高温热处理对SiBCN/HfC复相陶瓷物相组成及微观结构的影响

doi:10.15541/jim20190595

无机材料学报 ›› 2020, Vol. 35 ›› Issue (8): 931-938.DOI: 10.15541/jim20190595 CSTR: 32189.14.10.15541/jim20190595

所属专题：结构陶瓷论文精选(2020)；【虚拟专辑】分离膜，复相陶瓷(2020~2021)

高温热处理对SiBCN/HfC复相陶瓷物相组成及微观结构的影响

魏玉全^1,^2,³(),杨勇^1,²(),刘盟^1,²,郦其乐^1,²,黄政仁^1,²()

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
3.中国科学院大学, 北京 100049

收稿日期:2019-11-25 修回日期:2019-12-10 出版日期:2020-08-20 网络出版日期:2020-01-15
作者简介:魏玉全(1990–), 男, 博士研究生. E-mail: weiyq@shanghaitech.edu.cn
WEI Yuquan (1990–), male, PhD candidate. E-mail: weiyq@shanghaitech.edu.cn
基金资助:
国家重点研发计划(2017YFB0310600);国家自然科学基金重点项目(51471182);上海国际科技合作基金(17520711700);上海国际科技合作基金(18520744200)

Effect of High Temperature Heat Treatment on Phase Composition and Microstructure of SiBCN/HfC Ceramic Composites

WEI Yuquan^1,^2,³(),YANG Yong^1,²(),LIU Meng^1,²,LI Qile^1,²,HUANG Zhengren^1,²()

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. Structural Ceramics and Composites Engineering Research Center, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
3. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2019-11-25 Revised:2019-12-10 Published:2020-08-20 Online:2020-01-15
Supported by:
National Program on Key Basic Research Project(2017YFB0310600);National Natural Science Foundation of China(51471182);Cooperation Fund of Shanghai International Science and Technology(17520711700);Cooperation Fund of Shanghai International Science and Technology(18520744200)

摘要/Abstract

摘要：

采用高能球磨-机械合金化法制备出非晶SiBCN粉末, 并用放电等离子烧结(SPS)法制备SiBCN/HfC复相陶瓷。用X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)、场发射透射电镜(TEM)和扫描电镜(SEM)等研究了高温热处理对其物相组成与微观形貌的影响。研究结果表明, 在机械合金化制备非晶SiBCN粉体过程中引入的氧, 使BN氧化生成B₂O₃。在陶瓷烧结时部分HfC发生氧化生成HfO₂, 使1600 ℃热处理后, HfO₂经碳热还原反应还原成HfB₂, 并在陶瓷基体内产生气孔。在1650和1800 ℃热处理过程中, HfO₂被还原成HfB₂后, 基体中的HfC按照HfC + 2C + B₂O₃ = HfB₂ + 3CO反应转化为HfB₂。引入氧使SiBCN/HfC陶瓷在高温下发生物相转化, 陶瓷基体也因气体产物的挥发变得疏松多孔。因此, 控制氧含量对SiBCN/HfC复相陶瓷的高温应用具有一定的借鉴意义。

关键词: SiBCN, HfC, HfB₂, 高温热处理

Abstract:

Amorphous SiBCN powders were prepared by high-energy ball milling-mechanical alloying method. The SiBCN/HfC ceramic composites were consolidated by spark plasma sintering (SPS). The influence of high temperature heat treatment on the microstructural evolution and phase composition was investigated. The results showed that the oxygen was introduced during the mechanical alloying process, leading to the oxidation of BN to form B₂O_3. HfO₂ was formed in the sintering process result from HfC oxydation and reduced to HfB₂ by carbothermal reduction reaction after heat-treatment at 1600 ℃ for 1 h. Both HfO₂ and HfC were reduced to HfB₂ during the heat-treatment at 1650 ℃ and 1800 ℃ by reaction of HfC + C + B₂O₃ → HfB₂ + CO. Introduction of oxygen causes phase transformation of the SiBCN/HfC ceramic composites after heat treatment at high temperatures, during which ceramic matrix becomes loose and porous due to volatilization of the gaseous byproducts. Therefore, control of oxygen content is the key to the real applications of SiBCN/HfC ceramic composites at high temperatures.

