The effect of bond coat oxidation on the microstructure and endurance of a thermal barrier coating system

Abstract

Isothermal oxidation tests have been carried out on a thermal barrier coating (TBC) system consisting of a nickel-based superalloy, CoNiCrAlY bond coat applied by HVOF and yttria-stabilised zirconia (YSZ) top coat applied by EB-PVD. Bond coat microstructure, coating cracking and failure were characterised using high resolution scanning electron microscopy complemented with compositional analyses using energy dispersive X-ray spectrometry. A protective alumina layer formed during the deposition of the YSZ top coat and this grew with sub-parabolic kinetics during subsequent isothermal oxidation at temperatures in the range 950 to 1150°C. After short exposures at 1050°C and final cooling, small sub-critical cracks were found to exist within the YSZ but adjacent to bond coat protuberances. Their formation is related to the development of local tensile strains associated with the growth of an alumina layer (TGO) on the non-planar bond coat surface. However, for the specimens examined, these cracks did not propagate, in contrast to other TBC systems, and final spallation was always found to have occurred at the bond coat/TGO interface. This shows that the strain energy within the TGO layer made a significant contribution to the delamination process.     

Failure mechanism of a thermal barrier coating system on a nickel-base superalloy

An investigation was carried out to determine the failure mechanism of a thermal barrier coating system on an Ni-base superalloy. The coating system consisted of an outer layer of yttria-stabilized zirconia (top coat), and an inner layer of Pt-aluminide (bond coat). Specimens were exposed at 1010 and 1150 °C with a 24-h cycling period to room temperature. Scanning electron microscopy combined with energy dispersive X-ray spectroscopy as well as X-ray diffraction were used in microstructural characterization. Spallation of the oxide scale developed by the bond coat was found to be the mode of failure. Experimental results indicated that the breakdown of oxide was affected by internal oxidation of Hf diffusing from the alloy substrate into the bond coat surface developing localized high levels of stress concentration at the oxide–bond coat interface. It was concluded that the cause of failure was degradation of thermal stability of the bond coat accelerating its oxidation rate and permitting outward diffusional transport of elements from the substrate.     

On the performance and failure mechanism of thermal barrier coating systems used in gas turbine blade applications: Influence of bond coat/superalloy combination

Surface engineering plays a major role in achieving the performance and design lives of gas turbine components such as the high pressure turbine aerofoils which operate under the most arduous conditions of temperature and stress leading to a wide range of thermal and mechanical loading during service. In this study, emphasis is placed upon the role of composite systems consisting of bond coat and superalloy substrate in determining the performance and useful life of thermal barrier coatings using yttria-stabilized zirconia as top coat processed by electron-beam physical vapor deposition. Three platinum-modified bond coats of the diffusion type and three nickel-based superalloys are included in the study. Thermal exposure tests at 1150 °C in air with a 24-hour cycling period to room temperature have been used to rank the performance of the coating systems. Various electron-optical techniques have been used to characterize the sequence of events leading to coating failure as marked by spallation of the top ceramic coat. It is shown that for a given superalloy substrate, the coating performance is dependent upon the type of bond coat. Conversely, for a given bond coat, the performance becomes a function of the superalloy composition used in the application. However, in both cases, coating failure is found to be predominated by loss of adhesion between the thermally grown oxide and bond coat indicating that the respective interface is the weakest link in the system. The results are interpreted in terms of the phase transformations which occur in the bond coats during exposure at elevated temperatures and the corresponding effects on their oxidation behavior.     

