C-cntf / hf c-sic ceramic matrix composite and method for manufacturing the same

Abstract

The application relates to a C-CNTF / HfC-SiC ceramic matrix composite material and a preparation method thereof. The preparation method comprises the following steps: performing shear dispersion treatment on HfC powder and optional graphene in a solvent to prepare a slurry dispersion liquid; impregnating a fiber cloth with the slurry dispersion liquid, and drying and solidifying; stacking the fiber cloth, and performing Z-directional stitching with continuous carbon nanotube fibers; impregnating with HfC slurry, and drying and solidifying; impregnating with a polycarbosilane precursor, and then solidifying and cracking to obtain the ceramic matrix composite material. The application also relates to a composite material prepared by the method. The method of the application utilizes graphene-assisted shear dispersion to obtain a solid slurry with stable dispersity; a multistage vacuum-pressurized impregnation mode is adopted to realize uniform impregnation of the slurry; Z-directional stitching with carbon nanotube fibers is adopted to realize directional regulation of thermal conductivity; and finally, a composite material with excellent mechanical properties and thermal protection performance is obtained.

Description

Technical Field

[0001] This invention relates to the field of ceramic matrix composite material preparation technology, specifically to a C-CNTF / HfC-SiC ceramic matrix composite material and its preparation method. Background Technology

[0002] In recent years, in response to the problem of rapid temperature rise in parts such as the leading edge and nose cone of high-speed aircraft caused by aerodynamic heating during ultra-high-speed flight, there is an urgent need to develop ultra-high temperature ceramic matrix composite materials that have both excellent mechanical properties and resistance to oxidation and ablation.

[0003] Currently, research on continuous carbon fiber reinforced ultra-high temperature ceramic matrix composites (C / UHTCs) involves preparation processes, material systems, and failure mechanisms under extreme environments. This research primarily focuses on zirconium (Zr)-based ultra-high temperature ceramic matrix composites such as C / ZrC, C / ZrC-SiC, and C / ZrB2-SiC.

[0004] However, compared to Zr-based ultra-high temperature ceramics, hafnium carbide (HfC) and hafnium boride (HfB2) have higher melting points. Among them, hafnium oxide (HfO2) has a lower oxygen diffusion rate and vapor pressure, enabling it to maintain long-term stability and excellent oxygen barrier properties in extreme environments. Therefore, hafnium (Hf)-based ultra-high temperature ceramic matrix composites with higher temperature resistance are expected to become important thermal protection materials for aircraft thermal structural components that can withstand temperatures of 2500–3000℃.

[0005] Currently, commonly used processes for preparing Hf-based ultra-high temperature ceramic matrix composites, such as precursor impregnation pyrolysis (PIP), reactive metal infiltration (RMI), chemical vapor infiltration (CVI), and slurry impregnation (SI), all suffer from problems such as carbothermic reduction damaging fibers and unstable slurries preventing uniform impregnation into the preform.

[0006] To address the aforementioned technical problems, the inventors have innovatively employed a novel shear dispersion technology to achieve uniform and stable dispersion of solid slurries and control over particle size. A graded vacuum-pressurized layer-by-layer impregnation method is used to achieve uniform filling of the spaces between and within fiber bundles by the slurry.

[0007] Furthermore, to further enhance the thermal protection performance of the material, this invention employs a strategy combining high-efficiency thermal conductivity with high-temperature heat resistance. As a typical representative of novel high-performance fibers, carbon nanotube fibers (CNTFs), a one-dimensional macroscopic material composed of oriented carbon nanotubes, exhibit excellent properties such as high strength, high toughness, and high thermal conductivity. Compared with traditional metals or alloys, carbon nanotube fiber reinforced composite materials possess higher specific performance (specific strength and specific modulus).

[0008] This invention utilizes the excellent properties of carbon nanotubes to improve the heat resistance of materials. By stitching continuous carbon nanotube fibers together, the thermal conductivity of the materials is directionally increased, effectively reducing the stagnation temperature and improving the ablation resistance of the materials. Summary of the Invention

[0009] To address the problems of carbothermic reduction damaging fibers and unstable slurry preventing uniform impregnation into the preform in existing technologies, this invention provides a C-CNTF / HfC-SiC ceramic matrix composite material and its preparation method in a first aspect. The method includes the following steps:

[0010] (1) HfC powder and optional graphene are sheared and dispersed in a solvent to prepare at least two slurry dispersions with different solid particle sizes;

[0011] (2) The fiber cloth is impregnated with the slurry dispersion in descending order of solid particle size, and then dried and cured to obtain the impregnated fiber cloth.

[0012] (3) The impregnated fiber cloth is stacked and then Z-direction stitched using continuous carbon nanotube fibers to obtain a preform structure;

[0013] (4) Impregnate the preform structure with HfC slurry, and then dry and cure it to obtain a C / HfC preform;

[0014] (5) The C / HfC preform was impregnated with a polycarbosilane precursor, then cured and pyrolyzed to obtain a C-CNTF / HfC-SiC ceramic matrix composite material.

[0015] The present invention provides, in a second aspect, a C-CNTF / HfC-SiC ceramic matrix composite material prepared by the method described in the first aspect of the present invention.

[0016] The beneficial effects of this invention compared to the prior art are as follows:

[0017] (1) This invention employs a novel shear dispersion technology to achieve efficient dispersion of solid slurry, while also allowing for control of the particle size of solid particles. When graphene is used to assist in shear dispersion, the effective coating of graphene on the particle surface can prevent particle re-aggregation, resulting in a solid slurry that can be stored for a long time and maintain dispersion stability.

[0018] (2) The present invention uses a multi-stage vacuum-pressure impregnation method to achieve uniform impregnation of slurry inside and between fiber bundles. First, submicron large particle slurry is used to quickly fill the larger pores between fiber bundles to improve densification efficiency. Then, small particle HfC slurry is used to further fill the pores inside the fiber bundles to further increase the slurry impregnation density, reduce porosity, and improve the mechanical properties of the composite material.

