A high-strength ceramic matrix composite material and a method for producing the same

Abstract

The application relates to a high-strength ceramic matrix composite material and a preparation method thereof. The method comprises the following steps: (1) taking Ti3AlC2 and ZrC ceramic powders as solid components, taking liquid polycarbosilane as a liquid component, uniformly mixing the solid components and the liquid component, and obtaining a ceramic slurry; (2) impregnating porous carbon / carbon material with the ceramic slurry, sequentially going through solidification and pyrolysis, and obtaining a C / ZrC-SiC intermediate; (3) repeating step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%; and (4) performing sintering treatment on the C / ZrC-SiC intermediate prepared in step (3), and obtaining a high-strength C / ZrC-SiC composite material. The C / ZrC-SiC composite material prepared by the method has the advantages of high sintering degree of the matrix, high density, high strength, excellent high-temperature anti-ablation performance and the like, and has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of ceramic matrix composite material preparation, and particularly relates to a high-strength ceramic matrix composite material and a preparation method thereof. BACKGROUND

[0002] The ceramic matrix composite material with carbon fibers as reinforcing bodies and ceramic components as matrices has excellent comprehensive properties such as low density, high temperature resistance, oxidation resistance and thermal shock resistance.

[0003] The C / ZrC-SiC composite material is a typical ceramic matrix composite material, is suitable for super-high-temperature oxidation / gas environments, is widely applied in the fields of aerospace, and is a thermal structure composite material with great development prospects.

[0004] The preparation processes of the C / ZrC-SiC composite material mainly include a precursor impregnation and pyrolysis (PIP) method, a chemical vapor infiltration (CVI) method and a reaction melt infiltration (RMI) method. Among them, the PIP method has strong designability and is suitable for the preparation of large-size complex components, for example, the ablation-resistant C / ZrC-SiC composite material is prepared by the PIP method in Chinese patents CN202111128803.1 and CN202011237631.7; the C / ZrC-SiC composite material is rapidly prepared by the RMI method in Chinese patent CN201810368778.6; the high-crystallinity ceramic matrix can be prepared by the CVI method, and the CVI method is suitable for the preparation of thin-walled components, for example, the high-temperature-resistant C / ZrC-SiC composite material is prepared by the CVI method in Chinese patent CN202111156221.4.

[0005] However, the PIP method and the CVI method have long preparation periods, the prepared composite material has high porosity, and the comprehensive strength is not high; and the RMI method has a high preparation temperature, the carbon fibers are easily damaged, and the comprehensive performance of the material is low. Therefore, it is urgent to develop a new method capable of rapidly preparing the high-strength ceramic matrix composite material. SUMMARY

[0006] In order to solve the technical problems in the prior art, the application provides a high-strength ceramic matrix composite material and a preparation method thereof. The C / ZrC-SiC composite material prepared by the method has a high sintering degree and high density of the matrix, and has high strength and high-temperature ablation resistance.

[0007] In order to achieve the above-mentioned purpose, the application provides, in a first aspect, a preparation method of a high-strength ceramic matrix composite material, and the method comprises the following steps:

[0008] (1) preparing a ceramic slurry: taking Ti3AlC2 ceramic powder and ZrC ceramic powder as solid components, taking liquid polycarbosilane as liquid component, mixing the solid components and the liquid component uniformly to obtain a ceramic slurry;

[0009] (2) preparing a C / ZrC-SiC intermediate: impregnating the porous carbon / carbon material with the ceramic slurry prepared in step (1), and sequentially going through solidification and pyrolysis to obtain a C / ZrC-SiC intermediate;

[0010] (3) repeating step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0011] (4) subjecting the C / ZrC-SiC intermediate prepared in step (3) to high-temperature sintering treatment to obtain a high-strength C / ZrC-SiC composite material.

[0012] It is noted herein that the "C / ZrC-SiC intermediate" or the term "C / ZrC-SiC composite material" herein does not only contain the elements shown in the name, but also contains elements such as Ti or Al introduced by the Ti3AlC2 ceramic powder, although the content is relatively small and thus not reflected in the name.

[0013] The present inventors have found that when a ceramic slurry containing Ti3AlC2 ceramic powder and ZrC ceramic powder is used to prepare a ceramic matrix composite material, the pyrolysis yield of the ceramic slurry is high, and the preparation cycle is short. Moreover, the liquid polycarbosilane used in the present application has a small amount of small molecules released during pyrolysis, and the ceramic matrix has few cracks and high density, and the prepared composite material has high strength.

