Microstructure evolution of CMAS glass below melting temperature and its potential influence on thermal barrier coatings

CaO–MgO–Al₂O₃–SiO₂ (CMAS) deposition significantly degrades the performance of thermal barrier coatings (TBCs). In this study, the microstructure evolution of CMAS glass at temperatures below its melting point was investigated in order to study the potential influence of temperature on the applicability of CMAS glass in TBCs. The CMAS glass fabricated in this study had a melting point of 1240 °C, became opaque, and underwent self-crystallization when the temperature reached 1000 °C. After heat treatment at 1050 °C, diopside and anorthite phases precipitated from the glass; at a higher temperature (1150 °C), diopside, anorthite, and wollastonite were formed as the self-crystallization products. An increase in the dwelling time resulted in the transformation of diopside to wollastonite and anorthite. At 1250 °C, all products formed a eutectic microstructure and melted. The results indicate that even at low temperatures, CMAS glass underwent microstructure evolution, which could influence the coating surface and stress distribution when deposited on TBCs.     

The mechanical and thermal properties,CMAS corrosion resistance,and the wettability of novel thermal barrier material GdTaO4

Because the CMAS corrosion and phase transformation at elevated temperatures above 1250 °C have limited the applications of traditional YSZ, the design of novel thermal barrier materials is a hotspot. GdTaO₄ is considered as a type of potential novel thermal barrier material owing to its low thermal conductivity. In this study, the mechanical and thermal properties, CMAS corrosion resistance, and the wettability of the GdTaO₄ were studied and compared with that of YSZ. The results show that the coefficient of thermal expansion and hardness of GdTaO₄ are 14.1 × 10⁻⁶ K⁻¹ (1350 °C) and 534.2 Hv_0.3 respectively. The thickness of CMAS reaction layer of GdTaO₄ is ~30.8 μm after 24 h reaction at 1350 °C, which is thinner than that of YSZ. After corrosion reaction, the CMAS glass aggregated instead of completely disappearing or continuously extending over the surface of GdTaO₄. The main reaction product is Ca₂Ta₂O₇, and the anorthite phase may not be detected, which is similar to YTaO₄. By comparison, the dense substrate of YSZ became porous and CMAS glass has disappeared after 10 h. CMAS corrosion at 1350 °C. The on-line contact angle results show that the wettability of CMAS on GdTaO₄ is worse than that on YSZ at 1350 °C, while the opposite of the work of adhesion, which indicates that GdTaO₄ can remove liquid CMAS more easily than YSZ TBCs during the service. Furthermore, the corrosion depth and areas of GdTaO₄ are smaller than those of YSZ in the same situation. These findings suggest that GdTaO₄ possesses better high-temperature properties and CMAS corrosion resistance than YSZ as a kind of potential of thermal barrier material.     

Corrosion behavior of air plasma spraying zirconia-based thermal barrier coatings subject to Calcium–Magnesium–Aluminum-Silicate (CMAS) via burner rig test

Three different kinds of thermal barrier coatings (TBCs) — 8YSZ, 38YSZ and a dual-layered (DL) TBCs with pure Y₂O₃ on the top of 8YSZ were produced on nickel-based superalloy substrate by air plasma spraying (APS). The Calcium–Magnesium–Aluminum-Silicate (CMAS) corrosion resistance of these three kinds of coatings were researched via burner rig test at 1350 °C for different durations. The microstructures and phase compositions of the coatings were characterized by SEM, EDS and XRD. With the increase of Y content, TBCs exhibit better performance against CMAS corrosion. The corrosion resistance against CMAS of different TBCs in descending was 8YSZ + Y₂O₃, 38YSZ and 8YSZ, respectively. YSZ diffused from TBCs into the CMAS, and formed Y-lean ZrO₂ in TBCs because of the higher diffusion rate and solubility of Y³⁺ in CMAS than Zr⁴⁺. At the same time, 38YSZ/8YSZ + Y₂O₃ reacts with CAMS to form Ca₄Y₆(SiO₄)₆O/Y_4·67(SiO₄)₃O with dense structure, which can prevent further infiltration of CMAS. The failure of 8YSZ coatings occurred at the interface between the ceramic coating and the thermally grown oxide scale (TGO)/bond coating. During the burner rig test, the Y₂O₃ layer of the DL TBCs peeled off progressively and the 8YSZ layer exposed gradually. DL coatings keep roughly intact and did not meet the failure criteria after 3 h test. 38YSZ coating was partially ablated, the overall thickness of the coating is thinned simultaneously after 2 h. Therefore, 8YSZ + Y₂O₃ dual-layered coating is expected to be a CMAS corrosion-resistant TBC with practical properties.     