[0019] (3) This invention uses continuous carbon nanotube fibers to form a preform structure through Z-axis stitching. By adjusting the stitching spacing and the number of carbon nanotube strands, the thermal conductivity of the composite material is directionally controlled. In the preferred embodiment using graphene, the overall thermal conductivity of the material can be further controlled by adjusting the graphene content in the slurry. C-CNTF / HfC-SiC ceramic matrix composite materials with directionally controlled thermal conductivity are prepared through a combination of slurry impregnation and precursor impregnation pyrolysis process. This invention utilizes a strategy combining high-efficiency thermal conductivity and high-temperature heat resistance to further enhance the thermal protection performance of the material. Detailed Implementation

[0020] In a first aspect, this invention provides a method for preparing ceramic matrix composites with directionally modulated thermal conductivity through multi-stage impregnation with graphene-assisted slurry dispersion, the method comprising the following steps:

[0021] (1) HfC powder and optional graphene are sheared and dispersed in a solvent to prepare at least two slurry dispersions with different solid particle sizes;

[0022] (2) The fiber cloth is impregnated with the slurry dispersion in descending order of solid particle size, and then dried and cured to obtain the impregnated fiber cloth.

[0023] (3) The impregnated fiber cloth is stacked and then Z-direction stitched using continuous carbon nanotube fibers to obtain a preform structure;

[0024] (4) Impregnate the preform structure with HfC slurry, and then dry and cure it to obtain a C / HfC preform;

[0025] (5) The C / HfC preform was impregnated with a polycarbosilane precursor, then cured and pyrolyzed to obtain a C-CNTF / HfC-SiC ceramic matrix composite material.

[0026] The preferred embodiments of the method of the present invention will be further described step by step below.

[0027] Step (1)

[0028] In step (1), HfC powder is sheared and dispersed in a solvent to prepare at least two slurry dispersions with different solid particle sizes.

[0029] In some preferred embodiments, when preparing at least two slurry dispersions with different solid particle sizes, graphene (graphene as an optional or preferred additive component) may be added to assist in shear dispersion treatment. In this case, it is preferable to first sonicate the graphene dispersion (which can be prepared by adding graphene to the solvent), and then add HfC powder for shear dispersion treatment to prepare at least two slurry dispersions with different solid particle sizes.

[0030] The purpose of the ultrasonic treatment is to improve surface wettability. There are no particular limitations to the ultrasonic treatment described in this invention. For example, it can be achieved by using an ultrasonic cell disruptor for 20 to 40 minutes (e.g., 30 minutes).

[0031] This invention does not impose particular limitations on the initial particle size of graphene, but mainly focuses on a preferred particle size range after shear dispersion treatment. For example, the initial particle size of graphene can be from 0.5 μm to 1 μm, such as 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0 μm.

[0032] This invention does not impose any particular limitation on the initial particle size of the added HfC powder, because the subsequent shearing process will ensure that the particle size of the HfC powder is within the expected range of solid particle size. For example, the initial particle size of the HfC powder can be the same as or different from that of the graphene, for example, less than 10 μm.

[0033] Alternatively, it is preferred that the solvent in the graphene dispersion is ethanol.

[0034] Preferably, the HfC in the slurry dispersion is 15% to 25% by volume, for example, 20% by volume.

[0035] Preferably, the graphene in the slurry dispersion is from 0% to 45% by volume, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40 or 45% by volume.

[0036] Preferably, the shear dispersion treatment is a vertical liquid particle shear dispersion treatment. In this invention, "vertical liquid particle shear dispersion treatment" means oscillating a liquid containing particles in a vertical direction to generate a predetermined amount of shear force, thereby dispersing the particles in the liquid by means of this shear force. More preferably, the shear force of the shear dispersion treatment is 50N to 100N (e.g., 60, 70, 80 or 90N), and the treatment time is 30min to 150min (e.g., 60, 90 or 120min). The inventors have discovered that the shearing action generated between solid particles and between particles and solvent molecules when solid particles oscillate in a vertical direction in a liquid can efficiently disperse solid particles and achieve efficient adhesion of graphene, resulting in a slurry dispersion in which the solid particles are very stably dispersed. Conventional dispersion methods (e.g., ball milling) cannot achieve good dispersion of HfC powder, and even when using graphene-assisted dispersion, effective coating of graphene on the surface of HfC powder cannot be achieved.

[0037] This step achieves rapid and uniform dispersion of particles in the HfC slurry by combining small-sized graphene with shear dispersion treatment (preferably vertical liquid particle shear dispersion treatment). When using graphene, it also achieves uniform coating of the particle surface. By adjusting the processing shear force and duration, the particle size can be controlled. Especially with the surface coating of small-sized graphene, it is more effective to prevent particle re-aggregation in the solution, extend the slurry storage time, and improve slurry stability.

[0038] Step (2)

[0039] In step (2), the fiber cloth is impregnated with the slurry dispersion in descending order of solid particle size, and then dried and cured to obtain the impregnated fiber cloth.

[0040] Preferably, the fiber cloth is carbon fiber cloth or carbon nanotube fiber cloth, preferably a single-layer fiber cloth, and more preferably a single-layer plain weave fiber cloth.

[0041] More preferably, the solid particle sizes of the at least two slurry dispersions are each independently within the range of 200 nm to 2 μm. In some preferred embodiments, the solid particle size of the slurry dispersion with a larger solid particle size is 1.5 to 2 μm, while the solid particle size of the slurry dispersion with a smaller solid particle size is 0.2 to 1.2 μm.

[0042] In some preferred embodiments, the at least two slurry dispersions include a first slurry dispersion with a solid particle size of 1.5 to 2 μm and a second slurry dispersion with a solid particle size of 0.8 μm to 1.2 μm.

[0043] In some other preferred embodiments, the at least two slurry dispersions include a first slurry dispersion with a solid particle size of 1.5 to 2 μm, a second slurry dispersion with a solid particle size of 0.8 to 1.2 μm, and a third slurry dispersion with a solid particle size of 0.2 to 0.5 μm.

[0044] Of course, more slurry dispersions with different solid particle sizes can also be prepared and then used in order of decreasing solid particle size.

[0045] In some preferred embodiments, the at least two slurry dispersions may include a first slurry dispersion with a solid particle size of 1.5 μm to 2 μm, a second slurry dispersion with a solid particle size of 0.8 μm to 1.2 μm, and a third slurry dispersion with a solid particle size of 200 nm to 500 nm.

[0046] More preferably, the impregnation includes vacuum impregnation and pressure impregnation, with vacuum impregnation performed first and then pressure impregnation performed.

