(La0.2Nd0.2Tm0.2Yb0.2Lu0.2)2Zr2O7 高熵陶瓷的制备及其在熔融氧化物膜CaO-MgO-Al2O3-SiO2 下的腐蚀行为

doi:10.11902/1005.4537.2024.402

中国腐蚀与防护学报

2025, Vol. 45

Issue (5): 1244-1252 CSTR: 32134.14.1005.4537.2024.402 DOI: 10.11902/1005.4537.2024.402

研究报告

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(La_0.2Nd_0.2Tm_0.2Yb_0.2Lu_0.2)₂Zr₂O₇ 高熵陶瓷的制备及其在熔融氧化物膜CaO-MgO-Al₂O₃-SiO₂ 下的腐蚀行为

耿浩钧¹^,², 谢芳坤¹^,², 杨凌旭²^,³, 王艳丽¹, 刘会军²(

), 曾潮流²

1 广西大学化学化工学院南宁 530004
2 松山湖材料实验室东莞 523808
3 广州航海学院海洋装备工程学院广州 510725

Preparation and Corrosion Behavior of (La_0.2Nd_0.2Tm_0.2Yb_0.2-Lu_0.2)₂Zr₂O₇ High Entropy Ceramic Beneath Deposits of Molten CaO-MgO-Al₂O₃-SiO₂

GENG Haojun¹^,², XIE Fangkun¹^,², YANG Lingxu²^,³, WANG Yanli¹, LIU Huijun²(

), ZENG Chaoliu²

1 College of Chemistry and Chemical Engineer, Guangxi University, Nanning 530004, China
2 Songshan Lake Materials Laboratory, Dongguan 523808, China
3 School of Ocean Engineering, Guangzhou Maritime University, Guangzhou 510725, China

引用本文:

耿浩钧, 谢芳坤, 杨凌旭, 王艳丽, 刘会军, 曾潮流. (La_0.2Nd_0.2Tm_0.2Yb_0.2Lu_0.2)₂Zr₂O₇ 高熵陶瓷的制备及其在熔融氧化物膜CaO-MgO-Al₂O₃-SiO₂ 下的腐蚀行为[J]. 中国腐蚀与防护学报, 2025, 45(5): 1244-1252.
Haojun GENG, Fangkun XIE, Lingxu YANG, Yanli WANG, Huijun LIU, Chaoliu ZENG. Preparation and Corrosion Behavior of (La_0.2Nd_0.2Tm_0.2Yb_0.2-Lu_0.2)₂Zr₂O₇ High Entropy Ceramic Beneath Deposits of Molten CaO-MgO-Al₂O₃-SiO₂[J]. Journal of Chinese Society for Corrosion and protection, 2025, 45(5): 1244-1252.

全文: PDF(17956 KB) HTML

摘要:

采用高温固相法和热压烧结法分别制备了(La _0.2 Nd _0.2 Tm _0.2 Yb _0.2 Lu _0.2 )₂Zr₂O₇高熵陶瓷粉体及块体材料，表征和分析其微观组织结构，并研究了高熵陶瓷在1300 ℃的熔融氧化物膜CaO-MgO-Al₂O₃-SiO₂ (CMAS)下的腐蚀行为。结果表明，高熵陶瓷由70.15%的缺陷萤石和29.85%的烧绿石双相结构组成。在1300 ℃的熔融CMAS中腐蚀一定时间后，其腐蚀产物主要为稀土(RE)元素与Ca共同稳定的(RE, Ca)-ZrO₂和磷灰石型(Ca₂RE₈(SiO₄)₆O₂)产物。腐蚀机制为：高熵陶瓷在熔融CMAS中部分溶解，其中大离子半径的轻稀土元素(La, Nd)易与CMAS中的Ca和Si结合形成磷灰石型Ca₂RE₈(SiO₄)₆O₂结构，而小离子半径的重稀土元素(Tm, Yb, Lu)则继续留在ZrO₂中形成稀土与Ca共同稳定的(RE, Ca)-ZrO₂。