Erosion behavior of EB-PVD 7YSZ coatings under corrosion/erosion regime: Effect of TBC microstructure and the CMAS chemistry

Aero-engines operating in dust-laden environments often encounter a lot of dust/sand that causes a severe problem to the TBCs by means of erosion. As the turbine entry temperatures are rising, molten sand is also a big concern to the life-time of TBCs.This paper deals with the TBC behavior under the combined influence of erosion and corrosion attack. Variations in TBC morphology, CMAS infiltration time and CMAS composition and their influence on the erosion resistance at room temperature were investigated. Two different EB-PVD 7YSZ morphologies consisting of a different porosity arrangement were tested in the erosion/corrosion regime. The more ‘Feathery’ structure has a better resistance to erosion compared to a more columnar ‘Normal’ structure, which leads to less degradation of the TBC. However, under the influence of CMAS infiltration the effect was found to be reversed. In general, CMAS-infiltrated EB-PVD TBCs exhibit a higher erosion resistance than the non-infiltrated ones.     

Environmental-barrier coating ceramics for resistance against attack by molten calcia-magnesia-aluminosilicate (CMAS) glass: Part I,YAlO3 and γ-Y2Si2O7

The high-temperature (1500?°C) interactions of two promising dense, polycrystalline EBC ceramics, YAlO₃ (YAP) and γ-Y₂Si₂O₇, with a calcia-magnesia-aluminosilicate (CMAS) glass have been explored as part of a model study. Despite the fact that the optical basicities of both the EBC ceramics and the CMAS are similar, they both react with the CMAS. In the case of the Si-free YAlO₃, the reaction zone is small and it comprises three regions of reaction-crystallization products, including Y-Ca-Si apatite solid-solution (ss) and Y₃Al₅O₁₂ (YAG)(ss). In contrast, only Y-Ca-Si apatite(ss) forms in the case of Si-containing γ-Y₂Si₂O₇, and the reaction zone is an order-of-magnitude thicker. These CMAS interactions are analyzed in detail, and are found to be strikingly different than those observed in Y-free EBC ceramics (β-Yb₂Si₂O₇ and β-Sc₂Si₂O₇) in the accompanying Part II paper. This is attributed to the presence of the Y in the YAlO₃ and γ-Y₂Si₂O₇ EBC ceramics.     

EB-PVD alumina (Al2O3) as a top coat on 7YSZ TBCs against CMAS/VA infiltration: Deposition and reaction mechanisms

Al₂O₃ was deposited as a top coat on a standard 7YSZ layer (or layers) by means of EB-PVD technique and the corresponding morphology of the Al₂O₃/7YSZ coatings was studied in detail. This multi-layer TBC system was tested against calcium-magnesium-aluminium-silicate (CMAS) recession by performing infiltration experiments for different time intervals from 5?min to 50?h at 1250?°C using two types of synthetic CMAS compositions and Eyjafjallajökull volcanic ash (VA) from Iceland. The results show that the studied EB-PVD Al₂O₃/7YSZ coatings react quickly with CMAS or VA melt and form crystalline spinel (MgAl_2-xFe_xO₄) and anorthite (CaAl₂Si₂O₄) phases. The presence of Fe-oxide in the CMAS has been found to be key element in influencing the spinel formation which was proved to be more efficient against CMAS sealing in comparison to the Fe-free CMAS compositions. Even though a rapid crystallization was assured, shrinkage cracks in the EB-PVD alumina layer produced during the crystallization heat treatment have proven to be detrimental for the CMAS/VA infiltration resistance. To overcome these microstructural drawbacks, an additional alumina deposition method, namely reaction-bonded alumina oxide (RBAO), was applied on top of EB-PVD Al₂O_3. RBAO acts as a sacrificial layer forming stable reaction products inhibiting further infiltration.     

