Microstructure and luminescence properties of YSZ-based thermal barrier coatings modified by Eu2O3

In order to study the variation of rare earth oxides during thermal failure of thermal barrier coatings, Eu2O3-doped YSZ coatings with 0.5 mol%, 1.0 mol% and 1.5 mol% were prepared by explosive spraying. SEM, XRD, EDS and microhardness tester were used to analyze the effect of different rare earth oxide doping content on the morphology, composition and mechanical properties of the coatings. The results showed that with the increase of rare earth oxide doping content, the porosity of the coatings decreased, and the microhardness and fracture toughness increased. When the doping amount of rare earth oxide is 1.0 mol%, the bonding strength and thermal cycle times of the coating are the highest, 33.4 Mpa and 185 times respectively. With the increase of the doping amount of rare earth, the luminous intensity of the sprayed coating increases. After thermal shock test, the luminous intensity of Eu2O3-doped YSZ coatings at 592 and 608 nm decreased to a certain extent.     

Preparation and performance of thermal barrier coatings made of BNw-containing modified Nd2O3-doped yttria-stabilized zirconia

To enhance the fracture toughness and thermal shock resistance of the thermal barrier coatings (TBCs), detonation spraying has been used to prepare modified neodymium (Ⅲ) oxide (Nd₂O₃)-doped yttria-stabilized zirconia (YSZ) TBCs containing 20 vol% (D1 coating) and 30 vol% (D2 coating) of boron nitride whiskers (BNws). Analyses were performed using a scanning electron microscope (SEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), and a microhardness tester to examine the manner in which the doping content of different rare earth oxides affected the coating morphology, composition, and mechanical properties. The results denoted that the porosity of the D2 coating was 47.9% higher than that of the D1 coating; the whisker content was 30 vol% in the former and 20 vol% in the latter. The increased porosity reduced the microhardness and bond strength of the coating. However, the fracture toughness (KIC) of the D2 coating was increased to 2.67 MPa·m^1/2 because the whisker content was 8.5% higher than that in the D1 coating. The thermal cycling life of the D2 coating was 245 cycles, and its thermal shock resistance was 9.9% higher when compared with that of the D1 coating. A TBC with better overall performance was obtained when BNw reached 30 vol%.     

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.     

Microstructure and thermal properties of inflight rare-earth doped thermal barriers prepared by suspension plasma spray

Rare-earth doped yttria-stabilized zirconia (YSZ) coatings with lower thermal conductivity have been fabricated via suspension plasma spray by dissolving rare-earth nitrates into YSZ powder-ethanol suspensions prior to plasma spraying. The effect of dopant concentration and dopant type on properties of the coatings was determined by comparing two coatings containing different concentrations of the same dopant pair (Nd₂O₃/Yb₂O₃), and three coatings having similar concentrations of different dopant pairs (Nd₂O₃/Yb₂O₃, Nd₂O₃/Gd₂O₃, and Gd₂O₃/Yb₂O₃). The porosity content of the coating was found to increase with increased total rare-earth dopant concentration but did not significantly change with dopant pairs. The cross-sectional morphology of every coating displayed a cauliflower-like structure. However, the most heavily doped coating exhibited a larger surface roughness and feathery features in the columnar structures. The thermal conductivity measurement showed that the thermal conductivity decreased with increased Nd₂O₃/Yb₂O₃ concentration. Among coatings containing different dopant pairs, the Gd₂O₃/Yb₂O₃ doped coating exhibited lowest conductivity.     

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.     

Characterisation of the microstructure and thermal properties of Nd2Zr2O7 and Nd2Zr2O7/YSZ thermal barrier coatings

The microstructure of following thermal barrier coatings (TBC) was characterised in this paper: monolayer coatings Nd₂Zr₂O₇ and 8YSZ; a double ceramic layered (DCL) coating. Coatings were characterised by thicknesses that did not exceed 300 μm and porosities of approx. 5%. The chemical and phase composition analysis of the DCL layers revealed an external Nd₂Zr₂O₇ ceramic layer approx. 80 μm thick, a transitional zone approx. 120 μm thick and an internal 8YSZ layer 100 μm thick. For the case of the monolayer coating, the Nd₂Zr₂O₇ pyrochlore phase was the only one-phase component. The surface topography of both TBC systems was typical for plasma sprayed coatings, and compressive stress state had a value of approx. 5–10 MPa. Measurements of the thermal parameters, i.e., thermal diffusivity, point to considerably better insulative properties for both new types of layers when compared to the standard 8YSZ layers.     

