Effect of physical vapor deposited Al2O3 film on TGO growth in YSZ/CoNiCrAlY coatings

Thermal barrier coatings (TBCs) comprising of yttria stabilized zirconia (YSZ) ceramic top coat and CoNiCrAlY metallic bond coat have been widely used in gas turbines. However, the developed oxides layer in the interface of the top and bond coats during thermal exposure of the TBCs always results in the destruction of the system. In order to restrain the growth of oxides layer and improve the thermal shock resistance of TBCs, a thin Al₂O₃ film was pre-deposited on CoNiCrAlY bond coat by physical vapor deposition (PVD) technology. After thermal exposure, morphologies and phase compositions of the thermal growth oxides (TGO) layer in the conventional and pre-deposited Al₂O₃ film TBCs were examined by scanning electron microscopy (SEM) equipped with energy dispersive spectrometer (EDS). The residual stresses in the coatings were analyzed using micro-Raman spectroscopy (LabRam-1B). It was found that TGO layer formed in the conventional TBCs was mainly composed of Al₂O₃, (Cr,Al)₂O₃ + (Co,Ni)(Cr,Al)₂O₄ + NiO (CSN), and (Cr,Al)₂O₃ + (Co,Ni)(Cr,Al)₂O₄ (CS), while in the treated TBCs, the formed TGO layer appeared more uniform and compact. The CSN and CS clusters, which are normally considered as a weakness for TBCs, were greatly limited. The residual stresses in the TBCs after thermal shock were also reduced by the deposition of Al₂O₃ film.     

Porosity analysis and oxidation behavior of plasma sprayed YSZ and YSZ/LaPO4 abradable thermal barrier coatings

In this research, the high temperature oxidation behavior, porosity, and microstructure of four abradable thermal barrier coatings (ATBCs) consisting of micro- and nanostructured YSZ, YSZ-10%LaPO₄, and YSZ-20%LaPO₄ coatings produced by atmospheric (APS) method were evaluated. Results show that the volume percentage of porosity in the coatings containing LaPO₄ was higher than the monolithic YSZ sample. It was probably due to less thermal conductivity of LaPO₄ phases. Furthermore, the results showed that the amount of the remaining porosity in the composite coatings was higher than the monolithic YSZ at 1000 °C for 120 h. After 120 h isothermal oxidation, the thickness of thermally growth oxide (TGO) layer in composite coatings was higher than that of YSZ coating due to higher porosity and sintering resistance of composite coatings. Finally, the isothermal oxidation resistance of conventional YSZ and nanostructured YSZ coating was investigated.     

Thermal stability and sintering behavior of plasma sprayed nanostructured 7YSZ, 15YSZ and 5.5SYSZ coatings at elevated temperatures

Nanostructured scandia, yttria doped zirconia (5.5SYSZ), 7 wt% yttria stabilized zirconia (7YSZ) and 15YSZ thermal barrier coatings (TBCs) were produced by plasma spraying on nickel-based superalloy substrates with NiCrAlY as the bond coat. The thermal stability and sintering behavior of the three as-sprayed TBCs at 1480 °C were investigated. The results indicated that the thermal stability of SYSZ and TBCs was longer than the 7YSZ TBCs due to higher amount of tetragonal phase. Furthermore, the results demonstrated that the nanostructured 7YSZ coating exhibits higher sintering resistance than 5.5SYSZ TBC.     

Effect of molten V2O5 salt on the corrosion behavior of micro- and nano-structured thermal sprayed SYSZ and YSZ coatings

The corrosion resistance of micro-and nano-structured scandia and yttria codoped zirconia (nano-4 mol%SYSZ and micro-8.6SYSZ) and yttria doped zirconia (4YSZ) in the presence of molten vanadium oxide were investigated. To this end, duplex TBCs (thermal barrier coatings), composed of a bond coat (NiCrAlY) and a top coat (4SYSZ or 4YSZ), were deposited on the IN738LC Ni-based supper-alloy by atmospheric plasma spraying (APS). The corrosion studies of plasma sprayed TBCs were conducted in 25 mg V₂O₅ molten salt at 910 °C for different times. The nanostructured coating, as compared to its micro-structured counterpart, in spite of a further reaction with the V₂O₅ salt, showed a higher degradation resistance during the corrosion test due to increased compliance capabilities resulting from the presence of an extra source of porosity associated with the nano-zones. Finally, the corrosion resistance and degradation mechanism of SYSZ and YSZ coatings were compared with the presence of molten NaVO₃ and V₂O₅ salt, respectively.     

