CN107629224B - Preparation method of double-sizing agent modified carbon fiber reinforced epoxy resin matrix composite material - Google Patents
Preparation method of double-sizing agent modified carbon fiber reinforced epoxy resin matrix composite material Download PDFInfo
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Abstract
The invention relates to a preparation method of a double-sizing agent modified carbon fiber reinforced epoxy resin matrix composite material, which utilizes OA-POSS mixed SiO2The sizing agent and the CNT sizing agent are modified in a multilayer mode, so that the introduction of complex chemical bonds is avoided, the surface of carbon fibers is modified in a grafting mode, and the modified carbon fiber reinforced epoxy resin matrix composite material is obtained through normal-temperature curing of a vacuum auxiliary forming process, so that the shearing performance of the composite material is improved by 24%, the tensile performance of the composite material is improved by 29%, and the mechanical performance of the composite material is higher than that of a thermosetting forming process.
Description
Technical Field
The invention belongs to the technical field of surface modification of composite materials, relates to a preparation method of a hybrid modified carbon fiber reinforced epoxy resin matrix composite material, and more particularly relates to exploration of a preparation method of a double-sizing agent modified carbon fiber reinforced epoxy resin matrix composite material, preparation of the carbon fiber reinforced epoxy resin matrix composite material and detection of mechanical properties.
Background
The carbon fiber reinforced epoxy resin matrix composite material is widely applied to the fields of aerospace, building, automobile industry and the like due to light weight and high strength, and is the key point of development and application of high-strength industrial products. Therefore, how to ensure the high strength of the carbon fiber and solve the problems of stretching and impact damage delamination of the carbon fiber are the problems faced at present. In the prior art, in order to improve the interlayer bonding force of carbon fibers, a method of modifying carbon fibers or an epoxy resin matrix is often adopted. For two modification methods, the modification of the epoxy resin matrix can improve the mechanical property of the matrix and also improve the bonding property of the interface between the carbon fiber and the resin matrix to a certain extent, but the modified matrix carbon fiber has weaker chemical bond bonding property and changes the original epoxy group content of the matrix, so the bonding principle of the two is more complex and relatively difficult to control. The modification of the carbon fiber has purposiveness, a substance which is easy to combine with an epoxy group is selected for modification, the modification process is easier to control, and the existing modification method comprises various processes such as chemical infiltration, electroplating, vapor deposition, plasma deposition and the like, wherein the chemical infiltration is widely applied due to the advantages of low cost, easiness in treatment of reaction liquid and the like. In the current research, there are many methods for surface modification, and scholars have modified the epoxy resin matrix with CNT to improve the toughness of the matrix to some extent; in the aspect of preparation of mixed organic-inorganic modification, the mixed modification of organic materials and inorganic materials is used and then applied to the composite material, and the method causes the defect increase caused by the mixed modification, thereby causing the performance of the composite material to be not greatly improved. For the multi-component modified carbon fiber composite material, similar research has been carried out on CN102912626A and CN104277421A, but because the composite material is applied to a thermosetting molding process and a sizing agent infiltration method is not applied in the modification process, the modification is directly carried out through chemical treatment processes such as acid oxidation and the like, the modification is not complete enough, certain influence is generated on the physical and chemical properties of a graft, the carbon fiber and the semi-siloxane belong to different chemical systems, good interface bonding cannot be realized by the chemical action of functional groups close to substances, and the tensile strength and the strain performance of the composite material are effectively improved by various complex chemical bonding actions such as chemical bonds, van der Waals force and the like, but adverse influence is generated on the bending toughness and the impact resistance of the composite material.
Disclosure of Invention
In view of the above pointsThe invention aims to provide a preparation method of a double-sizing agent modified carbon fiber reinforced epoxy resin matrix composite material. The preparation method utilizes OA-POSS to mix SiO2The sizing agent and the CNT sizing agent are modified in a multilayer mode, so that the introduction of complex chemical bonds is avoided, the surface of carbon fibers is modified in a grafting mode, and the modified carbon fiber reinforced epoxy resin matrix composite material is obtained through normal-temperature curing of a vacuum auxiliary forming process, so that the shearing performance of the composite material is improved by 24%, the tensile performance of the composite material is improved by 29%, and the mechanical performance of the composite material is higher than that of a thermosetting forming process.
