CN112479730A - Preparation method of curved carbon nanofiber reinforced C/C composite material - Google Patents
Preparation method of curved carbon nanofiber reinforced C/C composite material Download PDFInfo
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- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
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- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
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Abstract
The invention discloses a preparation method of a curved nano carbon fiber reinforced C/C composite material, which comprises the following steps: ultrasonically dipping the carbon felt in a copper tartrate solution for a period of time; using acetylene as a carbon source and nitrogen as a protective gas, controlling the flow rate of the acetylene to be 0.2-0.5L/min, and performing catalytic chemical vapor deposition at the temperature of 270-290 ℃ and under the working pressure of 50-80kPa to obtain a carbon felt containing curved nano-fibers; carbonizing the carbon felt at 950-; and performing CVI densification on the carbon felt containing the bent nano carbon fibers by using propylene as a carbon source and argon as a carrier gas to obtain the bent nano carbon fiber reinforced C/C composite material. The preparation method of the curved nano carbon fiber reinforced C/C composite material provided by the invention has the advantages of simple process and low energy consumption, and the nano carbon fiber grown in situ is well combined with the carbon fiber in the carbon felt, and the nano carbon fiber is curved and has a good reinforcing effect on the C/C composite material.
Description
Technical Field
The invention relates to the technical field of composite material preparation, in particular to a preparation method of a curved nano carbon fiber reinforced C/C composite material.
Background
The C/C composite material is a pure carbon multiphase structure which is composed of carbon fibers or fabrics thereof as a reinforcing phase and chemical vapor infiltration pyrolytic carbon or liquid impregnation-carbonization resin carbon and pitch carbon as matrixes. The C/C composite material not only has low density and thermal expansion coefficient, high strength, modulus and fracture toughness, but also has excellent wear resistance, ablation resistance, thermal conductivity and thermal shock resistance, and thus, it is often used as an ultra-high temperature structural material in the aerospace field, for example: airplane brake disc, wing leading edge, rocket nozzle, diffusion section, missile end cap and other parts.
The phenomena of cracking and block breaking sometimes occur in the practical use of the currently commonly used 2D needling, puncturing and 3D C/C composite material, and the analysis shows that the reasons mainly include the following aspects: 1) the carbon matrix in the carbon fiber bundle is not reinforced enough; 2) the reinforcement of the carbon matrix among the carbon fiber bundles is insufficient; 3) the carbon matrix in the gaps is not reinforced enough; 4) the processing damage of the carbon fiber seriously interferes the effect of enhancing the carbon matrix and has fatal influence on sharp-angled sharp parts; 5) the carbon fiber/carbon matrix interface bonding strength is insufficient. The problems seriously restrict the full play of the mechanical property of the C/C composite material, greatly limit the application of the C/C composite material to special components such as thin walls, sharp corners, complex integral components and the like, and restrict the development of national defense high-tech equipment. Therefore, it is important to improve the microstructure of the material to improve the performance of the C/C composite material.
Aiming at the problem of improving the microstructure of the C/C composite material, the method for introducing the carbon nano material into the C/C composite material and constructing the micron carbon fiber and carbon nano material multi-scale preform reinforced C/C composite material is an effective method. From the existing research reports, the multi-scale preform obviously can achieve the purpose of improving the microstructure of the C/C composite material and further improving the performance of the C/C composite material, and can realize the control and design of the microstructure, the interface combination and the material performance of the C/C composite material. The most used carbon nanomaterials today are Carbon Nanotubes (CNTs), Carbon Nanofibers (CNFs), graphene. At present, the methods for introducing CNTs/CNFs into carbon fiber preforms are mainly divided into two methods: firstly, CNTs/CNFs are grafted to carbon fibers by a physical or chemical method; and secondly, growing CNTs/CNFs on the surface of the carbon fiber in situ by means of a catalyst and a CVD method. Because the CNTs/CNFs grafted on the surface are mostly in a lodging shape, the CNTs/CNFs cannot fully play a role of rivet when being combined with a substrate, and the CNTs/CNFs introduced by an in-situ growth method can well overcome the problem, so that the enhancement effect of the CNTs/CNFs is fully exerted, and the CNTs/CNFs is favored by researchers at home and abroad.