Improvement in thermal shock resistance of gadolinium zirconate coating by addition of nanostructured yttria partially-stabilized zirconia

Gadolinium zirconate (Gd₂Zr₂O₇, GZ) as one of the promising thermal barrier coating materials for high-temperature application in gas turbine was toughened by nanostructured 3 mol% yttria partially-stabilized zirconia (YSZ) incorporation. The fracture toughness of the composite of 90 mol% GZ-10 mol% YSZ (GZ–YSZ) was increased by about 60% relative to the monolithic GZ. Both the GZ and GZ–YSZ composite coatings were deposited by atmospheric plasma spraying on Ni-base superalloys and then thermal-shock tested under the same conditions. The thermal-shock lifetime of GZ–YSZ composite coating was improved, which is believed to be mainly attributed to the enhancement of fracture toughness by the addition of YSZ. In addition, the failure mechanisms of the thermal-shock tested GZ–YSZ composite coatings were discussed.     

Thermal conductivity of yttria-stabilized zirconia thin films grown by plasma-enhanced atomic layer deposition

Zirconia doped with yttrium, widely known as yttria-stabilized zirconia (YSZ), has found recent applications in advanced electronic and energy devices, particularly when deposited in thin film form by atomic layer deposition (ALD). Although ample studies reported the thermal conductivity of YSZ films and coatings, these data were typically limited to Y₂O₃ concentrations around 8 mol% and thicknesses greater than 1 μm, which were primarily targeted for thermal barrier coating applications. Here, we present the first experimental report of the thermal conductivity of YSZ thin films (∼50 nm), deposited by plasma-enhanced ALD (PEALD), with variable Y₂O₃ content (0–36.9 mol%). Time-domain thermoreflectance measures the effective thermal conductivity of the film and its interfaces, independently confirmed with frequency-domain thermoreflectance. The effective thermal conductivity decreases from 1.85 to 1.22 W m⁻¹ K⁻¹ with increasing Y₂O₃ doping concentration from 0 to 7.7 mol%, predominantly due to increased phonon scattering by oxygen vacancies, and exhibits relatively weak concentration dependence above 7.7 mol%. The effective thermal conductivities of our PEALD YSZ films are higher by ∼15%–128% than those reported previously for thermal ALD YSZ films with similar composition. We attribute this to the relatively larger grain sizes (∼23–27 nm) of our films.     

Thermophysical properties and cyclic lifetime of plasma sprayed SrAl12O19 for thermal barrier coating applications

About 6-8 wt% yttria-stabilized zirconia (YSZ) is the industry standard material for thermal barrier coatings (TBC). However, it cannot meet the long-term requirements for advanced engines due to the phase transformation and sintering issues above 1200°C. In this study, we have developed a magnetoplumbite-type SrAl₁₂O₁₉ coating fabricated by atmospheric plasma spray, which shows potential capability to be operated above 1200°C. SrAl₁₂O₁₉ coating exhibits large concentrations of cracks and pores (~26% porosity) after 1000 hours heat treatment at 1300°C, while the total porosity of YSZ coatings progressively decreases from the initial value of ~18% to ~5%. Due to the contribution of porous microstructure, an ultralow thermal conductivity (~1.36 W m⁻¹ K⁻¹) can be maintained for SrAl₁₂O₁₉ coating even after 1000 hours aging at 1300°C, which is far lower than that of the YSZ coating (~1.98 W m⁻¹ K⁻¹). In thermal cyclic fatigue test, the SrAl₁₂O₁₉/YSZ double-ceramic-layer coating undertakes a thermal cycling lifetime of ~512 cycles, which is not only much longer than its single-layer counterpart (~163 cycles), but also superior to that of YSZ coating (~392 cycles). These preliminary results suggest that SrAl₁₂O₁₉ might be a promising alternative TBC material to YSZ for applications above 1200°C.     

