A heat dissipation erosion-resistant ceramic matrix composite material and a preparation method thereof

Abstract

The application relates to a heat-dissipating anti-erosion ceramic matrix composite material and a preparation method thereof. The method comprises the following steps: weaving high-heat-conducting carbon fibers into high-heat-conducting carbon cloth; uniformly applying phenolic resin on the high-heat-conducting carbon cloth to obtain high-heat-conducting prepreg; sequentially performing mold pressing, curing and cracking on the high-heat-conducting prepreg to obtain high-heat-conducting carbon / carbon blank; performing reaction infiltration on the high-heat-conducting carbon / carbon blank and hafnium-zirconium-silicon alloy to obtain a heat-dissipating ceramic matrix; and preparing an anti-erosion coating on the surface of the heat-dissipating ceramic matrix by a chemical vapor deposition method to obtain the heat-dissipating anti-erosion ceramic matrix composite material. The heat-dissipating anti-erosion ceramic matrix composite material prepared by the application has high heat conductivity, excellent high-temperature ablation resistance and excellent high-temperature erosion resistance, and has a wide application prospect in aerospace vehicles.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of ceramic matrix composite material preparation, and particularly relates to a heat dissipation and erosion resistance ceramic matrix composite material and a preparation method thereof. BACKGROUND

[0002] The ceramic matrix composite material has the properties of light weight, high strength, high temperature resistance, oxidation resistance, etc., and is widely applied to aerospace vehicles. With the increasing flight speed of the aerospace vehicles, the service temperature of the hot end components of the vehicles is increasingly high, and higher requirements are put forward for the temperature resistance and erosion resistance of the ceramic matrix composite material. The traditional ceramic matrix composite material has been difficult to meet the needs of future aerospace vehicles.

[0003] The heat dissipation ceramic matrix composite material has high thermal conductivity and high heat conduction efficiency in the service environment, can quickly reduce the surface temperature of the component, and further improves the high-temperature ablation resistance of the composite material, and is expected to meet the needs of future aerospace vehicles. The heat dissipation ceramic matrix composite material generally uses high-thermal-conductivity carbon fibers as reinforcing bodies. Since the high-thermal-conductivity carbon fibers have high modulus, they are easily damaged in the weaving process. In addition, the general heat dissipation ceramic matrix composite material also has the problem that the high-temperature ablation resistance and / or high-temperature erosion resistance need to be further improved.

[0004] Therefore, it is necessary to provide a heat dissipation and erosion resistance ceramic matrix composite material and a preparation method thereof, so as to realize the rapid preparation of the high-performance heat dissipation ceramic matrix composite material and lay a foundation for the application of the heat dissipation ceramic matrix composite material. SUMMARY

[0005] In order to solve one or more technical problems in the prior art, the application provides a heat dissipation and erosion resistance ceramic matrix composite material and a preparation method thereof. The heat dissipation ceramic matrix composite material prepared by the method has high thermal conductivity, excellent high-temperature ablation resistance and excellent high-temperature erosion resistance, and has a wide application prospect in aerospace vehicles.

[0006] In a first aspect, the application provides a preparation method of a heat dissipation and erosion resistance ceramic matrix composite material, which comprises the following steps:

[0007] (1) weaving high-thermal-conductivity carbon fibers into high-thermal-conductivity carbon cloth;

[0008] (2) uniformly coating phenolic resin on the high-thermal-conductivity carbon cloth to obtain high-thermal-conductivity prepreg;

[0009] (3) sequentially performing mold pressing, curing and pyrolysis on the high-thermal-conductivity prepreg to obtain high-thermal-conductivity carbon / carbon blank;

[0010] (4) reacting and infiltrating the high-thermal-conductivity carbon / carbon blank with hafnium-zirconium-silicon alloy to obtain a heat dissipation ceramic matrix;

[0011] (5) preparing an anti-erosion coating on the surface of the heat-dissipating ceramic matrix by chemical vapor deposition to obtain a heat-dissipating anti-erosion ceramic matrix composite material.

[0012] Preferably, the thermal conductivity of the high-thermal-conductivity carbon fiber is not less than 200 W / (m·K); and / or the residual carbon rate of the phenolic resin at 800 ℃ is not less than 10%.

[0013] Preferably, the volume fraction of the high-thermal-conductivity carbon fiber contained in the high-thermal-conductivity prepreg is 40-60%.

[0014] Preferably, the molding is performed at a temperature of 40-60 ℃ and a pressure of 2-8 MPa for 2-5 hours; the curing is performed at 110-130 ℃ for 1-3 hours and then at 140-160 ℃ for 2-5 hours; and / or the pyrolysis is performed at 800-1000 ℃ for 2-5 hours.

[0015] Preferably, the sum of the mole fractions of hafnium and zirconium in the hafnium-zirconium-silicon alloy is 40%-60%; and / or in the hafnium-zirconium-silicon alloy, the mole ratio of hafnium to zirconium is (1-3):1, preferably, in the hafnium-zirconium-silicon alloy, the mole ratio of hafnium, zirconium and silicon is (1-3):1:(2-4).

[0016] Preferably, the temperature of the reaction infiltration is 1500-1700 ℃, and / or the time of the reaction infiltration is 2-5 hours; the number of times of the chemical vapor deposition is 2-5; and / or the anti-erosion coating is a HfC coating, preferably, the thickness of the HfC coating is 50-300 microns.

[0017] Preferably, the anti-erosion coating is a HfC coating doped with HfN.

[0018] Preferably, the preparation of the anti-erosion coating on the surface of the heat-dissipating ceramic matrix comprises the following steps:

[0019] (a) performing chemical vapor deposition on the surface of the heat-dissipating ceramic matrix with hafnium tetrachloride, propane and hydrogen as the reaction sources until a first preset thickness is reached; wherein the flow rate of hafnium tetrachloride is 0.05-0.2 sccm, the flow rate of propane is 0.2-0.8 sccm, and the flow rate of hydrogen is 0.2-0.8 sccm;

[0020] (b) on the basis of step (a), performing chemical vapor deposition with hafnium tetrachloride, propane, ammonia and hydrogen as the reaction sources until a second preset thickness is reached; wherein the flow rate of hafnium tetrachloride is 0.05-0.2 sccm, the flow rate of propane is 0.1-0.4 sccm, the flow rate of ammonia is 0.1-0.4 sccm, and the flow rate of hydrogen is 0.1-0.4 sccm.

