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.     

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.     

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.     

Investigation on Failure in Thermal Barrier Coatings on Gas Turbine First-Stage Rotor Blade

Failure in turbine blades can affect the safety and performance of the gas turbine engine. Results of coating decohesion, erosion and cracking at the first-stage high-pressure (HPT) blade working in gas turbine engine are being reported in this paper. This investigation was carried out for the possibility of various failure mechanisms in the thermal barrier coating exposed to high operating temperature. The blade was made of nickel-based superalloy, having directionally solidified grain structure coated with thermal barrier coatings of yttria-stabilized zirconia with EB-PVD process and platinum-modified aluminum (Pt–Al) bond coat with electro-deposition. The starting point of analysis was apparent coating decohesion close to the leading edge on the suction side of blade. The coating decohesion was found to be widening of interdiffusion zone toward the bond coat at higher operating temperature which could change the composition and induce thermal stresses in the bond coat. The erosion, cracking and decohesion of the coating on the pressure side was also observed during failure investigation. The erosion of the coating was coupled by two factors: one by increase in temperature as demonstrated by change in microstructure of the substrate and second by increase in coating inclination toward the trailing side. As a result of high operating temperature, swelling and thickening of TGO was observed due to outward diffusion of aluminum from the bond coat to form alumina (non-protective oxide) which causes internal stresses that leads to top coat decohesion and cracking. The possibility of hot corrosion was also investigated, and it was found that top coat decohesion did not involve this failure mechanism. Visual inspection, optical microscopy, scanning electron microscopy and energy-dispersive spectroscopy have been used as characterization tools.     

Microstructural characterization of the failures of thermal barrier coatings on Ni-base superalloys

Abstract

Typical thermal barrier coating (TBC) systems consist of a nickel-base superalloy substrate coated with a MCrAlY or diffusion aluminide bond coat, onto which is deposited a yttria-stabilized zirconia (YSZ) TBC. The bond coats are usually deposited via diffusion aluminizing processes or low pressure plasma spray processes (LPPS). The YSZ can be deposited by air plasma spraying (APS) or electron beam physical vapor deposition (EBPVD). A layer of thermally-grown oxide (TGO), which is usually alumina, forms between the bond coat and YSZ during TBC deposition and subsequent high-temperature exposure. The conventional wisdom is that APS coatings tend to fail in the YSZ and that EBPVD coatings tend to fail at the interface between the TGO and bond coat. However, current research has shown that the situation is much more complex and that the actual fracture path can be a function of the type of bond coat, the type of high-temperature exposure, and coating process parameters. This paper describes the results of a study of the failure of state-of-the-art EBPVD TBCs deposited on NiCoCrAlY and platinum-modified diffusion aluminide bond coats. The failure times and fracture morphology are described as a function of bond coat type. The failure times were found to be a strong function of temperature for both bond coats. The failure for NiCoCrAlY bond coats was found to initiate at defects in the coating, particularly at the TGO/YSZ interface, but the fracture propagated primarily along the TGO–bond coat interface. The failure times and morphologies for platinum-modified diffusion aluminide bond coats depended strongly on bond coat surface preparation. The mechanisms for failure of the two bond coats are described. Also, the effects of modifications to the bond coats and variations in processing parameters on these mechanisms are presented.     

Anisotropic Thermal Diffusivities of Plasma-Sprayed Thermal Barrier Coatings

Thermal barrier coatings (TBCs) are used to shield the blades of gas turbines from heat and wear. There is a pressing need to evaluate the thermal conductivity of TBCs in the thermal design of advanced gas turbines with high energy efficiency. These TBCs consist of a ceramic-based top coat and a bond coat on a superalloy substrate. Usually, the focus is on the thermal conductivity in the thickness direction of the TBC because heat tends to diffuse from the surface of the top coat to the substrate. However, the in-plane thermal conductivity is also important in the thermal design of gas turbines because the temperature distribution within the turbine cannot be ignored. Accordingly, a method is developed in this study for measuring the in-plane thermal diffusivity of the top coat. Yttria-stabilized zirconia top coats are prepared by thermal spraying under different conditions. The in-plane and cross-plane thermal diffusivities of the top coats are measured by the flash method to investigate the anisotropy of thermal conduction in a TBC. It is found that the in-plane thermal diffusivity is higher than the cross-plane one for each top coat and that the top coats have significantly anisotropic thermal diffusivity. The cross-sectional and in-plane microstructures of the top coats are observed, from which their porosities are evaluated. The thermal diffusivity and its anisotropy are discussed in detail in relation to microstructure and porosity.     

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.     

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.     