Evaluation of stress distribution and failure mechanism in lanthanum–titanium–aluminum oxides thermal barrier coatings

LaTi₂Al₉O₁₉ (LTA) is one of the most promising materials for new thermal barrier coatings (TBCs) to fulfill the demand of advanced gas turbines owing to its high temperature stability and low thermal conductivity. In the present study, a finite element (FE) based numerical study has been carried out to investigate the stress distribution in LTA single layered coating system in comparison with traditional yttria stabilized zirconia (YSZ) TBC. Stresses in YSZ/LTA double ceramic layer TBC system are also determined and presented for comparative analysis. The thermal cycling effect is simulated by sequent increment in TGO thickness in a series of FE simulations. In-plane stresses (σ_xx), out-of-plane stresses (σ_yy) and shear stresses (σ_xy) are determined for all systems, and peak stress values are presented for quantitative comparison. Elastic strain energy stored in TGO of all systems is calculated from FE results for TBC structural integrity assessment. It has been found that maximum in-plane and shear stresses are lower in the double ceramic layer coating system than in the single layer ceramic coating system. However, peak axial tensile and compressive stresses in the double ceramic layer coating are very close or higher than those in the single layer topcoat. Calculation of elastic store energy shows that double ceramic layer TBC system may exhibit better stability as compared to single layer systems. Results are presented to explain the failure mechanism in LTA coatings.     

Thermal shock behavior of 8YSZ and double-ceramic-layer La2Zr2O7/8YSZ thermal barrier coatings fabricated by atmospheric plasma spraying

The single-ceramic-layer (SCL) 8YSZ (conventional and nanostructured 8YSZ) and double-ceramic-layer (DCL) La₂Zr₂O₇ (LZ)/8YSZ thermal barrier coatings (TBCs) were fabricated by plasma spraying on nickel-based superalloy substrates with NiCrAlY as the bond coat. The thermal shock behavior of the three as-sprayed TBCs at 1000 °C and 1200 °C was investigated. The results indicate that the thermal cycling lifetime of LZ/8YSZ TBCs is longer than that of SCL 8YSZ TBCs due to the fact that the DCL LZ/8YSZ TBCs further enhance the thermal insulation effect, improve the sintering resistance ability and relieve the thermal mismatch between the ceramic layer and the metallic layer at high temperature. The nanostructured 8YSZ has higher thermal shock resistance ability than that of the conventional 8YSZ TBC which is attributed to the lower tensile stress in plane and higher fracture toughness of the nanostructured 8YSZ layer. The pre-existed cracks in the surface propagate toward the interface vertically under the thermal activation. The nucleation and growth of the horizontal crack along the interface eventually lead to the failure of the coating. The crack propagation modes have been established, and the failure patterns of the three as-sprayed coatings during thermal shock have been discussed in detail.     

Comparison of hot corrosion behaviors of plasma-sprayed nanostructured and conventional YSZ thermal barrier coatings exposure to molten vanadium pentoxide and sodium sulfate

The purpose of the current study was evaluation and comparison of hot corrosion behaviors of plasma-sprayed conventional and nanostructured yttria stabilized zirconia (YSZ) thermal barrier coatings (TBCs). Hot corrosion studies were performed on the surface of coatings in the presence of a molten mixture of V₂O₅+Na₂SO₄ at 1000 °C for 30 h. Results indicated that the hot corrosion mechanisms of conventional and nanostructured YSZ coatings were similar. The reaction between corrosive salt and Y₂O₃ produced YVO₄, leaching Y₂O₃ from YSZ and causing the detrimental phase transformation of zirconia from tetragonal to monoclinic. The nanostructured coating, as compared to its conventional counterpart, in spite of a further reaction with the corrosive salt, showed a higher degradation resistance during the hot corrosion test due to increased compliance capabilities resulting from the presence of an extra source of porosity associated with the nano-zones.     