[0021] (c) repeating steps (a) and (b) 2-5 times in sequence, and then performing an annealing treatment, thereby obtaining the anti-erosion coating on the surface of the heat-dissipation ceramic matrix.

[0022] Preferably, the first preset thickness is 30-50 microns, and the second preset thickness is 10-20 microns; in step (a) and / or step (b), the temperature of the chemical vapor deposition is 1000-1200℃; the temperature of the annealing treatment is 1200-1600℃, the time of the annealing treatment is 1-3h, and after the annealing treatment for 1-3h, cooling to room temperature at a rate of 3-5℃ / min; and / or the annealing treatment is performed in an inert atmosphere.

[0023] The present application provides, in a second aspect, a heat-dissipation anti-erosion ceramic matrix composite prepared by the preparation method described in the first aspect of the present application; preferably, the heat-dissipation anti-erosion ceramic matrix composite has a thermal conductivity of not less than 80 W / (m·K), a linear ablation rate of not more than 1×10 -3 mm / s

[0024] Compared with the prior art, the present application has at least the following beneficial effects:

[0025] (1) The present application uses a high-thermal-conductivity carbon cloth prepreg molding method to prepare a high-thermal-conductivity carbon fiber reinforcement (high-thermal-conductivity carbon / carbon blank), which avoids damage to high-modulus high-thermal-conductivity carbon fibers during weaving and can improve the performance of the composite material.

[0026] (2) The present application uses a prepreg combined with a reaction infiltration method to prepare a heat-dissipation ceramic matrix (C / HfC-ZrC-SiC matrix), which has a short preparation cycle, is suitable for preparing special-shaped components, and is easy to implement industrially.

[0027] (3) The heat-dissipation anti-erosion ceramic matrix composite prepared by the present application has high thermal conductivity, can quickly reduce the surface temperature of the material at high temperatures, and has excellent high-temperature ablation resistance.

[0028] (4) The heat-dissipation anti-erosion ceramic matrix composite prepared by the present application has high matrix density and high near-surface ultra-high-temperature ceramic component content, has excellent anti-erosion performance, and has broad application prospects in aerospace vehicles. DETAILED DESCRIPTION

[0029] In order to make the objects, technical solutions and advantages of the present application clearer, the technical solutions of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0030] The present application provides a preparation method of a heat-dissipating anti-erosion ceramic matrix composite material, which comprises the following steps:

[0031] (1) high-thermal-conductivity carbon fibers are woven into high-thermal-conductivity carbon cloth; the present application does not make specific limitation on the high-thermal-conductivity carbon fibers, and preferably, the thermal conductivity of the high-thermal-conductivity carbon fibers is ≥200 W / (m·K); the present application does not make specific limitation on the process of weaving high-thermal-conductivity carbon fibers into high-thermal-conductivity carbon cloth, which is a conventional technology in the art;

[0032] (2) phenolic resin is uniformly coated on the high-thermal-conductivity carbon cloth to obtain high-thermal-conductivity prepreg; in the present application, the phenolic resin is uniformly coated on the high-thermal-conductivity carbon cloth, the phenolic resin is compounded with the high-thermal-conductivity carbon cloth by hot melting to obtain high-thermal-conductivity prepreg;

[0033] (3) the high-thermal-conductivity prepreg is sequentially subjected to mold pressing, curing and pyrolysis to obtain high-thermal-conductivity carbon / carbon green body;

[0034] (4) the high-thermal-conductivity carbon / carbon green body is reacted with hafnium-zirconium-silicon alloy for melt infiltration to obtain a heat-dissipating ceramic matrix (also recorded as C / HfC-ZrC-SiC matrix);

[0035] (5) an anti-erosion coating layer is prepared on the surface of the heat-dissipating ceramic matrix by chemical vapor deposition to obtain a heat-dissipating anti-erosion ceramic matrix composite material.

[0036] The method of the present application solves the problems of low thermal conductivity, poor high-temperature ablation resistance and poor high-temperature erosion resistance of the existing ceramic matrix composite material, and realizes the synergy of high-temperature ablation resistance and erosion resistance of the heat-dissipating ceramic matrix composite material. Meanwhile, the method has a short preparation period, is convenient for industrial implementation, and is suitable for preparing special-shaped components. The heat-dissipating anti-erosion ceramic matrix composite material prepared by the present application has high thermal conductivity and can rapidly reduce the surface temperature of the material at high temperature, so that the high-temperature ablation resistance of the material is excellent. The heat-dissipating anti-erosion ceramic matrix composite material prepared by the present application has high matrix density and high content of near-surface ultra-high-temperature ceramic components in the matrix, and has excellent erosion resistance, so that it has a broad application prospect in aerospace vehicles.

[0037] According to some preferred embodiments, the high-thermal-conductivity carbon fiber has a thermal conductivity of not less than 200 W / (m·K); and / or the phenolic resin has a carbon residue rate at 800℃ of not less than 10%; the present application does not make specific limitation to the phenolic resin, preferably, the carbon residue rate of the phenolic resin at 800℃ is ≥10%, preferably, the carbon residue rate of the phenolic resin is, for example, 14%, 15%, 16%.

[0038] According to some preferred embodiments, the high-thermal-conductivity carbon fiber has a thermal conductivity of not less than 200 W / (m·K); and / or the phenolic resin has a carbon residue rate at 800℃ of not less than 10%; the present application does not make specific limitation to the phenolic resin, preferably, the carbon residue rate of the phenolic resin at 800℃ is ≥10%, preferably, the carbon residue rate of the phenolic resin is, for example, 14%, 15%, 16%.

[0039] According to some preferred embodiments, the molding is molded at a temperature of 40-60℃ (for example, 40℃, 50℃ or 60℃) and a pressure of 2-8 MPa (for example, 2, 3, 4, 5, 6, 7 or 8 MPa) for 2-5 hours (for example, 2, 3, 4 or 5 hours); the curing is first cured at 110-130℃ (for example, 110℃, 120℃ or 130℃) for 1-3 hours (for example, 1, 2 or 3 hours), and then cured at 140-160℃ (for example, 140℃, 150℃ or 160℃) for 2-5 hours (for example, 2, 3, 4 or 5 hours); and / or the pyrolysis is pyrolyzed at 800-1000℃ (for example, 800℃, 850℃, 900℃, 950℃ or 1000℃) for 2-5 hours (for example, 2, 3, 4 or 5 hours); in the present application, the pyrolysis is carried out under inert gas protection.

