Observation of Subcritical Spall Propagation of a Thermal Barrier Coating

Observations are reported of the room-temperature propagation of a spalling failure mode of a thermal barrier coating (TBC) from its bond coat after oxidation. The coating is a Y₂O₃-stabilized ZrO₂ coating formed by electron-beam deposition on a Ni-Co-Cr-Al-Y bond coat. The spall shape evolution and stress redistribution as the spall propagates are reported. The failure propagates primarily as an interface crack between the bond coat and the thermally grown aluminum oxide (TGO) formed on the underside of the TBC during oxidation. The observations are consistent with subcritical propagation of an interface crack between the TGO and bond coat assisted by the presence of moisture. An estimate of 9 J/m² is made of the fracture resistance in air of the interface.     

Effect of segmented cracks on TGO growth and life of thick thermal barrier coating under isothermal oxidation conditions

This paper is devoted to a comparative study on the isothermal oxidation of thick thermal barrier coating (TTBC) with and without segmented cracks produced by atmospheric plasma spray (APS) process. Accordingly, the growth of thermally grown oxide (TGO) and its effect on the degradation of the coating were investigated. Thick top coat in both segmented crack and conventional thick TBC reduced the double layered TGO growth rate slightly. The segmented crack thick TBC demonstrated longer isothermal oxidation life in comparison with that of the conventional thick TBC at 1100 °C. The dominant failure mechanism was spallation due to lateral cracking within the TGO and/or within TBC near the TGO layer, called mixed failure. Stress, and consequently strain, induced on the TTBC due to progressive TGO growth, seems to be primarily responsible for the crack initiation and propagation leading to the coating failure. Increment of elastic energy stored within the top coat due to the increasing of TGO thickness, finally causes thick thermal barrier coating failure in high temperature isothermal oxidation.     

An innovative model coupling TGO growth and crack propagation for the failure assessment of lamellar structured thermal barrier coatings

The failure of plasma-sprayed thermal barrier coating (TBC) is often caused by the coating spallation due to crack propagation. In this study, a new model with stacking lamellae is developed based on the cross-section micrograph to explore crack propagation behavior within the ceramic top coat (TC) during isothermal cycling. The dynamic growth process of thermally grown oxide (TGO) is simulated via material properties change step by step. The stress profiles in the lamellar model are first evaluated, and the pore and lamellar interface crack effects on the stress state are further explored. Then, the successive crack growth, linkage, and ultimate coating spallation process is simulated. The results show that the stress intensity in TC enhances with thermal cycling. Large stress concentration always occurs near the pore and lamellar interface crack, which can result in the incipient crack growth. Moreover, the lamellar interface crack also changes the stress distribution within the TC and at the TC/bond coat interface. The multiple crack propagation upon temperature cycling is explored, and the possible coalescence mechanism is proposed. The lamellar crack steadily propagates at the early stage. The crack length sharply increases before the occurrence of coating spallation. The simulated coat spalling path is in line with the experimental result. Therefore, the new lamellar model developed in this work is beneficial to further reveal coating failure mechanism and predict coating lifetime.     

Research status of bond coats in environmental barrier coatings

Bond coats in environmental barrier coatings (EBCs) prevent oxidants from penetrating the substrate, mediate the mismatch of the coefficient of thermal expansion (CTE), and improve the adhesion strength between adjacent layers. However, the development of bond coats is rarely studied systematically. In this paper, the research status of the bond coats in EBCs is introduced in detail, including the materials and deposition methods. Thus far, Si, modified-Si, mullite, etc., have been employed as bond coats. Nevertheless, visible drawbacks of each bond coat limit their application at high-temperatures in extreme environments. Si bond coat is easily oxidized and forms thermally grown oxides that form cracks, resulting in delamination, spallation, and failure of EBCs. In the Si–HfO₂ bond coat, the optimal ratios of Si/HfO₂, deposition methods, distribution of Si and HfO₂, and oxidation of Si remain completely unsolved. For mullite bond coat, SiO₂ suffers selective evaporation in the water vapor environment, and the ratios of the Al₂O₃ and SiO₂ in mullite coatings restrict its service lifetime. HfSiO₄ is a potential candidate acting as a next-generation bond coat in EBCs is proposed. Furthermore, choosing reasonable deposition methods is beneficial to improve the performances of the bond coats in EBCs.     

