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Gd3+和Yb3+对CMAS腐蚀产物结晶行为的影响及协同作用机理

张广珩1,2, 石金瑜1,2, 沈泓宇1,3, 张洁1, 王京阳1   

  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.东北大学 材料科学与工程学院,沈阳 110016
  • 收稿日期:2025-02-20 修回日期:2025-05-14
  • 通讯作者: 张洁, 研究员. E-mail: jiezhang@imr.ac.cn
  • 作者简介:张广珩(1996-), 男, 博士. E-mail: ghzhang@lam.ln.cn
  • 基金资助:
    国家自然科学基金(U21A2063, 52372071, 52302076, 92360304); 国家重点研发计划 (2021YFB3702300); 中国航发集团产学研合作项目(HFZL2023CXY022); 辽宁省‘兴辽英才计划’项目(XLYC2002018, XLYC2203090); 中国科学院国际伙伴计划项目(172GJHZ2022094FN); 沈阳市中青年科技创新人才支持计划(RC2204062)

Synergistic Mechanism of Gd3+ and Yb3+ on Crystallization Behavior of CMAS Corrosion Products

ZHANG Guangheng1,2, SHI Jinyu1,2, SHEN Hongyu1,3, ZHANG Jie1, WANG Jingyang1   

  1. 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. School of Materials Science and Engineering, Northeastern University, Shenyang 110819, China
  • Received:2025-02-20 Revised:2025-05-14
  • Contact: ZHANG Jie, professor. E-mail: jiezhang@imr.ac.cn
  • About author:ZHANG Guangheng (1996-), male, PhD. E-mail: ghzhang@lam.ln.cn
  • Supported by:
    National Natural Science Foundation of China (U21A2063, 52372071, 52302076, 92360304); National Key Research and Development Program of China (2021YFB3702300); Aero Engine Corporation of China Industry-university-research Cooperation Project (HFZL2023CXY022); "Revitalize Liaoning Talent Plan" Project of Liaoning Province (XLYC2002018, XLYC2203090); Chinese Academy of Sciences International Partnership Program (172GJHZ2022094FN); Shenyang Young and Middle-aged Scientific and Technological Innovation Talent Support Program (RC2204062)

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摘要： 随着航空发动机服役温度的升高,低熔点钙镁铝硅酸盐(CaO-MgO-AlO1.5-SiO2, CMAS)腐蚀成为导致热结构部件防护涂层失效的重要因素。在典型热障涂层及环境障涂层的CMAS腐蚀过程中,稀土组分对反应产物的结晶以及CMAS腐蚀渗透过程具有显著影响。本研究聚焦热障涂层和环境障涂层体系中广泛采用的两种稀土元素——钆和镱,制备一系列钆-镱氧化物((GdxYb1-x)2O3, x = 0、0.05、0.10、0.20、0.30、0.50和1.00),系统研究其与CMAS沉积物在1300 oC下的反应产物,并探讨这两种稀土元素的协同作用机理。结果表明,钆离子有效诱导磷灰石结构产物的形成,但熔体消耗效率较低;镱离子促进石榴石和磷硅酸钙结构产物的形成,但其产物结晶动力学迟滞。进一步讨论了钆和镱离子在产物中的配分特征以及残余CMAS熔体成分的变化,提出在一定比例范围内(钆摩尔分数为5% ~ 20%)两者之间存在协同效应。通过合理设计涂层中钆和镱元素的比例,可以促进磷灰石结晶,阻止熔体渗透,同时改善石榴石和磷硅酸钙迟滞的结晶动力学,从而加速熔体消耗。协同作用的探究为热障或环境障涂层的抗CMAS腐蚀改性成分设计提供理论支撑。

关键词: 钆-镱氧化物, CMAS腐蚀, 反应结晶产物, 协同作用

Abstract: As the operating temperature of aero-engine rises, the degradation of thermal barrier coatings and environmental barrier coatings on hot-section components due to the infiltration of calcium-magnesium-alumina-silicate (CMAS) has garnered increasing attention. Rare earth constituents play an essential role in the formation of corrosion products and the subsequent melt penetration when conventional thermal barrier coatings and environmental barrier coatings are attacked by CMAS deposits. This study focused on the preparation of a series of gadolinium-ytterbium oxides ((GdxYb1-x)2O3, x = 0, 0.05, 0.10, 0.20, 0.30, 0.50 and 1.00), with particular emphasis on the roles of ytterbium and gadolinium, which were commonly utilized in thermal barrier coatings and environmental barrier coatings. Their reaction with CMAS deposits was systematically investigated at 1300 oC to explore the synergistic mechanism associated with these two rare earth elements. The results indicate that gadolinium cations can efficiently induce the crystallization of products with apatite structure which have a low melt consumption. Conversely, ytterbium cations can induce the formation of products with garnet and silicocarnotite structure which have a sluggish kinetic. Furthermore, the partitioning of gadolinium and ytterbium ions within corrosion products, along with variation of residual CMAS melt composition, was further discussed. It is proposed that these two rare earth ions exhibit a synergistic effect within a certain composition range (5%-20% of gadolinium content(in mol)). The optimized ratio of gadolinium and ytterbium within coatings is anticipated to promote apatite crystallization, prevent melt penetration, and modify the sluggish crystallization kinetic of garnet and silicocarnotite, thereby significantly improving the melt consumption. The investigation on synergistic effect of gadolinium and ytterbium cations provides theoretical support for the anti-CMAS-corrosion composition modification of thermal and/or environmental barrier coating.

Key words: Gadolinium-ytterbium oxides, CMAS corrosion, reactive crystallization products, synergistic effect

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