磁铅石型稀土六铝酸盐热障涂层材料的制备与性能

doi:10.15541/jim20250386

无机材料学报 ›› 2026, Vol. 41 ›› Issue (8): 1103-1109.DOI: 10.15541/jim20250386

磁铅石型稀土六铝酸盐热障涂层材料的制备与性能

许茗奕¹(), 熊瑛², 王博², 张艺馨², 陈文博³(), 曹学强³

¹ THL贵州先进功能涂层创新中心, 贵州 550000
² 中国航发沈阳黎明航空发动机有限责任公司, 沈阳 110043
³ 武汉理工大学硅酸盐科学与先进建材全国重点实验室, 武汉 430070

收稿日期:2025-10-02 修回日期:2025-12-04 出版日期:2026-08-20 网络出版日期:2025-12-11
通讯作者: 陈文博, 研究员. E-mail: wchen@whut.edu.cn
作者简介:许茗奕(1996-), 男, 博士研究生. E-mail: xumingyi96925@163.com
基金资助:
国家自然科学基金重大研究计划项目(92360304);国家自然科学基金青年项目(52302109);湖北省自然科学基金青年项目(2023AFB075);国家自然科学基金重点支持项目(92060201)

Fabrication and Properties of Magnetoplumbite-type Rare-earth Hexaaluminate Thermal Barrier Coating Materials

XU Mingyi¹(), XIONG Ying², WANG Bo², ZHANG Yixin², CHEN Wenbo³(), CAO Xueqiang³

¹ Guizhou Advanced Functional Coatings Innovation Center of THL, Guiyang 550000, China
² AECC Shenyang Liming Aero-Engine Corporation Ltd., Shenyang 110043, China
³ State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, China

Received:2025-10-02 Revised:2025-12-04 Published:2026-08-20 Online:2025-12-11
Contact: CHEN Wenbo, professor. E-mail: wchen@whut.edu.cn
About author:XU Mingyi (1996-), male, PhD candidate. E-mail: xumingyi96925@163.com
Supported by:
National Natural Science Foundation of China(92360304);National Natural Science Foundation of China(52302109);Natural Science Foundation of Hubei Province, China(2023AFB075);National Natural Science Foundation of China(92060201)

摘要/Abstract

摘要：

磁铅石型稀土六铝酸盐RMgAl₁₁O₁₉ (RMA, R=La, Pr, Nd, Sm, Gd)因其高熔点、低热导率和优异的抗烧结性能, 成为服役温度超过1300 ℃的潜在热障涂层材料。为揭示稀土离子取代对材料结构与性能的影响规律, 采用固相反应法合成不同稀土离子取代的RMA粉体, 并通过放电等离子烧结制备致密陶瓷块体。结合不同测试手段, 系统分析了稀土离子半径变化对晶体结构、晶粒生长、热物理及红外辐射性能的作用机理。结果表明, 所有样品均呈六方磁铅石型结构, 晶胞参数及体积随稀土离子半径减小而收缩, 晶粒生长速率整体提高。RMA陶瓷的热扩散系数和热导率随温度升高而降低, 热导率最低为2.86~3.19 W/(m·K) (25~1000 ℃), 平均热膨胀系数为8.22×10^-6~8.70×10^-6 K^-1 (200~1300 ℃)。不同稀土离子取代对热物理性能影响有限, 然而, 材料在3~5 μm波段的红外发射率差异显著。其中, PrMA样品平均红外发射率最高(0.746), LaMA样品最低(0.493)。本研究揭示了稀土离子取代对磁铅石型六铝酸盐热辐射性能的影响, 为设计在高温服役条件下兼具低热导率与高红外辐射性能的热障涂层材料提供了科学依据。

关键词: 热障涂层, RMgAl₁₁O₁₉, 晶粒生长速率, 热物理性能, 红外辐射性能

Abstract:

