Bond coats used in thermal barrier coatings (TBCs) for gas-turbine engine applications are studied in this thesis, with a focus on oxidation behaviour, surface rumpling and stress evolution. Bond coats made of γ/γ’ Ni-Al-Pt alloys have been widely used in TBCs and it has been found that addition of platinum greatly improves the oxidation resistance of the coatings. The mechanisms behind this benefit, however, are not well understood. For this reason, the oxidation behaviour of four γ/γ’ Ni-20Al-xPt (x= 0, 5, 10 and 15 at. %) alloys at 1150 °C is studied and compared in terms of oxide spallation, oxide microstructure and growth, residual stress in the oxide scale and oxide/alloy interface morphology. The progressive increase of platinum addition into the alloys results in (1) greater resistance to oxide spallation, (2) reduction in oxidation of nickel, (3) lower stresses in the α-Al2O3 scale and (4) more planar oxide/alloy interfaces. It is found that the selective oxidation of aluminium promoted by platinum plays a central role in the evolution of the oxidation behaviour of the alloys. Surface rumpling of a NiCoCrAlY bond coat deposited on a Ni-base superalloy during cyclic oxidation at 1150 °C is studied. The extent of rumpling is found to depend on thermal history, coating thickness and exposure atmosphere. While the coating surface progressively roughens with cyclic oxidation, bulk NiCoCrAlY alloys with the same nominal composition show a much less tendency to rumple under the same thermal cycling condition. The coatings, especially the thin ones, experience substantial degradation (e.g. β to γ phase transformation and exhaustion of yttrium) induced by oxidation and coating/substrate interdiffusion during thermal exposure. The observations together suggest that rumpling is driven by the lateral growth of the thermally grown oxide (TGO) and the coating deforms in compliance with the TGO. While the dependence of rumpling development on experimental conditions is generally in agreement with the prediction of the existing model, it is suggested that the degradation of the NiCoCrAlY coating and its dependence on coating thickness need to be taken into consideration when predicting the rumpling development of NiCoCrAlY coatings. The residual stresses in a NiCoCrAlY bond coat deposited on a Ni-base superalloy are studied by X-ray diffraction using the sin2Ψ technique. The stresses at room temperature are found to be tensile; they first increase and then decrease with oxidation time. The stress develops and builds up upon cooling, predominantly within the temperature range from 1150 °C to 600 °C. Due to the limited penetration depth into the bond coat, the X-ray only probes the stress in a thin surface layer consisting of a single γ-phase formed through aluminium depletion during oxidation. Above 600 °C, the volume fraction of the β-phase in the bond coat increases with decreasing temperature. The mechanisms of stress generation in the coating are examined and discussed based on experiments designed to isolate the contribution of possible stress generation factors. It is found that the measured bond coat stresses are mainly induced by the volume change of the bond coat associated with the precipitation of the β-phase upon cooling.

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Residual stresses are generally considered to be the driving forces for the failure of APS TBCs. In this thesis, the residual stress distribution as a function of depth in APS TBC has been measured by synchrotron XRD and explained by image based modelling based on the microstructure detailed studied by SEM and CT. The residual stress/ strain distribution as a function of depth was measured by synchrotron XRD in transmission and reflection geometry. The residual stress/ strain values were analysed using full pattern Rietveld refinement, the sin square psi method and XRD2 method. For the reflection geometry, a new method was developed to deconvolute the residual stress value in each depth from the measured averaged values. Two types of residual stress/strain distribution were observed. The first kind of residual stress was found to be compressive and followed a non-linear trend, which increased from the surface to the interface, decreased slightly and increased again to the interface. This trend showed a jump feature near the interface. The second kind of residual stress distribution possessed two jump features: one near the interface similar to the first kind and another jump feature near the sample surface. The residual stress in both beta and gama phase in the bond coat were also investigated which showed a tensile stress state. The stress trend predicted by our analytical model followed a linear relationship. Comparing this with the first kind of residual stress distribution, two main differences were shown. Firstly the jump feature near the interface and secondly the much larger overall stress gradient. The 3D and 2D microstructure of the sample with the first kind of residual stress distribution was observed by X-ray CT and SEM. The effect of pores, inter-splat cracks and the rumpling interface on the residual stress distribution was investigated by image based modelling. It was proved that the pores and the inter-splat cracks had no large influence on the stress distribution and the jump feature near the interface was a result of the rumpling interface. The much larger stress gradient observed in the measured residual stress distribution was an indication of the stress relaxation in the coating which was proved by a specially designed mechanical test. To explain the jump feature near the sample surface in the second kind of stress distribution. 3D microstructures of the measured samples were observed using X-ray CT. The effect of vertical and the side cracks on the stress distribution were investigated by image based modelling. It was found that the vertical crack had no large influence on the residual stress distribution and the jump feature in the stress trend near the surface could be attributed to the side crack. The effect of other kinds of cracks that were not directly observed in our samples, such as middle or through side cracks, were also investigated. These results were used to develop a semi-destructive method to determine the existence and distribution of cracks in APS TBC.