Thermally grown oxide scales on γ-TiAl coated with thermal protection systems

Abstract

Thermal barrier coatings (TBCs) of yttria partially stabilized zirconia were deposited on gamma TiAl samples using electron-beam physical vapour deposition. The specimens were coated with intermetallic Ti –Al – Cr layers and CrAlYN/CrN nanoscale multilayer coatings. The lifetime of the TBC systems was determined performing cyclic oxidation tests in air at temperatures between 850 and 950–C. The TBC systems with Ti –Al – Cr and CrAlYN/CrN layers did not fail at 850 and 900–C during the maximum exposure time period of 1000 cycles of 1 h dwell time at high temperature. No spallation of the thermal barrier coatings was observed. As revealed by post-oxidation microstructural analysis, the protective coatings were severely degraded when exposed at 900–C, resulting in growth of mixed oxides on the substrate. Underneath the thermal barrier coating an outer oxide scale with a columnar structure was observed, consisting of rutile and α-Al₂O₃. Energy-dispersive X-ray spectroscopy analysis revealed zirconia and chromia being dissolved in the outer oxide scale. The columnar structure and the presence of zirconia indicated an effect of the TBC on the morphology of the outer oxide scale. The zirconia top coat exhibited an excellent adherence to this oxide scale formed on the protective layers when degraded, and at defects like cracks. When thermally cycled at 950–C, the TBC system on specimens coated with Ti –Al – Cr failed by spallation of the thermally grown mixed oxides, whereas the thermal barrier coating was well adherent to the outer oxide scale at this temperature, too.     

Effect of superalloy substrate composition on the performance of a thermal barrier coating system

An investigation was carried out to determine the performance of a thermal barrier coating system consisting of (ZrO₂-8% Y₂O₃)/(Pt) on two single-crystal Ni-base superalloys. Coating/alloy behavior was studied with reference to: (i) initial microstructural features, (ii) oxidation properties, (iii) thermal stability characteristics, and (iv) failure mechanism. All thermal exposure tests were carried out at 1150°C in still air with a 24-h cycling period to room temperature. Failure of the coating system was indicated by macroscopic spallation of the ceramic top coat. Scanning electron microscopy combined with energy dispersive X-ray spectroscopy as well as X-ray diffraction were used to characterize the microstructure.Decohesion between the thermally grown oxide and bond coat was found to be the mode of failure of the coating system for both alloys. This was correlated with the formation of Ti-rich and/or Ti+Ta-rich oxide particles near the oxide-bond coat interface degrading the adherence of the thermally grown oxide. However, the thickening rate of the oxide had very little or no effect on the relative coating performance. It was concluded that the coating performance is critically dependent on alloy substrate composition particularly the concentration of elements, which could have adverse effects on oxidation resistance such as Ti.     

Thermal cycling behaviour of thermal barrier coating systems based on first- and fourthgeneration Ni-based superalloys

Abstract

This study deals with the cyclic oxidation behaviour of thermal barrier coating systems. The systems consist of an yttria-stabilised zircona ceramic top coat deposited by EB-PVD, a β-(Ni,Pt)Al bond coat and a Ni-based superalloy. Two different superalloys are studied: a first-generation one and a fourthgeneration one containing Re, Ru and Hf. The aim of this work is to characterise the microstructural evolution of those systems and to correlate it to their resistance to spallation. Thermal cycling is carried out at 1100°C in laboratory air, with the number of cycles ranging between 10 and 1000. Each cycle consists of a 1 h dwell followed by forced-air cooling for 15 min down to room temperature. Among the main results of this work, it is shown that the MCNG-based system is significantly more resistant to spallation than the AM1-based one. Up to 50 cycles, both systems exhibit similar oxidation rate and phase transformations but major differences are observed after long-term ageing. In particular, a Ru-rich β-phase is formed in the bond coat of the MCNG-based system while the AM1- based one undergoes strong rumpling of the TGO/bond coat interface due to the loss of the thermal barrier coating.     

Comparative performance of selected bond coats in advanced thermal barrier coating systems

An investigation was carried out to determine the comparative performance of selected bond coats representing the diffusion aluminides and overlays in thermal barrier coating systems. Emphasis was placed upon oxidation behavior, thermal stability, and failure mechanism. Isothermal oxidation tests were carried out attemperatures in the range of 1000 °C to 1150 °C. Scanning electron microscopy combined with energy dispersive x-ray spectroscopy, x-ray diffraction, and transmission electron microscopy were used to characterize the coating microstructure. Among the bond coats examined, overlays exhibited the best performance followed by Pt-aluminides and simple alunimides for a given alloy substrate. However, for all types of bond coats, failure of the coating system occurred by decohesion of the oxide scale at the oxide-bond coat interface. All bond coats examined were found to be degraded by oxidation and interdiffusion with the alloy substrate permitting the formation of non-protective oxide scale near the bond coat surface. Platinum as well as active elements such as Hf and Y were identified as key elements in improving the performance of thermal barrier coating systems.     

