稀土钽酸盐(RETaO4)高熵陶瓷的制备与热学性能研究

doi:10.15541/jim20200426

无机材料学报 ›› 2021, Vol. 36 ›› Issue (4): 411-417.DOI: 10.15541/jim20200426 CSTR: 32189.14.10.15541/jim20200426

稀土钽酸盐(RETaO₄)高熵陶瓷的制备与热学性能研究

朱嘉桐, 楼志豪, 张萍, 赵佳, 孟轩宇, 许杰(), 高峰

西北工业大学材料学院, 凝固技术国家重点实验室, 西安 710072

收稿日期:2020-08-05 修回日期:2020-09-14 出版日期:2021-04-20 网络出版日期:2020-10-30
通讯作者: 许杰, 副教授. E-mail: xujie@nwpu.edu.cn
作者简介:朱嘉桐(1997-), 男, 硕士研究生. E-mail: zhujiatong@mail.nwpu.edu.cn
基金资助:
国家自然科学基金(51702259);国家自然科学基金(52072301);陕西省基础研究计划(2019JM-432)

Preparation and Thermal Properties of Rare Earth Tantalates (RETaO₄) High-Entropy Ceramics

ZHU Jiatong, LOU Zhihao, ZHANG Ping, ZHAO Jia, MENG Xuanyu, XU Jie(), GAO Feng

State Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi’an 710072, China

Received:2020-08-05 Revised:2020-09-14 Published:2021-04-20 Online:2020-10-30
Contact: XU Jie, associate professor. E-mail: xujie@nwpu.edu.cn
About author:ZHU Jiatong(1997-), male, Master candidate. E-mail: zhujiatong@mail.nwpu.edu.cn
Supported by:
Natural Science Foundation of China(51702259);Natural Science Foundation of China(52072301);Natural Science Basic Research Program of Shaanxi Province(2019JM-432)

摘要/Abstract

摘要：

采用固相法制备了三种具有单斜结构的单相固溶体稀土钽酸盐高熵陶瓷(Nd_1/6Sm_1/6Eu_1/6Gd_1/6Dy_1/6Ho_1/6)TaO₄ (6RETaO₄)、(Nd_1/5Sm_1/5Eu_1/5Gd_1/5Dy_1/5)TaO₄(5RETaO₄)和(Nd_1/4Sm_1/4Eu_1/4Gd_1/4)TaO₄(4RETaO₄), 扫描透射电子显微镜- X射线能谱(STEM-EDS)的分析表明掺杂的稀土元素分布均匀。通过扫描电子显微镜(SEM)观察到由四方-单斜的二级铁弹相变形成的铁弹畴。热膨胀测试表明RETaO₄高熵陶瓷在1200 ℃以下具有良好的热稳定性, 其中6RETaO₄的热膨胀系数可以达到9.25×10^-6 K^-1 (1200 ℃)。由于高熵效应带来的声子散射增加, RETaO₄高熵陶瓷具有较低的晶格热导率(2.98~1.23 W·m^-1·K^-1, 100~1000 ℃), 并且表现出良好的力学性能(6RETaO₄, (9.97±2.2) GPa), 是潜在的下一代热障涂层材料。

关键词: 热障涂层, 稀土钽酸盐, 高熵陶瓷, 热学性能

Abstract:

Single-phase solid solution monoclinic structure high-entropy tantalates (Nd_1/6Sm_1/6Eu_1/6Gd_1/6Dy_1/6Ho_1/6) TaO₄(6RETaO₄), (Nd_1/5Sm_1/5Eu_1/5Gd_1/5Dy_1/5)TaO₄(5RETaO₄), (Nd_1/4Sm_1/4Eu_1/4Gd_1/4)TaO₄(4RETaO₄) were prepared by solid state method. STEM-EDS result shows the rare earth elements are uniformly distributed without segregation. The ferroelastic domain observed through SEM derived from the second ferroelastic phase transition. The thermal expansion experiment suggests the good thermal stability below 1200 ℃, where the thermal expansion coefficient of 6RETaO₄ reaches 9.25×10^-6K^-1 at 1200 ℃. Due to the increase of phonon scattering derived from high-entropy effect, RETaO₄ ceramics exhibit lower intrinsic thermal conductivity (2.98-1.23 W·m^-1·K^-1, 100-1000 ℃) and enhanced mechanical properties (6RETaO₄, (9.97±2.2) GPa), which indicates that it is a potential material for thermal barrier coatings.

Key words: thermal barrier coating, rare earth tantalate, high-entropy ceramics, thermal property

中图分类号:

TQ174

朱嘉桐, 楼志豪, 张萍, 赵佳, 孟轩宇, 许杰, 高峰. 稀土钽酸盐(RETaO₄)高熵陶瓷的制备与热学性能研究[J]. 无机材料学报, 2021, 36(4): 411-417.

