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.     

Performance of YSZ and Gd2Zr2O7/YSZ double layer thermal barrier coatings in burner rig tests

Double layer thermal barrier coatings (TBCs) consisting of a Gd₂Zr₂O₇ (GZO) top and an ytrria stabilized zirconia (YSZ) interlayer have been tested in a burner rig facility and the results compared to the ones of conventional YSZ single layers. In order to gain insight in the high temperature capability of the alternative TBC material, high surface temperatures of up to 1550 °C have been chosen while keeping the bond coat temperature similar. It turned out that the performance of all systems is largely depending on the microstructure of the coatings especially reduced porosity levels of GZO being detrimental. In addition, it was more difficult in GZO than in YSZ coatings to obtain highly porous and still properly bonded microstructures. Another finding was the reduced lifetime with increasing surface temperatures, the amount of reduction is depending on the investigated system. The reasons for this behavior are analyzed and discussed in detail.     

Modelling and evaluating thermal conductivity of porous thermal barrier coatings at elevated temperatures

Thermal conductivity of various porous thermal barrier coatings (TBCs) used at elevated temperatures for gas turbines has been evaluated using the proposed six-phase model. These TBCs rely on microstructural properties and yield different types of porosities. This paper studies the thermal conductivity of TBCs based on microstructural features to evaluate the effect of different types of porosities on thermal conductivity. The first part of this paper investigates the microstructural characterization of various TBCs using image analysis (IA) technique. The second part of this paper evaluates the thermal conductivity using the image analysis. The volumetric fraction of porosities along with their orientation, shape and morphology, shows a considerable impact on the overall thermal conductivity of TBCs. The proposed six-phase model can predict thermal conductivity of porous TBCs with a good agreement with the measured values. The model results can help to better understand the effect of microstructural changes on thermal conductivity and can provide useful guide to fabricate TBCs with low thermal conductivity.     

Durable aluminate toughened zirconate composite thermal barrier coating (TBC) materials for high temperature operation

Research on advanced thermal barrier coating (TBC) materials capable of operating beyond 1200°C has primarily focused on the rare earth zirconate pyrochlores, particularly gadolinium zirconate (Gd₂Zr₂O₇ – GZO). The drawback of this material is a significant reduction in durability due to a low fracture toughness. This study investigates utilization of a thermodynamically compatible gadolinia alumina perovskite (GdAlO₃ – GAP) toughening phase to improve the durability of GZO. Dense pellets were fabricated to assess the material properties with minimal microstructural influence. Thermal stability, elastic modulus, hardness, indentation fracture resistance and erosion durability were evaluated for GZO, GAP, and composite pellets containing 10, 30, and 50 wt.% GAP. It was demonstrated that GAP and GZO are thermodynamically compatible through 1600°C and thus capable of operating well beyond the limits of traditional 7 wt.% yttria stabilized zirconia (YSZ). Grain sizes are maintained due to a lack of diffusion, and thus microstructural stability is enhanced. The GAP fracture toughness was shown to be over 2X that of GZO while exhibiting a lower elastic modulus and similar hardness. The 50:50 GZO-GAP composite exhibited a 63% reduction in the absolute erosion rate, demonstrating the immense toughening capabilities of this system. The implications for composite TBCs utilizing this system are discussed, along with future work.     

The morphology,thermal property,and failure mechanism of GdNdZrO thermal barrier coatings by EB-PVD

Nowadays, the Gd₂Zr₂O₇ thermal barrier coatings (TBCs) have been evaluated as a promising alternative to yttria-stabilized zirconia (YSZ). Thus, this investigation focuses on the thermal property, morphology, and failure mechanism of double ceramic layers (DCLs) GdNdZrO/YSZ advanced TBCs. The GdNdZrO coatings with columnar morphology have been deposited on NiCoCrAlYHf bond coating using an electron beam physical vapor deposition method. Material characterizations mainly include X-ray diffraction, scanning electron microscope, and transmission electron microscopy. The thermal conductivity of GdNdZrO ceramic material is 0.494 W/mK at 1200°C. The thermal shock life of GdNdZrO/YSZ TBCs shows an average shock life of 5235 cycles. The TBC degradation occurs on the crack area within thermally grown oxide layer leading to the interface instability. The interface broken might play an important role in the failure mechanism of TBCs.     