Einfluss einer PVD‐Al‐Zwischenschicht auf die Eigenschaften eines thermisch gespritzten Wärmedämmschichtsystems nach Temperaturwechselbelastung

Thermal barrier coatings (TBC) generally consist of a metallic bond coat (BC) and a ceramic top coat (TC). Co–Ni–Cr–Al–Y metallic super alloys and Yttria stabilised zirconia (YSZ) have been widely used as bond coat and top coat for thermal barrier coatings systems, respectively. As a result of long‐term exposure of thermal barrier coatings systems to oxygen‐containing atmospheres at high temperatures, a diffusion of oxygen through the porous ceramic layer occurs and consequently an oxidation zone is formed in the interface between ceramic top coat and metallic bond coat. Alloying components of the BC layer create a so‐called thermally grown oxides layer (TGO). One included oxide type is α‐Al₂O₃. α‐Al₂O₃ lowers oxygen diffusion and thus slows down the oxidation process of the bond coat and consequently affects the service life of the coating system positively. The distribution of the alloying elements in the bond coat layer, however, generally causes the formation of mixed oxide phases. The different oxide phases have different growth rates, which cause local stresses, micro‐cracking and, finally, delamination and failure of the ceramic top coat layer. In the present study, a thin Al inter‐layer was deposited by DC‐Magnetron Sputtering on top of the Co–Ni–Cr–Al–Y metallic bond coat, followed by thermal spraying of yttria‐stabilised zirconia (YSZ) as a top coat layer. The deposited Al inter‐layer is meant to transform under operating conditions into a closed layer with high share of α‐Al₂O₃ that slows down the growth rate of the resulting thermally grown oxides layer. Surface morphology and microstructure characteristics as well as thermal cycling behaviour were investigated to study the effect of the intermediate Al layer on the oxidation of the bond coat compared to standard system. The system with Al inter‐layer shows a smaller thermally grown oxides layer thickness compared to standard system after thermal cycling under same conditions.     

Effect of platinum on the oxide-to-metal adhesion in thermal barrier coating systems

An investigation was conducted to determine the role of Pt in a thermal barrier coating system deposited on a nickel-base superalloy. Three coating systems were included in the study using a layer of yttria-stabilized zirconia as a model top coat, and simple aluminide, Pt-aluminide, and Pt bond coats. Thermal exposure tests at 1,150 °C with a 24-h cycling period to room temperature were used to compare the coating performance. Additional exposure tests at 1,000, 1,050, and 1,100 °C were conducted to study the kinetics of interdiffusion. Microstructural features were characterized by scanning electron microscopy and transmission electron microscopy combined with energy dispersive X-ray spectroscopy as well as X-ray diffraction. Wavelength dispersive spectroscopy was also used to qualitatively distinguish among various refractory transition metals. Particular emphasis was placed upon: (i) thermal stability of the bond coats, (ii) thickening rate of the thermally grown oxide, and (iii) failure mechanism of the coating. Experimental results indicated that Pt acts as a “cleanser” of the oxide-bond coat interface by decelerating the kinetics of interdiffusion between the bond coat and superalloy substrate. This was found to promote selective oxidation of Al resulting in a purer Al₂O₃ scale of a slower growth rate increasing its effectiveness as “glue” holding the ceramic top coat to the underlying metallic substrate. However, the exact effect of Pt was found to be a function of the state of its presence within the outermost coating layer. Among the bond coats included in the study, a surface layer of Pt-rich γ′-phase (L1₂ superlattice) was found to provide longer coating life in comparison with a mixture of PtAl₂ and β-phase.     

An oxidation study of an MCrAlY overlay coating

Abstract

Metallic overlay coatings of the MCrAlY type (where M is Ni, Co or a combination of both) are regularly used in high-temperature plant to provide resistance to oxidation and high-temperature corrosion through the formation of a protective surface layer of alumina. Such coatings are also frequently used as a bond coat in thermal barrier coating systems. For both applications, the endurance of the coating system depends on the maintenance of the protective alumina layer. In particular, a high resistance to spallation is required and also a sufficient reservoir of aluminium within the coating so that re-healing of the alumina layer will occur should spallation occur.

