Method for preparing 2.5 D woven Cf / ZrB2-ZrC-SiC composite material with assistance of multistage ceramic skeleton

Abstract

The invention discloses a method for preparing a 2.5 D woven Cf / ZrB2-ZrC-SiC composite material under the assistance of a multistage ceramic skeleton, and relates to the technical field of ceramic matrix composite material preparation. The method comprises the following steps: introducing ZrB2 particle-phenolic resin with different particle fractions into a low-density Cf / PyC composite material by adopting an ultrasonic-assisted slurry impregnation process, then constructing a multi-stage carbon-rich ZrB2-SiC ceramic skeleton in the composite material by adopting a precursor impregnation cracking method, and finally obtaining the 2.5 D woven Cf / ZrB2-ZrC-SiC composite material by adopting an RMI permeation Zr-Si alloy densification process. According to the method, millimeter-scale large-size pores in the carbon fiber preform can be segmented, grain refinement of an in-situ generated ceramic phase is achieved, residues of local large-size pores of a matrix are avoided, and thermal stress concentration in the matrix is relieved. The method has a good application prospect for improving the service stability of the composite material in an extremely severe environment.

Description

Technical Field

[0001] This invention belongs to the field of ceramic matrix composite material preparation technology, specifically relating to a multi-level ceramic skeleton-assisted preparation of 2.5D woven C f Methods for creating ZrB2-ZrC-SiC composite materials. Background Technology

[0002] The rapid development of high-speed aircraft has placed higher demands on the thermo-mechanical load-bearing capacity of thermal structural materials. Developing ceramic matrix composites with lightweight, high strength and toughness, high temperature resistance, and excellent oxidation and ablation resistance has become a key research direction in the aerospace field. Ultra-high temperature ceramics (UHTCs) are a series of high-temperature resistant materials represented by transition metal borides, carbides, and nitrides, such as ZrC, HfC, TaC, ZrB2, and HfB2. UHTCs generally have melting points above 3000℃ and possess excellent oxidation resistance and high-temperature ablation resistance, showing broad application prospects under extreme high-temperature conditions. Among them, ZrB2 (melting point 3245℃) and ZrC (melting point 3540℃) have high hardness, strong erosion resistance, and excellent chemical stability. In particular, combining them with SiC can further improve their high-temperature oxidation resistance. Studies have shown that ZrB2-ZrC-SiC has good resistance to ablation / oxidation over a wide temperature range, but the inherent brittleness of multiphase ceramics severely limits its application in aerospace.

[0003] 2.5D woven carbon fiber preforms, with their interlocking warp and weft yarn weave structure, are a high-strength carbon fiber reinforcement. This structure exhibits good strength and toughness, excellent interlaminar properties, and allows for integral net molding, leading to its expanding application in aerospace hot-end components. Therefore, combining 2.5D woven carbon fiber preforms with ZrB2-ZrC-SiC can yield ceramic matrix composites with excellent strength, toughness, and ablation resistance.

[0004] Currently, commonly used methods for preparing ceramic matrix composites include chemical vapor infiltration, precursor impregnation and pyrolysis, slurry impregnation, and reactive infiltration. Among these, reactive infiltration involves the alloy melt being driven by capillary force to infiltrate the composite material at high temperatures and react with the carbon matrix to form a ceramic phase. Compared to the previous processes, reactive infiltration has advantages such as short preparation cycle, high density, and the ability to achieve near-net-shape molding, making it an effective method for preparing complex-shaped components. However, 2.5D woven structures suffer from uneven pore distribution due to their unique yarn orientation, particularly the presence of micron-sized intra-fiber bundle pores and millimeter-sized inter-fiber bundle pores. During reactive infiltration, uneven melt infiltration can easily be induced, leading to the formation of localized "molten pools" due to incomplete reaction. This results in residual metal remaining in the composite material, affecting its high-temperature mechanical properties and reliability, or causing severe fiber damage due to excessive infiltration of the molten phase into the fiber bundle pores. Therefore, the pore structure of the preform is crucial for regulating melt infiltration behavior and chemical reaction processes. Currently, there is limited research on the regulation of the pore structure of 2.5D woven preforms, and it is still in the exploratory stage.

[0005] Chinese patent publication number CN120518403A discloses a 2.5D woven ceramic matrix composite material based on C / C composite material and its preparation method. This method uses a 2.5D woven carbon fiber preform as a reinforcement, introduces C / C waste into a low-density 2.5D woven composite material, and obtains a dense C / C-ZrC-SiC composite material after reactive melting, which can reduce the residual metal content in the composite material. However, the ceramic matrix obtained by this method has coarse grains that are difficult to control, and is prone to defects such as cracks in the matrix due to excessive local stress during the preparation process.

[0006] Reference 1, "Zhuang L, Fu QG, Liu TY, Ablation resistance of wedge-shaped C / C-ZrB2-ZrC-SiC composites exposed to an oxyacetylene torch, Corrosion Science, 2016;112:462-470," describes the preparation of C / C-ZrB2-ZrC-SiC composites using a precursor impregnation-pyrolysis method. This method introduces ZrC-SiC and ZrB2 precursors into low-density C / C composites, and obtains the C / C-ZrB2-ZrC-SiC composites through multiple impregnation-pyrolysis processes. The final density and porosity are 2.1 g / cm³. 3 And 10%. This method is simple, but it has low filling efficiency for large pores at the millimeter level and a long preparation cycle.

