阅读说明：本技术 一种超高温陶瓷基复合材料及制备方法 (Ultrahigh-temperature ceramic matrix composite and preparation method thereof ) 是由 范尚武 寇思捷 王乐 姬彪 栾承华 于 2020-12-24 设计创作，主要内容包括：本发明涉及一种超高温陶瓷基复合材料及制备方法,在C/C复合材料预制体中引入B-4C,以及C的有机前驱体,固化裂解后得到C/B-4C-C预制体。之后采用反应熔体浸渗法,利用硅铪合金和硅锆合金熔体与B-4C-C反应,原位生成HfC-ZrC-HfB-2-ZrB-2-SiC多组分抗烧蚀基体,其中HfC与ZrC组成(Hf,Zr)C固溶体,HfB-2与ZrB-2组成(Hf,Zr)B-2固溶体,有效提高了复合材料的抗氧化烧蚀性能。制备的C/(Hf,Zr)C-(Hf,Zr)B-2-SiC复合材料超高温陶瓷组分体积含量高,具有良好的力学性能。本方法采用真空-压力浸渍方法,适用于(Hf,Zr)C-(Hf,Zr)B-2-SiC改性C/C和C/SiC复合材料的制备,有效提高复合材料在极端环境下的抗烧蚀能力。(The invention relates to an ultrahigh temperature ceramic matrix composite and a preparation method thereof, wherein B is introduced into a C/C composite preform 4 C, and C organic precursor, curing and cracking to obtain C/B 4 A C-C preform. Then adopting reaction melt infiltration method to utilize silicon-hafnium alloy, silicon-zirconium alloy melt and B 4 C-C reaction to generate HfC-ZrC-HfB in situ 2 ‑ZrB 2 -SiC multicomponent ablation-resistant matrix, in which HfC and ZrC constitute a (Hf, Zr) C solid solution, HfB 2 And ZrB 2 Composition (Hf, Zr) B 2 The solid solution effectively improves the oxidation and ablation resistance of the composite material. Prepared C/(Hf, Zr) C- (Hf, Zr) B 2 the-SiC composite material ultrahigh-temperature ceramic has high volume content and good mechanical property. The method adopts a vacuum-pressure impregnation method, and is suitable for (Hf, Zr) C-(Hf,Zr)B 2 The preparation of the-SiC modified C/C and C/SiC composite material can effectively improve the ablation resistance of the composite material in an extreme environment.)

1. C/(Hf, Zr) C- (Hf, Zr) B₂-SiC ultra high temperature ceramic matrix composite characterized by: introducing B into pores of C/C composite material preform₄C and C, and silicon-hafnium alloy and silicon-zirconium alloy; the mass ratio of the silicon-hafnium alloy to the silicon-zirconium alloy is 1.5-2.5: 1.

2. The C/(Hf, Zr) C- (Hf, Zr) B as claimed in claim 1₂-SiC ultra high temperature ceramic matrix composite characterized by: the mass fraction of each component of the silicon-hafnium alloy powder is 70-75 wt% of Hf and 25-30 wt% of Si.

3. The C/(Hf, Zr) C- (Hf, Zr) B as claimed in claim 1₂-SiC ultra high temperature ceramic matrix composite characterized by: the silicon-zirconium alloy powder comprises, by mass, 60-75 wt% of Zr and 25-40 wt% of Si.

4. The C/(Hf, Zr) C- (Hf, Zr) B as claimed in claim 1₂-SiC ultra high temperature ceramic matrix composite characterized by: the C organic precursor is phenolic resin, furan resin or silane resin.

5. A method for preparing the C/(Hf, Zr) C- (Hf, Zr) B as defined in any one of claims 1-4₂The method for preparing the-SiC superhigh temperature ceramic matrix composite material is characterized by comprising the following steps:

step 1, B₄C, preparation of slurry: dissolving sodium carboxymethylcellulose in distilled water, stirring to dissolve, adding B₄C powder is ball-milled for 24-48 h to obtain B₄C, sizing agent; the mass fraction of sodium carboxymethylcellulose dissolved in distilled water is 0.5-1%, and B₄The mass ratio of C to distilled water is 1-4: 10;

step 2, C, preparing an organic precursor solution: dissolving the organic precursor C and hexamethylenetetramine in absolute ethyl alcohol, uniformly stirring until the mixture is dissolved, and performing ball milling for 24-48 h to obtain an organic precursor C solution; the mass ratio of hexamethylene tetramine to the C organic precursor is 1:10, and the viscosity of the C organic precursor solution is controlled to be 20-200mPa.s through absolute ethyl alcohol;

step 3, preparing mixed alloy powder: mixing and ball-milling the silicon-hafnium alloy and the silicon-zirconium alloy in a mass ratio of 1.5-2.5: 1 for 24-36 h to obtain silicon-hafnium-silicon-zirconium alloy powder;

the mass fraction of each component in the silicon-hafnium alloy powder is 70-75 wt% of Hf and 25-30 wt% of Si;

the silicon-zirconium alloy powder comprises, by mass, 60-75 wt% of Zr and 25-40 wt% of Si;

and 4, step 4: the open porosity of the C/C composite material preform is 10 vol% to 40 vol%.

