Microstructure and thermal shock resistance of Nd2O3-doped YSZ-based thermal barrier coatings

To study the impact of rare earth oxide doping on the thermal failure of thermal barrier coatings, 0.5 mol%, 1.0 mol% and 1.5 mol% Nd₂O₃-doped YSZ coatings were prepared by explosive spraying. SEM, XRD, EDS and microhardness testing were used to analyse the effect of different rare earth oxide doping contents on the morphology, composition and mechanical properties of the coatings. With an increase in the Nd₂O₃ doping content, the porosity of the coatings was reduced. The decrease in the porosity increased the compactness of the coatings and improved the microhardness and fracture toughness. The bonding strength and thermal shock resistance of the coatings were the highest among the samples herein when the rare earth doping content was 1.0 mol%, and the values were 37.6 MPa and 200 times, respectively. The thermal shock failure mode of the coating was mainly due to the exfoliation of the inner layer of the ceramic layer. The luminous intensity of the coating increased with increasing rare earth oxide doping content, and the emission spectrum of the Nd₂O₃-modified YSZ coating after the thermal shock test produced a new emission peak at 594 nm, which decreased at 708 nm.     

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%.     

A simple non-destructive method to indicate the spallation and damage degree of the double-ceramic-layer thermal barrier coating of La2(Zr0.7Ce0.3)2O7 and 8YSZ:Eu

Double-ceramic-layer (DCL) thermal barrier coatings (TBCs) of La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) and Eu³⁺-doped zirconia, which was partially stabilised by 8 wt% yttria (8YSZ:Eu), were prepared by atmospheric plasma spraying. A thermal cycling test was carried out. The 8YSZ:Eu sublayer exposed during thermal cycling could produce visible luminescence under ultraviolet (UV) illumination, providing an indication of the spallation and damage degree of the coating. The result shows that the application of a Eu³⁺-doped luminescence sublayer can be a very simple and useful non-destructive technique to indicate the spallation and damage degree of DCL coatings.     

Preoxidation of bond coat in IN-738LC/NiCrAlY/LaMgAl11O19 thermal barrier coating system

The low thickness of thermally grown oxide (TGO) layer and presence of amorphous phase in the as-sprayed LaMgAl₁₁O₁₉ (LaMA) coating reduce the thermal cycling lifetime of thermal barrier coatings (TBCs). In the present study, the as-sprayed Ni-22Cr-10Al-1.0Y bond coat was preoxidized at 1060?°C to produce a continuous oxide scale prior to subsequent deposition of the ceramic top coat. The optimum time of peroxidation treatment and thickness of the continuous aluminum oxide layer were estimated 15?h and 2?µm respectively. The oxidized layer due to the preoxidation treatment of bond coating reduces the amorphous phase in as-sprayed LaMA coating and increases the microhardness of LaMA coating from approximately 600 to 900HV. Also, preoxidation of the NiCrAlY bond coating increases adhesion strength of the LaMA top coating, even slightly more than the adhesion strength of the as-spray 8YSZ coating. The LaMA coatings have a lower hardness in compared with the 8YSZ coating (~ 1010Hv), which results a better elastic behavior.     

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.     

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.     

Lanthanum-titanium-aluminum oxide: A novel thermal barrier coating material for applications at 1300 °C

Considerable efforts are being invested to explore new thermal barrier coating (TBC) materials with higher temperature capability to meet the demand of advanced turbine engines. In this work, LaTi₂Al₉O₁₉ (LTA) is proposed and investigated as a novel TBC material for application at 1300 °C. LTA showed excellent phase stability up to 1600 °C. The thermal conductivities for LTA coating are in a range of 1.0-1.3 W m⁻¹ K⁻¹ (300-1500 °C) and the values of thermal expansion coefficients increase from 8.0 to 11.2 × 10⁻⁶ K⁻¹ (200-1400 °C), which are comparable to those of yttria stabilized zirconia (YSZ). The microhardness of LTA and YSZ coatings were in the similar level of ∼7 GPa, however, the fracture toughness value was relatively lower than that of YSZ. The lower fracture toughness was compensated by the double-ceramic LTA/YSZ layer design, and the LTA/YSZ TBC exhibited desirable thermal cycling life of nearly 700 h at 1300 °C.     