Thermal cycling behavior of nanostructured 8YSZ，SZ/8YSZ and 8CSZ/8YSZ thermal barrier coatings fabricated by atmospheric plasma spraying

The nanostructured single-ceramic-layer (SCL) 8YSZ thermal barrier coatings (TBCs), double-ceramic-layer (DCL) Sm₂Zr₂O₇ (SZ)/8YSZ and SZ doped with 8 wt% CeO₂ nanoscale particles (8CSZ)/8YSZ TBCs were fabricated by atmospheric plasma spraying (APS) on nickel-based superalloy substrates with NiCoCrAlY as the bond coating. The thermal cycling behavior of the three as-sprayed TBCs was investigated systematically at 1000 ℃ and 1200 ℃. The results reveal that the thermal cycling lifetime of the nanostructured DCL 8CSZ/8YSZ TBCs is the longest among them, which is largely due to the fact that the intermediate layer buffer effect of the DCL structure, more porosity and improvement of thermal expansion coefficient from doping CeO₂ nanoparticles can relieve thermal stress to a great extent at elevated temperature. The failure mechanism of the nanostructured TBCs has been discussed in detail.     

Local residual stress evolution of highly irregular thermally grown oxide layer in thermal barrier coatings

Local residual stress in thermally grown oxide (TGO) layers is the primary cause of failure of thermal barrier coating (TBC) systems, especially TBCs prepared by air plasma spray (APS) with a highly irregular TGO. Herein, the distribution of residual stress and the evolution of the irregular TGO layer in APS TBCs were investigated as a function of oxidation time. The stress was measured from cross-sectional micrographs and converted to the actual stress inside the coatings before sectioning. The TGO exhibited significant inhomogeneity at different locations. Stress conversion occurred across the TGO thickness; the layer near the yttria-stabilised zirconia (YSZ) component exhibited compressive stress, whereas that along the bond coat was under tensile stress. The evolution of the compressive stress is also discussed. These analyses may provide a better understanding of the mechanism of APS TBCs.     

Effect of scandia content on the thermal shock behavior of SYSZ thermal sprayed barrier coatings

Nanostructured 4SYSZ (scandia (3.5 mol%) yttria (0.5 mol%) stabilized zirconia) and 5.5 SYSZ (5 mol% scandia and 0.5 mol% yttria) thermal barrier coatings (TBCs) were deposited on nickel-based superalloy using NiCrAlY as the bond coat by plasma spraying process. The thermal shock response of both as-sprayed TBCs was investigated at 1000 °C. Experimental results indicated that the nanostructured 5.5SYSZ TBCs have better thermal shock performance in contrast to 4SYSZ TBCs due to their higher tetragonal phase content and higher fracture toughness of this coating     

Thermal cyclic life and failure mechanism of nanostructured 13 wt%Al2O3 doped YSZ coating prepared by atmospheric plasma spraying

Nanostructured 13 wt%Al₂O₃ doped nanostructured 8 wt% yttria stabilized zirconia (nano-13AlYSZ) coatings were deposited by atmospheric plasma spray (APS). The isothermal oxidation and thermal cyclic life of the nano-13AlYSZ coating at 1100 °C were investigated. The isothermal oxidation test results indicate that the oxidation kinetics of nano-13AlYSZ follows a parabolic law. The parabolic rate constant at 1100 °C is calculated 0.04365 mg² cm^?4 h^?1. The thermal cyclic life of nano-13AlYSZ coating is about 953 times at 1100 °C. The failure of the nano-13AlYSZ coating occurs at the interface between the nano-13AlYSZ coating and the thermal growth oxide (TGO). A finite element method is employed to analyze the stress distribution in the nano-13AlYSZ coating. The results show that maximum stresses occur at the top coat/TGO interface.     

Effect of TGO Thickness on Thermal Cyclic Lifetime and Failure Mode of Plasma‐Sprayed TBCs

Gradient thermal cycling test was performed on atmospheric plasma‐sprayed (APS) thermal barrier coatings (TBCs) with different thermally grown oxide (TGO) thicknesses. The TBCs with a thickness of TGO from 1.3 μm to 7.7 μm were prepared by controlling isothermal oxidation time of cold‐sprayed MCrAlY bond coat. The gradient thermal cycling test was performed at a peak surface temperature of 1150°C with 150°C difference across 250 μm thick YSZ with a duration of 240 s for each cycle. Results indicate that the thermal cyclic lifetime of APS TBCs is significantly influenced by TGO thickness. When initial TGO thickness increases from 1.3 μm to 7.7 μm, the thermal cyclic lifetime decreases following a power functions by a factor of about 20. It was revealed that there exists a critical TGO thickness over which the thermal cyclic lifetime is reduced more significantly with the increase in TGO thickness. Moreover, two typical failure modes were observed. The failure mode changes from the cracking within APS YSZ at a TGO thickness less than the critical value to through YSZ/TGO interface at TGO thickness range higher than the critical value.     