Step 5, vacuum pressure impregnation B₄C, slurry: placing the C/C composite material prefabricated body into a vacuum pressure impregnation tank, firstly vacuumizing until the vacuum degree is-0.05 to-0.10 Mpa, keeping for 30 to 60 minutes, and then opening a slurry impregnation valve at the bottom of the tank body to enable the slurry prepared in the step 2B to be impregnated into the tank body₄C, reversely sucking the slurry into the tank body, completely immersing the prefabricated body, closing the immersion valve, continuously keeping the vacuum degree of-0.05 to-0.10 Mpa for 30 to 60 minutes, and closing a vacuum system valve and a vacuum pump; opening the high-pressure valve, filling compressed gas into the impregnation tank, keeping the pressure in the tank body to be 0.8-1.0 Mpa, and maintaining the pressure for 30-60 minutes to finish the step B₄C, dipping the slurry;

step 6, vacuum pressure impregnation of the organic precursor solution C: impregnating B prepared in step 5₄Placing the C/C composite material prefabricated body of C in a vacuum pressure impregnation tank, firstly vacuumizing the vacuum pressure impregnation tank until the vacuum degree is-0.05 to-0.10 Mpa, keeping the vacuum pressure impregnation tank for 30 to 60 minutes,opening a slurry impregnation valve at the bottom of the tank body, sucking the organic precursor solution C prepared in the step (3) into the tank body, completely immersing the prefabricated body, closing the impregnation valve, keeping the vacuum degree of-0.05 to-0.10 Mpa for 30 to 60 minutes, and closing a vacuum system valve and a vacuum pump; opening a high-pressure valve, filling compressed gas into the impregnation tank, keeping the pressure in the tank body to be 0.8-1.0 Mpa for 30-60 minutes, and finishing impregnation of the C organic precursor solution;

step 7, curing and cracking: placing the impregnated preform in the step 6 in an oven for drying at 60-80 ℃, then curing at 150-200 ℃ for 1h, and then carrying out heat treatment at 900-1800 ℃ for 2h in an argon or vacuum environment to obtain C/B₄A C-C composite material;

step 8, C/(Hf, Zr) C- (Hf, Zr) B₂-preparation of SiC composite: embedding the material processed in the step 7 into silicon hafnium-silicon zirconium alloy powder, and infiltrating the silicon hafnium-silicon zirconium alloy powder into C/B in a vacuum environment at the temperature of 1700-₄In the C-C composite material, heat preservation is carried out for 1-2h, and alloy melt and B are mixed₄In-situ generation of HfC-ZrC-HfB by C-C reaction₂-ZrB₂-SiC multicomponent ablation-resistant matrix, in which HfC and ZrC constitute a (Hf, Zr) C solid solution, HfB₂And ZrB₂Composition (Hf, Zr) B₂Obtaining C/(Hf, Zr) C- (Hf, Zr) B through solid solution₂-SiC ultra high temperature ceramic matrix composite.

6. The method of claim 5, wherein: the pretreatment of the C/C composite material preform is as follows: ultrasonically cleaning the C/C composite material preform for 1-2 hours, and drying in a forced air drying oven at 110-150 ℃ to obtain a dry and clean composite material preform.

7. The method of claim 5, wherein: the grain size of each different alloy powder in the step 3 is 30-80 μm.

8. The method of claim 5, wherein: b is₄The particle size of the C powder is 0.5 to 1 μm.

9. The method of claim 5, wherein: the C/C composite material prefabricated body is a three-dimensional puncture, three-dimensional needling or two-dimensional laminated C/C composite material prefabricated body prepared by a chemical vapor infiltration or slurry impregnation cracking process.

Technical Field

The invention belongs to the technical field of ceramic matrix composite preparation, relates to an ultrahigh-temperature ceramic matrix composite and a preparation method thereof, and particularly relates to C/(Hf, Zr) C- (Hf, Zr) B₂the-SiC superhigh temperature ceramic base composite material is one kind of composite material prepared with (Hf, Zr) C- (Hf, Zr) B₂the-SiC multi-component ceramic matrix modifies the C/C and C/SiC composite material to improve the oxidation and ablation resistance of the composite material.

Background

The spacecraft can be subjected to extreme aerodynamic thermal environment when entering the atmosphere at a super high speed or cruising in a near space, and a Thermal Protection System (TPS) plays a vital role in order to prevent the spacecraft from being damaged. During hypersonic flight, the materials of the thermal protection system need to withstand high temperature oxidation (above 2000 ℃), severe thermal shock and severe air current scouring. The C/C composite material can still maintain good structural strength at the temperature of more than 3000 ℃, but under the conditions of ultrahigh temperature oxidation and erosion of high-speed airflow, a C matrix can be rapidly oxidized and ablated, so that the application of the C/C composite material in the field of advanced space systems is limited to a great extent. In addition, the long-term service temperature of the C/SiC composite material in an oxidizing environment also exists in a neck bottle because of the active oxidation of the SiC matrix, and is generally not higher than 1650 ℃. Compared with C/C and C/SiC composite materials, the composite material containing the carbon fiber reinforcement and the UHTC or the C/SiC-UHTC composite material has better oxidation resistance and ablation resistance; in addition, the fracture toughness, thermal shock resistance and damage tolerance are better, so the material is considered to be an ideal candidate material for serving under the ultrahigh-temperature environment in the future.

Ultra-High Temperature Ceramics (UHTCs) refer to a ceramic material capable of maintaining physical and chemical stability in High Temperature environment and reaction atmosphere, and mainly comprise boride, carbide and nitride formed from hafnium, zirconium and molybdenum, such as ZrB₂、HfB₂TaC, HfC, ZrC, HfN, etc., these compounds generally have melting points in excess of 3000 ℃. The UHTCs have the characteristics of ultrahigh temperature resistance, high thermal conductivity, high strength and the like, and can be used as a heat-bearing structural component of a reusable spacecraft nose cone, a wing leading edge and the like. In all UHTCs that have been investigated，ZrB₂And HfB₂The UHTCs have higher thermal conductivity, moderate thermal expansion coefficient and good oxidation and ablation resistance, can realize long-time non-ablation in an oxidation environment with the temperature of more than 2000 ℃, and are very promising non-ablation type ultra-high temperature heat-proof materials.

