含锆、硅有机陶瓷前驱体的制备及其陶瓷化研究

玻璃钢/复合材料 ›› 2019, Vol. 0 ›› Issue (3): 43-48.

含锆、硅有机陶瓷前驱体的制备及其陶瓷化研究

杨明泽, 周权^*, 彭峥强, 宋宁

华东理工大学材料科学与工程学院,特种功能高分子材料及相关技术教育部重点实验室,上海200237

收稿日期:2018-07-31 出版日期:2019-03-28 发布日期:2019-03-28
通讯作者: 周权(1973-),男,博士,副教授,硕士生导师,主要从事高性能基体树脂方面的研究,qzhou@ecust.edu.cn。
作者简介:杨明泽(1992-),男,硕士,主要从事超高温复相陶瓷前驱体的制备及其陶瓷化方面的研究。
基金资助:
国家自然科学基金资助项目(51573044)

PREPARATION AND CERAMIZATION OF ZIRCONIUM AND SILICON CONTAINING ORGANIC PRECURSORS

YANG Ming-ze, ZHOU Quan^*, PENG Zheng-qiang, SONG Ning

Key Laboratory of Special Functional Polymer Materials and Related Technology, Ministry of Education,
School of Materials Science and Engineering, East China University of Science
and Technology, Shanghai 200237, China

Received:2018-07-31 Online:2019-03-28 Published:2019-03-28

摘要/Abstract

摘要： 以正丙醇锆、乙酰丙酮,1,2-丙二醇为原料,制备主链为-Zr-O-CH₂-CH-,侧链含有不饱和基团的含锆聚合物(ZMP)并作为锆源。将主链为-SiH、-C≡C-的硅炔树脂(PTSA)作为硅源。将二者以质量比2∶5进行复配,制得陶瓷前驱体(PMS)。采用FT-IR和NMR对ZMP结构进行表征,EDS分析了ZMP的元素组成;利用原位红外分别探讨了PMS的固化行为,运用TGA研究了PMS的耐热性能;TGA测试表明,陶瓷前驱体具有良好的耐热及热稳定性能,在氮气和空气气氛下1000℃时的质量保留率分别为90.24%和88.53%。通过XRD、SEM、TEM和Raman研究了PMS的陶瓷化演变。陶瓷化演变结果表明,PMS在1600℃下的陶瓷转化率高达57.4%,且陶瓷产物中含高结晶度的ZrC、SiC晶体。

关键词: 陶瓷前驱体, 后聚合, 陶瓷化

Abstract: Zirconium-containing polymer (ZMP) with a main chain of-Zr-O-CH₂-CH- and an unsaturated group in the side was prepared by using zirconium n-propoxide, acetylacetone and 1,2-propanediol as raw materials of zirconium source. A silicon alkyne resin (PTSA) with a main chain of -SiH, -C≡C- was used as a silicon source. The two were reconstituted at a mass ratio of 2∶5 to obtain a ceramic precursor (PMS). The ZMP structure was characterized by FT-IR and NMR. The elemental composition of ZMP was analyzed by EDS. The curing behavior of PMS was investigated by DSC and in-situ infrared, and the heat resistance of PMS was studied by TGA. The TGA test shows that the precursor has good heat and thermal stability, and the mass retention rates at 1000 ℃ under nitrogen and air atmosphere are 90.24% and 88.53%, respectively. The ceramization evolution of PMS was studied by XRD, SEM, TEM and Raman. The ceramization evolution results show that the ceramic conversion rate of PMS at 1600 ℃ is as high as 57.4%, and the ceramic products contain high crystallinity ZrC and SiC crystals.

Key words: precursor, post polymerization, ceramization

中图分类号:

TB332

杨明泽, 周权, 彭峥强, 宋宁. 含锆、硅有机陶瓷前驱体的制备及其陶瓷化研究[J]. 玻璃钢/复合材料, 2019, 0(3): 43-48.

YANG Ming-ze, ZHOU Quan, PENG Zheng-qiang, SONG Ning. PREPARATION AND CERAMIZATION OF ZIRCONIUM AND SILICON CONTAINING ORGANIC PRECURSORS[J]. Fiber Reinforced Plastics/Composites, 2019, 0(3): 43-48.

参考文献

[1] Paul A, Jayaseelan D D, Venugopal S, et al. UHTC composites for hypersonic applications[J]. American Ceramic Society Bulletin, 2012, 91(1): 22-29.
[2] Padture N P. Advanced structural ceramics in aerospace propulsion[J]. Nature Materials, 2016, 15(8): 804.
[3] Marschall J, Pejakovic D, Fahrenholtz W G, et al. Temperature jump phenomenon during plasmatron testing of ZrB₂-SiC ultrahigh-temperature ceramics[J]. Journal of Thermophysics& Heat Transfer, 2013, 26(4): 559-572.
[4] Kim S, Szlufarska I, Morgan D. Ab initio study of point defect structures and energetics in ZrC[J]. Journal of Applied Physics, 2010, 107(5): 163-05.
[5] 黄传进, 王明存. SiC-ZrC陶瓷单组分前驱体树脂的制备与性能[J]. 固体火箭技术, 2015(2): 291-294.
[6] Shi J M, Feng J C, Tian X Y, et al. Interfacial microstructure and mechanical property of ZrC-SiC ceramic and Ti₆Al₄V joint brazed with AgCuTi alloy[J]. Journal of the European Ceramic Society, 2017, 37(8): 2769-2778.
[7] Cai T, Qiu W F, Liu D, et al. Synthesis of soluble poly-yne polymers containing zirconium and silicon and corresponding conversion to nanosized ZrC/SiC composite ceramics[J]. Dalton Transactions, 2013, 42(12): 4285-4290.
[8] 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.
[9] Peter Snedden, A I C, Keith Scott A, et al. Cross-linked polymer-ionic liquid composite materials[J]. Macromolecules, 2003, 36(12): 4549-4556.
[10] Juanli Y U, Wang T, Yi L V, et al. Continuous SiBN fiber reinforced nitride ceramic matrix composites fabricated by PIP I-Performance analysis of precursor and fibers[J]. Aerospace Materials & Technology, 2015, 3(5): 19-23.
[11] Yu Z, Yang L, Zhan J, et al. Preparation, cross-linking and ceramization of AHPCS/Cp₂ ZrCl₂, hybrid precursors for SiC/ZrC/C composites[J]. Journal of the European Ceramic Society, 2012, 32(6): 1291-1298.
[12] 郭建辉, 张治军. 二氧化硅修饰纳米氧化锆陶瓷材料的制备及性能[J]. 化学研究, 2012, 23(2): 68-72.
[13] Zhao Y, Wang L J, Zhang G J, et al. Effect of holding time and pressure on properties of ZrB₂-SiC composite fabricated by the spark plasma sintering reactive synthesis method[J]. International Journal of Refractory Metals & Hard Materials, 2009, 27(1): 177-180.
[14] 赵光辉. ZrB₂和SiC在高温低氧压下氧化的原位研究[D]. 浙江: 浙江大学, 2014.
[15] Lv X, Yu S, Ge M, et al. Synthesis and microstructure of continuous composite ceramic fibres of ZrC/ZrB₂-SiC derived from polymeric precursors[J]. Ceramics International, 2016, 42(7): 9299-9303.
[16] 刘长青. 有机含锆陶瓷前驱体的合成研究[D]. 西安: 西北工业大学, 2016.