Low thermal conductivity of atomic layer deposition yttria-stabilized zirconia (YSZ) thin films for thermal insulation applications

Thermal insulation applications have long required materials with low thermal conductivity, and one example is yttria (Y₂O₃)-stabilized zirconia (ZrO₂) (YSZ) as thermal barrier coatings used in gas turbine engines. Although porosity has been a route to the low thermal conductivity of YSZ coatings, nonporous and conformal coating of YSZ thin films with low thermal conductivity may find a great impact on various thermal insulation applications in nanostructured materials and nanoscale devices. Here, we report on measurements of the thermal conductivity of atomic layer deposition-grown, nonporous YSZ thin films of thickness down to 35 nm using time-domain thermoreflectance. We find that the measured thermal conductivities are 1.35–1.5 W m⁻¹ K⁻¹ and do not strongly vary with film thickness. Without any reduction in thermal conductivity associated with porosity, the conductivities we report approach the minimum, amorphous limit, 1.25 W m⁻¹ K⁻¹, predicted by the minimum thermal conductivity model.     

Atmospheric plasma sprayed 7%-YSZ thick thermal barrier coatings with controlled segmentation crack densities and its thermal cycling behavior

Yttria-stabilized zirconia (YSZ)-coatings are deposited on Ni-based superalloy IN738 by atmospheric plasma spraying (APS). For the first time, controlled segmentation crack densities are manually developed in the coatings, even after the APS deposition. This method allows to user to control segmentation densities as well as cracks depth, which could be designed as per coating thickness and required application. Thermal cycling test shows promising strain tolerance behavior for the segmented coatings, whereas coating without segmentation could not sustain even for its first thermal cycle period. Further, microstructural studies reveal that a very thin layer of TGO was formed and obvious no coating failure or spallation was observed after thermal cycling test at 1150 °C for 500 cycles.     

Evaluation of microstructural evolution in thermal barrier coatings during thermal cycling using impedance spectroscopy

Air plasma sprayed thermal barrier coatings are thermally cycled in air up to 1030 °C and evaluated using impedance spectroscopy in conjunction with scanning electron microscopy. When the number of cycles is less than 15, impedance measurements cannot be used to detect the thermally grown oxide (TGO, usually alumina) scale because it does not fully cover the top coat-bond coat interface and the YSZ (yttria-stabilised zirconia used as the top coat) is much more electrically conductive than the alumina, leading to most of the current passing through the YSZ rather than the alumina. After the specimens are subjected to 100 until 250 cycles, impedance measurements show that a continuous alumina scale is formed. In the impedance spectra, there are four relaxation processes, which correspond to the YSZ grains, the YSZ grain boundaries, the TGO, and the electrode effect. Impedance analyses demonstrate that the resistance of the alumina scale increases and the capacitance decreases with increasing cycling. When the specimen is subjected to 400 cycles, the impedance response to the continuous TGO vanishes due to the TGO degradation.     

Influence of original powders on the microstructure and properties of thermal barrier coatings deposited by supersonic atmospheric plasma spraying,Part I: Microstructure

In this work, two types of yttria-stabilised zirconia (YSZ) powders, a microsized powder and a reconstituted nanostructured powder, were used as the original feedstock for depositing thermal barrier coatings (TBCs) using a high-efficiency supersonic atmospheric plasma spraying (SAPS) system. The effect of the original powder on the coating microstructure was studied by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The results indicated that the microsized powder was fully melted in the plasma jet and that the as-sprayed conventional coating (named MC) was composed of regular-shaped tetragonal ZrO₂ with grain size of 200–500 nm. However, the cross-section morphology of the water-quenched powders revealed that the reconstituted nanostructured powder was partially melted during plasma spraying and that the as-sprayed nanostructured coating (named NC) exhibited a multi-modal microstructure that mainly consisted of unmelted nanoparticles (30–50 nm) and nanograins (60–110 nm), with the latter being the main microstructure of the coating. One visible polycrystalline region consisting of 10 nm grains was also found in NC. In addition, due to the full melting of the microsized powder in the plasma jet, MC exhibited a lower porosity and higher microhardness and Weibull modulus compared with those of NC. In the following paper (Part II), the thermo-mechanical properties, such as thermal shock resistance, oxidation resistance and thermal insulation performance, of the above two coating types will be further studied.     