Preparation C_fThe most commonly used process for UHTC involves: polymer impregnation cracking (PIP) process, Slurry Impregnation (SI) process, and Reaction Melt Infiltration (RMI) process, among others. Document' super-high temperature ablation performance research of integrated antioxidant C/C-ZrC-SiC composite material of Malus martensii, Wei seal, Bian spring, and the like]The inorganic material bulletin, 2011,26:852-856, "describes the preparation of C/C-ZrC-SiC composite materials with different ZrC and SiC contents by soaking ZrC and SiC mixture precursors into porous C/C materials. The documents "S.F.Tang, J.Y.Deng, S.J.Wang, W.C.Liu, company of thermal and amplification terms of C/SiC composites and C/ZrB₂C prepared by Slurry Impregnation (SI) process was investigated in SiC composites, Corros. Sci.51(2009) 54-61 ″_f/SiC-ZrB₂The ablation mechanism of the composite material is considered to be ZrB₂Low emissivity of and B₂O₃-SiO₂The high uniformity and compactness of the film synergistically contribute to good ablation resistance. Literature "Chen Y, Sun W, Xiong X, et al. Micromicroscopy, thermal Properties, and relationship resistance of C/HfC-ZrC-SiC composites [ J]4685-Si 4691' reports that Hf, Zr and Si powder is used as raw materials (ball milling and mixing in advance), and the temperature is kept for 1-2h under the Ar atmosphere of 1900-2000 ℃ by adopting an RMI process to prepare the C/HfC-ZrC-SiC composite material. Since microscopic defects such as pores, cracks, etc. tend to be the primary pathway for oxygen to rapidly enter the interior of the material, porosity has a significant impact on the oxidative ablatability of the material. Compared with other methods, the rapid densification advantage of RMI enables the material to have higher density and show more excellent oxidation and ablation resistance. Pure Hf resources are scarce, if pure Zr and pure Hf are infiltrated, or high Hf (94-99 wt% Hf) alloy and high Zr (90-99 wt% Zr) alloy, the infiltration temperature is too high (> 1855 ℃), and the carbon fiber is easy to suffer from melt erosion, which leads to serious deterioration of mechanical properties of the material. The Hf-Si and Zr-Si alloys used in the method canEffectively reduces the infiltration temperature and saves the process cost.

Disclosure of Invention

Technical problem to be solved

In order to avoid the defects of the prior art, the invention provides C/(Hf, Zr) C- (Hf, Zr) B₂-SiC superhigh temperature ceramic matrix composite material and preparation method thereof, in-situ generation HfC-ZrC-HfB₂-ZrB₂-SiC multicomponent ablation-resistant matrix, in which HfC and ZrC constitute a (Hf, Zr) C solid solution, HfB₂And ZrB₂Composition (Hf, Zr) B₂The solid solution effectively improves the oxidation and ablation resistance of the composite material. The obtained material has high density and good mechanical property, and the prepared composite material ultrahigh-temperature ceramic has high volume content of components, so that the process steps are reduced, and the cost is reduced.

Technical scheme

C/(Hf, Zr) C- (Hf, Zr) B₂-SiC ultra high temperature ceramic matrix composite characterized by: introducing B into pores of C/C composite material preform₄C and C, and silicon-hafnium alloy and silicon-zirconium alloy; the mass ratio of the silicon-hafnium alloy to the silicon-zirconium alloy is 1.5-2.5: 1.

The mass fraction of each component of the silicon-hafnium alloy powder is 70-75 wt% of Hf and 25-30 wt% of Si.

The silicon-zirconium alloy powder comprises, by mass, 60-75 wt% of Zr and 25-40 wt% of Si.

The C organic precursor is phenolic resin, furan resin or silane resin.

Preparing the C/(Hf, Zr) C- (Hf, Zr) B₂The method for preparing the-SiC superhigh temperature ceramic matrix composite material is characterized by comprising the following steps:

step 1, B₄C, preparation of slurry: dissolving sodium carboxymethylcellulose in distilled water, stirring to dissolve, adding B₄C powder is ball-milled for 24-48 h to obtain B₄C, sizing agent; the mass fraction of sodium carboxymethylcellulose dissolved in distilled water is 0.5-1%, and B₄The mass ratio of C to distilled water is 1-4: 10;

step 2, C, preparing an organic precursor solution: dissolving the organic precursor C and hexamethylenetetramine in absolute ethyl alcohol, uniformly stirring until the mixture is dissolved, and performing ball milling for 24-48 h to obtain an organic precursor C solution; the mass ratio of hexamethylene tetramine to the C organic precursor is 1:10, and the viscosity of the C organic precursor solution is controlled to be 20-200mPa.s through absolute ethyl alcohol;

step 3, preparing mixed alloy powder: mixing and ball-milling the silicon-hafnium alloy and the silicon-zirconium alloy in a mass ratio of 1.5-2.5: 1 for 24-36 h to obtain silicon-hafnium-silicon-zirconium alloy powder;

the mass fraction of each component in the silicon-hafnium alloy powder is 70-75 wt% of Hf and 25-30 wt% of Si;

the silicon-zirconium alloy powder comprises, by mass, 60-75 wt% of Zr and 25-40 wt% of Si;

and 4, step 4: the open porosity of the C/C composite material preform is 10 vol% to 40 vol%.