In order to realize the purpose of the invention, the invention provides a preparation method of a double-sizing agent modified carbon fiber reinforced epoxy resin matrix composite material, which comprises the following steps:
1) preparing a carbon nano tube modified solution: dissolving a silane coupling agent in an ethanol solution, and stirring to obtain a silane coupling agent sol; then adding the silane coupling agent sol and the amino multi-walled carbon nano-tube into the dispersing agent respectively, and stirring uniformly at the rotating speed of 800-; the carbon nano tube modified solution comprises the following substances in percentage by mass: 0.1-0.8% of silane coupling agent sol, 0.5-2.0% of amino multi-walled carbon nanotube and 97.2-99.4% of dispersant;
2) carbon fiber surface pretreatment: soaking the carbon fiber cloth in an impurity removing agent for surface cleaning, and then drying and carrying out high-temperature oxidation treatment on the cleaned carbon fiber cloth, wherein the high-temperature oxidation temperature is 300-600 ℃, and the high-temperature oxidation time is 10-60 min; cooling the carbon fiber cloth subjected to oxidation treatment to normal temperature, and placing the carbon fiber cloth in a sample bag;
3) primary modification treatment of carbon fibers: dipping the carbon fiber cloth pretreated in the step 2) in a carbon nano tube modified solution, taking out the carbon fiber cloth after ultrasonic oscillation for 50-90s, and drying at normal temperature; then placing the carbon fiber cloth in a tube furnace filled with argon, sintering for 2-5h at the temperature of 900 ℃ with 600-;
4) preparing a secondary modified sizing agent: preparing SiO with particle size of 20nm-1 μm from tetraethoxysilane2Powder; then adding octa-aminopropyl to make polyhedralOligomeric silsesquioxane (OA-POSS) with SiO2Dissolving the powder in distilled water, and mixing with octa-aminopropyl polyhedral oligomeric silsesquioxane (OA-POSS) and SiO2The mass percentage of the powder and the distilled water is 0.5%: 0.5-1.0%: 98.5 to 99.0 percent; stirring the mixture to be completely mixed under the conditions that the water bath temperature is 60-100 ℃ and the rotating speed is 500-1500r/min, stopping heating, and standing the mixture to room temperature to obtain the required secondary modified sizing agent;
5) and (3) carbon fiber secondary modification treatment: soaking the sample subjected to the primary modification treatment in the step 3) in the secondary modification sizing agent in the step 4), performing ultrasonic treatment at normal temperature for more than 48 hours to obtain a sample subjected to secondary modification treatment, and drying the sample in a forced air drying oven to obtain a modified carbon fiber sample;
6) and (3) introducing the modified carbon fiber sample obtained in the step 5) into a resin transfer molding process through vacuum to obtain the modified carbon fiber reinforced epoxy resin matrix composite material.
The product is prepared from the modified carbon fiber reinforced epoxy resin matrix composite material.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the invention has the remarkable improvements that: the surface of the carbon fiber is modified by adopting double-sizing agent hybridization modification, and the secondary modification treatment improves the microscopic morphology of the surface of the carbon fiber by using a material analysis method for analysis. Specifically, the interface shear performance is effectively improved, and the interface bonding force is improved by 24%; after the composite material is prepared, the tensile property of the composite material is improved, and the maximum tensile strength of the composite material is improved by 29 percent; in the process of a tensile experiment, the bonding force between the carbon fiber and the resin is increased, so that the carbon fiber is obviously less pulled out of the composite material, the tensile fracture of the composite material plate is mainly the fracture of the carbon fiber, and the mechanical property of the carbon fiber reinforced epoxy resin matrix composite material is obviously improved.
The preparation method has the prominent substantive characteristics that:
1) dissolving a proper amount of amino multi-walled carbon nanotubes in a solution containing a silane coupling agent to prepare a pre-dipping sizing agent, and modifying the surface of the carbon fiber by a sizing agent soaking and high-temperature sintering method;
2) using OA-POSS with SiO2And infiltrating the surface of the carbon fiber subjected to primary modification by the mixed secondary modification sizing agent, and drying to obtain the carbon fiber with the final modification layer. The final modified layer can be an interface layer, which is different from the multi-interface characteristics of other multi-component modification, and the interface is only a layer of cage structure of OA-POSS, because the space inside the cage structure is larger, so that the dendritic structure and SiO of the carbon nano tube are enabled to be larger2The powdery particles are doped in the carbon fiber/epoxy resin composite material, so that an interface layer between the carbon fiber and the epoxy resin is finally formed, and the bonding force between the carbon fiber and the resin is better increased by fewer interface layers, so that the composite material shows better interface characteristics. The interface characteristics comprise interface phase components, modified material components and purity, modified positions, interface layer thickness, interface peeling strength and the like.
3) Laying carbon fiber cloth, forming by utilizing a Vacuum resin Transfer Molding process (VARTM), and preparing the composite material under the atmospheric pressure of 0.1MPa, thereby preparing the carbon fiber reinforced epoxy resin matrix composite material plate which is compact, uniform and good in flatness.