Magnetoplumbite-type rare-earth hexaaluminates RMgAl₁₁O₁₉ (RMA, R=La, Pr, Nd, Sm, Gd) emerged as promising candidates for next-generation thermal barrier coatings (TBCs) capable of operating at temperatures exceeding 1300 ℃, owing to their high melting points, low thermal conductivity, and remarkable sintering resistance. To elucidate the influence of rare-earth ion substitution on the structural and functional properties, a series of single rare-earth cation substituted RMA ceramics were synthesized via a solid-state reaction route and densified using spark plasma sintering. Their phase composition, microstructure, thermophysical, and infrared radiative properties were systematically characterized by different measurements. All samples crystallize in a hexagonal magnetoplumbite-type structure, with both lattice parameters and unit cell volumes exhibiting a gradual contraction as the rare-earth ionic radius decreases. The grain growth rate generally increases with a reduction in ionic radius. The thermal diffusivity and conductivity of RMA ceramics decrease with increasing temperature, reaching a minimum of 2.86-3.19 W/(m·K) in the temperature range of 25-1000 ℃. The average thermal expansion coefficients vary from 8.22×10^-6 to 8.70×10^-6 K^-1 between 200 and 1300 ℃, indicating comparable thermo-physical properties across different compositions. In contrast, notable differences appear in the 3-5 μm infrared band, where PrMA exhibits the highest average emissivity (0.746) and LaMA exhibits the lowest (0.493), reflecting the critical role of rare-earth cation electronic structure in radiative behavior. This work elucidates the coupled thermal-radiative modulation mechanism induced by rare-earth ion substitution in magnetoplumbite-type hexaaluminates, offering valuable insights for the design of high-temperature TBC materials that combine low thermal conductivity with high infrared radiative performance.

Key words: thermal barrier coating, RMgAl₁₁O₁₉, grain growth rate, thermo-physical property, infrared radiation property

中图分类号:

TB306

许茗奕, 熊瑛, 王博, 张艺馨, 陈文博, 曹学强. 磁铅石型稀土六铝酸盐热障涂层材料的制备与性能[J]. 无机材料学报, 2026, 41(8): 1103-1109.

XU Mingyi, XIONG Ying, WANG Bo, ZHANG Yixin, CHEN Wenbo, CAO Xueqiang. Fabrication and Properties of Magnetoplumbite-type Rare-earth Hexaaluminate Thermal Barrier Coating Materials[J]. Journal of Inorganic Materials, 2026, 41(8): 1103-1109.

图/表 9

图1 RMA陶瓷块体的(a) XRD图谱及(b)晶胞参数

Fig. 1 (a) XRD patterns and (b) lattice parameters of RMA ceramic bulks

表1 RMA陶瓷的密度与致密度

Table 1 Density and relative density of RMA ceramic bulks

Sample	Theoretical density/(g·cm^-3)	Archimedes’ density/(g·cm^-3)	Relative density/%	Sample	Theoretical density/(g·cm^-3)	Archimedes’ density/(g·cm^-3)	Relative density/%
LaMA	4.268	4.063	95.20	SmMA	4.371	4.039	92.40
PrMA	4.300	4.295	99.88	GdMA	4.418	4.106	92.94
NdMA	4.326	4.183	96.69

图2 热侵蚀后(a) LaMA、(b) PrMA、(c) NdMA、(d) SmMA、(e) GdMA陶瓷的表面形貌及其(f)平均晶粒宽度

Fig. 2 Surface morphologies of (a) LaMA, (b) PrMA, (c) NdMA, (d) SmMA, (e) GdMA ceramics and corresponding (f) average width of grains after thermal etching

图3 SmMA陶瓷的Sm3d XPS图谱

Fig. 3 Sm3d XPS spectra of SmMA ceramic

图4 (a) RMA热膨胀系数随温度的变化曲线和(b)平均热膨胀系数

Fig. 4 (a) Temperature-dependent thermal expansion coefficients and (b) average thermal expansion coefficients of RMA ceramics