In the prior art, the method of introducing CNTs/CNFs by adopting an in-situ growth method adopts transition metals Fe, Co, Ni or alloys thereof as catalysts, the synthesis process temperature is about 650-800 ℃, the energy consumption is high, and the industrial popularization is difficult; and the carbon fiber material is easy to be damaged due to the higher temperature; when the catalyst is used for synthesizing the bent nano carbon fiber, carbon source gas is generally required to pass through S-containing or P-containing solution (growth auxiliary agent of the bent nano carbon fiber) such as thiophene, and the process is relatively complicated.
In view of the above, it is necessary to provide a new process to solve the above technical problems.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a curved nano carbon fiber reinforced C/C composite material, which has the advantages of simple process and low energy consumption, and the nano carbon fiber grown in situ is well combined with the carbon fiber in the carbon felt, the nano carbon fiber is curved, the reinforcing effect on the C/C composite material is good, and the continuous industrial production can be realized.
In order to solve the problems, the technical scheme of the invention is as follows:
a preparation method of a curved carbon nanofiber reinforced C/C composite material comprises the following steps:
step S1, ultrasonically dipping the carbon felt in a copper tartrate solution for a period of time, taking out and drying, wherein the concentration of the copper tartrate solution is 0.01-0.015 mol/mL;
s2, using acetylene as a carbon source and nitrogen as a protective gas, controlling the flow of the acetylene to be 0.2-0.5L/min, carrying out catalytic chemical vapor deposition at the temperature of 270-290 ℃ and under the working pressure of 50-80kPa, and growing curved nanofibers on the carbon fibers in situ to obtain a carbon felt containing the curved nanofibers;
step S3, carbonizing the carbon felt at 950-1050 ℃ by taking nitrogen as protective gas, and preserving heat for 3-5h to obtain the carbon felt containing bent nano carbon fibers;
step S4, performing CVI densification on the carbon felt containing the curved nano-carbon fibers by taking propylene as a carbon source and argon as a carrier gas to obtain a curved nano-carbon fiber reinforced C/C composite material;
in the CVI densification process, the propylene flow is controlled to be 1-2L/min, the argon flow is controlled to be 1-2L/min, the deposition temperature is 920 and 1050 ℃, and the working pressure is 2-7 kPa.
Further, in step S1, the ultrasonic immersion time is 10-20 min.
Furthermore, in the catalytic chemical vapor deposition process, the temperature rise rate is controlled to be less than 3 ℃/min.
Further, the time of the catalytic chemical vapor deposition is 30-60 min.
Further, the CVI densification process employs a self-induction heating chemical vapor deposition furnace.
Further, a differential pressure method CVI is adopted for densification.
Further, from induction heating chemical vapor deposition stove includes the furnace body, locates in the furnace body by the heat preservation felt enclose close the reaction chamber who forms, encircle the electrical coil that the heat preservation felt set up, be used for detecting the temperature detection component of temperature in the reaction chamber, locate the graphite frock in the reaction chamber, with the graphite apron that the graphite frock set up relatively, run through the intake pipe of furnace body diapire, heat preservation felt diapire and graphite frock in proper order, be used for piling up annular charcoal felt between graphite frock and the graphite apron, gaseous passing through the intake pipe gets into annular charcoal felt, graphite frock and graphite apron and encloses in the region that closes the formation to along the radial flow of annular charcoal felt.
Furthermore, the self-induction heating chemical vapor deposition furnace also comprises a cooling water inlet, a cooling water outlet, an exhaust valve and a tail gas outlet which are arranged on the furnace body.
Furthermore, the diameter of the curved nanometer carbon fiber in the carbonized carbon felt is 20-240nm, and the length is 2-30 μm.