[0014] The present application does not have a particular limitation on the particle size of the ceramic powder. However, in some preferred embodiments, the particle size of the Ti3AlC2 ceramic powder and the ZrC ceramic powder is independently 200 nm to 2000 nm (for example, it can be 300, 400, 500, 800, 1000 or 1500 nm), preferably 300 to 1000 nm.

[0015] In some preferred embodiments, the molar ratio of the Ti3AlC2 ceramic powder and the ZrC ceramic powder is (1:8) to (1:12), preferably 1:9 to 1:11, for example, preferably 1:9, 1:10 or 1:11. The present inventors have found that using relatively small amounts of Ti3AlC2 ceramic powder in combination with ZrC ceramic powder can promote the grain rearrangement of silicon carbide and zirconium carbide ceramic during high-temperature sintering and achieve recrystallization at the interface, resulting in high crystallinity and sintering degree of the ceramic matrix, which not only makes the ceramic matrix itself have high strength, but also makes it have excellent ablation resistance.

[0016] In some preferred embodiments, the weight fraction of the solid component is 25% to 50%, preferably 30% to 40%, for example preferably 30%, 35% or 40%, based on the total weight of the ceramic slurry.

[0017] In some preferred embodiments, the liquid polycarbosilane has a molecular weight of 800 to 5000 g / mol, preferably 1000 g / mol to 3000 g / mol, for example preferably 1000 g / mol, 2000 g / mol or 3000 g / mol.

[0018] The porous carbon / carbon material used in the present application is a composite material composed of carbon fibers and matrix carbon, which is a known composite material in the art. The source of the porous carbon / carbon material is not particularly limited in the present application, and for example, it can be purchased from the Aerospace Special Material and Process Technology Institute. In some preferred embodiments, the porous carbon / carbon material has a density of 0.4 to 1.4 g / cm 3 , preferably 0.6 g / cm 3 to 1.0 g / cm 3 , for example preferably 0.6 g / cm 3 , 0.8 g / cm 3 or 1.0 g / cm 3 .

[0019] In some preferred embodiments, the temperature of the curing is 220 to 320°C, preferably 250°C to 280°C, for example preferably 250°C, 265°C or 280°C.

[0020] The curing time is not particularly limited in the present application, and it can be generally 3 to 8 hours, preferably 3 to 4 hours. If the curing time is too short, it can result in insufficient curing, but a longer curing time is not necessary because there is no further gain in the material properties by prolonging the time.

[0021] In some preferred embodiments, the temperature of the pyrolysis is 900 to 1500°C, preferably 1000°C to 1400°C, for example preferably 1000°C, 1200°C or 1400°C.

[0022] The pyrolysis time is not particularly limited in the present application, and it can be generally 2 to 6 hours, preferably 2 to 3 hours. If the pyrolysis time is too short, it can result in insufficient pyrolysis, but a longer pyrolysis time results in increased time cost, prolonged production cycle and unnecessary energy consumption.

[0023] In some preferred embodiments, the number of repetitions of step (2) is 2 to 8, for example, it can be 3, 4, 5, 6 or 7, as long as the weight ratio of the C / ZrC-SiC intermediate after repeating a cycle of impregnation, solidification and cracking is less than 0.5% of the weight ratio before the repetition, for example, less than 0.4%, less than 0.3%, less than 0.2% or less than 0.1%.

[0024] In some preferred embodiments, the high-temperature sintering treatment is under the following conditions: pressure is 1 to 5 MPa (for example, it can be 2, 3 or 4 MPa), temperature is 1600 to 1900℃ (for example, it can be 1700 or 1800℃), and time is 2 to 8 hours (for example, it can be 3, 4, 5, 6 or 7 hours), preferably 2 to 3 hours, so as to ensure sufficient sintering without causing unnecessary energy consumption and prolonging the production cycle.

[0025] In a second aspect, the present application provides a high-strength C / ZrC-SiC ceramic matrix composite material prepared by the preparation method described in the first aspect of the present application.

[0026] In some preferred embodiments, the C / ZrC-SiC composite material has a room-temperature tensile strength ≥ 300 MPa, more preferably ≥ 330 MPa, further preferably ≥ 350 MPa, and more further preferably ≥ 400 MPa; a room-temperature bending strength ≥ 400 MPa, more preferably ≥ 500 MPa, further preferably ≥ 550 MPa, and more further preferably ≥ 600 MPa; and a linear ablation rate after arc tunnel or oxyacetylene test above 2300℃ ≤ 5×10 -4 mm / s, more preferably ≤ 4×10 -4 mm / s, and further preferably ≤ 3×10 -4 mm / s.