Step 5, vacuum pressure impregnation B₄C, slurry: placing the C/C composite material prefabricated body into a vacuum pressure impregnation tank, firstly vacuumizing until the vacuum degree is-0.05 to-0.10 Mpa, keeping for 30 to 60 minutes, and then opening a slurry impregnation valve at the bottom of the tank body to enable the slurry prepared in the step 2B to be impregnated into the tank body₄C, reversely sucking the slurry into the tank body, completely immersing the prefabricated body, closing the immersion valve, continuously keeping the vacuum degree of-0.05 to-0.10 Mpa for 30 to 60 minutes, and closing a vacuum system valve and a vacuum pump; opening the high-pressure valve, filling compressed gas into the impregnation tank, keeping the pressure in the tank body to be 0.8-1.0 Mpa, and maintaining the pressure for 30-60 minutes to finish the step B₄C, dipping the slurry;

step 6, vacuum pressure impregnation of the organic precursor solution C: impregnating B prepared in step 5₄Placing the C/C composite material preform of C in a vacuum pressure impregnation tank, firstly vacuumizing the vacuum pressure impregnation tank until the vacuum degree is-0.05 to-0.10 Mpa, keeping the vacuum degree for 30 to 60 minutes, then opening a slurry impregnation valve at the bottom of the tank body, enabling the C organic precursor solution prepared in the step 3 to be sucked into the tank body and completely immerse the preform, closing the impregnation valve, then continuously keeping the vacuum degree for 30 to 60 minutes at-0.05 to-0.10 Mpa, and closing a vacuum system valve and a vacuum pump; opening a high-pressure valve, filling compressed gas into the impregnation tank, keeping the pressure in the tank body to be 0.8-1.0 Mpa for 30-60 minutes, and finishing the step CDipping the organic precursor solution;

step 7, curing and cracking: placing the impregnated preform in the step 6 in an oven for drying at 60-80 ℃, then curing at 150-200 ℃ for 1h, and then carrying out heat treatment at 900-1800 ℃ for 2h in an argon or vacuum environment to obtain C/B₄A C-C composite material;

step 8, C/(Hf, Zr) C- (Hf, Zr) B₂-preparation of SiC composite: embedding the material processed in the step 7 into silicon hafnium-silicon zirconium alloy powder, and infiltrating the silicon hafnium-silicon zirconium alloy powder into C/B in a vacuum environment at the temperature of 1700-₄In the C-C composite material, heat preservation is carried out for 1-2h, and alloy melt and B are mixed₄In-situ generation of HfC-ZrC-HfB by C-C reaction₂-ZrB₂-SiC multicomponent ablation-resistant matrix, in which HfC and ZrC constitute a (Hf, Zr) C solid solution, HfB₂And ZrB₂Composition (Hf, Zr) B₂Obtaining C/(Hf, Zr) C- (Hf, Zr) B through solid solution₂-SiC ultra high temperature ceramic matrix composite.

The pretreatment of the C/C composite material preform is as follows: ultrasonically cleaning the C/C composite material preform for 1-2 hours, and drying in a forced air drying oven at 110-150 ℃ to obtain a dry and clean composite material preform.

The grain size of each different alloy powder in the step 3 is 30-80 μm.

B is₄The particle size of the C powder is 0.5 to 1 μm.

The C/C composite material prefabricated body is a three-dimensional puncture, three-dimensional needling or two-dimensional laminated C/C composite material prefabricated body prepared by a chemical vapor infiltration or slurry impregnation cracking process.

Advantageous effects

The invention provides C/(Hf, Zr) C- (Hf, Zr) B₂The preparation method of-SiC superhigh temperature ceramic matrix composite material is characterized by that in the C/C composite material prefabricated body B is introduced₄C, and C organic precursor, curing and cracking to obtain C/B₄A C-C preform. Then adopting reaction melt infiltration method to utilize silicon-hafnium alloy, silicon-zirconium alloy melt and B₄C-C reaction to generate HfC-ZrC-HfB in situ₂-ZrB₂-a SiC multicomponent ablation-resistant matrix in which HfC and ZrC constitute a (Hf, Zr) C solid solution,HfB₂and ZrB₂Composition (Hf, Zr) B₂The solid solution effectively improves the oxidation and ablation resistance of the composite material. The prepared composite material ultrahigh-temperature ceramic has high volume content and good mechanical property. The method adopts a vacuum-pressure impregnation method and is suitable for (Hf, Zr) C- (Hf, Zr) B₂The preparation of the-SiC modified C/C and C/SiC composite material can effectively improve the ablation resistance of the composite material in an extreme environment.

(Hf, Zr) C- (Hf, Zr) B of the present invention₂The SiC is used for modifying the C/C and C/SiC composite material, and the ablation resistance of the C/C and C/SiC composite material under extreme environments is improved. Simple preparation process, low requirement on equipment, low preparation cost and easy realization of C/(Hf, Zr) C- (Hf, Zr) B₂And (3) rapidly preparing the-SiC ultrahigh-temperature ceramic matrix composite, wherein the porosity of the prepared composite is less than 8%, and the bending strength is more than 220 Mpa.

Drawings

FIG. 1: the C/(Hf, Zr) C- (Hf, Zr) B prepared by the invention₂-SiC ultra high temperature ceramic matrix composite X-ray diffraction pattern;

FIG. 2: the C/(Hf, Zr) C- (Hf, Zr) B prepared by the invention₂-scanning electron microscope photograph of the section of the SiC superhigh temperature ceramic matrix composite;

FIG. 3: the C/(Hf, Zr) C- (Hf, Zr) B prepared by the invention₂-a double back-scattered electron picture in the section of the SiC ultra-high temperature ceramic matrix composite;

FIG. 4: the C/(Hf, Zr) C- (Hf, Zr) B prepared by the invention₂-a high-power back-scattered electron picture of the section of the SiC superhigh temperature ceramic matrix composite;

Detailed Description

The invention will now be further described with reference to the following examples and drawings:

C/(Hf,Zr)C-(Hf,Zr)B₂the preparation steps of the-SiC superhigh temperature ceramic matrix composite material are as follows:

step 1, preparing a composite material preform: ultrasonically cleaning a C/C composite material preform with the open porosity of 10-40 vol% for 1-2 hours, and drying in a forced air drying oven at 110-150 ℃ to obtain a dry and clean composite material preform;

step 2, B₄C, preparation of slurry: dissolving a certain amount of sodium carboxymethylcellulose in distilled water, stirring to dissolve, and adding a certain amount of B₄C powder is ball-milled for 24-48 h to obtain B₄C, sizing agent; the mass fraction of sodium carboxymethylcellulose dissolved in distilled water is 0.5-1%, and B₄The mass ratio of C to distilled water is 1-4: 10;

step 3, C, preparing an organic precursor solution: dissolving a certain amount of C organic precursor and hexamethylenetetramine in absolute ethyl alcohol, uniformly stirring until the C organic precursor and the hexamethylenetetramine are dissolved, and performing ball milling for 24-48 h to obtain a C organic precursor solution; the mass ratio of hexamethylene tetramine to the C organic precursor is 1:10, and the viscosity of the C organic precursor solution is controlled to be 20-200mPa.s through absolute ethyl alcohol;

step 4, preparing mixed alloy powder: weighing different alloy powder with the particle size of 30-80 mu m, wherein the mass fraction of each component in the silicon-hafnium alloy powder is 70-75 wt% of Hf and 25-30 wt% of Si, and the mass fraction of each component in the silicon-zirconium alloy powder is 60-75 wt% of Zr and 25-40 wt% of Si; the sum of the mass fractions of the components in each alloy powder is 100%. And (3) mixing and ball-milling the weighed silicon-hafnium alloy powder and silicon-zirconium alloy powder for 24-36 h to obtain the silicon-hafnium-silicon-zirconium alloy powder. The mass ratio of the silicon-hafnium alloy to the silicon-zirconium alloy is 1.5-2.5: 1.

Step 5, vacuum pressure impregnation B₄C, slurry: placing the C/C composite material prefabricated body into a vacuum pressure impregnation tank, firstly vacuumizing the C/C composite material prefabricated body until the vacuum degree is-0.05 to-0.10 Mpa, keeping the vacuum degree for a period of time, and then opening a slurry impregnation valve at the bottom of the tank body to ensure that the slurry impregnation valve at the bottom of the tank body prepared in the step 2 is opened to ensure that the slurry impregnation valve is positioned at the bottom of the tank body₄C, reversely sucking the slurry into the tank body, completely immersing the prefabricated body, closing the immersion valve, continuously keeping the vacuum degree of-0.05 to-0.10 Mpa for a period of time, and closing a vacuum system valve and a vacuum pump; opening the high-pressure valve, filling compressed gas into the impregnation tank, keeping the pressure in the tank body to be 0.8-1.0 Mpa, and maintaining the pressure for a period of time to finish the step B₄C, dipping the slurry; taking out the dip B₄C, drying the sample of the slurry for later use;

step 6, vacuum pressure impregnation of the organic precursor solution C: impregnating B prepared in step 5₄Placing the C/C composite material prefabricated body of C in a vacuum pressure impregnation tank, firstly aligningVacuumizing until the vacuum degree is-0.05 to-0.10 Mpa, keeping for a period of time, then opening a slurry impregnation valve at the bottom of the tank body, sucking the organic precursor solution C prepared in the step 3 into the tank body in a pouring manner, completely immersing the prefabricated body, closing the impregnation valve, then continuously keeping the vacuum degree for a period of time of-0.05 to-0.10 Mpa, and closing a vacuum system valve and a vacuum pump; opening a high-pressure valve, filling compressed gas into the impregnation tank, keeping the pressure in the tank body to be 0.8-1.0 Mpa for a period of time, and finishing impregnation of the C organic precursor solution;

step 7, curing and cracking: placing the impregnated preform in the step 6 in an oven for drying at 60-80 ℃, then curing at 150-200 ℃ for 1h, and then carrying out heat treatment at 900-1800 ℃ for 2h in an argon or vacuum environment to obtain C/B₄A C-C composite material;

step 8, C/(Hf, Zr) C- (Hf, Zr) B₂-preparation of SiC composite: embedding the material processed in the step 7 into silicon hafnium-silicon zirconium alloy powder, and infiltrating the silicon hafnium-silicon zirconium alloy powder into the C/B obtained in the step 7 in a vacuum environment at the temperature of 1700-1800 DEG C₄In the C-C composite material, heat preservation is carried out for 1-2h, and alloy melt and B are mixed₄In-situ generation of HfC-ZrC-HfB by C-C reaction₂-ZrB₂-SiC multicomponent ablation-resistant matrix, in which HfC and ZrC constitute a (Hf, Zr) C solid solution, HfB₂And ZrB₂Composition (Hf, Zr) B₂Obtaining C/(Hf, Zr) C- (Hf, Zr) B through solid solution₂-SiC ultra high temperature ceramic matrix composite.

The C/C composite material prefabricated body is a three-dimensional puncture, three-dimensional needling or two-dimensional laminated C/C composite material prefabricated body prepared by a chemical vapor infiltration or slurry impregnation cracking process.

B is₄The particle size of the C powder is 0.5 to 1 μm.

The C organic precursor is phenolic resin, furan resin or silane resin.

Example 1: preparation of C/(Hf, Zr) C- (Hf, Zr) B by using three-dimensional puncture C/C composite material₂-SiC ultra high temperature ceramic matrix composite.