4) The surface secondary modified material after the carbon fiber pretreatment is respectively amino multi-walled carbon nano-tube and octaaminopropyl polyhedral oligomeric silsesquioxane mixed SiO2. The modification technology adopted by the invention can further improve the bonding effect between the carbon fiber and the resin on the premise of ensuring the performance and the lightness of the carbon fiber. The surface of the carbon fiber is modified by 0.5-2.0% of amino multi-walled carbon nano-tubes, so that the surface active bonds of the carbon fiber, such as amino, carboxyl and the like, can be increased, and the surface roughness of the carbon fiber is increased, thereby enhancing the bonding effect between the carbon fiber and resin; when the content of the carbon nano tube is less than 0.5 percent, the content of the carbon nano tube grafted on the surface of the carbon fiber is too low, the roughness of the surface of the fiber cannot be increased well, when the content of the carbon nano tube is more than 1.0 percent, a slight agglomeration phenomenon occurs, and when the content of the carbon nano tube is more than 1.0 percent, the carbon nano tube is slightly agglomeratedAfter the carbon fiber is increased to 2.0 percent in one step, the content of the carbon nano tubes on the surface of the carbon fiber is too high, so that the carbon nano tubes are easy to agglomerate, the carbon nano tubes become a fragile phase of an interface, and the bonding effect between the carbon fiber and resin is weakened on the contrary; the content of the amino multi-walled carbon nanotube is preferably 0.5-1.0%. Aiming at the problem that the carbon nano tube in the primary modified sizing agent is inconsistent with the epoxy resin system, OA-POSS is used in the method for treating the secondary modified sizing agent, the high polymer is easier to combine with the epoxy resin, and the high polymer belongs to SiO2System, if appropriate, SiO is added2The carbon fiber is distributed in the cage-shaped high polymer and forms good mixing with the carbon nano tube, so that the interaction between modified interfaces is stronger, the bonding between the interfaces and epoxy resin is more facilitated, and the bonding force between the surface of the carbon fiber and epoxy resin is obviously enhanced; in addition, the prepared composite material adopts a vacuum infusion resin transfer molding process VARTM, and the mechanical properties of the prepared composite material are improved to a certain extent by analyzing an interface shear experiment and a tensile experiment, wherein the shear property is improved by 24 percent, and the tensile property is improved by 29 percent.
Drawings
Fig. 1 is a schematic view of a VARTM apparatus for use in the present invention.
Fig. 2 is a scanning electron micrograph analysis of the surface of the modified carbon fiber according to comparative example 1, comparative example 2, example 1, example 2 and example 3, respectively.
Fig. 3 is a comparative graph of interfacial shear strength of the surface of carbon fibers modified according to comparative example 1, comparative example 2, example 1, example 2, and example 3, respectively.
Fig. 4 is a stress-strain graph of tensile strength of composite sheets prepared according to comparative example 1, comparative example 2, example 1, example 2, and example 3, respectively.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention discloses a preparation method (called preparation method for short) of a double-sizing agent modified carbon fiber reinforced epoxy resin matrix composite, which comprises the following steps:
1) preparing a carbon nano tube modified solution: dissolving a silane coupling agent in an ethanol solution, and stirring to obtain a silane coupling agent sol; then adding the silane coupling agent sol and the amino multi-walled carbon nanotube into a dispersing agent respectively, and uniformly stirring at the rotating speed of 800-; the carbon nano tube modified solution comprises the following substances in percentage by mass: 0.1-0.8% of silane coupling agent sol, 0.5-2.0% of amino multi-walled carbon nanotube and 97.2-99.4% of dispersant; the dispersing agent is acetone, alcohol solution or other agents capable of playing a dispersing role;
2) carbon fiber surface pretreatment: soaking the carbon fiber cloth in an impurity removing agent for surface cleaning, and then drying and carrying out high-temperature oxidation treatment on the cleaned carbon fiber cloth, wherein the high-temperature oxidation temperature is 300-600 ℃, and the high-temperature oxidation time is 10-60 min; cooling the carbon fiber cloth subjected to oxidation treatment to normal temperature, and placing the carbon fiber cloth in a sample bag;
the impurity removing agent is acetone, alcohol solution or mixed solution of the acetone and the alcohol solution in any proportion;
3) primary modification treatment of carbon fibers: dipping the carbon fiber cloth pretreated in the step 2) in a carbon nano tube modified solution, taking out the carbon fiber cloth after ultrasonic oscillation for 50-90s, and drying at normal temperature; then placing the carbon fiber cloth in a tube furnace filled with argon, sintering for 2-5h at the temperature of 900 ℃ with 600-;
4) preparing a secondary modified sizing agent: preparing SiO with particle size of 20nm-1 μm from tetraethoxysilane2Powder; then octa-aminopropyl polyhedral oligomeric silsesquioxane (OA-POSS) and SiO2Dissolving the powder in distilled water, and mixing with octa-aminopropyl polyhedral oligomeric silsesquioxane (OA-POSS) and SiO2The mass percentage of the powder and the distilled water is 0.5%: 0.5-1.0%: 98.5-99.0 percent, stirring for 0.5-2 hours at the water bath temperature of 60-100 ℃ and the rotating speed of 500-1500r/min, stopping heating, and standing to room temperature to obtain the required productThe secondary modified sizing agent of (4);
5) and (3) carbon fiber secondary modification treatment: soaking the sample subjected to the primary modification treatment in the step 3) in the secondary modification sizing agent in the step 4), performing ultrasonic treatment at normal temperature for more than 48 hours to obtain a sample subjected to secondary modification treatment, and drying the sample in a forced air drying oven at normal temperature for 0.5-3 hours to obtain a modified carbon fiber sample;
6) and (3) introducing the modified carbon fiber sample obtained in the step 5) into a resin transfer molding (VARTM) process through vacuum to obtain the modified carbon fiber reinforced epoxy resin matrix composite material.