图5 RMA陶瓷的(a)热容、(b)热扩散系数和(c)热导率随温度的变化

Fig. 5 Temperature-dependent (a) heat capacity, (b) thermal diffusivity and (c) thermal conductivity of RMA ceramics

图6 (a) RMA陶瓷在8~14 μm红外发射率随温度的变化和(b)该波段的平均红外发射率

Fig. 6 (a) Temperature-dependent infrared emissivity and (b) average emissivity in the range of 8-14 μm of RMA ceramics

图7 (a) RMA陶瓷在3~5 μm红外发射率随温度的变化和(b)该波段的平均红外发射率

Fig. 7 (a) Temperature-dependent infrared emissivity and (b) average emissivity in the range of 3-5 μm of RMA ceramics

图8 (a)稀土氧化物在3~5 μm红外发射率随温度的变化和(b)该波段的平均红外发射率

Fig. 8 (a) Temperature-dependent infrared emissivity and (b) average emissivity in the range of 3-5 μm of rare-earth oxides

参考文献 28

[1]	XU M Y, CHEN W B, LU X R, et al. Effect of high-temperature infrared emissivity on thermal cycling performance of magnetoplumbite- type thermal barrier coatings under thermal gradient condition. Journal of the European Ceramic Society, 2024, 44: 448. DOI URL
[2]	PURWAR A, BASU B. Thermo-structural design of ZrB₂-SiC-based thermal protection system for hypersonic space vehicles. Journal of the American Ceramic Society, 2017, 100: 1618. DOI URL
[3]	SZIROCZAK D, SMITH H. A review of design issues specific to hypersonic flight vehicles. Progress in Aerospace Sciences, 2016, 84: 1 DOI URL
[4]	TAN W, PETORAK C A, TRICE R W. Rare-earth modified zirconium diboride high emissivity coatings for hypersonic applications. Journal of the European Ceramic Society, 2014, 34(1): 1.
[5]	VAN WIE D M, DREWRY D G, KING D E, et al. The hypersonic environment: required operating conditions and design challenges. Journal of Materials Science, 2004, 39(19): 5915.
[6]	WANG G Y, SANG S B, WANG Q H, et al. Infrared radiation property and enhancement mechanism of MgCr₂O₄ doped with NiO prepared at different temperature. Ceramics International, 2024, 50(1, Part A): 9.
[7]	MANDAL J, FU Y, OVERVIG A C, et al. Hierarchically porous polymer coatings for highly efficient passive daytime radiative cooling. Science, 2018, 362(6412): 315.
[8]	MU Y, YAN L W, LIU P S, et al. High-temperature-resistant ZrO₂ coating with SiC-whisker-enhanced interfacial bonding strength and improved emissivity for flexible silica fibre fabric. Ceramics International, 2023, 49(4): 6825.
[9]	SHAO G F, WU X D, CUI S, et al. High emissivity MoSi₂- TaSi₂-borosilicate glass porous coating for fibrous ZrO₂ ceramic by a rapid sintering method. Journal of Alloys and Compounds, 2017, 690: 63. DOI URL
[10]	GADOW R, LISCHKA M. Lanthanum hexaaluminate—novel thermal barrier coatings for gas turbine applications—materials and process development. Surface and Coatings Technology, 2002, 151/152: 392. DOI URL
[11]	RAM Y N V S, TARASASANKA C, PRABAKARAN J. Preparation and characterization of lanthanum hexa aluminate powders for high temperature applications. Materials Today: Proceedings, 2021, 39: 1472. DOI URL
[12]	LU X R, YUAN J Y, XU M Y, et al. Improvement on thermophysical and mechanincal properties of LaMgAl₁₁O₁₉ magnetoplumbite by Nd₂O₃ and Sc₂O₃ co-doping. Ceramics International, 2021, 47(20): 28892.