[0040] According to some preferred embodiments, the hafnium-zirconium-silicon alloy contains hafnium and zirconium in a total molar fraction of 40% to 60% (e.g. 40%, 45%, 50%, 55% or 60%), and in the present application, the hafnium-zirconium-silicon alloy contains hafnium, zirconium and silicon in a total molar fraction of 100%; and / or in the hafnium-zirconium-silicon alloy, the molar ratio of hafnium to zirconium is (1-3): 1 (e.g. 1:1, 1.5:1, 2:1, 2.5:1 or 3:1), and preferably, in the hafnium-zirconium-silicon alloy, the molar ratio of hafnium, zirconium and silicon is (1-3): 1: (2-4) (e.g. 1:1:2, 1:1:3, 1:1:4, 2:1:2, 2:1:3, 2:1:4, 3:1:2, 3:1:3 or 3:1:4); in the present application, preferably, the total molar fraction of hafnium and zirconium in the hafnium-zirconium-silicon alloy is controlled to be 40% to 60%, and in the hafnium-zirconium-silicon alloy, the molar ratio of hafnium, zirconium and silicon is (1-3): 1: (2-4), and this optimized composition ratio is conducive to forming a thermal diffusion erosion-resistant ceramic matrix composite material not only having excellent thermal conductivity and being able to rapidly dissipate heat to avoid local overheating, but also being able to exhibit excellent stability and durability in high-temperature oxidation, ablation and erosion environments, and the present application finds that controlling the molar ratio of hafnium, zirconium and silicon to be (1-3): 1: (2-4) is helpful to form an optimized hard ceramic phase structure, which is conducive to protecting the ceramic matrix from ablation and erosion damage at high temperatures and improving the overall ablation and erosion resistance.

[0041] According to some preferred embodiments, the temperature of the reaction infiltration is 1500-1700°C (e.g. 1500°C, 1550°C, 1600°C, 1650°C or 1700°C), and / or the time of the reaction infiltration is 2-5 hours (e.g. 2, 3, 4 or 5 hours); the number of times of the chemical vapor deposition is 2-5 times (e.g. 2, 3, 4 or 5 times); and / or the erosion-resistant coating is a HfC coating, and preferably, the thickness of the HfC coating is 50-300 microns (e.g. 50, 100, 150, 200, 250 or 300 microns).

[0042] According to some preferred embodiments, the erosion-resistant coating is a HfC (hafnium carbide) coating doped with HfN (hafnium nitride).

[0043] According to some preferred embodiments, the preparation of the erosion-resistant coating on the surface of the thermal diffusion ceramic matrix comprises the following steps:

[0044] (a) performing chemical vapor deposition on the surface of the thermal diffusion ceramic matrix with hafnium tetrachloride, propane and hydrogen as the reaction source until a first preset thickness is reached; wherein the flow rate of hafnium tetrachloride is 0.05-0.2 sccm, the flow rate of propane is 0.2-0.8 sccm, and the flow rate of hydrogen is 0.2-0.8 sccm;

[0045] (b) performing chemical vapor deposition on the basis of step (a) with hafnium tetrachloride, propane, ammonia and hydrogen as the reaction sources until a second preset thickness is reached; wherein the flow rate of hafnium tetrachloride is 0.05-0.2 sccm, the flow rate of propane is 0.1-0.4 sccm, the flow rate of ammonia is 0.1-0.4 sccm, and the flow rate of hydrogen is 0.1-0.4 sccm; in the present application, it is preferred that argon is introduced as a carrier gas in the chemical vapor deposition of step (a) and step (b), and the flow rate of the argon is, for example, 10-20 sccm; in the present application, the chemical vapor deposition is performed under a vacuum degree of 1x10 -2 to 1x10 -4 Torr; the present application does not make a specific limitation on the time for performing the chemical vapor deposition, and the preset thickness is reached; in the present application, the first preset thickness and the second preset thickness are independent of each other, the first preset thickness does not include the second preset thickness, and the second preset thickness does not include the first preset thickness;

[0046] (c) repeating step (a) and step (b) 2-5 times in turn, and then performing annealing treatment, thereby obtaining the anti-erosion coating (HfC coating doped with HfN) on the surface of the heat dissipation ceramic matrix; in the present application, the HfC coating doped with HfN is formed by alternately arranging HfC layers and HfC layers doped with HfN, and the number of alternations is 2-5 times.

[0047] In the present application, it is preferred that the HfC coating doped with HfN is obtained through step (a) to step (c), and the present application finds that, in the multiple chemical vapor depositions, the doping of HfN in the chemical vapor deposition of step (b) can fill the pores in the HfC layer, improve the compactness of the coating, reduce the microcracks and pores in the coating, reduce the structural defects in the coating, and improve the mechanical strength and thermal stability of the coating, thereby improving the high-temperature ablation resistance of the coating, and the design of alternately arranging the HfC layers doped with HfN in the present application can help to optimize the thermal conductivity, so that the coating can better conduct heat, and ultimately help to improve the thermal conductivity, high-temperature ablation resistance and high-temperature erosion resistance of the heat dissipation anti-erosion ceramic matrix composite.

[0048] According to some preferred embodiments, the first preset thickness is 30-50 microns, and the second preset thickness is 10-20 microns; in the present application, the total thickness of the HfC coating doped with HfN is preferably 150-200 microns; in the present application, it is preferred that the first preset thickness is 30-50 microns, and the second preset thickness is 10-20 microns, so that, while ensuring the formation of a high-temperature-resistant and ablation-resistant HfC layer of sufficient thickness, the relatively thin HfN-doped HfC layer can enable hafnium nitride to effectively fill pores, further enhancing the ablation resistance and erosion resistance.

[0049] According to some preferred embodiments, in step (a) and / or step (b), the temperature for chemical vapor deposition is 1000-1200℃.

