The influence of thermal barrier coating dissolution on CMAS melt viscosities

Glassy deposits, largely consisting of CaO-MgO-Al₂O₃-SiO₂ (CMAS), are a common product on thermal barrier coatings (TBCs) within gas-turbines after an interaction with airborne particles. Here, in order to facilitate the quantification and modelling of the spreading and infiltration behavior of CMAS melts onto and into TBCs we have determined the high temperature viscosities of four widely used synthetic “CMAS” melts and the influence of TBC materials (yttria-stabilized zirconia (YSZ) and gadolinium zirconate (GZO)) dissolution upon them. After a dissolution of 6.5 wt% YSZ or GZO one out of four CMAS melts shows no significant change in viscosity, while the other three melts exhibit a viscosity increase at lower temperatures that continuously changes to a decrease in viscosity towards higher temperatures. The influence of the doping amount on the viscosity was investigated in detail for one CMAS melt (C₃₅M₁₀A₇S₄₈) and parametrized.     

Equimolar YO1.5 and TaO2.5 co-doped ZrO2 as a potential CMAS-resistant material for thermal barrier coatings

Calcium-magnesium-alumino-silicates (CMAS) corrosion in thermal barrier coatings (TBCs) is becoming more serious with increasing operation temperature of turbine engines. Here, we report an equimolar YO_1.5 and TaO_2.5 co-doped ZrO₂ (Zr_0.66Y_0.17Ta_0.17O₂, ZYTO) as a potential CMAS-resistant material for TBCs, which shows a significantly enhanced CMAS resistance than the conventional 17 mol% YO_1.5-stabilized ZrO₂ (17YSZ). After exposure at 1300°C for 100 hours, the CMAS infiltration depth in ZYTO bulk is ~80 μm (for a 20 mg/cm² CMAS deposition), in contrast to ~700 μm in 17YSZ bulk (50 hours). Compositional and morphological analyses on the CMAS reaction zone reveal that the excellent CMAS resistance of ZYTO originates from the uniform corrosion through grain and grain boundary, along with densification of the reaction layer. The high CMAS infiltration rate of 17YSZ is attributed to the severe dissolution and infiltration through grain boundary. The reaction mechanisms of CMAS with ZYTO and 17YSZ bulks are discussed and a strategy of enhancing the CMAS resistance is proposed for ZrO₂-based TBC materials.     

Thermal cycling performances of multilayered yttria-stabilized zirconia/gadolinium zirconate thermal barrier coatings

Gadolinium zirconate (Gd₂Zr₂O₇, GZO) as an advanced thermal barrier coating (TBC) material, has lower thermal conductivity, better phase stability, sintering resistance, and calcium-magnesium-alumino-silicates (CMAS) attack resistance than yttria-stabilized zirconia (YSZ, 6-8 wt%) at temperatures above 1200°C. However, the drawbacks of GZO, such as the low fracture toughness and the formation of deleterious interphases with thermally grown alumina have to be considered for the application as TBC. Using atmospheric plasma spraying (APS) and suspension plasma spraying (SPS), double-layered YSZ/GZO TBCs, and triple-layered YSZ/GZO TBCs were manufactured. In thermal cycling tests, both multilayered TBCs showed a significant longer lifetime than conventional single-layered APS YSZ TBCs. The failure mechanism of TBCs in thermal cycling test was investigated. In addition, the CMAS attack resistance of both TBCs was also investigated in a modified burner rig facility. The triple-layered TBCs had an extremely long lifetime under CMAS attack. The failure mechanism of TBCs under CMAS attack and the CMAS infiltration mechanism were investigated and discussed.     

Tailoring the EB-PVD columnar microstructure to mitigate the infiltration of CMAS in 7YSZ thermal barrier coatings

The CMAS associated degradation of 7YSZ TBC layers is one of the serious problems in the aero engines that operate in dusty environments. CMAS infiltrates into TBC at high temperatures and stiffens the TBC which ultimately loses its strain tolerance and gets delaminated. The EB-PVD technique is used to coat TBCs exhibiting a columnar microstructure on parts such as blades and on vanes. By varying the EB-PVD process parameters, columnar morphology and porosity of the 7YSZ coating is changed and its effect on the CMAS infiltration behaviour is studied in detail. Two different TBC pore geometries were created and infiltration experiments were carried out at 1250 °C and 1225 °C for different time intervals. The 7YSZ coating with more ‘feathery’ features has resulted in higher CMAS resistance by at least by a factor of 2 than its less ‘feathery’ counterpart. These results are explained on the basis of a proposed physical model.     

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.     