[0007] Document 2 "Chen X, Feng Q, Kan Y, et al., Effects of preform porestructure on infiltration kinetics and microstructure evolution of RMI-derived C f "ZrC-ZrB2-SiC composite, Journal of the European Ceramic Society, 2020;40(7):2683-2690." A porous B4C-C intermediate was introduced into the needle-punched carbon fiber preform using the sol-gel method, and C was obtained after ZrSi2 melt infiltration. f The SiC-ZrC-ZrB2 composite material exhibits a more uniform ceramic phase distribution and superior mechanical properties. However, this method is complex and has a narrow range for pore structure adjustment. Furthermore, large-sized pores are easily formed in the porous preform due to incomplete matrix filling. After reactive infiltration (RMI), there are localized residual metals and uneven distribution of the ceramic phase. Summary of the Invention

[0008] To overcome the shortcomings of the prior art, the present invention aims to provide a multi-level ceramic skeleton-assisted preparation method for 2.5D woven C f The method for using ZrB2-ZrC-SiC composite materials aims to solve the technical problems in the prior art, such as the difficulty in controlling the large-sized pores of 2.5D woven preforms and the excessively large grain size of the ceramic phase generated by reaction melting.

[0009] To achieve the above objectives, the present invention employs the following technical solution: In a first aspect, the present invention provides a multi-level ceramic skeleton-assisted preparation method for 2.5D woven C f The method for producing ZrB2-ZrC-SiC composite materials includes the following steps: S1, ZrB2 particles of different grades, phenolic resin, C / C waste scrap and anhydrous ethanol are mixed and stirred to obtain ZrB2-resin mixed solution; S2, using chemical vapor infiltration to deposit a pyrolytic carbon interface layer in a 2.5D woven carbon fiber preform, yields a low-density 2.5D woven carbon fiber. f / PyC composite material; S3: Low-density 2.5D woven C f The PyC composite material was placed in a ZrB2-resin mixture, ultrasonically impregnated, dried, and then subjected to high-temperature heat treatment to obtain porous 2.5D woven PyC. f / ZrB2-C composite material; S4: High-temperature heat-treated porous 2.5D woven C f / ZrB2-C composite material was immersed in a polycarbosilane solution, followed by vacuum impregnation-drying and heat treatment to obtain porous C f / ZrB2-SiC-C composite material; S5: Heat-treated porous C f After reactive melt infiltration, 2.5D woven C2B2-SiC-C composite material was obtained. f / ZrB2-ZrC-SiC composite material.

[0010] A further improvement of the present invention is that, in S1, the particle sizes of ZrB2 particles with different gradations are 10~20μm, 1~3μm, and 50~100nm, respectively, and their mass ratio is 1~1.5:1~3:1~3.

[0011] A further improvement of the present invention is that, in S1, the mixing mass ratio of ZrB2 particles, phenolic resin, C / C waste fragments and anhydrous ethanol is 4.5~5:0.5:0.5:10, and the size of the C / C waste fragments is less than 100μm.

[0012] A further improvement of this invention is that, in step S2, the 2.5D woven carbon fiber preform is a 2.5D layer-to-layer interlocking woven preform with a shallow cross-linked structure, having 2 warp yarns, 4 weft yarns, a weft density of 3.3 yarns / cm, a warp density of 12 yarns / cm, and a density of 0.7~0.9 g / cm³. 3 The volume fraction is 40%~50%.

[0013] A further improvement of the present invention is that, in S2, the low-density 2.5D woven C f The density of the PyC composite material is 1.2~1.6 g / cm³. 3 In step S3, the ultrasonic impregnation time is 20-40 min; the drying temperature is 145-155℃, the drying time is 6-8 h, the heat treatment temperature is 1500-1600℃, and the heat treatment time is 2-3 h.

[0014] A further improvement of the present invention is that, in step S4, the mass ratio of polycarbosilane to xylene solvent in the polycarbosilane solution is 1:1~2, the vacuum degree during vacuum impregnation is 0.5~1kPa, the impregnation time is 30~60min, the drying temperature is 80~120℃, the drying time is 24~48h, the heat treatment temperature is 1100~1300℃, and the heat treatment time is 2~3h.

[0015] A further improvement of the present invention is that the ultrasonic impregnation and drying process in S3 and the heat treatment process after vacuum impregnation-drying in S4 are repeated 1 to 3 times.

[0016] A further improvement of the present invention is that, in S5, the raw material for reactive melting and infiltration is a Zr-Si alloy.

[0017] A further improvement of the present invention is that, in step S5, the reaction melting temperature is 1650~1900℃, the vacuum degree is 0.01~0.3Pa, and the holding time is 0.5~2h.

[0018] Secondly, the present invention also provides a 2.5D woven C f The ZrB2-ZrC-SiC composite material comprises a multi-component ceramic matrix and a 2.5D woven carbon fiber preform; wherein the multi-component ceramic matrix includes ZrB2-SiC introduced by ultrasonic impregnation and precursor impregnation pyrolysis, as well as ZrC and SiC phases generated by in-situ reaction; the 2.5D woven carbon fiber preform... f The density of the ZrB2-ZrC-SiC composite material is 2.51~2.66 g / cm³. 3 The porosity is 8.16~10.00%, and the average grain size of ZrC grains is 3~8μm.

[0019] Compared with the prior art, the present invention has the following beneficial effects: This invention provides a multi-level ceramic skeleton-assisted preparation of 2.5D woven C f The method for constructing ZrB2-ZrC-SiC composite materials involves building a multi-level ceramic framework to adjust the pore structure of the preform, thereby achieving synergistic control over the melt penetration path, penetration rate, and interfacial chemical reaction kinetics during the melting and infiltration process. On the one hand, the multi-level pore structure of the framework provides penetration channels for the melt, while the steric hindrance effect provided by the heterogeneous interface restricts the local aggregation of the melt. On the other hand, the interfacial constraint between the framework and the melt regulates the formation range of the reaction interface and the product precipitation rate, inhibiting abnormal grain growth during the melting and infiltration-reaction process, and ultimately achieving fine grain refinement of the matrix, resulting in a composite material with excellent comprehensive mechanical properties and high-temperature stability.