Furthermore, the silane coupling agent used in the preparation of the carbon nano tube modified solution is a coupling agent KH550, and the dispersing agent is an absolute ethanol solution of oleic acid, octadecanol and sodium dodecyl benzene sulfonate in the ratio of (4-8) to (2-4) to (1-2).
Further, SiO is prepared2The specific steps of the powder are as follows: dissolving tetraethoxysilane in an ethanol solution, continuously stirring at the temperature of 40-70 ℃ and the rotating speed of 800-1500r/min, and dropwise adding ammonia water to keep the pH value of the solution at 9.5-11, wherein the mass percentage of tetraethoxysilane to the ethanol solution is 40-70%; stopping heating and stirring when the solution is transparent colloid, drying the obtained transparent colloid in a drying oven at 80-120 deg.C to obtain solid, and grinding into white particles with corresponding particle size to obtain SiO2And (3) powder.
Furthermore, the modifying material acts on the surface of the carbon fiber to form an interface layer with the epoxy resin, and the thickness of the interface layer is 0.8-12 μm.
The bisphenol A epoxy resin can be at least one of E51, E44, E42, E54, E20, E06 and E35; the phenolic aldehyde amine curing agent is any one matched with the corresponding resin.
The thickness of the composite material plate is 1-2mm, and the hybrid modified material is a chemically bonded high molecular compound; the polymer compound is characterized in that: the chemical bonding mode comprises amino carboxyl bonding, electron cloud pi electrostatic interaction, sp hybridization bonding of carbon bonds and semi-siloxane and other bonding modes.
The invention also protects the carbon fiber cloth obtained after the secondary modification treatment.
The invention also discloses the modified carbon fiber reinforced epoxy resin matrix composite material plate prepared by the preparation method.
The thickness of the composite material plate is 1.0-2.5mm, and the tensile strength is improved by 15-30% compared with that before the composite material plate is modified.
The carbon fiber cloth is T300, T800, T1200 and the like, the epoxy resin is epoxy resin E51 or other bisphenol A type epoxy resin, and the curing agent used in the vacuum auxiliary molding can be T31, 651 and the like.
The device (see figure 1) used for vacuum assisted molding in the invention comprises a polytetrafluoroethylene mold 2, a demolding cloth 8 coated with a demolding agent, a flow guide net 7, a flow guide pipe 6, a vacuum pipe 1, a vacuum bag 5, a resin collector and the like. The release agent is paraffin or other chemical agents which can play a role in releasing. The die is made of polytetrafluoroethylene materials through machining. Placing the carbon fiber cloth sample obtained in the step 5) on a polytetrafluoroethylene mold 2, and layering, wherein the carbon fiber cloth 4, the demolding cloth 8, the flow guide net 7 and the vacuum bag 5 are sequentially arranged from bottom to top in the layering sequence; the vacuum bag is fixed on the polytetrafluoroethylene mould by the vacuum glue 3, and the vacuum tubes 1, 9 are respectively fixed on the moulds at both sides of the carbon fiber cloth, and one end of the vacuum tube is connected with the draft tube 6. The specific process comprises the following steps: clamping the vacuum tube 1 by using a clamp, connecting the vacuum tube 9 with a vacuum pump, vacuumizing the vacuum tube 9, clamping the vacuum tube 9 by using the clamp when the vacuum pressure is-0.1 MPa, closing the vacuum pump, maintaining the pressure for 1 hour under-0.1 MPa, and inserting the vacuum tube 1 into the prepared vacuumized epoxy resin solution if the reading is kept unchanged; the clamp of vacuum tube 1 and vacuum tube 9 is removed, the vacuum pump is opened, epoxy enters into the vacuum space, so that the epoxy is soaked on the surface of the carbon fiber cloth, the curing is carried out for about 6 hours, the process is disassembled, the carbon fiber plate with good surface quality is obtained, the obtained carbon fiber plate is cut, and the tensile experiment test is carried out.