关键词 ：稀土锆酸盐, 高熵陶瓷, 热障涂层, CMAS腐蚀

Abstract：

(La _0.2 Nd _0.2 Tm _0.2 Yb _0.2 Lu _0.2 )₂Zr₂O₇ high-entropy ceramic powders and bulks were prepared by high-temperature solid reaction and hot-pressed sintering method, respectively. The microstructure of the powder and the bulk were characterized, and the corrosion behavior of the high-entropy ceramic was also investigated beneath deposits of molten CaO-MgO-Al₂O₃-SiO₂(CMAS) at 1300 ℃. The results indicate that the (La _0.2 Nd _0.2 Tm _0.2 Yb _0.2 Lu _0.2 )₂Zr₂O₇ high-entropy ceramic is composed of 70.15% defective fluorite and 29.85% pyrochlore structure. After molten CMAS corrosion at 1300 ℃, the main corrosion products are rare-earth (RE) elements stabilized zirconia and Ca (RE, Ca)-ZrO₂and apatite type (Ca₂RE₈(SiO₄)₆O₂). The corrosion mechanism of the high-entropy ceramic in molten CMAS is as follows: firstly, the high-entropy ceramic partially dissolve in molten CMAS; then the light rare-earth elements with large ionic radii (La, Nd) combine with Ca and Si in molten CMAS to form apatite type Ca₂RE₈(SiO₄)₆O₂, while the heavy rare-earth elements with small ionic radii (Tm, Yb, Lu) continue to remain in zirconia to form rare earth and Ca stabilized zirconia, namely (RE, Ca)-ZrO₂.

Key words： rare earth zirconate high-entropy ceramics thermal barrier coating CMAS corrosion

收稿日期: 2024-10-20 32134.14.1005.4537.2024.402

ZTFLH:

TG174.4

基金资助:广东省基础与应用基础研究基金(2022A1515140146);广东省基础与应用基础研究基金(2021A1515010466)

通讯作者: 刘会军，E-mail：hui_jun_liu@163.com，研究方向为金属的腐蚀与防护

Corresponding author: LIU Huijun, E-mail: hui_jun_liu@163.com

作者简介: 耿浩钧，男，2000年生，硕士生

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https://www.jcscp.org/CN/10.11902/1005.4537.2024.402 或 https://www.jcscp.org/CN/Y2025/V45/I5/1244

图1 (La0.2Nd0.2Tm0.2Yb0.2Lu0.2)2Zr2O7高熵陶瓷粉体的XRD图谱与单组元RE2Zr2O7 (RE = La、Nd、Tm、Yb、Lu)的XRD标准图谱

图2 1600 ℃热压0.5 h制备的(La0.2Nd0.2Tm0.2Yb0.2Lu0.2)2Zr2O7高熵陶瓷的表面SEM图和对应的EDS元素面扫描图

图3 (La0.2Nd0.2Tm0.2Yb0.2Lu0.2)2Zr2O7高熵陶瓷在1300 ℃熔融CMAS腐蚀1 h后的表面和截面SEM图像

表1 图3中标记位置的EDS能谱分析结果 (atomic fraction / %)