Dynamic crack growth mechanism and lifetime assessment in plasma sprayed thermal barrier system upon temperature cycling

Failure of plasma-sprayed thermal barrier coatings (TBCs) is very complicated upon temperature cycling, therefore, to ascertain the crack propagation behavior is beneficial to understand the failure mechanism and life prediction of TBCs. In this paper, a finite element model is developed by coupling the dynamic growth of thermally grown oxide and dynamic crack propagation to explore the failure of TBCs induced by the instability of the interface between top coat (TC) and bond coat (BC). The thermal cyclic lifetime is deduced by obtaining the thermal cycles corresponding to the occurrence of complete delamination. The influence of the non-uniformity of the interface on thermal cyclic lifetime is quantitatively evaluated. Sensitivity studies including the effects of constituent properties and crack distance to the interface on the thermal cyclic lifetime are further examined. The results show that the incipient cracks usually nucleate above the valley due to the large tensile stress, and the shear stress near the peak plays a very crucial role. The crack growth involves three stages with different fracture dominated-mode. The crack propagation behavior obtained by simulation is in line with that observed by experiments. The TBCs system with a uniform interface exhibits a longer thermal cyclic lifetime compared to the non-uniform interface. Coating optimization methods proposed in this work may provide an alternative option for developing a TBCs system with longer service lifetime.     

High temperature performances of tri-layer environmental barrier coating with Si bond layer modified by Yb2O3

Environmental barrier coatings (EBCs) have been expected to be applied on the surface of ceramic matrix composites (CMCs). However, the oxidation and propagation cracking of the silicon bond layer are the most direct causes to induce the failure of EBCs under high temperature service environment. The modification of silicon bond layer has become an important method to prolong the service life of EBCs. In this work, the Yb₂O₃ have been introduced to the silicon bond layer, and three kinds of tri-layer Yb₂SiO₅/Yb₂Si₂O₇/(Si-xYb₂O₃) EBCs with modified Si bond layer by different contents of Yb₂O₃ (x = 0, 10 vol%, 15 vol%) were prepared by vacuum plasma spray technique. The thermal shock performance and long-term oxidation resistance of the EBCs at 1350 °C were investigated. The results showed that the addition of appropriate amount of Yb₂O₃ (10 vol%) can improve the structural stability and reduce the cracks of the mixed thermal growth oxide (mTGO) layer by forming the oxidation product of Yb₂Si₂O₇ during long-term oxidation. The excessive addition of Yb₂O₃ increased the stress during thermal shock as well as accelerated the oxygen diffusion during long-term oxidation, leading to the failure of EBCs. Moreover, the distribution uniformity of Yb₂O₃ deserves further consideration and improvement.     

Environmental barrier coatings using low pressure plasma spray process

Yb₂Si₂O₇/Si bilayer environmental barrier coatings (EBCs) on SiC ceramic substrate were produced by low pressure plasma spray (LPPS) process. Phase composition, microstructure, and thermal durability of LPPS Yb₂Si₂O₇/Si coating were investigated. XRD analysis indicated that the coating is mainly composed of Yb₂Si₂O₇ with ~15.5v% Yb₂SiO₅ phases. The LPPS EBCs have a dense microstructure with porosity less than 4%. Adhesion strength measurement indicated the LPPS EBCs have an average adhesion strength of 29.1 ± 0.8 MPa. Furnace cycle test (FCT) on the coatings in air at 1316°C was performed and the test ran for 900 cycles and there was no coating spallation/failure for LPPS Yb₂Si₂O₇/Si EBCs. The FCT results demonstrated the excellent thermal cycle durability of LPPS EBCs. Oxidation kinetics investigation of LPPS EBCs in flowing 90% H₂O (g)+10% air at 1316°C showed that the thermally grown oxide (TGO) growth rate is close to the oxidation rate of pure Si in dry air and is significantly lower than that in water vapor environment. The LPPS process is promising in making highly durable Yb2Si2O7-based dense EBCs by impeding diffusion and ingression of water vapor/O₂.     

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.     

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.     

Vertical crack distribution effect on the TBC delamination induced by crack growth from the ceramic surface and near the interface

The propagation of vertical crack on the surface of thermal barrier coatings (TBCs) may affect the interface cracking and local spallation. This research aims to establish a TBC model incorporating multiple cracks to comprehensively understand the effects of vertical crack distribution on the coating failure. The continuous TGO growth and ceramic sintering are together introduced in this model. The influence of the vertical crack spacing and non-uniform distribution on the stress state, crack driving force, and dynamic propagation is examined. Moreover, the influence of coating thickness on the crack growth driving is also explored. The results show that large spacing will lead to early crack propagation. The uniform distribution of vertical cracks can delay the spallation. When the spacing is less than 4 times ceramic coat thickness, the cracking driving force will come in a steady-state stage with the increase of vertical crack length. Prefabrication of vertical cracks with spacing less than 0.72 mm on the coating surface can greatly decrease the strain energy. The results in this study will contribute to the construction of an advanced TBC system with long lifetime.     