2ZrO2·Y2O3 Thermal Barrier Coatings Resistant to Degradation by Molten CMAS: Part I,Optical Basicity Considerations and Processing

The higher operating temperatures in gas‐turbine engines enabled by thermal barrier coatings (TBCs) engender new materials issues, viz silicate particles (sand, volcanic ash, fly ash) ingested by the engine melt on the hot TBC surfaces and form calcium–magnesium–alumino–silicate (CMAS) glass deposits. The molten CMAS glass degrades TBCs, leading to their premature failure. In this context, we have used the concept of optical basicity (OB) to provide a quantitative chemical basis for the screening of CMAS‐resistant TBC compositions, which could also be extended to environmental barrier coatings (EBCs). By applying OB difference considerations to various major TBC compositions and two types of important CMASs—desert sand and fly ash—the 2ZrO₂·Y₂O₃ solid solution (ss) TBC composition, with the potential for high CMAS‐resistance, is chosen for this study. Here, we also demonstrate the feasibility of processing of 2ZrO₂·Y₂O₃(ss) air‐plasma sprayed (APS) TBC using commercially developed powders. The resulting TBCs with typical APS microstructures are found to be single‐phase cubic fluorite, having a thermal conductivity <0.9 W·(m·K)^?1 at elevated temperatures. The accompanying Part II paper presents results from experiments and analyses of high‐temperature interactions between 2ZrO₂·Y₂O₃(ss) APS TBC and the two types of CMASs.     

A new approach to protect and extend longevity of the thermal barrier coating by an impermeable layer of silicon nitride

A sample representation of a gas turbine engine blade, consisting of a nickel superalloy substrate with a deposited thermal barrier coating (TBC), was covered with silicon nitride, Si₃N₄, as an impermeable layer using plasma enhanced chemical vapor deposition (PECVD). The silicon nitride layer was used to seal the topcoat of yttria-stabilized zirconia (YSZ) surface of the TBC to mitigate calcium–magnesium–aluminum–silicon oxide (CMAS) attack. CMAS testing was carried out on the covered and uncovered surfaces by melting a ratio of 25 mg/cm² of CMAS powder onto the surface of each sample in a furnace at 1100°C for 1 h. The conformal surface reaction of the sealed layer confirmed no cracking or delamination at high temperatures. Scanning electron microscopy (SEM) micrographs confirmed that the surface of YSZ was successfully sealed. The new coating of silicon nitride was shown to be a viable solution and technique to significantly block CMAS infiltration in porous thermal barrier coatings.     

2ZrO2·Y2O3 Thermal Barrier Coatings Resistant to Degradation by Molten CMAS: Part II,Interactions with Sand and Fly Ash

Based on the application of OB considerations (Part I) to various major thermal barrier coating (TBC) compositions and two types of important calcium–magnesium–alumino–silicates (CMAS)—desert sand and fly ash—the 2ZrO₂·Y₂O₃ solid solution (ss) TBC composition, with high CMAS‐resistance potential, is chosen for studying molten‐CMAS/TBC interactions. It is demonstrated that 2ZrO₂·Y₂O₃(ss) air plasma sprayed (APS) TBCs are highly resistant to high‐temperature attack by both sand‐CMAS and fly‐ash‐CMAS. Despite the differences in the compositions of the two CMASs, the overall CMAS‐attack mitigation mechanisms in both cases appear to be similar, viz reaction between 2ZrO₂·Y₂O₃(ss) APS TBC and the CMAS, and the formation of main reaction products of Y‐depleted c‐ZrO₂ and nonstoichiometric Ca–Y apatite. Large differences in the OBs (ΔΛ) between the 2ZrO₂·Y₂O₃(ss) and the CMASs are good predictors of ready reaction between this TBC and these CMASs. While the details of the CMAS‐mitigation mechanisms can depend critically on various other aspects, the OB difference (ΔΛ) calculations could be used for the initial screening of CMAS‐resistant TBC compositions.     

CMAS corrosion of YSZ thermal barrier coatings obtained by different thermal spray processes

Degradation of yttria-stabilized zirconia (YSZ) layers by molten CaO-MgO-Al₂O₃-SiO₂ (CMAS)-based deposits is an important failure mode of thermal barrier coating (TBC) systems in modern gas turbines. The present work aimed to understand how the chemical purity and microstructure of plasma-sprayed YSZ layers affect their response to CMAS corrosion. To this end, isothermal corrosion tests (1 h at 1250 °C) were performed on four different kinds of YSZ coatings: atmospheric plasma-sprayed (APS) layers obtained from standard- and high-purity feedstock powders, a dense – vertically cracked (DVC) layer, and a suspension plasma sprayed (SPS) one. Characterization of corroded and non-corroded samples by FEG-SEM, EBSD and micro-Raman spectroscopy techniques reveals that, whilst all YSZ samples suffered grain-boundary corrosion by molten CMAS, its extent could vary considerably. High chemical purity limits the extent of grain-boundary dissolution by molten CMAS, whereas high porosity and/or fine crystalline grain structure lead to more severe degradation.     

