基于固体聚硅氧烷的前驱体浸渍裂解法(PIP)制备C/SiOC复合材料及其微结构与力学性能研究

doi:10.15541/jim20190080

无机材料学报 ›› 2019, Vol. 34 ›› Issue (12): 1349-1356.DOI: 10.15541/jim20190080

所属专题：陶瓷基复合材料

• 研究快报 • 上一篇

基于固体聚硅氧烷的前驱体浸渍裂解法(PIP)制备C/SiOC复合材料及其微结构与力学性能研究

吴青青^1,²,王震^1,³(),丁奇^1,^2,⁴,倪德伟^1,³,阚艳梅^1,³,董绍明^1,⁵()

^1. 中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050
^2. 中国科学院大学, 北京 100049
^3. 中国科学院上海硅酸盐研究所结构陶瓷与复合材料工程研究中心, 上海 200050
^4. 上海科技大学, 上海 201210
^5. 中国科学院大学材料与光电研究中心, 北京 100049

收稿日期:2019-02-25 修回日期:2019-03-24 出版日期:2019-12-20 网络出版日期:2019-05-22
作者简介:WU Qing-Qing (1994-), female, master. E-mail: wuqq_sic_2017@163.con

C/SiOC Composites by a Modified PIP Using Solid Polysiloxane: Fabrication, Microstructure and Mechanical Properties

WU Qing-Qing^1,²,WANG Zhen^1,³(),DING Qi^1,^2,⁴,NI De-Wei^1,³,KAN Yan-Mei^1,³,DONG Shao-Ming^1,⁵()

^1. The State Key Lab of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
^2. University of Chinese Academy of Sciences, Beijing 100049, China
^3. Structural Ceramics and Composites Engineering Research Center, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
^4. ShanghaiTech University, Shanghai 201210, China
^5. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2019-02-25 Revised:2019-03-24 Published:2019-12-20 Online:2019-05-22
Supported by:
Foundation item: National Key Research and Development Program of China(2018YFB0704103);Youth Innovation Promotion Association CAS(2015202)

摘要/Abstract

摘要：

以熔融的MK树脂(聚甲基倍半硅氧烷)为前驱体, 采用改进的前驱体浸渍裂解法(PIP)制备了致密的C/SiOC复合材料。为了降低MK树脂的固化温度, 选择有机磺酸作为交联剂, 并采用红外光谱分析仪(FT-IR)和热重分析-差热分析仪(TG-DTA)研究了MK树脂的固化机理和陶瓷化行为。研究表明: MK树脂的陶瓷产率高达85wt%, 其裂解得到的SiOC陶瓷自由碳含量低于3wt%, 有利于提高陶瓷的高温稳定性。经过8次PIP制备的C/SiOC复合材料的密度可达1.82 g/cm ³。对得到的C/SiOC复合材料进行三点弯曲测试, 其弯曲强度为(312±25) MPa, 表现出明显的非脆性断裂行为。

关键词: C/SiOC复合材料, 高效PIP, 微观结构, 交联机理

Abstract:

A modified polymer infiltration and pyrolysis method (PIP) was developed to enhance the densification of C/SiOC composites, using molten MK resin (polymethylsilsesquioxane) as precursor. Organic sulfonic acid was added as cross-linking agent to lower the curing temperature. The cross-linking mechanism and ceramization behavior of MK resin was studied. A high ceramic yield of about 85wt% and low free carbon content below 3wt% are achieved, with excellent high-temperature stability of the derived SiOC. The modified PIP approach presents a high densification efficiency. After only 8 PIP cycles, the final C/SiOC composites possess a density of about 1.81 g/cm ³. Compared with those composites fabricated by conventional PIP process, the C/SiOC composites prepared by modified PIP process show a much denser microstructure with much more improved densification efficiency. Bending strength of the as-fabricated C/SiOC composites is of (312±25) MPa, showing obvious non-brittle fracture behavior.

Key words: C/SiOC composite, high-efficient PIP, microstructure, cross-linking mechanism

中图分类号:

TQ174

吴青青, 王震, 丁奇, 倪德伟, 阚艳梅, 董绍明. 基于固体聚硅氧烷的前驱体浸渍裂解法(PIP)制备C/SiOC复合材料及其微结构与力学性能研究[J]. 无机材料学报, 2019, 34(12): 1349-1356.

WU Qing-Qing, WANG Zhen, DING Qi, NI De-Wei, KAN Yan-Mei, DONG Shao-Ming. C/SiOC Composites by a Modified PIP Using Solid Polysiloxane: Fabrication, Microstructure and Mechanical Properties[J]. Journal of Inorganic Materials, 2019, 34(12): 1349-1356.

图/表 13

Fig. 1 Scheme of the possible structure of MK resin[15]

Fig. 2 Schematic diagram of the modified PIP process

Fig. 3 (a) Change of geometric size of MK resin as a function of temperature; (b) Temperature dependence of the viscosity of MK resin

Fig. 4 Optical photographs of MK resin with different contents of CLA after heat treatment at 160 ℃

Fig. 5 Storage moduli and loss moduli versus curing time for MK resin with 0.05wt% CLA at 160 ℃

Fig. 6 (a) Cross-linking reactions during the curing process; (b) FT-IR spectra of as-obtained MK resin without curing and MK resin with 0.01wt% CLA after curing at 160 ℃ for different time; (c) details in enlarged view of wavenumber in the range from 1250 cm-1 to 500 cm-1

Fig. 7 FT-IR spectra of MK resin with various contents of CLA after being treated at 160 ℃ for 8 h

Fig. 8 TGA-DTA curves of the decomposition behavior for MK resin

Table 1 The ceramic yield and the element composition for MK resin with different CLA contents pyrolized at 1000 ℃

CLA content/wt%	Ceramic yield/wt%	Si/wt%	O/wt%	C/wt%	Empirical formula	Free C/wt%
0	83.7	53.17	33.96	12.87	0.56SiO₂·0.44SiC+0.12C_free	2.82
0.01	85.1	53.13	33.89	12.98	0.56SiO₂·0.44SiC+0.13C_free	2.92
0.05	85.7	53.89	33.05	13.06	0.54SiO₂·0.46SiC+0.10C_free	2.36
0.1	84.7	54.46	33.15	13.39	0.54SiO₂·0.46SiC+0.13C_free	2.91
0.5	84.1	54.74	31.54	13.72	0.50SiO₂·0.50SiC+0.09C_free	2.09
1	82.9	53.86	32.57	13.57	0.53SiO₂·0.47SiC+0.12C_free	2.70

Fig. 9 Density and open porosity variation of C/SiOC composites during the PIP process

Fig. 10 SEM images of the polished cross sections of (a) C-C/SiOC composites; (b-d) M-C/SiOC composites

Fig. 11 Typical bending stress vs. strain curve for the C/SiOC composites

Fig. 12 SEM micrographs of the fracture surfaces of M-C/ SiOC composites

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基于固体聚硅氧烷的前驱体浸渍裂解法(PIP)制备C/SiOC复合材料及其微结构与力学性能研究

C/SiOC Composites by a Modified PIP Using Solid Polysiloxane: Fabrication, Microstructure and Mechanical Properties

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