[0050] According to some preferred embodiments, the temperature for annealing is 1200-1600℃, the time for annealing is 1-3h, and after 1-3h of annealing, cooling is performed at a rate of 3-5℃ / min to room temperature; and / or the annealing is performed in an inert atmosphere. In the present application, after chemical vapor deposition, annealing is further performed, and the present application finds that the annealing is conducive to eliminating coating defects, optimizing microstructure, improving the uniformity of ceramic phase, enhancing the densification of the coating, and improving the overall thermal conductivity and high-temperature stability of the material, thereby facilitating the obtaining of the heat-dissipating and erosion-resistant ceramic matrix composite material with high thermal conductivity, excellent high-temperature ablation resistance, and excellent high-temperature erosion resistance; in the present application, it is preferred that the annealing is performed at a temperature of 1200-1600℃.

[0051] In a second aspect, the present application provides a heat-dissipating and erosion-resistant ceramic matrix composite material prepared by the preparation method described in the first aspect of the present application; preferably, the heat-dissipating and erosion-resistant ceramic matrix composite material has a thermal conductivity of not less than 80 W / (m·K), and a linear ablation rate of not more than 1×10 -3 mm / s after an arc wind tunnel test at a stagnation temperature of not less than 2000℃ and a stagnation pressure of not less than 20kPa. In the present application, the high-temperature arc wind tunnel with a stagnation temperature of ≥2000℃ and a stagnation pressure of ≥20kPa can simulate the thermal environment of an aircraft in the atmosphere, including high temperature, high speed, high pressure, and other complex conditions; a certain stagnation pressure in the arc wind tunnel test indicates that the environment has erosion, and therefore the linear ablation rate measured under this condition can be used to measure the erosion resistance and ablation resistance of the material.

[0052] The present application will be further described below in conjunction with examples. These examples are only used to illustrate the preferred embodiments of the present application, and the protection scope of the present application should not be interpreted as being limited to these examples.

[0053] Example 1

[0054] ①Preparation of high thermal conductivity carbon cloth: high thermal conductivity carbon fibers with a thermal conductivity of 600 W / (m·K) are woven into high thermal conductivity carbon cloth.

[0055] ②Preparation of high thermal conductivity prepreg: phenolic resin with a carbon residue of 15% at 800℃ is uniformly coated on the high thermal conductivity carbon cloth obtained in step ①, and the phenolic resin is compounded with the high thermal conductivity carbon cloth by hot melting method to obtain a high thermal conductivity prepreg, and the volume fraction of high thermal conductivity carbon fibers in the high thermal conductivity prepreg is controlled to be 50%.

[0056] ③Preparation of high thermal conductivity carbon / carbon body: the high thermal conductivity prepreg obtained in step ② is molded at 50℃ under a pressure of 5MPa for 3 hours, then cured at 120℃ for 2 hours, cured at 150℃ for 3 hours, and finally pyrolyzed at 900℃ in an argon atmosphere for 3 hours to obtain a high thermal conductivity carbon / carbon body.

[0057] ④Preparation of heat-diffusing ceramic matrix: the high thermal conductivity carbon / carbon body obtained in step ③ is infiltrated with hafnium-zirconium-silicon alloy (hafnium, zirconium and silicon in a molar ratio of 2:1:3) at 1550℃ for 3 hours to obtain a heat-diffusing ceramic matrix (C / HfC-ZrC-SiC matrix).

[0058] ⑤Preparation of anti-erosion coating: an HfC coating (anti-erosion coating) with a total thickness of 150 microns is prepared on the surface of the heat-diffusing ceramic matrix obtained in step ④ by three times of chemical vapor deposition, each time under a vacuum degree of 3×10 -3 Torr, using hafnium tetrachloride, propane and hydrogen as the reaction source, and argon as the carrier gas, with a flow rate of hafnium tetrachloride of 0.1sccm, propane of 0.6sccm, hydrogen of 0.6sccm, and argon of 15sccm, and a chemical vapor deposition temperature of 1200℃.

[0059] The heat-diffusing anti-erosion ceramic matrix prepared in this example is tested for thermal conductivity, and the thermal conductivity is 154 W / (m·K).

[0060] The heat-diffusing anti-erosion ceramic matrix prepared in this example is tested for high-temperature ablation resistance and high-temperature erosion resistance, and the linear ablation rate is 6.5×10 -4 mm / s after an arc wind tunnel test (test time 500s) at a stagnation temperature of 2000℃ and a stagnation pressure of 20kPa.

[0061] Example 2

[0062] ①Preparation of high thermal conductivity carbon cloth: high thermal conductivity carbon fibers with a thermal conductivity of 800 W / (m·K) are woven into high thermal conductivity carbon cloth.

[0063] (2) Preparation of high thermal conductive prepreg: phenolic resin with 15% carbon residue at 800°C is uniformly coated on the high thermal conductive carbon cloth obtained in step (1), and the phenolic resin is compounded with the high thermal conductive carbon cloth by hot melting to obtain a high thermal conductive prepreg, and the volume fraction of the high thermal conductive carbon fiber in the high thermal conductive prepreg is controlled to be 50%.

[0064] (3) Preparation of high thermal conductive carbon / carbon blank: the high thermal conductive prepreg obtained in step (2) is molded at 50°C under a pressure of 5 MPa for 3 hours, then cured at 120°C for 2 hours, cured at 150°C for 3 hours, and finally pyrolyzed at 900°C in an argon atmosphere for 3 hours to obtain a high thermal conductive carbon / carbon blank.

[0065] (4) Preparation of thermal conduction ceramic matrix: the high thermal conductive carbon / carbon blank obtained in step (3) is infiltrated with hafnium-zirconium-silicon alloy (molar ratio of hafnium, zirconium and silicon is 2:1:3) at 1550°C for 3 hours to obtain a thermal conduction ceramic matrix (C / HfC-ZrC-SiC matrix).

[0066] (5) Preparation of anti-erosion coating: an HfC coating (anti-erosion coating) with a total thickness of 150 microns is prepared on the surface of the thermal conduction ceramic matrix obtained in step (4) by three times of chemical vapor deposition, each time of chemical vapor deposition is carried out under a vacuum degree of 3x10 -3 Torr, using hafnium tetrachloride, propane and hydrogen as reaction sources, and argon as carrier gas, the flow rate of hafnium tetrachloride is 0.1 sccm, the flow rate of propane is 0.6 sccm, the flow rate of hydrogen is 0.6 sccm, the flow rate of argon is 15 sccm, and the temperature of chemical vapor deposition is 1200°C.