Sintering behavior of a nanostructured thermal barrier coating deposited using electro-sprayed particles

During high temperature service, a series of microstructure and phase evolutions occur in thermal barrier coatings (TBCs), which result in degradation of thermal insulation and durability. In this study, the sintering behavior of an air plasma sprayed 8 wt% YSZ coating deposited using electro-sprayed nanostructured particles (ESP) as feedstock powder was investigated and compared with conventional YSZ coating deposited using hollow spherical powders (HOSP). Due to the distinct asymmetric porous structure formed by nanosized YSZ particles, the ESP powder was partially melted in the plasma jet during the deposition, which resulted in the formation of a nanostructured coating that consisted of porous nanozones and dense zones. The ESP coating not only shows a significantly lower initial thermal conductivity of 0.70 W/mK, but also exhibits a stronger sintering resistance in terms of phase stability and thermal insulation compared to the conventional coating. When subjected to prolonged sintering at 1400°C for 128 hours, the thermal conductivity of the ESP coating would gradually increase to about half that of the HOSP coating at 1.29 W/mK. These differences are ascribed to the interaction among different sintering behavior between nanozones and dense zones.     

Microstructure and thermal cycling behavior of thermal barrier coating on near-α titanium alloy

Two kinds of thermal barrier coatings (TBCs), consisting of NiCoCrAlY bond coats (BCs) deposited by electron beam-physical vapor deposition (EB-PVD) and high velocity oxy-fuel (HVOF) thermal spraying, respectively, and top 8 wt%Y₂O₃–ZrO₂ (8YSZ) ceramic layers deposited by EB-PVD were prepared on near-α titanium alloys. The field emission scanning electronic microscopy and microhardness indentation are used to study the microstructure and microhardness. Different failure features including cracking patterns and the delamination degree of these two TBCs are discussed according to the thermal cycling tests in the atmosphere. It is found that the morphology of the two BCs deposited by different methods (EB-PVD and HVOF) determines the microstructure and microhardness of their corresponding top 8YSZ layers. The BC prepared by EB-PVD is dense and homogeneous, which leads to a dense and hard 8YSZ with clustered slim columnar grains. The BC prepared by HVOF, however, is porous and inhomogeneous in microstructure and, as a result, the top ceramic layer is loose with low microhardness and clustered coarse columnar grains.     

Porosity–Property Relationships of Plasma‐Sprayed Gd2Zr2O7/YSZ Thermal Barrier Coatings

During the past decade, gadolinium zirconate (Gd₂Zr₂O₇, GZO) has attracted interest as an alternative material to partially yttria‐stabilized zirconia (YSZ) for thermal barrier coatings (TBCs). Despite the well‐known benefits of GZO, such as lower thermal conductivity and superior temperature capability compared to YSZ, processing of GZO via atmospheric plasma spraying (APS) still remains a challenge. Here, we report on APS experiments which were performed to investigate the influence of processing on GZO microstructure and lifetime of GZO/YSZ double‐layer TBCs. Different microstructures of GZO were produced and characterized in terms of porosity, stoichiometry, Young′s modulus, and their effects on the lifetime of YSZ/GZO double‐layer TBCs were discussed. Particle diagnostics were utilized for the optimization of the process parameters with respect to different microstructures of GZO and stoichiometry. It was found that both cumulative porosity of GZO and pore size distribution, which alter the Young′s modulus significantly, govern the lifetime of double layers. In addition, it was shown that the deviation in GZO stoichiometry due to gadolinia evaporation in the investigated range does not display any critical effect on lifetime.     

Low–thermal–conductivity and high–toughness CeO2–Gd2O3 co–stabilized zirconia ceramic for potential thermal barrier coating applications

Yttria partially stabilized zirconia (～4.0?mol% Y₂O₃–ZrO₂, 4YSZ) has been widely employed as thermal barrier coatings (TBCs) to protect the high–temperature components of gas–turbine engines. The phase stability problem existing in the conventional 4YSZ has limited it to application below 1200?°C. Here we report an excellent zirconia system co–doped with 16?mol% CeO₂ and 4?mol% Gd₂O₃ (16Ce–4Gd) presenting nontransformable feature up to 1500?°C, in which no detrimental monoclinic (m) ZrO₂ phase formed on partitioning. It also exhibits a high fracture toughness of ～46?J m^?2 and shows high sintering resistance. Besides, the thermal conductivity and thermal expansion coefficient of 16Ce–4Gd are more competent for TBCs applications as compared to the 4YSZ. The combination of properties suggests that the 16Ce–4Gd system could be of potential use as a thermal barrier coating at 1500?°C.     

Thermal shock resistance of thermal barrier coatings modified by selective laser remelting and alloying techniques

Aiming to improve the thermal shock resistance of thermal barrier coatings (TBCs), the plasma-sprayed 7YSZ TBCs were modified by selective laser remelting and selective laser alloying, respectively, in this study. A self-healing agent TiAl₃ was introduced into the 7YSZ TBCs by selective laser alloying to fill cracks during thermal cycling. The thermal shock experiments of the plasma-sprayed, laser-remelted, and laser-alloyed TBCs were conducted by a means of heating and water-quenching method. Results revealed that some segmented microcracks were distributed on the surface of the laser-remelted and the laser-alloyed zones, showing a dense columnar crystal structure. After thermal shock tests, the numbers of segmented microcracks on the laser-remelted coating increased, whereas, in the laser-alloyed condition, some irregular particles formed, leading to the decreased numbers of segmented microcracks. The laser-alloyed coating exhibited the best thermal shock resistance, followed by the laser-remelted condition, with the thermal shock lifetime 3.3 and 2.7 times higher than that of the as-sprayed coating, respectively. On the one hand, both columnar grains and segmented microcracks in the laser-treated zone could effectively improve the strain tolerance of coatings. On the other hand, the oxidation products of TiAl₃ under high-temperature condition could seal the microcracks to postpone the crack connection. Thus, the thermal shock resistance of the laser-treated coatings was significantly improved.     