[0020] Furthermore, through gradation design, the method of "coarse particles building the skeleton and fine particles filling some gaps" can be used. By adding smaller particles to fill the gaps between larger particles, the space occupancy of the particles is increased, making the particles densely packed. For slurry systems, particle gradation can increase the solid content of the slurry and help improve the density of the skeleton.

[0021] Furthermore, introducing C / C waste scraps as a carbon source to achieve the recycling of industrial waste is beneficial for reducing costs, protecting the environment, and promoting green and sustainable development.

[0022] Furthermore, this invention introduces ZrB2 particles with particle size distribution combined with highly active nano-SiC introduced through precursor impregnation and pyrolysis. Low-temperature sintering can improve the strength of the porous framework, and the porous ceramic can still maintain its framework structure during reactive infiltration (RMI). This framework structure is adjustable in size, which can meet the application requirements of different pore sizes, different melt characteristics, and different preform structures.

[0023] The present invention also provides a 2.5D woven C f The ZrB2-ZrC-SiC composite material has a density of 2.51~2.66 g / cm³. 3 The porosity is 8.16%~10.00%, and the size of the ZrC grains generated by the reaction is reduced to below 5μm. Compared with 2.5D woven composites without a multi-level ceramic framework, the density is increased by 29.76%, and the porosity is reduced by 52.28%. Under the action of capillary force, the melt penetrates into the ceramic framework and reacts in situ to generate a micro-nano ceramic matrix. The ceramic phase is evenly distributed and the grains are refined, which helps to simultaneously improve mechanical and ablation resistance properties. Attached Figure Description

[0024] The accompanying drawings described herein are for illustrative purposes only and are not intended to limit the scope of the invention in any way. Furthermore, the shapes and proportions of the components in the drawings are merely illustrative to aid in understanding the invention and do not specifically limit the shapes and proportions of the components of the invention.

[0025] Figure 1 To assist in the preparation of 2.5D woven C for the multi-level ceramic skeleton of this invention f Flowchart of the method for producing ZrB2-ZrC-SiC composite materials; Figure 2 SEM images of the composite material after introducing ZrB2 particles of different sizes in Example 3; where (a) is a low-magnification SEM image and (b) is a high-magnification SEM image. Figure 3 SEM images of the composite material after introducing a carbon-rich multi-level ZrB2-SiC ceramic skeleton in Example 2; where (a) is a low-magnification SEM image, and (b)-(c) are high-magnification SEM images; Figure 4 2.5D woven C was prepared for Example 4. f SEM images and EDS spectra of the cross section of the ZrB2-ZrC-SiC composite material; where (a) is a low-magnification SEM image, (b) is a high-magnification SEM image, and (c)-(f) are EDS spectra of points 1-4. Figure 5 2.5D woven C was prepared for Examples 1-4. fSEM images of the cross section of the ZrB2-ZrC-SiC composite material and ZrC particle size distribution diagram; where (a)-(c) are Example 1, (d)-(f) are Example 2, (g)-(i) are Example 3, and (j)-(l) are Example 4; Figure 6 2.5D woven porous C was prepared for Example 4. f / ZrB2-SiC-C and C f X-ray diffraction pattern of ZrB2-ZrC-SiC composite material; Figure 7 C prepared for Comparative Example 1 f SEM image of the cross section of the ZrC-SiC composite material. Detailed Implementation

[0026] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0027] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0028] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0029] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”

[0030] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0031] To achieve 2.5D woven C fThe efficient preparation of ZrB2-ZrC-SiC composites hinges on the precise control of the porous structure. It is crucial to avoid both excessive ZrB2-SiC ceramic introduction hindering Zr-Si alloy infiltration and resulting in numerous closed pores within the matrix, and excessive infiltration of molten Zr-Si alloy leading to incomplete reaction, excessive residual alloy, and severe fiber damage. Therefore, the construction of a multi-level ceramic framework and the control of its pore structure are essential for achieving the reactive infiltration preparation of dense 2.5D woven CSiC composites. f The key breakthroughs needed for / ZrB2-ZrC-SiC composite materials.

[0032] like Figure 1 As shown, this invention provides a multi-level ceramic skeleton-assisted preparation of 2.5D woven C f The method for producing ZrB2-ZrC-SiC composite materials includes the following steps: S1, ZrB2 particles of different grades, phenolic resin, C / C waste scrap and anhydrous ethanol are mixed and stirred to obtain ZrB2-resin mixed solution; S2, using chemical vapor infiltration to deposit a pyrolytic carbon interface layer in a 2.5D woven carbon fiber preform, yields a low-density 2.5D woven carbon fiber. f / PyC composite material; S3: Low-density 2.5D woven C f The PyC composite material was placed in a ZrB2-resin mixture, ultrasonically impregnated, dried, and then subjected to high-temperature heat treatment to obtain porous 2.5D woven PyC. f / ZrB2-C composite material; S4: High-temperature heat-treated porous 2.5D woven C f / ZrB2-C composite material was immersed in a polycarbosilane solution, followed by vacuum impregnation-drying and heat treatment to obtain porous C f / ZrB2-SiC-C composite material; S5: Heat-treated porous C f After reactive melt infiltration, 2.5D woven C2B2-SiC-C composite material was obtained. f / ZrB2-ZrC-SiC composite material.

[0033] The method of this invention first prepares a low-density C / PyC composite material by depositing a PyC interface on the surface of a 2.5D woven carbon fiber preform. Then, using an ultrasonic-assisted slurry impregnation process, ZrB2 particles of different sizes and C / C waste are selected to prepare a ZrB2-phenolic resin solution. This solution is then impregnated and dried to introduce a carbon-rich ZrB2 intermediate into the low-density C / C composite material. Next, nano-SiC is introduced into the interstices of the ZrB2 particles using a precursor impregnation pyrolysis method, thereby constructing a multi-level carbon-rich ZrB2-SiC ceramic framework within the low-density C / C composite material. Finally, a reactive infiltration process is used, where the Zr-Si alloy infiltrates into the multi-level ceramic framework under capillary force, resulting in in-situ reactive densification to obtain a 2.5D woven carbon fiber preform. f / ZrB2-ZrC-SiC composite material.

