To meet the requirement of rapid development in near spacecraft, continuous research efforts have been focused on the anti-oxidation materials which can be applied in very harsh environmental conditions. Carbon fiber reinforced SiC matrix (C/SiC) composites have overall advantages including lower density, good mechanical performance, and strong anti-oxidation capability, etc. Therefore, it can be used as various aerospace structural materials. However, C/SiC composites can only endure the short-time use (1000 s) when the temperature is lower than 1800℃, and longer-time use below 1600℃ in oxidizing environment. In this case, ZrC has been considered as a good candidate, owing to its melting point of 3540℃. Adding ZrC could increase the anti-oxidation capability of C/SiC composites, and besides, preceramic polymer processing is a good way to obtain ceramic matrix composites at a relatively low temperature. Various precursors of ceramic have been synthesized, but very little systematic work has been done regarding to the pyrolysis mechanism of polymeric precursor to zirconium carbide ceramics. In this work, pyrolysis process of an organic polymeric precursor of zirconium carbide (PZC) was investigated, the conversion mechanism of the precursor to ceramics was studied in detail as well. The methodology involved the microstructure analysis and phase composition of products by FT-IR, XRF, TG?DSC, MS-online, XRD and SEM. Furthermore, thermodynamics of carbothermal reduction reaction was calculated as well. The results showed that there was the decomposition of PZC with the temperature up to 600℃, including the release of small-molecule gases, such as water vapor, carbon monoxide, carbon dioxide, methane, acetone, and tetrahydrofuran, which were formed from the rearrangement of pyrolysis species. Then the solid inorganic products of amorphous-free carbon and m-ZrO2 were formed with the temperature range from 600℃ to 1200℃. Cubic ZrC crystalline in nano size can be formed above 1300℃, via the carbothermal reduction reaction between carbon and m-ZrO2, and this temperature was lower than the temperature from thermodynamic calculations. The ceramization of PZC could be completed with temperature at 1500℃, and the yield of ceramic was 33.45%.
Weijia KONG Shouquan YU Min GE Weigang ZHANG Lingzhong DU
. Pyrolysis of an organic polymeric precursor of zirconium carbide ceramics[J]. The Chinese Journal of Process Engineering, 2019
, 19(3)
: 623
-630
.
DOI: 10.12034/j.issn.1009-606X.218299
[1] Kontinos D, Gee K, Prabbu D. Temperature constraints at the sharp leading edge of a crew transfer vehicle[C]//AIAA Thermophysics Conference, 35th, Anaheim, 2001.
[2] 闫联生，崔万继，崔红，等. 超高温抗氧化碳陶复合材料研究进展[J]. 宇航材料工艺, 2014, 44(3): 6–11.
[3] Li Q, Zhou H, Dong S, et al. Fabrication of a ZrC–SiC matrix for ceramic matrix composites and its properties[J]. Ceram Int, 2012, 38(5): 4379-4384.
[4] Li H, Zhang L, Cheng L, et al. Fabrication of 2D C/ZrC–SiC composite and its structural evolution under high-temperature treatment up to 1800℃[J]. Ceram Int, 2009, 35(7): 2831-2836.
[5] 黄传进，王明存，韩伟键，等. ZrC–SiC复相陶瓷先驱体的制备与性能[J]. 硅酸盐学报, 2015, 43(9): 1177-1185.
[6] Kodama H, Sakamoto H, Miyoshi T. Silicon Carbide Monofilament‐Reinforced Silicon Nitride or Silicon Carbide Matrix Composites[J]. Journal of the American Ceramic Society, 1989, 72(4):551-558.
[7] Moene R, Boon H T, Schoonman J, et al．Coating of activated carbon with silicon carbide by chemical vapour deposition[J]. Carbon, 1996, 34(5): 567-579.
[8] Isola C, Appendino P, Bosco F, et al. Protective glass coating for carbon–carbon composites[J]. Carbon, 1998, 36(7-8): 1213-1218.
[9] Cheng L, Xu Y, Zhang L, et al. Oxidation behavior of three dimensional C/SiC composites in air and combustion gas environments[J]. Composites Part A, 2000, 38(15):2103-2108.
[10] 宋瑞颖，刘宁，张红芹，等. ZrC陶瓷的性能、制备及应用[J]. 硬质合金, 2009, 26(2): 134-140.
[11] Fang H T, Yin Z D, Zhu J C, et al. Effect of Al additive in Si slurry coating on liquid Si infiltration into carbon-carbon composites[J]. Carbon, 2001, 39(13): 2035-2041.
[12] 马彦，马青松，陈朝辉. 先驱体作粘结剂低温制备SiC多孔陶瓷[J]. 稀有金属材料与工程, 2007, 36(s1): 531-533.
[13] Xue Y T, Qiu W F, Li H, et al. New route to synthesize preceramic polymers for zirconium carbide[J]. Chinese Chemical Letters, 2012, 23(9): 1075-1078.
[14] 曹淑伟，谢征芳，王军，等. 聚锆碳硅烷陶瓷先驱体的制备与表征[J]. 有机硅材料, 2008, 1(4):621-625.
[15] 张伟刚，戈敏，魏玺. 一种碳化锆和二硼化锆陶瓷有机前驱体材料及其制备方法：201110010110.2 [P]. 2011-01-28.
[16] 解静，李克智，付前刚，等. 聚合物浸渍裂解法制备C/C-ZrC-SiC-ZrB2复合材料及其性能研究[J]. 无机材料学报, 2013, 28(6): 605-610.
[17] 杨星，崔红，闫联生，等. 陶瓷前驱体配比对C/C-ZrC-SiC复合材料烧蚀性能的影响[J]. 材料导报, 2015, 29(2): 52-56.
[18] Feng B, Li H J, Zhang Y L, rt al. Effect of SiC/ZrC ratio on the mechanical and ablation properties of C/C–SiC–ZrC composites[J]. Corrosion Science, 2014, 82(5): 27-35.
[19] 王玲玲，嵇阿琳，崔红，等. ZrC改性C/C-SiC复合材料的力学和抗烧蚀性能[J]. 复合材料学报, 2016, 33(2): 373-378.
[20] 刘丹，邱文丰，蔡涛，等. 碳化锆液相陶瓷前驱体的制备及陶瓷化[J]. 宇航材料工艺, 2014, 44(1): 79-83.
[21] 叶大伦，胡建华. 实用无机物热力学数据手册-第2版[M]. 冶金工业出版社, 2002.
[22] 化学工业出版社辞书编辑部，化学化工大辞典无机化学[M]. 化学工业出版社, 2003.
[23] 陈明伟，邱海鹏，张伟刚. 碳化锆有机前驱体陶瓷化过程研究[C]//第17届全国复合材料学术会议论文集. 北京: 2012: 936-939.
[24] Sacks M D, Wang C A, Yang Z, et al. Carbothermal reduction synthesis of nanocrystalline zirconium carbide and hafnium carbide powders using solution-derived precursors[J]. Journal of Materials Science, 2004, 39(19):6057-6066.
[25] 熊炳昆. 锆铪及其化合物应用[M].冶金工业出版社, 2002, 07: 75-76.
