高熵陶瓷固溶结构的透射电镜研究

doi:10.15541/jim20200654

无机材料学报 ›› 2021, Vol. 36 ›› Issue (4): 365-371.DOI: 10.15541/jim20200654 CSTR: 32189.14.10.15541/jim20200654

所属专题：【虚拟专辑】新型材料表征技术(2020~2021)

高熵陶瓷固溶结构的透射电镜研究

郭晓杰¹^,³(), 鲍伟超¹(), 刘吉轩², 王新刚¹, 张国军²(), 许钫钫¹

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.东华大学, 功能材料研究所, 纤维材料改性国家重点实验室, 上海 200051
3.中国科学院大学, 材料科学与光电子功能中心, 北京 100049

收稿日期:2020-11-16 修回日期:2020-12-28 出版日期:2021-04-20 网络出版日期:2020-12-30
通讯作者: 鲍伟超, 助理研究员. E-mail: baoweichao@mail.sic.ac.cn; 张国军, 研究员. E-mail: gjzhang@dhu.edu.cn
作者简介:郭晓杰(1991-), 女, 博士研究生. E-mail: guoxiaojie20@mails.ucas.ac.cn
基金资助:
国家自然科学基金(52032001);国家自然科学基金(51532009);上海市青年科技英才扬帆计划资助(20YF1455500);上海市科学技术委员会科学基金会(18ZR1401400);上海市无机材料测试与表征平台(19DZ2290700)

Study on the Solid Solution Structures of High-Entropy Ceramics by Transmission Electron Microscopy

GUO Xiaojie¹^,³(), BAO Weichao¹(), LIU Jixuan², WANG Xingang¹, ZHANG Guojun²(), XU Fangfang¹

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Institute of Functional Materials, Donghua University, Shanghai 201620, China
3. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2020-11-16 Revised:2020-12-28 Published:2021-04-20 Online:2020-12-30
Contact: BAO Weichao, assistant professor. E-mail: baoweichao@mail.sic.ac.cn; ZHANG Guojun, professor. E-mail: gjzhang@dhu.edu.cn
About author:GUO Xiaojie(1991-), female, PhD candidate. E-mail: guoxiaojie20@mails.ucas.ac.cn
Supported by:
Natural Science Foundation of China(52032001);Natural Science Foundation of China(51532009);Shanghai Sailing Program(20YF1455500);Science and Technology Commission of Shanghai Municipality(18ZR1401400);Shanghai Technical Platform for Testing and Characterization on Inorganic Materials(19DZ2290700)

摘要/Abstract

摘要：

高熵会带来热力学上的高熵效应、结构上的晶格畸变效应、动力学上的迟滞扩散效应以及性能上的“鸡尾酒”效应, 通过高熵设计来提高陶瓷材料的性能是目前研究的热点, 而通过透射电镜揭示高熵结构及其与性能相关性的研究还很缺乏。本研究以相应金属氧化物、碳化硼和石墨为原材料, 在制备高熵硼化物和高熵碳化物粉体的基础上, 利用放电等离子体烧结制备得到高熵(TiZrHfNbTa)B₂和(TiZrHfNbTa)C陶瓷。采用透射电子显微镜及其能谱分析手段对两种高熵陶瓷进行了纳米尺度和原子尺度的结构表征, 发现过渡金属元素固溶后保持了晶体结构的完整性, 五种元素分布均匀, 但在原子尺度存在固溶元素的浓度振荡、原子离散和晶格应变。本工作获得的原子尺度的固溶结构信息将有助于对高熵陶瓷构效关系的理解, 并为高熵陶瓷的组分和结构设计提供实验依据。

关键词: 高熵陶瓷, 透射电镜, 纳米尺度结构, 原子尺度结构

Abstract:

High-entropy brings high-entropy effect on thermodynamics, lattice distortion effect on structure, diffusion retardation effect on dynamics and “cocktail” effect on properties in materials. It is a hotspot to improve the properties of ceramics by high-entropy design. However, it still lacks the study of high-entropy structures and their correlation to the properties through transmission electron microscopy (TEM). In this study, high-entropy borides and carbides powders were fabricated by using metal oxides, boron carbide and graphite as raw materials. The high-entropy (TiZrHfNbTa)B₂ and (TiZrHfNbTa)C ceramics were then synthesized by spark plasma sintering of the as-fabricated powders. Transmission electron microscope and energy dispersive spectrometry were used to characterize the structure of the two high-entropy ceramics at the nano-scale and atomic-scale. The integrity of crystal structure maintained after solid solution of five transition metal elements which were found to uniformly distribute in the ceramics. However, at atomic scales, concentration oscillations of solid solution elements, atomic dispersion and lattice strain were observed. The solid solution structures at atomic scales as-obtained in this work can help to understand the structure-property relationship of high-entropy ceramics and provide experimental basis for the composition and structure design of high-entropy ceramics.

Key words: high-entropy ceramics, transmission electron microscopy (TEM), structure in nano-scale, structure in atomic-scale

中图分类号:

O766

郭晓杰, 鲍伟超, 刘吉轩, 王新刚, 张国军, 许钫钫. 高熵陶瓷固溶结构的透射电镜研究[J]. 无机材料学报, 2021, 36(4): 365-371.

GUO Xiaojie, BAO Weichao, LIU Jixuan, WANG Xingang, ZHANG Guojun, XU Fangfang. Study on the Solid Solution Structures of High-Entropy Ceramics by Transmission Electron Microscopy[J]. Journal of Inorganic Materials, 2021, 36(4): 365-371.

图/表 5

图1 (TiZrHfNbTa)B2陶瓷的TEM明场像(a, d, g), 相应晶粒的SAD花样(b, e, h)和高分辨图像(c, f, i)

Fig. 1 Bright field TEM images (a, d, g), SAD patterns (b, e, h) and high-resolution images (c, f, i) of the (TiZrHfNbTa)B2 ceramic

图2 (TiZrHfNbTa)C陶瓷的TEM明场像(a, d, g), 相应晶粒的SAD花样(b, e, h)和高分辨图像(c, f, i)

Fig. 2 Bright field TEM images (a, d, g), SAD patterns (b, e, h) and high-resolution images (c, f, i) of the (TiZrHfNbTa)C ceramic

图3 (TiZrHfNbTa)B2(a)和(TiZrHfNbTa)C(e)的高分辨TEM图像, 右上角插图是相应的傅里叶变换的衍射花样; (TiZrHfNbTa)B2(b~d)和(TiZrHfNbTa)C(f~h)样品GPA处理的不同方向上的应力分布图

Fig. 3 High-resolution TEM images of (TiZrHfNbTa)B2 (a) and (TiZrHfNbTa)C (e) with SAD patterns inserted in the upper right corner; and corresponding phase images of (TiZrHfNbTa)B2 (b-d) and (TiZrHfNbTa)C (f-h) in different directions processed by GPA

图4 (TiZrHfNbTa)B2(a)和(TiZrHfNbTa)C(d)的HAADF图像及其相应的原子离散分布图((b, c)和(e, f))

Fig. 4 HAADF images of (TiZrHfNbTa)B2 (a) and (TiZrHfNbTa)C (d); Corresponding atomic discrete distribution maps ((b, c) and (e, f))

图5 (TiZrHfNbTa)B2(a)和(TiZrHfNbTa)C(b)的原子级HADDF图像及其EDS面分布

Fig. 5 Atomic HADDF images and corresponding EDS mappings of (TiZrHfNbTa)B2 (a) and (TiZrHfNbTa)C (b)

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高熵陶瓷固溶结构的透射电镜研究

Study on the Solid Solution Structures of High-Entropy Ceramics by Transmission Electron Microscopy

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