Compared with the prior art, the preparation method of the curved nano carbon fiber reinforced C/C composite material has the beneficial effects that:
according to the preparation method of the curved nano carbon fiber reinforced C/C composite material, the curved nano carbon fiber is synthesized by taking the copper tartrate as a catalyst precursor, catalytic chemical vapor deposition is carried out at the temperature of 270-290 ℃, and the reaction is carried out at a relatively low temperature, so that the carbon fiber is not greatly damaged, a large amount of energy can be saved, and industrial popularization can be realized.
Secondly, the preparation method of the curved nano carbon fiber reinforced C/C composite material provided by the invention is characterized in that the curved nano carbon fiber is synthesized by taking copper tartrate as a catalyst precursor, and the solubility of C atoms in Cu is low, so that the damage to the carbon fiber is relatively small by taking Cu as a catalyst; and when the copper tartrate is used as a catalyst precursor to synthesize the bent nano carbon fiber, no growth auxiliary agent is needed, and the process is simple.
The preparation method of the curved nano-carbon fiber reinforced C/C composite material provided by the invention comprises the steps of firstly carrying out catalytic chemical vapor deposition to grow the curved nano-carbon fibers in situ in the carbon fiber preform, and then carrying out subsequent densification, so that the thickness, length and shape of the nano-carbon fibers can be accurately controlled, the competitive growth between the curved nano-carbon fibers and pyrolytic carbon is effectively avoided, and the catalyst is prevented from being inactivated due to the fact that the catalyst is covered by the pyrolytic carbon when the curved nano-carbon fibers are still short.
Fourthly, according to the preparation method of the curved nano carbon fiber reinforced C/C composite material, the catalyst precursor is soaked by ultrasonic waves, so that the catalyst precursor is easy to land in a large pore area in the carbon fiber preform, and after the nano carbon fiber grows in situ, the existence of the nano carbon fiber increases nucleation points, so that the deposition rate of the large pore area is increased and the large pore area is filled, thereby avoiding the formation of closed pores, and being beneficial to the improvement of the mechanical property of the material.
The preparation method of the curved nano-carbon fiber reinforced C/C composite material is characterized in that the nano-carbon fibers are coiled, and because the coiled nano-carbon fibers are easy to crosslink, the reinforcing effect of the coiled nano-carbon fiber reinforced C/C composite material is theoretically stronger than that of linear nano-carbon fibers.
Sixth, the preparation method of the curved nanometer carbon fiber reinforced C/C composite material provided by the invention can prepare nanometer carbon fibers with the diameter within a certain range, so that certain reinforcing effect can be generated on carbon matrixes and interfaces of the carbon matrixes and the carbon fibers at different scales, and the reinforcing effect is theoretically stronger than that of nanometer carbon fibers with a single scale.
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In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a self-induction heating chemical vapor deposition furnace applied in a preparation method of a curved nano carbon fiber reinforced C/C composite material;
FIG. 2 is a scanning electron microscope image of the obtained curved nano carbon fiber;
FIG. 3 is a cross-sectional scanning electron microscope image of the curved nanocarbon fiber reinforced C/C composite material prepared in example 1;
FIG. 4 is a scanning electron microscope image of a cross section of the curved carbon nanofiber reinforced C/C composite material prepared in example 2.
Detailed Description
The following description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
A preparation method of a curved carbon nanofiber reinforced C/C composite material comprises the following steps:
step S1, ultrasonically dipping the carbon felt in a copper tartrate solution for a period of time, taking out and drying, wherein the concentration of the copper tartrate solution is 0.01-0.015mol/mL, and the ultrasonic dipping time is 10-20 min;
s2, using acetylene as a carbon source and nitrogen as a protective gas, controlling the flow of the acetylene to be 0.2-0.5L/min, carrying out catalytic chemical vapor deposition at the temperature of 270-290 ℃ and under the working pressure of 50-80kPa, and growing curved nanofibers on the carbon fibers in situ to obtain a carbon felt containing the curved nanofibers;
wherein in the catalytic chemical vapor deposition, the temperature rise rate is controlled to be less than 3 ℃/min, and the time of the catalytic chemical vapor deposition is 30-60 min;
step S3, carbonizing the carbon felt at 950-1050 ℃ by taking nitrogen as protective gas, and preserving heat for 3-5h to obtain the carbon felt containing bent nano carbon fibers;
the diameter of the curved nano carbon fiber in the carbonized carbon felt is 20-240nm, and the length is 2-30 μm;
step S4, performing CVI densification on the carbon felt containing the curved nano-carbon fibers by taking propylene as a carbon source and argon as a carrier gas to obtain a curved nano-carbon fiber reinforced C/C composite material; in the CVI densification process, the propylene flow is controlled to be 1-2L/min, the argon flow is controlled to be 1-2L/min, the deposition temperature is 920 and 1050 ℃, and the working pressure is 2-7 kPa.