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.     

Comparison of corrosion behaviors and wettability of CMAS on Ta2O5-Y2O3 co-stabilized ZrO2 and YSZ thermal barrier coatings

High-temperature degradation of the plasma sprayed 16 mol% TaO_2.5 + 16 mol% YO_1.5 co-stabilized ZrO₂ (YTZ) and YSZ (7.6 wt% Y₂O₃-stabilized ZrO₂) coatings under calcium-magnesium-aluminon-silicate (CMAS) attack at 1200 °C and 1250 °C were comparatively investigated. Results indicated that the coatings were insensitive to the infiltration of CMAS after 10 h corrosion at 1200 °C. At 1250 °C, the entire YSZ cross-section completely failed and also underwent serious chemical corrosion after 3 h hot corrosion. Even after 10 h corrosion, the penetration depth of CMAS into the YTZ was only about 80 µm. For YTZ coating, the YTaO₄ stabilizer could not easily dissolve in CMAS and precipitated out of the YTZ crystal lattice owing to the strong chemical interaction between Ta⁵⁺ and Y³⁺. The wettability of CMAS on YTZ coating was worse than that on YSZ coating. Compared with YSZ coating, the YTZ coating showed better resistance to CMAS corrosion.     

Multilayer GZ/YSZ thermal barrier coating from suspension and solution precursor thermal spray

Rare-earth (RE) zirconates, such as gadolinium zirconate (GZ), gained much attraction to be used for the next generation TBC. A double-layer and triple-layer TBC were deposited using the suspension and solution precursor high velocity oxy fuel (HVOF) thermal spray. A dense solution precursor GZ layer was intended to minimise the crack propagation from underneath, thereby inhibiting the CMAS infiltration. In the furnace cycling test, the double- and triple-layer coatings had a comparable cyclic lifetime. For the CMAS test, both the double- and triple-layer coatings were exposed to CMAS at 1250 °C for 30 mins. The CMAS deposits melted and infiltrated both coatings through the dense vertical cracks (DVCs). Interestingly, the GZ reacted with the molten CMAS to form a gadolinium apatite phase (Ca₂Gd₈(SiO₄)₆O₂) that was detected in the double- and triple-layer TBC. Both the double- and triple-layer TBCs succeeded in reacting with CMAS.     

Solution combustion synthesis of calcia-magnesia-aluminosilicate powder and its interaction with yttria-stabilized zirconia and co-doped yttria-stabilized zirconia

Thermal Barrier Coatings (TBCs) play a significant role in improving the efficiency of gas turbines by increasing their operating temperatures. The TBCs in advanced turbine engines are prone to silicate particles attack while operating at high temperatures. The silicate particles impinge on the hot TBC surfaces and melt to form calcia-magnesia-aluminosilicate (CMAS) glass deposits leading to coating premature failure. Fine powder of CMAS with the composition matching the desert sand has been synthesized by solution combustion technique. The present study also demonstrates the preparation of flowable yttria-stabilized zirconia (YSZ) and cluster paired YSZ (YSZ-Ln₂O₃, Ln = Dy and Gd) powders by single-step solution combustion technique. The as-synthesized powders have been plasma sprayed and the interaction of the free standing TBCs with CMAS at high-temperatures (1200 °C, 1270 °C and 1340 °C for 24 h) has been investigated. X-ray diffraction analysis of CMAS attacked TBCs revealed a reduction in phase transformation of tetragonal to monoclinic zirconia for YSZ-Ln₂O₃ (m-ZrO₂: 44%) coatings than YSZ (m-ZrO₂: 67%). The field emission scanning electron microscopic images show improved CMAS resistance for YSZ-Ln₂O₃ coatings than YSZ coatings.     

Enhanced properties of Al-modified EB-PVD 7YSZ thermal barrier coatings

7 wt% yttria-stabilized zirconia (7YSZ) thermal barrier coating (TBC) prepared by electron beam-physical vapor deposition (EB-PVD) has been used in gas turbine engines for many years, where the TBC must successfully withstands the damage caused by a variety of environmental and mechanical aspects. The primary failure modes for TBC are oxidation of bond coating, particle erosion and CMAS (calcium-magnesium-alumina-silicates) corrosion. The lifetime of TBC associated with above three failure factors will be reduced significantly. In order to prolong the operation time, an alternative approach depositing Al film on 7YSZ TBC surface by magnetron sputtering is proposed. An α-Al₂O₃ overlay was in-situ synthesized on each 7YSZ column through reaction of Al and ZrO₂ during vacuum heat treatment. And the results indicate that the Al-modified EB-PVD 7YSZ TBC shows better oxidation resistance, as well as lower particulate erosion and CMAS corrosion.     