The preparation method comprises the following specific steps:

1. preparing a composite material preform: ultrasonically cleaning a three-dimensional puncture C/C composite material preform with an open pore rate of about 20 vol% for 1 hour, and drying the three-dimensional puncture C/C composite material preform in a forced air drying oven at 120 ℃ for 2 hours to obtain a dry and clean composite material preform;

2、B₄c, preparation of slurry: dissolving a certain amount of sodium carboxymethylcellulose in distilled water, stirring to dissolve, and adding a certain amount of B₄C powder is ball milled for 48 hours to obtain B₄C, sizing agent; the mass fraction of sodium carboxymethylcellulose dissolved in distilled water is 0.5%, B₄The mass ratio of C to distilled water is 1: 5;

3. preparing a phenolic resin solution: dissolving a certain amount of phenolic resin and hexamethylenetetramine in absolute ethyl alcohol, uniformly stirring until the phenolic resin and the hexamethylenetetramine are dissolved, and performing ball milling for 24 hours to obtain a phenolic resin solution; the mass ratio of hexamethylene tetramine to the phenolic resin is 1:10, and the viscosity of the phenolic resin solution is controlled to be 120mPa.s by absolute ethyl alcohol;

4. preparing mixed alloy powder: weighing different alloy powder with the grain diameter of about 45 mu m, wherein the mass fraction of each component in the silicon-hafnium alloy powder is 71 wt% of Hf and 29 wt% of Si, and the mass fraction of each component in the silicon-zirconium alloy powder is 62 wt% of Zr and 38 wt% of Si. And mixing and ball-milling the weighed silicon-hafnium alloy powder and silicon-zirconium alloy powder for 24 hours to obtain the silicon-hafnium-silicon-zirconium alloy powder. When the silicon-hafnium alloy powder and the silicon-zirconium alloy powder are weighed, the mass ratio of the silicon-hafnium alloy powder to the silicon-zirconium alloy powder is 1.6: 1.

5. Vacuum pressure impregnation B₄C, slurry: placing the C/C composite material preform in a vacuum pressure impregnation tank, vacuumizing the vacuum pressure impregnation tank until the vacuum degree is-0.096 Mpa, keeping the vacuum pressure for 30min, and then opening a slurry impregnation valve at the bottom of the tank body to enable the slurry impregnation valve B prepared in the step 2 to be in a non-vacuum state₄C, reversely sucking the slurry into the tank body, completely immersing the prefabricated body, closing the immersion valve, continuously keeping the vacuum degree of-0.096 Mpa, maintaining for 30min, and closing a vacuum system valve and a vacuum pump; opening the high pressure valve and charging the impregnation tank with compressed N₂Maintaining the pressure in the tank body at 0.9MPa for 30min to complete the process B₄C, dipping the slurry; taking out the dip B₄C, drying the sample of the slurry for later use;

6. vacuum pressure impregnation of phenolic resin solution: impregnating B prepared in step 5₄Placing the C/C composite material prefabricated body of C in a vacuum pressure impregnation tank, firstly vacuumizing itKeeping the vacuum degree at-0.096 MPa for 30min, then opening a slurry impregnation valve at the bottom of the tank body, sucking the phenolic resin solution prepared in the step (3) into the tank body, completely immersing the prefabricated body, closing the impregnation valve, then continuously keeping the vacuum degree at-0.096 MPa, keeping the vacuum degree for 30min, and closing a vacuum system valve and a vacuum pump; opening the high pressure valve and charging the impregnation tank with compressed N₂Keeping the pressure in the tank body to be 0.9Mpa for 30min to finish the impregnation of the phenolic resin solution;

7. curing and cracking: placing the impregnated preform in the step 6 in an oven to dry at 70 ℃, then curing at 170 ℃ for 1h, and then carrying out heat treatment at 1800 ℃ for 2h in a vacuum environment to obtain C/B₄A C-C composite material;

8、C/(Hf,Zr)C-(Hf,Zr)B₂-preparation of SiC composite: embedding the material processed in the step 7 into silicon hafnium-silicon zirconium alloy powder, and infiltrating the silicon hafnium-silicon zirconium alloy powder into the C/B obtained in the step 7 in a vacuum environment at the temperature of 1700-1800 DEG C₄In the C-C composite material, heat preservation is carried out for 1h, and alloy melt and B are mixed₄In-situ generation of HfC-ZrC-HfB by C-C reaction₂-ZrB₂-SiC multicomponent ablation-resistant matrix, in which HfC and ZrC constitute a (Hf, Zr) C solid solution, HfB₂And ZrB₂Composition (Hf, Zr) B₂Obtaining C/(Hf, Zr) C- (Hf, Zr) B through solid solution₂-SiC ultra high temperature ceramic matrix composite.

C/(Hf, Zr) C- (Hf, Zr) B prepared in example 1₂The content of carbon fiber in the-SiC superhigh temperature ceramic matrix composite material exceeds 60 vol%, and the apparent density is 2.79g/cm³The open porosity was about 6% and the bending strength was 265 MPa.

Example 2: preparation of C/(Hf, Zr) C- (Hf, Zr) B by using three-dimensional needling C/C composite material₂-SiC ultra high temperature ceramic matrix composite.