According to the modified carbon fiber reinforced epoxy resin matrix composite material, through related performance experiment tests, the peel strength is 0.7-10N, and the interface shear strength is 75.89-80.48 MPa; the monofilament tensile strength of the modified carbon fiber sample was 297 and 592 MPa.
Example 1
The amino multi-walled Carbon Nanotubes (CNTs) used in the embodiment are purchased from Beijing Boyu high-tech new materials technology Co., Ltd, and the purity is 98-99.999%; octaaminopropyl polyhedral oligomeric silsesquioxane (OA-POSS) is provided by chemical industry academy of Hebei university of industry, and the purity is 97-99.988%; tetraethoxysilane (TEOS) with a concentration of 95% or more and ethanol (C)2H5OH) concentration of 70% -90%, ammonia (NH)3OH) concentration is 70-80%, and the basic chemical materials are chemical analysis pure substances. The carbon fiber cloth is T300.
The preparation method of the double-sizing agent modified carbon fiber reinforced epoxy resin matrix composite material comprises the following steps:
1) preparing a carbon nano tube modified solution: dissolving a silane coupling agent in an ethanol solution, and stirring at the rotating speed of 1000r/min to obtain silane coupling agent sol; then adding the silane coupling agent sol and the amino multi-walled carbon nanotube into a dispersing agent respectively, and stirring uniformly at the rotating speed of 1500r/min to obtain a carbon nanotube modified solution, namely a primary modified sizing agent; the carbon nano tube modified solution comprises the following substances in percentage by mass: 0.5% of silane coupling agent sol, 0.8% of amino multi-walled carbon nanotube and 98.7% of dispersing agent; the dispersing agent is acetone;
2) carbon fiber surface pretreatment: soaking the carbon fiber cloth in an impurity removing agent for surface cleaning, then drying and carrying out high-temperature oxidation treatment on the cleaned carbon fiber cloth, arranging the carbon fiber in a blast dryer at the temperature of 80 ℃, drying for 1h, arranging the carbon fiber in a muffle furnace, carrying out high-temperature oxidation for 30min at the temperature of 400 ℃, cooling to normal temperature, and placing in a sample bag. The impurity removing agent is acetone;
3) primary modification treatment of carbon fibers: dipping the carbon fiber cloth pretreated in the step 2) in a carbon nano tube modified solution, taking out the carbon fiber cloth after ultrasonic oscillation for 60s, and drying for 2h at normal temperature; then placing the carbon fiber cloth in a tube furnace filled with argon, sintering for 5 hours at 900 ℃, cooling to normal temperature, closing the argon, and taking out a sample;
4) preparing a secondary modified sizing agent: dissolving tetraethoxysilane in an ethanol solution, continuously stirring at the temperature of 60 ℃ and the rotating speed of 1500r/min, and dropwise adding ammonia water to keep the pH value of the solution at 10, wherein the mass percentage of tetraethoxysilane to the ethanol solution is 70%; stirring until the solution is transparent colloid, stopping heating and stirring, drying the obtained transparent colloid in a drying oven at 100 deg.C to obtain solid, grinding into white particles with corresponding particle size to obtain SiO 100nm2Powder; then octa-aminopropyl polyhedral oligomeric silsesquioxane (OA-POSS) and SiO2Dissolving the powder in distilled water, and mixing with octa-aminopropyl polyhedral oligomeric silsesquioxane (OA-POSS) and SiO2The mass percentage of the powder and the distilled water is 0.5%: 1.0%: 98.5 percent, stirring for 1 hour under the conditions that the water bath temperature is 80 ℃ and the rotating speed is 1500r/min, stopping heating, and standing to room temperature to obtain the required secondary modified sizing agent;
5) and (3) carbon fiber secondary modification treatment: soaking the sample subjected to the primary modification treatment in the step 3) in the secondary modification sizing agent in the step 4), performing ultrasonic treatment for 72 hours at normal temperature to obtain a sample subjected to secondary modification treatment, placing the sample in a forced air drying oven, and drying for 1 hour at normal temperature to obtain a modified carbon fiber sample;
6) and (3) introducing the modified carbon fiber sample obtained in the step 5) into a resin transfer molding (VARTM) process through vacuum to obtain the modified carbon fiber reinforced epoxy resin matrix composite material.