The structure of the self-induction heating chemical vapor deposition furnace used in the CVI densification process is shown in figure 1. The self-induction heating chemical vapor deposition furnace comprises a furnace body 1, a cooling water inlet 11, a cooling water outlet 12, an exhaust valve 13 and a tail gas outlet 14 which are arranged in the furnace body 1, a reaction chamber 21 which is formed by enclosing a heat preservation felt 2 and is arranged in the furnace body 1, an electrified coil 3 which is arranged around the heat preservation felt, a temperature detection element 4 for detecting the temperature in the reaction chamber, a graphite tool 5 arranged in the reaction chamber, a graphite cover plate 6 which is arranged opposite to the graphite tool, and an air inlet pipe 7 which sequentially penetrates through the bottom wall of the furnace body, the bottom wall of the heat preservation felt and the graphite tool, wherein an annular carbon felt 8 is stacked between the graphite tool 5 and the graphite cover plate 6, and air enters an area 9 which is formed by enclosing the annular carbon felt, the graphite tool and the graphite cover plate through the air inlet pipe and.
According to the self-induction heating chemical vapor deposition furnace, CVI densification is achieved through a differential pressure method, annular carbon felts are stacked on a graphite tool 5 and then are compressed through a graphite cover plate 6. Propylene and argon enter an area 9 formed by enclosing the annular carbon felt, the graphite tool and the graphite cover plate through an air inlet pipe 7, and then flow along the radial direction of the annular carbon felt, so that the reactant propylene is fully contacted with the annular carbon felt.
The preparation method of the curved nanocarbon fiber reinforced C/C composite material according to the present invention is described in detail below with reference to specific examples.
Example 1
Firstly, ultrasonically dipping a carbon felt in 0.01mol/mL copper tartrate solution for 10min, taking out the carbon felt, and then placing the carbon felt in a drying oven at 90 ℃ for heat preservation for 12h for drying; then carrying out catalytic chemical vapor deposition on the carbon felt impregnated with the copper tartrate for 30min under the conditions of 280 ℃, 80kPa and Q (acetylene) being 0.3L/min by taking acetylene as a carbon source, and growing curved nanofibers on the surface of the carbon fibers in situ to obtain the carbon felt containing the curved nanofibers; then, carbonizing the carbon felt at 950 ℃ by taking nitrogen as protective gas to obtain the carbon felt containing 21.55 mass percent of bent nano-carbon fibers, wherein the diameter of the bent nano-carbon fibers is about 30-220 nm, and the length of the bent nano-carbon fibers is about 2-15 mu m; and finally, performing CVI densification on the carbon felt containing the bent nano carbon fibers for 20 hours by using propylene as a carbon source and argon as a carrier gas through an auto-induction heating chemical vapor deposition furnace under the conditions of 950 ℃ and 7kPa, wherein Q (propylene) is 1.5L/min, and Q (argon) is 1.5L/min, so as to obtain the bent nano carbon fiber reinforced C/C composite material.
Please refer to fig. 2 and fig. 3 in combination, wherein fig. 2 is a scanning electron microscope image of the obtained curved nano-carbon fiber; FIG. 3 is a scanning electron microscope image of a cross section of the curved nanocarbon fiber reinforced C/C composite material prepared in example 1. Through CVI densification, the mechanical property of the composite material can be improved.