Interfacial fracture toughness of APS bond coat/substrate under high temperature

Thermal barrier coating (TBC) is an essential requirement of a modern gas turbine engine. The TBC failure is the delamination and spallation. The failure mechanism is interfacial expansion mismatch and oxidation of bond coat (BC). The oxidation damage under high temperature results in the reduction of interfacial adhesion. The interfacial fracture toughness is an important property to analyze the TBC failure. Using the simple tensile test, pushout test method and three-point or four-point-bending test and so on, the interfacial fracture toughness of ceramic top coat/BC has been researched in the past. However, the fracture toughness of the BC/substrate due to the Al depletion was very few studied. In this study, a NiCrAlY bond coat by air plasma spray (APS) was deposited. The substrate is directionally solidified superalloy (DZ40M). The Young’s modulus of bond coat was obtained by the nanoindentation and average Young’s modulus of bond coat is 66.9 GPa. Isothermal oxidation was performed at 1,050^?C for 100 h. Using the HXZ-1000 micro-hardness equipment and fracture mechanics approach, the five different times was chosen to test the hardness and the crack length, and then the fracture toughness was obtained. While the oxidation exposure time increased at 1,050^?C, the hardness of the substrate close to the bond coat decreased with the increase of the bond coat in hardness. Meanwhile, the interfacial fracture toughness of the bond coat–substrate decreased because of the Al depletion.     

Hot Isostatic Pressing of Plasma Sprayed Thermal Barrier Coating Systems

Thermal barrier coatings (TBC) are important to aerospace and high performance gas turbine engines because they help to keep the temperature experienced by the base metal low; thus, prolonging the life span of the material. Plasma spraying is a technique commonly used to deposit the ceramic-based TBC. An intermediate layer is applied to enhance the bond between the substrate and the ceramic top coat. However, the oxidation of the bond coat due to the infiltration of gas through the porous ceramic layer is a major problem encountered in TBC. This in turn leads to spalling and eventual destruction of the whole coating system. Hot isostatic pressing (HIP) was performed on a number of plasma sprayed thermal barrier coating systems to investigate the effects the process has on micro structure and other physical properties. Due to the fact that the majority of TBC is exposed to thermal cycling and thermal fatigue, it is hoped that the changes brought about by HIP in the porosity and microstructure will improve the life span and performance of TBC. HIP was performed in the temperature range 750-1300° C and pressures of 50-200 MPa. The bond coats that were studied include Ni-5% Al, Ni-20 percnt; Al, NiCrAl and NiCrAlY, while the ceramic coat was Zr0₂-5 wt percnt; CaO. Characterization of the coatings was carried out using scanning electron microscopy (SEM) and image analyser. The results showed the porosity of the coatings to be dramatically reduced to near zero levels. In addition, the other physical properties like hardness and Young's modulus increased over a wide temperature range.     

EB‐PVD Thermal Barrier Coatings for Aeroengines and Gas Turbines

Ceramic thermal barrier coatings (TBCs) offer the potential to significantly improve efficiencies of aero engines as well as stationary gas turbines for power generation. On internally cooled turbine parts temperature gradients of the order of 100 to 150 °C can be achieved. Today, state‐of‐the‐art TBCs, typically consisting of an yttria‐stabilised zirconia top coat and a metallic bond coat deposited onto a superalloy substrate, are mainly used to extend lifetime. Further efficiency improvements require TBCs being an integral part of the component which, in turn, requires reliable and predictable TBC performance. Presently, TBCs fabricated by electron beam physical vapor deposition are favoured for high performance applications. The paper highlights critical research and development needs for advanced TBC systems, such as reduced thermal conductivity, increased temperature capability, lifetime prediction modelling, process modelling, bond coat oxidation, and hot corrosion resistance as well as improved erosion behaviour.     

On debonding of graded thermal barrier coatings

Thermal barrier coatings generally consist of a metallic substrate which is the primary structural component, a metallic bond coat which serves as oxygen diffusion barrier, a very thin layer of thermally grown oxide and a ceramic top coat that provides the main thermal shielding. Homogeneous ceramic coatings as top coats appear to have certain undesirable features such as high residual and thermal stresses, generally low toughness and relatively poor bonding strength. The new concept of compositional grading of the top coat may help to overcome some of these shortcomings by eliminating the material property discontinuities. A common mode of failure in thermal barrier coatings seems to be the debonding of the top coat. In this study the related interface crack problem for a graded ceramic/metal top coat is considered. It is assumed that the thermophysical properties of the top coat continuously vary between that of the bond coat at the top coat-bond coat interface and that of the ceramic at and near the free surface. The main objective of the study is to examine the influence of the material nonhomogeneity parameters and relative dimensions on the stress intensity factors and the crack opening displacements.     

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.     

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.     

