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CN-117125989-B - Preparation method of low-cost superhigh-temperature ceramic matrix composite large-size member

CN117125989BCN 117125989 BCN117125989 BCN 117125989BCN-117125989-B

Abstract

The invention relates to a preparation method of a large-size component of a low-cost ultrahigh-temperature ceramic matrix composite. The method comprises the steps of adopting a method of combining a reaction infiltration process (RMI) and a precursor impregnation pyrolysis process (PIP), firstly adopting the PIP process to impregnate, solidify and pyrolyze one end of a large-size component by adopting a hafnium-silicon integrated ceramic precursor solution or a zirconium-silicon integrated ceramic precursor solution, then adopting phenolic resin to impregnate the other end of the large-size component, then carrying out solidification and pyrolysis, and embedding the end into an ultra-high temperature alloy penetrating agent for reaction infiltration. The ultra-high temperature ceramic matrix composite material prepared by the invention has the advantages of low cost, high density and excellent oxidation and ablation resistance.

Inventors

  • FENG SHIJIE
  • YU XINMIN
  • LIU JUNPENG
  • ZHANG BAOPENG
  • SONG HUANJUN
  • YANG LIANGWEI
  • SUN YANAN
  • CHEN HAORAN
  • YANG XIAOJIAN
  • LI XIAODONG
  • LIU WEI

Assignees

  • 航天特种材料及工艺技术研究所

Dates

Publication Date
20260505
Application Date
20220926

Claims (9)

  1. 1. The preparation method of the large-size component of the low-cost ultrahigh-temperature ceramic matrix composite material comprises the following steps: Depositing pyrolytic carbon interface layers on the fiber surfaces of large-size carbon fiber preform components by adopting a chemical vapor deposition method, wherein the density of the carbon fiber preform after depositing pyrolytic carbon is 0.9-1.1g/cm 3 ; Carrying out PIP working procedure of the large-size component, which comprises the steps of dipping, solidifying and high-temperature cracking one end of the large-size carbon fiber preform component deposited with the pyrolytic carbon interface layer by adopting hafnium-silicon integrated ceramic precursor solution or zirconium-silicon integrated ceramic precursor solution; The RMI process of the large-size component comprises the steps of impregnating the other end of the large-size carbon fiber preform component with phenolic resin, then solidifying and carrying out high-temperature pyrolysis, wherein when the density of a porous low-density C/C substrate obtained after the phenolic resin impregnation is 1.2-1.4g/cm 3 , embedding the other end into an ultra-high-temperature alloy penetrating agent for reaction infiltration to obtain the large-size component of the ceramic matrix composite, wherein the ultra-high-temperature alloy penetrating agent is hafnium silicon alloy powder or zirconium silicon alloy powder, when one end of the large-size carbon fiber preform component adopts a hafnium silicon integrated ceramic precursor solution, the ultra-high-temperature alloy penetrating agent adopted by the other end of the large-size carbon fiber preform component is hafnium silicon alloy powder, and when the other end of the large-size carbon fiber preform component adopts a zirconium silicon integrated ceramic precursor solution, the ultra-high-temperature alloy penetrating agent adopted by the other end of the large-size carbon fiber preform component is zirconium silicon alloy powder, so that the components of the two ends of the prepared ceramic matrix composite are identical, and the large-size component cannot generate larger abrupt stress in the high-temperature application process.
  2. 2. The method according to claim 1, wherein the carbon source used in the chemical vapor deposition method is propylene, the carrier gas is nitrogen, the deposition temperature is 800-1100 ℃, and the deposition time depends on the density of the carbon fiber preform after depositing pyrolytic carbon.
  3. 3. The preparation method of the hafnium silicon integrated ceramic precursor solution according to claim 1, wherein the hafnium silicon integrated ceramic precursor solution comprises poly hafnium alkane, poly carbon silane and phenolic resin, the molar ratio of poly hafnium alkane, poly carbon silane and phenolic resin is 1 (0.25-4): 2-6, the zirconium silicon integrated ceramic precursor solution comprises poly zirconium alkane, poly carbon silane and phenolic resin, the molar ratio of poly zirconium alkane, poly carbon silane and phenolic resin is 1 (0.25-4): 2-6, and the viscosity of the hafnium silicon integrated ceramic precursor solution or the zirconium silicon integrated ceramic precursor solution is 50-500 mPa.s.
  4. 4. The preparation method according to claim 1, wherein the curing temperature of the hafnium-silicon integrated ceramic precursor solution or the zirconium-silicon integrated ceramic precursor solution is 200-300 ℃ for 1-10 hours, and the temperature of the high-temperature pyrolysis in the steps of dipping, curing and high-temperature pyrolysis is 1200-1800 ℃ for 1-5 hours.
  5. 5. The preparation method according to claim 1, wherein the phenolic resin is vacuum impregnated for 1-3 hours under the condition of a vacuum degree of 5-100kPa, the curing temperature in the curing and high-temperature cracking is 100-350 ℃, the curing pressure is 3-10MPa, the curing time is 0.5-2 hours, the high-temperature cracking temperature is 700-1000 ℃, and the cracking time is 2-4 hours.
  6. 6. The method according to claim 1, wherein the atomic weight of hafnium or zirconium in the hafnium silicon alloy powder or the zirconium silicon alloy powder is 10 to 39%.
  7. 7. The method according to claim 1, wherein the temperature of the reaction infiltration is 1600-1800 ℃ and the incubation time is 1-2h.
  8. 8. The method according to claim 1, wherein the carbon fiber preform is a needled preform having a density of 0.45-0.65g/cm 3 and/or the carbon fiber preform is subjected to a high-temperature preheating treatment before depositing the pyrolytic carbon interface layer, the high-temperature preheating treatment being performed at a temperature of 1800-2000 ℃ for a holding time of 2-3 hours.
  9. 9. A low cost ultra high temperature ceramic matrix composite large size component made according to the method of any one of claims 1-8.