The preparation method comprises the following specific steps:

1. preparing a composite material preform: ultrasonically cleaning a three-dimensional puncture C/C composite material preform with the air opening rate of about 30 vol% for 2 hours, and drying the three-dimensional puncture C/C composite material preform in a forced air drying oven at 150 ℃ for 1 hour to obtain a dry and clean composite material preform;

2、B₄c, preparation of slurry: taking a certain amount of carboxymethyl celluloseDissolving sodium in distilled water, stirring to dissolve, adding a certain amount of B₄C powder is ball milled for 48 hours to obtain B₄C, sizing agent; the mass fraction of sodium carboxymethylcellulose dissolved in distilled water is 0.5%, B₄The mass ratio of C to distilled water is 2: 5;

3. preparing a phenolic resin solution: dissolving a certain amount of phenolic resin and hexamethylenetetramine in absolute ethyl alcohol, uniformly stirring until the phenolic resin and the hexamethylenetetramine are dissolved, and performing ball milling for 24 hours to obtain a phenolic resin solution; the mass ratio of hexamethylene tetramine to the phenolic resin is 1:10, and the viscosity of the phenolic resin solution is controlled to be 145mPa.s by absolute ethyl alcohol;

4. preparing mixed alloy powder: weighing different alloy powder with the grain diameter of about 45 mu m, wherein the mass fraction of each component in the silicon-hafnium alloy powder is 75 wt% of Hf and 25 wt% of Si, and the mass fraction of each component in the silicon-zirconium alloy powder is 60 wt% of Zr and 40 wt% of Si. And mixing and ball-milling the weighed silicon-hafnium alloy powder and silicon-zirconium alloy powder for 24 hours to obtain the silicon-hafnium-silicon-zirconium alloy powder. When the silicon-hafnium alloy powder and the silicon-zirconium alloy powder are weighed, the mass ratio of the silicon-hafnium alloy powder to the silicon-zirconium alloy powder is 2: 1.

5. Vacuum pressure impregnation B₄C, slurry: placing the C/C composite material preform in a vacuum pressure impregnation tank, vacuumizing the vacuum pressure impregnation tank until the vacuum degree is-0.096 Mpa, keeping the vacuum pressure for 30min, and then opening a slurry impregnation valve at the bottom of the tank body to enable the slurry impregnation valve B prepared in the step 2 to be in a non-vacuum state₄C, reversely sucking the slurry into the tank body, completely immersing the prefabricated body, closing the immersion valve, continuously keeping the vacuum degree of-0.096 Mpa, maintaining for 30min, and closing a vacuum system valve and a vacuum pump; opening the high pressure valve and charging the impregnation tank with compressed N₂Maintaining the pressure in the tank body at 0.9MPa for 30min to complete the process B₄C, dipping the slurry; taking out the dip B₄C, drying the sample of the slurry for later use;

6. vacuum pressure impregnation of phenolic resin solution: impregnating B prepared in step 5₄Placing the C/C composite material preform of C in a vacuum pressure impregnation tank, vacuumizing the vacuum pressure impregnation tank until the vacuum degree is-0.096 Mpa, keeping the vacuum degree for 30min, opening a slurry impregnation valve at the bottom of the tank body, sucking the phenolic resin solution prepared in the step (3) into the tank body in a pouring manner, completely immersing the preform, closing the impregnation valve, keeping the vacuum degree to-0.096 Mpa, keeping the vacuum degree for 30minVacuum system valves and vacuum pumps; opening the high pressure valve and charging the impregnation tank with compressed N₂Keeping the pressure in the tank body to be 0.9Mpa for 30min to finish the impregnation of the phenolic resin solution;

7. curing and cracking: placing the impregnated preform in the step 6 in an oven for drying at 80 ℃, then curing at 200 ℃ for 1h, and then carrying out heat treatment at 900 ℃ for 2h under the protection of argon to obtain C/B₄A C-C composite material;

8、C/(Hf,Zr)C-(Hf,Zr)B₂-preparation of SiC composite: embedding the material processed in the step 7 into silicon hafnium-silicon zirconium alloy powder, and infiltrating the silicon hafnium-silicon zirconium alloy powder into the C/B obtained in the step 7 in a vacuum environment at the temperature of 1700-1800 DEG C₄In the C-C composite material, the temperature is kept for 1.5h, and the alloy melt and the B are mixed₄In-situ generation of HfC-ZrC-HfB by C-C reaction₂-ZrB₂-SiC multicomponent ablation-resistant matrix, in which HfC and ZrC constitute a (Hf, Zr) C solid solution, HfB₂And ZrB₂Composition (Hf, Zr) B₂Obtaining C/(Hf, Zr) C- (Hf, Zr) B through solid solution₂-SiC ultra high temperature ceramic matrix composite.

C/(Hf, Zr) C- (Hf, Zr) B prepared in example 2₂The content of carbon fiber in the-SiC superhigh temperature ceramic matrix composite material is about 40 vol%, and the apparent density is 2.81g/cm³The open porosity was about 8% and the bending strength was 227 MPa.

Example 3: preparation of C/(Hf, Zr) C- (Hf, Zr) B by two-dimensional laminated C/C composite material₂-SiC ultra high temperature ceramic matrix composite.

The preparation method comprises the following specific steps:

1. preparing a composite material preform: ultrasonically cleaning a two-dimensional laminated C/C composite material preform with the open porosity of about 40 vol% for 2 hours, and drying the two-dimensional laminated C/C composite material preform in a forced air drying oven at 120 ℃ for 2 hours to obtain a dry and clean composite material preform;

2、B₄c, preparation of slurry: dissolving a certain amount of sodium carboxymethylcellulose in distilled water, stirring to dissolve, and adding a certain amount of B₄C powder is ball milled for 48 hours to obtain B₄C, sizing agent; the mass fraction of sodium carboxymethylcellulose dissolved in distilled water is 0.5%, B₄The mass ratio of C to distilled water is 2: 5;

3. preparation of furan resin solution: dissolving a certain amount of furan resin and hexamethylenetetramine in absolute ethyl alcohol, uniformly stirring until the furan resin and the hexamethylenetetramine are dissolved, and performing ball milling for 24 hours to obtain a furan resin solution; the mass ratio of hexamethylene tetramine to furan resin is 1:10, and the viscosity of the phenolic resin solution is controlled to be 145mPa.s by absolute ethyl alcohol;

4. preparing mixed alloy powder: weighing different alloy powder with the grain diameter of about 45 mu m, wherein the mass fraction of each component in the silicon-hafnium alloy powder is 70 wt% of Hf and 30 wt% of Si, and the mass fraction of each component in the silicon-zirconium alloy powder is 70 wt% of Zr and 30 wt% of Si. And mixing and ball-milling the weighed silicon-hafnium alloy powder and silicon-zirconium alloy powder for 24 hours to obtain the silicon-hafnium-silicon-zirconium alloy powder. When the silicon-hafnium alloy powder and the silicon-zirconium alloy powder are weighed, the mass ratio of the silicon-hafnium alloy powder to the silicon-zirconium alloy powder is 1.8: 1.