The specific process of vacuum infusion resin transfer molding is as follows: placing the carbon fiber cloth sample obtained in the step 5) on a polytetrafluoroethylene mould, and layering, wherein the carbon fiber cloth 4, the demoulding cloth 8, the flow guide net 7 and the vacuum bag 5 are sequentially arranged from bottom to top in the layering sequence; the vacuum bag is fixed on the polytetrafluoroethylene mould by the vacuum glue 3, and the vacuum tubes 1, 9 are respectively fixed on the moulds at both sides of the carbon fiber cloth, and one end of the vacuum tube is connected with the draft tube 6. The specific process comprises the following steps: clamping the vacuum tube 1 by using a clamp, connecting the vacuum tube 9 with a vacuum pump, vacuumizing the vacuum tube 9, clamping the vacuum tube 9 by using the clamp when the vacuum pressure is-0.1 MPa, closing the vacuum pump, maintaining the pressure for 1 hour under-0.1 MPa, and inserting the vacuum tube 1 into the prepared vacuumized epoxy resin solution if the reading is kept unchanged; the clamp of vacuum tube 1 and vacuum tube 9 is removed, the vacuum pump is opened, epoxy enters into the vacuum space, so that the epoxy is soaked on the surface of the carbon fiber cloth, the curing is carried out for about 6 hours, the process is disassembled, the carbon fiber plate with good surface quality is obtained, the obtained carbon fiber plate is cut, and the tensile experiment test is carried out.
Example 2
The steps for preparing the modified carbon fiber reinforced epoxy resin-based composite material in this embodiment are the same as those in embodiment 1, except that the mass percentages of the substances in the carbon nanotube modified solution in this embodiment are as follows: 0.5% of silane coupling agent sol, 1.0% of amino multi-walled carbon nano-tube and 98.5% of dispersing agent.
Example 3
The steps of the modified carbon fiber reinforced epoxy resin-based composite material of the embodiment are the same as those of embodiment 1, except that the mass percentages of the substances in the carbon nanotube modified solution in the embodiment are as follows: 0.5 percent of silane coupling agent sol, 2.0 percent of amino multi-walled carbon nano-tube and 97.5 percent of dispersant.
Comparative example 1
The carbon fiber epoxy resin matrix composite material prepared by the comparative example comprises the following specific steps:
1) carbon fiber surface pretreatment: soaking carbon fiber cloth in an impurity removing agent which is acetone for 30min, arranging the carbon fiber in a blast dryer, setting the temperature to be 80 ℃, drying for 1h, arranging the dried carbon fiber in a muffle furnace, oxidizing at the high temperature of 400 ℃ for 30min, cooling to the normal temperature, and placing in a sample bag.
2) And (3) introducing the pretreated carbon fiber cloth into a resin transfer molding (VARTM) process through vacuum to obtain the carbon fiber epoxy resin matrix composite material.
Comparative example 2
The carbon fiber epoxy resin matrix composite modified by the primary modified sizing agent is prepared according to the comparative example, and the carbon nanotube modified solution preparation, the carbon fiber surface pretreatment and the carbon fiber primary modified treatment are carried out according to the steps of the example 1, and then the vacuum resin transfer molding (VARTM) process is directly carried out, so that the carbon fiber epoxy resin matrix composite modified by the primary modified sizing agent is obtained.
The following are experimental analyses of comparative example 1, comparative example 2, example 1, example 2 and example 3.
As shown in fig. 2, scanning electron micrographs of carbon fiber filaments for testing prepared according to the methods of comparative example 1, comparative example 2, example 1, example 2 and example 3 are shown, wherein the comparative example 1 is an unmodified carbon fiber filament, and the surface of the carbon fiber filament after being cleaned by ethanol and acetone can be seen in the texture of the carbon fiber surface after being cleaned; while comparative example 2 was treated with the carbon nanotube-modifying solution, some CNT-aggregated protrusions were clearly present on the surface. Comparing comparative example 1 with comparative example 2 with example 1, it can be seen that the surface of the carbon fiber of example 1 after two modifications has no significant ravines, and the overflowing carbon fiber dendritic projections are almost absent, which indicates that a proper amount of CNTs are inserted into the cage structure of OA-POSS, and moderate amounts of CNTs and OA-POSS/SiO are present2Two wettings result in a better interfacial layer. The CNT modification means and processes with different mass fractions have different effects on the surface morphology of the carbon fiber, and in fig. 2, example 1, example 2, and example 3 are modifications with different concentrations, respectively, and it can be seen that different concentrations also have certain effects on the surface modification of the carbon fiber, and it is found through observation that when the mass fraction of the carbon nanotubes is appropriate, as shown in example 1, CNTs more uniformly penetrate through the cage structure of OA-POSS, resulting in the distribution of the interface layer on the surface of the carbon fiber. Example 2 in the case of a small amount, the surface of the carbon fiber showed different gloss because some of OA-POSS penetrated into the CNT and some did not, resulting in less uniform color distribution and poor surface flatness on the surface of the carbon fiber. In example 3, the amount of CNTs was large, the degree of aggregation of the penetrated CNTs was large, and the phenomenon of aggregation of the CNTs occurred, which also affected the binding ability between the interface and the resin. However, it can be seen from the CNTs processed in examples 2 and 3 that although the protrusions on the surface are not uniform, the CNTs completely cover the carbon fiber itself, so that OA-POS exists between the carbon fiber and the resinS(SiO2) The presence of CNTs, leading to the bonding of-NH 2-to-COOH, the epoxy group between-SiO-and the resin, makes the interface between example 2 and example 3 significantly stronger than comparative example 1 and comparative example 2.