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.     

Preparation and properties of LaMgAl11O19 thermal barrier coatings doped with Gd2O3

As a rare earth hexaaluminate, LaMgAl₁₁O₁₉ (LMA) has been one of the most promising materials used as thermal barrier coatings (TBCs). A large amount of amorphous phase, however, often exists in the plasma-sprayed LMA coating and significantly reduces the service lifetime of TBCs. In this study, La_1-xGd_xMgAl₁₁O₁₉ (x = 0, 0.2, 0.4, 0.6, and 0.8) ceramic powders are synthesised by solid-state reaction, and all of these powders are employed to prepare the corresponding coatings. The phase compositions and microstructures of samples are examined by X-ray diffraction and scanning electron microscopy, respectively. The linear thermal expansion behaviour and thermal cycling behaviour of the coatings are also analysed. The results show that the amorphous phase content is decreased and the thermal expansion behaviour is improved by doping the coatings with Gd₂O₃. The thermal cycling lifetime of the coating, however, basically remains unchanged.     

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.     

Microstructure and thermo-physical properties of yttria stabilized zirconia coatings with CMAS deposits

Yttria stabilized zirconia (YSZ) thermal barrier coatings (TBCs) are used to protect hot-components in aero-engines from hot gases. In this paper, the microstructure and thermo-physical and mechanical properties of plasma sprayed YSZ coatings under the condition of calcium-magnesium-alumina-silicate (CMAS) deposits were investigated. Si and Ca in the CMAS rapidly penetrated the coating at 1250 °C and accelerated sintering of the coating. At the interface between the CMAS and YSZ coating, the YSZ coating was partially dissolved in the CMAS, inducing the phase transformation from tetragonal phase to monoclinic phase. Also, the porosity of the coating was reduced from ∼25% to 5%. As a result, the thermal diffusivity at 1200 °C increased from 0.3 mm²/s to 0.7 mm²/s, suggesting a significant degradation in the thermal barrier effect. Also, the coating showed a ∼40% increase in the microhardness. The degradation mechanism of TBC induced by CMAS was discussed.     

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.     

Influence of solution-precursor plasma spray (SPPS) processing parameters on the mechanical and thermodynamic properties of 8 YSZ

8?mol% yttria stabilized zirconia (8YSZ) coatings are prepared by solution precursor plasma spray (SPPS) technique under different spray conditions. Phase analysis is performed using X-ray diffraction (XRD) and Electron back scattered diffraction (EBSD) techniques. Irrespective of the processing conditions and the heat treatment temperatures, all samples displayed cubic and tetragonal zirconia phases. Vertical and horizontal cracks appeared in the microstructural analysis of the coatings. Coating prepared under spray conditions having 40?mm distance between the spray gun and the sample exhibit high hardness, both at 0?h and 10?h heat treatment holding time. To explore the suitability of the coatings for the heat insulating applications, the thermal diffusivity and thermal conductivity are calculated. The coating with 42?mm distance between the spray gun and the sample displayed lowest thermal conductivity from 400 to 1200?℃.     

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.     

Sol-gel processing and characterization of (RE-Y)-zirconia powders for thermal barrier coatings

The effect of doping on the structural, morphological and thermal properties of ZrO₂-XO_1.5 (X = Y, La, Sm, Er) solid solutions for thermal barrier (TBC) applications was investigated. Oxide powders of various compositions from 9.7 to 40 mol% XO_1.5 (X = Y, La, Sm, Er) were synthesised by the sol-gel route. The structural analysis of the powders was performed using X-ray diffraction analysis coupled with Rietveld refinements and the measurement of their specific surface area with the BET method. For each rare earth dopant, the morphology of the powders varies from monoliths to agglomerates of thinner particles when the doping amount increases. In order to determine the specific heat, the thermal diffusivity at room temperature and the thermal expansion coefficient of some selected compositions, DSC, laser thermal diffusivity and high-temperature dilatometry measurements were performed on samples densified by Spark Plasma Sintering. Working thermal characterisation indicated that zirconia doped with 30 mol% SmO_1.5 and ErO_1.5 have better insulation properties and a lower thermal expansion coefficient than our reference YSZ ceramic. These various compositions are very promising for the elaboration of multilayer TBCs by the sol-gel process.     