[0047] This invention does not impose particular limitations on vacuum conditions, as long as sufficient impregnation can be achieved. For example, the vacuum degree of the vacuum impregnation can be 10. -3 The impregnation time can be 5 to 10 hours (e.g., 6, 7, 8 or 9 hours); the pressure of the pressurized impregnation is 15 MPa to 25 MPa (e.g., 20 MPa), and the impregnation time is 2 hours to 4 hours (e.g., 3 hours).

[0048] Alternatively, the drying and curing temperature is 180°C to 220°C (e.g., 200°C), and the time is 3 hours to 5 hours (e.g., 4 hours).

[0049] Preferably, the impregnation and drying curing of each of the at least two slurry dispersions can be independently repeated 2 to 4 times, for example, 3 times. For instance, the slurry dispersion with the largest solid particle size can be impregnated first, then dried and cured, repeated 2 to 4 times; then the slurry dispersion with the second largest solid particle size can be impregnated, then dried and cured, repeated independently 2 to 4 times; then the slurry dispersion with the smallest solid particle size can be impregnated, then dried and cured, and repeated independently 2 to 4 times again. That is, the number of repetitions of impregnation and drying curing for each slurry dispersion can be the same or different.

[0050] In some more specific embodiments, the single-layer carbon fiber cloth can first undergo a multi-stage impregnation treatment with HfC slurry. For example, the single-layer carbon fiber cloth can first be vacuum-pressurized with a 0.8μm to 1μm HfC slurry to fill the pores between the fiber bundles. The vacuum impregnation time is 5 to 10 hours, followed by impregnation at 20 MPa for 2 to 4 hours, and then drying and curing at 200°C for 4 hours. Then, a 200nm to 500nm HfC slurry is used to fill the pores inside the fiber bundles, under the same conditions. This process can be repeated 2 to 4 times.

[0051] This step employs a multi-stage vacuum-pressure impregnation method to achieve uniform impregnation of the slurry within and between fiber bundles. First, submicron-sized slurry particles are used to rapidly fill the larger pores between fiber bundles, improving densification efficiency. Then, small-particle HfC slurry is used to further fill the pores within the fiber bundles, further increasing the slurry impregnation density, reducing porosity, and improving the mechanical properties of the composite material. When using graphene, the graphene in the slurry dispersion can also be used to assist in improving thermal conductivity. This graphene includes graphene coated on the HfC surface and graphene not coated on the HfC surface; the latter can fill the fiber interior or coat the fiber surface, thereby assisting in improving thermal conductivity.

[0052] Step (3)

[0053] In step (3), the impregnated carbon fiber cloth is laminated and then Z-direction stitched using continuous carbon nanotube fibers to obtain a preform structure.

[0054] Preferably, the continuous carbon nanotube fibers have a tensile strength greater than 3 GPa, a single filament diameter of 10 μm to 15 μm (e.g., 11, 12, 13, or 14 μm), a room temperature thermal conductivity of 400 to 600 W / m·K (e.g., 450, 500, or 550 W / m·K), and an elongation at break of 4% to 6% (e.g., 5%). Such continuous carbon nanotube fibers possess excellent toughness, which can further improve the mechanical properties of the resulting composite material.

[0055] More preferably, the linear density of the continuous carbon nanotube fibers is 50 tex to 70 tex.

[0056] More preferably, the number of strands in the suture is 1 to 5 (e.g., 2, 3 or 4 strands).

[0057] More preferably, the suture spacing is from 1.5 mm to 4.0 mm (e.g., 2.0, 2.5, 3.0, or 3.5 mm). More specific examples of suture spacing may be, for example, 1.5 mm × 1.5 mm, 2 mm × 2 mm, 2.5 mm × 2.5 mm, 3 mm × 3 mm, 3.5 mm × 3.5 mm, or 4 mm × 4 mm.

[0058] In this invention, there is no particular limitation on the number of layers, which can be increased or decreased as needed. In some preferred embodiments, the number of layers can be 5 to 20 (e.g., 10 or 15 layers).

[0059] In this step, the impregnated single-layer fiber cloth is laminated and then stitched together in the Z-direction using continuous carbon nanotube fibers (CNTF) to obtain a preform structure. Furthermore, the thermal conductivity of the composite material can be directionally controlled by adjusting the stitching spacing and the number of strands of the continuous carbon nanotube fibers.

[0060] Step (4)

[0061] In step (4), the preform structure is impregnated with HfC slurry (this is the last HfC slurry impregnation after stitching), and then dried and cured to obtain a C / HfC preform.

[0062] Preferably, the particle size of the HfC slurry is 100 nm to 300 nm (e.g., 200 nm).

[0063] More preferably, the solvent for the HfC slurry can be ethanol.

[0064] More preferably, the HfC in the HfC slurry can be 15 vol% to 25 vol% (e.g., 20 vol%).

[0065] More preferably, the drying and curing temperature is 200°C to 400°C, and the curing time is 2 hours to 4 hours.

[0066] Step (5)

[0067] In step (5), the C / HfC preform is impregnated with a polycarbosilane precursor, then cured and pyrolyzed to obtain a C-CNTF / HfC-SiC ceramic matrix composite material.

[0068] Preferably, the curing temperature (or crosslinking temperature) of the polycarbosilane precursor is 200 to 400°C (e.g., 300°C), the curing time is 100 to 360 min (e.g., 150, 200, 250, 300 or 350 min), and the pyrolysis temperature is 800 to 1000°C (e.g., 900°C). It can be repeatedly impregnated and pyrolyzed until the mass increment is less than 1%.

[0069] In this step, a polycarbosilane impregnation-pyrolysis process is used to densify the preform. The thermal conductivity-oriented C-CNTF / HfC-SiC ceramic matrix composite material is prepared by combining slurry impregnation with precursor impregnation-pyrolysis.

[0070] This invention proposes a novel shear dispersion technique for highly efficient dispersion of solid slurries, enabling control over the particle size of solid particles. By using graphene-assisted shear dispersion, effective coating of graphene onto the particle surface can be achieved. Effective filling between and within fiber bundles is achieved through a graded vacuum-pressurized layer-by-layer impregnation technique. This invention also utilizes carbon nanotube fibers to construct thermally conductive pathways, achieving directional control of the composite material's thermal conductivity. Furthermore, this invention combines a precursor impregnation-pyrolysis densification process to prepare a novel high-temperature resistant, ablation-resistant ceramic matrix composite material with directionally regulated thermal conductivity. This composite material not only exhibits high thermal conductivity but also shows significant improvements in its mechanical and oxidation resistance properties.