[0067] The thermal conductivity of the thermal conduction anti-erosion ceramic matrix prepared in this embodiment is tested, and the thermal conductivity is 202 W / (m·K).

[0068] The high-temperature ablation resistance and high-temperature erosion resistance of the thermal conduction anti-erosion ceramic matrix prepared in this embodiment are tested, and the linear ablation rate is 4.3x10 -4 mm / s after the arc wind tunnel test (test time 500s) at a stagnation temperature of 2000°C and a stagnation pressure of 20kPa.

[0069] Example 3

[0070] (1) Preparation of high thermal conductive carbon cloth: high thermal conductive carbon fibers with a thermal conductivity of 1000 W / (m·K) are woven into high thermal conductive carbon cloth.

[0071] (2) Preparation of high-thermal-conductivity pre-impregnated material: uniformly apply phenolic resin with a carbon residue of 15% at 800°C to the high-thermal-conductivity carbon cloth obtained in step (1), and use a hot melt method to combine the phenolic resin and the high-thermal-conductivity carbon cloth to obtain a high-thermal-conductivity pre-impregnated material, and control the volume fraction of high-thermal-conductivity carbon fibers in the high-thermal-conductivity pre-impregnated material to be 50%.

[0072] (3) Preparation of high-thermal-conductivity carbon / carbon body: mold the high-thermal-conductivity pre-impregnated material obtained in step (2) at 50°C under a pressure of 5 MPa for 3 hours, then solidify at 120°C for 2 hours, solidify at 150°C for 3 hours, and finally pyrolyze at 900°C in an argon atmosphere for 3 hours to obtain a high-thermal-conductivity carbon / carbon body.

[0073] (4) Preparation of thermal-shedding ceramic matrix: perform a melt infiltration reaction on the high-thermal-conductivity carbon / carbon body obtained in step (3) and hafnium-zirconium-silicon alloy (molar ratio of hafnium, zirconium, and silicon is 2:1:3) at 1550°C for 3 hours to obtain a thermal-shedding ceramic matrix (C / HfC-ZrC-SiC matrix).

[0074] (5) Preparation of anti-erosion coating: prepare a HfC coating (anti-erosion coating) with a total thickness of 150 microns on the surface of the thermal-shedding ceramic matrix obtained in step (4) by three times of chemical vapor deposition, and prepare a thermal-shedding anti-erosion ceramic matrix composite material; each time of chemical vapor deposition is performed under a vacuum degree of 3 x 10 -3 Torr, using hafnium tetrachloride, propane, and hydrogen as the reaction source, using argon as the carrier gas, the flow rate of hafnium tetrachloride being 0.1 sccm, the flow rate of propane being 0.6 sccm, the flow rate of hydrogen being 0.6 sccm, the flow rate of argon being 15 sccm, and the temperature of chemical vapor deposition being 1200°C.

[0075] The thermal conductivity of the thermal-shedding anti-erosion ceramic matrix composite material prepared in this embodiment is tested, and the thermal conductivity is 255 W / (m·K).

[0076] The high-temperature ablation resistance and high-temperature anti-erosion performance of the thermal-shedding anti-erosion ceramic matrix composite material prepared in this embodiment are tested, and the linear ablation rate is 2.1 x 10 -4 mm / s after an arc wind tunnel test (test time is 500 s) with a stagnation temperature of 2000°C and a stagnation pressure of 20 kPa.

[0077] Embodiment 4

[0078] (1) Preparation of high-thermal-conductivity carbon cloth: weave high-thermal-conductivity carbon fibers with a thermal conductivity of 600 W / (m·K) into high-thermal-conductivity carbon cloth.

[0079] (2) Preparation of high-thermal-conductivity pre-impregnated material: uniformly apply phenolic resin with a carbon residue of 15% at 800°C to the high-thermal-conductivity carbon cloth obtained in step (1), and use a hot melt method to combine the phenolic resin and the high-thermal-conductivity carbon cloth to obtain a high-thermal-conductivity pre-impregnated material, and control the volume fraction of the high-thermal-conductivity carbon fiber in the high-thermal-conductivity pre-impregnated material to be 50%.

[0080] (3) Preparation of high-thermal-conductivity carbon / carbon body: mold the high-thermal-conductivity pre-impregnated material obtained in step (2) at 50°C under a pressure of 5 MPa for 3 hours, then solidify at 120°C for 2 hours, solidify at 150°C for 3 hours, and finally pyrolyze at 900°C in an argon atmosphere for 3 hours to obtain a high-thermal-conductivity carbon / carbon body.

[0081] (4) Preparation of thermal-shedding ceramic matrix: perform a melt infiltration reaction on the high-thermal-conductivity carbon / carbon body obtained in step (3) and hafnium-zirconium-silicon alloy (molar ratio of hafnium, zirconium, and silicon is 3:1:4) at 1550°C for 3 hours to obtain a thermal-shedding ceramic matrix (C / HfC-ZrC-SiC matrix).

[0082] (5) Preparation of anti-erosion coating: prepare a HfC coating (anti-erosion coating) with a total thickness of 150 microns on the surface of the thermal-shedding ceramic matrix obtained in step (4) by three times of chemical vapor deposition, and prepare a thermal-shedding anti-erosion ceramic matrix composite material; each time of chemical vapor deposition is performed under a vacuum degree of 3 x 10 -3 Torr, using hafnium tetrachloride, propane, and hydrogen as the reaction source, using argon as the carrier gas, the flow rate of hafnium tetrachloride being 0.1 sccm, the flow rate of propane being 0.6 sccm, the flow rate of hydrogen being 0.6 sccm, the flow rate of argon being 15 sccm, and the temperature of the chemical vapor deposition being 1200°C.

[0083] The thermal conductivity of the thermal-shedding anti-erosion ceramic matrix composite material prepared in this embodiment is tested, and the thermal conductivity is 151 W / (m·K).

[0084] The high-temperature ablation resistance and high-temperature anti-erosion performance of the thermal-shedding anti-erosion ceramic matrix composite material prepared in this embodiment are tested, and the linear ablation rate is 5.0 x 10 -4 mm / s after an arc wind tunnel test (test time is 500 s) with a stagnation temperature of 2000°C and a stagnation pressure of 20 kPa.

