先驱体转化法制备 SiC/TiC 复合陶瓷及其 1600 ℃ 氧丙烷烧蚀行为

Preparation of SiC/TiC composite ceramics by precursor conversion method and their oxy-propane ablation behavior at 1600 ℃

摘要

针对单一 SiC 陶瓷在极端环境下氧化膜易挥发、抗氧化/烧蚀性能不足的问题，以聚硅氧烷为陶瓷先驱体，乙酰丙酮钛（TiO（acac）₂）为改性剂，采用先驱体转化法结合放电等离子烧结技术制备得到 SiC/TiC 复合陶瓷，系统探究先驱体交联固化机制与高温裂解规律，揭示 Ti 掺杂改性对复合陶瓷抗氧化/烧蚀的影响机制。结果表明，Ti 通过形成 Si―O―Ti 键促进先驱体交联，使先驱体陶瓷产率高达 79%。当 TiO（acac）₂ 添加量（质量分数，下同）为 20%，复合陶瓷中 TiC 含量增加至 19%，烧结致密度显著提高。1600 ℃氧丙烷烧蚀测试显示，20% 改性样品抗烧蚀性能大幅提升，线烧蚀率与质量烧蚀率分别为 0.017 μm/s 和−0.140 mg/s。该复合陶瓷优异的抗烧蚀性能归因于 TiO₂ 与 SiO₂ 形成的连续复合氧化层，抑制了 SiO₂ 挥发与 O₂ 的进一步扩散。

Abstract

To address the issues of volatile oxide scale and insufficient oxidation/ablation resistance of monolithic SiC ceramics in extreme environments, this study employs polysiloxane as a ceramic precursor and titanium acetylacetonate (TiO(acac)₂) as a modifier. SiC/TiC composite ceramics are prepared via a precursor conversion method combined with spark plasma sintering. The cross-linking and curing mechanism of the precursor, as well as the high-temperature pyrolysis behavior, are systematically investigated, and the influence mechanism of Ti doping on the oxidation/ablation resistance of the composite ceramics is elucidated. The results show that Ti promotes precursor cross-linking through the formation of Si―O―Ti bonds, achieving a ceramic yield as high as 79.18%. When the TiO(acac)₂ mass content reaches 20%, the TiC mass content in the composite increases to 19%, and the densification of the sintered ceramic is significantly improved. Oxy-propane ablation tests at 1600 ℃ demonstrate that the 20% modified sample exhibits greatly enhanced ablation resistance, with linear and mass ablation rates of 0.017 μm/s and −0.140 mg/s, respectively. This superior ablation resistance is attributed to the formation of a continuous composite oxide layer consisting of TiO₂ and SiO₂, which suppresses the volatilization of SiO₂ and further oxygen diffusion.

关键词

先驱体转化法 / 放电等离子烧结 / SiC/TiC 复合陶瓷 / 氧丙烷烧蚀

Key words

polymer-derived ceramics / spark plasma sintering / SiC/TiC composite ceramics / oxy-propane ablation

参考文献

[1] Sciti D, Zili L, Reimer T, et al. A systematic approach for horizontal and vertical scale up of sintered ultra—high temperature ceramic matrix composites for aerospace—advances and perspectives[J].Composites Part B, 2022, 234: 109709.

[2] Feng G H, Zhang R X, Yao X Y, et al. A sol—gel strategy of constructing nanosized Hf₆Ta₂O₁₇ encapsulated graphite flakes and its enhancement on the ablation property of carbon/carbon composites[J].Journal of Materials Science & Technology, 2025, 204: 292-301.

[3] 张雨雷，付艳芹，付前刚，等. 纳米管/线多尺度强韧化 C/C 复合材料研究现状与展望[J].航空材料学报，2021，41（3）：11-24.

[4] Zhang Y L, Fu Y Q, Fu Q G, et al. Research status and prospect on nanotube/nanowire multi—scale—reinforced C/C composites[J].Journal of Aeronautical Materials, 2021, 41(3): 11-24.

[5] Wen Q B, Yu Z J, Riedel R. The fate and role of in situ formed carbon in polymer—derived ceramics[J].Progress in Materials Science, 2020, 109: 100623.

[6] Liu G W, Zhang X Z, Yang J, et al. Recent advances in joining of SiC—based materials (monolithic SiC and SiC_f/SiC composites): joining processes, joint strength, and interfacial behavior[J].Journal of Advanced Ceramics, 2019, 8(1): 19-38.

[7] 王海润，郝自清，刘刘，等. SiC/SiC 陶瓷基复合材料面内剪切模量测试方法[J].航空材料学报，2025，45（2）：91-101.

[8] Wang H R, Hao Z Q, Liu L, et al. In—plane shear mechanical properties of SiC/SiC ceramic matrix composites study of test methods[J].Journal of Aeronautical Materials, 2025, 45(2): 91-101.

[9] Zheng G B, Sano H, Uchiyama Y. A carbon nanotube—enhanced SiC coating for the oxidation protection of C/C composite materials[J].Composites Part B, 2011, 42(8): 2158-2162.