ZHU Jiatong, LOU Zhihao, ZHANG Ping, ZHAO Jia, MENG Xuanyu, XU Jie, GAO Feng. Preparation and Thermal Properties of Rare Earth Tantalates (RETaO₄) High-Entropy Ceramics[J]. Journal of Inorganic Materials, 2021, 36(4): 411-417.

图/表 12

表1 RETaO4高熵陶瓷的理论密度、实测密度、气孔率及平均晶粒尺寸

Table 1 Theoretical density, experimental density, porosity, and average grain size of high-entropy tantalates

Sample	ρ_thr/(g·cm^-3)	ρ_exp/(g·cm^-3)	Porosity/%	d_grain/μm
4RETaO₄	8.593	8.441	1.77	2.96
5RETaO₄	8.735	8.597	1.58	6.63
6RETaO₄	8.983	8.758	2.50	3.29

图1 在1500 ℃下烧结10 h得到的RETaO4高熵陶瓷的XRD图谱

Fig. 1 XRD patterns of high-entropy RETaO4 ceramics after sintering at 1500 ℃ for 10 h (a) 2θ=10°-65°; (b) The main peak patterns of (ˉ121) and (121)

表2 稀土高熵钽酸盐晶体结构信息及掺杂稀土离子平均半径

Table 2 Detail structure information of high-entropy RETaO4 ceramics and the average radii of doped rare-earth ions

Sample	a/nm	b/nm	c/nm	β/(°)	$r_{RE^{3+}}$/nm
4RETaO₄	0.544	1.112	0.508	95.65	10.767
5RETaO₄	0.542	1.108	0.508	95.64	10.668
6RETaO₄	0.537	1.099	0.504	95.57	10.581

图2 RETaO4高熵陶瓷的拉曼光谱

Fig. 2 Raman spectra of high-entropy RETaO4 ceramics

图3 RETaO4高熵陶瓷的STEM-EDS 图谱

Fig. 3 STEM-EDS of high-entropy tantalates (a) 6RETaO4; (b) 5RETaO4; (c) 4RETaO4

图4 (a1)4RETaO4、(b1)5RETaO4和(c1)6RETaO4的选区电子衍射花样; (a2)4RETaO4、(b2)5RETaO4和(c2)6RETaO4的高分辨透射电镜照片

Fig. 4 SAED patterns of (a1) 4RETaO4, (b1) 5RETaO4 and (c1) 6RETaO4; HRTEM images of (a2) 4RETaO4, (b2) 5RETaO4 and (c2) 6RETaO4

图5 5RETaO4的晶体结构示意图

Fig. 5 Schematic diagram of 5RETaO4 crystal structure

图6 RETaO4高熵陶瓷的扫描电镜照片

Fig. 6 SEM images of high-entropy tantalates (a,d) 4RETaO4; (b,e) 5RETaO4; (c,f) 6RETaO4

表3 RETaO4高熵陶瓷的维氏硬度

Table 3 HV hardness of high-entropy tantalates

Sample	HV/GPa
4RETaO₄	(7.92±2.33)
5RETaO₄	(6.15±1.60)
6RETaO₄	(9.97±2.20)

图7 RETaO4高熵陶瓷的热膨胀曲线

Fig. 7 Thermal expansion of high-entropy RETaO4 (a) Thermal expansion rates; (b) Thermal expansion coefficients

图8 RETaO4高熵陶瓷的热性能曲线

Fig. 8 Thermal properties of high-entropy RETaO4 (a) Thermal diffusivity; (b) Constant pressure heat capacity; (c) Thermal conductivity; (d) Reciprocal thermal conductivity; (e) Intrinsic thermal diffusivity; (f) Intrinsic thermal conductivity

表4 6RETaO4与单组元稀土钽酸盐和YSZ热导率(100~900 ℃)对比

Table 4 Thermal conductivity of 6RETaO4, single rare earth tantalates, and YSZ (100-900 ℃)

Material	6RETaO₄	NdTaO₄	SmTaO₄	EuTaO₄	GdTaO₄	DyTaO₄	HoTaO₄	YSZ
Thermal conductivity/(W·m^-1·K^-1)	2.78-1.30	3.41-1.75	2.70-1.45	3.23-1.26	3.94-1.28	3.45-1.80	3.35-1.47	3.02-2.38

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稀土钽酸盐(RETaO₄)高熵陶瓷的制备与热学性能研究

Preparation and Thermal Properties of Rare Earth Tantalates (RETaO₄) High-Entropy Ceramics

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