[0085] Embodiment 5

[0086] (1) Preparation of high-thermal-conductivity carbon cloth: weave high-thermal-conductivity carbon fiber with a thermal conductivity of 600 W / (m·K) into high-thermal-conductivity carbon cloth.

[0087] (2) preparing high-thermal-conductivity pre-impregnated material: uniformly applying phenolic resin with a carbon residue rate of 15% at 800°C on the high-thermal-conductivity carbon cloth obtained in step (1), and using a hot melt method to combine the phenolic resin and the high-thermal-conductivity carbon cloth to obtain a high-thermal-conductivity pre-impregnated material, and controlling the volume fraction of the high-thermal-conductivity carbon fiber in the high-thermal-conductivity pre-impregnated material to be 50%.

[0088] (3) preparing high-thermal-conductivity carbon / carbon blank: molding the high-thermal-conductivity pre-impregnated material obtained in step (2) at 50°C under a pressure of 5 MPa for 3 hours, then curing at 120°C for 2 hours, curing at 150°C for 3 hours, and finally pyrolyzing at 900°C in an argon atmosphere for 3 hours to obtain a high-thermal-conductivity carbon / carbon blank.

[0089] (4) preparing thermal-shedding ceramic matrix: subjecting the high-thermal-conductivity carbon / carbon blank obtained in step (3) to a melt infiltration reaction with hafnium-zirconium-silicon alloy (hafnium, zirconium, and silicon in a molar ratio of 1:1:2) at 1550°C for 3 hours to obtain a thermal-shedding ceramic matrix (C / HfC-ZrC-SiC matrix).

[0090] (5) preparing anti-erosion coating: preparing a HfC coating (anti-erosion coating) with a total thickness of 150 microns on the surface of the thermal-shedding ceramic matrix obtained in step (4) by three times of chemical vapor deposition, each time of chemical vapor deposition being performed under a vacuum degree of 3x10 -3 Torr, using hafnium tetrachloride, propane, and hydrogen as the reaction source, using argon as the carrier gas, the flow rate of hafnium tetrachloride being 0.1 sccm, the flow rate of propane being 0.6 sccm, the flow rate of hydrogen being 0.6 sccm, the flow rate of argon being 15 sccm, and the temperature of the chemical vapor deposition being 1200°C.

[0091] The thermal conductivity of the thermal-shedding anti-erosion ceramic matrix composite prepared in this embodiment was tested, and the thermal conductivity was 155 W / (m·K).

[0092] The high-temperature ablation resistance and high-temperature anti-erosion performance of the thermal-shedding anti-erosion ceramic matrix composite prepared in this embodiment were tested, and the linear ablation rate was 7.4x10 -4 mm / s after the arc wind tunnel test (test time: 500 s) at a stagnation temperature of 2000°C and a stagnation pressure of 20 kPa.

[0093] Example 6

[0094] (1) preparing high-thermal-conductivity carbon cloth: weaving high-thermal-conductivity carbon fiber with a thermal conductivity of 600 W / (m·K) into high-thermal-conductivity carbon cloth.

[0095] (2) preparing high-thermal-conductivity prepreg: uniformly applying phenolic resin with a carbon residue ratio of 15% at 800°C on the high-thermal-conductivity carbon cloth obtained in step (1), and using a hot melt method to composite the phenolic resin and the high-thermal-conductivity carbon cloth to obtain high-thermal-conductivity prepreg, and controlling the volume fraction of high-thermal-conductivity carbon fiber in the high-thermal-conductivity prepreg to be 50%.

[0096] (3) preparing high-thermal-conductivity carbon / carbon body: molding the high-thermal-conductivity prepreg obtained in step (2) at 50°C under a pressure of 5 MPa for 3 hours, then curing at 120°C for 2 hours, curing at 150°C for 3 hours, and finally pyrolyzing at 900°C in an argon atmosphere for 3 hours to obtain a high-thermal-conductivity carbon / carbon body.

[0097] (4) preparing thermal-shedding ceramic matrix: subjecting the high-thermal-conductivity carbon / carbon body obtained in step (3) to a melt infiltration reaction with hafnium-zirconium-silicon alloy (molar ratio of hafnium, zirconium and silicon is 2:1:3) at 1550°C for 3 hours to obtain a thermal-shedding ceramic matrix (C / HfC-ZrC-SiC matrix).

[0098] (5) preparing anti-erosion coating: preparing a HfC coating (anti-erosion coating) with a total thickness of 200 microns on the surface of the thermal-shedding ceramic matrix obtained in step (4) by 4 times of chemical vapor deposition, to obtain a thermal-shedding anti-erosion ceramic matrix composite; each time of chemical vapor deposition is carried out under a vacuum degree of 3x10 -3 Torr, and in the chemical vapor deposition, hafnium tetrachloride, propane and hydrogen are used as the reaction source, argon is used as the carrier gas, the flow rate of hafnium tetrachloride is 0.1 sccm, the flow rate of propane is 0.6 sccm, the flow rate of hydrogen is 0.6 sccm, the flow rate of argon is 15 sccm, and the temperature of the chemical vapor deposition is 1200°C.

[0099] The thermal conductivity of the thermal-shedding anti-erosion ceramic matrix composite prepared in this embodiment is tested, and the thermal conductivity is 156 W / (m·K).

[0100] The high-temperature ablation resistance and high-temperature anti-erosion performance of the thermal-shedding anti-erosion ceramic matrix composite prepared in this embodiment are tested, and the linear ablation rate is 4.9x10 -4 mm / s after the arc wind tunnel test (test time is 500s) with a stagnation temperature of 2000°C and a stagnation pressure of 20 kPa.

