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CN-118771904-B - Ceramic matrix composite material with organic nanofiber modified carbon nanotube fibers as heat dredging passages and preparation method thereof

CN118771904BCN 118771904 BCN118771904 BCN 118771904BCN-118771904-B

Abstract

The invention relates to a ceramic matrix composite material taking organic nanofiber modified carbon nanotube fibers as a heat dredging passage and a preparation method thereof. The method comprises the steps of placing carbon nano tube fibers in strong acid for swelling, preparing an organic nano fiber solution, immersing the swelled carbon nano tube fibers in the organic nano fiber solution, circularly drafting, performing coagulating bath treatment, washing and drying to obtain organic nano fiber modified carbon nano tube fibers, weaving the organic nano fiber modified carbon nano tube fibers into fiber preforms, depositing a carbon interface layer on the fiber surfaces of the fiber preforms through a chemical vapor deposition method, performing microwave instant high-temperature treatment to obtain high-heat-conductivity preform frameworks, and reacting a ceramic precursor with the high-heat-conductivity preform frameworks through a dipping pyrolysis method to obtain the ceramic-based composite material with the organic nano fiber modified carbon nano tube fibers serving as heat-dredging passages. The ceramic matrix composite prepared by the invention has high heat-conducting property and high mechanical strength, and can meet the requirements of long-time oxidation resistance and service reliability.

Inventors

  • YAN DAN
  • Hao Nairong
  • FENG SHIJIE
  • LI JIMENG
  • LI ZHIJIAN
  • YANG LIANGWEI
  • LIU WEI

Assignees

  • 航天特种材料及工艺技术研究所

Dates

Publication Date
20260512
Application Date
20240730

Claims (8)

  1. 1. A method for preparing a ceramic matrix composite material with organic nanofiber modified carbon nanotube fibers as heat conduction paths, which is characterized by comprising the following steps: (1) Placing the carbon nano tube fiber into strong acid for swelling treatment to obtain a swelled carbon nano tube fiber; (2) Preparing organic nanofiber into an organic nanofiber solution by using strong acid, wherein in the step (2), the strong acid is concentrated sulfuric acid and/or chlorosulfonic acid, the organic nanofiber is one or more of poly-p-benzimidazole-terephthalamide nanofiber, poly-p-phenylene terephthalamide nanofiber and poly-p-phenylene benzobisoxazole nanofiber, the concentration of the organic nanofiber solution is 0.01-1wt%, the diameter of the organic nanofiber is 10-50 nm, and the length of the organic nanofiber is 500-1000 nm; (3) Soaking the swelling carbon nano tube fiber in an organic nano fiber solution, circularly stretching the swelling carbon nano tube fiber, and then carrying out coagulation bath treatment, water washing and drying to obtain an organic nano fiber modified carbon nano tube fiber; (4) Weaving organic nanofiber modified carbon nanotube fibers into a fiber preform, depositing a carbon interface layer on the fiber surface of the fiber preform by a chemical vapor deposition method, and performing microwave instantaneous high-temperature treatment to obtain a high-heat-conductivity preform skeleton, wherein in the step (4), the microwave instantaneous high-temperature treatment is performed at 1800-3200 ℃ for 60-300 seconds, and the microwave instantaneous high-temperature treatment is performed in a nitrogen atmosphere; (5) And reacting the ceramic precursor with the high-heat-conductivity prefabricated body skeleton by an impregnation cracking method to prepare the ceramic matrix composite material with the organic nanofiber modified carbon nanotube fiber as a heat dredging passage.
  2. 2. The method of claim 1, wherein in step (1): the carbon nanotube fiber is continuous carbon nanotube fiber prepared by a floating catalyst chemical vapor deposition method and/or The tensile strength of the carbon nanotube fiber is 1.8-3.2 GPa, the elongation at break is 6-8%, the density is 1.1-1.2 g/cm 3 , and the fiber porosity is 40-60%.
  3. 3. The method of claim 1, wherein in step (1): The swelling treatment time is 1-10 min; the strong acid is concentrated sulfuric acid and/or chlorosulfonic acid, and/or And placing the carbon nano tube fiber into strong acid for swelling treatment under the action of certain tension.
  4. 4. The method of claim 1, wherein in step (3): The total number of the cyclic drafting is 50-100 times; the cyclic drafting is to draft the swelling carbon nano tube fiber for 3-20 s under the condition of the draft ratio of 1-1.5 and then reduce for 3-20 s, and/or The coagulation bath is acetone.
  5. 5. The method of claim 1, wherein in step (4): weaving the organic nanofiber modified carbon nanotube fibers into a fiber preform by adopting 2.5D weaving or three-way orthogonal weaving; The fiber volume content in the fiber preform is 40-50%, and/or The content of the organic nanofiber modified carbon nanotube fibers in the fiber preform is 10-50%.
  6. 6. The method of claim 1, wherein in step (4): The deposition temperature of the chemical vapor deposition method is 900-1100 ℃, the deposition time is 50-150 h, and the deposition pressure is 10-150 Pa.
  7. 7. The method of claim 1, wherein in step (5): The ceramic precursor is one or more of a zirconium silicon precursor, a silicon carbide precursor, a zirconium carbide precursor and a hafnium carbide precursor, and/or The density of the ceramic matrix composite material taking the organic nanofiber modified carbon nanotube fiber as a heat conduction path is 2.0-2.5 g/cm 3 .
  8. 8. Ceramic matrix composite material having organic nanofiber modified carbon nanotube fibers as thermal conduction paths made by the method of any one of claims 1 to 7.

