SiBCN陶瓷先驱体合成、固化动力学及陶瓷化产物性能研究

doi:10.19936/j.cnki.2096-8000.20240628.002

复合材料科学与工程 ›› 2024, Vol. 0 ›› Issue (6): 15-21.DOI: 10.19936/j.cnki.2096-8000.20240628.002

SiBCN陶瓷先驱体合成、固化动力学及陶瓷化产物性能研究

彭喆^1,2, 姚利超^1,2, 柴笑笑^1,2, 李松^1,2*

1.北京玻钢院复合材料有限公司,北京 102101;
2.特种纤维复合材料国家重点实验室,北京 102101

收稿日期:2023-02-01 出版日期:2024-06-28 发布日期:2024-07-26
通讯作者: 李松(1977—),男,博士,教授级高级工程师,研究方向为高温透波及烧蚀防热复合材料,lis@sinomatech.com。
作者简介:彭喆(1988—),男,博士,高级工程师,研究方向为高温透波陶瓷基复合材料。
基金资助:
特种纤维复合材料国家重点实验室应用基础性研究项目(YJ2018SYS03);中国建材集团攻关专项资助(2021YCJS02)

Study on synthesis, curing kinetics and ceramic product’s properties of SiBCN ceramic precursor

PENG Zhe^1,2, YAO Lichao^1,2, CHAI Xiaoxiao^1,2, LI Song^1,2*

1. Beijing Composite Materials Co., Ltd., Beijing 102101, China;
2. State Key Laboratory of Advanced Fiber Composites, Beijing 102101, China

Received:2023-02-01 Online:2024-06-28 Published:2024-07-26

摘要/Abstract

摘要： 采用脱氢偶联聚合方法,以聚硅氮烷和环硼氮烷制备了四种低黏度SiBCN陶瓷先驱体,通过红外表征了SiBCN陶瓷先驱体的结构,通过非等温DSC研究了SiBCN陶瓷先驱体的固化动力学过程,通过超高温TG,XRD,XPS等手段表征了SiBCN陶瓷化产物的性能。结果表明:四种SiBCN陶瓷先驱体的室温黏度为198~275 mPa·S,固化温度范围为120~235 ℃。SiBCN陶瓷先驱体的固化过程为双放热峰,通过Kissinger,Ozawa,Crane方程对主放热峰进行分析得到SiBCN陶瓷先驱体P1、P2、P3、P4固化动力学参数,其中活化能E_a分别为96.9 kJ/mol、88.4 kJ/mol、119.5 kJ/mol、268.2 kJ/mol,反应级数n分别为0.933,0.930,0.940,0.943。SiBCN陶瓷先驱体P4经过1 300 ℃裂解后的SiBCN陶瓷结构为非晶态,其B含量为4.67%,分解温度高达1 651 ℃。四种SiBCN陶瓷先驱体裂解产物的分解温度与B含量表现出一定的关系:当B含量超过一定浓度时,陶瓷化产物的高温稳定性得到有效提高。

关键词: SiBCN先驱体, SiBCN陶瓷, 脱氢偶联, 固化动力学, 耐高温性, 复合材料

Abstract: Four SiBCN precursors with low viscosity were synthesized by dehydrogenation of polysilazane and borazine. The precursor molecular structure, curing kinetics and ceramicized product’s properties of SiBCN precursorswere investigated by fourier transform infrared spectrometry (FTIR), differential scanning calorimetry (DSC), ultra-high temperature thermogravimetric analysis (TG), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. The results show that four SiBCN precursors are the viscosity of 198~275 mPa·S at room temperature and curing temperature of 120~235 ℃. The curing process of SiBCN precursors make double exothermic peaks. The kinetic parameters of SiBCN precursor P1, P2, P3, P4 are calculated by Kissinger, Ozawa and Crane equations depended on main exothermic peak, where the results are summarized as follows: Apparent activation energy are 96.9 kJ/mol, 88.4 kJ/mol, 119.5 kJ/mol, 268.2 kJ/mol with reaction order of 0.933, 0.930, 0.940, 0.943. The XRD results indicate that the ceramic product of P4 maintains amorphous structure by sintering at 1 300 ℃. The content of B in the ceramic product of P4 is 4.67% and decomposition temperature is higher than 1 650 ℃. The decomposition temperature shows a certain relationship with content of B in ceramic product of SiBCN precursors: The high-temperature stability of the ceramic product is effectively improved when the B content of SiBCN precursor exceeds a certain concentration.