As shown in fig. 3, which is a comparison graph of the interfacial shear strength of the carbon fiber filaments prepared according to comparative example 1, comparative example 2, example 1, example 2 and example 3, it can be seen that the interfacial shear strength of example 1, example 3 and example 3 is improved to a certain extent, the shear strength is obviously improved compared with that of untreated comparative example 1 and comparative example 2, the shear strength of example 1 is 80.47MPa, and the shear strength is improved by 24.07% and 15.15% compared with 64.86MPa of comparative example 1 and 69.88MPa of comparative example 2, respectively; the different mass fractions of the carbon nanotubes also have different influences on the shearing performance of the composite material, and when the mass fraction of the carbon nanotubes is 0.5% to 1.0%, the shearing performance is the strongest and is 80.47 MPa.
As shown in fig. 4, a graph comparing tensile stress-strain curves of the carbon fiber sheets prepared according to comparative example 1, comparative example 2, example 1, example 2 and example 3: the comparison shows that the elastic modulus of the carbon fiber composite material in the embodiments 1, 2 and 3 is changed, particularly the tensile property of the embodiment 1 is greatly influenced, so that the elastic modulus reaches 5000MPa, and the performance of the carbon fiber composite material is improved and optimized. Examples 2 and 3 do not change much in stress strength compared to comparative examples 1 and 2 because too little or too high content of CNT makes the interface layer uneven, but because some degree of-NH 2-bonding with-COOH, -SiO-bonding with the resin epoxy groups and the presence of the cage structure of OA-POSS increases the strain coefficient, changing from 0.065%, 0.068% of comparative examples 1 and 2 to 0.074%, 0.080% of examples 2 and 3, which results in an improvement in plasticity of examples 1, 2, and 3.
In conclusion, the mode of modifying by adopting the double sizing agents of the invention has certain influence on the interfacial shear property and the tensile strength of the carbon fiber, and the mechanical property of the modified carbon fiber yarn is relatively obviously improved. In addition, for the modified amino multi-walled carbon nanotube, a proper concentration should be selected, and the strength of the carbon fiber reinforced resin matrix composite material is adversely affected by over-high or over-low concentration.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A preparation method of a double-sizing agent modified carbon fiber reinforced epoxy resin matrix composite material comprises the following steps:
1) preparing a carbon nano tube modified solution: dissolving a silane coupling agent in an ethanol solution, and stirring to obtain a silane coupling agent sol; then adding the silane coupling agent sol and the amino multi-walled carbon nano-tube into the dispersing agent respectively, and stirring uniformly at the rotating speed of 800-; the carbon nano tube modified solution comprises the following substances in percentage by mass: 0.1-0.8% of silane coupling agent sol, 0.5-2.0% of amino multi-walled carbon nanotube and 97.2-99.4% of dispersant; the silane coupling agent is a coupling agent KH 550;
2) carbon fiber surface pretreatment: soaking the carbon fiber cloth in an impurity removing agent for surface cleaning, and then drying and carrying out high-temperature oxidation treatment on the cleaned carbon fiber cloth, wherein the high-temperature oxidation temperature is 300-600 ℃, and the high-temperature oxidation time is 10-60 min; cooling the carbon fiber cloth subjected to oxidation treatment to normal temperature, and placing the carbon fiber cloth in a sample bag;
3) primary modification treatment of carbon fibers: dipping the carbon fiber cloth pretreated in the step 2) in a carbon nano tube modified solution, taking out the carbon fiber cloth after ultrasonic oscillation for 50-90s, and drying at normal temperature; then placing the carbon fiber cloth in a tube furnace filled with argon, sintering for 2-5h at the temperature of 900 ℃ with 600-;
4) preparing a secondary modified sizing agent: preparing SiO with particle size of 20nm-1 μm from tetraethoxysilane2Powder; then oligomerizing the octaaminopropyl polyhedral oligomeric silsesquioxaneSiloxane OA-POSS with SiO2Dissolving the powder in distilled water, and mixing with OA-POSS and SiO2The mass percentage of the powder and the distilled water is 0.5%: 0.5-1.0%: 98.5 to 99.0 percent; stirring the mixture to be completely mixed under the conditions that the water bath temperature is 60-100 ℃ and the rotating speed is 500-1500r/min, stopping heating, and standing the mixture to room temperature to obtain the required secondary modified sizing agent;
5) and (3) carbon fiber secondary modification treatment: soaking the sample subjected to the primary modification treatment in the step 3) in the secondary modification sizing agent in the step 4), performing ultrasonic treatment at normal temperature for more than 48 hours to obtain a sample subjected to secondary modification treatment, and drying the sample in a forced air drying oven to obtain a modified carbon fiber sample;
6) and (3) introducing the modified carbon fiber sample obtained in the step 5) into a resin transfer molding process through vacuum to obtain the modified carbon fiber reinforced epoxy resin matrix composite material.