LZC/YSZ DCL TBCs by EB-PVD: Microstructure,low thermal conductivity and high thermal cycling life

Thermal barrier coatings (TBCs) with low thermal conductivity have triggered tremendous attention due to their promising application in the gas turbine engines. Albeit recent studies have investigated double ceramic layers (DCL) with pyrochlore (A₂B₂O₇) phase, it still remains a big challenge for controlling element content and investigating the relationship between the complex hierarchical architectures and their thermal performances. Here we describe a series of DCL La₂O₃-ZrO₂-CeO₂ (LZC)/Y₂O₃-stabilized ZrO₂ (YSZ) coating under different current of electron beam by electron beam-physical vapor deposition (EB-PVD). The formation of hierarchical architecture with feathery microstructure and intra-columnar have been investigated in detail. The DCL coatings achieve a high thermal cycling life and relatively low thermal conductivity at controlling current of electron beam from 1.0 A to 1.3 A. This work may open new opportunities to rationally design other promising TBCs.     

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.     

Thermal cycling behavior and bonding strength of single-ceramic-layer Sm2Zr2O7 and double-ceramic-layer Sm2Zr2O7/8YSZ thermal barrier coatings deposited by atmospheric plasma spraying

The single-ceramic-layer (SCL) Sm₂Zr₂O₇ (SZO) and double-ceramic-layer (DCL) Sm₂Zr₂O₇ (SZO)/8YSZ thermal barrier coatings (TBCs) were deposited by atmospheric plasma spraying on nickel-based superalloy substrates with NiCoCrAlY as the bond coat. The mechanical properties of the coatings were evaluated using bonding strength and thermal cycling lifetime tests. The microstructures and phase compositions of the coatings were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The results show that both coatings demonstrate a well compact state. The DCL SZO/8YSZ TBCs exhibits an average bonding strength approximately 1.5 times higher when compared to the SCL SZO TBCs. The thermal cycling lifetime of DCL SZO/8YSZ TBCs is 660 cycles, which is much longer than that of SCL 8YSZ TBCs (150 cycles). After 660 thermal cycling, only a little spot spallation appears on the surface of the DCL SZO/8YSZ coating. The excellent mechanical properties of the DCL LZ/8YSZ TBCs can be attributed to the underlying 8YSZ coating with the combinational structures, which contributes to improve the toughness and relieve the thermal mismatch between the ceramic layer and the metallic bond coat at high temperature.     

Synthesis and thermophysical properties of RETa3O9 (RE = Ce,Nd, Sm,Eu, Gd,Dy, Er) as promising thermal barrier coatings

Thermal barrier coatings (TBCs) are one of the most important materials in gas turbine to protect the high temperature components. RETa₃O₉ compounds have a defect‐perovskite structure, indicating that they have low thermal conductivity, which is the critical property of TBCs. Herein, dense RETa₃O₉ bulk ceramics were fabricated via solid‐state reaction. The crystal structure was characterized by X‐ray diffraction (XRD) and Raman Spectroscope. Scanning electron microscope (SEM) was used to observe the microstructure. The thermophysical properties of RETa₃O₉ were studied systematically, including specific heat, thermal diffusivity, thermal conductivity, thermal expansion coefficients, and high‐temperature phase stability. The thermal conductivities of RETa₃O₉ are very low (1.33‐2.37 W/m·K, 373‐1073 K), which are much lower than YSZ and La₂Zr₂O₇; and the thermal expansion coefficients range from 4.0 × 10^?6 K^?1 to 10.2×10^?6 K^?1 (1273 K), which is close to La₂Zr₂O₇ and YSZ. According to the differential scanning calorimetry (DSC) curve there is not phase transition at the test temperature. Due to the high melting point and excellent high‐temperature phase stability with these oxides, RETa₃O₉ ceramics were promising candidate materials for TBCs.     

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.     

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.     

