目的 阐明56%（质量分数）氧化钇稳定氧化锆（56YSZ）涂层1 350 ℃条件下CMAS（钙镁铝硅酸盐）腐蚀行为,分析腐蚀产物及其演变规律,揭示等离子喷涂56YSZ涂层高温CMAS腐蚀机理。方法 利用大气等离子喷涂方法制备56YSZ涂层,在1 350 ℃条件下对表面涂敷CMAS（33CaO-9MgO-13AlO1.5-45SiO2）的56YSZ涂层进行CMAS腐蚀试验。结合X射线衍射仪（XRD）、扫描电镜（SEM）和能谱分析仪（EDS）,表征经1 350 ℃腐蚀不同时间后涂层物相结构与微观形貌,以分析1 350 ℃条件下56YSZ涂层CMAS腐蚀行为。结果 在1 350 ℃高温环境下,涂层CMAS腐蚀速率随时间延长呈明显的下降趋势,8 h后涂层CMAS腐蚀速率最低（0.50 μm/h）,且经过50 h腐蚀后CMAS腐蚀深度由(150.9±11.0) μm增至(172.5±18.3) μm。在腐蚀初期,CMAS熔体快速渗透,与涂层反应生成了磷灰石相;然而,随着CMAS熔体中Si4+/Al3+比值逐渐降低,熔体与涂层反应生成了石榴石相,且c-ZrO2包裹磷灰石相与石榴石相形成了致密的保护层;最终涂层腐蚀区反应产物主要为c-ZrO2、磷灰石相及石榴石相。结论 56YSZ涂层在1 350 ℃条件下展现出优异的抗CMAS腐蚀性能,腐蚀反应生成的磷灰石相、石榴石相以及c-ZrO2共同组成了致密保护层,有效阻滞了CMAS熔体的腐蚀渗透,并快速消耗CMAS熔体活性元素,在56YSZ涂层抗腐蚀过程中起到了积极作用。
Abstract
The CMAS (calcium-magnesium-alumino-silicate) corrosion behavior of the free-standing 56 wt.% yttria stabilized zirconia (56YSZ) coatings fabricated via atmospheric plasma spraying process at 1 350 ℃ is investigated and its corrosion mechanism is also elucidated in the research. Firstly, the mixture powders composed of 33% CaO, 9% MgO, 13% AlO1.5, and 45% SiO2 are uniformly mixed and coated to the surface of as-deposited coatings, and then the coated samples are subject to high-temperature exposure in a muffle furnace at 1 350 ℃ for different times. After corrosion at 1 350 ℃ for different times, the phase composition and microstructure of the corrosion products are characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with an energy dispersive X-ray spectroscopy (EDS). As a result, the corrosion depth of 56YSZ coating is increased rapidly from (57.6±6.7) μm to (150.9±11.0) μm with the prolonged exposure time after being exposed at 1 350 ℃, and the final corroded layer with the thickness of (172.5±18.3) μm is achieved after corrosion for 50 h. It is easy to note that a positive relationship between the depth of the corroded layer and the corrosion duration is obtained. During the initial stage of corrosion, the CMAS mixture powders are deposited on the coating surface and gradually melted with the increasing temperature, which could be infiltrated into the coating through the presence of cracks and pores. As we all know, the CMAS corrosion rate is directly related to the viscosity of the melt and its element content. In this corrosion stage, the CMAS melt would quickly react with Y3+ to form an apatite phase, and the corrosion rate is also increased, which is mainly attributed to the richest CMAS melt and its highest viscosity. However, the viscosity of the CMAS melt is then reduced under the combined effect of the decreasing SiO2/CaO ratio and the permeate of Y3+. With the reaction proceeding, the apatite phase consumes large amounts of Si4+ and Ca2+, and lower Si4+/Al3+ ratio in the CMAS melt creates favorable conditions for the formation of garnet, resulting in the decrease of the corrosion rate from 28.8 μm/h to 15.9 μm/h. After corrosion for 4 hours, it is observed that the two dense layers appear in the inner region and the outer region of the corrosion layer. Based on the element distribution, the outer region of the corrosion layer is mainly consisted of c-ZrO2 and the apatite phase, while the c-ZrO2 and the garnet phase present in the inner region. Due to the formation of dense layers, the CMAS melt penetration is blocked. When the corrosion time is prolonged to 8 hours, the elements in the melt are nearly consumed and the corrosion rate is significantly reduced to 0.5 μm/h. At this stage of corrosion reaction, the appearance of element diffusion and segregation is present in the corrosion products, and large-scale pores appear in the corrosion layer, while a thin calcium-rich layer is formed on the surface. Consequently, the CMAS corrosion behavior of plasma-sprayed 56YSZ coating could be divided into three stages, including the initial rapid corrosion dominated by the thermal penetration of CMAS melt, followed by the formation of a dense layer composed of apatite and garnet phases via thermochemical reactions, and the arreargae of the CMAS corrosion resulting in the slowly increase of corrosion layer. The primary phases in the CMAS corrosion products are found to be c-ZrO2, apatite, and garnet. It is concluded that the 56YSZ coating could be considered to be a promising candidate material for thermal barrier coatings (TBCs) with exceptional CMAS corrosion resistance.
关键词
高氧化钇稳定氧化锆 /
CMAS腐蚀 /
热障涂层 /
腐蚀机理 /
热渗透 /
大气等离子喷涂
Key words
high yttria stabilized zirconia /
CMAS corrosion /
thermal barrier coating /
corrosion mechanism /
thermal penetration /
atmospheric plasma spraying
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基金
国家自然科学基金（52371087）; 湖南省自然科学基金（2025JJ20043）
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