Key words: SiBCN, HfC, HfB₂, high temperature heat treatment

中图分类号:

TQ174

魏玉全,杨勇,刘盟,郦其乐,黄政仁. 高温热处理对SiBCN/HfC复相陶瓷物相组成及微观结构的影响[J]. 无机材料学报, 2020, 35(8): 931-938.

WEI Yuquan,YANG Yong,LIU Meng,LI Qile,HUANG Zhengren. Effect of High Temperature Heat Treatment on Phase Composition and Microstructure of SiBCN/HfC Ceramic Composites[J]. Journal of Inorganic Materials, 2020, 35(8): 931-938.

图/表 10

图1 原始粉末与高能球磨后(SFC05)粉末的XRD图谱

Fig. 1 XRD patterns of raw powders and milled powders

图2 非晶SiBCN粉末的微观形貌与EDS谱图

Fig. 2 Microstructure and EDS element mapping of the amorphous SiBCN powders (a) TEM image with inset showing selected area electron diffraction; (b) HRTEM image; (c) EDS spot analysis of (a); (d) SEM image and (e) EDS elemental maps of (d)

图3 非晶SiBCN粉末的XPS图谱

Fig. 3 XPS spectra of amorphous SiBCN powders

图4 非晶SiBCN粉末的EFTEM照片(a)与EELS图谱(b)

Fig. 4 EFTEM images (a) and EELS spectra (b) of the amorphous SiBCN powders

图5 经不同温度热处理1 h后SiBCN/HfC复相陶瓷的XRD图谱

Fig. 5 XRD patterns of the SiBCN/HfC ceramic composites before and after heat-treatement for 1 h at different temperatures

图6 SiBCN/HfC复相陶瓷微观形貌的SEM照片(a), EDS元素重叠面分布图(b)及对应各元素的面分布图

Fig. 6 Microstructure (a) and EDS element overlap mapping (b) of the as-sintered SiBCN/HfC ceramic composites, and its corresponding element distribution displayed in lower two rows

图7 SiBCN/HfC复相陶瓷热处理前(a)和热处理后(b)的TEM照片, 插图为黑色区域的选区电子衍射图 Fig. 7 TEM images of the SiBCN/HfC ceramic composites (a) before and (b) after heat treatment at 1800 ℃with insets showing the corresponding SAED patterns of dark area in (a) and (b)

图8 反应(1)~(9)的标准吉布斯自由能随温度的变化

Fig. 8 Change of standard Gibbs free energies of reactions (1)-(9) as a function of temperature

表1 反应(6~9)在不同热处理温度下的吉布斯自由能

Table 1 Change of standard Gibbs free energies of reactions (6-9) at different heat treatment temperature

Reaction	ΔG_{1300 ℃}/(kJ·mol^-1)	ΔG_{1400 ℃}/(kJ·mol^-1)	ΔG_{1500 ℃}/(kJ·mol^-1)	ΔG_{1600 ℃}/(kJ·mol^-1)	ΔG_{1650 ℃}/(kJ·mol^-1)	ΔG_{1800 ℃}/(kJ·mol^-1)
HfO₂ + B₂O₃ + 5C = HfB₂ + 5CO(g)	169.8	91.0	12.6	-65.3	-104.1	-210.0
HfO₂ + 2BN + 2C = HfB₂ + 2CO(g) + N₂(g)	246.5	196.6	146.9	97.4	72.8	-0.7
HfO₂ + 3C = HfC + 2CO(g)	115.6	82.1	48.8	15.7	-0.8	-50.1
HfC + 2C + B₂O₃ = HfB₂ + 3CO(g)	54.1	8.8	-36.2	-81.0	-103.3	-169.9

图9 SiBCN/HfC复相陶瓷经不同热处理温度表面形貌的SEM照片和相应的EDS谱图

Fig. 9 Surface morphologies and corresponding EDS results of the SiBCN/HfC ceramic composites before and after heat treatment at different temperatures (a) As sintered; (b)1400 ℃; (c)1600 ℃; (d)1800 ℃

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高温热处理对SiBCN/HfC复相陶瓷物相组成及微观结构的影响

Effect of High Temperature Heat Treatment on Phase Composition and Microstructure of SiBCN/HfC Ceramic Composites

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