高熵稀土氧化物热障涂层材料弹性及热物性的第一性原理研究

doi:10.15541/jim20250272

无机材料学报

高熵稀土氧化物热障涂层材料弹性及热物性的第一性原理研究

王禹贺^1,2, 罗颐秀¹, 郭会明³, 张广珩⁴, 张思岩⁴, 孙鲁超¹, 王杰民¹, 王京阳¹

1.中国科学院金属研究所,沈阳 110016;
2.中国科学技术大学材料科学与工程学院, 沈阳 110016;
3.中国航发四川燃气涡轮研究院,成都 610500;
4.辽宁材料实验室燃氢防护技术研究所,沈阳 110167

收稿日期:2025-06-27 修回日期:2025-08-22
作者简介:王禹贺(2001-), 男, 硕士研究生. E-mail: yhwang23s@imr.ac.cn
基金资助:
国家重点研发计划(2021YFB3702303); 辽宁省自然科学基金计划项目(2024-MSBA-73); 中国航空发动机集团产学研合作项目(HFZL2023CXY022); 中国科学院金属研究所创新基金项目(2023-PY01)

First-Principles Investigation of Elastic and Thermophysical Properties of High-Entropy Rare-Earth Oxide Thermal Barrier Coating Materials

WANG Yuhe^1,2, LUO Yixiu¹, Guo Huiming³, ZHANG Guangheng⁴, ZHANG Siyan⁴, SUN Luchao¹, WANG Jiemin¹, WANG Jingyang¹

1. 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, Shenyang 110016, China;
3. AECC Sichuan Gas Turbine Research Establishment, Chengdu 610500, China;
4. Institute of Coating Technology for Hydrogen Gas Turbines, Liaoning Academy of Materials, Shenyang 110167, China

Received:2025-06-27 Revised:2025-08-22
About author:WANG Yuhe (2001–), male, Master candidate. E-mail: yhwang23s@imr.ac.cn
Supported by:
National Key R&D Program of China(2021YFB3702303); Natural Science Foundation Program of Liaoning Province (2024-MSBA-73); Industry-University-Research Cooperation Project of AECC(HFZL2023CXY022); IMR Innovation Fund (2023-PY01)

摘要/Abstract

摘要： 连续纤维增强碳化硅陶瓷基复合材料应用于高推重比航空发动机热端部件需采用热/环境障涂层进行防护,为了得到兼具低热导率、适配的热膨胀系数适配及良好的高温相稳定性的新型稀土氧化物热障涂层材料,高熵化设计概念为其成分设计和性能调控提供了新思路和新契机。本研究针对复杂高熵陶瓷体系的结构建模和性能预测难题,提出了一种基于特殊准随机结构法(SQS)的新型高熵建模策略。该方法在保证计算精度的同时,实现了对复杂结构陶瓷性能的快速预测。随后,通过结合第一性原理计算方法,预测并比较了四种高熵稀土氧化物材料的晶体结构、弹性性质及热物理性质,重点揭示了不同稀土成分及Hf掺杂对材料低热导率性能的调控作用及原子尺度根源。研究结果为航空发动机热端部件用热/环境障涂层材料的理论模拟和选材设计提供科学思路与基础数据。

关键词: 高熵稀土氧化物, 热障涂层, 第一性原理, 弹性性质, 热物理性质

Abstract: Continuous fiber-reinforced silicon carbide ceramic matrix composites utlized in hot-section components of high thrust-to-weight ratio aero-engines require protection via thermal/environmental barrier coatings. To develop novel rare-earth oxide thermal barrier coatings materials with low thermal conductivity, compatible thermal expansion coefficients, and excellent high-temperature phase stability, the introduction of the high-entropy design concept offers a promising approach and opportunity for composition design and performance optimization. Addressing the challenges of structural modeling and property prediction for complex high-entropy ceramic systems, this study first introduces a novel high-entropy ceramic modeling strategy based on the Special Quasi-random Structure(SQS) method. This strategy facilitates the rapid prediction of complex ceramic properties while maintaining computational accuracy. Subsequently, the crystal structures, elastic properties, and thermophysical characteristics of four high-entropy rare-earth oxide materials are predicted and compared by integrating first-principles calculations. The research particularly aims to elucidate the regulatory effects and atomic-scale origins of different rare-earth compositions and Hf doping on the material's low thermal conductivity performance. The research results provide scientific insights and fundamental data for the theoretical simulation and material selection design of thermal/environmental barrier coatings for aero-engine hot-section components.

Key words: high-entropy rare-earth oxide, thermal barrier coating, first-principle, elastic property, thermophysical

中图分类号:

TQ174

王禹贺, 罗颐秀, 郭会明, 张广珩, 张思岩, 孙鲁超, 王杰民, 王京阳. 高熵稀土氧化物热障涂层材料弹性及热物性的第一性原理研究[J]. 无机材料学报, DOI: 10.15541/jim20250272.