The aim of this thesis is to investigate the effects of additives, reactive elements and impurities, on the lifetime of thermal barrier coatings. The thesis consists of a number of studies on interface adhesion, impurity diffusion, grain boundary sliding and cleavage processes and their impact on the mechanical behaviour of grain boundaries. The effects of additives and impurity on interface adhesion were elaborated by using total energy calculations, electron localization and density of states, and by looking into the atomic separations. The results of these calculations allow the assessment of atomic level contributions to changes in the adhesive trend. Formation of new bonds across the interface is determined to improve the adhesion in reactive element(RE)-doped structures. Breaking of the cross interface bonds and sulfur(S)-oxygen(O) repulsion is found responsible for the decreased adhesion after S segregation. Interstitial and vacancy mediated S diffusion and the effects of Hf and Pt on the diffusion rate of S in bulk NiAl are studied. Hf is shown to reduce the diffusion rate, and the preferred diffusion mechanism of S and the influence of Pt are revealed to be temperature dependent. Finally, the effects of reactive elements on alumina grain boundary strength are studied. Reactive elements are shown to improve both the sliding and cleavage resistance, and the analysis of atomic separations suggest an increased ductility after the addition of quadrivalent Hf and Zr to the alumina grain boundaries.

Yttria Partially Stabilized Zirconia (Y-PSZ) plasma-sprayed coatings are widely used in turbine engines as thermal barrier coatings. However, in diesel engines Y-PSZ TBCs have not met with wide success. To reach the desirable temperature of 850-900˚C in the combustion chamber from the current temperature of 400-600˚C, a coating with a thickness of approximately 1mm is required. This introduces different considerations than in the case of turbine blade coatings, which are on the order of 100µm thick. Of the many factors affecting the durability and failure mechanism of TBCs, in service and residual stresses play an especially important role as the thickness of the coating increases. For decreasing the residual stress in the system, a multi-layer coating is helpful. The design of a multilayer coating employing relatively low cost materials with complementary thermal properties is described. Numerical models were used to describe the residual stress after deposition and under operating conditions for a multilayer coating that exhibited the desired temperature gradient. Results showed that the multilayer coating had a lower maximum stress under service conditions than a conventional Y-PSZ coating. Model validation with experiments showed a good match between the two.

The effects on heat transfer of piston crown surface finish and use of a metal based thermal barrier coating (TBC) on the piston crown were studied in an SI engine. Measured engine parameters such as power, fuel consumption, emissions and cylinder pressure were used to identify the effects of the coating and its surface finish. Two piston coatings were tested: a baseline copper coating and a metal TBC. Reducing surface roughness of both coatings increased in-cylinder temperature and pressure as a result of reduced heat transfer through the piston crown. These increases resulted in small improvements in both power and fuel consumption, while also having measurable effect on emissions. Oxides of nitrogen emissions were increased while total hydrocarbon emissions were decreased. Improvements attributed to the TBC were found to be small, but statistically significant. At an equivalent surface finish, the TBC performed better than the baseline copper finish.

