大厚度SiC素坯的脱脂分析及其无压高致密制备

doi:10.15541/jim20230126

无机材料学报 ›› 2023, Vol. 38 ›› Issue (10): 1163-1168.DOI: 10.15541/jim20230126 CSTR: 32189.14.10.15541/jim20230126

大厚度SiC素坯的脱脂分析及其无压高致密制备

黄毅华¹(), 黄政仁¹, 沙闻浩¹^,², 周雅斌¹, 谭周茜¹^,², 张明康¹

1.中国科学院上海硅酸盐研究所, 高性能陶瓷与超微结构国家重点实验室, 上海 200050
2.中国科学院大学材料科学与光电技术学院, 北京 100049

收稿日期:2023-03-10 修回日期:2023-05-18 出版日期:2023-10-20 网络出版日期:2023-05-24
作者简介:黄毅华(1982-), 男, 研究员. E-mail: wyu@mail.sic.ac.cn
基金资助:
国家重点研发计划(2022YFB3706200)

Thick SiC Green Bodies: Degreasing Analysis and Pressureless High Density Sintering

HUANG Yihua¹(), HUANG Zhengren¹, SHA Wenhao¹^,², ZHOU Yabin¹, TAN Zhouxi¹^,², ZHANG Mingkang¹

1. State Key Laboratory of High-Performance Ceramics and Ultrastructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2023-03-10 Revised:2023-05-18 Published:2023-10-20 Online:2023-05-24
About author:HUANG Yihua (1982-), male, professor. E-mail: wyu@mail.sic.ac.cn
Supported by:
National Key Research and Development Program of China(2022YFB3706200)

摘要/Abstract

摘要：

高致密的大厚度SiC陶瓷在装甲防护领域具有显著优势, 但是制备厚度100 mm以上的块体SiC陶瓷具有极大的挑战性。针对大厚度SiC陶瓷烧结易开裂、不致密等问题, 本工作着重对大厚度SiC素坯的脱脂产物、压力-不完全脱脂分析等开展了研究。采用TG-MS分析了大厚度陶瓷脱脂过程中的酚醛树脂裂解残余, 其中甲醛等小分子裂解物易脱除, 而二甲基苯酚等高分子产物易滞留芯部, 导致大厚度陶瓷的烧结不致密。经脱脂优化, 素坯表层-芯部密度一致, 均在1.81~1.84 g/cm³范围。经2150 ℃烧结后, 得到不开裂、不变形的大厚度SiC陶瓷, 块体陶瓷表层与芯部的密度均达到3.14 g/cm³。大厚度陶瓷表层与芯部微观结构相似, 表层抗弯强度为(433±48) MPa、芯部抗弯强度达到(411±84) MPa。经分析认为, 大厚度陶瓷芯部不完全脱脂是导致开裂和不致密的主要原因。

关键词: 大厚度, SiC陶瓷, 脱脂分析, 不完全脱脂

Abstract:

SiC ceramics with high thickness and high density are highly advantageous for armor protection, but it is difficult to produce bulk SiC ceramics with thicknesses more than 100 mm. This work was concentrated on the problems of easy cracking and non-densification in the thick SiC ceramic sintering, and degreasing products as well as pressure-incomplete degreasing process were investigated. In order to degrease thick ceramics, phenolic resin’s pyrolysis residue was examined using TG-MS. Formaldehyde and other small-molecule byproducts of breakdown were quickly eliminated, but macromolecule byproducts like dimethylphenol were easily retained in the core, leading to the noncompact sintering of thick ceramics. After degreasing optimization, the blank’s surface-core density is almost constant, ranging from 1.81 to 1.84 g/cm³. In contrast, the test group shows no cracking or deformation after sintering at 2150 ℃, and both surface and core of the large thickness ceramics obtain a density up to 3.14 g/cm³ with similar microstructure. The fracture strength of the core is (411±84) MPa, while the fracture strength of the surface is (433±48) MPa. According to the investigation, the ceramic core’s insufficient degreasing is the primary reason for the cracking and poor density.

Key words: large thickness, SiC ceramics, degreasing effect analysis, insufficient degreasing

中图分类号:

TQ174

黄毅华, 黄政仁, 沙闻浩, 周雅斌, 谭周茜, 张明康. 大厚度SiC素坯的脱脂分析及其无压高致密制备[J]. 无机材料学报, 2023, 38(10): 1163-1168.

HUANG Yihua, HUANG Zhengren, SHA Wenhao, ZHOU Yabin, TAN Zhouxi, ZHANG Mingkang. Thick SiC Green Bodies: Degreasing Analysis and Pressureless High Density Sintering[J]. Journal of Inorganic Materials, 2023, 38(10): 1163-1168.

图/表 9

图1 大厚度SiC块体陶瓷取样示意图(单位: mm)

Fig. 1 Schematic diagram of sampling of large thickness SiC bulk ceramics (Unit: mm)

表1 酚醛树脂主要裂解物及其分子量

Table 1 Main pyrolysis products of phenolic resin and their molecular weight

Pyrolysis product	Molecular weight	Result	Pyrolysis product	Molecular weight	Result
Methane	16	Yes	Naphthalene	128	Yes
Acetylene	26	No	Naphthalene trimethylphenol	136	Yes
Carbon monoxide	28	Yes	Methylnaphthalene	142	No
Formaldehyde	30	Yes	Diphenylmethane	168	No
Carbon dioxide	44	Yes	Dibenzofuran	168	No
Benzene	78	Yes	Anthracene	178	No
Toluene	92	Yes	Methyldiphenyl furan	182	No
Phenol	94	Yes	Xanthine	182	No
Xylene	106	Yes	Methylxanthine	196	No
Cresol	108	Yes	Dimethyl xanthine	210	No
Mesitylene	120	Yes	Trimethylxanthine	224	No
Dimethyl phenol	122	Yes

图2 SiC粉体脱脂产物TG-MS检测的离子流强度

Fig. 2 Ion current intensity of silicon carbide powder degreasing products tested by TG-MS

图3 大厚度SiC素坯表层(a)与芯部(b)脱脂前后(不完全)的失重曲线

Fig. 3 Weight loss before and after (incomplete) degreasing of surface (a) and core (b) of large thickness SiC bulk

图4 不完全脱脂前后甲醛(a)与苯(b)离子流强度变化

Fig. 4 Changes of formaldehyde (a) and benzene (b) ion current intensity before and after incomplete degreasing Colorful figures are available on website

图5 脱脂前后及不完全脱脂二甲基苯酚离子流强度变化

Fig. 5 Changes of ion current intensity of dimethyl phenol before and after degreasing and incomplete degreasing Colorful figures are available on website

表2 大厚度块体素坯不同部位脱脂前后的密度

Table 2 Densities before and after degreasing of different parts of large thickness block bulk

Position	Density after degreasing/(g·cm^-3)	Density before degreasing/(g·cm^-3)
A1	1.84	1.92
A2	1.81	1.86
C3	1.81	1.89
E4	1.83	1.86

图6 大厚度块体SiC陶瓷照片

Fig. 6 Photo of large thickness bulk SiC ceramics

图7 大厚度SiC陶瓷表层(a)与芯部(b)微观结构

Fig. 7 Microstructures of surface (a) and core (b) of large thickness SiC ceramics

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大厚度SiC素坯的脱脂分析及其无压高致密制备

Thick SiC Green Bodies: Degreasing Analysis and Pressureless High Density Sintering

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