In situ microstructure characterization of ZrO2 coating at high temperature

Thermal barrier coatings (TBCs) are key materials of turbines for propulsion and power generation. The failure mechanism of TBCs is a crucial problem in scientific community and need to be resolved. Failure of TBCs is a complicated process affected by its own performance, microstructure and service environment. In this study, thermal barrier coatings of ZrO₂ were prepared by plasma spraying method. A SEM with heating system is used to study in situ microstructure change of TBCs at service temperature. Changes in microstructure and interfaces as well as healing and development of cracks are revealed. It is expected that the investigation of the failure mechanism of the TBCs from a microscopic point help to improve service life of the TBCs by providing a reliable basis to solve the failure problem.     

Laser thermal gradient testing of air plasma sprayed multilayered,multi-material thermal barrier coatings

Air plasma sprayed (APS) thermal barrier coatings (TBCs) are a widely used technology in the gas turbine industry to thermally insulate and protect underlying metallic superalloy components. These TBCs are designed to have intrinsically low thermal conductivity while also being structurally compliant to withstand cyclic thermal excursions in a turbine environment. This study examines yttria-stabilized zirconia (YSZ) TBCs of varying architecture: porous and dense vertically cracked (DVC), which were deposited onto bond-coated superalloys and tested in a novel CO₂ laser rig. Additionally, multilayered TBCs: a two-layered YSZ (dense + porous) and a multi-material YSZ/GZO TBC were evaluated using the same laser rig. Cyclic exposure under simulative thermal gradients was carried out using the laser rig to evaluate the microstructural change of these different TBCs over time. During the test, real-time calculations of the normalized thermal conductivity of the TBCs were also evaluated to elucidate information about the nature of the microstructural change in relation to the starting microstructure and composition. It was determined that porous TBCs undergo steady increases in conductivity, whereas DVC and YSZ/GZO systems experience an initial increase followed by a monotonic decrease in conductivity. Microstructural studies confirmed the difference in coating evolution due to the cycling.     

Constrained sintering and cracking of air plasma sprayed thermal barrier coatings: Experimental observation and modeling

The development of vertical cracks in air plasma sprayed (APS) thermal barrier coatings (TBCs) during thermal cycling and constrained sintering under a temperature gradient is investigated. Microstructural analysis shows that the development of the vertical cracks is associated with multiple processes, including sintering during the hold period and cleavage during cooldown. Inspired by the experimental observations, an image-based sintering model is used to simulate the development of vertical cracks as the coating sinters while constrained by a substrate. The computational results show that microstructural imperfections can develop into vertical cracks, which then propagate toward the interface. A simple analytical model is presented for the threshold level of in-plane stress for the onset of propagation of a vertical crack during constrained sintering. By combining the results of these different modeling approaches, the cross-coupling of the material and geometric parameters, and how this determines the sintering response (microstructure evolution) and vertical crack formation is evaluated. In addition, the growth of vertical cracks by a cleavage mechanism during cooldown is examined and the coupling between sintering, cleavage crack growth, and TBC lifetime is explored.     

Crack propagation studies of thermal barrier coatings under bending

The trends recently observed in crack propagation studies under bending for thermal barrier coatings (TBCs) in power plant application are highlighted in this paper. These studies described were performed with plasma sprayed zirconia bonded by a MCrAlY layer to Ni-base superalloy. Such thermal barrier composites are currently considered as candidate materials for advanced stationary gas turbine components. The crack propagation behaviour of the ceramic thermal barrier coatings (TBCs) at room temperature, in as received and oxidized conditions reveals that cracks grow linearly in the TBC with increase in bending load until about the yield point of the superalloy is reached. Approaching the interface between the ceramic layer and the bond coat, a high threshold load is required to propagate the crack further into the bond coat. Once the threshold is surpassed, the crack grows rapidly into the brittle bond coat without an appreciable increase in the load. At a temperature of 800°C, the crack is found to propagate only in the TBC (ceramic layer), as the ductile bond coat offers an attractive sink for stress relaxation. Effects of bond coat oxidation on crack propagation in the interface regime have been examined and are discussed. ©     

Failure analysis of thermally cycled columnar thermal barrier coatings produced by high-velocity-air fuel and axial-suspension-plasma spraying: A design perspective