Key words: SiBCN precursor, SiBCN ceramic, dehydrogenation, curing kinetics, high temperature resistance, composites

中图分类号:

TB332

彭喆, 姚利超, 柴笑笑, 李松. SiBCN陶瓷先驱体合成、固化动力学及陶瓷化产物性能研究[J]. 复合材料科学与工程, 2024, 0(6): 15-21.

PENG Zhe, YAO Lichao, CHAI Xiaoxiao, LI Song. Study on synthesis, curing kinetics and ceramic product’s properties of SiBCN ceramic precursor[J]. COMPOSITES SCIENCE AND ENGINEERING, 2024, 0(6): 15-21.

参考文献

[1] MORSCHER G N. Fiber-reinforced ceramic matrix composites for aero engines[J]. Encyclopedia of Aerospace Engineering, 2014, 1-10.
[2] SCHMIDT S, BEYER S, IMMICH H, et al. Ceramic matrix composites: A challenge in space-propulsion technology applications[J]. International Journal of Applied Ceramic Technology, 2005, 2(2): 85-96.
[3] WANG H, SINGH R N, LOWDEN R A. Thermal shock behavior of two-dimensional woven fiber-reinforced ceramic composites[J]. Journal of the American Ceramic Society, 1996, 79(7): 1783-1792.
[4] 陈玉峰, 洪长青, 胡成龙, 等. 空天飞行器用热防护陶瓷材料[J]. 现代技术陶瓷, 2017, 38(5): 311-390.
[5] VIARD A, FONBLANC D, LOPEZ-FERBER D, et al. Polymer derived Si-B-C-N ceramics: 30 years of research[J]. Advance Engineering Materials, 2018, 20(10): 1800360.
[6] RIEDEL R, KIENZLE A, DRESSLER W, et al. A silicoboron carbonitride ceramic stable to 2 000 ℃[J]. Nature, 1996, 382: 796-798.
[7] WEINMANN M, SCHUHMACHER J, KUMMER H, et al. Synthesis and thermal behavior of novel Si-B-C-N ceramic precursors[J]. Chemistry Materials, 2000, 12(3): 623-632.
[8] MULLER A, ZERN A, GERSTEL P, et al. Boron-modified poly(propenylsilazane)-derived Si-B-C-N ceramics: Preparation and high temperature properties[J]. Journal of the European Ceramic Society, 2002, 22(9-10): 1631-1643.
[9] MULLER A, GERSTEL P, WEINMANN M, et al. Correlation of boron content and high temperature stability in Si-B-C-N ceramics[J]. Journal of the European Ceramic Society, 2000, 20(14-15): 2655-2659.
[10] ZHANG Z, ZENG F, HAN J, et al. Synthesis and characterization of a new liquid polymer precursor for Si-B-C-N ceramics[J]. Journal of Materials Science, 2011, 46(18): 5940-5947.
[11] YU Z, ZHOU C, LI R, et al. Synthesis and ceramic conversion of a novel processible polyboronsilazane precursor to SiBCN ceramic[J]. Ceramics International, 2012, 38(6): 4635-4643.
[12] ZHAO H, CHEN L, LUAN X, et al. Synthesis, pyrolysis of a novel liquid SiBCN ceramic precursor and its application in ceramic matrix composites[J]. Journal of the European Ceramic Society, 2017, 37(4): 1321-1329.
[13] WANG X, WANG H, SHI J. Synthesis, characterization, and ceramic conversion of a liquid polymeric precursor to SiBCN ceramic via borazine-modified polymethylsilane[J]. Journal of Materials Science, 2018, 53(16): 11242-11252.
[14] 张晨乾, 陈蔚, 叶宏军, 等. 具有双峰反应特性的高韧性双马来酰亚胺树脂固化动力学和TTT图[J]. 材料工程, 2016, 44(10): 17-23.
[15] KISSUNGER E D. Reaction kinetics in differential thermal analysis[J].Analytical Chemistry, 1957, 29(11): 1702-1706.
[16] OZAWA T. A new method of analyzing thermogravimetric data[J]. Bulletin of the Chemical Society of Japan, 1965, 38(11): 1881-1886.
[17] CRANE L W, DYNES P J, KAELBLE D H. Analysis of curing kinetics in polymer composites[J]. Journal of Polymer Science: Polymer Letter Edition, 1973, 11(8): 533-540.
[18] TAVAKOLI A M, GOLCZEWSKI J A, BILL J, et al. Effect of boron on the thermodynamic stability of amorphous polymer-derived Si-(B-)C-N ceramics[J]. Acta Materialia, 2012, 60: 4514-4522.

SiBCN陶瓷先驱体合成、固化动力学及陶瓷化产物性能研究

Study on synthesis, curing kinetics and ceramic product’s properties of SiBCN ceramic precursor

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