolyte water bath is 50-100W, the temperature is 20-30 ℃, and then drying the fiber in a forced air oven at 80-100 ℃ for 12-18h to obtain the surface-deposited nanoparticle carbon fiber;
high temperature resistant polymer coating: adding a high-temperature-resistant polymer into a solvent, heating, stirring and dissolving to obtain a high-temperature-resistant polymer solution with the mass concentration of 1% -1.5%, naturally cooling the high-temperature-resistant polymer solution to room temperature, immersing the surface-deposited nano particle carbon fiber obtained in the step II into the high-temperature-resistant polymer solution, performing low-power ultrasound with the ultrasonic power of 30-50W for 30-60s, and finally drying the fiber in a blast oven at the temperature of 80-100 ℃ for 12-24h to obtain the high-temperature-resistant polymer-coated carbon fiber;
(2) preparation of the high-temperature resistant resin system:
mechanically stirring and mixing the main resin, the curing agent and the accelerator of the high-temperature resistant resin system according to the proportion, wherein the mixing conditions are as follows: the oil bath temperature is 40-60 ℃, the stirring speed is 400-;
(3) preparing a composite material:
and (2) impregnating and compounding the carbon fiber coated with the high-temperature-resistant polymer on the surface prepared in the step (1) and the high-temperature-resistant resin system prepared in the step (2), curing for 1-2h at 80-100 ℃, curing for 1-2h at 120-190 ℃ and curing for 2-3h at 160-190 ℃ by adopting a gradient heating curing mode, and then cooling to room temperature to obtain the carbon fiber composite material with the multi-scale high-temperature-resistant interface structure.
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