[0101] Example 7

[0102] Example 7 is basically the same as Example 1, except that:

[0103] ⑤Preparation of the anti-erosion coating: a HfC coating doped with HfN (anti-erosion coating) with a total thickness of 150 microns is prepared on the surface of the heat dissipation ceramic matrix obtained in step ④ to obtain a heat dissipation anti-erosion ceramic matrix composite; the preparation of the HfC coating doped with HfN is as follows: (a) chemical vapor deposition is performed on the surface of the heat dissipation ceramic matrix with hafnium tetrachloride, propane and hydrogen as the reaction sources until a first preset thickness of 40 microns is reached; wherein the flow rate of hafnium tetrachloride is 0.1 sccm, the flow rate of propane is 0.6 sccm, and the flow rate of hydrogen is 0.6 sccm; (b) on the basis of step (a), chemical vapor deposition is performed with hafnium tetrachloride, propane, ammonia and hydrogen as the reaction sources until a second preset thickness of 10 microns is reached; wherein the flow rate of hafnium tetrachloride is 0.1 sccm, the flow rate of propane is 0.3 sccm, the flow rate of ammonia is 0.2 sccm, and the flow rate of hydrogen is 0.4 sccm; (c) steps (a) and (b) are repeated sequentially for 3 times, and then annealing treatment is performed at 1500℃ for 2h in an argon atmosphere, and then cooled to room temperature at a rate of 3℃ / min, thereby obtaining the anti-erosion coating (HfC coating doped with HfN) on the surface of the heat dissipation ceramic matrix; in steps (a) and (b), chemical vapor deposition is performed under the condition of a vacuum degree of 3x10 -3 Torr, the chemical vapor deposition temperature is 1200℃, and argon is introduced as the carrier gas, and the flow rate of the argon is 15sccm.

[0104] The heat conductivity of the heat dissipation anti-erosion ceramic matrix composite prepared in this embodiment is tested, and the heat conductivity is 181 W / (m·K).

[0105] The high-temperature ablation resistance and high-temperature anti-erosion performance of the heat dissipation anti-erosion ceramic matrix composite prepared in this embodiment are tested, and the linear ablation rate is 1.8x10 -4 mm / s after the arc wind tunnel test (test time 500s) with a stagnation temperature of 2000℃ and a stagnation pressure of 20kPa.

[0106] Example 8

[0107] Example 8 is basically the same as Example 7, except that:

[0108] ⑤Preparation of an anti-erosion coating: an anti-erosion coating with a total thickness of 150 microns is prepared on the surface of the heat dissipation ceramic matrix obtained in step ④, thereby obtaining a heat dissipation anti-erosion ceramic matrix composite; the anti-erosion coating is prepared as follows: (a) chemical vapor deposition is performed on the surface of the heat dissipation ceramic matrix with hafnium tetrachloride, propane and hydrogen as the reaction sources until a first preset thickness of 40 microns is reached; wherein the flow rate of hafnium tetrachloride is 0.1 sccm, the flow rate of propane is 0.6 sccm, and the flow rate of hydrogen is 0.6 sccm; (b) on the basis of step (a), chemical vapor deposition is performed with hafnium tetrachloride, propane, ammonia and hydrogen as the reaction sources until a second preset thickness of 10 microns is reached; wherein the flow rate of hafnium tetrachloride is 0.1 sccm, the flow rate of propane is 0.3 sccm, the flow rate of ammonia is 0.2 sccm, and the flow rate of hydrogen is 0.4 sccm; (c) steps (a) and (b) are repeated sequentially for 3 times, thereby obtaining the anti-erosion coating on the surface of the heat dissipation ceramic matrix; in steps (a) and (b), chemical vapor deposition is performed under a vacuum degree of 3 x 10 -3 Torr, the chemical vapor deposition temperature is 1200℃, and argon is introduced as a carrier gas with a flow rate of 15 sccm.

[0109] The heat conductivity of the heat dissipation anti-erosion ceramic matrix composite prepared in this embodiment is tested, and the heat conductivity is 162 W / (m·K).

[0110] The high-temperature ablation resistance and high-temperature anti-erosion performance of the heat dissipation anti-erosion ceramic matrix composite prepared in this embodiment are tested, and the linear ablation rate is 3.7 x 10 -4 mm / s after the arc wind tunnel test (test time 500s) with a stagnation temperature of 2000℃ and a stagnation pressure of 20kPa.

[0111] Example 9

[0112] Example 9 is basically the same as Example 1, except that:

[0113] ⑤Preparation of an anti-erosion coating: an anti-erosion coating with a total thickness of 150 microns is prepared on the surface of the heat dissipation ceramic matrix obtained in step ④, to obtain a heat dissipation anti-erosion ceramic matrix composite material; the anti-erosion coating is prepared as follows: (a) chemical vapor deposition is performed on the surface of the heat dissipation ceramic matrix with hafnium tetrachloride, propane and hydrogen as the reaction source until a first preset thickness of 40 microns is reached; wherein the flow rate of hafnium tetrachloride is 0.1 sccm, the flow rate of propane is 0.6 sccm, and the flow rate of hydrogen is 0.6 sccm; (b) on the basis of step (a), chemical vapor deposition is performed with hafnium tetrachloride, ammonia and hydrogen as the reaction source until a second preset thickness of 10 microns is reached; wherein the flow rate of hafnium tetrachloride is 0.1 sccm, the flow rate of ammonia is 0.2 sccm, and the flow rate of hydrogen is 0.4 sccm; (c) steps (a) and (b) are repeated 3 times in turn, thereby obtaining the anti-erosion coating on the surface of the heat dissipation ceramic matrix; in steps (a) and (b), chemical vapor deposition is performed under a vacuum degree of 3 x 10 -3 Torr, and the chemical vapor deposition temperature is 1200℃, and argon is introduced as the carrier gas, and the flow rate of the argon is 15 sccm.

[0114] The heat dissipation anti-erosion ceramic matrix composite material prepared in this embodiment is subjected to high-temperature ablation resistance and high-temperature anti-erosion performance testing, and the linear ablation rate is 1.3 x 10 -3 mm / s after arc wind tunnel testing (test time 500s) at a stagnation temperature of 2000℃ and a stagnation pressure of 20kPa.

[0115] Example 10

[0116] Example 10 is basically the same as Example 1, except that:

[0117] ⑤Preparation of an anti-erosion coating: an anti-erosion coating with a total thickness of 150 microns is prepared on the surface of the heat dissipation ceramic matrix obtained in step ④, to obtain a heat dissipation anti-erosion ceramic matrix composite material; the anti-erosion coating is prepared as follows: (a) chemical vapor deposition is performed on the surface of the heat dissipation ceramic matrix with hafnium tetrachloride, propane and hydrogen as the reaction source until a first preset thickness of 40 microns is reached; wherein the flow rate of hafnium tetrachloride is 0.1 sccm, the flow rate of propane is 0.6 sccm, and the flow rate of hydrogen is 0.6 sccm; (b) on the basis of step (a), chemical vapor deposition is performed with hafnium tetrachloride, ammonia and hydrogen as the reaction source until a second preset thickness of 10 microns is reached; wherein the flow rate of hafnium tetrachloride is 0.1 sccm, the flow rate of ammonia is 0.2 sccm, and the flow rate of hydrogen is 0.4 sccm; (c) steps (a) and (b) are repeated 3 times in turn, thereby obtaining the anti-erosion coating on the surface of the heat dissipation ceramic matrix; in steps (a) and (b), chemical vapor deposition is performed under a vacuum degree of 3 x 10 -3 Torr, and the chemical vapor deposition temperature is 1200℃, and argon is introduced as the carrier gas, and the flow rate of the argon is 15 sccm.