[13]	XU M Y, YUAN J Y, LU X R, et al. Infrared radiation and thermal cyclic performance of a high-entropy rare-earth hexaaluminate coating prepared by atmospheric plasma spraying. Ceramics International, 2022, 48(18): 26003.
[14]	牛璐玥. 稀土及过渡金属离子掺杂氧化物发光玻璃的制备及性能研究. 济南: 齐鲁工业大学硕士学位论文, 2019.
[15]	HUANG Y, DONG S J, LÜ K Y, et al. Compatibility of low thermal conductivity and high infrared emissivity of plasma-sprayed Sm₂Hf₂O₇ and Pr₂Hf₂O₇ coatings. Surface and Coatings Technology, 2023, 457: 129312. DOI URL
[16]	YIN J H, ZHOU T, ZHANG M, et al. Exploring the mechanism of infrared emissivity control in YSZ-based ceramics doped with Yb₂O₃. Optical Materials, 2024, 157: 116107. DOI URL
[17]	CHEN X L, ZHANG Y F, ZHONG X H, et al. Thermal cycling behaviors of the plasma sprayed thermal barrier coatings of hexaluminates with magnetoplumbite structure. Journal of the European Ceramic Society, 2010, 30(7): 1649.
[18]	陈小龙. 磁铅石型稀土六铝酸盐热障涂层材料. 长春: 中国科学院长春应用化学研究所博士学位论文, 2012.
[19]	BRUNCKOVA H, KANUCHOVA M, KOLEV H, et al. XPS characterization of SmNbO₄ and SmTaO₄ precursors prepared by Sol-Gel method. Applied Surface Science, 2019, 473: 1. DOI URL
[20]	ZHANG J F, ZHONG X H, CHENG Y L, et al. Thermal-shock resistance of LnMgAl₁₁O₁₉ (Ln = La, Nd, Sm, Gd) with magnetoplumbite structure. Journal of Alloys and Compounds, 2009, 482(1/2): 376.
[21]	CHEN S G, YIN Y S, WANG D P, et al. Reduced activation energy and crystalline size for yttria-stabilized zirconia nano-crystals. Journal of Crystal Growth, 2004, 267(1/2): 100.
[22]	SHUKLA S S S, RASHMI V, SRI B. Reduced activation energy for grain growth in nanocrystalline yttria-stabilized zirconia. Nano Letters, 2003, 3: 397. DOI URL
[23]	LEITNER J, VOŇKA P, SEDMIDUBSKÝ D, et al. Application of Neumann-Kopp rule for the estimation of heat capacity of mixed oxides. Thermochimica Acta, 2010, 497(1/2): 7.
[24]	ZHOU X, SONG W J, YUAN J Y, et al. Thermophysical properties and cyclic lifetime of plasma sprayed SrAl₁₂O₁₉ for thermal barrier coating applications. Journal of the American Ceramic Society, 2020, 103(10): 5599.
[25]	LIU H Z, LIU Z G, OUYANG J H, et al. Influences of lattice vibration and electron transition on thermal emissivity of Nd³⁺ doped LaMgAl₁₁O₁₉hexaaluminates for metallic thermal protection system. Applied Physics Letters, 2012, 101: 161903. DOI URL
[26]	DONG S J, ZHANG F N, LI N, et al. Thermal radiation and cycling properties of (Ca, Fe) or (Sr, Mn) co-doped La₂Ce₂O₇ coatings. Journal of the European Ceramic Society, 2020, 40(5): 2020.
[27]	BELANÇON M P, MARCONI J D, ANDO M F, et al. Near-IR emission in Pr³⁺single doped and tunable near-IR emission in Pr³⁺/Yb³⁺ codoped tellurite tungstate glasses for broadband optical amplifiers. Optical Materials, 2014, 36(6): 1020.
[28]	LIU S P, MA Z, LIU Y B, et al. Infrared radiative performance and ablation resistance of coatings sprayed with Pr₆O₁₁ core-shell-structured ZrB₂-SiC powders. Ceramics International, 2025, 51(3): 3879.

磁铅石型稀土六铝酸盐热障涂层材料的制备与性能

Fabrication and Properties of Magnetoplumbite-type Rare-earth Hexaaluminate Thermal Barrier Coating Materials

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