图4 (La0.2Nd0.2Tm0.2Yb0.2Lu0.2)2Zr2O7高熵陶瓷在1300 ℃熔融CMAS腐蚀5 h后的表面和截面SEM图

表2 图4中标记区域的EDS能谱分析结果

图5 (La0.2Nd0.2Tm0.2Yb0.2Lu0.2)2Zr2O7高熵陶瓷在1300 ℃熔融CMAS腐蚀10 h后的表面和截面SEM图

表3 图5中标记区域的EDS能谱分析结果

图6 (La0.2Nd0.2Tm0.2Yb0.2Lu0.2)2Zr2O7高熵陶瓷在1300 ℃熔融CMAS腐蚀20 h后的表面和截面SEM图

表4 图6中标记区域的EDS能谱分析结果

图7 5种稀土元素在磷灰石型结构和ZrO2中的含量

图8 (La0.2Nd0.2Tm0.2Yb0.2Lu0.2)2Zr2O7高熵陶瓷在1300 ℃熔融CMAS中腐蚀不同时间后的表面XRD图谱

[1]	Padture N P, Gell M, Jordan E H. Thermal barrier coatings for gas-turbine engine applications [J]. Science, 2002, 296: 280 pmid: 11951028
[2]	Gao D, Liu Y D, Huang A H. Preparation and properties comparison of two novel rare earth modified ceramic ingots used for thermal barrier coatings [J]. Adv. Ceram., 2024, 45: 434
[2]	高栋, 刘燚栋, 黄爱华. 两种稀土掺杂改性热障涂层陶瓷靶材制备及其性能比较分析研究 [J]. 现代技术陶瓷, 2024, 45: 434
[3]	Lipkin D M, Krogstad J A, Gao Y, et al. Phase evolution upon aging of air-plasma sprayed t′-zirconia coatings: I—Synchrotron X-Ray diffraction [J]. J. Am. Ceram. Soc., 2013, 96: 290
[4]	Wang K, Zou L X, Guo L, et al. High-temperature corrosion and protection of thermal barrier coatings for aeroengines and gas turbines [J]. J. Chin. Soc. Corros. Prot., 2025, 45: 1
[4]	王昆, 邹兰欣, 郭磊等. 航空发动机及燃气轮机热障涂层高温腐蚀与防护 [J]. 中国腐蚀与防护学报, 2025, 45: 1
[5]	Boissonnet G, Chalk C, Nicholls J R, et al. Phase stability and thermal insulation of YSZ and erbia-yttria co-doped zirconia EB-PVD thermal barrier coating systems [J]. Surf. Coat. Technol., 2020, 389: 125566
[6]	Zeng Z J, Mao J, Deng Z Q, et al. Study on molten salt corrosion resistance of YSZ thermal barrier coating prepared by PS-PVD [J]. Mater. Res. Appl., 2023, 17: 503
[6]	曾卓见, 毛杰, 邓子谦等. PS-PVD制备YSZ热障涂层抗熔盐腐蚀研究 [J]. 材料研究与应用, 2023, 17: 503
[7]	Rost C M, Sachet E, Borman T, et al. Entropy-stabilized oxides [J]. Nat. Commun., 2015, 6: 8485 doi: 10.1038/ncomms9485 pmid: 26415623
[8]	Ren B, Liu Y F, Meng Z Q, et al. Preparation and electrical properties study of non-equimolar Sr (Ti, Zr, Y, Sn, Hf)O_3- _σ high-entropy perovskite oxide [J]. Adv. Ceram., 2023, 44: 497
[8]	任贝, 刘宇峰, 孟子茜等. 非等摩尔比Sr (Ti, Zr, Y, Sn, Hf)O_3- _σ 高熵钙钛矿氧化物的制备及电学性能研究 [J]. 现代技术陶瓷, 2023, 44: 497
[9]	Liu L, Dong H Y, Zhang P, et al. Design and experimental investigation of potential low-thermal-conductivity high-entropy rare-earth zirconates [J]. J. Adv. Ceram., 2024, 13: 1132
[10]	Wang X Z, Guo L, Zhang H L, et al. Structural evolution and thermal conductivities of (Gd_1- _x Yb _x )₂Zr₂O₇ (x = 0, 0.02, 0.04, 0.06, 0.08, 0.1) ceramics for thermal barrier coatings [J]. Ceram. Int., 2015, 41: 12621
[11]	Zhao Z F, Xiang H M, Dai F Z, et al. (La_0.2Ce_0.2Nd_0.2Sm_0.2Eu_0.2)₂Zr₂O₇: a novel high-entropy ceramic with low thermal conductivity and sluggish grain growth rate [J]. J. Mater. Sci. Technol., 2019, 35: 2647
[12]	Dong H, Liang X H, Wang Y, et al. Research progress on plasma spray-physical vapor deposition protective coatings and their failure mechanisms [J]. Mater. Res. Appl., 2023, 17: 234
[12]	董浩, 梁兴华, 王玉等. 等离子喷涂-物理气相沉积防护涂层及其失效机理研究进展 [J]. 材料研究与应用, 2023, 17: 234
[13]	Tu T Z, Liu J X, Zhou L, et al. Graceful behavior during CMAS corrosion of a high-entropy rare-earth zirconate for thermal barrier coating material [J]. J. Eur. Ceram. Soc., 2022, 42: 649
[14]	Yan R X, Liang W P, Miao Q, et al. Mechanical, thermal and CM-AS resistance properties of high-entropy (Gd_0.2Y_0.2Er_0.2Tm_0.2Yb_0.2)₂-Zr₂O₇ ceramics [J]. Ceram. Int., 2023, 49: 20729
[15]	Tian Y, Zhao X Y, Sun Z P, et al. Improved thermal properties and CMAS corrosion resistance of high-entropy RE zirconates by tuning fluorite-pyrochlore structure [J]. Ceram. Int., 2024, 50: 19182