WANG Yuhe, LUO Yixiu, Guo Huiming, ZHANG Guangheng, ZHANG Siyan, SUN Luchao, WANG Jiemin, WANG Jingyang. First-Principles Investigation of Elastic and Thermophysical Properties of High-Entropy Rare-Earth Oxide Thermal Barrier Coating Materials[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250272.

参考文献

[1] LEE K N, FOX D S, BANSAL N P.Rare earth silicate environmental barrier coatings for SiC/SiC composites and Si₃N₄ ceramics.Journal of the European Ceramic Society, 2005, 25(10): 1705.
[2] MARTIN D, BENNETT C, HUSSAIN T.A review on environmental barrier coatings: history, current state of the art and future developments.Journal of the European Ceramic Society, 2021, 41(3): 1747.
[3] DUAN Z, DENG L, LU K, et al. Thermal cycle and water oxygen performance of multi-layered Y₃Al₅O₁₂/Yb₂SiO₅/Yb₂Si₂O₇ thermal/envir-
onmental barrier coatings.Ceramics International, 2024, 50(9): 16309.
[4] ZINKEVICH M.Thermodynamics of rare earth sesquioxides.Progress in Materials Science, 2007, 52(4): 597.
[5] ZHANG G H, ZHANG J, WANG J Y.Synthesis and characterization of ytterbium oxide: a novel CMAS-resistant environmental barrier coating material.Journal of the American Ceramic Society, 2023, 106(1): 621.
[6] ZHANG G H, SHI J Y, ZHANG J,et al. Investigation on crystallization behavior between (Sc_xYb₁-_x)O_1.5 and CMAS: A new insight in the effect of Sc substitution. Journal of Advanced Ceramics, 2024, 13(6): 789.
[7] WRIGHT A J, WANG Q Y, HUANG C Y,et al. From high-entropy ceramics to compositionally-complex ceramics: a case study of fluorite oxides. Journal of the European Ceramic Society, 2020, 40(5): 2120.
[8] SUN L C, REN X M, DU T F, et al. High Entropy engineering: new strategy for the critical property optimizations of rare earth silicates. Journal of Inorganic Materials, 2021, 36(4): 339.
[9] WANG Y D, GUO Q, ZHOU Q J,et al. Research progress in high temperature functional coatings for advanced aeroengines. Journal of Aeronautical Materials, 2024, 44(5): 48.
[10] PAN W, LIU G H,WANG X L, et al. Review of the development of thermal barrier coating materials and technologies. Thermal Spray Technology,2025(1):1.
[11] LUO X W, XU C H, DUAN S S,et al. Research progress of high-entropy thermal barrier coatings ceramic materials. Aeronautical Manufacturing Technology, 2022, 65(3): 82.
[12] SUN Y N, XIANG H M, DAI F Z,et al. Preparation and properties of CMAS resistant bixbyite structured high-entropy oxides RE₂O₃(RE= Sm, Eu, Er, Lu, Y, and Yb): promising environmental barrier coating materials for Al₂O_3f/Al₂O₃ composites. Journal of Advanced Ceramics, 2021, 10: 596.
[13] ARDREY K D, RIDLEY M J, Wang K,et al. Opportunities for novel refractory alloy thermal/environmental barrier coatings using multicomponent rare earth oxides. Scripta Materialia, 2024, 251: 116206.
[14] PING X Y, MENG B, YU X H,et al. Structural, mechanical and thermal properties of cubic bixbyite-structured high-entropy oxides. Chemical Engineering Journal, 2023, 464: 142649.
[15] MENG H, YU R, TANG Z,et al. Formation ability descriptors for high-entropy diborides established through high-throughput experiments and machine learning. Acta Materialia, 2023, 256: 119132.
[16] GYORFFY B L.Coherent-potential approximation for a nonoverlap muffin-tin-potential model of random substitutional alloys.Physical Review B, 1972, 5(6): 2382.
[17] BELLAICHE L, VANDERBILT D.Virtual crystal approximation revisited: Application to dielectric and piezoelectric properties of perovskites.Physical Review B, 2000, 61(12): 7877.
[18] VAN A, TIWARY P, DE M,et al. Efficient stochastic generation of special quasirandom structures. Calphad, 2013, 42: 13.
[19] REN X M, TIAN Z L, ZHANG J,et al. Equiatomic quaternary (Y_1/4Ho_1/4Er_1/4Yb_1/4)₂SiO₅ silicate: a perspective multifunctional thermal and environmental barrier coating material. Scripta Materialia, 2019, 168: 47.