Axial-suspension-plasma spraying (ASPS) is a fairly recent thermal spray technology which enables production of ceramic top coats in TBCs, incorporating simultaneously the properties of both the conventional-plasma sprayed (highly insulating porous structures) and electron-beam-physical-vapor-deposited (strain-tolerant columnar structures) top coats. TBCs are required to insulate the hot components in a gas turbine engine against high temperature and harsh operating conditions. Periodic heating and cooling of turbine engines during operation can create severe thermal cyclic fatigue conditions which can degrade the performance of these coatings eventually leading to the failure. An in-depth experimental investigation was performed to understand the failure behavior of columnar TBCs subjected to thermal cyclic fatigue (TCF) test at 1100?C. The study revealed that the TCF performance was influenced to an extent, by the top coat microstructure, but was primarily affected by the severity of thermally grown oxide (TGO) growth at the bond coat-top coat interface. Mixed failure modes comprising crack propagation through the bond coat-TGO interface, through TGO and within the top coat were identified. Based on the analysis of the experimental results and thorough discussion a novel design of microstructure for the high TCF performance columnar TBC is proposed.     

Understanding the Formation of Vertical Cracks in Solution Precursor Plasma Sprayed Yttria‐Stabilized Zirconia Coatings

Yttria‐stabilized zirconia (YSZ) deposition by the solution precursor plasma spraying (SPPS) route has been of interest for potential thermal barrier coating (TBC) applications. It has been surmised that realization of unique microstructural features like vertical cracks, nanosized pores and fine splats in the TBCs can significantly enhance coating durability and performance. However, satisfactory control over the YSZ coating microstructure has been elusive in the absence of an adequate understanding of the mechanism responsible for coating deposition in SPPS. This study demonstrates the ability to tailor microstructure of deposited YSZ coatings over a wide range, from nano‐porous coatings to a vertically cracked microstructure. Varying of precursor flow rate has been shown to dictate the pyrolysis events occurring in situ and, adopting this approach, YSZ coatings with widely varying microstructural features have been developed. The coatings have been characterized in detail and the observations correlated with in‐flight particle generation and splat formation. These studies also provide useful insights into the possible origin of vertical cracks in the coating for which a mechanism is proposed.     

Stress states and crack behavior in plasma sprayed TBCs based on a novel lamellar structure model with real interface morphology

To ascertain the crack growth behavior and coalescence mechanism in thermal barrier coatings (TBCs) is beneficial for understanding the failure of TBCs and proposing the probable optimization methods. In this work, a novel lamellar structure model with real interface morphology is developed to explore the crack growth behavior and the failure mechanism of TBCs during thermal cycling. Three typical defects which include pore, inter-splat crack, and intra-splat are incorporated in the model. To simulate the oxidation process of the bond coat (BC) realistically, The oxidation growth process is simulated via changing the BC properties to thermally grown oxide (TGO) properties layer by layer. The effects of the lateral growth strain distribution through TGO thickness on the stress states are executed. Moreover, the influences of BC creep on the crack growth and coating lifetime are further elaborated. The results show that the larger the lateral growth strain gradient, the smaller the residual tensile stress. The irregular interface morphology results in the redistribution of residual stresses. Although the pores and cracks can alleviate the tensile stress near the valley, large stress concentration will occur near them. At the early phase of thermal cycling, the cracks grow steadily. After more cycles, the cracks propagate rapidly and merge with others. The simulated delamination path is in agreement with the experiment results. Not only does BC creep change the crack coalescence mechanism, it also decreases the thermal cyclic lifetime of TBCs. The coating optimization method proposed in this study provides another option for developing advanced TBCs with longer lifetime.     

Peridynamic-based investigation of the cracking behavior of multilayer thermal barrier coatings

Numerical simulations of the cracking behavior of the top layers of multilayer thermal barrier coatings (TBCs) can effectively reveal the failure mechanisms of the TBCs. Current finite element method (FEM)-based simulation means have been applied to solve certain simple cracking problems in TBCs; however, they cannot effectively describe complex cracking problems in TBCs such as coalescence, intersection, and interference among multiple cracks. Peridynamic (PD), a newly developed mechanical theory, has been widely studied to provide analysis for cracking problems in TBCs. In this paper, a numerical model of TBCs is built by the bond-based PD (BB-PD) theory. Complex cracking behaviors, such as spontaneous crack propagation at both interfacial and internal regions, coalescence, and interference among multiple cracks, are simulated under isothermal cooling and gradient cooling conditions. In addition, the effects of interfacial roughness and calcium–magnesium–alumina–silicate (CMAS) inclusions on the cracking behavior are discussed. The results show that the PD model accurately captures complex cracking behaviors observed via scanning electron microscopy (SEM). Given the ability of the model for analyzing discontinuities in TBCs, it can help to further clarify the fracture mechanisms of TBCs.     