Description

Preparation method of low-cost superhigh-temperature ceramic matrix composite large-size member Technical Field The invention belongs to the field of ultra-high temperature ceramic matrix composite materials, and particularly relates to a preparation method of a large-size component of a low-cost ultra-high temperature ceramic matrix composite material. Background The preparation technology of the ultra-high temperature ceramic matrix composite mainly comprises chemical vapor deposition (CVI), precursor impregnation cracking (PIP) and reaction infiltration (RMI) processes. The CVI and PIP processes have the advantages of long production period, high cost, low density of the prepared composite material, low cost, short period, high density of the prepared composite material and the like. The basic principle of the RMI process is a method of preparing a composite material by impregnating molten metal into the composite material by capillary action within the preform, and thus, the infiltration depth is limited, which has a certain limitation in the preparation of large-sized components. The PIP process for preparing large-size components has long period, and the raw materials of polymers such as hafnocarbonane, polyzirconium carborane, polycarbosilane and the like have high price and high production cost. Disclosure of Invention In order to solve the defects in the prior art, the invention provides a preparation method of a large-size component of a low-cost ultrahigh-temperature ceramic matrix composite. In order to achieve the above object, the present invention provides the following technical solutions: The preparation method of the large-size component of the low-cost ultrahigh-temperature ceramic matrix composite material comprises the following steps: (1) Depositing a pyrolytic carbon interface layer on the fiber surface of the large-size carbon fiber preform component by adopting a chemical vapor deposition method; (2) A PIP process of the large-size component, namely dipping, solidifying and high-temperature cracking one end of the large-size component by adopting a hafnium-silicon integrated ceramic precursor solution or a zirconium-silicon integrated ceramic precursor solution; (3) And a large-size component RMI process, namely on the basis of the PIP process, impregnating the other end of the large-size component with phenolic resin, then curing and high-temperature cracking, embedding the end into an ultrahigh-temperature alloy penetrating agent, and performing reaction infiltration to obtain the ceramic matrix composite large-size component. Preferably, a chemical vapor deposition method is adopted to deposit a pyrolytic carbon interface layer on the fiber surface of the large-size carbon fiber preform component, wherein the carbon source is propylene, the carrier gas is nitrogen, the deposition temperature is 800-1100 ℃, and the deposition time is determined according to the density of the carbon fiber preform after depositing pyrolytic carbon. Preferably, the density of the carbon fiber preform after depositing pyrolytic carbon is 0.9-1.1g/cm 3. Preferably, the hafnium silicon integrated ceramic precursor solution comprises hafnane, polycarbosilane and phenolic resin, wherein the molar ratio of the hafnane, the polycarbosilane and the phenolic resin is 1 (0.25-4): 2-6; the zirconium silicon integrated ceramic precursor solution comprises polyzirconium carboane, polycarbosilane and phenolic resin, the molar ratio of the polyzirconium carboane, the polycarbosilane and the phenolic resin is 1 (0.25-4): 2-6), and/or The viscosity of the hafnium-silicon integrated ceramic precursor solution or the zirconium-silicon integrated ceramic precursor solution is 50-500 mPa.s. Preferably, the curing temperature of the hafnium-silicon integrated ceramic precursor solution or the zirconium-silicon integrated ceramic precursor solution is 200-300 ℃ for 1-10 hours, and/or the pyrolysis temperature is 1200-1800 ℃ for 1-5 hours. Preferably, the phenolic resin is subjected to vacuum impregnation for 1-3 hours under the condition of the vacuum degree of 5-100kPa, the curing temperature is 100-350 ℃, the curing pressure is 3-10MPa, the curing time is 0.5-2 hours, the high-temperature cracking temperature is 700-1000 ℃, and the cracking time is 2-4 hours. Preferably, the porous low density C/C substrate obtained after impregnation with the phenolic resin has a density of 1.2-1.4g/cm 3. Preferably, the ultra-high temperature alloy penetrating agent is hafnium silicon alloy powder or zirconium silicon alloy powder, and the atomic weight of hafnium or zirconium in the hafnium silicon alloy powder or the zirconium silicon alloy powder is 10-39%. Preferably, the temperature of the reaction infiltration is 1600-1800 ℃ and the heat preservation time is 1-2h. The invention also provides a large-size component of the low-cost ultrahigh-temperature ceramic matrix composite material prepared by adopting the method. Compared wi