[0034] In some embodiments, in S1, the particle sizes of ZrB2 particles with different gradations are 10~20μm, 1~3μm, and 50~100nm, respectively, and their mass ratio is 1~1.5:1~3:1~3.

[0035] In some embodiments, in S1, the mixing mass ratio of ZrB2 particles, phenolic resin, C / C waste chips and anhydrous ethanol is 4.5~5:0.5:0.5:10; phenolic resin serves as a dispersant and carbon source, C / C waste chips can serve as a carbon source, and the C / C waste chips contain carbon fibers and PyC particles, with the waste chips having a size of less than 100μm.

[0036] In some embodiments, in step S2, the 2.5D woven carbon fiber preform is a 2.5D layer-to-layer interlocking woven preform with a shallow cross-linked structure, having 2 warp yarns, 4 weft yarns, a weft density of 3.3 yarns / cm, a warp density of 12 yarns / cm, and a density of 0.7~0.9 g / cm³. 3 The volume fraction is 40%~50%.

[0037] In some embodiments, in S2, low-density 2.5D woven C f The density of the PyC composite material is 1.2~1.6 g / cm³. 3 In step S3, the ultrasonic impregnation time is 20-40 min; the drying temperature is 145-155℃, the drying time is 6-8 h; the heat treatment temperature is 1500-1600℃, and the holding time is 2-3 h. The ultrasonic impregnation and drying process in step S3 is repeated 1-3 times, and the sample weight gain is 16.30%-80.92%.

[0038] In some embodiments, in step S4, the mass ratio of polycarbosilane to xylene solvent in the polycarbosilane solution is 1:1~2; the vacuum degree during vacuum impregnation is 0.5~1 kPa; the impregnation time is 30~60 min; the drying temperature is 80~120℃; the drying time is 24~48 h; the heat treatment temperature is 1100~1300℃; and the holding time is 2~3 h. The vacuum impregnation-drying followed by heat treatment process in step S4 is repeated 1~3 times, resulting in a sample weight gain of 3.13%~5.99%.

[0039] In some embodiments, in step S5, the raw material for reactive infiltration is a Zr-Si alloy with a Zr to Si atomic ratio of 1:2, a purity of 99.5%, and a particle size of 1~3μm.

[0040] In some embodiments, in S5, the porous C obtained in S4 is... f After cleaning and drying, the ZrB2-SiC-C composite material was placed in a graphite crucible, covered with Zr-Si alloy powder, and subjected to high-temperature reaction melting and infiltration under vacuum to obtain 2.5D woven C. f / ZrB2-ZrC-SiC composite material; the reaction melting temperature is 1650~1900℃, the vacuum degree is 0.01~0.3Pa, and the holding time is 0.5~2h.

[0041] The 2.5D woven C fabric prepared by the above method in this invention f The ZrB2-ZrC-SiC composite material possesses advantages such as high ceramic phase content, uniform distribution, and fine grain size. The aforementioned method introduces a multi-level carbon-rich ZrB2-SiC framework into the millimeter-scale pores of a 2.5D woven preform. During the reaction infiltration process, the melt, under the action of capillary force, enters the framework and reacts with carbon in situ to form ceramics. The ceramic phase has fine, dense, and uniform grains, which can reduce thermal stress concentration and improve its mechanical and ablation resistance properties.

[0042] The present invention also provides a 2.5D woven C material prepared by the above-described method. f / ZrB2-ZrC-SiC composite material, the 2.5D woven C f The ZrB2-ZrC-SiC composite material incorporates particle-graded ZrB2, nano-sized SiC, and micron-sized C / C waste materials through ultrasonic-assisted slurry impregnation combined with precursor impregnation and pyrolysis. This is achieved in a low-density 2.5D woven C... f The PyC composite material forms a multi-level ZrB2-SiC ceramic framework, which is then reacted in situ to generate a ZrB2-ZrC-SiC ceramic matrix, consisting of a multi-component ceramic matrix and a 2.5D woven carbon fiber preform; the 2.5D woven carbon fiber preform... f The density of the ZrB2-ZrC-SiC composite material is 2.51~2.66 g / cm³.3 The porosity is 8.16%~10.00%, and the average particle size of the ZrC generated in the reaction is 3~8μm.

[0043] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0044] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.

[0045] Example 1 This embodiment provides a multi-level ceramic skeleton-assisted preparation of 2.5D woven C f The method for producing ZrB2-ZrC-SiC composite materials includes the following steps: Step 1: Preparation of ZrB2-resin solution Phenolic resin was dissolved in anhydrous ethanol. ZrB2 particles and C / C waste fragments of different grades were added to the phenolic solution, and the suspension was stirred for 2 hours to obtain a mixed solution. The particle sizes of ZrB2 particles were 10 μm, 1 μm, and 50 nm, and their mass ratio was 1:3:1. The size of C / C waste fragments was less than 100 μm. The mass ratio of ZrB2 particles, phenolic resin, C / C waste fragments and anhydrous ethanol was 5:0.5:0.5:10.

[0046] Step 2: Low-density 2.5D woven C f Preparation of PyC composite materials The 2.5D woven carbon fiber preform used is a shallowly cross-linked 2.5D layer-to-layer angle interlocking woven preform with 2 warp plies, 4 weft plies, a weft density of 3.3 ends / cm, a warp density of 12 ends / cm, and a density of 0.8 g / cm³. 3 The volume fraction was 45.8%; a PyC interface layer was deposited in the carbon fiber preform using a chemical vapor infiltration process, resulting in a low density of 1.34 g / cm³. 3 2.5D woven C / PyC composite material.