[0027] The method of the present application solves the problems of low density and low strength of the existing ultra-high-temperature ceramic matrix composite material, and has high strength and high-temperature resistance and ablation resistance of the ultra-high-temperature ceramic matrix composite material. At the same time, the preparation process of the method of the present application is simple, the cycle is short, and it is easy to implement industrialization, and it is especially suitable for preparing large-size special-shaped members.

[0028] Compared with the prior art, the present application has at least the following beneficial effects:

[0029] (1) The present application uses a ceramic slurry containing Ti3AlC2 ceramic powder and ZrC ceramic powder to prepare a ceramic matrix composite material, the ceramic slurry has high cracking yield and short preparation cycle; the liquid polycarbosilane used in the present application has a small amount of small molecule release during cracking, and the ceramic matrix has few cracks and high density, and the prepared composite material has high strength.

[0030] (2) The ceramic powder Ti3AlC2 used in this invention exists as plate-like crystals at low temperature and decomposes during high-temperature sintering. This can promote the rearrangement of grains of silicon carbide and zirconium carbide ceramics during high-temperature sintering and achieve recrystallization at the interface, resulting in high crystallinity and sintering degree of the ceramic matrix. This not only makes the ceramic matrix itself strong, but also makes it have excellent ablation resistance.

[0031] (3) The C / ZrC-SiC composite material prepared by this invention is a material that combines high strength and excellent high temperature ablation resistance. It is suitable for preparing complex irregular components and has broad application potential in high-speed aircraft power and projectile structure. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be fully described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0033] Example 1

[0034] This embodiment provides a method for preparing a high-strength ceramic matrix composite material, the specific steps of which are as follows:

[0035] (1) Preparation of ceramic slurry: Using Ti3AlC2 ceramic powder and ZrC ceramic powder as solid components and liquid polycarbosilane as liquid component, Ti3AlC2 ceramic powder and ZrC ceramic powder with a particle size of 300nm (molar ratio of the two ceramic powders is 1:9) are mixed with liquid polycarbosilane with a molecular weight of 1000g / mol at a weight ratio of 30:70 to obtain ceramic slurry;

[0036] (2) Preparation of C / ZrC-SiC intermediate: The ceramic slurry prepared in step (1) has an impregnation density of 0.6 g / cm³. 3 Porous carbon / carbon materials (from the Institute of Aerospace Special Materials and Process Technology) were cured at 250℃ for 3 hours and pyrolyzed at 1000℃ for 2 hours to obtain C / ZrC-SiC intermediates.

[0037] (3) Repeat step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0038] (4) The C / ZrC-SiC intermediate prepared in step (3) is subjected to high-temperature sintering treatment at 2MPa and 1600℃ for 2 hours to obtain high-strength C / ZrC-SiC composite material.

[0039] Example 2

[0040] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and specific steps are as follows:

[0041] (1) preparing a ceramic slurry: taking Ti3AlC2 ceramic powder and ZrC ceramic powder as solid components, taking liquid polycarbosilane as a liquid component, uniformly mixing Ti3AlC2 ceramic powder and ZrC ceramic powder with a particle size of 300 nm (the molar ratio of the two ceramic powders is 1:9) and liquid polycarbosilane with a molecular weight of 1000 g / mol at a weight ratio of 35:65 to obtain the ceramic slurry;

[0042] (2) preparing a C / ZrC-SiC intermediate: using the ceramic slurry prepared in step (1), impregnating porous carbon / carbon material with a density of 0.6 g / cm 3 , and then performing solidification at 250 DEG C for 3 hours and pyrolysis at 1000 DEG C for 2 hours to obtain the C / ZrC-SiC intermediate;

[0043] (3) repeating step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0044] (4) performing high-temperature sintering treatment on the C / ZrC-SiC intermediate prepared in step (3) at 2 MPa and 1600 DEG C for 2 hours to obtain the high-strength C / ZrC-SiC composite material.