[0071] Furthermore, the overall processing temperature of this invention is relatively low, avoiding damage to the fibers caused by high temperatures during the carbothermic reduction preparation of HfC, thus achieving uniform and stable dispersion of the slurry and uniform and dense distribution within the fibers. The thermally conductive pathways constructed by carbon nanotube fibers can directionally improve the thermal conductivity of the material, reduce the stagnation temperature, and enhance the material's high-temperature resistance and ablation resistance.

[0072] The present invention provides, in a second aspect, a C-CNTF / HfC-SiC ceramic matrix composite material prepared by the method described in the first aspect of the present invention.

[0073] Preferably, the content of Z-axis continuous carbon nanotube fibers in the C-CNTF / HfC-SiC ceramic matrix composite material is preferably 5 vol% to 15 vol% (e.g., 10 vol%).

[0074] Preferably, the graphene content in the C-CNTF / HfC-SiC ceramic matrix composite material can be from 0 vol% to 30 vol% (e.g., 1, 5, 10, 15, 20 or 25 vol%), and is more preferably from 10 vol% to 30 vol%.

[0075] Example

[0076] The present invention will now be described in detail with reference to specific embodiments. However, it should be understood that these embodiments are for illustrative purposes only and do not constitute a limitation on the scope of the invention. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods. Unless otherwise specified, the materials, reagents, etc. used in the following embodiments are commercially available. Unless otherwise stated, all percentages and parts are by weight.

[0077] Example 1

[0078] (1) Preparation of HfC slurry: Small-sized graphene (0.5 μm to 1 μm) was ultrasonically pulverized in 500 mL of ethanol for 30 min to obtain a graphene dispersion. HfC powder (initial particle size less than 10 μm) was added to the above graphene dispersion for vertical liquid particle shear dispersion to obtain a slurry dispersion with a graphene volume ratio of 30% and an HfC volume ratio of 25%. Specifically, under the condition of a shear force of 50 N and a treatment time of 60 min for vertical liquid particle shear dispersion, a first slurry dispersion with a solid particle size of 1.5-2 μm was obtained; under the condition of a shear force of 80 N and a treatment time of 100 min for vertical liquid particle shear dispersion, a second slurry dispersion with a solid particle size of 0.8-1.2 μm was obtained; under the condition of a shear force of 100 N and a treatment time of 150 min for vertical liquid particle shear dispersion, a third slurry dispersion with a solid particle size of 200-500 nm was obtained.

[0079] (2) Multi-stage vacuum-pressure impregnation method for uniform impregnation of the fiber bundle interior and between fiber bundles. First, the single-layer plain weave carbon fiber fabric undergoes a three-stage impregnation treatment with HfC slurry dispersion. Firstly, a 1.5-2 μm HfC slurry dispersion (i.e., the first slurry dispersion) is used to vacuum-pressure impregnate the single-layer plain weave carbon fiber fabric, filling the pores between fiber bundles. The vacuum impregnation time is 5 hours, followed by pressure impregnation (20 MPa) for 2 hours, and drying and curing at 200℃ for 4 hours to complete the first-stage impregnation treatment. Then, a 0.8-1.2 μm HfC slurry dispersion (i.e., the second slurry dispersion) is used to fill the remaining pores between fiber bundles, with the same treatment conditions as the first-stage impregnation, completing the second-stage impregnation treatment. Finally, a 200-500nm slurry dispersion (i.e., the third slurry dispersion) was used for vacuum impregnation to fill the voids inside the fiber bundle. The vacuum impregnation time was 5 hours, followed by pressure (20MPa) impregnation for 4 hours. The curing temperature was 200℃ and the curing time was 4 hours, thus completing the third-stage impregnation treatment.

[0080] (3) After pressing and stacking the above-impregnated single-layer fiber cloth (15 layers), Z-direction stitching is performed using continuous carbon nanotube fibers (CNTF) to obtain a prefabricated structure. The continuous carbon nanotube fibers have a tensile strength greater than 3 GPa, a single filament diameter of 14 μm, a room temperature thermal conductivity of 600 W / m·K, and a breaking elongation of 4%. The stitching spacing is 4 mm × 4 mm, the number of continuous carbon nanotube fibers is 2 strands, the linear density is 60 tex, and the Z-direction continuous carbon nanotube fiber content (hereinafter referred to as "Z-direction fiber content") is 5%.

[0081] (4) After stitching, perform a final HfC slurry impregnation (slurry particle size is 100-300nm, solvent is ethanol), vacuum impregnation time is 8h, pressure (20MPa) impregnation for 4h, dry and cure at 200℃ for 4h to obtain C / HfC preform.

[0082] (5) The above-mentioned preform was densified using a polycarbosilane impregnation-pyrolysis process. The crosslinking temperature of the polycarbosilane precursor was 200℃, the curing time was 240 min, and the pyrolysis temperature was 900℃. The impregnation and pyrolysis were repeated until the mass increment was less than 1%, to obtain C-CNTF / HfC-SiC ceramic matrix composite material (where the volume content of HfC was 20% and the volume content of graphene was 24%).

[0083] (6) Mechanical properties and thermal conductivity tests: The prepared C-CNTF / HfC-SiC ceramic matrix composite material was tested. The test results are as follows: flexural strength is 297 MPa, and Z-direction thermal conductivity is 50 W / m·K.

[0084] Example 2

[0085] (1) Preparation of HfC slurry: Small-sized graphene (0.5 μm to 1 μm) was ultrasonically pulverized in 500 mL of ethanol for 30 min to obtain a graphene dispersion. HfC powder was added to the above graphene dispersion for vertical liquid particle shear dispersion to obtain a slurry dispersion with a graphene volume ratio of 30% and an HfC volume ratio of 25%. Specifically, under the condition of vertical liquid particle shear dispersion treatment with a shear force of 50 N and a treatment time of 60 min, a first slurry dispersion with a solid particle size of 1.5-2 μm was obtained; under the condition of vertical liquid particle shear dispersion treatment with a shear force of 80 N and a treatment time of 100 min, a second slurry dispersion with a solid particle size of 0.8-1.2 μm was obtained; under the condition of vertical liquid particle shear dispersion treatment with a shear force of 100 N and a treatment time of 150 min, a third slurry dispersion with a solid particle size of 200-500 nm was obtained.