Wetting,infiltration and interaction behavior of CMAS towards columnar YSZ coatings deposited by plasma spray physical vapor

Thermal barrier coatings (TBCs) produced by electron beam physical vapor deposition (EB-PVD) or plasma spray (PS) usually suffer from molten calcium-magnesium-alumino-silicate (CMAS) attack. In this study, columnar structured YSZ coatings were fabricated by plasma spray physical vapor deposition (PS-PVD). The coatings were CMAS-infiltrated at 1250?°C for short terms (1, 5, 30?min). The wetting and spreading dynamics of CMAS melt on the coating surface was in-situ investigated using a heating microscope. The results indicate that the spreading evolution of CMAS melt can be described in terms of two stages with varied time intervals and spreading velocities. Besides, the PS-PVD columnar coating (～100?μm thick) was fully penetrated by CMAS melt within 1?min. After the CMAS attack for 30?min, the original feathered-YSZ grains (tetragonal phase) in both PS-PVD and EB-PVD coatings were replaced by globular shaped monoclinic ZrO₂ grains in the interaction regions.     

CMAS对热障涂层界面裂纹和残余应力的影响

随着航空发动机涡轮叶片工作温度的提升,使得一种主要由CaO,MgO,Al₂O₃和SiO₂组成的玻璃态物质(CMAS)对热障涂层的危害越来越严重,从而对热障涂层的性能和耐久性有了更高的要求。本文以电子束物理气相沉积热障涂层为研究对象,利用有限元方法研究了CMAS的渗入对界面裂纹扩展及CMAS对陶瓷层(TC)内部残余应力的影响规律。采用波长固定、振幅变化的正弦曲线表示不同粗糙度的涂层界面,同时考虑了CMAS的弹性模量变化的影响及不同界面形貌与CMAS之间的相互作用。结果表明：CMAS弹性模量的增加对界面裂纹具有抑制作用,并且TGO幅值和厚度越小,抑制作用越明显。CMAS弹性模量对TC层最大残余应力S₂₂的影响存在临界点,在临界点之前,CMAS弹性模量的变化对TC层最大残余应力的影响较大,随着CMAS弹性模量的增加,TC层最大残余应力大幅度减小；在临界点之后,TC层最大残余应力基本不受CMAS弹性模量变化的影响。这些结果对电子束物理气相沉积喷涂的热障涂层失效机理的研究具有重要意义,可以为热障涂层界面的优化提供指导。     

镍渣微晶玻璃核化及晶化制度的研究

以金川镍渣为主要原料采用熔融法制备建筑装饰用微晶玻璃。在成分研究的基础上，通过DSC测试、XRD、SEM和光学显微镜等分析手段，对添加了10wt％TiO2作为晶核剂的CaO-MgO-Al2O3-SiO2系统镍渣微晶玻璃试样的主晶相及微观结构进行了分析，得出了适用于该系统镍渣微晶玻璃的最佳热处理制度。     

Enhanced calcium–magnesium–aluminosilicate (CMAS) resistance of GdAlO3 (GAP) for composite thermal barrier coatings

The impact of calcium–magnesium–alumino-silicate (CMAS) degradation is a critical factor for development of new thermal and environmental barrier coatings. Several methods of preventing damage have been explored in the literature, with formation of an infiltration inhibiting reaction layer generally given the most attention. Gd₂Zr₂O₇ (GZO) exemplifies this reaction with the rapid precipitation of apatite when in contact with CMAS. The present study compares the CMAS behavior of GZO to an alternative thermal barrier coating (TBC) material, GdAlO₃ (GAP), which possesses high temperature phase stability through its melting point as well as a significantly higher toughness compared with GZO. The UCSB laboratory CMAS (35CaO–10MgO–7Al₂O₃–48SiO₂) was utilized to explore equilibrium behavior with 50:50 mol% TBC:CMAS ratios at 1200, 1300, and 1400°C for various times. In addition, 8 and 35 mg/cm² CMAS surface exposures were performed at 1425°C on dense pellets of each material to evaluate the infiltration and reaction in a more dynamic test. In the equilibrium tests, it was found that GAP appears to dissolve slower than GZO while producing an equivalent or higher amount of pore blocking apatite. In addition, GAP induces the intrinsic crystallization of the CMAS into a gehlenite phase, due in part to the participation of the Al₂O₃ from GAP. In surface exposures, GAP experienced a substantially thinner reaction zone compared with GZO after 10 h (87 ± 10 vs. 138 ± 4 μm) and a lack of strong sensitivity to CMAS loading when tested at 35 mg/cm² after 10 h (85 ± 13 versus 246 ± 10 μm). The smaller reaction zone, loading agnostic behavior, and intrinsic crystallization of the glass suggest this material warrants further evaluation as a potential CMAS barrier and inclusion into composite TBCs.