Thermal properties of plasma-sprayed thermal barrier coating with bimodal structure

Nanostructured zirconia coatings have been prepared by atmospherical plasma spraying (APS) on NiCrAlY-coated superalloy substrates. The isothermal oxidation test results indicate that the oxidation kinetics of nanostructured TBC follows a parabolic law and the oxidation resistance of the nanostructured TBC is comparable to that of the conventional TBC. The nanostructured thermal barrier coatings exhibit excellent thermal cyclic resistance and low thermal diffusivity. The failure of the nanostructured TBC occurs within the top coat and close to the YSZ/thermal growth oxide interface. The thermal diffusivity of the coating is 90% of that of conventional thermal barrier coatings, and it increases after heat treatment at 1050 °C for 34 h. The increase in the thermal diffusivity of the coating is ascribed to grain growth, the crack healing as well as sintering neck formation.     

The sintering behavior of plasma-sprayed YSZ coating over the delamination crack in low temperature environment

The sintering behavior of plasma-sprayed yttria-stabilized zirconia (YSZ) coating over the delamination crack and its influence on YSZ cracking were investigated via gradient thermal cycling test and finite element model (FEM). The gradient thermal cycling test was performed at a peak surface temperature of 1150 °C with a duration of 240 s for each cycle. A three-dimensional model including delamination cracks with different lengths was employed to elaborate the temperature evolution characteristics in YSZ coating over the delamination cracks. The temperature over the delamination crack increases linearly with the crack propagation, which continuously promotes the sintering of YSZ coating in the region. As a result, the YSZ coating over the delamination crack sinters dramatically despite of the low temperature exposure. Meanwhile, the temperature distribution difference in YSZ coating induces an nonuniform sintering along both free surface and thickness of YSZ coating. Correspondingly, the maximum vertical crack driving force locates at the YSZ free surface over the delamination crack center, which makes the vertical cracks generate in this region and propagate to the interface of YSZ /bond coat with YSZ further sintering. The vertical crack promotes the delamination crack propagation via accelerating the oxidation velocity of the bond coat. The influence of temperature rise on delamination crack propagation can be divided into two stages: the little contribution stage and the promotion stage. For the actual engine exposure to low temperature, the study of phase transformation of YSZ over the delamination crack is indeed needed because of an extended remarkable temperature rise period.     

Oxidation kinetics of atmospheric plasma sprayed environmental barrier coatings

Three different Si/Yb-silicate environmental barrier coating systems (EBCs) were atmospheric plasma sprayed using various spray currents (275, 325, 375 A) for Yb-silicate deposition. The EBCs were thermally cycled between room temperature and 1300 °C up to 1000 h in air. Additionally, bare Si coatings were tested under isothermal and thermal cycling conditions in the as-sprayed state and after polishing at 1300 °C in air. Parabolic oxidation kinetics were observed and oxidation protection provided by Yb-silicate was found to be influenced by the spray conditions, i.e. only at 325 A, Yb-silicate was effectively protecting the bond coat. The controlling mechanism was attributed to densification in the Yb-silicate layer during thermal cycling, which was quantified via image analysis. The surface finish of the Si coating was also found to be influencing the oxidation rate. The TGO was thinner and less cracked on polished APS Si coating in comparison with the as-sprayed Si coating surface.     

Analysis of interfacial crack initiation mechanism of thermal barrier coatings in isothermal oxidation process based on interfacial stress state

In this paper, the interfacial stress state is used to analyze the interfacial crack initiation mechanism of the thermal barrier coatings (TBCs) during isothermal oxidation. The influence of thermal growth stress, initial residual stress, and creep behavior on the stress distribution is considered to have an accurate simulation result. A parameter that integrates the effects of interfacial normal and tangential stress is modified for evaluating interfacial crack initiation. It is found that, in the cooling stage, the interfacial cracks sprout at the top coat (TC)/thermally grown oxide (TGO) interface valley region and the TGO/bond coat (BC) interface peak region, which agrees with the experimental results. Furthermore, the influence of interfacial roughness on crack initiation is investigated. The result shows that different interfacial roughness affects the sprouting region of interfacial cracks and cracks within the TC layer.     

The initial oxidation of beryllium by water vapor

The initial stage of adsorption and beryllium oxidation by water (clearly a nonadiabatic process) was studied for a wide temperature range, using AES, XPS, DRS, and CPD measurements. The mechanism of room temperature (RT) oxidation by water vapor was found to be by nucleation and growth of 3 monolayer oxide islands, laterally spreading until coalescence takes place. When a full oxide layer is achieved, a further slow oxidation takes place, virtually stopping at ∼6 monolayer depth. Exposure of the surface to water vapor at 150 K yielded dissociation to H and OH, chemisorbed on the surface, as detected by an XPS chemical shift. The lack of such a shift at RT indicates a full dissociation of the water molecule on the surface. A giant effect of Be electron-stimulated oxidation (ESO) by water vapor, as opposed to Be mild ESO by O₂, was observed, reaching the maximal possible oxidation rate for the ratio of ≥150 impinging electrons per water molecule. It is suggested that the mechanism is a Mott—Cabrera-like one, enabled by a combination of an electric field applied by negative OH and/or oxygen ions formed at the surface, probably by secondary electron attachment, and a very fast diffusion of Be²⁺ ions enabled by the presence of hydrogen in the oxide bulk. The water vapor ESO exhibits an inverse dependence on the substrate temperature, presumably due to the decrease with temperature of hydroxyl surface concentration, leading to the weakening of the electric field formed across the oxide.     