[0047] Step 3: Ultrasonic-assisted slurry impregnation and drying The low-density 2.5D woven C / PyC composite material obtained in step 2 was immersed in the mixed solution obtained in step 1 and ultrasonically impregnated in an ultrasonic instrument for 30 min; then dried in an oven at 150℃ for 7 h, and this step was repeated 3 times to obtain a composite material with a weight gain of 80.92%.

[0048] Step 4: High-temperature heat treatment The composite material obtained in step 3 was subjected to high-temperature heat treatment. Under an argon protective atmosphere, the temperature was increased to 1600℃ at a rate of 5℃ / min and held for 2 hours to cause resin pyrolysis and ZrB2 sintering, resulting in porous 2.5D woven C. f / ZrB2-C composite material.

[0049] Step 5: Precursor impregnation and pyrolysis A precursor solution was prepared by mixing polycarbosilane and xylene in a 1:1 ratio. The porous 2.5D woven C obtained in step 4 was then used in this solution. f The ZrB2-C composite material was immersed in a precursor solution and placed in a vacuum chamber at a vacuum level of 1 kPa for 30 min. It was then removed and dried in an oven at 120℃ for 24 h. Under argon protection, the temperature was increased to 1300℃ at a rate of 3℃ / min and held for 2 h to convert polycarbosilane into SiC. This impregnation-drying-heat treatment process was repeated three times to obtain porous C with a weight gain of 3.13%. f / ZrB2-SiC-C composite material.

[0050] Step 6: Reactive Melting The porous C obtained in step 5 f After cleaning and drying, the ZrB2-SiC-C composite material was placed in a graphite crucible, and Zr-Si alloy powder (Zr:Si atomic ratio of 1:2, purity of 99.5%, particle size of 1μm) was placed around it. Reaction melting and infiltration were then carried out under vacuum at a heating rate of 10℃ / min, reaching 1800℃ under a vacuum of 0.2Pa for 2 hours. Afterwards, the temperature was lowered by disconnecting the power, resulting in a density of 2.51 g / cm³. 3 2.5D woven C with a porosity of 10.00% f The ZrB2-ZrC-SiC composite material has an average ZrC particle size of 7.87 μm.

[0051] Example 2 This embodiment provides a multi-level ceramic skeleton-assisted preparation of 2.5D woven C f The method for producing ZrB2-ZrC-SiC composite materials includes the following steps: Step 1: Preparation of ZrB2-resin solution Phenolic resin was dissolved in anhydrous ethanol. ZrB2 particles of different grades and C / C waste fragments were added to the phenolic solution, and the suspension was stirred for 2 hours to obtain a mixed solution. The ZrB2 particles had diameters of 15 μm, 2 μm, and 75 nm, with a mass ratio of 1:1:3. The C / C waste fragments had a size less than 100 μm. The mass ratio of ZrB2 particles, phenolic resin, C / C waste fragments, and anhydrous ethanol was 4.5:0.5:0.5:10.

[0052] Step 2: Low-density 2.5D woven C f Preparation of PyC composite materials The 2.5D woven carbon fiber preform used is a shallowly cross-linked 2.5D layer-to-layer angle interlocking woven preform with 2 warp plies, 4 weft plies, a weft density of 3.3 ends / cm, a warp density of 12 ends / cm, and a density of 0.8 g / cm³. 3 The volume fraction was 45.8%. A PyC interface layer was deposited in the carbon fiber preform using a chemical vapor infiltration process, resulting in a low density of 1.34 g / cm³. 3 2.5D woven C / PyC composite material.

[0053] Step 3: Ultrasonic-assisted slurry impregnation and drying The low-density 2.5D woven C / PyC composite material obtained in step 2 was immersed in the mixed solution obtained in step 1 and ultrasonically impregnated in an ultrasonic instrument for 20 min; then dried in an oven at 145℃ for 8 h, and this step was repeated 3 times to obtain a composite material with a weight gain of 47.13%.

[0054] Step 4: High-temperature heat treatment The composite material obtained in step 3 was subjected to high-temperature heat treatment. Under an argon protective atmosphere, the temperature was increased to 1500℃ at a rate of 5℃ / min and held for 3 hours to cause resin pyrolysis and ZrB2 sintering, resulting in porous 2.5D woven C. f / ZrB2-C composite material.

[0055] Step 5: Precursor impregnation and pyrolysis A precursor solution was prepared by mixing polycarbosilane and xylene in a 1:1 ratio. The porous 2.5D woven C obtained in step 4 was then used in this solution. f The ZrB2-C composite material was immersed in a precursor solution and placed in a vacuum chamber at a vacuum level of 0.5 kPa for 60 min. It was then removed and dried in an oven at 80 °C for 48 h. Under argon protection, the temperature was increased to 1100 °C at a rate of 3 °C / min and held for 3 h to convert polycarbosilane into SiC. This impregnation-drying-heat treatment process was repeated three times to obtain porous C with a weight gain of 4.44%. f / ZrB2-SiC-C composite material.

[0056] Step 6: Reactive Melting The porous C obtained in step 5 f After cleaning and drying, the ZrB2-SiC-C composite material was placed in a graphite crucible, surrounded by Zr-Si alloy powder (Zr:Si atomic ratio of 1:2, purity of 99.5%, particle size of 2μm). Reaction melting and infiltration were carried out under vacuum at a heating rate of 10℃ / min, reaching 1650℃ under a vacuum of 0.3Pa for 0.5h. The mixture was then cooled to obtain a density of 2.60 g / cm³. 3 2.5D woven C with a porosity of 9.68% f The ZrB2-ZrC-SiC composite material has an average ZrC particle size of 3.81 μm.