Comprehensive dynamic failure mechanism of thermal barrier coatings based on a novel crack propagation and TGO growth coupling model

Comprehensive understanding of failure mechanism of thermal barrier coatings (TBCs) is essential to develop the next generation advanced TBCs with longer lifetime. In this study, a novel numerical model coupling crack propagation and thermally grown oxide (TGO) growth is developed. The residual stresses induced in the top coat (TC) and in the TGO are calculated during thermal cycling. The stresses in the TC are used to calculate strain energy release rates (SERRs) for in-plane cracking above the valley of undulation. The overall dynamic failure process, including successive crack propagation, coalescence and spalling, is examined using extended finite element method (XFEM). The results show that the tensile stress in the TC increases continuously with an increase in an undulation amplitude. The SERRs for TC cracks accumulate with cycling, resulting in the propagation of crack toward the TC/TGO interface. The TGO cracks nucleate at the peak of the TGO/bond coat (BC) interface and propagate toward the flank region of the TC/TGO interface. Both TC cracks and TGO cracks successively propagate and finally linkup leading to coating spallation. The propagation and coalescence behavior of cracks predicted by this model are in accordance with the experiment observations. Therefore, this study proposed coating optimization methods towards advanced TBCs with prolonged thermal cyclic lifetime.     

Optimizing the structure and properties of Y2O3 stabilized zirconia: An atmospheric plasma spray (APS) and solution precursor plasma spray (SPPS) based comparative study

The yttria stabilized zirconia (8%YSZ) is widely used to insulate the metallic components of the engine from high temperature and improve the operating temperature of gas turbine engines. With different processing parameters, 8YSZ coatings are prepared by atmospheric plasma spray (APS) and solution precursor plasma spray (SPPS) techniques and the microstructural features and thermodynamics properties are compared. The electron back scattered diffraction (EBSD) analysis indicate that the substitutional point defects (Zr_0.86Y_0.14O_1.93) in the 8YSZ APS coatings are considerably higher than the corresponding SPPS coatings. The replacement of Zr⁴⁺ by Y³⁺ disturbs the charge neutrality of the system which might be compensated by the creation of oxygen vacancy. Both the substitutional point defects and the oxygen vacancies are the sources of phonon scattering, modifying the thermal conductivity of the coating. Pores and cracks are qualitatively and quantitatively analyzed in the microstructure of 8YSZ coatings. Strain tolerant and high thermal cycling life coatings are prepared by SPPS due to the existence of vertical cracks in the microstructure. Comparing the thermal insulation properties of the coatings, the APS coating provided lower thermal conductivities relative to the SPPS coatings which might be due to the high concentration of point defects and low concentration of the mixed oxide phase.     

Isothermal Oxidation Behavior of Gd2Zr2O7/YSZ Multilayered Thermal Barrier Coatings

Efficiency of a gas turbine can be increased by increasing the operating temperature. Yttria‐stabilized zirconia (YSZ) is the standard thermal barrier coating (TBC) material used in gas turbine applications. However, above 1200°C, YSZ undergoes significant sintering and CMAS (calcium magnesium alumino silicate) infiltration. New ceramic materials of rare earth zirconate composition such as gadolinium zirconate (GZ) are promising candidates for thermal barrier coating applications (TBC) above 1200°C. Suspension plasma spray of single‐layer YSZ, double‐layer GZ/YSZ, and a triple‐layer TBC comprising denser GZ on top of GZ/YSZ TBC was attempted. The overall coating thickness in all three TBCs was kept the same. Isothermal oxidation performance of the three TBCs along with bare substrate and bond‐coated substrate was investigated for time intervals of 10 h, 50 h, and 100 h at 1150°C in air environment. Weight gain/loss analysis was carried out by sensitive weighing balance. Microstructural analysis was carried out using scanning electron microscopy (SEM). As‐sprayed single‐layer YSZ and double‐layer GZ/YSZ showed columnar microstructure, whereas the denser layer in the triple‐layer TBC was not columnar. Phase analysis of the top surface of as‐sprayed TBCs was carried out using XRD. Porosity measurements were made by water intrusion method. In the weight gain analysis and SEM analysis, multilayered TBCs showed lower weight gain and lower TGO thickness compared to single‐layer YSZ.     