Example 2
Firstly, ultrasonically dipping a carbon felt in 0.015mol/mL copper tartrate solution for 10min, taking out the carbon felt, and then placing the carbon felt in a drying oven at 90 ℃ for heat preservation for 12h for drying; then carrying out catalytic chemical vapor deposition on the carbon felt impregnated with the copper tartrate for 60min under the conditions of 280 ℃, 80kPa and Q (acetylene) being 0.3L/min by taking acetylene as a carbon source, and growing curved nanofibers on the surface of the carbon fibers in situ to obtain the carbon felt containing the curved nanofibers; then, taking nitrogen as protective gas, and carrying out carbonization treatment on the carbon felt at 950 ℃ to obtain a carbon felt containing 64.06% of curved nano-carbon fibers in mass fraction, wherein the diameter of the curved nano-carbon fibers is about 20-160 nm, and the length of the curved nano-carbon fibers is about 10-25 mu m; and finally, performing CVI densification on the carbon felt containing the bent nano carbon fibers for 20 hours by using propylene as a carbon source and argon as a carrier gas through an auto-induction heating chemical vapor deposition furnace under the conditions of 950 ℃ and 7kPa, wherein Q (propylene) is 1.5L/min, and Q (argon) is 1.5L/min, so as to obtain the bent nano carbon fiber reinforced C/C composite material.
Example 3
Firstly, ultrasonically dipping a carbon felt in 0.012mol/mL copper tartrate solution for 20min, taking out the carbon felt, and then placing the carbon felt in a drying oven at 90 ℃ for heat preservation for 12h for drying; then carrying out catalytic chemical vapor deposition on the carbon felt impregnated with the copper tartrate for 60min under the conditions of 270 ℃, 70kPa and 0.5L/min Q (acetylene), and growing curved nanofibers on the surface of the carbon fibers in situ to obtain the carbon felt containing the curved nanofibers; then, taking nitrogen as protective gas, and carrying out carbonization treatment on the carbon felt at 1000 ℃ to obtain the carbon felt containing 72.47% of bent nano-carbon fibers in mass fraction, wherein the diameter of the bent nano-carbon fibers is about 50-150nm, and the length of the bent nano-carbon fibers is about 10-30 μm; and finally, performing CVI densification on the carbon felt containing the bent nano carbon fibers for 20 hours by using propylene as a carbon source and argon as a carrier gas through an auto-induction heating chemical vapor deposition furnace at the temperature of 920 ℃ and under the conditions of 5kPa, Q (propylene) being 1L/min and Q (argon) being 1L/min, so as to obtain the bent nano carbon fiber reinforced C/C composite material.
Example 4
Firstly, ultrasonically dipping a carbon felt in 0.014mol/mL copper tartrate solution for 15min, taking out the carbon felt, and then placing the carbon felt in a drying oven at 90 ℃ for heat preservation for 12h for drying; then carrying out catalytic chemical vapor deposition on the carbon felt impregnated with the copper tartrate for 50min under the conditions of 290 ℃ and 50kPa (acetylene) and Q (acetylene) being 0.2L/min, and growing curved nanofibers on the surface of the carbon fibers in situ to obtain the carbon felt containing the curved nanofibers; then, taking nitrogen as protective gas, and carrying out carbonization treatment on the carbon felt at 1050 ℃ to obtain a carbon felt containing 45.36% of bent nano-carbon fibers in mass fraction, wherein the diameter of the bent nano-carbon fibers is about 50-240nm, and the length of the bent nano-carbon fibers is about 5-25 mu m; and finally, performing CVI densification on the carbon felt containing the bent nano carbon fibers for 20 hours by using propylene as a carbon source and argon as a carrier gas through a self-induction heating chemical vapor deposition furnace at the temperature of 1000 ℃ and the pressure of 2kPa, wherein Q (propylene) is 2L/min, and Q (argon) is 2L/min, so as to obtain the bent nano carbon fiber reinforced C/C composite material.
