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.     

Hot corrosion behavior of Y4Al2O9 ceramics for thermal barrier coatings exposed to calcium-magnesium-alumina-silicate at 1250 °C

The degradation of thermal barrier coatings (TBCs) by calcium-magnesium-alumina-silicate (CMAS) attack has become increasingly dramatic. Y₄Al₂O₉ ceramic, a new potential TBC candidate, has received an increasing attention. In this study, porous Y₄Al₂O₉ ceramic pellets, instead of actual TBCs, are used to investigate the CMAS corrosion resistance at 1250 °C. Results indicate that Y₄Al₂O₉ reacts with CMAS melt to form an impervious sealing layer mainly containing Ca-Y-Si apatite, which could mitigate CMAS further penetration. Once the sealing layer formed, further reaction would occur above the layer accompanying by the recession of sealing layer. This process is probably related to a solid state diffusion.     

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.     

Crystallization behavior of CMAS and NaVO3+CMAS mixture and its potential effect to thermal barrier coatings corrosion

Calcium-magnesium-alumina-silicate (CMAS) and molten salt corrosion pose great threats to thermal barrier coatings (TBCs), and recently, a coupling effect of CMAS and molten salt has been found to cause even severer corrosion to TBCs. In this study, the crystallization behavior of CMAS and CMAS+NaVO₃ is investigated for potentially clarifying their corrosion mechanisms to TBCs. Results indicated that at 1000 °C and 1100 °C, CMAS was crystallized to form CaMgSi₂O₆, while at 1200 °C, the crystallization products were CaMgSi₂O₆, CaSiO₃ and CaAl₂Si₂O₈. The introduction of NaVO₃ in CMAS reduced the crystallization ability, and as the NaVO₃ content increased, glass crystallization occurred at a lower temperature, with crystallization products mainly consisting of CaAl₂Si₂O₈ and CaMgSi₂O₆. At 1200 °C, CMAS+10 wt% NaVO₃ was in a molten state without any crystallization, which suggested that NaVO₃ addition in CMAS could reduce its melting point, indicating enhanced penetration ability in TBCs and thus increased corrosiveness.     

CMAS (CaO–MgO–Al2O3–SiO2) resistance of Y2O3-stabilized ZrO2 thermal barrier coatings with Pt layers

Calcium–magnesium–alumina–silicate (CMAS) corrosion significantly affects the durability of thermal barrier coatings (TBCs). In this study, Y₂O₃ partially stabilized ZrO₂ (YSZ) TBCs are produced by electron beam-physical vapor deposition, followed by deposition of a Pt layer on the coating surfaces to improve the CMAS resistance. After exposure to 1250 °C for 2 h, the YSZ TBCs were severely attacked by molten CMAS, whereas the Pt-covered coatings exhibited improved CMAS resistance. However, the Pt layers seemed to be easily destroyed by the molten CMAS. With increased heat duration, the Pt layers became thinner. After CMAS attack at 1250 °C for 8 h, only a small amount of Pt remained on the coating surfaces, leading to accelerated degradation of the coatings. To fully exploit the protectiveness of the Pt layers against CMAS attack, it is necessary to improve the thermal compatibility between the Pt layers and molten CMAS.     

The corrosion behaviors of thermal barrier material of M-YTaO4 attacked by CMAS at 1250 °C

The corrosion of YSZ TBCs attacked by calcium–magnesium–aluminosilicate (CMAS) is a serious problem. Yttrium tantalite (YTaO₄), a new kind of potential thermal barrier ceramic material, was expected to replace the YSZ to manufacture the TBCs because of its great thermophysical characteristics. In this study, porous YTaO₄ ceramic pellets, instead of actual TBCs, were used to investigate the CMAS corrosion resistance at 1250 °C. Results indicated that CMAS couldn't cover the whole surface of YTaO₄ pellets homogeneously because of low wettability between liquid CMAS and YTaO₄, in addition, there was almost no reaction layer after 4 h reaction. The XRD results showed that M-YTaO₄, M′-YTaO₄, Ca₂Ta₂O₇ and Y₂Si₂O₇ were the main four phases after reaction and there was no phase containing the elements of Mg and Al. Compared with YSZ TBCs, this new kind of potential thermal barrier ceramic material showed well resistance to CMAS corrosion.     

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.     

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.     

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.     

CMAS corrosion resistance in high temperature and rainwater environment of double-layer thermal barrier coatings odified by rare earth