[0086] (2) Multi-stage vacuum-pressure impregnation method for uniform impregnation of the fiber bundle interior and between fiber bundles. First, the single-layer plain weave carbon fiber fabric undergoes a three-stage impregnation treatment with HfC slurry dispersion. Firstly, a 1.5-2 μm HfC slurry dispersion is used to vacuum-pressure impregnate the single-layer plain weave carbon fiber fabric, filling the pores between fiber bundles. The vacuum impregnation time is 5 h, followed by pressure impregnation (20 MPa) for 2 h, and drying and curing at 200℃ for 4 h to complete the first-stage impregnation treatment. Then, a 0.8-1.2 μm HfC slurry dispersion is used to fill the remaining pores between fiber bundles, with the same treatment conditions as the first-stage impregnation treatment, completing the second-stage impregnation treatment. Finally, a 200-500 nm slurry dispersion is used to fill the internal voids of the fiber bundles. The vacuum impregnation time is 5 h, followed by pressure impregnation (20 MPa) for 4 h, and drying and curing at 200℃ for 4 h to complete the third-stage impregnation treatment. Each of the above three-stage impregnation treatment steps is repeated twice (i.e., the first-stage impregnation treatment is repeated twice, then the second-stage impregnation treatment is repeated twice, and then the third-stage impregnation treatment is repeated twice).

[0087] (3) After pressing and stacking the above-impregnated single-layer fiber cloth (15 layers), a prefabricated structure is obtained by Z-direction stitching using continuous carbon nanotube fibers (CNTF). The continuous carbon nanotube fibers have a tensile strength greater than 3 GPa, a single filament diameter of 14 μm, a room temperature thermal conductivity of 600 W / m·K, and a breaking elongation of 4%. The stitching spacing is 3 mm × 3 mm, the continuous carbon nanotube fibers have 3 strands, and the Z-direction fiber content is 10%.

[0088] (4) After stitching, perform a final HfC slurry impregnation (slurry particle size is 100-300nm, solvent is ethanol), vacuum impregnation time is 8h, pressure (20MPa) impregnation for 4h, dry and cure at 200℃ for 4h, repeat twice to obtain C / HfC preform.

[0089] (5) The above-mentioned preform was densified by a polycarbosilane impregnation-pyrolysis process. The crosslinking temperature of the polycarbosilane precursor was 200℃, the curing time was 240 min, and the pyrolysis temperature was 900℃. The impregnation and pyrolysis were repeated until the mass increment was less than 1%, and C-CNTF / HfC-SiC ceramic matrix composite material (where the volume content of HfC was 25% and the volume content of graphene was 30%) was obtained.

[0090] (6) Mechanical properties and thermal conductivity tests: The prepared C-CNTF / HfC-SiC ceramic matrix composite material was tested. The test results are as follows: flexural strength is 317 MPa, and Z-direction thermal conductivity is 90 W / m·K.

[0091] Example 3

[0092] (1) Preparation of HfC slurry: Small-sized graphene (0.5 μm to 1 μm) was ultrasonically pulverized in 500 mL of ethanol for 30 min to obtain a graphene dispersion. HfC powder was added to the graphene dispersion for vertical liquid particle shear dispersion to obtain a slurry dispersion with a graphene volume ratio of 30% and an HfC volume ratio of 25%. Specifically, a slurry dispersion with a solid particle size of 1.5-2 μm was obtained when the vertical liquid particle shear dispersion treatment force was 50 N and the treatment time was 60 min; a slurry dispersion with a solid particle size of 0.8-1.2 μm was obtained when the vertical liquid particle shear dispersion treatment force was 80 N and the treatment time was 100 min.

[0093] (2) Multi-stage vacuum-pressure impregnation method for uniform impregnation of the fiber bundle interior and between fiber bundles. First, a two-stage impregnation treatment with HfC slurry was performed on the single-layer plain weave carbon fiber fabric. Firstly, a 1.5-2 μm HfC slurry dispersion was used to vacuum-pressure impregnate the single-layer plain weave carbon fiber fabric, filling the pores between the fiber bundles. The vacuum impregnation time was 5 hours, followed by pressure impregnation (20 MPa) for 2 hours, and drying and curing at 200℃ for 4 hours to complete the first-stage impregnation treatment. Then, a 0.8-1.2 μm HfC slurry dispersion was used to fill the remaining pores between the fiber bundles, with the same treatment conditions as the first-stage impregnation treatment, to complete the second-stage impregnation treatment. Each of the above two-stage impregnation treatment steps was repeated twice.

[0094] (3) After pressing and stacking the above-impregnated single-layer fiber cloth (15 layers), Z-direction stitching is performed using continuous carbon nanotube fibers (CNTF) to obtain a prefabricated structure. The continuous carbon nanotube fibers have a tensile strength greater than 3 GPa, a single filament diameter of 14 μm, a room temperature thermal conductivity of 600 W / m·K, and a breaking elongation of 4%. The stitching spacing is 3 mm × 3 mm, the continuous carbon nanotube fibers have 3 strands, and the Z-direction fiber content is 10%.

[0095] (4) After stitching, perform the final HfC slurry impregnation (slurry particle size is 100-300nm, vacuum impregnation time is 8h, pressure (20MPa) impregnation for 4h, and dry and cure at 200℃ for 4h to obtain C / HfC preform.

[0096] (5) The above-mentioned preform was densified by a polycarbosilane impregnation-pyrolysis process. The crosslinking temperature of the polycarbosilane precursor was 200℃, the curing time was 240 min, the pyrolysis temperature was 900℃, and the impregnation and pyrolysis were carried out until the mass increment was less than 1%, to obtain C-CNTF / HfC-SiC ceramic matrix composite material (where the volume content of HfC was 15% and the volume content of graphene was 18%).

[0097] (6) Mechanical properties and thermal conductivity tests: The prepared C-CNTF / HfC-SiC ceramic matrix composite material was tested. The test results are as follows: flexural strength is 250 MPa, and Z-direction thermal conductivity is 80 W / m·K.

