高熵化设计: 稀土硅酸盐材料关键性能优化新策略

doi:10.15541/jim20200611

无机材料学报 ›› 2021, Vol. 36 ›› Issue (4): 339-346.DOI: 10.15541/jim20200611 CSTR: 32189.14.10.15541/jim20200611

高熵化设计: 稀土硅酸盐材料关键性能优化新策略

孙鲁超¹(), 任孝旻¹^,², 杜铁锋¹, 罗颐秀¹, 张洁¹, 王京阳¹()

1.中国科学院金属研究所, 陶瓷及复合材料研究部, 沈阳 110016
2.中国科学技术大学, 材料科学与工程学院, 合肥 230026

收稿日期:2020-10-27 修回日期:2020-12-14 出版日期:2021-04-20 网络出版日期:2020-12-10
通讯作者: 王京阳, 研究员. E-mail: jywang@imr.ac.cn
作者简介:孙鲁超(1984-), 男, 副研究员. E-mail: lcsun@imr.ac.cn
基金资助:
航空发动机及燃气轮机重大专项基础研究项目(2017-VI-0020-0093);国家自然科学基金(51772302);中科院国际伙伴计划对外合作重点项目(174321KYSB20180008);辽宁省自然基金(2020-MS-006)

High Entropy Engineering: New Strategy for the Critical Property Optimizations of Rare Earth Silicates

SUN Luchao¹(), REN Xiaomin¹^,², DU Tiefeng¹, LUO Yixiu¹, ZHANG Jie¹, WANG Jingyang¹()

1. Advanced Ceramics and Composites Division, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2. School of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, China

Received:2020-10-27 Revised:2020-12-14 Published:2021-04-20 Online:2020-12-10
Contact: WANG Jingyang, professor. E-mail: jywang@imr.ac.cn
About author:SUN Luchao(1984-), male, associate professor. E-mail: lcsun@imr.ac.cn
Supported by:
National Science and Technology Major Project(2017-VI-0020-0093);National Natural Science Foundation of China(51772302);International Cooperation Key Program(174321KYSB20180008);Natural Science Foundation of Liaoning Province(2020-MS-006)

摘要/Abstract

摘要：

环境障涂层是先进航空发动机高温结构部件用碳化硅纤维增强碳化硅(SiC_f/SiC)陶瓷基复合材料的关键防护。稀土硅酸盐具有低热膨胀系数、优良的抗水氧/CMAS腐蚀性能以及与硅基陶瓷良好的化学相容性, 是目前国际公认的优选环境障涂层体系。常规含单一稀土元素的稀土硅酸盐环境障涂层材料, 存在热应力失配、高温相转变和耐腐蚀性能差等问题, 尚无法完全满足极端燃气环境中的长寿命服役要求。本综述介绍了为解决稀土硅酸盐环境障涂层的关键性能局限, 利用高熵化合物设计方法, 针对稀土硅酸盐热学性能(热膨胀系数和热导率)调控、耐CMAS腐蚀性能提升和相结构稳定性优化方面获得的新进展。这些研究进展为稀土硅酸盐材料的创新设计提供了新思路, 为其作为下一代环境障涂层的性能突破提供了支撑。

关键词: 高熵化设计, 高熵陶瓷, 稀土硅酸盐, 环境障涂层, 综述

Abstract:

Environmental barrier coatings (EBCs) have been developed to improve the durability of SiC_f/SiC CMC components against harsh combustion environment. Among the most promising EBC candidates, rare-earth (RE) silicates attract attentions for their low thermal expansion coefficient, excellent high temperature water vaper and CMAS corrosion resistance, and good thermal and chemical compatibility with silicon-based ceramics and composites. Herein, we reviewed the optimizations of critical key properties of rare-earth silicates through strategic high entropy design to modify the current performance deficiencies of rare-earth silicates like thermal properties (coefficient of thermal expansion and thermal conductivity), CMAS corrosion resistance and high temperature phase stability. The present advancements demonstrate the merits of high entropy engineering for advanced EBCs for the improvement of crucial properties in engine applications.

Key words: high entropy engineering, high entropy ceramics, rare earth silicate, environmental barrier coatings, review

中图分类号:

TQ174

孙鲁超, 任孝旻, 杜铁锋, 罗颐秀, 张洁, 王京阳. 高熵化设计: 稀土硅酸盐材料关键性能优化新策略[J]. 无机材料学报, 2021, 36(4): 339-346.