In this paper the results of a study into the oxidation behaviour of an LPPS MCrAlY coating on a CM186LC alloy are presented. During the study extensive TGO thickness measurements were made at varying times at 1100°C from which the oxidation kinetics have been calculated up to the point where extensive spallation occurred. Over the time range where partial spallation of the TGO occurred, between 50 to 100 h, a duplex structure in the oxide scale was revealed. Micrographs and analyses of the oxide are presented and the two values of TGO thickness at this time at temperature are shown and discussed in terms of the early oxidation kinetics.     

The effect of superalloy substrate on the behaviour of high-purity low-density air plasma sprayed thermal barrier coatings

Abstract

Several superalloy-bond coat couples were prepared without ceramic topcoat layers to better understand the effects of superalloy substrate on the oxidation behaviour of NiCoCrAlY bond coats. The same composition NiCoCrAlY bond coats were deposited on three superalloy substrates (Inconel 718, Haynes 188 and Rene’ N5) via argon-shrouded plasma spraying. The specimens were exposed to cyclic oxidation in laboratory air at 1100°C in a bottom loading furnace. Scaling behaviour and rate of aluminum depletion were compared between the various specimens. The bond coats on all three superalloys experienced some form of chemical failure after an extended number of cycles. The number of cycles until chemical failure was shortest for the IN718 specimen followed by the HA188 specimen, both of which experienced complete bond coat chemical failure, and then the Rene’ N5 specimen, which experienced localized chemical failure. The cycles to chemical failure coincide with the cycles to thermal barrier coating (TBC) spallation from previous work, indicating chemical failure of the bond coat is a critical event in the lifetime of TBCs. The effect of bond coat surface finish and porosity on the scaling behaviour has been investigated using specimens with the same superalloy substrate but with different bond coat surface finishes and porosity levels which were produced by utilizing two separate sized starting bond coat metallic powders. Bond coats with minimal porosity and smooth surface finishes did not experience chemical failure, at least in the time frame they were tested; however, oxide scale spallation was more apparent in the smooth bond coats as compared to the specimens with the rough surface finishes and high levels of porosity.     

Evaluation of mixed oxide formation and sintering behavior in thermal barrier coatings on nickel‐based superalloy

Thermal barrier coatings are widely used in aircraft turbines to protect nickel‐based superalloys from the effect of high temperature oxidation and hot corrosion. In this study, both NiCrAlY bond coat and yttria‐stabilized zirconia top coat were deposited using atmospheric plasma spray technique. After coating production, specimens were exposed to oxidation in air atmosphere at 900 °C, 1000 °C and 1100 °C for different periods of time up to 50 h. Microstructural transformations in the ceramic top coat and growth behavior of the thermally grown oxide layer were examined using scanning electron microscopy, porosity calculation, elemental mapping and hardness measurement. Formation of different types of oxides in the thermally grown oxide layer shows that this process strongly depends on deposition technique as well as on oxidation time and temperature. Hardness values of the top coat increased with a decrease in the porosity of the top coat. Uniformity and homogeneity of the thermally grown oxide layer and densification of the top coat were evaluated in terms of the structural durability of thermal barrier coating systems.     

Microstructural changes to metal bond coatings on gas turbine alloys with time at high temperature

Complex coating systems are required to protect nickel-based super alloys from high temperature oxidation and corrosion. Industrial gas turbine blades and heat shields are generally plasma sprayed with a metal bond coating containing nickel, chromium, cobalt, aluminium and yttrium, and then an external thermal barrier coating of yttria-stabilised zirconia is applied. In this study, samples of an IN939 alloy heat shield with both a metal bond coat and a ceramic thermal barrier coating have been heated in air at high temperature for up to 2000 hours to assess the long term stability of the metal bond coat. Polished sections of the heat treated samples were examined by SEM and EDX to determine microstructural changes. The Ni-Cr-Co-Al-Y coating was found to be a very effective barrier against oxidation; the only apparent oxidation being the growth of an alumina layer between the bond coat and ceramic thermal barrier coating. With time, the growth of the Ni₃Al phase in the metallic bond coat was observed, with extensive diffusion of other elements to and from the bond coat.     