[0057] Example 3 A multi-level ceramic skeleton-assisted preparation of 2.5D woven C f The method for producing ZrB2-ZrC-SiC composite materials includes the following steps: Step 1: Preparation of ZrB2-resin solution Phenolic resin was dissolved in anhydrous ethanol. ZrB2 particles of different grades and C / C waste fragments were added to the phenolic solution, and the suspension was stirred for 2 hours to obtain a mixed solution. The ZrB2 particles had particle sizes of 20 μm, 3 μm, and 100 nm, with a mass ratio of 1:2:2. The C / C waste fragments had a size of less than 100 μm. The mass ratio of ZrB2 particles, phenolic resin, C / C waste fragments, and anhydrous ethanol was 4.7:0.5:0.5:10.

[0058] Step 2: Low-density 2.5D woven C f Preparation of PyC composite materials The 2.5D woven carbon fiber preform used is a shallowly cross-linked 2.5D layer-to-layer angle interlocking woven preform with 2 warp plies, 4 weft plies, a weft density of 3.3 ends / cm, a warp density of 12 ends / cm, and a density of 0.8 g / cm³. 3 The volume fraction was 45.8%. A PyC interface layer was deposited in the carbon fiber preform using a chemical vapor infiltration process, resulting in a low density of 1.34 g / cm³. 3 2.5D woven C / PyC composite material.

[0059] Step 3: Ultrasonic-assisted slurry impregnation and drying The low-density 2.5D woven C / PyC composite material obtained in step 2 was immersed in the mixed solution obtained in step 1 and ultrasonically impregnated in an ultrasonic instrument for 40 min; then dried in an oven at 155℃ for 6 h, and this step was repeated 3 times to obtain a composite material with a weight gain of 16.30%.

[0060] Step 4: High-temperature heat treatment The composite material obtained in step 3 was subjected to high-temperature heat treatment. Under an argon protective atmosphere, the temperature was increased to 1550℃ at a rate of 5℃ / min and held for 2.5h to cause resin pyrolysis and ZrB2 sintering, resulting in porous 2.5D woven C f / ZrB2-C composite material.

[0061] Step 5: Precursor impregnation and pyrolysis A precursor solution was prepared by mixing polycarbosilane and xylene in a 1:1 ratio. The porous 2.5D woven C obtained in step 4 was then used in this solution. f The ZrB2-C composite material was immersed in a precursor solution and placed in a vacuum chamber at a vacuum level of 1 kPa for 45 min. It was then removed and dried in a 100℃ oven for 32 h. Under argon protection, the temperature was increased to 1200℃ at a rate of 3℃ / min and held for 2.5 h to convert polycarbosilane into SiC. This impregnation-drying-heat treatment process was repeated three times to obtain porous C with a weight gain of 3.42%. f / ZrB2-SiC-C composite material.

[0062] Step 6: Reactive Melting The porous C obtained in step 5 f After cleaning and drying, the ZrB2-SiC-C composite material was placed in a graphite crucible and surrounded by Zr-Si alloy powder (Zr:Si atomic ratio of 1:2, purity of 99.5%, particle size of 3μm). Reaction melting and infiltration were carried out under vacuum at a heating rate of 10℃ / min, reaching 1900℃ under a vacuum of 0.01 Pa for 2 hours. Afterward, the temperature was lowered by removing the power, resulting in a density of 2.66 g / cm³. 3 2.5D woven C with a porosity of 8.16% f The ZrB2-ZrC-SiC composite material has an average ZrC particle size of 4.39 μm.

[0063] Example 4 A multi-level ceramic skeleton-assisted preparation of 2.5D woven C f The method for producing ZrB2-ZrC-SiC composite materials includes the following steps: Step 1: Preparation of ZrB2-resin solution Phenolic resin was dissolved in anhydrous ethanol. ZrB2 particles and C / C waste fragments of different grades were added to the phenolic solution, and the suspension was stirred for 2 hours to obtain a mixed solution. The ZrB2 particles had particle sizes of 15 μm, 2 μm, and 75 nm, with a mass ratio of 1.5:1.5:1.5. The C / C waste fragments had a size of less than 100 μm. The mass ratio of ZrB2 particles, phenolic resin, C / C waste fragments, and anhydrous ethanol was 4.5:0.5:0.5:10.

[0064] Step 2: Low-density 2.5D woven C f Preparation of PyC composite materials The 2.5D woven carbon fiber preform used is a shallowly cross-linked 2.5D layer-to-layer angle interlocking woven preform with 2 warp plies, 4 weft plies, a weft density of 3.3 ends / cm, a warp density of 12 ends / cm, and a density of 0.8 g / cm³. 3 The volume fraction was 45.8%. A PyC interface layer was deposited in the carbon fiber preform using a chemical vapor infiltration process, resulting in a low density of 1.34 g / cm³. 3 2.5D woven C / PyC composite material.

[0065] Step 3: Ultrasonic-assisted slurry impregnation and drying The low-density 2.5D woven C / PyC composite material obtained in step 2 was immersed in the mixed solution obtained in step 1 and ultrasonically impregnated in an ultrasonic instrument for 30 min; then dried in an oven at 150℃ for 7 h, and this step was repeated 3 times to obtain a composite material with a weight gain of 29.82%.

[0066] Step 4: High-temperature heat treatment The composite material obtained in step 3 was subjected to high-temperature heat treatment. Under an argon protective atmosphere, the temperature was increased to 1600℃ at a rate of 5℃ / min and held for 2 hours to cause resin pyrolysis and ZrB2 sintering, resulting in porous 2.5D woven C. f / ZrB2-C composite material.