Experimental and Finite Element Study of an Air Plasma Sprayed Thermal Barrier Coating under Fixed Cycle Duration at Various Temperatures

Cyclic furnace tests were conducted on Air Plasma Sprayed (APS) Thermal Barrier Coating (TBC) samples which were coated with NiCoCrAlY on a nickel‐based superalloy at three temperatures. From these tests the following were determined: oxidation kinetics and activation energy, bond coat rumpling rate, and cyclic failure lives. All failures occurred in the top coat consistent with engine experience. The measured rumpling rate and oxidation kinetics were used as input for a finite element model that utilized a highly realistic top coat constitutive model that included creep and relaxation behavior as well as tension/compression flow stress asymmetry consistent with available experimental data. The modeling results based on these measured inputs show that the primary sources of stress and strain in descending order are rumpling, oxide growth and finally thermal expansion mismatch between the top coat and underlying metal. Three important implications of these results are; predicted stresses are too low to predict failure based on single crack fracture mechanics, cycling increases accumulated inelastic strain in a fixed time interval providing an additional reason why cycling is damaging and finally to get realistic stresses and strains it is necessary to accurately characterize the geometry changes associated with rumpling.     

Effects of the chemistry of coating and substrate on the steam oxidation kinetics of environmental barrier coatings for ceramic matrix composites

Environmental barrier coatings (EBCs) are an enabler for SiC/SiC ceramic matrix composites (CMCs) in gas turbines by protecting CMCs from environmental degradation. A critical EBC failure mode is the EBC spallation due to a build-up of elastic strains caused by the formation of SiO₂ scale, known as TGO (thermally grown oxide). H₂O, a byproduct of combustion reactions, accelerates the TGO-induced EBC failure by increasing TGO growth rates by orders of magnitude. NASA’s approach to improve the EBC life, therefore, is to reduce TGO growth rates. NASA discovered that modifying the TGO chemistry by modifying the EBC chemistry of Gen 2 EBC (Si / Yb₂Si₂O₇) reduces the TGO thickness by up to ～80 %. A study was undertaken to understand the oxidation mechanism of modified Gen 2 EBCs as well as to investigate the effect of EBC and CMC chemistry on TGO growth rates. This study confirmed the previously proposed TGO-controlled oxidation mechanism of modified Gen 2 EBCs and determined the correlations between the EBC and CMC chemistry, TGO chemistry, and TGO growth rates.     

Analysis of crack initiation and propagation in Thermal Barrier Coatings using SEM-Based geometrical model with extended finite element method

Thermal Barrier Coatings (TBC) are widely used to protect the metallic components that operate at harsh conditions of elevated temperatures and oxidizing environments. Thermally grown oxide (TGO) causes cracks formation in the top coat (TC) that may lead to spallation failure of TBC. This work investigates effect of pores and TGO thickness on crack initiation and propagation due to thermal mismatch between TBC layers. Image processing is used to convert an SEM image, including pores, into a finite element (FE) model. An FE model using XFEM implemented in ABAQUS was developed to investigate crack initiation and propagation for various TGO thicknesses considering the effect of plastic deformation of BC, TGO and substrate. Results show that presence of pores changes the critical sites for crack initiation from the TC/TGO interface to be around the pores within the TC. Crack initiation temperatures and crack lengths were found to be affected with both TGO thickness and pores.     

Measurement of ceramics cracking during water quenching by digital image correlation

Measuring the thermal shock crack growth process is crucial for revealing ceramic materials and structures’ thermal shock failure mechanisms and evaluating their reliability. We used a self-made water quenching system to conduct thermal shock tests on alumina and zirconia ceramics. The thermal shock process was recorded by high-speed digital image correlation (DIC) during the test. The process of thermal shock crack initiation and propagation in two kinds of ceramics was determined by analyzing the speckle image change on the sample’s surface. It is found that the crack growth rate of alumina is faster than that of zirconia, which is caused by different material parameters. This paper presents an in-situ measurement method for the initiation and propagation of thermal shock cracking in ceramic materials. It can provide a measurement method to identify and predict the thermal shock damage of ceramic components.