Plasma-sprayed nanostructured YSZ thermal barrier coatings: Thermal insulation capability and adhesion strength

Adhesion strength and thermal insulation of nanostructured Yttria Stabilized Zirconia (YSZ) thermal barrier coatings (TBC) were investigated and compared with those of conventional YSZ TBCs. A Nickel based superalloy (IN-738LC) was used as the substrate with NiCrAlY bond coat, and nanostructured and conventional YSZ top coats were applied by using air plasma spray (APS). The adhesion strength of coatings was evaluated according to ASTM C633-01, and their thermal insulation capability was evaluated using a specially designed test setup at an electrical furnace. The results revealed the nanostructured YSZ coating to have a bimodal microstructure consisting of nanosized particles and microcolumnar grains. The bimodal microstructure of nanostructured coatings prevented crack propagation by splat boundaries and unmelted particles, thereby improving the bonding strength. Also, due to the presence of nano-zones in the microstructure of nano TBCs, coatings exhibited superior thermal insulation capability.     

Liquid-phase-infiltration of EB-PVD-TBCs with ageing inhibitor

Partially yttria stabilized zirconia (PYSZ) is the state-of-the-art material for current thermal barrier coating (TBC) applications at aircraft engines. It introduces intrinsic properties leading to increased lifetime of superalloy turbine blades and engine efficiency. The new generation turbines generate higher gas temperatures, which seriously affects the thermal stability of the state-of-the-art TBC materials, mainly because of considerable phase transformation- and/or sintering-induced volume changes. These processes cause degradation of columnar microstructure of electron-beam physical vapor deposited (EB-PVD) coatings and raise modulus of elasticity and as a result, the internal stresses. One of the suggested strategies for the improvement of sintering resistance is to infiltrate TBCs with another oxide. This aims to reduce the diffusion rate at the nano-structured feather-arm features and to avoid inter-columnar pore closure.This paper deals with infiltration of EB-PVD PYSZ-structures with a liquid-phase precursor based on alumina and titania to inhibit sintering. After heat-treatment of infiltrated coatings at 1000 and 1100 °C, microstructure is characterized by SEM/EDX and compared with as-coated state-of-the-art material aged under same conditions. The mechanism, which may stop or inhibit the sintering at TBCs is discussed. Attributions to the thermal stability and the potential use of the infiltration technique in EB-PVD-coatings are addressed.     

Introducing segmentation cracks in air plasma-sprayed thermal barrier coatings by controlling residual stress

Segmentation cracks are crucial for enhancing the strain tolerance and decreasing the propensity of delamination for thermal barrier coatings (TBCs). In this study, segmentation cracks were prepared in air plasma-sprayed TBCs by controlling the residual stress. The evolution of the stress in the coating was characterized via photoluminescence piezospectroscopy using trace α-Al₂O₃ impurities as stress sensor. Tensile stress (~170 MPa) formed in the as-deposited coating was converted into compressive stress through further thermal exposure. The relationship between the formation of the segmentation cracks and stress in the coating was investigated. It was demonstrated that the segmentation cracks could be formed when a critical coating thickness is achieved. The critical coating thickness and spacing of the segmentation cracks dependent on the tensile stress in the as-deposited coating, and they could be manipulated by controlling the deposition and substrate temperatures. In addition, the evolution of the microstructure and phase composition of the yttria-stabilized zirconia coating was examined.     

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.     

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.     

Evolution of internal cracks and residual stress during deposition of TBC

Thermal barrier coating (TBCs) are ceramic coatings that are deposited on metallic substrates to provide high thermal resistance. Residual stress is among the critical factors that affect the performance of TBCs. It evolves during the process of coating deposition and in-service loading. High residual stresses result in significant cracking and premature delamination of the TBC layer. In the present study, a hybrid computational approach is used to predict the evolution of internal cracks and residual stress in TBC. Smooth particle hydrodynamics (SPH) is first used to model the deposition of yttria-stabilized zirconia (YSZ) layer that contains various interfaces and micropores on a steel substrate. Then, three-dimensional (3D) finite element analysis is utilized to predict the evolution of internal cracks and residual stress in the ceramic coating layer. It is found that multiple cracks emerge during the solidification of the coating layer due to the development of high tensile (quenching) stresses. The cracking density is higher at regions near the coating interface. It is also found that compressive (residual) stresses are developed when the deposited coating is cooled to room temperature. The residual stress state is equibiaxial and nonlinear across the thickness/width of the TBC layer. The residual stress profile predicted compares well with that of hole drilling experiments.     