5. Vacuum pressure impregnation B₄C, slurry: placing the C/C composite material preform in a vacuum pressure impregnation tank, vacuumizing to-0.096 Mpa, maintaining for 30min, and opening a slurry impregnation valve at the bottom of the tank body to enable the B to be immersed₄C, reversely sucking the slurry into the tank body, completely immersing the prefabricated body, closing the immersion valve, continuously keeping the vacuum degree of-0.096 Mpa, maintaining for 30min, and closing a vacuum system valve and a vacuum pump; opening the high pressure valve and charging the impregnation tank with compressed N₂Maintaining the pressure in the tank body at 0.9MPa for 30min to complete the process B₄C, dipping the slurry; taking out the dip B₄C, drying the sample of the slurry for later use;

6. vacuum pressure impregnation of furan resin solution: impregnating B prepared in step 5₄Placing the C/C composite material preform of C in a vacuum pressure impregnation tank, firstly vacuumizing the vacuum pressure impregnation tank until the vacuum degree is-0.096 Mpa, keeping the vacuum degree for 30min, then opening a slurry impregnation valve at the bottom of the tank body to suck furan resin solution into the tank body and completely immerse the preform, closing the impregnation valve, then continuously keeping the vacuum degree at-0.096 Mpa, keeping the vacuum degree for 30min, and closing a vacuum system valve and a vacuum pump; opening the high pressure valve and charging the impregnation tank with compressed N₂Maintaining the pressure in the tank body to 0.9Mpa for 30min to finish the impregnation of the furan resin solution;

7. curing and cracking: placing the preform subjected to the impregnation in the step 6 in an oven at 80 DEG CDrying, curing at 200 deg.C for 1h, and heat treating at 900 deg.C under argon protection for 2h to obtain C/B₄A C-C composite material;

8、C/(Hf,Zr)C-(Hf,Zr)B₂-preparation of SiC composite: embedding the material processed in the step 7 into silicon hafnium-silicon zirconium alloy powder, and infiltrating the silicon hafnium-silicon zirconium alloy powder into the C/B obtained in the step 7 in a vacuum environment at the temperature of 1700-1800 DEG C₄In the C-C composite material, heat preservation is carried out for 2 hours, and alloy melt and B are mixed₄In-situ generation of HfC-ZrC-HfB by C-C reaction₂-ZrB₂-SiC multicomponent ablation-resistant matrix, in which HfC and ZrC constitute a (Hf, Zr) C solid solution, HfB₂And ZrB₂Composition (Hf, Zr) B₂Obtaining C/(Hf, Zr) C- (Hf, Zr) B through solid solution₂-SiC ultra high temperature ceramic matrix composite.

C/(Hf, Zr) C- (Hf, Zr) B prepared in example 3₂The content of carbon fiber in the-SiC superhigh temperature ceramic matrix composite material is about 40 vol%, and the apparent density is 2.84g/cm³The open porosity was about 7% and the bending strength was 231 MPa.

FIG. 1 shows C/(Hf, Zr) C- (Hf, Zr) B prepared by the present invention₂The X-ray diffraction pattern of the-SiC superhigh temperature ceramic matrix composite material shows that HfC and ZrC have the same diffraction peak and HfB has the same diffraction peak as shown in figure 1₂、ZrB₂The diffraction peaks are the same, the intensity of the diffraction peaks is high and sharp, and solid solutions of (Hf, Zr) C and (Hf, Zr) B are formed in the material₂In addition, the high-intensity sharp beta-SiC diffraction peak is also present, which shows that (Hf, Zr) C solid solution and (Hf, Zr) B in the material₂The solid solution and SiC have good crystallinity; the material also contains HfSi₂、ZrSi₂The alloy has the same diffraction peak, namely (Hf, Zr) Si is formed₂Solid solution. As can be seen from FIG. 1, there are several ablation-resistant components in the material, (Hf, Zr) C, (Hf, Zr) B₂SiC and (Hf, Zr) Si₂The borosilicate glass protective layer can be formed by oxidation in the ablation process, absorbs heat and covers the surface of the material to prevent the material from being further damaged;

FIG. 2 shows C/(Hf, Zr) C- (Hf, Zr) B prepared by the present invention₂And (3) scanning electron microscope photos of the section of the-SiC ultrahigh-temperature ceramic matrix composite, wherein a black area in the photos is a fiber bundle, and a white area is an ultrahigh-temperature ceramic phase. Ultra-high temperature ceramicThe phases are distributed among the fiber bundles in a large quantity and are compact, and the whole material has high compactness;

FIG. 3 and FIG. 4 show C/(Hf, Zr) C- (Hf, Zr) B prepared by the present invention₂Back scattering electron pictures of medium and high power in section of-SiC ultrahigh temperature ceramic matrix composite, wherein bright white areas in the pictures are (Hf, Zr) C solid solution phases, and dark white areas are (Hf, Zr) B₂Phase, dark gray areas as SiC phase, black areas as fiber bundles, (Hf, Zr) B in FIG. 4₂And is in dispersion distribution with SiC. A large amount of (Hf, Zr) C and (Hf, Zr) B are distributed in the material₂The volume content of the anti-ablation component is high.