Effects of heat treatment on adhesion strength of thermal barrier coating systems

Thermal barrier coatings (TBCs) are widely used as protective and insulative coatings on hot section components of gas turbines and their applications, like blades and combustion chambers. The quality and performance properties of TBCs are of great importance in terms of their resistance to service conditions. In a TBC system, there is a close relationship between the adhesion properties of coating layers. The adhesion strength of TBCs varies depending on the coating technique used and the surface treatments. In this study, CoNiCrAlY and YSZ (ZrO₂ + Y₂O₃) powders were deposited on stainless steel substrate. High Velocity Oxy-Fuel (HVOF) and Atmospheric Plasma Spraying (APS) techniques were used to produce the bond coats. The ceramic top layers on CoNiCrAlY bond coats were produced by the APS technique. The TBC specimens were subjected to heat-treatment tests. Adhesion strength for top coat/bond coat interface of as-sprayed and heat-treated samples was investigated. The results showed that the heat treatment of the coatings in different temperatures led to an increase in the adhesion strength of TBCs.     

Characterization of alumina interfaces in TBC systems

Interfacial segregants in thermally grown α-Al₂O₃ scales formed during high temperature exposure of thermal barrier coating systems reflect the oxygen-active dopants present in the bond coating and substrate, such as Y and Hf. These dopants diffuse outward and segregate to the substrate-alumina interface and the alumina grain boundaries. Related studies suggest that these segregants affect the growth and mechanical properties of the alumina-scale; however, the characterization of segregation in alumina formed on coated superalloy systems has been limited. Segregation examples evaluated using analytical transmission electron microscopy are given from traditional Pt-modified aluminide coatings and newer Pt diffusion coatings. Model systems are used to illustrate that grain boundary segregants on the columnar alumina boundaries are not because of the reverse diffusion of cations from the Y₂O₃-stabilized ZrO₂ top coating, and that interstitial elements in the substrate likely affect the outward flux of cation dopants. The dynamic nature of this segregation and oxygen-potential gradient-driven diffusion is discussed in light of observations of substrate dopant and interstitial contents affecting coating performance.     

Failure during thermal cycling of plasma-sprayed thermal barrier coatings

The thermal cycling behavior of plasma-sprayed ZrO₂?12wt.%Y₂O₃ coatings was studied. Coatings were produced with and without bond coats of Ni-Cr-Al-Zr and in some cases the substrates were heated to above the optimum temperature prior to spraying. The coatings (attached to the substrate) were thermal cycled to 1200 °C and their cracking behavior was followed by acoustic emission (AE) techniques. It was possible to examine the failure mechanisms by statistical analysis of the AE data and to evaluate the influence of preheating and bond coating. It is shown that the AE spectrum changes when a bond coat is used because of the presence of microcracks which, in turn, dissipate energy and improve the coating integrity. The preheating effect is reflected by a decrease in the peak count rate and an increase in the temperature at which AE activity is initiated.     

Influence of Water Vapor on the Isothermal Oxidation Behavior of Thermal Barrier Coatings

The oxidation of specimens with thermal barrier coating (TBC) consisted of nickel-base superalloy, low-pressure plasma sprayed Ni-28Cr-6AI-0.4Y (wt pct) bond coating and electron beam physical vapor deposited 7.5 wt pct yttria stabilized zirconia (YSZ) top coating was studied at 1050℃ respectively in flows of 02, and mixture of O2 and 5%H2O under atmospheric pressure. The thermal barrier coating has relatively low oxidation rate at 1050℃ in pure O2. Oxidation rate of thermal barrier coating in the atmosphere of O% and 5%H2O is increased The oxidation kinetics obeys almost linear law after long exposure time in the presence of 5% water vapor. Oxide formed along the interface between bond coat and top coat after oxidation at 1050℃ in pure O2 consisted of Al2O3, whereas interfacial scales formed after oxidation at 1050℃ in a mixture of O2 and 5%H2O were mainly composed of Ni(AI,Cr)2O4,NiO and AI2O3. It is suggested that the effect of water vapor on the oxidation of the NiCrAlY coating may be attributed     

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.     

Observations of the spallation modes in an overlay coating and the corresponding thermal barrier coating system

Abstract

The oxidation dynamics of an overlay coating and the corresponding thermal barrier coating system are presented. The particular systems examined are composed of a nickel-based superalloy with an air plasma-sprayed NiCrAlY bond coat and the thermal barrier coating system consists of air plasmasprayed yttria stabilized zirconia layer. Failure can occur in these systems by crack propagation within the ceramic outer layer at the interface with the bond coat. Defects, such as microcracks and pores, are common in plasma-sprayed coatings and within the thermally grown oxide scales. These can act as initiation sites for cracks. The subsequent growth of these cracks can lead to loss of the outer protective materials. Considerable information is available by microscopic examination of sections through test specimens that have been held at temperature for varying amounts of time. By careful sample preparation it is possible to monitor the development of the oxide scale formed during high temperature testing and the sites of failure. Identification of the initiation sites and growth of cracks is important in understanding the spallation process. In this study, scanning electron microscopy is used to provide evidence of the processes involved in the two systems. A comparison of the two coating systems reveals the effect the outer ceramic layer has on the oxide scale growth, and the spallation processes crucial to the understanding of the failure mechanisms of these coating systems.