Hot Corrosion of Stabilized Zirconia Thermal Barrier Coatings and the Role of Mg Inhibitor

The 3–4 mol% yttria‐stabilized zirconia (YSZ) is widely used as a material for thermal barrier coating; however, the corrosive constituents present in fuel typically result in mechanical disintegration of YSZ coatings. The 3–4 mol% YSZ coatings with respective porosity of ~3% and ~22% have been undertaken with the objective to compare the hot corrosion behavior in air and sulfur‐rich atmospheres. The coatings are kept in contact with V₂O₅ + MgO powder mixture at 750°C for different dwell times of 24 and 76 h. The samples kept in air have shown intact YSZ layer for both the coatings, whereas a delamination of YSZ layer is observed for high porosity sample kept in sulfur‐rich atmosphere. XRD patterns of all the samples treated in sulfur‐rich atmosphere have indicated a phase transformation in YSZ from tetragonal to monoclinic. However, no such phase transformation has been found for samples treated in air. The V₂O₅‐induced hot corrosion attack on YSZ coating in air has been successfully inhibited by MgO, which forms a thermally stable Mg₃V₂O₈ compound. However, in sulfur‐rich atmosphere, MgO is partially consumed to form sulfates, which allows certain fraction of V₂O₅ to react with Y₂O₃ causing the degradation of top coat.     

Microstructure and thermal properties of nanostructured gadolinia doped yttria-stabilized zirconia thermal barrier coatings produced by air plasma spraying

In this article, the nanostructured 2 mol% Gd₂O₃-4.5 mol% Y₂O₃-ZrO₂(2GdYSZ) coating was developed by the atmospheric plasma spraying technique. And the microstructure and thermal properties of plasma-sprayed 2GdYSZ coating were investigated. The result from the investigation indicates that the as-sprayed coating is characterized by typical microstructure consisting of melted zones, nano-zones, splats, nano-pores, high-volume spheroidal pores and micro-cracks. The 2GdYSZ coating shows a lower resistance to destabilization of the metastable tetragonal (t′) phase compared to the yttria stabilized zirconia(YSZ). The thermal diffusivity and thermal conductivity of the nano-2GdYSZ coating at room temperature are 0.431 mm² s⁻¹ and 1.042 W/m K, respectively. Addition of gadolinia to the nano-YSZ can significantly reduce the thermal conductivity compared to the nano-YSZ and the conventional YSZ. The reduction is mainly attributed to the synergetic effect of gadolinia doping along with nanostructure.     

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.     

Thermal shock performance and failure behavior of Zr6Ta2O17-8YSZ double-ceramic-layer thermal barrier coatings prepared by atmospheric plasma spraying

Zr₆Ta₂O₁₇ has higher fracture toughness, better phase stability, thermal insulation performance and calcium-magnesium-alumino-silicates (CMAS) attack resistance than yttria-stabilized zirconia (8 YSZ, 7–8 wt%) at temperatures above 1200 °C. However, the thermal expansion coefficients between Zr₆Ta₂O₁₇ coating and bond coating do not match well. A double-ceramic-layer design is applied to alleviate the thermal stress mismatch. The Zr₆Ta₂O₁₇/8 YSZ double-ceramic-layer thermal barrier coatings (TBCs) are prepared by atmospheric plasma spraying (APS). During the thermal shock test, Zr₆Ta₂O₁₇/8 YSZ double-ceramic-layer TBCs exhibit a better thermal shock resistance than 8 YSZ and Zr₆Ta₂O₁₇ single-layer TBCs. The thermal shock performance and failure mechanism of TBCs in the thermal shock test are investigated and discussed in detail.     