[0045] Example 3

[0046] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and specific steps are as follows:

[0047] (1) preparing a ceramic slurry: taking Ti3AlC2 ceramic powder and ZrC ceramic powder as solid components, taking liquid polycarbosilane as a liquid component, uniformly mixing Ti3AlC2 ceramic powder and ZrC ceramic powder with a particle size of 300 nm (the molar ratio of the two ceramic powders is 1:9) and liquid polycarbosilane with a molecular weight of 1000 g / mol at a weight ratio of 40:60 to obtain the ceramic slurry;

[0048] (2) preparing a C / ZrC-SiC intermediate: using the ceramic slurry prepared in step (1), impregnating porous carbon / carbon material with a density of 0.6 g / cm 3 , and then performing solidification at 250 DEG C for 3 hours and pyrolysis at 1000 DEG C for 2 hours to obtain the C / ZrC-SiC intermediate;

[0049] (3) repeating step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0050] (4) The C / ZrC-SiC intermediate prepared in step (3) is high-temperature sintered at 2 MPa and 1600°C for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0051] Example 4

[0052] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and specific steps are as follows:

[0053] (1) Preparing a ceramic slurry: Ti3AlC2 ceramic powder and ZrC ceramic powder are used as solid components, and liquid polycarbosilane is used as a liquid component; Ti3AlC2 ceramic powder and ZrC ceramic powder with a particle size of 300 nm (molar ratio of the two ceramic powders is 1:10) and liquid polycarbosilane with a molecular weight of 1000 g / mol are uniformly mixed at a weight ratio of 30:70 to obtain the ceramic slurry;

[0054] (2) Preparing a C / ZrC-SiC intermediate: porous carbon / carbon material with a density of 0.6 g / cm 3 is impregnated with the ceramic slurry prepared in step (1), and then cured at 250°C for 3 hours and pyrolyzed at 1000°C for 2 hours to obtain the C / ZrC-SiC intermediate;

[0055] (3) Repeating step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0056] (4) The C / ZrC-SiC intermediate prepared in step (3) is high-temperature sintered at 2 MPa and 1600°C for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0057] Example 5

[0058] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and specific steps are as follows:

[0059] (1) Preparing a ceramic slurry: Ti3AlC2 ceramic powder and ZrC ceramic powder are used as solid components, and liquid polycarbosilane is used as a liquid component; Ti3AlC2 ceramic powder and ZrC ceramic powder with a particle size of 300 nm (molar ratio of the two ceramic powders is 1:11) and liquid polycarbosilane with a molecular weight of 1000 g / mol are uniformly mixed at a weight ratio of 30:70 to obtain the ceramic slurry;

[0060] (2) Preparing a C / ZrC-SiC intermediate: porous carbon / carbon material with a density of 0.6 g / cm 3 is impregnated with the ceramic slurry prepared in step (1), and then cured at 250°C for 3 hours and pyrolyzed at 1000°C for 2 hours to obtain the C / ZrC-SiC intermediate;

[0061] (3) Repeat step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0062] (4) High-temperature sintering treatment of the C / ZrC-SiC intermediate prepared in step (3) at 2 MPa and 1600℃ for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0063] Example 6

[0064] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and specific steps are as follows:

[0065] (1) Preparation of ceramic slurry: Ti3AlC2 ceramic powder and ZrC powder are used as solid components, liquid polycarbosilane is used as a liquid component, Ti3AlC2 ceramic powder and ZrC ceramic powder (molar ratio of the two ceramic powders is 1:9) with a particle size of 300 nm and liquid polycarbosilane with a molecular weight of 1000 g / mol are uniformly mixed at a weight ratio of 30:70 to obtain a ceramic slurry;

[0066] (2) Preparation of C / ZrC-SiC intermediate: the ceramic slurry prepared in step (1) is used to impregnate porous carbon / carbon material with a density of 0.6 g / cm 3 , and then the impregnated material is cured at 250℃ for 3 hours and pyrolyzed at 1000℃ for 2 hours to obtain a C / ZrC-SiC intermediate;

[0067] (3) Repeat step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0068] (4) High-temperature sintering treatment of the C / ZrC-SiC intermediate prepared in step (3) at 2 MPa and 1700℃ for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0069] Example 7

[0070] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and specific steps are as follows:

[0071] (1) Preparation of ceramic slurry: Ti3AlC2 ceramic powder and ZrC ceramic powder are used as solid components, liquid polycarbosilane is used as a liquid component, Ti3AlC2 ceramic powder and ZrC ceramic powder (molar ratio of the two ceramic powders is 1:9) with a particle size of 300 nm and liquid polycarbosilane with a molecular weight of 1000 g / mol are uniformly mixed at a weight ratio of 30:70 to obtain a ceramic slurry;

[0072] (2) Preparation of C / ZrC-SiC intermediate: the ceramic slurry prepared in step (1) is impregnated into a porous carbon / carbon material with a density of 0.6 g / cm 3 , cured at 250℃ for 2 hours, and pyrolyzed at 1000℃ for 2 hours to obtain a C / ZrC-SiC intermediate;