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.     

Thermal behaviour of multilayer and functionally-graded YSZ/Gd2Zr2O7 coatings

Zirconates with pyrochlore structure, such as Gd₂Zr₂O₇, are new promising thermal barrier coatings because of their very low thermal conductivity and good chemical resistance against molten salts. However, their coefficient of thermal expansion is low, therefore their thermal fatigue resistance is compromised. As a solution, the combination of yttria-stabilised zirconia (YSZ) and Gd₂Zr₂O₇ can reduce the thermal contraction mismatch between the thermal barrier coating parts.In the present study, two possible designs have been performed to combine YSZ/Gd₂Zr₂O₇. On the one hand, a multilayer coating was obtained where YSZ layer was deposited between a Gd₂Zr₂O₇ layer and a bond coat. On the other hand, a functionally-graded coating was designed where different layers with variable ratios of YSZ/Gd₂Zr₂O₇ were deposited such that the composition gradually changed along the coating thickness.Multilayer and functionally-graded coatings underwent isothermal and thermally-cycled treatments in order to evaluate the oxidation, sintering effects and thermal fatigue resistance of the coatings. The YSZ/Gd₂Zr₂O₇ multilayer coating displayed better thermal behaviour than the Gd₂Zr₂O₇ monolayer coating but quite less thermal fatigue resistance compared to the conventional YSZ coating. However, the functionally-graded coating displays a good thermal fatigue resistance. Hence, it can be concluded that this kind of design is ideal to optimise the behaviour of thermal barrier coatings.     

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.     

Mechanical properties of lanthanum zirconate-based composite thermal barrier coatings

Lanthanum zirconate is a promising candidate material for thermal barrier coating (TBC) applications due to its low thermal conductivity and high temperature phase stability. However, its application is limited by thermal durability caused by low fracture toughness and low coefficient of thermal expansion. We recently developed LZ/8YSZ composite TBC systems using blended LZ and 8YSZ powders, which have demonstrated excellent thermal cycling performance. In this study, the mechanical properties of the composite TBCs were characterised using both nanoindentation and Vicker’s microhardness tests. The nanoindentation results show that both Young’s modulus and nanohardness increase with increasing 8YSZ content, suggesting the mechanical properties can be tailored by changing the volume ratio of 8YSZ. The ratios of Young’s modulus to nanohardness remain constant, ～18, irrespective to the coating’s composition. The microhardness results show the same dependence with 8YSZ content, which is confirmed by the analytic models based on composite theory.     

Evaluation of Rare‐Earth Modified ZrB2–SiC Ablation Resistance Using an Oxyacetylene Torch

Rare‐earth modified ZrB₂–SiC coatings were prepared via mechanical mixing Sm₂O₃ or Tm₂O₃ powders with spray‐dried ZrB₂, or by chemically doping samarium ions into spray‐dried ZrB₂. In either approach, SiC powders were also added and coatings were fabricated via shrouded air plasma spray. An oxyacetylene torch was utilized to evaluate the coatings under high heat flux conditions for hold times of 30 and 60 s. The resulting phases and microstructures were evaluated as a function of rare‐earth type, modification approach, and ablation time. A brittle m‐ZrO₂ scale was observed in the ZrB₂/SiC‐only coating after ablative tests; during cooling this scale detached from the unreacted coating. In contrast, rare‐earth modified coatings formed a protective oxide scale consisting primarily of either Sm_0.2Zr_0.8O_1.9 or Tm_0.2Zr_0.8O_1.9, along with small amount of m‐ZrO₂. These rare‐earth oxide scales displayed high thermal stability and remained adhered to the unreacted coating during heating and cooling, offering additional oxidation protection.