Evaluation of mechanical properties of YSZ TBCs doped by different ratios of Eu3+ ions after isothermal oxidation

Thermal barrier coatings (TBCs) are essential to improve the thermal insulation performance of high-temperature components. Rare earth element (Eu³⁺) doped yttrium stabilized zirconia (YSZ) TBCs have been proved to be an ideal solution for non-destructive testing of internal damages. Based on this theory, two types of coatings deposited by air plasma spray (APS) on Hastelloy-X were investigated: (1) Eu³⁺ doped YSZ (dopant ratios 1 mol%, 2 mol%, 4 mol%, respectively), (2) traditional undoped 8YSZ. Isothermal oxidation treatment at 1100 °C, in increments of 10h until the failure of the coatings are conducted to evaluate the mechanical properties of different coatings. The microscopic morphology and phase of the coatings were analyzed by scanning electron microscope (SEM) and X-ray diffraction (XRD) patterns, respectively. The indentation testing methods were used to study the apparent interfacial fracture toughness and the hardness of the ceramic top coat. Results show that the Vickers hardness of the top coat increases with the decrease of porosity in the early stage and then decreases with the heat treatment time increasing in the long-term stage. Simultaneously, compared with the undoped 8YSZ coating, the fracture toughness increased with the dopant of Eu³⁺ ions increasing, from 1 mol% to 2 mol%, nevertheless, that of 4 mol% Eu³⁺ doped YSZ decreased compared with in the undoped 8 YSZ. For all types of specimens, the interfacial fracture toughness decreases with the increase of isothermal oxidation time. Results also indicate that the content of Eu³⁺ doping does not affect the microstructure and interfacial morphology of the YSZ coating as well as the growth law of thermally grown oxides (TGO). Furthermore, EDS detection found that the Eu³⁺ ions almost do not diffuse inside the TBCs system after isothermal oxidation treatment.     

Thermal shock resistance and mechanical properties of La2Ce2O7 thermal barrier coatings with segmented structure

La₂Ce₂O₇ (LCO) is a promising candidate material for thermal barrier coatings (TBCs) application because of its higher temperature capability and better thermal insulation property relative to yttria stabilized zirconia (YSZ). In this work, La₂Ce₂O₇ TBC with segmentation crack structure was produced by atmospheric plasma spray (APS). The mechanical properties of the sprayed coatings at room temperature including microhardness, Young's modulus, fracture toughness and tensile strength were evaluated. The Young's modulus and microhardness of the segmented coating were measured to be about 25 and 5 GPa, relatively higher than those of the non-segmented coating, respectively. The fracture toughness of the LCO coating is in a range of 1.3–1.5 MPa m^1/2, about 40% lower than that of the YSZ coating. The segmented TBC had a lifetime of more than 700 cycles, improving the lifetime by nearly two times as compared to the non-segmented TBC. The failure of the segmented coating occurred by chipping spallation and delamination cracking within the coating.     

Microstructure and thermal shock resistance of AlBOw- and BNw-whisker-modified thermal barrier coatings

To improve the crack propagation resistance of YSZ thermal barrier coatings during the thermal cycle, three kinds of thermal barrier coatings were prepared by atmospheric plasma spraying: YSZ, AlBOw-modified YSZ and BNW-modified YSZ. SEM, EDS and XRD were used to analyse the morphology, composition and phase composition of the sprayed powder and coating section. The phase structures of the YSZ, YSZ+AlBOw and YSZ+BNw coatings were t' phase. The cross-section of the coating presents a layered structure with pores inside. The porosity values of the YSZ, YSZ+AlBOw and YSZ+BNw coatings are 10.33%, 14.17% and 12.52%, respectively. The thermal shock resistance of three groups of coatings after 5 min at 1000 °C was analysed. The failure behaviour of the coatings after several thermal cycles was studied. The results show that the thermal shock resistance of the coatings with AlBOw is slightly lower than that of the YSZ coatings. The thermal shock resistance of the BNw coatings is 62.2% higher than that of the YSZ coatings. The whisker inhibits the crack propagation and prolongs the life of the coatings via crack deflection, whisker pull-out and whisker bridging.     