In order to explore the difference of CMAS corrosion resistance in high temperature and rainwater environment of single-layer and double-layer thermal barrier coatings (TBCs), and further reveal the mechanism of CMAS corrosion resistance in above environment of double-layer TBCs modified by rare earth, two TBCs were prepared by air plasma spraying, whose ceramic coating were single-layer ZrO₂–Y₂O₃ (YSZ) and double-layer La₂Zr₂O₇(LZ)/YSZ, respectively. Subsequently, CMAS corrosion resistance tests at 1200 °C and rainwater environment of two TBCs were carried out. Results demonstrate that after high temperature CMAS corrosion for the same time, due to phase transformation, the volume of YSZ ceramic coating in single-layer TBCs shrank and surface cracks formed, which would lead to coating failure. When LZ ceramic coating of double-layer TBCs reacted with CMAS, compact apatite phases and fluorite phases formed, the penetration of CMAS into ceramic coating was inhibited effectively. Raman analysis and calculation results show that both of the surface residual stress of ceramic coating in two TBCs were compressive stress, and the residual stress of ceramic coating in double-layer TBCs were smaller than that of single-layer TBCs. Atomic force microscopy of TBCs after CMAS corrosion show that surface of double-layer TBCs was more uniform and compact than that of single-layer TBCs. The electrochemical properties in simulated rainwater of two TBCs after high temperature CMAS corrosion showed that double-layer TBCs possessed higher free corrosion potential, lower corrosion current and higher polarization resistance than those of single-layer TBCs. Consequently, the presence of LZ ceramic coating effectively improved CMAS corrosion resistance in high temperature and rainwater environment of double-layer TBCs.     

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.     

Doped effect of Gd and Y elements on corrosion resistance of ZrO2 in CMAS melt: First-principles and experimental study

The effects of Gd and Y doping on the corrosion resistance of ZrO₂ in CMAS (CaO, MgO, Al₂O₃, SiO₂) melts were investigated via first-principle calculations and experimental investigations. It is found that, although Gd₂Zr₂O₇ with single Gd-doped ZrO₂ has the lowest cohesive energy E_cohesive and formation enthalpy H_formation, YSZ(Gd) exhibits the lowest chemical activity with Y and Gd composite doping. The small Griffith’s rupture work (W = −3.498 J m⁻²) is beneficial to the flow of the CMAS melt on the YSZ(Gd) surface. Furthermore, the low Fermi energy and low O and Y electronegativities cause the weakest chemical activity. Additionally, the diffusion coefficients of Y, Zr, and O elements are also decreased through Gd-doping in YSZ. EDS investigations also demonstrate that the CMAS/YSZ(Gd) has the smallest reaction depth (6.65 μm) and the lowest elements penetration ability. Thus, the best corrosion resistance is originated from Y and Gd composite doping in YSZ(Gd) 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.     

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.     

Residual stress trend in thermal barrier coatings in through thickness direction measured by photoluminescence piezospectroscopy

Abstract

Photoluminescence piezospectroscopy (PLPS) has been used to determine residual stresses in sapphire, alumina in the yttria stablised zirconia (YSZ)/Al₂O₃ composite and alumina in thermal barrier coatings (TBCs). The TBC of YSZ containing 0·5?wt-% alumina has been produced using electron beam physical vapour deposition. The stress profile through the TBC thickness was measured using a depth sensing method. Reasonable residual stress profiles have been obtained using PLPS with the confocal system for all three material systems. Measurements of TBCs suggest that stress distribution in a TBC system is not uniform in general. However, uniform stress distribution has been found in some positions where damage in TBCs might occur.     

High-temperature interactions between Yttria-stabilized zirconia thermal barrier coatings and Na-Rich calcia-magnesia-aluminosilicate deposits

We have evaluated the effectiveness of optical basicity, a chemical model, to predict and categorize the reaction behavior between calcia-magnesia-aluminosilicate (CMAS) deposits and ZrO₂-based thermal barrier coatings (TBCs), which are used to insulate and protect metallic components in gas-turbine engines. The attack behavior of two CMAS compositions (Na-lean and Na-rich) with 7 wt% Y₂O₃-partially-stabilized ZrO₂ (7YSZ) and 2ZrO₂·Y₂O₃(ss) free-standing TBCs at 1340 °C were evaluated and compared to previous studies. The behavior of Y³⁺ in the reaction is correlated with the optical basicity of the CMAS; more basic Na-rich CMAS melt resulted in lower Y-solubility and higher Y-content in the reprecipitated ZrO₂ grains than observed in the highly acidic CMAS attack for both tested TBCs. This behavior is consistent with previous studies of basic and acidic melts, and suggests that less acidic CMASs pose a unique danger to ZrO₂-based TBCs that rely on Y-rich secondary phases for CMAS mitigation.     

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.     

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.     

Anti-CMAS corrosion mechanism of Al2O3 pore sealing and laser remelting on thermal barrier coatings

The sol-dip-coating method and surface laser remelting technology are applied to form an Al₂O₃ layer on a YSZ coating surface to effectively block the environmental sediment CMAS. The behaviour and mechanism for CMAS corrosion of the coating are investigated, and the interfacial reliability of the coating and matrix is calculated by using the Monte Carlo method. The bonding force between the Al₂O₃ sol and YSZ coating can be effectively improved by laser surface treatment. Samples subjected to a laser pretreatment and posttreatment (YL-AL) of the YSZ coating are found to show the best interfacial bonding strength between Al₂O₃ and YSZ. Furthermore, the YL-AL sample shows a higher CMAS resistance than the laser posttreatment (Y-AL) samples, which effectively combines the chemical resistance of Al₂O₃ to CMAS and the physical resistance of the laser re-melted densification layer against CMAS penetration.