圆柱基体热障涂层热冲击下失效的瞬态应力分析

用等离子喷涂方法在合金圆柱体上制备了热障涂层,并用水冷的方法进行了热冲击实验,试样的失效现象为轴向的开裂和剥落.利用有限元分析工具对热障涂层的热冲击进行模拟,通过对涂层内部应力随时间分布的分析发现:热冲击过程中陶瓷层表面的周向应力随着时间由拉转变为压,冷却初期陶瓷层的周向拉应力值较大,超过了陶瓷层的抗拉强度,因而淬冷初期的周向应力是导致轴向裂纹萌发的主要原因;陶瓷层与粘结层接触面上的径向拉应力与粘结层的氧化生长引起界面开裂;轴向裂纹和界面开裂共同导致陶瓷层的剥落.     

Creep effects on early damage initiation in a TBC system

High temperature superalloys coated with thermal barrier coating (TBC) may induce creep effects in different layers such as in the bond coat and the thermally grown oxide (TGO) layer. The effects of creep deformation in these layers were investigated on the magnitude of residual stresses in these layers. Results indicated that the residual stress after creep was considerably higher when compared with the stress without creep. This larger value of stresses is likely to enhance the initiation of microcracks and debonding of the TBC leading to spallation.     

Determining a critical strain for APS thermal barrier coatings under service relevant loading conditions

Despite the huge progress made in recent years in analysing the degradation behavior and the reliability of thermal barrier coating systems, there is still some deficit in the capability to predict damage evolution in terms of crack initiation and crack growth, which ultimately leads to macroscopic delamination and spallation of the coating system. In order to obtain this prediction capability, a fundamental understanding of the damage evolution processes under isothermal, thermo-cyclic and under thermo-mechanical loading conditions has to be developed.The aim of the presented work is to determine the critical strain, i.e. the strain at which cracking initiates, and to analyse the evolution of a network of cracks for widely used atmospheric plasma sprayed (APS) thermal barrier coating (TBC) systems. The TBC system has been exposed in our study to service relevant loading conditions, namely to thermal gradient mechanical fatigue (TGMF). TGMF tests for in-phase as well as out-of-phase loading cycles were performed on hollow cylindrical specimens made of the single crystal super alloy CMSX-4, loaded mechanically in 〈0 0 1〉 orientation, and being coated with a duplex system comprised of a CoNiCrAlY bond coat and a 8 wt.% Yttria partially stabilized Zirconia (YSZ) TBC. The CoNiCrAlY bond coat was deposited by Low Pressure Plasma Spraying (LPPS), while the ceramic top coat was deposited using the APS process. The loading cycles were chosen to represent an industrial gas turbine engine. Critical strains measured for delamination (within the ceramic coating or at the CoNiCrAlY – TBC interface) and through cracking, i.e. segmentation of the ceramic top coat was determined using a special compression test equipped with in situ acoustic emission technique. The mechanical testing was performed at room temperature after TGMF exposure. In order to study the impact of thermally grown oxide (TGO), specimens have been TGMF tested in the “as received” conditions as well as after isothermal aging (up to 3000 h at 1000 °C). To correlate the signal obtained by acoustic emission (AE) with the evolution of (micro-) cracks, the specimens have been carefully sectioned and investigated by standard metallographic means.The measured critical strains are used as a data basis for a strain-based lifetime model developed for isothermal and cyclic oxidation as well as thermo-mechanical loading. The lifetime model considers two failure modes, namely delamination and (vertical) through cracking.Metallographically obtained crack patterns within the TBC system have been incorporated into finite element models to quantify stress–relaxation as a consequence of damage evolution in the TBC system.The observations show that thermal gradient fatigue loading under in-phase loading leads to a shorter lifetime compared to out-of-phase loading.For the delamination mode, the critical strain values of the model are in good agreement with the experimental data of the TGMF experiments. The modeled critical strain for through cracking, on the other hand, is consistently lower than the experimentally determined failure strains, implying that the model describes the failure situation in a conservative manner.     

