Microstructural characterization of GZ/CYSZ thermal barrier coatings after thermal shock and CMAS+hot corrosion test

In this study, first, Gd₂Zr₂O₇/ceria–yttria stabilized zirconia (GZ/CYSZ) TBCs having multilayered and functionally graded designs were subjected to thermal shock (TS) test. The GZ/CYSZ functionally graded coatings displayed better thermal shock resistance than multilayered and single layered Gd₂Zr₂O₇ coatings. Second, single layered YSZ and functionally graded eight layered GZ/CYSZ coating (FG8) having superior TS life time were selected for CMAS + hot corrosion test. CMAS + hot corrosion tests were carried out in the same experiment at once. Furthermore, to generate a thermal gradient, specimens were cooled from the back surface of the substrate while heating from the top surface of the TBC by a CO₂ laser beam. Microstructural characterizations showed that the reaction products were penetrated locally inside of the YSZ. On the other hand, a reaction layer having ∼6 μm thickness between CMAS and Gd₂Zr₂O₇ was seen. This reaction layer inhibited to further penetration of the reaction products inside of the FG8.     

Solution precursor thermal spraying of gadolinium zirconate for thermal barrier coating

Gadolinium zirconate (GZ) is an attractive material for thermal barrier coatings (TBCs). However, a single layer GZ coating has poor thermal cycling life compared to Yttria Stabilized Zirconia (YSZ). In this study, Solution Precursor High Velocity Oxy-Fuel (SP-HVOF) thermal spray was used to produce a double layer GZ/YSZ TBC and compared the thermal cycling performance with the single layer YSZ TBC. The temperature behaviour of the solution precursor GZ was studied, and single splat tests were carried out to obtain an optimised spray parameter. In thermal cycling tests, the single-layer YSZ reached 20 % failure at 85 ± 5 cycles, whereas the double-layer GZ/YSZ was at 70 ± 15 cycles. The single-layer failed at the topcoat/TGO interface, whereas the double-layer failed at GZ/YSZ interface and topcoat/TGO interface. Moreover, Gd diffusion occurred near the GZ/YSZ interface, resulting in porosities in the GZ layer.     

Reaction mechanisms of Gd2Zr2O7 in silicate melts derived from CAS

Infiltration mechanisms at high temperatures of sand & ashes (CAS) in aircraft thermal barrier coatings (TBC) have been widely studied using the pyrochlore phase Gd₂Zr₂O₇ (GZ) as TBC. Novelty of this study is GZ reactivity with each or a mix of oxides derived from CMAS have been scrutinized in order to better assess the diffusion, stability and role of each reactivity products in mitigation mechanisms across the CAS-GZ system. In particular, Gd^+III, Si^+IV, O^-II diffusion mechanisms at the GZ/SiO₂ interface have been discussed. These mechanisms shed light on why Gd-oxyapatites are the predominant phases at interfaces between silica-rich medium such as CAS and GZ when reactions are not complete, in contrast to thermodynamic data. Moreover, Gd₂Si₂O₇ phases are closely linked to the growth of Gd-oxyapatites and are the seat of the diffusion barrier to Si^+IV species, which further explains why GZ coatings shortly stops CMAS infiltration.     

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.     

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.     

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.     

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.     

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.     

Calcium-magnesium-alumina-silicate (CMAS) resistance characteristics of LnPO4 (Ln = Nd,Sm, Gd) thermal barrier oxides

Calcium-magnesium-alumina-silicate (CMAS) attack has been considered as a significant failure mechanism for thermal barrier coatings (TBCs). As a promising series of TBC candidates, rare-earth phosphates have attracted increasing attention. This work evaluated the resistance characteristics of LnPO₄ (Ln = Nd, Sm, Gd) compounds to CMAS attack at 1250 °C. Due to the chemical reaction between molten CMAS and LnPO₄, a dense, crack-free reaction layer, mainly composed of Ca₃Ln₇(PO₄)(SiO₄)₅O₂ apatite, CaAl₂Si₂O₈ and MgAl₂O₄, was formed on the surface of compounds, which had positive effect on suppressing CMAS infiltration. The depth of CMAS penetration in LnPO₄ (Ln = Nd, Sm, Gd) decreased in the sequence of NdPO₄, SmPO₄ and GdPO₄. GdPO₄ had the best resistance characteristics to CMAS attack among the three compounds. The related mechanism was discussed based on the formation ability of apatite phase caused by the reaction between molten CMAS and LnPO₄.     

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.     

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.     

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.     