Example 5
Firstly, ultrasonically dipping a carbon felt in 0.01mol/mL copper tartrate solution for 20min, taking out the carbon felt, and then placing the carbon felt in a drying oven at 90 ℃ for heat preservation for 12h for drying; then carrying out catalytic chemical vapor deposition on the carbon felt impregnated with the copper tartrate for 60min under the conditions of 285 ℃, 60kPa and Q (acetylene) being 0.4L/min by taking acetylene as a carbon source, and growing curved nanofibers on the surface of the carbon fibers in situ to obtain the carbon felt containing the curved nanofibers; then, taking nitrogen as protective gas, and carrying out carbonization treatment on the carbon felt at 980 ℃ to obtain a carbon felt containing 83.25% of curved nano-carbon fibers, wherein the diameter of the curved nano-carbon fibers is about 20-180nm, and the length of the curved nano-carbon fibers is about 10-30 μm; and finally, carrying out CVI densification on the carbon felt containing the bent nano carbon fibers for 20 hours by using propylene as a carbon source and argon as a carrier gas through an auto-induction heating chemical vapor deposition furnace under the conditions of 1050 ℃ and 6kPa, Q (propylene) being 1.8L/min and Q (argon) being 1.8L/min, so as to obtain the bent nano carbon fiber reinforced C/C composite material.
Compared with the prior art, the preparation method of the curved nano carbon fiber reinforced C/C composite material has the beneficial effects that:
according to the preparation method of the curved nano carbon fiber reinforced C/C composite material, the curved nano carbon fiber is synthesized by taking the copper tartrate as a catalyst precursor, catalytic chemical vapor deposition is carried out at the temperature of 270-290 ℃, and the reaction is carried out at a relatively low temperature, so that the carbon fiber is not greatly damaged, a large amount of energy can be saved, and industrial popularization can be realized.
Secondly, the preparation method of the curved nano carbon fiber reinforced C/C composite material provided by the invention is characterized in that the curved nano carbon fiber is synthesized by taking copper tartrate as a catalyst precursor, and the solubility of C atoms in Cu is low, so that the damage to the carbon fiber is relatively small by taking Cu as a catalyst; and when the copper tartrate is used as a catalyst precursor to synthesize the bent nano carbon fiber, no growth auxiliary agent is needed, and the process is simple.
The preparation method of the curved nano-carbon fiber reinforced C/C composite material provided by the invention comprises the steps of firstly carrying out catalytic chemical vapor deposition to grow the curved nano-carbon fibers in situ in the carbon fiber preform, and then carrying out subsequent densification, so that the thickness, length and shape of the nano-carbon fibers can be accurately controlled, the competitive growth between the curved nano-carbon fibers and pyrolytic carbon is effectively avoided, and the catalyst is prevented from being inactivated due to the fact that the catalyst is covered by the pyrolytic carbon when the curved nano-carbon fibers are still short.
Fourthly, according to the preparation method of the curved nano carbon fiber reinforced C/C composite material, the catalyst precursor is soaked by ultrasonic waves, so that the catalyst precursor is easy to land in a large pore area in the carbon fiber preform, and after the nano carbon fiber grows in situ, the existence of the nano carbon fiber increases nucleation points, so that the deposition rate of the large pore area is increased and the large pore area is filled, thereby avoiding the formation of closed pores, and being beneficial to the improvement of the mechanical property of the material.
The preparation method of the curved nano-carbon fiber reinforced C/C composite material is characterized in that the nano-carbon fibers are coiled, and the coiled nano-carbon fibers are easy to crosslink, so that the reinforcing effect of the coiled nano-carbon fiber reinforced C/C composite material is stronger than that of linear nano-carbon fibers and spiral nano-fibers; and the technology control of the coiled nano carbon fiber in the subsequent CVI densification process is simple, and the industrial production is easy to carry out.