[16]	Poerschke D L, Levi C G. Effects of cation substitution and temperature on the interaction between thermal barrier oxides and molten CMAS [J]. J. Eur. Ceram. Soc., 2015, 35: 681
[17]	Deng S X, He G, Yang Z C, et al. Calcium-magnesium-alumina-silicate (CMAS) resistant high entropy ceramic (Y_0.2Gd_0.2Er_0.2Yb_0.2Lu_0.2)₂-Zr₂O₇ for thermal barrier coatings [J]. J. Mater. Sci. Technol., 2022, 107: 259
[18]	Teng Z, Tan Y Q, Zeng S F, et al. Preparation and phase evolution of high-entropy oxides A₂B₂O₇ with multiple elements at A and B sites [J]. J. Eur. Ceram. Soc., 2021, 41: 3614
[19]	Torres-Rodriguez J, Gutierrez-Cano V, Menelaou M, et al. Rare-earth zirconate Ln₂Zr₂O₇ (Ln: La, Nd, Gd, and Dy) powders, xerogels, and aerogels: preparation, structure, and properties [J]. Inorg. Chem., 2019, 58: 14467 doi: 10.1021/acs.inorgchem.9b01965 pmid: 31613608
[20]	Wang Y H, Jin Y J, Wei T, et al. Size disorder: a descriptor for predicting the single- or dual-phase formation in multi-component rare earth zirconates [J]. J. Alloy. Compd., 2022, 918: 165636
[21]	Yang H B, Lin G Q, Bu H P, et al. Single-phase forming ability of high-entropy ceramics from a size disorder perspective: a case study of (La_0.2Eu_0.2Gd_0.2Y_0.2Yb_0.2)₂Zr₂O₇ [J]. Ceram. Int., 2022, 48: 6956
[22]	Wang Y L, Lin G Q, Yang L X, et al. Preparation and thermophysical properties of a novel dual-phase and single-phase rare-earth-zirconate high-entropy ceramics [J]. J. Alloy. Compd., 2023, 938: 168551
[23]	Zhu J T, Meng X Y, Zhang P, et al. Dual-phase rare-earth-zirconate high-entropy ceramics with glass-like thermal conductivity [J]. J. Eur. Ceram. Soc., 2021, 41: 2861
[24]	Zhou X, Zou B L, He L M, et al. Hot corrosion behaviour of La₂(Zr_0.7Ce_0.3)₂O₇ thermal barrier coating ceramics exposed to molten calcium magnesium aluminosilicate at different temperatures [J]. Corros. Sci., 2015, 100: 566
[25]	Chen Z Y, Lin C C, Zheng W, et al. Investigation on improving corrosion resistance of rare earth pyrosilicates by high-entropy design with RE-doping [J]. Corros. Sci., 2022, 199: 110217
[26]	Cong L K, Li W, Guo Y, et al. Calcium magnesium aluminosilicate (CMAS) corrosion behaviors of apatite Ca₂La₈(SiO₄)₆O₂ thermal barrier coating material [J]. Corros. Sci., 2022, 203: 110322
[27]	Zhang C G, Fan Y, Zhao J L, et al. Corrosion resistance of nonstoichiometric gadolinium zirconate coatings against CaO-MgO-Al₂O₃-SiO₂ silicate [J]. J. Eur. Ceram. Soc., 2021, 41: 3687
[28]	Lin G Q, Wang Y L, Yang L X, et al. CMAS corrosion behavior of a novel high entropy (Nd_0.2Gd_0.2Y_0.2Er_0.2Yb_0.2)₂Zr₂O₇ thermal barrier coating materials [J]. Corros. Sci., 2023, 224: 111529
[29]	Reddy R R, Nazeer Ahammed Y, Abdul Azeem P, et al. Electronic polarizability and optical basicity properties of oxide glasses through average electronegativity [J]. J. Non-Cryst. Solids, 2001, 286: 169
[30]	Sato S, Takahashi R, Kobune M, et al. Basic properties of rare earth oxides [J]. Appl. Catal., 2009, 356A: 57
[31]	Deng J L, Lu B F, Hu K Y, et al. Interaction between Y-Al-Si-O glass-ceramics for environmental barrier coating materials and Ca-Mg-Al-Si-O melts [J]. Ceram. Inter., 2020, 46: 18262
[32]	Qu W W, Chen Z H, Pei Y L, et al. Spreading and corrosion behavior of CMAS melt on different materials for thermal barrier coating [J]. J. Chin. Soc. Corros. Prot., 2023, 43: 1407
[32]	曲卫卫, 陈泽浩, 裴延玲等. CMAS熔体在不同热障涂层用材料表面的铺展和腐蚀行为 [J]. 中国腐蚀与防护学报, 2023, 43: 1407 doi: 10.11902/1005.4537.2022.362

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