[0073] (3) Repeat step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0074] (4) The C / ZrC-SiC intermediate prepared in step (3) is high-temperature sintered at 2 MPa and 1800℃ for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0075] Example 8

[0076] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and the specific steps are as follows:

[0077] (1) Preparation of ceramic slurry: Ti3AlC2 ceramic powder and ZrC ceramic powder are used as solid components, and liquid polycarbosilane is used as a liquid component. The Ti3AlC2 ceramic powder and the ZrC ceramic powder with a particle size of 300 nm (the molar ratio of the two ceramic powders is 1:9) and the liquid polycarbosilane with a molecular weight of 1000 g / mol are uniformly mixed in a weight ratio of 30:70 to obtain a ceramic slurry;

[0078] (2) Preparation of C / ZrC-SiC intermediate: the ceramic slurry prepared in step (1) is impregnated into a porous carbon / carbon material with a density of 0.6 g / cm 3 , cured at 250℃ for 3 hours, and pyrolyzed at 1000℃ for 2 hours to obtain a C / ZrC-SiC intermediate;

[0079] (3) Repeat step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0080] (4) The C / ZrC-SiC intermediate prepared in step (3) is high-temperature sintered at 3 MPa and 1600℃ for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0081] Example 9

[0082] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and the specific steps are as follows:

[0083] (1) Preparation of ceramic slurry: Ti3AlC2 ceramic powder and ZrC ceramic powder were used as solid components, and liquid polycarbosilane was used as liquid component. Ti3AlC2 ceramic powder and ZrC ceramic powder with a particle size of 300 nm (molar ratio of the two ceramic powders was 1:9) and liquid polycarbosilane with a molecular weight of 1000 g / mol were uniformly mixed at a weight ratio of 30:70 to obtain a ceramic slurry;

[0084] (2) Preparation of C / ZrC-SiC intermediate: porous carbon / carbon material with a density of 0.6 g / cm 3 was impregnated with the ceramic slurry prepared in step (1), and then cured at 250℃ for 2 hours and pyrolyzed at 1000℃ for 2 hours to obtain a C / ZrC-SiC intermediate;

[0085] (3) Step (2) was repeated until the weight gain of the C / ZrC-SiC intermediate was less than 0.5%;

[0086] (4) The C / ZrC-SiC intermediate prepared in step (3) was high-temperature sintered at 4 MPa and 1600℃ for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0087] Example 10

[0088] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and the specific steps are as follows:

[0089] (1) Preparation of ceramic slurry: Ti3AlC2 ceramic powder and ZrC ceramic powder were used as solid components, and liquid polycarbosilane was used as liquid component. Ti3AlC2 ceramic powder and ZrC ceramic powder with a particle size of 300 nm (molar ratio of the two ceramic powders was 1:9) and liquid polycarbosilane with a molecular weight of 2000 g / mol were uniformly mixed at a weight ratio of 30:70 to obtain a ceramic slurry;

[0090] (2) Preparation of C / ZrC-SiC intermediate: porous carbon / carbon material with a density of 0.6 g / cm 3 was impregnated with the ceramic slurry prepared in step (1), and then cured at 250℃ for 3 hours and pyrolyzed at 1000℃ for 2 hours to obtain a C / ZrC-SiC intermediate;

[0091] (3) Step (2) was repeated until the weight gain of the C / ZrC-SiC intermediate was less than 0.5%;

[0092] (4) The C / ZrC-SiC intermediate prepared in step (3) was high-temperature sintered at 2 MPa and 1600℃ for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0093] Example 11

[0094] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and specific steps are as follows:

[0095] (1) preparing a ceramic slurry: taking Ti3AlC2 ceramic powder and ZrC ceramic powder as solid components, taking liquid polycarbosilane as a liquid component, uniformly mixing Ti3AlC2 ceramic powder and ZrC ceramic powder with a particle size of 300 nm (the molar ratio of the two ceramic powders is 1:9) and liquid polycarbosilane with a molecular weight of 3000 g / mol at a weight ratio of 30:70 to obtain the ceramic slurry;

[0096] (2) preparing a C / ZrC-SiC intermediate: using the ceramic slurry prepared in step (1), impregnating a porous carbon / carbon material with a density of 0.6 g / cm 3 , and then performing solidification at 250 DEG C for 3 hours and pyrolysis at 1000 DEG C for 2 hours to obtain the C / ZrC-SiC intermediate;

[0097] (3) repeating step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0098] (4) performing high-temperature sintering treatment on the C / ZrC-SiC intermediate prepared in step (3) at 2 MPa and 1600 DEG C for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0099] Embodiment 12

[0100] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and specific steps are as follows:

[0101] (1) preparing a ceramic slurry: taking Ti3AlC2 ceramic powder and ZrC ceramic powder as solid components, taking liquid polycarbosilane as a liquid component, uniformly mixing Ti3AlC2 ceramic powder and ZrC ceramic powder with a particle size of 500 nm (the molar ratio of the two ceramic powders is 1:9) and liquid polycarbosilane with a molecular weight of 1000 g / mol at a weight ratio of 30:70 to obtain the ceramic slurry;

[0102] (2) preparing a C / ZrC-SiC intermediate: using the ceramic slurry prepared in step (1), impregnating a porous carbon / carbon material with a density of 0.6 g / cm 3 , and then performing solidification at 250 DEG C for 3 hours and pyrolysis at 1000 DEG C for 2 hours to obtain the C / ZrC-SiC intermediate;

[0103] (3) repeating step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0104] (4) The C / ZrC-SiC intermediate prepared in step (3) is high-temperature sintered at 2 MPa and 1600°C for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0105] Example 13

[0106] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and specific steps are as follows:

[0107] (1) Preparing a ceramic slurry: Ti3AlC2 ceramic powder and ZrC ceramic powder are used as solid components, and liquid polycarbosilane is used as a liquid component; Ti3AlC2 ceramic powder and ZrC ceramic powder with a particle size of 800 nm (the molar ratio of the two ceramic powders is 1:9) and liquid polycarbosilane with a molecular weight of 1000 g / mol are uniformly mixed at a weight ratio of 30:70 to obtain the ceramic slurry;

[0108] (2) Preparing a C / ZrC-SiC intermediate: porous carbon / carbon material with a density of 0.6 g / cm 3 is impregnated with the ceramic slurry prepared in step (1), and then cured at 250°C for 3 hours and pyrolyzed at 1000°C for 2 hours to obtain the C / ZrC-SiC intermediate;

[0109] (3) Repeating step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0110] (4) The C / ZrC-SiC intermediate prepared in step (3) is high-temperature sintered at 2 MPa and 1600°C for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0111] Example 14

[0112] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and specific steps are as follows:

[0113] (1) Preparing a ceramic slurry: Ti3AlC2 ceramic powder and ZrC ceramic powder are used as solid components, and liquid polycarbosilane is used as a liquid component; Ti3AlC2 ceramic powder and ZrC ceramic powder with a particle size of 800 nm (the molar ratio of the two ceramic powders is 1:9) and liquid polycarbosilane with a molecular weight of 1000 g / mol are uniformly mixed at a weight ratio of 30:70 to obtain the ceramic slurry;

[0114] (2) Preparing a C / ZrC-SiC intermediate: porous carbon / carbon material with a density of 0.6 g / cm 3 is impregnated with the ceramic slurry prepared in step (1), and then cured at 250°C for 3 hours and pyrolyzed at 1000°C for 2 hours to obtain the C / ZrC-SiC intermediate;

[0115] (3) Repeat step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0116] (4) High-temperature sintering treatment of the C / ZrC-SiC intermediate prepared in step (3) at 2 MPa and 1600°C for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0117] Example 15

[0118] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and specific steps are as follows:

[0119] (1) Preparation of ceramic slurry: Ti3AlC2 ceramic powder and ZrC ceramic powder are used as solid components, and liquid polycarbosilane is used as a liquid component. The Ti3AlC2 ceramic powder and the ZrC ceramic powder with a particle size of 300 nm (the molar ratio of the two ceramic powders is 1:9) and the liquid polycarbosilane with a molecular weight of 1000 g / mol are uniformly mixed at a weight ratio of 30:70 to obtain a ceramic slurry;

[0120] (2) Preparation of a C / ZrC-SiC intermediate: The ceramic slurry prepared in step (1) is used to impregnate a porous carbon / carbon material with a density of 1.0 / cm 3 , and then the porous carbon / carbon material is cured at 250°C for 3 hours and pyrolyzed at 1000°C for 2 hours to obtain a C / ZrC-SiC intermediate;

[0121] (3) Repeat step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0122] (4) High-temperature sintering treatment of the C / ZrC-SiC intermediate prepared in step (3) at 2 MPa and 1600°C for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0123] Example 16

[0124] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and specific steps are as follows:

[0125] (1) Preparation of ceramic slurry: Ti3AlC2 ceramic powder and ZrC ceramic powder are used as solid components, and liquid polycarbosilane is used as a liquid component. The Ti3AlC2 ceramic powder and the ZrC ceramic powder with a particle size of 300 nm (the molar ratio of the two ceramic powders is 1:9) and the liquid polycarbosilane with a molecular weight of 1000 g / mol are uniformly mixed at a weight ratio of 30:70 to obtain a ceramic slurry;