[0098] Example 4

[0099] (1) Preparation of HfC slurry: HfC powder was added to 500 mL of ethanol and vertically dispersed by liquid particle shearing to obtain a slurry dispersion with an HfC volume ratio of 25%. Specifically, when the vertical liquid particle shearing dispersion treatment had a shear force of 50 N and a treatment time of 60 min, a slurry dispersion with a solid particle size of 1.5-2 μm was obtained; when the vertical liquid particle shearing dispersion treatment had a shear force of 80 N and a treatment time of 100 min, a slurry dispersion with a solid particle size of 0.8-1.2 μm was obtained; and when the vertical liquid particle shearing dispersion treatment had a shear force of 100 N and a treatment time of 150 min, a slurry dispersion with a solid particle size of 200-500 nm was obtained.

[0100] (2) Multi-stage vacuum-pressure impregnation method for uniform impregnation of the fiber bundle interior and inter-fiber bundles. First, the single-layer plain weave carbon fiber fabric undergoes a three-stage impregnation treatment with HfC slurry dispersion. Firstly, a 1.5-2 μm HfC slurry dispersion is used to vacuum-pressure impregnate the single-layer plain weave carbon fiber fabric, filling the pores between the fiber bundles. Vacuum impregnation time is 5 h, followed by pressure impregnation (20 MPa) for 2 h, and drying and curing at 200℃ for 4 h to complete the first-stage impregnation treatment. Then, a 0.8-1.2 μm HfC slurry dispersion is used to fill the remaining pores between the fiber bundles, with the same treatment conditions as the first-stage impregnation treatment, completing the second-stage impregnation treatment. Finally, a 200-500 nm slurry dispersion is used to fill the internal voids of the fiber bundles. Vacuum impregnation time is 5 h, followed by pressure impregnation (20 MPa) for 4 h, and drying and curing at 200℃ for 4 h to complete the third-stage impregnation treatment. This process is repeated twice.

[0101] (3) After pressing and stacking the above-impregnated single-layer fiber cloth, a prefabricated structure is obtained by Z-direction stitching using continuous carbon nanotube fibers (CNTF). The continuous carbon nanotube fibers have a tensile strength greater than 3 GPa, a single filament diameter of 14 μm, a room temperature thermal conductivity of 600 W / m·K, and a breaking elongation of 4%, exhibiting excellent toughness. The stitching spacing is 3 mm × 3 mm, the continuous carbon nanotube fibers are 3 strands, and the Z-direction fiber content is 10% by volume.

[0102] (4) After stitching, perform the final HfC slurry impregnation. The slurry particle size is 100-300nm. Vacuum impregnation time is 8h, pressure is applied for 20MPa impregnation for 4h, and drying and curing is carried out at 200℃ for 4h. Repeat twice to obtain C / HfC preform.

[0103] (5) The above-mentioned preform was densified by a polycarbosilane impregnation-pyrolysis process. The polycarbosilane precursor crosslinking temperature was 200℃, the curing time was 240 min, the pyrolysis temperature was 900℃, and the impregnation and pyrolysis were carried out until the mass increment was less than 1%, to obtain C-CNTF / HfC-SiC ceramic matrix composite material (where the volume content of HfC was 25% and the volume content of graphene was 0%).

[0104] (6) Mechanical properties and thermal conductivity test: The prepared C-CNTF / HfC-SiC ceramic matrix composite material was tested and found to have a flexural strength of 307MPa and a Z-direction thermal conductivity of 65W / m·K.

[0105] Example 5

[0106] (1) Preparation of HfC slurry: Small-sized graphene (0.5 μm to 1 μm) was ultrasonically pulverized in 500 mL of ethanol for 30 min to obtain a graphene dispersion. HfC powder was added to the graphene dispersion for vertical liquid particle shear dispersion to obtain a slurry dispersion with a graphene volume ratio of 30% and an HfC volume ratio of 25%. Specifically, a slurry dispersion with a solid particle size of 1.5-2 μm was obtained when the vertical liquid particle shear dispersion treatment force was 50 N and the treatment time was 60 min; a slurry dispersion with a solid particle size of 0.8-1.2 μm was obtained when the vertical liquid particle shear dispersion treatment force was 80 N and the treatment time was 100 min; and a slurry dispersion with a solid particle size of 200-500 nm was obtained when the vertical liquid particle shear dispersion treatment force was 100 N and the treatment time was 150 min.

[0107] (2) Multi-stage vacuum-pressure impregnation method for uniform impregnation of the fiber bundle interior and inter-fiber bundles. First, the single-layer plain weave carbon fiber fabric undergoes a three-stage impregnation treatment with HfC slurry dispersion. Firstly, a 1.5-2 μm HfC slurry dispersion is used to vacuum-pressure impregnate the single-layer plain weave carbon fiber fabric, filling the pores between the fiber bundles. Vacuum impregnation time is 5 h, followed by pressure impregnation (20 MPa) for 2 h, and drying and curing at 200℃ for 4 h to complete the first-stage impregnation treatment. Then, a 0.8-1.2 μm HfC slurry dispersion is used to fill the remaining pores between the fiber bundles, with the same treatment conditions as the first-stage impregnation treatment, completing the second-stage impregnation treatment. Finally, a 200-500 nm slurry dispersion is used to fill the internal voids of the fiber bundles. Vacuum impregnation time is 5 h, followed by pressure impregnation (20 MPa) for 4 h, and drying and curing at 200℃ for 4 h to complete the third-stage impregnation treatment. The above three-stage impregnation treatment steps are repeated twice.

[0108] (3) After pressing and stacking the above-impregnated single-layer fiber cloth (15 layers), Z-direction stitching is performed using continuous carbon nanotube fibers (CNTF) to obtain a prefabricated structure. The continuous carbon nanotube fibers have a tensile strength greater than 3 GPa, a single filament diameter of 14 μm, a room temperature thermal conductivity of 600 W / m·K, and a breaking elongation of 4%. The stitching spacing is 2 mm × 2 mm, the number of continuous carbon nanotube fibers is 5, and the Z-direction fiber content is 15%.

[0109] (4) After stitching, perform the final HfC slurry impregnation (slurry particle size is 100-300nm) for 8 hours of vacuum impregnation, followed by pressure (20MPa) impregnation for 4 hours, and drying and curing at 200℃ for 4 hours. Repeat twice to obtain C / HfC preform.

[0110] (5) The above-mentioned preform was densified by a polycarbosilane impregnation-pyrolysis process. The crosslinking temperature of the polycarbosilane precursor was 200℃, the curing time was 240 min, the pyrolysis temperature was 900℃, and the impregnation and pyrolysis were carried out until the mass increment was less than 1%, to obtain C-CNTF / HfC-SiC ceramic matrix composite material (where the volume content of HfC was 25% and the volume content of graphene was 30%).