The effects on heat transfer of piston crown surface finish and use of a metal based thermal barrier coating (TBC) on the piston crown were studied in an SI engine. Measured engine parameters such as power, fuel consumption, emissions and cylinder pressure were used to identify the effects of the coating and its surface finish. Two piston coatings were tested: a baseline copper coating and a metal TBC. Reducing surface roughness of both coatings increased in-cylinder temperature and pressure as a result of reduced heat transfer through the piston crown. These increases resulted in small improvements in both power and fuel consumption, while also having measurable effect on emissions. Oxides of nitrogen emissions were increased while total hydrocarbon emissions were decreased. Improvements attributed to the TBC were found to be small, but statistically significant. At an equivalent surface finish, the TBC performed better than the baseline copper finish.

Yttria Partially Stabilized Zirconia (Y-PSZ) plasma-sprayed coatings are widely used in turbine engines as thermal barrier coatings. However, in diesel engines Y-PSZ TBCs have not met with wide success. To reach the desirable temperature of 850-900˚C in the combustion chamber from the current temperature of 400-600˚C, a coating with a thickness of approximately 1mm is required. This introduces different considerations than in the case of turbine blade coatings, which are on the order of 100µm thick. Of the many factors affecting the durability and failure mechanism of TBCs, in service and residual stresses play an especially important role as the thickness of the coating increases. For decreasing the residual stress in the system, a multi-layer coating is helpful. The design of a multilayer coating employing relatively low cost materials with complementary thermal properties is described. Numerical models were used to describe the residual stress after deposition and under operating conditions for a multilayer coating that exhibited the desired temperature gradient. Results showed that the multilayer coating had a lower maximum stress under service conditions than a conventional Y-PSZ coating. Model validation with experiments showed a good match between the two.

The aim of this thesis is to investigate the effects of additives, reactive elements and impurities, on the lifetime of thermal barrier coatings. The thesis consists of a number of studies on interface adhesion, impurity diffusion, grain boundary sliding and cleavage processes and their impact on the mechanical behaviour of grain boundaries. The effects of additives and impurity on interface adhesion were elaborated by using total energy calculations, electron localization and density of states, and by looking into the atomic separations. The results of these calculations allow the assessment of atomic level contributions to changes in the adhesive trend. Formation of new bonds across the interface is determined to improve the adhesion in reactive element(RE)-doped structures. Breaking of the cross interface bonds and sulfur(S)-oxygen(O) repulsion is found responsible for the decreased adhesion after S segregation. Interstitial and vacancy mediated S diffusion and the effects of Hf and Pt on the diffusion rate of S in bulk NiAl are studied. Hf is shown to reduce the diffusion rate, and the preferred diffusion mechanism of S and the influence of Pt are revealed to be temperature dependent. Finally, the effects of reactive elements on alumina grain boundary strength are studied. Reactive elements are shown to improve both the sliding and cleavage resistance, and the analysis of atomic separations suggest an increased ductility after the addition of quadrivalent Hf and Zr to the alumina grain boundaries.

The aim of this thesis is to investigate the effects of additives, reactive elements and impurities, on the lifetime of thermal barrier coatings. The thesis consists of a number of studies on interface adhesion, impurity diffusion, grain boundary sliding and cleavage processes and their impact on the mechanical behaviour of grain boundaries. The effects of additives and impurity on interface adhesion were elaborated by using total energy calculations, electron localization and density of states, and by looking into the atomic separations. The results of these calculations allow the assessment of atomic level contributions to changes in the adhesive trend. Formation of new bonds across the interface is determined to improve the adhesion in reactive element(RE)-doped structures. Breaking of the cross interface bonds and sulfur(S)-oxygen(O) repulsion is found responsible for the decreased adhesion after S segregation. Interstitial and vacancy mediated S diffusion and the effects of Hf and Pt on the diffusion rate of S in bulk NiAl are studied. Hf is shown to reduce the diffusion rate, and the preferred diffusion mechanism of S and the influence of Pt are revealed to be temperature dependent. Finally, the effects of reactive elements on alumina grain boundary strength are studied. Reactive elements are shown to improve both the sliding and cleavage resistance, and the analysis of atomic separations suggest an increased ductility after the addition of quadrivalent Hf and Zr to the alumina grain boundaries.