Hot corrosion studies of nanostructured gadolinium zirconate thermal barrier coatings

Improvement of hot corrosion resistance is one of the important parameters governing the lifetime and efficiency of the thermal barrier coatings (TBCs). In this study, the Gadolinium Zirconate (GZ) was synthesized by ball milling method and deposited by Electron Beam-Physical Vapour Deposition (EB-PVD) on Ni-based superalloy substrate with NiCrAlY as an intermediate bond coat. The effect of nanostructured GZ TBCs on hot corrosion resistance were studied under three different salt mixture environments viz; SM1, SM2 and SM3 in isothermal condition at 900 °C for 12 h. The results indicated that EB-PVD coated nanostructured GZ TBCs have improved the hot corrosion resistance and performed well under SM1 and SM3 conditions with minimal weight gain and without any spallation, whereas, the TBC suffered severe spallation under of SM2 salt condition with higher weight gain among the other two conditions. The formation of microcracks along the columnar gaps of the topcoat were found in the SM2 condition, have allowed the molten salts infiltration up to the coating interface. The formation of dense corrosive products GdVO₄ and m-ZrO₂ phases were identified after hot corrosion in SM1 and SM3 condition, which were absent in SM2 condition.     

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.     

Calcium-magnesium-alumina-silicate (CMAS) resistant Ba2REAlO5 (RE = Yb,Er, Dy) ceramics for thermal barrier coatings

Calcium-magnesium-alumina-silicate (CMAS) attack has been a great challenge for the application of thermal barrier coatings (TBCs) in modern turbine engines. In this study, a series of prospective TBC candidate materials, Ba₂REAlO₅ (RE = Yb, Er, Dy), are found to have high resistance to CMAS attack. The rapid formation of a continuous crystalline layer on sample surface contributes to this desirable attribute. At 1250 °C, Ba₂REAlO₅ dissolve in the molten CMAS, accumulating Ba, RE and Al in the melt, which could trigger the crystallization of celsian, apatite and wollastonite crystals. Especially, the formation of the crystalline layer in the Ba₂DyAlO₅ sample is the fastest. This study also reveals that Ba is a useful element for altering CMAS composition to precipitate celsian. Thus, doping Ba²⁺ in yttria partially stabilized zirconia or other novel TBCs might be an attractive way of mitigating CMAS attack.     

Interaction of CMAS on thermal sprayed ytterbium disilicate environmental barrier coatings: A story of porosity

Molten calcium magnesium alumina-silicates (CMAS) represent a challenge for the current generation of rare earth silicates environmental barrier coatings (EBCs). Their interaction with ytterbium disilicate (Yb₂Si₂O₇) free-standing coatings deposited using thermal spraying technique has been studied to further understand the reaction mechanisms. Three coatings, deposited with different porosity levels and thickness, representing traditional EBCs (<3% porosity and ～350 μm thickness) and abradable coatings (～20% porosity and 500–1000 μm thickness) were exposed to CMAS at 1350 °C. The results show that higher porosity levels facilitates CMAS infiltration in the first hour of exposure, in combination with infiltration through the inter-splat boundaries. Preferential dissolution of ytterbium monosilicate (Yb₂SiO₅) takes place, forming a 10–15 μm Ca₂Yb₈(SiO₄)₆O₂ apatite layer as the reaction product, producing a network of fine porosity (<10 μm) as the inter-splat boundary material is consumed. After exposure for 48 h, CMAS has completely infiltrated all three coatings, with apatite crystals present across the coatings, up to a depth of ～550 μm. Despite the extensive CMAS infiltration and apatite formation, no damage could be observed in any of the coatings, providing a promising first step for environmental barrier abradable 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.     

Wetting,infiltration, and interaction behavior of calcium-magnesium-alumino-silicate towards Gd/Yb-modified SrZrO3 coatings deposited by solution precursor plasma spray

Wetting of thermal barrier coatings (TBCs) with calcium-magnesium- alumino-silicate (CMAS) leads to sintering and phase transition, which are major issues in the aerospace industry. We prepared Sr(Zr_1−2xYb_xGd_x)O_3−x (x = 0, 0.05, 0.1, and 0.15) coatings using solution precursor plasma spraying with inter-pass boundaries (IPBs) and vertical cracks, and analyzed the CMAS wettability at 1350 °C using the sessile-drop method. The wetting and diffusion dynamics of the CMAS melt on the surface of the coating were studied using a CCD camera, revealing that the Sr(Zr_0.7Yb_0.15Gd_0.15)O_2.85 coating had the lowest spreading speed (2.60 × 10⁻⁴ mm/s, spreading balance process). Furthermore, a greater extent of crack bending and smaller crack diameter can prevent the coatings from penetration of the CMAS melt.     

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.     

Plasma-sprayed La2Ce2O7 thermal barrier coatings against calcium–magnesium–alumina–silicate penetration

As one of promising thermal barrier coating (TBC) candidates, La₂Ce₂O₇ (LC) has attracted increasing attention because of its low thermal conductivity and potential capability to be operated above 1250 °C. In this paper, the microstructure evolution and mechanical properties of the plasma-sprayed LC TBC with calcium–magnesium–alumina–silicate (CMAS) glassy deposits at 1250 °C were investigated. Due to chemical reaction between the CMAS deposits and LC coating, a dense sealing layer, mainly composed of Ca₂(La_xCe_1−x)₈(SiO₄)₆O_6−4x and CeO₂, was formed on the coating after heat-treatment at 1250 °C and effectively prevented CMAS from further penetration. The interaction layer had the micro-hardness of ∼10–12 GPa, relatively harder than the LC coating.