Sixth, the preparation method of the curved nanometer carbon fiber reinforced C/C composite material provided by the invention can prepare nanometer carbon fibers with the diameter within a certain range, so that certain reinforcing effect can be generated on carbon matrixes and interfaces of the carbon matrixes and the carbon fibers at different scales, and the reinforcing effect is theoretically stronger than that of nanometer carbon fibers with a single scale. In the invention, the diameter of the generated curled nano carbon fiber is 20-240nm, the generated curled nano carbon fiber contains small-particle-size nano carbon fiber with the diameter of 20-100nm, the smaller the diameter of the generated curled nano carbon fiber is, the better the reinforcing effect on the carbon matrix and the interface of the carbon matrix and the carbon fiber is, and the mechanical property of the material is favorably improved.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. Various changes, modifications, substitutions and alterations to these embodiments will occur to those skilled in the art without departing from the spirit and scope of the present invention.
Claims (9)
1. A preparation method of a curved carbon nanofiber reinforced C/C composite material is characterized by comprising the following steps:
step S1, ultrasonically dipping the carbon felt in a copper tartrate solution for a period of time, taking out and drying, wherein the concentration of the copper tartrate solution is 0.01-0.015 mol/mL;
s2, using acetylene as a carbon source and nitrogen as a protective gas, controlling the flow of the acetylene to be 0.2-0.5L/min, carrying out catalytic chemical vapor deposition at the temperature of 270-290 ℃ and under the working pressure of 50-80kPa, and growing curved nanofibers on the carbon fibers in situ to obtain a carbon felt containing the curved nanofibers;
step S3, carbonizing the carbon felt at 950-1050 ℃ by taking nitrogen as protective gas, and preserving heat for 3-5h to obtain the carbon felt containing bent nano carbon fibers;
step S4, performing CVI densification on the carbon felt containing the curved nano-carbon fibers by taking propylene as a carbon source and argon as a carrier gas to obtain a curved nano-carbon fiber reinforced C/C composite material;
in the CVI densification process, the propylene flow is controlled to be 1-2L/min, the argon flow is controlled to be 1-2L/min, the deposition temperature is 920 and 1050 ℃, and the working pressure is 2-7 kPa.
2. The method for preparing the curved nanocarbon fiber reinforced C/C composite material according to claim 1, wherein the ultrasonic impregnation time in step S1 is 10-20 min.
3. The method for preparing the curved nanocarbon fiber reinforced C/C composite material according to claim 1, wherein in the catalytic chemical vapor deposition process, the temperature rise rate is controlled to be less than 3 ℃/min.
4. The method for preparing the curved nanocarbon fiber reinforced C/C composite material according to claim 1, wherein the time for the catalytic chemical vapor deposition is 30 to 60 min.
5. The method for preparing the curved nanocarbon fiber reinforced C/C composite material according to claim 1, wherein a self-induction heating chemical vapor deposition furnace is used in the CVI densification process.
6. The method for preparing the curved nanocarbon fiber reinforced C/C composite material according to claim 5, wherein the densification is performed by a differential pressure CVI method.
7. The method for preparing the curved nanocarbon fiber reinforced C/C composite material according to claim 6, wherein the self-induction heating chemical vapor deposition furnace comprises a furnace body, a reaction chamber formed by enclosing a heat preservation felt in the furnace body, an electrified coil arranged around the heat preservation felt, a temperature detection element for detecting the temperature in the reaction chamber, a graphite tool arranged in the reaction chamber, a graphite cover plate arranged opposite to the graphite tool, and an air inlet pipe sequentially penetrating through the bottom wall of the furnace body, the bottom wall of the heat preservation felt and the graphite tool, wherein the air is used for stacking the annular carbon felt between the graphite tool and the graphite cover plate, and enters an area formed by enclosing the annular carbon felt, the graphite tool and the graphite cover plate through the air inlet pipe and flows in the radial direction of the annular carbon felt.
8. The method for preparing the curved nanocarbon fiber reinforced C/C composite material according to claim 7, wherein the self-induction heating chemical vapor deposition furnace further comprises a cooling water inlet, a cooling water outlet, an exhaust valve and a tail gas outlet which are arranged on the furnace body.
9. The method for preparing the curved nano-carbon fiber reinforced C/C composite material according to any one of claims 1 to 8, wherein the curved nano-carbon fibers in the carbonized carbon felt have a diameter of 20 to 240nm and a length of 2 to 30 μm.
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