[0126] (2) Preparation of C / ZrC-SiC intermediate: the ceramic slurry prepared in step (1) is impregnated into a porous carbon / carbon material with a density of 0.6 g / cm 3 After curing at 265 ℃ for 3 hours and pyrolysis at 1000 ℃ for 2 hours, a C / ZrC-SiC intermediate is obtained;

[0127] (3) Repeat step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0128] (4) The C / ZrC-SiC intermediate prepared in step (3) is subjected to high-temperature sintering treatment at 2 MPa and 1600 ℃ for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0129] Example 17

[0130] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and specific steps are as follows:

[0131] (1) Preparation of ceramic slurry: Ti3AlC2 ceramic powder and ZrC ceramic powder are used as solid components, and liquid polycarbosilane is used as a liquid component. The Ti3AlC2 ceramic powder and the ZrC ceramic powder with a particle size of 300 nm (the molar ratio of the two ceramic powders is 1:9) and the liquid polycarbosilane with a molecular weight of 1000 g / mol are uniformly mixed at a weight ratio of 30:70 to obtain a ceramic slurry;

[0132] (2) Preparation of C / ZrC-SiC intermediate: the ceramic slurry prepared in step (1) is impregnated into a porous carbon / carbon material with a density of 0.6 g / cm 3 After curing at 280 ℃ for 3 hours and pyrolysis at 1000 ℃ for 2 hours, a C / ZrC-SiC intermediate is obtained;

[0133] (3) Repeat step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0134] (4) The C / ZrC-SiC intermediate prepared in step (3) is subjected to high-temperature sintering treatment at 2 MPa and 1600 ℃ for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0135] Example 18

[0136] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and specific steps are as follows:

[0137] (1) Preparation of ceramic slurry: Ti3AlC2 ceramic powder and ZrC ceramic powder were used as solid components, and liquid polycarbosilane was used as liquid component. Ti3AlC2 ceramic powder and ZrC ceramic powder with a particle size of 300 nm (molar ratio of the two ceramic powders was 1:9) and liquid polycarbosilane with a molecular weight of 1000 g / mol were uniformly mixed at a weight ratio of 30:70 to obtain a ceramic slurry;

[0138] (2) Preparation of C / ZrC-SiC intermediate: porous carbon / carbon material with a density of 0.6 g / cm 3 was impregnated with the ceramic slurry prepared in step (1), and then cured at 250℃ for 3 hours and pyrolyzed at 1200℃ for 2 hours to obtain a C / ZrC-SiC intermediate;

[0139] (3) Step (2) was repeated until the weight gain of the C / ZrC-SiC intermediate was less than 0.5%;

[0140] (4) The C / ZrC-SiC intermediate prepared in step (3) was subjected to high-temperature sintering treatment at 2 MPa and 1600℃ for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0141] Example 19

[0142] The embodiment provides a preparation method of a high-strength ceramic matrix composite material, and the specific steps are as follows:

[0143] (1) Preparation of ceramic slurry: Ti3AlC2 ceramic powder and ZrC ceramic powder were used as solid components, and liquid polycarbosilane was used as liquid component. Ti3AlC2 ceramic powder and ZrC ceramic powder with a particle size of 300 nm (molar ratio of the two ceramic powders was 1:9) and liquid polycarbosilane with a molecular weight of 1000 g / mol were uniformly mixed at a weight ratio of 30:70 to obtain a ceramic slurry;

[0144] (2) Preparation of C / ZrC-SiC intermediate: porous carbon / carbon material with a density of 0.6 g / cm 3 was impregnated with the ceramic slurry prepared in step (1), and then cured at 250℃ for 3 hours and pyrolyzed at 1400℃ for 2 hours to obtain a C / ZrC-SiC intermediate;

[0145] (3) Step (2) was repeated until the weight gain of the C / ZrC-SiC intermediate was less than 0.5%;

[0146] (4) The C / ZrC-SiC intermediate prepared in step (3) was subjected to high-temperature sintering treatment at 2 MPa and 1600℃ for 2 hours to obtain a high-strength C / ZrC-SiC composite material.