Multilayer gradient rare earth disilicate coating prepared by in-situ melt infiltration and sintering method with high thermal shock resistance on porous Si3N4 ceramics

Dense multilayer gradient rare earth disilicate (γ-Y₂Si₂O₇ /β-Yb₂Si₂O₇ /β-Lu₂Si₂O₇) coatings were in-situ prepared by melt-infiltration /sintering procedure on porous Si₃N₄ ceramics for water resistance. Experimental and numerical simulation methods were used to study their thermal shock behavior. As a control, thermal shock behavior of pure γ-Y₂Si₂O₇ coatings were also compared. FEM results showed that the gradient design of modulus in ceramic coating can effectively avoid the mismatch of mechanical properties between coating layer and internal substrate, reducing the transient thermal stress in each layer during thermal shock. All of the pure γ-Y₂Si₂O₇ coatings were failed after thermal shock tests with ΔT ≈ 1200 ℃. However, when sintering temperature of multi-layer disilicate coatings were higher than 1400 ℃, the water absorption rates after thermal shock were all less than 5%, still showing good waterproof performance. The gradient design of modulus could effectively improve the structural stability of ceramic coatings.     

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.     

Effect of Fe2O3 doping on sintering of yttria-stabilized zirconia

This paper reports the effect of Fe₂O₃ doping on the densification and grain growth in yttria-stabilized zirconia (YSZ) during sintering at 1150 °C for 2 h. Fe₂O₃ doped 3 mol% YSZ (3YSZ) and 8 mol% YSZ (8YSZ) coatings were produced using electrophoretic deposition (EPD). For 0.5 mol% Fe₂O₃ doping, both 3YSZ and 8YSZ coatings during sintering at 1150 °C has similar densification. However, a significant grain growth occurred in 8YSZ during sintering, whereas grain size remains almost constant in 3YSZ. XRD results suggest that Fe₂O₃ addition substitutionally and interstitially dissolved into the lattice of 3YSZ and 8YSZ. In addition, colour of 3YSZ and 8YSZ changes differently with doping of Fe₂O₃. A Fe³⁺ ion interstitial diffusion mechanism is proposed to explain the densification and grain growth behaviour in the Fe₂O₃ doped 3YSZ and 8YSZ. A retard grain growth observed in the Fe₂O₃ doped 3YSZ is attributed to Fe³⁺ segregation at grain boundary.     

Phase stability,thermo-physical properties and thermal cycling behavior of plasma-sprayed CTZ,CTZ/YSZ thermal barrier coatings

ZrO₂ co-stabilized by CeO₂ and TiO₂ with stable, nontransformable tetragonal phase has attracted much attention as a potential material for thermal barrier coatings (TBCs) applied at temperatures >?1200?°C. In this study, ZrO₂ co-stabilized by 15?mol% CeO₂ and 5?mol% TiO₂ (CTZ) and CTZ/YSZ (zirconia stabilized by 7.4?wt% Y₂O₃) double-ceramic-layer TBCs were respectively deposited by atmospheric plasma spraying. The microstructures, phase stability and thermo-physical properties of the CTZ coating were examined using scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric-differential scanning calorimeter (TG-DSC), laser pulses and dilatometry. Results showed that the CTZ coating with single tetragonal phase was more stable than the YSZ coating during isothermal heat-treatment at 1300?°C. The CTZ coating had a lower thermal conductivity than that of YSZ coating, decreasing from 0.89?W?m^?1 K^?1 to 0.76?W?m^?1 K^?1 with increasing temperature from room temperature to 1000?°C. The thermal expansion coefficients were in the range of 8.98?×?10^?6 K^?1 – 9.88 ×10^?6 K^?1. Samples were also thermally cycled at 1000?°C and 1100?°C. Failure of the TBCs was mainly a result of the thermal expansion mismatch between CTZ coating and superallloy substrate, the severe coating sintering and the reduction-oxidation of cerium oxide. The thermal durability of the TBCs at 1000?°C can be effectively enhanced by using a YSZ buffer layer, while the thermal cycling life of CTZ/YSZ double-ceramic-layer TBCs at 1100?°C was still unsatisfying. The thermal shock resistance of the CTZ coating should be improved; otherwise the promising properties of CTZ could not be transferred to a well-functioning coating.