[0111] (6) Mechanical properties and thermal conductivity tests: The prepared C-CNTF / HfC-SiC ceramic matrix composite material was tested. The test results are as follows: flexural strength is 330 MPa, and Z-direction thermal conductivity is 120 W / m·K.

[0112] Example 6

[0113] (1) Preparation of HfC slurry: Small-sized graphene (0.5 μm to 1 μm) was ultrasonically pulverized in 500 mL of ethanol for 30 min to obtain a graphene dispersion. HfC powder was added to the above graphene dispersion and ball-milled to mix evenly, resulting in a slurry dispersion with a solid particle size of 1-1.2 μm. The volume ratio of graphene in the slurry dispersion was 30%, and the volume ratio of HfC was 25%.

[0114] (2) Vacuum-pressure impregnation method for slurry impregnation. A 1-1.2 μm HfC slurry dispersion was used to impregnate the single-layer plain weave carbon fiber cloth under vacuum and pressure. The vacuum impregnation time was 5 h, followed by pressure impregnation (20 MPa) for 2 h, and drying and curing at 200℃ for 4 h. This impregnation process was repeated 4 times.

[0115] (3) After pressing and stacking the above-impregnated single-layer fiber cloth (15 layers), Z-direction stitching is performed using continuous carbon nanotube fibers (CNTF) to obtain a prefabricated structure. The continuous carbon nanotube fibers have a tensile strength greater than 3 GPa, a single filament diameter of 14 μm, a room temperature thermal conductivity of 600 W / m·K, and a breaking elongation of 4%. The stitching spacing is 3 mm × 3 mm, the continuous carbon nanotube fibers have 3 strands, and the Z-direction fiber content is 10%.

[0116] (4) After stitching, perform the final HfC slurry impregnation (slurry particle size is 100-300nm), vacuum impregnation time is 8h, pressure (20MPa) impregnation for 4h, dry and cure at 200℃ for 4h, repeat twice to obtain C / HfC preform.

[0117] (5) The above-mentioned preform was densified by a polycarbosilane impregnation-pyrolysis process. The crosslinking temperature of the polycarbosilane precursor was 200℃, the curing time was 240 min, the pyrolysis temperature was 900℃, and the impregnation and pyrolysis were carried out until the mass increment was less than 1%, to obtain C-CNTF / HfC-SiC ceramic matrix composite material (where the volume content of HfC was 12% and the volume content of graphene was 14%).

[0118] (6) Mechanical properties and thermal conductivity tests: The prepared C-CNTF / HfC-SiC ceramic matrix composite material was tested. The test results are as follows: flexural strength is 220 MPa, and Z-direction thermal conductivity is 70 W / m·K.

[0119] Example 7

[0120] (1) Preparation of HfC slurry: Small-sized graphene (0.5 μm to 1 μm) was ultrasonically pulverized in 500 mL of ethanol for 30 min to obtain a graphene dispersion. HfC powder was added to the graphene dispersion for vertical liquid particle shear dispersion to obtain a slurry dispersion with a graphene volume ratio of 30% and an HfC volume ratio of 25%. Specifically, a slurry dispersion with a solid particle size of 1.5-2 μm was obtained when the vertical liquid particle shear dispersion treatment force was 50 N and the treatment time was 60 min; a slurry dispersion with a solid particle size of 0.8-1.2 μm was obtained when the vertical liquid particle shear dispersion treatment force was 80 N and the treatment time was 100 min; and a slurry dispersion with a solid particle size of 200-500 nm was obtained when the vertical liquid particle shear dispersion treatment force was 100 N and the treatment time was 150 min.

[0121] (2) Multi-stage vacuum-pressure impregnation method for uniform impregnation of the fiber bundle interior and inter-fiber bundles. First, the single-layer plain weave carbon fiber fabric undergoes a three-stage impregnation treatment with HfC slurry dispersion. Firstly, a 1.5-2 μm HfC slurry dispersion is used to vacuum-pressure impregnate the single-layer plain weave carbon fiber fabric, filling the pores between the fiber bundles. Vacuum impregnation time is 5 h, followed by pressure impregnation (20 MPa) for 2 h, and drying and curing at 200℃ for 4 h to complete the first-stage impregnation treatment. Then, a 0.8-1.2 μm HfC slurry dispersion is used to fill the remaining pores between the fiber bundles, with the same treatment conditions as the first-stage impregnation treatment, completing the second-stage impregnation treatment. Finally, a 200-500 nm slurry dispersion is used to fill the internal voids of the fiber bundles. Vacuum impregnation time is 5 h, followed by pressure impregnation (20 MPa) for 4 h, and drying and curing at 200℃ for 4 h to complete the third-stage impregnation treatment. The above three-stage impregnation treatment steps are repeated twice.

[0122] (3) After pressing and stacking the above-impregnated single-layer fiber cloth (15 layers), 6k T300 carbon fiber is used for Z-direction stitching to obtain the prefabricated structure.

[0123] (4) After stitching, perform the final HfC slurry impregnation (slurry particle size is 100-300nm) for 8 hours of vacuum impregnation, followed by pressure (20MPa) impregnation for 4 hours, and drying and curing at 200℃ for 4 hours. Repeat twice to obtain C / HfC preform.

[0124] (5) The above-mentioned preform was densified by a polycarbosilane impregnation-pyrolysis process. The crosslinking temperature of the polycarbosilane precursor was 200℃, the curing time was 240 min, the pyrolysis temperature was 900℃, and the impregnation and pyrolysis were carried out until the mass increment was less than 1%, to obtain C-CNTF / HfC-SiC ceramic matrix composite material (where the volume content of HfC was 25% and the volume content of graphene was 30%).

[0125] (6) Mechanical properties and thermal conductivity tests: The prepared C-CNTF / HfC-SiC ceramic matrix composite material was tested. The test results are as follows: flexural strength is 290 MPa, and Z-direction thermal conductivity is 20 W / m·K.