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.     

Effect of CMAS Deposits on MOCVD Coatings in the System Y2O3–ZrO2: Phase Relationships

Three metal‐organic chemical vapor deposition (MOCVD) coatings (ZrO₂, Y₂O₃·ZrO₂, Y₂O₃) were studied in contact with model CMAS to investigate the microstructural evolution and phase formation. The MOCVD coatings were covered with CMAS powder deposits and annealed for 1 h at 1250°C, respectively. The ZrO₂ coating was completely infiltrated by CMAS, whereas the yttria containing coatings show a higher resistance against CMAS infiltration. This is explained by the formation of a continuous oxyapatite layer in the reaction zone of the coating and the CMAS deposit. The Y₂O₃·ZrO₂ coating shows the best infiltration resistance despite the fact that the Y₂O₃–CMAS sample is the only completely crystallized. As crystallization products, oxyapatite, melilite, anorthite as well as new garnets bearing all available cations were formed. The garnet phase was confirmed by XRD and TEM. EDS measurements were used to calculate structural formula A₃B₂T₃O₁₂ (A = Ca, Y, Zr; B = Mg, Al; T = Al, Si).     

Evolution of porosity,crack density,and CMAS penetration in thermal barrier coatings subjected to burner rig testing

Degradation of thermal barrier coatings (TBCs) in gas-turbine engines due to calcium–magnesium–aluminosilicate (CMAS) glassy deposits from various sources has been a persistent issue since many years. In this study, state of the art electron microscopy was correlated with X-ray refraction techniques to elucidate the intrusion of CMAS into the porous structure of atmospheric plasma sprayed (APS) TBCs and the formation and growth of cracks under thermal cycling in a burner rig. Results indicate that the sparse nature of the infiltration as well as kinetics in the burner rig are majorly influenced by the wetting behavior of the CMAS. Despite the obvious attack of CMAS on grain boundaries, the interaction of yttria-stabilized zirconia (YSZ) with intruded CMAS has no immediate impact on structure and density of internal surfaces. At a later stage the formation of horizontal cracks is observed in a wider zone of the TBC layer.     

Isothermal Oxidation Behavior of Gd2Zr2O7/YSZ Multilayered Thermal Barrier Coatings

Efficiency of a gas turbine can be increased by increasing the operating temperature. Yttria‐stabilized zirconia (YSZ) is the standard thermal barrier coating (TBC) material used in gas turbine applications. However, above 1200°C, YSZ undergoes significant sintering and CMAS (calcium magnesium alumino silicate) infiltration. New ceramic materials of rare earth zirconate composition such as gadolinium zirconate (GZ) are promising candidates for thermal barrier coating applications (TBC) above 1200°C. Suspension plasma spray of single‐layer YSZ, double‐layer GZ/YSZ, and a triple‐layer TBC comprising denser GZ on top of GZ/YSZ TBC was attempted. The overall coating thickness in all three TBCs was kept the same. Isothermal oxidation performance of the three TBCs along with bare substrate and bond‐coated substrate was investigated for time intervals of 10 h, 50 h, and 100 h at 1150°C in air environment. Weight gain/loss analysis was carried out by sensitive weighing balance. Microstructural analysis was carried out using scanning electron microscopy (SEM). As‐sprayed single‐layer YSZ and double‐layer GZ/YSZ showed columnar microstructure, whereas the denser layer in the triple‐layer TBC was not columnar. Phase analysis of the top surface of as‐sprayed TBCs was carried out using XRD. Porosity measurements were made by water intrusion method. In the weight gain analysis and SEM analysis, multilayered TBCs showed lower weight gain and lower TGO thickness compared to single‐layer YSZ.     

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.     

Coprecipitation of CaCO3 and CaSO4

Coprecipitation characteristics of CaCO₃ and CaSO₄ were studied under various operating conditions. The investigations were carried out in temperature‐controlled batch tests. Coprecipitation results were compared with our experimental results of a single salt crystallization. It was found that the induction period and kinetics of coprecipitation of these two salts follow that of pure CaCO₃. However, thermodynamic concentrations of Ca in coprecipitation followed that of pure CaSO₄ at all times. The relationship between the thermodynamic concentrations of Ca for pure CaCO₃ and CaSO₄ solutions depended on the pH of the CaCO₃ solution. CaSO₄ precipitated in form of gypsum and had a needle shape structure; CaCO₃ had a spiral growth and precipitated in form of calcite. The precipitate structure was affected by the co‐existence of salts; the co‐precipitation resulted in CaCO₃ crystals interwoven by CaSO₄ crystals. This tends to result in a co‐precipitate that is stronger than pure CaSO₄ and weaker than pure CaCO₃ precipitate.