2. The preparation method of the double-sizing agent modified carbon fiber reinforced epoxy resin-based composite material as claimed in claim 1, wherein the dispersing agent is acetone or alcohol solution or absolute ethanol solution of oleic acid, octadecanol and sodium dodecyl benzene sulfonate in the ratio of (4-8) - (2-4) - (1-2).
3. The preparation method of the double-sizing agent modified carbon fiber reinforced epoxy resin-based composite material as claimed in claim 1, wherein the SiO is prepared2The specific steps of the powder are as follows: dissolving tetraethoxysilane in an ethanol solution, continuously stirring at the temperature of 40-70 ℃ and the rotating speed of 800-1500r/min, and dropwise adding ammonia water to keep the pH value of the solution at 9.5-11, wherein the mass percentage of tetraethoxysilane to the ethanol solution is 40-70%; stopping heating and stirring when the solution is transparent colloid, drying the obtained transparent colloid in a drying oven at 80-120 deg.C to obtain solid, and grinding into white particles with corresponding particle size to obtain SiO2And (3) powder.
4. The preparation method of the double-sizing agent modified carbon fiber reinforced epoxy resin-based composite material as claimed in claim 1, wherein an interface layer can be formed between the carbon fiber and the epoxy resin of the modified carbon fiber reinforced epoxy resin-based composite material, and the thickness of the interface layer is 0.8-12 μm.
5. The method for preparing the double-sizing agent modified carbon fiber reinforced epoxy resin-based composite material as claimed in claim 1, wherein the epoxy resin is at least one of E51, E44, E42, E54, E20, E06 and E35.
6. The preparation method of the double-sizing agent modified carbon fiber reinforced epoxy resin-based composite material according to claim 1, characterized in that the specific process of the vacuum infusion resin transfer molding process is as follows: clamping the vacuum tube (1) by using a clamp, connecting the vacuum tube with a vacuum pump, vacuumizing the vacuum tube (9), clamping the vacuum tube (9) by using the clamp when the vacuum pressure is-0.1 MPa, closing the vacuum pump, maintaining the pressure for 1h under-0.1 MPa, keeping the index unchanged, and then inserting the vacuum tube (1) into the prepared vacuumized epoxy resin solution; the clamp of vacuum tube (1) and vacuum tube (9) is removed, the vacuum pump is opened, epoxy enters into the vacuum space, epoxy soaks on the surface of carbon cloth from this, solidification 6h, disassembles this technology, and then obtains the carbon fiber board that surface quality is good, cuts the carbon fiber board who obtains again, and carries out tensile test.
7. An article characterized by being a modified carbon fiber-reinforced epoxy resin-based composite material produced by the method for producing a modified carbon fiber-reinforced epoxy resin-based composite material according to any one of claims 1 to 6.
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| CN108547151A (en) * | 2018-03-30 | 2018-09-18 | 王景硕 | A kind of aqueous epoxy resins carbon fiber sizing agent |
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| CN110872428A (en) * | 2018-08-31 | 2020-03-10 | 天津中科先进技术研究院有限公司 | Preparation method of double-layer oxide modified carbon fiber reinforced composite material |
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| CN113668239B (en) * | 2021-08-24 | 2023-03-31 | 杭州萧山红旗摩擦材料有限公司 | Modification method of carbon fiber for paper-based friction material |
| CN115073885A (en) * | 2022-06-23 | 2022-09-20 | 浙江中纯新材料有限公司 | Fiber hybrid composite material and manufacturing method thereof |
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