无压烧结制备(Y0.2Gd0.2Er0.2Yb0.2Lu0.2)2Zr2O7高熵陶瓷及其高温抗CMAS腐蚀性能

doi:10.15541/jim20240256

无机材料学报 ›› 2025, Vol. 40 ›› Issue (2): 159-167.DOI: 10.15541/jim20240256 CSTR: 32189.14.10.15541/jim20240256

无压烧结制备(Y_0.2Gd_0.2Er_0.2Yb_0.2Lu_0.2)₂Zr₂O₇高熵陶瓷及其高温抗CMAS腐蚀性能

樊文楷¹^,²(), 杨潇¹, 李宏华¹, 李永¹, 李江涛¹()

1.中国科学院理化技术研究所, 低温工程重点实验室, 北京 100190
2.中国科学院大学, 北京 100049

收稿日期:2024-05-22 修回日期:2024-08-03 出版日期:2025-02-20 网络出版日期:2024-08-19
通讯作者: 李江涛, 研究员. E-mail: lijiangtao@mail.ipc.ac.cn
作者简介:樊文楷(1998-), 男, 博士研究生. E-mail: fanwenkai21@mails.ucas.ac.cn
基金资助:
国家自然科学基金(92263205)

Pressureless Sintering of (Y_0.2Gd_0.2Er_0.2Yb_0.2Lu_0.2)₂Zr₂O₇ High-entropy Ceramic and Its High Temperature CMAS Corrosion Resistance

FAN Wenkai¹^,²(), YANG Xiao¹, LI Honghua¹, LI Yong¹, LI Jiangtao¹()

1. Key Laboratory of Cryogenic Science and Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2024-05-22 Revised:2024-08-03 Published:2025-02-20 Online:2024-08-19
Contact: LI Jiangtao, professor. E-mail: lijiangtao@mail.ipc.ac.cn
About author:FAN Wenkai (1998-), male, PhD candidate. E-mail: fanwenkai21@mails.ucas.ac.cn
Supported by:
National Natural Science Foundation of China(92263205)

摘要/Abstract

摘要：

稀土锆酸盐(Rare-earth zirconate, REZ)比传统钇稳定氧化锆(Yttrium stabilized zirconate, YSZ)材料更能抵抗环境中的钙镁铝硅氧化物(CMAS)腐蚀, 因此在热障涂层领域受到关注。研究表明, 对锆酸盐类材料进行高熵化设计是提升其高温抗CMAS腐蚀性能的有效方法。本工作采用固相反应法合成了单相缺陷萤石结构的(Y_0.2Gd_0.2Er_0.2Yb_0.2Lu_0.2)₂Zr₂O₇高熵稀土锆酸盐(High-entropy rare-earth zirconate, HE-REZ)粉体, 并将无压烧结(Pressureless sintering, PLS)与冷等静压(Cold isostatic pressing, CIP)技术相结合高效制备了块体样品, 表征了样品的物相组成、微观结构、元素分布、热学性能、力学性能, 重点研究了抗CMAS腐蚀性能。实验结果表明: CIP+PLS工艺可获得相对密度为98.6%的样品, 在1300 ℃、CMAS腐蚀条件下其腐蚀深度仅为7YSZ的2.6%、锆酸钆(GZO)的22.6%。REZ优异的化学稳定性再加上高熵化带来的迟滞扩散效应, 极大提升了样品的抗CMAS腐蚀性能。此外, 相比于GZO, HE-REZ具有更高的硬度与杨氏模量、更大的线膨胀系数、更低的热导率, 使得其力学、热学性能优于GZO。本研究制备的(Y_0.2Gd_0.2Er_0.2Yb_0.2Lu_0.2)₂Zr₂O₇高熵陶瓷在热障材料领域显示出良好的应用前景。

关键词: 高熵陶瓷, 热障材料, 锆酸盐, 无压烧结, 抗CMAS腐蚀性能

Abstract:

Rare-earth zirconates (REZs) have attracted attention in the field of thermal barrier materials because they are more resistant to calcium-magnesium-aluminum-silicon oxide (CMAS) corrosion than yttria stabilized zirconia (YSZ). High-entropy design of zirconates is an effective method to enhance CMAS corrosion resistance, but currently the ability of its corrosion resistance still does not meet the growing requirement. In this work, a solid-state reaction technique was used to synthesize high-entropy rare-earth zirconate (HE-REZ) (Y_0.2Gd_0.2Er_0.2Yb_0.2Lu_0.2)₂Zr₂O₇ powder with a single-phased defect fluorite structure, and pressureless sintering (PLS) combined with cold isostatic pressing (CIP) technique was used to efficiently prepare bulk samples. The phase composition, microstructure, element distribution, thermal and mechanical properties were studied, focusing on the CMAS corrosion resistance. According to the results, under the same CMAS corrosion environment at 1300 ℃, the corrosion depth of HE-REZ with a relative density of 98.6% is only 2.6% of 7YSZ and 22.6% of Gd₂Zr₂O₇ (GZO). The synergistic effect of zirconates' chemical inertness and high-entropy materials' sluggish diffusion accounts for this exceptional corrosion resistance. The obtained HE-REZ shows higher hardness and Young's modulus, larger coefficient of linear expansion, and lower thermal conductivity than ever, making its mechanical and thermal properties superior to GZO. All these outcomes demonstrate the good application potential of (Y_0.2Gd_0.2Er_0.2Yb_0.2Lu_0.2)₂Zr₂O₇ in the field of thermal barrier materials.

