Catalytic Thermal Curing and Ceramization Characterizations of Liquid Polysilazane

WANG Zi-han; LIU Yi-yang; HE Mei; ZHANG Cheng-shuang; WANG Ming-cun

doi:10.14028/j.cnki.1003-3726.2025.25.188

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Catalytic Thermal Curing and Ceramization Characterizations of Liquid Polysilazane

更新时间：2026-01-28

- Catalytic Thermal Curing and Ceramization Characterizations of Liquid Polysilazane
- Polymer Bulletin Vol. 39, Issue 2, Pages: 237-249(2026)
- 作者机构：
  
  北京航空航天大学化学学院　北京 102206
  中国航天科技集团公司第四研究院西安航天复合材料研究所陕西省航天复合材料重点实验室　西安 710025
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2025.25.188
  CLC：
- Received：22 October 2025，
  
  Accepted：11 November 2025，
  
  Published Online：22 December 2025，
  
  Published：20 February 2026
- 稿件说明：
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王子涵, 刘一阳, 何梅, 张承双, 王明存. 液态聚硅氮烷的催化热固化及其热解陶瓷化. 高分子通报, 2026, 39(2), 237–249.

Wang, Z. H.; Liu, Y. Y.; He, M.; Zhang, C. S.; Wang, M. C. Catalytic thermal curing and ceramization characterizations of liquid polysilazane. Polym. Bull. (in Chinese), 2026, 39(2), 237–249.
王子涵, 刘一阳, 何梅, 张承双, 王明存. 液态聚硅氮烷的催化热固化及其热解陶瓷化. 高分子通报, 2026, 39(2), 237–249. DOI： 10.14028/j.cnki.1003-3726.2025.25.188.

Wang, Z. H.; Liu, Y. Y.; He, M.; Zhang, C. S.; Wang, M. C. Catalytic thermal curing and ceramization characterizations of liquid polysilazane. Polym. Bull. (in Chinese), 2026, 39(2), 237–249. DOI： 10.14028/j.cnki.1003-3726.2025.25.188.

摘要

合成了以下4种含有不同特征官能团的聚硅氮烷：含硅氢的聚硅氮烷(Si―H containing polysilazane

PSZ-H)、含乙烯基的聚硅氮烷(Si-vinyl containing polysilazane

PSZ-V)、含乙烯基和硅氢的聚硅氮烷(Si―H and Si-vinyl containing polysilazane

PSZ-VH)、不含乙烯基和硅氢的聚硅氮烷(polysilazane without Si―H and Si-vinyl

PSZ)，并研究了在多种催化条件下的热固化与热解陶瓷化过程的性能。结果表明：催化热固化可显著降低PSZ-H(含硅氢聚硅氮烷)或PSZ-VH(含乙烯基和硅氢聚硅氮烷)的固化温度与固化失重率，但对PSZ-V(仅含乙烯基聚硅氮烷)和PSZ(不含乙烯基和硅氢的聚硅氮烷)影响很小。其中，使用异丙苯过氧化氢与环烷酸钴协同催化固化可使PSZ-VH在350 ℃的固化失重率仅为4.3% (350 ℃)，相比不使用协同催化固化剂时降幅达50.3%。热解陶瓷化结果表明，不同固化条件对聚硅氮烷固化物的高温陶瓷化转化率影响较小。随着热解温度的升高，所得热解陶瓷逐渐由非晶转变为晶态；固化时环烷酸钴的用量越大，所得热解陶瓷的结晶度越高；与环烷酸钴相比，环烷酸镍对热解陶瓷的结晶度有更高的促进作用。对催化热固化和热解陶瓷化的研究旨在优化聚硅氮烷前驱体的固化和陶瓷化过程，有助于聚硅氮烷在航空航天高温部件和耐热电子封装材料上的应用。

Abstract

Four types of polysilazanes with different functional groups were synthesized: Si―H containing polysilazane (PSZ-H)

Si-vinyl containing polysilazane (PSZ-V)

Si―H and Si-vinyl containing polysilazane (PSZ-VH)

and polysilazane without Si―H and Si-vinyl (PSZ). Their thermal curing behaviors and pyrolysis to ceramics were studied using various catalysts. The results indicate that for of PSZ-VH and PSZ-H

catalytic thermocuring of polysilazanes effectively reduced the curing temperature and weight loss

whereas little effect was observed for PSZ-V and PSZ. Under the synergistic catalytic curing by cumene hydroperoxide and cobalt naphthenate

the weight loss of PSZ-VH during curing was only 4.3% (at 350 ℃)

which was 50.3% lower than that of pure polysilazane. The ceramic conversion yield of the cured polysilazanes during high temperature pyrolysis was not significantly affected by the curing conditions. With an increase in pyrolysis temperature

the pyrolytic ceramic gradually transformed from an amorphous to crystalline state; the higher the amount of cobalt naphthenate used for curing

the higher the degree of crystallization of the pyrolytic ceramics. Compared with cobalt naphthenate

nickel naphthenate has a stronger promoting effect on the crystallinity of pyrolytic ceramics during high temperature pyrolysis. The study on catalytic thermal curing and pyrolysis to ceramics aimed to optimize the curing reactions and ceramization mechanism of polysilazane preceramics

which will contribute to the applications of polysilazane in aerospace high-temperature components and thermoresistant electronic packaging materials.

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Keywords

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