[0067] Step 5: Precursor impregnation and pyrolysis A precursor solution was prepared by mixing polycarbosilane and xylene in a 1:1 ratio. The porous 2.5D woven C obtained in step 4 was then used in this solution. f The ZrB2-C composite material was immersed in a precursor solution and placed in a vacuum chamber under a vacuum of 1 kPa for 30 min. It was then removed and dried in an oven at 80℃ for 24 h. Under argon protection, the temperature was increased to 1300℃ at a rate of 3℃ / min and held for 2 h to convert polycarbosilane into SiC. This impregnation-drying-heat treatment process was repeated three times to obtain porous C with a weight gain of 5.99%. f / ZrB2-SiC-C composite material.

[0068] Step 6: Reactive Melting The porous C obtained in step 5 f After cleaning and drying, the ZrB2-SiC-C composite material was placed in a graphite crucible, and Zr-Si alloy powder (Zr:Si atomic ratio of 1:2, purity of 99.5%, particle size of 1~3μm) was placed around it. Reaction melting and infiltration were then carried out under vacuum at a heating rate of 10℃ / min, reaching 1800℃ under a vacuum of 0.2Pa for 2 hours. Afterwards, the temperature was lowered by disconnecting the power, resulting in a density of 2.63 g / cm³. 3 2.5D woven C with a porosity of 8.31% f The ZrB2-ZrC-SiC composite material has an average ZrC particle size of 5.37 μm.

[0069] Comparative Example 1 A multi-level ceramic skeleton-assisted preparation of 2.5D woven C f The method for producing ZrB2-ZrC-SiC composite materials includes the following steps: Step 1, Low-density 2.5D woven C f Preparation of PyC composite materials The 2.5D woven carbon fiber preform used is a shallowly cross-linked 2.5D layer-to-layer angle interlocking woven preform with 2 warp plies, 4 weft plies, a weft density of 3.3 ends / cm, a warp density of 12 ends / cm, and a density of 0.8 g / cm³. 3 The volume fraction was 45.8%. A PyC interface layer was deposited in the carbon fiber preform using a chemical vapor infiltration process, resulting in a low density of 1.34 g / cm³. 3 2.5D woven C / PyC composite material.

[0070] Step 2: Precursor impregnation and pyrolysis A precursor solution was prepared by mixing polycarbosilane and xylene in a 1:1 ratio. The porous 2.5D woven C obtained in step 1 was then used in this solution. f The PyC composite material was immersed in a precursor solution and placed in a vacuum chamber at a vacuum level of 1 kPa for 30 min. It was then removed and dried in an oven at 80℃ for 24 h. Under argon protection, the temperature was increased to 1300℃ at a rate of 3℃ / min and held for 2 h to convert polycarbosilane into SiC. This impregnation-drying-heat treatment process was repeated three times to obtain porous C with a weight gain of 7.21%. f / SiC composite material.

[0071] Step 3: Reactive Melting The porous C obtained in step 2 fAfter cleaning and drying, the SiC composite material was placed in a graphite crucible, and Zr-Si alloy powder (Zr:Si atomic ratio of 1:2, purity of 99.5%, particle size of 1~3μm) was placed around it. Reaction melting and infiltration were then carried out under vacuum at a heating rate of 10℃ / min, reaching 1800℃ under a vacuum of 0.2Pa for 2 hours. Afterwards, the pressure was turned off and the material was cooled to obtain a density of 2.05 g / cm³. 3 2.5D woven C with a porosity of 17.10% f / ZrC-SiC composite material.

[0072] Compared with Comparative Example 1, the density of the 2.5D woven ceramic matrix composite material prepared in Example 1 increased by 22.44% and the porosity decreased by 41.52%; the density of the 2.5D woven ceramic matrix composite material prepared in Example 2 increased by 26.83% and the porosity decreased by 43.39%; the density of the 2.5D woven ceramic matrix composite material prepared in Example 3 increased by 29.76% and the porosity decreased by 52.28%; and the density of the 2.5D woven ceramic matrix composite material prepared in Example 4 increased by 28.29% and the porosity decreased by 51.40%.

[0073] Figure 2 Images (a) to (b) are SEM images of the composite material after introducing ZrB2 particles of different sizes in Example 3. Figure 2 It can be seen that ZrB2 and waste materials of different particle sizes were successfully introduced into the large pores of the carbon fiber preform. Micron-sized particles build the skeleton, and nano-sized particles fill part of the voids, increasing the space occupancy of the particles, and there are pores between the particles.

[0074] Figure 3 Images (a) to (c) are SEM images of the composite material after introducing a carbon-rich hierarchical ZrB2-SiC ceramic skeleton in Example 2. Figure 3 It can be seen that the distribution of nano-SiC among ZrB2 particles of different sizes makes the interparticle bonding more compact, forming a multi-level ceramic skeleton.

[0075] Figure 4 (a) to (f) are 2.5D woven C fabrics prepared in Example 4. f Cross-sectional SEM images and EDS spectra of the ZrB2-ZrC-SiC composite material, from Figure 4 It can be seen that the ceramic skeleton reacts with the melt to form a dense ceramic matrix. The light gray particles are ZrB2, the white particles are ZrC, the black particles are SiC, and the dark gray phase is ZrSi. Figure 5 Figures (a) to (l) show the 2.5D woven C fabrics obtained in Examples 1-4. f SEM images of the cross-section of the ZrB2-ZrC-SiC composite material and ZrC particle size distribution diagram, from Figure 5It can be seen that the large pores in Examples 1-4 are all filled with dense ceramic phase, and the average particle size of ZrC particles is about 3~8μm, indicating that the introduction of multi-level ceramic skeleton successfully reduced the grain size.