[0126] Example 8

[0127] (1) Preparation of HfC slurry: Small-sized graphene (0.5 μm to 1 μm) was ultrasonically pulverized in 500 mL of ethanol for 30 min to obtain a graphene dispersion. HfC powder was added to the above graphene dispersion for vertical liquid particle shear dispersion to obtain a slurry dispersion with a graphene volume ratio of 30% and an HfC volume ratio of 25%. Among them, when the vertical liquid particle shear dispersion treatment was performed with a shear force of 80 N and a treatment time of 100 min, a slurry dispersion with a solid particle size of 0.8-1.2 μm was obtained.

[0128] (2) Vacuum-pressure impregnation method for uniform impregnation of the fiber bundle interior and between fiber bundles. First, the single-layer plain weave carbon fiber fabric undergoes a three-stage impregnation treatment with HfC slurry dispersion. The single-layer plain weave carbon fiber fabric is vacuum-pressure impregnated with a 0.8-1.2 μm HfC slurry dispersion to fill the pores between fiber bundles. The vacuum impregnation time is 5 h, followed by pressure impregnation (20 MPa) for 2 h, and drying and curing at 200℃ for 4 h. This process is repeated 5 times. Finally, a second impregnation treatment is performed with a 0.8-1.2 μm slurry dispersion. The vacuum impregnation time is 5 h, followed by pressure impregnation (20 MPa) for 4 h, and drying and curing at 200℃ for 4 h.

[0129] (3) After pressing and stacking the above-impregnated single-layer fiber cloth (15 layers), Z-direction stitching is performed using continuous carbon nanotube fibers (CNTF) to obtain a prefabricated structure. The continuous carbon nanotube fibers have a tensile strength greater than 3 GPa, a single filament diameter of 14 μm, a room temperature thermal conductivity of 600 W / m·K, and a breaking elongation of 4%. The stitching spacing is 2 mm × 2 mm, the number of continuous carbon nanotube fibers is 5, and the Z-direction fiber content is 15%.

[0130] (4) After stitching, perform the final HfC slurry impregnation (slurry particle size is 100-300nm) for 8 hours of vacuum impregnation, followed by pressure (20MPa) impregnation for 4 hours, and drying and curing at 200℃ for 4 hours. Repeat twice to obtain C / HfC preform.

[0131] (5) The above-mentioned preform was densified by a polycarbosilane impregnation-pyrolysis process. The crosslinking temperature of the polycarbosilane precursor was 200℃, the curing time was 240 min, the pyrolysis temperature was 900℃, and the impregnation and pyrolysis were carried out until the mass increment was less than 1%, to obtain C-CNTF / HfC-SiC ceramic matrix composite material (where the volume content of HfC was 25% and the volume content of graphene was 30%).

[0132] (6) Mechanical properties and thermal conductivity tests: The prepared C-CNTF / HfC-SiC ceramic matrix composite material was tested. The test results are as follows: flexural strength is 280 MPa, and Z-direction thermal conductivity is 110 W / m·K.

[0133] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the appended claims.

Claims

1. A method for preparing a C-CNTF / HfC-SiC ceramic matrix composite material, characterized in that, The method includes the following steps: (1) HfC powder and optional graphene are sheared and dispersed in a solvent to prepare at least two slurry dispersions with different solid particle sizes, wherein the solid particle size of the at least two slurry dispersions is 200 nm to 2 μm. (2) The fiber cloth is impregnated with the slurry dispersion in descending order of solid particle size, and then dried and cured to obtain the impregnated fiber cloth, wherein the fiber cloth is carbon fiber cloth or carbon nanotube fiber cloth. (3) The impregnated fiber cloth is stacked and then Z-direction stitched using continuous carbon nanotube fibers to obtain a prefabricated structure; (4) The preform structure is impregnated again with nano-sized HfC slurry, and then dried and cured to obtain a C / HfC preform, wherein the particle size of the HfC slurry is 100 nm to 300 nm; (5) The C / HfC preform was impregnated with a polycarbosilane precursor, then cured and pyrolyzed to obtain a C-CNTF / HfC-SiC ceramic matrix composite material.

2. The preparation method according to claim 1, characterized in that, In step (1): The HfC in the slurry dispersion is 15% to 25% by volume; and / or The graphene content in the slurry dispersion is from 0% to 45% by volume.

3. The preparation method according to claim 1, characterized in that, In step (1): The shear dispersion treatment is a vertical liquid particle shear dispersion treatment.

4. The preparation method according to claim 3, characterized in that, In step (1): The shear force for the shear dispersion treatment is 50N to 100N, and the treatment time is 30min to 150min.

5. The preparation method according to any one of claims 1 to 4, characterized in that, In step (2): The fiber cloth is a single-layer fiber cloth.

6. The preparation method according to claim 5, characterized in that, In step (2): The fiber cloth is a single-layer plain weave fiber cloth.

7. The preparation method according to any one of claims 1 to 4, characterized in that, In step (2): The impregnation includes vacuum impregnation and pressure impregnation, with vacuum impregnation performed first, followed by pressure impregnation. The drying and curing temperature is 180°C to 220°C, and the time is 3 to 5 hours; and / or The impregnation and drying curing of each of the at least two slurry dispersions were each independently repeated 2 to 4 times.

8. The preparation method according to any one of claims 1 to 4, characterized in that, In step (3): The continuous carbon nanotube fiber has a tensile strength greater than 3 GPa, a single filament diameter of 10 μm to 15 μm, a room temperature thermal conductivity of 400 to 600 W / m•K, a breaking elongation of 4% to 6%, and a linear density of 50 tex to 70 tex.

9. The preparation method according to any one of claims 1 to 4, characterized in that, In step (4): The HfC in the HfC slurry is 15% to 25% by volume; and / or The curing temperature is 200℃ to 400℃, and the curing time is 2 hours to 4 hours.

10. The preparation method according to any one of claims 1 to 4, characterized in that, In step (5): The curing temperature of the polycarbosilane precursor is 200 to 400°C, the curing time is 100 to 360 min, the pyrolysis temperature is 800°C to 1000°C, and the impregnation and pyrolysis are repeated until the mass increment is less than 1%.

11. The C-CNTF / HfC-SiC ceramic matrix composite material prepared by the method according to any one of claims 1 to 10.

12. The C-CNTF / HfC-SiC ceramic matrix composite material according to claim 11, characterized in that: The Z-axis continuous carbon nanotube fiber content in the C-CNTF / HfC-SiC ceramic matrix composite material is 5% to 15%; and / or The graphene content in the C-CNTF / HfC-SiC ceramic matrix composite material is from 0% to 30% by volume.