Description

Ceramic matrix composite material with organic nanofiber modified carbon nanotube fibers as heat dredging passages and preparation method thereof Technical Field The invention belongs to the technical field of ceramic matrix composite preparation, and particularly relates to a ceramic matrix composite taking organic nanofiber modified carbon nanotube fibers as a heat dredging passage and a preparation method thereof. Background In recent years, with the rapid development of various novel spacecrafts, nose cones and wing front edge parts of the spacecrafts are subjected to the examination of extreme service conditions in a high-speed flight state, and extremely stringent requirements are placed on the thermophysical properties of related materials. The material with high heat conductivity can quickly transfer local high heat load to a low-temperature area, so that the heat damage of a local structure is quickly reduced, and the service life of the material is prolonged. The ceramic matrix composite material taking the fiber as the reinforcement and the ceramic material as the matrix is an important component of the composite material with the ultra-high temperature structure, combines the advantages of high-efficiency heat transfer and high-temperature heat resistance, and has the advantages of light weight, high strength and the like of the reinforced phase fiber besides the excellent performance of the ceramic material. The traditional fiber reinforcement materials, such as silicon carbide fiber, carbon fiber and the like, have the problems that the graphitization degree of the silicon carbide fiber and the common carbon fiber is low, the size of graphite microcrystal is small, the heat conductivity is low, and an effective heat conduction path is difficult to form, the high-heat-conductivity mesophase pitch-based carbon fiber has high modulus, the graphitized material is brittle, the thickness direction needs to be punctured and arranged by an auxiliary process, a three-dimensional continuous prefabricated body cannot be formed, the combination between the carbon fiber and a matrix is weak, the in-plane heat conductivity is about 10-100 times of the heat conductivity along the thickness, the heat conductivity is anisotropic and the like. The ceramic matrix composite material with the fiber as a toughening phase can not meet the requirements on the thermal dispersion performance, gao Wenwei performance and oxidation resistance of the material in extreme environments. The high-strength and high-heat-conductivity continuous fibers are adopted to form an effective heat conduction path, the ultra-high temperature ceramic is used as a main antioxidation and ablation-resistant material, and the obtained heat-conducting ceramic matrix composite material can meet the requirements of long-time antioxidation and service reliability while having high heat conduction performance. The fiber is used as a toughening phase and a main heat dredging phase, and the requirements of high strength, high toughness and high heat conduction are simultaneously met. As a typical representative of the novel high-performance fiber, a one-dimensional macroscopic material formed by directional arrangement of carbon nanotubes, carbon nanotube fiber (CNTF), exhibits excellent characteristics of light weight, high strength, high toughness, high thermal conductivity, and the like, and the preparation method of the carbon nanotube fiber mainly includes a floating catalyst chemical vapor deposition method, an array spinning method, and a wet spinning method. At present, a floating catalyst chemical vapor deposition method can obtain stable continuous carbon nanotube fibers, but due to uneven arrangement of carbon nanotubes in the fibers, more defects are caused in the fibers, and the porosity is larger, so that excellent thermal and mechanical properties of the carbon nanotubes are limited to be transferred from microscopic to macroscopic. Therefore, how to improve the orientation of the carbon nano tube, reduce the defects in the fiber, reduce the porosity, and effectively improve the mechanical strength and the heat conduction capability of the carbon nano tube is a key point for the preparation of the high-heat-conductivity ceramic matrix composite material by the carbon nano tube fiber to play an excellent role. In summary, it is highly necessary to provide a ceramic matrix composite material with organic nanofiber modified carbon nanotube fibers as a heat conduction path and a method for preparing the same. Disclosure of Invention In order to solve one or more technical problems in the prior art, the invention provides a ceramic matrix composite material taking organic nanofiber modified carbon nanotube fibers as a heat conduction path and a preparation method thereof. According to the method, the internal defects of the carbon nano tube fiber are reduced and the porosity is reduced by improving the orientation of the carbon nano tube fi