The influence of laser treatment on hot corrosion behavior of plasma-sprayed nanostructured yttria stabilized zirconia thermal barrier coatings

In this study, the effect of laser glazing on the hot corrosion behavior of nanostructured thermal barrier coatings (TBCs) was investigated. To this end, the hot corrosion test of plasma-sprayed and laser-glazed thermal barrier coatings conducted against 45 wt.% Na₂SO₄ + 55 wt.% V₂O₅ molten salt at 910 °C for 30 h in open air atmosphere. The results obtained from hot corrosion test showed that the reaction between Y₂O₃ and the corrosive salt produced YVO₄, leached Y₂O₃ from YSZ and led to the progressive destabilization transformation of YSZ from tetragonal to the monoclinic phase. The lifetimes of the plasma-sprayed TBCs were enhanced approximately twofold by laser glazing. Reducing the reactive specific surface area of the dense glazed layer with the molten salts and improving the stress accommodation through network cracks produced by laser glazing were the main enhancement mechanisms accounting for TBC life extension.     

Mechanical and electrochemical behavior of novel electrolytes based on partially stabilized zirconia for solid oxide fuel cells

In this study, 3 mol% yttria stabilized zirconia (3YSZ) is investigated as a SOFC electrolyte alternative to 8 mol% yttria stabilized zirconia (8YSZ). The mechanical and electrochemical properties of both materials are compared. The mechanical tests indicate that the thickness of 3YSZ can be reduced to half without sacrificing the strength compared to 8YSZ. By reducing the thickness of 3YSZ from 150 µm to 75 µm, the peak power density is shown to increase by around 80%. The performance is further enhanced by around 22% by designing of novel electrode structure with regular cut-off patterns previously optimized. However, the cell with novel designed 3YSZ electrolyte exhibits 30% lower maximum power density than that of the cell with 150 µm-thick standard 8YSZ electrolyte. Nevertheless, the loss in the performance may be tolerated by decreasing the fabrication cost revealing that 3YSZ electrolyte with cut-off patterns can be employed as SOFC electrolyte alternative to 8YSZ.     

High temperature creep and tensile properties of alumina formed on Fecralloy foils doped with yttrium

The three batches of Fecralloy foils, which differ from each other in contents of yttrium, that is, 10, 280 and 560 ppm, respectively, were chosen as the thermally grown oxide (TGO), alumina (α-Al₂O₃) forming substrate. The creep tests were performed with the Fecralloy foils, which have the α-Al₂O₃ TGO of 0–4 μm thickness, on the surfaces. The creep rates decreased as the TGO thickness increased. The yttrium content above 280 ppm delayed the creep rate of the Fecralloy substrate. The higher creep rate than that of the stand-alone polycrystalline alumina and the dependency of the creep rate on TGO thickness agrees with the hypothesis that the high temperature creep of the TGO is a consequence of the inter-grain growth of the TGO. The yttrium content of lower than 560 ppm did not affect on the creep rate of TGO. Tensile tests were performed with the same alloys, which have the α-Al₂O₃ TGO of 0–3 μm thickness. The tensile strength of the substrate itself increased with Y content by ～20%. The tensile stress of the α-Al₂O₃ TGO decreased with Y-content but it is almost constant, regardless of the TGO thickness. The peak stresses were found at the strain range of ? = 0.7–1.5%, regardless of the TGO thickness, and the batches, thereafter, the parallel cracks perpendicular to the loading direction, formed on the surface. The obtained stress–strain curves of TGO fluctuated. It showed a common feature, that is, a sharp stress drop after the initial yield point at σ_Y = 40–85 MPa, but the stress increased again until the peak points, σ_UTS = 50–110 MPa.     

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.