Key words: high-entropy ceramic, thermal barrier material, zirconate, pressureless sintering, CMAS corrosion resistance

中图分类号:

TQ174

樊文楷, 杨潇, 李宏华, 李永, 李江涛. 无压烧结制备(Y_0.2Gd_0.2Er_0.2Yb_0.2Lu_0.2)₂Zr₂O₇高熵陶瓷及其高温抗CMAS腐蚀性能[J]. 无机材料学报, 2025, 40(2): 159-167.

FAN Wenkai, YANG Xiao, LI Honghua, LI Yong, LI Jiangtao. Pressureless Sintering of (Y_0.2Gd_0.2Er_0.2Yb_0.2Lu_0.2)₂Zr₂O₇ High-entropy Ceramic and Its High Temperature CMAS Corrosion Resistance[J]. Journal of Inorganic Materials, 2025, 40(2): 159-167.

图/表 12

图1 稀土锆酸盐(REZs)的物相组成

Fig. 1 Phase composition of rare-earth zirconates (REZs) (a) XRD patterns of HE-REZ vs. other REZs with P indicating pyrochlore structure and F indicating defect fluorite structure; (b) Raman spectrum of HE-REZ; (c, d) XRD patterns of HE-REZ synthesized at different temperatures

表1 部分元素阳离子的香农离子半径

Table 1 Shannon ionic radii of some cations

Element	Coordination number	Valency	Ionic radius/pm
Zr	6	+4	72.0
Lu	8	+3	97.7
Yb	8	+3	98.5
Er	8	+3	100.4
Y	8	+3	101.9
Gd	8	+3	105.3
Sm	8	+3	107.9
Nd	8	+3	110.9
La	8	+3	116.0

表2 本研究制备的块体陶瓷样品部分特性的总结

Table 2 Summary of some properties of bulk ceramic samples prepared in this work

Sample	Preparation method	Relative density/%	Average grain size/μm	Corrosion depth (1300 ℃, 10 h)/μm
HE1	SPS	99.7	7.20±3.20	18±2
HE2	PLS	95.4	2.60±0.80	45±5
HE3	CIP+PLS	98.6	2.40±0.60	28±3
GZO	CIP+PLS	98.3	2.70±0.80	124±8
7YSZ	CIP+PLS	97.2	0.36±0.14	1070±10

图2 通过CIP+PLS制备的HE-REZ陶瓷块体(HE3)的宏观、微观形貌及EDS元素分析

Fig. 2 Macroscopic and microscopic morphologies and EDS analyses of HE-REZ bulk ceramic (HE3) prepared by CIP+PLS (a) Photo of bulk sample; (b) SEM image of surface; (c-h) EDS element mappings of Fig. (b)

图3 不同相对密度HE-REZ块体样品的晶粒形貌及对应的CMAS腐蚀深度

Fig. 3 Crystalline morphologies and CMAS corrosion depths of HE-REZ bulk samples with different relative densities (a, b) HE2 (by PLS); (c, d) HE3 (by CIP+PLS); (e, f) HE1 (by SPS)

图4 CIP+PLS制备的块体陶瓷在同条件下的CMAS腐蚀深度及Si元素分布

Fig. 4 Corrosion depths and Si distributions of bulk ceramic synthesized by CIP+PLS under the same CMAS corrosion condition (a) HE-REZ (HE3); (b) GZO; (c) 7YSZ

图5 对照组样品的晶粒形貌

Fig. 5 Crystalline morphologies of control groups (a) GZO; (b) 7YSZ

图6 CMAS腐蚀后HE-REZ陶瓷反应区域的微观形貌及对应元素分布

Fig. 6 Morphology and element distribution in the reaction zone of HE-REZ after CMAS corrosion (a) SEM image of reaction zone; (b-f) EDS element mappings of Fig. (a); (g-i) Partial enlarged images showing hexagonal apatite crystals (yellow box)

图7 HE-REZ块体陶瓷的CMAS腐蚀动力学

Fig. 7 CMAS corrosion kinetics of HE-REZ bulk ceramic (a-e) SEM images of HE-REZ after CMAS corrosion for different time; (f) Mathematical relationship between corrosion depth (H) and corrosion time

图8 HE-REZ陶瓷的CMAS腐蚀机理示意图

Fig. 8 Schematic diagram of CMAS corrosion kinetics for HE-REZ ceramic (a) RE3+ diffusing into CMAS; (b) ZrO2 forming; (c) Apatite precipitating out as RE3+ saturated

图9 HE-REZ、GZO和7YSZ块体陶瓷的力学性能

Fig. 9 Mechanical properties of HE-REZ, GZO and 7YSZ bulk ceramics

图10 HE-REZ和GZO块体陶瓷的热学性能

Fig. 10 Thermal properties of HE-REZ and GZO bulk ceramics (a) Thermal conductivity; (b) Linear expansion in temperature range of 30-1200 ℃

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无压烧结制备(Y_0.2Gd_0.2Er_0.2Yb_0.2Lu_0.2)₂Zr₂O₇高熵陶瓷及其高温抗CMAS腐蚀性能

Pressureless Sintering of (Y_0.2Gd_0.2Er_0.2Yb_0.2Lu_0.2)₂Zr₂O₇ High-entropy Ceramic and Its High Temperature CMAS Corrosion Resistance

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