[20] SUN L C, LUO Y X, TIAN Z L, et al. High temperature corrosion of (Er_1/4Tm_1/4Yb_1/4Lu_1/4)₂Si₂O₇ environmental barrier coating material subjected to water vapor and molten calcium-magnesium-aluminosilicate (CMAS). Corrosion Science, 2020, 175: 108881.
[21] KRESSE G, FURTHMULLER J.Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.Physical review B, 1996, 54(16): 11169.
[22] BLOCHL P E.Projector augmented-wave method.Physical review B, 1994, 50(24): 17953.
[23] PERDEW J P, BURKE K, ERNZERHOF M.Generalized gradient approximation made simple.Physical Review Letters, 1997, 77(18): 3865.
[24] MONKHORST H J, PACK J D.Special points for Brillouin-zone integrations.Physical review B, 1976, 13(12): 5188.
[25] LUO Y X, WANG J, SUN L C,et al. Phononic origin of the infrared dielectric properties of RE₂O₃(RE= Y, Gd, Ho, Lu) compounds. Modelling and Simulation in Materials Science and Engineering, 2024, 32(5): 055009.
[26] VOIG W.Lehrbuch der Kristallphysik 962. Leipzig: Teubner, 1928.
[27] REUSS A.Berechnung der fließgrenze von mischkristallen auf grund der plastizitätsbedingung für einkristalle.Journal of Applied Mathematics and Mechanics, 1929, 9(1): 49.
[28] HILL R.The elastic behaviour of a crystalline aggregate.Proceedings of the Physical Society. Section A, 1952, 65(5): 349.
[29] LUO Y X, WANG J M, LI J N,et al. Theoretical study on crystal structures, elastic stiffness, and intrinsic thermal conductivities of β-, γ-, and δ-Y₂Si₂O₇. Journal of Materials Research, 2015, 30(4): 493.
[30] NYE J F.Physical properties of crystals: their representation by tensors and matrices. Oxford: Oxford university press, 1985.
[31] KITTEL C, MCEUEN P.Introduction to solid state physics. New York: John Wiley & Sons, 2018.
[32] LUO Y X, SUN L C, WANG J M,et al. Material-genome perspective towards tunable thermal expansion of rare-earth di-silicates. Journal of the European Ceramic Society, 2018, 38(10): 3547.
[33] CLARKE D R.Materials selection guidelines for low thermal conductivity thermal barrier coatings.Surface and Coatings Technology, 2003, 163: 67.
[34] MORELLI D T, SLACK G A.High lattice thermal conductivity solids. New York: Springer New York, 2006: 37-68.
[35] ANDERSON O L.A simplified method for calculating the Debye temperature from elastic constants.Journal of Physics and Chemistry of Solids, 1963, 24(7): 909.
[36] SANDITOV B D, TSYDYPOV S B, SANDITOV D S.Relation between the Grüneisen constant and Poisson's ratio of vitreous systems.Acoustical Physics, 2007, 53: 594.
[37] BRULSR J.The thermal conductivity of magnesium silicon nitride, MgSiN₂, ceramics and related materials. Eindhoven: PhD in Chemical Engineering and Chemistry from Eindhoven University of Technology, 2000.
[38] LUO Y X, WANG JM J, LI Y R,et al. Giant phonon anharmonicity and anomalous pressure dependence of lattice thermal conductivity in Y₂Si₂O₇ silicate. Scientific Reports, 2016, 6: 29801.
[39] WEI G, ZUO Y, LUO F,et al. Investigation of mechanical and thermodynamic properties of La₂Zr₂O₇ pyrochlore. International Journal of Energy Research, 2022, 46(2): 2011.
[40] LUO F, LI B, GUO Z, et al. Ab initio calculation of mechanical and thermodynamic properties of Gd₂Zr₂O₇ pyrochlore. Materials Chemistry and Physics, 2020, 243: 122565.
[41] CAO X Q, VASSEN R, STOVER D.Ceramic materials for thermal barrier coatings.Journal of the European Ceramic Society, 2004, 24(1): 1.
[42] TIAN Z L, ZHENG L Y, WANG J M,et al. Theoretical and experimental determination of the major thermo-mechanical properties of RE₂SiO₅(RE= Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y) for environmental and thermal barrier coating applications. Journal of the European Ceramic Society, 2016, 36(1): 189.
[43] TIAN Z L, Zheng L Y, LI Z, et al. Exploration of the low thermal conductivities of γ-Y₂Si₂O₇, β-Y₂Si₂O₇, β-Yb₂Si₂O₇, and β-Lu₂Si₂O₇ as novel environmental barrier coating candidates. Journal of the European Ceramic Society, 2016, 36(11): 2813.