[0076] Figure 6 2.5D woven porous C was prepared for Example 4. f / ZrB2-SiC-C and C f X-ray diffraction pattern of ZrB2-ZrC-SiC composite material, from Figure 6 As can be seen from this, porous C f The XRD peaks of the ZrB2-SiC-C composite material are C peak, ZrB2 peak, and SiC peak. f The XRD peaks of the ZrB2-ZrC-SiC composite material are C peak, ZrB2 peak, SiC peak, ZrC peak and a small amount of ZrSi peak, proving that a high-density 2.5D woven ceramic matrix composite material was successfully prepared.

[0077] Figure 7 C prepared for Comparative Example 1 f SEM images of cross-sections of the ZrC-SiC composite material, from Figure 7 As can be seen, composite materials obtained without a multi-level ceramic skeleton are difficult to be dense, and a large number of large-sized pores are still retained in the composite materials.

[0078] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A method of multistage ceramic skeleton assisted fabrication of 2.5D woven C f / ZrB2-ZrC-SiC composites, characterized in that, The method comprises the following steps: S1, mixing and stirring ZrB2 particles with different gradations, phenolic resin, C / C waste chips and anhydrous ethanol to obtain a ZrB2-resin mixed solution; S2, a pyrolytic carbon interphase layer is deposited in the 2.5D woven carbon fiber preform by chemical vapor infiltration to obtain a low-density 2.5D woven C f / PyC composite material; S3: low-density 2.5D woven C f / PyC composite was placed in a ZrB2-resin mixed solution, dried after ultrasonic immersion and high-temperature heat treatment, and a porous 2.5D woven C f / ZrB2-C composite was obtained. S4: Porous 2.5D woven C f / ZrB2-C composites were immersed in a polycarbosilane solution, vacuum-impregnated, dried, and heat treated to obtain porous C f / ZrB2-SiC-C composites; S5: porous C f After the reaction infiltration of the ZrB2-SiC-C composite, a 2.5D woven C f / ZrB2-ZrC-SiC composite material is obtained.

2. A multistage ceramic scaffold for assisted production of 2.5D woven C f A method for producing a ZrB2-ZrC-SiC composite material, characterized by, In the S1, the particle sizes of the ZrB2 particles with different gradations are 10-20 μm, 1-3 μm and 50-100 nm, and the mass ratio is 1-1.5:1-3:1-3.

3. A multistage ceramic scaffold for assisted fabrication of 2.5D woven C / SiC composites according to claim 1. f Method for the production of / ZrB2-ZrC-SiC composites, characterized in that, In the S1, the mixing mass ratio of the ZrB2 particles, phenolic resin, C / C waste chips and anhydrous ethanol is 4.5-5:0.5:0.5:10, and the size of the C / C waste chips is less than 100 μm.

4. A multi-level ceramic scaffold for assisted fabrication of 2.5D woven C / SiC composites according to claim 1. f Method for the production of / ZrB2-ZrC-SiC composites, characterized in that, In the S2, the 2.5D woven carbon fiber preform is a 2.5D layer-layer angle interlocking woven preform with shallow interlaced structure, the warp yarn count is 2, the weft yarn count is 4, the weft density is 3.3 roots / cm, the warp density is 12 roots / cm, and the density is 0.7~0.9g / cm 3 , and the volume fraction is 40%~50%.

5. A multistage ceramic scaffold for assisted fabrication of 2.5D woven C / SiC composites according to claim 1. f Process for the production of ZrB2-ZrC-SiC composites, characterized in that, The S2 is low-density 2.5D woven C f The density of the / PyC composite material is 1.2-1.6 g / cm 3 The S3 is that the ultrasonic immersion time is 20-40 min; the drying temperature is 145-155 DEG C, the drying time is 6-8 h, the heat treatment temperature is 1500-1600 DEG C, and the holding time is 2-3 h.

6. A multi-level ceramic scaffold for use in the assisted production of 2.5D woven C / SiC composites according to claim 1. f Process for the production of / ZrB2-ZrC-SiC composites, characterized in that, In the S4, the mass ratio of polycarbosilane to solvent dimethylbenzene in the polycarbosilane solution is 1:1-2, the vacuum degree in the vacuum impregnation process is 0.5-1 kPa, the impregnation time is 30-60 min, the drying temperature is 80-120 ℃, the drying time is 24-48 h, the heat treatment temperature is 1100-1300 ℃, and the holding time is 2-3 h.

7. A multi-level ceramic scaffold for use in the assisted production of 2.5D woven C / SiC composites according to claim 1. f A method for the production of / ZrB2-ZrC-SiC composites, characterized in that, The ultrasonic impregnation and drying process in the S3 and the vacuum impregnation-drying and heat treatment process in the S4 are repeated for 1-3 times.

8. A multi-level ceramic scaffold for use in the assisted production of 2.5D woven C / SiC composites according to claim 1. f A method for producing a ZrB2-ZrC-SiC composite material, characterized in that, In the S5, the raw material for the reaction infiltration is a Zr-Si alloy.

9. A multi-level ceramic scaffold for use in the assisted production of 2.5D woven C / SiC composites according to claim 1. f A method for the production of ZrB2-ZrC-SiC composites, characterized in that, In the S5, the reaction infiltration temperature is 1650-1900 ℃, the vacuum degree is 0.01-0.3 Pa, and the holding time is 0.5-2 h.

10. A 2.5D woven C / SiC composite material produced by the production method according to any one of claims 1 to 9. f / ZrB2-ZrC-SiC composite material, characterized by The ceramic matrix composite comprises a plurality of groups of elements and a 2.5D woven carbon fiber preform; wherein the plurality of groups of elements comprises ZrB2-SiC introduced by ultrasonic impregnation and precursor impregnation pyrolysis and ZrC and SiC phases generated in situ; the 2.5D woven C f The density of the ZrB2-ZrC-SiC composite material is 2.51-2.66 g / cm 3 , the porosity is 8.16-10.00%, and the average grain size of the ZrC grains is 3-8 μm.

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