[0147] Example 20

[0148] The embodiment provides a preparation method of a ceramic matrix composite material, and specific steps are as follows:

[0149] (1) preparing a ceramic slurry: taking ZrC ceramic powder as a solid component, taking liquid polycarbosilane as a liquid component, uniformly mixing ZrC ceramic powder with a particle size of 300 nm and liquid polycarbosilane with a molecular weight of 1000 g / mol at a weight ratio of 30:70 to obtain the ceramic slurry;

[0150] (2) preparing a C / ZrC-SiC intermediate: impregnating porous carbon / carbon material with a density of 0.6 g / cm 3 prepared in step (1) at 250 DEG C for 3 hours and pyrolyzing at 1000 DEG C for 2 hours to obtain the C / ZrC-SiC intermediate;

[0151] (3) repeating step (2) until the weight gain of the C / ZrC-SiC intermediate is less than 0.5%;

[0152] (4) high-temperature sintering the C / ZrC-SiC intermediate prepared in step (3) at 2 MPa and 1600 DEG C for 2 hours to obtain the C / ZrC-SiC composite material.

[0153] The raw materials and process parameters used in the above embodiments can be seen from Table 1 below.

[0154] The C / ZrC-SiC composite materials prepared in the above embodiments are subjected to tensile property and bending property tests, and are subjected to oxidation resistance and ablation resistance tests (ablation for 300 s at a high temperature of 2300 DEG C) by using oxyacetylene, and the results are shown in Table 2 below.

[0155]

[0156] Table 2. Properties of the composite materials prepared in the embodiments.

[0157] Example Room temperature tensile strength (MPa) Room temperature bending strength (MPa) Linear ablation rate (10"4mm / s) 1 355 534 2.05 2 348 515 1.87 3 336 502 1.54 4 369 551 1.73 5 381 578 1.23 6 389 591 1.27 7 396 603 1.14 8 403 634 1.08 9 426 658 1.02 10 362 546 1.98 11 352 530 2.08 12 371 556 1.78 13 376 559 1.76 14 385 572 1.54 15 388 586 1.58 16 345 509 2.11 17 341 506 2.20 18 323 503 1.65 19 315 500 1.42 20 216 385 8.53

[0158] The part of the present application not described in detail is the technology known to the person skilled in the art.

[0159] 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 present application; although the present application has been described in detail with reference to the foregoing embodiments, the person 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 ceramic matrix composite material, characterized by, The method comprises the following steps: (1) taking Ti3AlC2 ceramic powder and ZrC ceramic powder as solid components, taking liquid polycarbosilane as liquid component, mixing the solid components and the liquid component uniformly to obtain ceramic slurry; (2) impregnating porous carbon / carbon material with the ceramic slurry prepared in step (1) and sequentially going through solidification and pyrolysis to obtain C / ZrC-SiC intermediate; (3) repeating step (2) until the weight gain of C / ZrC-SiC intermediate is less than 0.5%; (4) sintering the C / ZrC-SiC intermediate prepared in step (3) to obtain C / ZrC-SiC composite material; wherein the molar ratio of the Ti3AlC2 ceramic powder and the ZrC ceramic powder is (1:8) to (1:12); the weight fraction of the solid components is 25% to 50% based on the total weight of the ceramic slurry.

2. The preparation method according to claim 1, wherein: the particle size of the Ti3AlC2 ceramic powder and the ZrC ceramic powder is independently 200 nm to 2000 nm.

3. The preparation method according to claim 2, wherein: the particle size of the Ti3AlC2 ceramic powder and the ZrC ceramic powder is independently 300 to 1000 nm.

4. The preparation method according to any one of claims 1 to 3, wherein: the molecular weight of the liquid polycarbosilane is 800 to 5000 g / mol.

5. The preparation method according to any one of claims 1 to 3, wherein: The porous carbon / carbon material has a density of 0.4 to 1.4 g / cm 3 .

6. The preparation method according to any one of claims 1 to 3, wherein: the temperature of the solidification is 220 to 320℃, and the time of the solidification is 3 to 8 hours.

7. The preparation method according to any one of claims 1 to 3, wherein: the temperature of the pyrolysis is 900 to 1500℃, and the time of the pyrolysis is 2 to 6 hours.

8. The preparation method according to any one of claims 1 to 3, wherein: the sintering treatment is under the conditions of pressure 1 to 5 MPa, temperature 1600 to 1900℃, and time 2 to 8 hours.

9. The C / ZrC-SiC ceramic matrix composite prepared according to the preparation method of any one of claims 1 to 8, wherein the C / ZrC-SiC composite has a room temperature tensile strength of ≥ 300 MPa, a room temperature flexural strength of ≥ 400 MPa, and a linear ablation rate of ≤ 1 x 10 -3 mm / s after arc tunnel or oxyacetylene test at above 2300 °C.

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