[10] Dang X L, Zhao D L, Guo T, et al. Oxidation behaviors of carbon fiber reinforced multilayer SiC—Si₃N₄ matrix composites[J].Journal of Advanced Ceramics, 2022, 11(2): 354-364.

[11] Chen G H, Zhang Y L, Zhang P F, et al. Improvement of SiC/PyC coating on mechanical and anti—oxidation properties through biomimetic laminated structure design[J].Corrosion Science, 2022, 209: 110721.

[12] Chen R C, Zhang J, Hou J Q, et al. Residual mechanical properties of bio—inspired carbon—based composites with multilayer toughened shell—pearl structure[J].Composites Part A, 2025, 196: 108977.

[13] Lv J S, Li W, Guo L X, et al. Functionally graded multicomponent boride—SiC coating: a strategy for enhancing long—term ablation resistance above 2200 ℃[J].Journal of Materials Science & Technology, 2026, 261: 274-282.

[14] Katz—Demyanetz A, Popov V V J, Kovalevsky A, et al. Powder—bed additive manufacturing for aerospace application: techniques, metallic and metal/ceramic composite materials and trends[J].Manufacturing Review, 2019, 6: 5.

[15] Qi Y S, Xu J F, Fei Y H, et al. Preparation and friction properties of SiC—Al₂O₃/2A50 co—continuous composites[J].Ceramics International, 2024, 50(22): 45189-45199.

[16] Zhou L, Fu Q G, Hu D, et al. A dense ZrB₂—SiC—Si/SiC—Si coating to protect carbon/carbon composites against oxidation at 1773 K and 1973 K[J].Corrosion Science, 2021, 183: 109331.

[17] Li W, Lv J S, Li J T, et al. Superior ablation resistance of C/C—HfC SiC composite sharp leading edges above 2500 ℃ prepared by precursor infiltration and pyrolysis[J].Journal of Materiomics, 2025, 11(2): 100879.

[18] Fan Q Q, Fu Y Q, Zhou F, et al. Tailoring the Hf/(Ti+Ta) ratio to achieve synergistic oxide—induced ablation resistance in C/C—(Hf,Ti,Ta)C—SiC composites[J].Journal of the European Ceramic Society, 2026, 46(8): 118145.

[19] Hu D, Fu Q G, Liu T Y, et al. Structural design and ablation performance of ZrB₂/MoSi₂ laminated coating for SiC coated carbon/carbon composites[J].Journal of the European Ceramic Society, 2020, 40(2): 212-219.

[20] Baux A, Nouvian L, Arnaud K, et al. Synthesis and properties of multiscale porosity TiC—SiC ceramics[J].Journal of the European Ceramic Society, 2019, 39(8): 2601-2616.

[21] 李少峰. 碳化硅陶瓷复合材料的制备及抗氧化行为[J].陶瓷学报，2021，42（6）：1018-1025.

[22] Li S F. Preparation and antioxidant behavior of silicon carbide ceramic composites[J].Journal of Ceramics, 2021, 42(6): 1018-1025.

[23] 韩凌锋，赵义亮，张翠萍，等. TiC 含量对无压液相烧结 SiC—TiC 陶瓷复合材料结构和性能的影响[J].机械工程材料，2022，46（10）：34-38.

[24] Han L F, Zhao Y L, Zhang C P, et al. Effect of TiC content on structure and properties of SiC—TiC ceramic composites by pressureless liquid phase sintering[J].Materials for Mechanical Engineering, 2022, 46(10): 34-38.

[25] Ahmoye D, Bucevac D, Krstic V D. Mechanical properties of reaction sintered SiC—TiC composite[J].Ceramics International, 2018, 44(12): 14401-14407.

[26] Li X, Zhang Y L, Fu Y Q, et al. From molecular precursors to ultra—high temperature ceramics: a novel synthesis of hafnium carbonitride nanoceramics[J].Journal of Materials Science & Technology, 2025, 223: 11-21.

[27] Zhang Y Y, Sun J, Guo L X, et al. Ablation resistant ZrC coating modified by polymer—derived SiC/TiC nanocomposites for ultra—high temperature application[J].Journal of the European Ceramic Society, 2022, 42(1): 18-29.

[28] Lu L, Wen Q B, Hu J R, et al. Single—source—precursor synthesis and air—plasma ablation behavior of (Ti, Zr, Hf)C/SiC ceramic nanocomposites at 2200 ℃[J].Journal of Advanced Ceramics, 2024, 13(7): 1043-1059.

[29] Zeng G, Xu P, Zeng C, et al. Synthesis and pyrolysis of single—source precursor for HfC_xN_1−x—SiC ceramic with different SiC contents[J].Ceramics International, 2022, 48(16): 22967-22974.

[30] Hojamberdiev M, Prasad R M, Fasel C, et al. Single—source—precursor synthesis of soft magnetic Fe₃Si— and Fe₅Si₃—containing SiOC ceramic nanocomposites[J].Journal of the European Ceramic Society, 2013, 33(13/14): 2465-2472.

基金资助

国家重点研发计划(2021YFA0715803)

国家自然科学基金(52402113, 52293373)

河南省科技研发计划联合基金(235200810072)