Molten silicate interactions with plasma sprayed thermal barrier coatings: Role of materials and microstructure

Ingestion of siliceous particulate debris into both propulsion and energy turbines has introduced significant challenges in harnessing the benefits of enhanced operation efficiencies through the use of higher temperatures and thermal barrier coatings (TBCs). The so-called CMAS (for calcium-magnesium alumino-silicate) particles can melt in the gas path at temperatures greater than 1200C, where they will subsequently impact the coating surface and infiltrate through the carefully engineered porosity or cracks in a TBC. Ultimately, this CMAS attack causes premature spallation through its solidification and stiffening the ceramic during cooling. It has been noted in recent years, that TBCs based on yttria stabilized zirconia (YSZ) are completely non-resistant to CMAS attack due to their lack of reactivity with infiltrant liquid. New TBC ceramics such as Gadolinium Zirconate (GZO) show promise of CMAS resistance through rapid reaction-induced crystallization and solidification of the infiltrant, leading to its arrested infiltration. In both situations, the microstructure (porosity, micro and macro cracks) can be important differentiators in terms of the infiltration and subsequent failure mechanisms. This paper seeks to examine the interplay among microstructure, material, and CMAS attack in different scenarios. To do so, different types of YSZ & GZO single and multilayer coatings were fabricated using Air Plasma Spray (APS) and exposed to CMAS through isothermal and gradient mechanisms. In each of the cases, beyond their unique interactions with CMAS, it was observed the inherent microstructure and character of the porosity of the coating will have an additional role on the movement of the melt. For instance, vertical cracks can provide pathways for accelerated capillaric flow of the melt into both YSZ and GZO coatings. Based on these observations multilayer coatings have been proposed and realized toward potentially reducing complete coating failure and supporting multiple CMAS attack scenarios.     

Experimental and computational study on sintering of ceramic coating layers with complex porous structures

This study investigated the sintering behavior of an yttria-stabilized zirconia coating for thermal barrier coatings (TBCs) with a complicated porous structure via both experiment and simulation using the finite element method for samples with only a coating (free coating) and samples with coating on a substrate (constrained coating). Sintering and grain growth proceeded from the bottom of the coating, and the coating bent convex upward in the free coating. In the constrained coating, sintering and grain growth proceeded in a manner similar to the free coating; however, the degrees of sintering and grain growth were small. Furthermore, sintering and grain growth were delayed because of substrate constraints. As a simulation result, the free coating was bent in a manner similar to the experiment. The experimental results could be reproduced in terms of time dependency and temperature dependency. The decrease in the porosity of the constrained coating was delayed compared with that in the free coating because of substrate constraints. This simulation result was able to reproduce the experimental results. Thus, the sintering behavior for the complex porous structures of TBCs can be predicted by experimental research and simulation, which could aid in the development of a prediction technology for the delamination of coatings (TBC lifetime).     

Effect of CeO2 doping on high temperature oxidation resistance of YSZ TBCs

In the present work, YSZ TBCs and 10 wt% CeO₂-doped YSZ thermal barrier coatings (CeYSZ TBCs) were prepared via atmospheric plasma spraying(APS) respectively, whereupon high temperature oxidation experiment was carried out at 1100 °C to compare the high temperature oxidation behavior and mechanism of the two TBCs. The results showed that the doping of CeO₂ reduced the porosity of YSZ TBCs by 23%, resulting in smaller oxidation weight gain and lower TGO growth rates for CeYSZ TBCs. Besides, the TGO generated in CeYSZ TBCs was obviously thinner and there were fewer defects inside it. For YSZ TBCs, as the oxidation process proceeded, Al, Cr, Co and Ni elements in the bonding coating were oxidized successively to form loose and porous spinel type oxides (CS), which was apt to cause the spalling failure of TBCs. While, the Al₂O₃ layer of the TGO generated in CeYSZ TBCs ruptured later than that in YSZ TBCs, which delayed the oxidation of Cr, Co, and Ni elements and the formation of CS accordingly. Therefore, CeO₂ doping can effectively improve the high temperature oxidation resistance of YSZ TBCs.