Microstructure and thermal properties of a promising thermal barrier coating: YTaO4

High temperature gas turbine sealing can increase the thermal efficiency of a gas turbine. In this paper, monoclinic phase YTaO₄ ceramics were fabricated via solid-state reaction. Phase composition and microstructures of the high-temperature-sintered YTaO₄ ceramics were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and Raman Spectroscopy. Specific heat capacity rose gradually as temperature increased, due to volumetric expansion and phonon excitations. The thermal diffusivities and conductivities decreased significantly due to the effects of the porosity and phonon scattering. However, the thermal conductivities of the specimens were lower than that of 7–8 wt% yttria-stabilized zirconia (7-8YSZ), and YTaO₄ ceramics have better thermal stability than current (TBCs) material. The Vickers hardnesses of YTaO₄ ceramics as a function of sintering temperature were lower than that of 8YSZ, indicating YTaO₄ has better fracture toughness and thermal tolerance. The results demonstrate that YTaO₄ ceramics would be an excellent candidate for use as a thermal barrier coating material for high temperature gas turbines.     

Microstructure–Property Correlations in Industrial Thermal Barrier Coatings

This paper describes the results from multidisciplinary characterization/scattering techniques used for the quantitative characterization of industrial thermal barrier coating (TBC) systems used in advanced gas turbines. While past requirements for TBCs primarily addressed the function of insulation/life extension of the metallic components, new demands necessitate a requirement for spallation resistance/strain tolerance, i.e., prime reliance, on the part of the TBC. In an extensive effort to incorporate these TBCs, a design-of-experiment approach was undertaken to develop tailored coating properties by processing under varied conditions. Efforts focusing on achieving durable/high-performance coatings led to dense vertically cracked (DVC) TBCs, exhibiting quasi-columnar microstructures approximating electron-beam physical-vapor-deposited (EB-PVD) coatings. Quantitative representation of the microstructural features in these vastly different coatings is obtained, in terms of porosity, opening dimensions, orientation, morphologies, and pore size distribution, by means of small-angle neutron scattering (SANS) and ultra-small-angle X-ray scattering (USAXS) studies. Such comprehensive characterization, coupled with elastic modulus and thermal conductivity measurements of the coatings, help establish relationships between microstructure and properties in a systematic manner.     

Study on thermal shock resistance of Sc2O3 and Y2O3 co-stabilized ZrO2 thermal barrier coatings

In order to reveal the effect of Sc₂O₃ and Y₂O₃ co-doping system on the thermal shock resistance of ZrO₂ thermal barrier coatings, Y₂O₃ stabilized ZrO₂ thermal barrier coatings (YSZ TBCs) and Sc₂O₃–Y₂O₃ co-stabilized ZrO₂ thermal barrier coatings (ScYSZ TBCs) were prepared by atmospheric plasma spraying technology. The surface and cross-section micromorphologies of YSZ ceramic coating and ScYSZ ceramic coatings were compared, and their phase composition before and after heat treatment at 1200 °C was analyzed. Whereupon, the thermal shock experiment of the two TBCs at 1100 °C was carried out. The results show that the micromorphologies of YSZ ceramic coating and ScYSZ ceramic coating were not much different, but the porosity of the latter was slightly higher. Before heat treatment, the phase composition of both YSZ ceramic coating and ScYSZ ceramic coating was a single T′ phase. After heat treatment, the phase composition of YSZ ceramic coating was a mixture of M phase, T phase, and C phase, while that of ScYSZ ceramic coating was still a single T′ phase, indicating ScYSZ ceramic coating had better T′ phase stability, which could be attributed to the co-doping system of Sc₂O₃ and Y₂O₃ facilitated the formation of defect clusters. In the thermal shock experiment, the thermal shock life of YSZ TBCs was 310 times, while that of ScYSZ TBCs was 370 times, indicating the latter had better thermal shock resistance. The difference in thermal shock resistance could be attributed to the different sintering resistance of ceramic coatings and the different growth rates of thermally grown oxide in the two TBCs. Furthermore, the thermal shock failure modes of YSZ TBCs and ScYSZ TBCs were different, the former was delamination, while the latter was delamination and shallow spallation.     

Structure-property relationship and design of plasma-sprayed La2Ce2O7/8YSZ composite coatings for gas turbine blades

Novel lanthanum-cerium oxide/8?wt% yttria partially stabilized zirconia (LC/8YSZ) thermal barrier coatings (TBCs) were deposited by supersonic atmospheric plasma spraying. The thermal insulation temperature and thermal shock resistance of LC/8YSZ double-ceramic-layer TBCs (DCL-TBCs) were quantitatively evaluated by a burner rig test. The results showed that the thermal insulation temperature increased with the increase of LC layer thickness in DCL-TBCs. When the thickness ratio between LC layer and 8YSZ layer was close to 1:1, the DCL-TBCs had the highest thermal shock resistance. LC/8YSZ thickness ratio significantly affected the energy release rate and the stress induced by thermal gradient or sintering. The sintering stress was found to be the main reason that caused the delamination of LC layer, however, the stress induced by thermal gradient resulted in the spallation of YSZ layer.