Crack propagation studies and bond coat properties in thermal barrier coatings under bending

Ceramic based thermal barrier coatings (TBC) are currently considered as a candidate material for advanced stationary gas turbine components. Crack propagation studies under bending are described that were performed on plasma sprayed ZrO₂, bonded by MCrAlY layer to Ni base superalloy. The crack propagation behaviour of the coatings at room temperature in as received and oxidized conditions revealed a linear growth of the cracks on the coating till the yield point of the super alloy was reached. High threshold load at the interface between the ceramic layer and the bond coat was required to propagate the crack further into the bond coat. Once the threshold load was surpassed the crack propagated into the brittle bond coat without an appreciable increase in the load. At temperatures of 800°C the crack propagated only in the TBC (ceramic layer), as the ductile bond coat offered an attractive sink for the stress relaxation. Effects of bond coat oxidation on crack propagation in the interface region have been examined and are discussed.     

Formation of diffusion cells in LPPS MCrAlY coatings

Abstract

The formation of diffusionally isolated regions in air plasma-sprayed, APS, MCrAlY bond coat or overlay coatings has been established. The ‘diffusion cells’ experience greatly accelerated depletion of aluminium and an early onset of breakaway oxidation associated with the morphology and extent of the internal oxides. In this paper the effect of internal oxides produced in low pressure plasma sprayed, LPPS, CoNiCrAlY coatings are presented. Isothermal tests in laboratory air at 1200°C were conducted with post-test characterisation performed using scanning electron microscopy and energy dispersive X-ray analysis. A parabolic correlation was found between TGO growth rate and time at temperature. Importantly, compositional profiles of cross sections through the coatings demonstrated that no barriers to diffusion occurred throughout the body of the coating. What has been found in the LPPS coatings is a mechanism whereby diffusion cell formation is possible at sites where splat boundaries containing internal oxides intersect the outer surface. Gas access is possible at these sites and, with increasing time at temperature, formation of a continuous internal oxide layer forms. The sequence of events at these sites follows that of the diffusion cell model presented earlier and a prediction of time to failure is made.     

Correlation of processing technique and microstructure of platinum aluminide bond coats with performance of thermal barrier coatings deposited on nickel base superalloy

Abstract

We show that the performance of thermal barrier coating systems is critically dependent upon the processing technique and microstructure of platinum aluminides utilised as bond coats. It is demonstrated by thermal exposure tests at 1150°C in air with 24 h cycling period to room temperature that the average useful life of a coating system employing zirconia–7 wt-% yttria as top coat and alloy MAR M002DS as substrate is increased from 192 to 480 h by replacing a three-layer bond coat aluminised by conventional pack cementation with a two-layer bond coat aluminised by chemical vapour deposition. Before each aluminising process, the superalloy has been electroplated with a platinum layer about 7 μm in thickness. Microstructural characterisation using scanning electron microscopy combined with energy dispersive X-ray spectroscopy, electron-probe microanalysis, transmission electron microscopy and X-ray diffraction indicates that the superior performance provided by the two-layer bond coat is related to its higher thermal stability enhancing the adhesion of the thermally grown oxide. However, both coating systems are found to fail by the same mechanism involving loss of adhesion between the thermally grown oxide and bond coat.     

Microstructure and thermal behaviour of plasma sprayed zirconia/alumina composite coating

In thermal barrier coatings (TBC), failure occurs near or at the interface between the metallic bondcoat and topcoat. On high temperature conditions, an oxide scale which is named thermally grown oxide (TGO) occurs along the bond/topcoat interface. For diminishing the creation of TGO, a dense coating with low residual stress and thermal stress buffer layer was preferable. High hardness ceramic coatings could be obtained by gas tunnel type plasma spraying, and the deposited coating had superior property in comparison with those deposited by conventional type plasma spray method. In this study, the gas tunnel type plasma spraying system was utilized to produce a zirconia/alumina functionally graded thermal barrier coating and discussed its physical and mechanical properties, thermal behavior and high temperature oxidation resistance of the coating are discussed. Consequently, the proposed system exhibited superior mechanical properties and oxidation resistance at the expenses of a slightly lower thermal insulating effect. This interlayer is preferred in order to minimize the detrimental effect of the phase transformation of gamma-Al2O3 to alpha-Al2O3.