[0118] The heat dissipation anti-erosion ceramic matrix composite material prepared in this embodiment is subjected to high-temperature ablation resistance and high-temperature anti-erosion performance testing, and the linear ablation rate is 1.3 x 10 -3 mm / s after arc wind tunnel testing (test time 500s) at a stagnation temperature of 2000℃ and a stagnation pressure of 20kPa.

[0119] The performance indexes of the heat-dissipating erosion-resistant ceramic matrix composites prepared by the embodiments of the present application are shown in Table 1.

[0120] Table 1

[0121]

[0122] In Table 1, the symbol " / " means that the performance index is not tested.

[0123] The parts of the present application not described in detail are known to those skilled in the art.

[0124] Finally, it should be pointed out that the above embodiments are only used to illustrate the technical solutions of the present application, but not to limit the same; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that the technical solutions recorded in the embodiments can still be modified, or some technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for producing a heat dissipation erosion resistant ceramic matrix composite material, characterized by, The method comprises the following steps: (1) weaving high-thermal-conductivity carbon fibers into high-thermal-conductivity carbon cloth; (2) uniformly applying phenolic resin on the high-thermal-conductivity carbon cloth to obtain high-thermal-conductivity prepreg; (3) sequentially performing mold pressing, curing and pyrolysis on the high-thermal-conductivity prepreg to obtain high-thermal-conductivity carbon / carbon green body; (4) performing reactive infiltration on the high-thermal-conductivity carbon / carbon green body with hafnium-zirconium-silicon alloy to obtain thermal-conductivity ceramic matrix; (5) preparing an anti-erosion coating on the surface of the thermal-conductivity ceramic matrix by chemical vapor deposition to obtain thermal-conductivity anti-erosion ceramic matrix composite material.

2. The preparation method according to claim 1, wherein: the thermal conductivity of the high-thermal-conductivity carbon fiber is not less than 200 W / (m·K); and / or the carbon residue rate of the phenolic resin at 800℃ is not less than 10%.

3. The preparation method according to claim 1, wherein: the volume fraction of the high-thermal-conductivity carbon fiber contained in the high-thermal-conductivity prepreg is 40-60%.

4. The preparation method according to claim 1, wherein: the mold pressing is performed at a temperature of 40-60℃ and a pressure of 2-8 MPa for 2-5 hours; the curing is performed at 110-130℃ for 1-3 hours and then at 140-160℃ for 2-5 hours; and / or the pyrolysis is performed at 800-1000℃ for 2-5 hours.

5. The preparation method according to claim 1, wherein: the sum of the mole fractions of hafnium and zirconium in the hafnium-zirconium-silicon alloy is 40%-60%; and / or the mole ratio of hafnium, zirconium and silicon in the hafnium-zirconium-silicon alloy is (1-3):1:(2-4).

6. The preparation method according to claim 1, wherein: the temperature of the reactive infiltration is 1500-1700℃, and / or the time of the reactive infiltration is 2-5 hours; the number of times of the chemical vapor deposition is 2-5; and / or the anti-erosion coating is HfC coating, and the thickness of the HfC coating is 50-300 microns.

7. The preparation method according to claim 1, wherein: the anti-erosion coating is HfC coating doped with HfN. The preparation of the anti-erosion coating on the surface of the thermal-conductivity ceramic matrix comprises the following steps: (a) performing chemical vapor deposition on the surface of the thermal-conductivity ceramic matrix with hafnium tetrachloride, propane and hydrogen as reaction sources until a first preset thickness is reached; wherein the flow rate of hafnium tetrachloride is 0.05-0.2 sccm, the flow rate of propane is 0.2-0.8 sccm, and the flow rate of hydrogen is 0.2-0.8 sccm; (b) performing chemical vapor deposition on the basis of step (a) with hafnium tetrachloride, propane, ammonia and hydrogen as reaction sources until a second preset thickness is reached; wherein the flow rate of hafnium tetrachloride is 0.05-0.2 sccm, the flow rate of propane is 0.1-0.4 sccm, the flow rate of ammonia is 0.1-0.4 sccm, and the flow rate of hydrogen is 0.1-0.4 sccm; (c) sequentially repeating steps (a) and (b) 2-5 times, and then performing annealing treatment, thereby obtaining the anti-erosion coating on the surface of the thermal-conductivity ceramic matrix. ​ ​ ​ ​ ​ ​ ​ ​ 8. The preparation method according to claim 7, characterized in that, ​ ​ ​ ​ 9. The method of claim 8, wherein: the first predetermined thickness is 30-50 microns; the second predetermined thickness is 10-20 microns; the temperature of the chemical vapor deposition in step (a) and / or step (b) is 1000-1200 °C; the temperature of the annealing is 1200-1600 °C; the annealing time is 1-3 hours; and / or the annealing is performed in an inert atmosphere.

10. The heat-dissipating erosion-resistant ceramic matrix composite material prepared by the method of any one of claims 1-9, wherein: the first predetermined thickness is 30-50 microns; the second predetermined thickness is 10-20 microns; the temperature of the chemical vapor deposition is 1000-1200 °C; the temperature of the annealing is 1200-1600 °C; the annealing time is 1-3 hours; and / or the annealing is performed in an inert atmosphere. ​ ​ ​ ​ The heat conductivity of the heat-ducting anti-erosion ceramic matrix composite is not less than 80 W / (m*K), and the linear ablation rate after the electric arc wind tunnel test under the condition of a stagnation temperature of not less than 2000 DEG C and a stagnation pressure of not less than 20 kPa is not more than 1*10 -3 mm / s.

Images