SUN Luchao, REN Xiaomin, DU Tiefeng, LUO Yixiu, ZHANG Jie, WANG Jingyang. High Entropy Engineering: New Strategy for the Critical Property Optimizations of Rare Earth Silicates[J]. Journal of Inorganic Materials, 2021, 36(4): 339-346.

图/表 8

图1 高熵稀土单硅酸盐(Y1/4Ho1/4Er1/4Yb1/4)2SiO5的HAADF- STEM照片及其原子尺度元素分布图[40]

Fig. 1 HAADF-STEM image of high entropy (Y1/4Ho1/4Er1/4Yb1/4)2- SiO5, EDS mapping of uniform spatial distributions for each element[40]

图2 高熵稀土单硅酸盐(Y1/4Ho1/4Er1/4Yb1/4)2SiO5的热膨胀系数随温度变化关系[40]

Fig. 2 Temperature dependent thermal expansion coefficient of high entropy (Y1/4Ho1/4Er1/4Yb1/4)2SiO5[40]

图3 高熵稀土双硅酸盐(Er1/4Tm1/4Yb1/4Lu1/4)2Si2O7在1500 ℃高温CMAS腐蚀(a~b)4 h和(c~d)50 h后样品表面形貌[48]

Fig. 3 Surface observations of high entropy (Er1/4Tm1/4Yb1/4Lu1/4)2Si2O7 after CMAS corrosion at 1500 ℃ for 4 h (a-b) and 50 h (c-d) [48]

图4 高熵稀土双硅酸盐(Er1/4Tm1/4Yb1/4Lu1/4)2Si2O7在1500 ℃下CMAS腐蚀(a~b)4 h和(c~d)50 h截面形貌[48]

Fig. 4 Observations of the reaction front in the cross-sections of high entropy (Er1/4Tm1/4Yb1/4Lu1/4)2Si2O7 after CMAS corrosion at 1500 ℃ for 4 h (a,b) and 50 h (c,d)[48]

图5 (a)高熵稀土双硅酸盐(Gd1/6Tb1/6Dy1/6Tm1/6Yb1/4Lu1/6)2 Si2O7及RE2Si2O7 (RE = Y, Gd, Tb, Dy, Tm, Yb和Lu)的XRD图谱和(b)高熵稀土双硅酸盐(Gd1/6 Tb1/6Dy1/6Tm1/6Yb1/4Lu1/6)2Si2O7的 XRD图谱Rietveld精修结果[50]

Fig. 5 (a) XRD patterns of (Gd1/6Tb1/6Dy1/6Tm1/6Yb1/4Lu1/6)2 Si2O7, along with the standard XRD patterns of RE2Si2O7 (RE = Y, Gd, Tb, Dy, Tm, Yb and Lu) and (b) Rietveld refinement of XRD pattern for (Gd1/6Tb1/6Dy1/6Tm1/6Yb1/4Lu1/6)2Si2O7[50]

图6 高熵稀土双硅酸盐(Gd1/6Tb1/6Dy1/6Tm1/6Yb1/4Lu1/6)2Si2O7的(a) SEM照片和各元素分布的面扫描能谱分析; (b) HAADF-STEM及原子尺度元素分布; (c)稀土双硅酸盐全新相稳定模式示意图[50]

Fig. 6 (a) SEM image of (Gd1/6Tb1/6Dy1/6Tm1/6Yb1/4Lu1/6)2Si2O7 surface with EDS mappings of Si, Gd, Tb, Dy, Tm, Yb and Lu, (b) STEM high angle annular dark field (HAADF) image and corresponding selected compositional EDS maps of high entropy (Gd1/6Tb1/6Dy1/6Tm1/6Yb1/4Lu1/6)2Si2O7, and (c) schematic diagram of the phase formation of (6RE1/6)2Si2O7[50]

图7 高熵稀土双硅酸盐(Gd1/6Tb1/6Dy1/6Tm1/6Yb1/4Lu1/6)2 Si2O7的(a)热重-差热分析曲线和(b)1800及1900 ℃热处理2 h后样品的XRD图谱[50]

Fig. 7 (a)TG/DTA curves of (Gd1/6Tb1/6Dy1/6Tm1/6Yb1/4Lu1/6)2 Si2O7 and (b) XRD patterns of specimens after being heat-treated at 1800 and 1900 ℃ for 2 h[50]

图8 稀土双硅酸盐多晶型转变温度及熔点示意图[50]

Fig. 8 Schematics of the polymorphic transformation temperatures and melting points of RE2Si2O7 disilicates[50]

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高熵化设计: 稀土硅酸盐材料关键性能优化新策略

High Entropy Engineering: New Strategy for the Critical Property Optimizations of Rare Earth Silicates

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