The dissertation is split into two parts. The first part will be focused on changes in material properties found at the nanoscale, as miscibility and electronic structure can change significantly with size. The formation of classically-immiscible bimetallic nanoparticles (BNPs) becomes favorable at the nanoscale and novel catalytic properties can emerge from the bimetallic alloying. The formation of alloyed and non-alloyed BNPs is achieved through pulse laser ablation (PLA) and a significant increase in catalytic activity is observed for both. Recently discovered, the increased activity in the non-alloyed BNPs, deemed multicomponent photocatalysis, is examined and the proposed mechanism discussed. The second part of the talk will focus on thermal barrier coatings (TBCs), which are advanced, multi-layered coatings used to protect materials in high temperature environments. MCrAlY (M=Ni, Co) bond coats deposited via atmospheric plasma spray (APS) are intrinsically rough and initially the roughness provides a high surface area platform for the mechanical interlocking of the yttria stabilized zirconia (YSZ) top coat, which provides the bulk of the thermal insulation. After high temperature exposure, a protective oxide scale forms at the top coat/bond coat interface however the convex asperities of the bond coat can grow non-α-Al2O3 type oxides that can be detrimental for coating lifetime. A surface modification technique that removes the asperities while leaving intact the concavities is used to examine the role that roughness distribution has on 1100°C APS coating lifetime. Lastly, recent work validating a modelling strategy for evaluating 900°C TBC lifetimes, which can typically surpass 25 kh, is presented. Differences in coating-substrate interdiffusion behavior over 5-20 kh of 900°C exposure are discussed and reproduced with Thermo- Calc/DICTRA for three superalloys (1483, 247, X4) deposited with high velocity oxy fuel (HVOF) NiCoCrAlY coatings.

Thermal barrier coatings (TBCs) thermally insulate the substrate from high temperature exposure. This work attempted to simulate real engine thermal cyclic conditions by designing a test method to evaluate the thermal cyclic fatigue (TCF) performance of different coatings applied inside exhaust manifold of a diesel engine. The coatings investigated in this work comprised of two plasmas-sprayed TBCs (conventional 8YSZ and nanostructured 8YSZ) and one bond coat (NiCoCrAlY). Additionally, these coatings were exposed to isothermal testing and their oxidation behavior was evaluated.   All the coatings along with only substrate were exposed to temperature around 525°C for 150 cycles in thermal cyclic testing carried out on Scania’s heavy-duty diesel engine. For isothermal testing, all coatings along with only substrate material were exposed to 650°C and 750°C for 168 hours respectively. Microstructural analysis by SEM/EDS was carried out to compare the microstructural evolution of the tested coatings with the as sprayed TBCs. In the case of thermal cyclic test, all coatings showed no failure and no TGO growth up to 150 cycles. In the EDS analysis for isothermally tested coatings, oxidation of the substrate at bond coat- substrate interface instead of TGO growth was observed. Bond coat showed lowest oxide layer thickness at 650°C and 750°C followed by conventional YSZ and then nanostructured YSZ. But, conventional YSZ showed microcracks in top coat near top coat- bond coat interface after isothermal testing. Thermal cyclic and isothermal exposure test results showed that bond coated substrate and nanostructured YSZ have the potential to be implemented inside the real manifold.

Electrophoretic deposition (EPD) has been used to produce the yttria-stabilized zirconia (YSZ) coatings on metal substrates. Sintering of YSZ with and without doping has been carried out at 1150 °C for 2hrs. The properties of these coatings have been examined in light of thermal barrier applications. For EPD, the green density increases with an initial increase in the HCl concentration and the EPD time. This suggests that particle packing was influenced by a time dependent re-arrangement, in addition to the initial suspension dispersion state. The green density peaks at a electrical conductivity of around 10×10-4 S/m achieved by an 0.5 mM HCl addition for the 20 g/l suspensions with the EPD time of around 8 ~10 minute. For sintered coatings, the HCl concentration had a marked effect on the neck size to grain size ratio of the 8 mol% yttria-stabilized zirconia (8YSZ) coatings. The presence of ZrCl4 and ZrOCl2, and a high concentration of oxygen vacancies at the grain boundaries are believed to promote neck growth in the early stage of sintering at 1150 °C. During sintering of 3 mol% and 8 mol% yttria-stabilized zirconia (3YSZ and 8YSZ) at 1150 ºC for 2hrs, the densification rate substantially increased with a small amount of Fe2O3 addition (0.5 mol%) to the 3YSZ/8YSZ deposits. A more pronounced graingrowth was present in the Fe2O3 doped 8YSZ deposits. The increased Zr4+ diffusion coefficient is mainly responsible to the rapid densification rate of the Fe2O3 doped 3YSZ/8YSZ deposits. A small grain growth observed in the Fe2O3 doped 3YSZ deposits is attributed to the Fe3+ segregation at grain boundary. A small amount of CeO2 doping was found to substantially inhibit the densification rate of the doped 3YSZ deposits with a minor grain growth. Fe2O3 doping reduced the thermal conductivities of 3YSZ/8YSZ. It is found that Rayleigh-type phonon scattering due to the mass difference alone is inadequate to explain the thermal conductivity of Fe2O3 doped YSZ systems. The lattice strain effects due to the ionic radius difference could more effectively reduce thermal conductivity of the Fe2O3-doped 3YSZ. A decrease in the growth rate of the TGO scale with the increasing Fe2O3 additions was observed for the oxidized FeCrAlY metal substrates with the Fe2O3-doped 3YSZ coating, which was found to be attributed to the early formation of the stable and dense α-Al2O3 phase due to the presence of Fe3+ ions.

Thesis (MTech (Mechanical Engineering))--Cape Peninsula University of Technology. / For the last few decades, methods to improve the engine efficiency and reduce the fuel consumption of jet engines have received increased attention. One of the solutions is to increase the operating temperature in order to increase the exhaust gas temperature, resulting in an increased engine power. However, this approach can be degrading for some engine parts such as turbine blades, which are required to operate in a very hostile environment (at ≈ 90% of their melting point temperature). Thus, an additional treatment must be carried out to protect these parts from corrosion, oxidation and erosion, as well as to maintain the substrate’s mechanical properties which can be modified by the high temperatures to which these parts are exposed. Coating, as the most known protection method, has been used for the last few decades to protect aircraft engine parts. According to Wolfe and Co-workers [1], 75% of all engine components are now coated. The most promising studies show that the thermal barrier coating (TBC) is the best adapted coating system for these high temperature applications. TBC is defined as a fine layer of material (generally ceramic or metallic material or both) directly deposited on the surface of the part In order to create a separation between the substrate and the environment to reduce the effect of the temperature aggression. However, the application of TBCs on surfaces of components presents a challenge in terms of the consistency of the thickness of the layer. This is due to the nature of the processes used to apply these coatings. It has been found that variations in the coating thickness can affect the thermodynamic performance of turbine blades as well as lead to premature damage due to higher thermal gradients in certain sections of the blade. Thus, it is necessary to optimise the thickness distribution of the coating.

State of the art thermal barrier coatings (TBCs) for gas turbine applications comprise (7 wt.%) yttria partially stabilized zirconia (7YSZ). 7YSZ offers a range of attractive functional properties – low thermal conductivity, high thermal expansion coefficient and high in-plane strain tolerance. However, as turbine entry temperatures are raised, the performance of 7YSZ coatings will be increasingly affected by sintering and environmental contamination, by calcia-magnesia-alumina-silica (CMAS) deposits. The effect of sintering-induced stiffening on the driving force for spallation of plasma-sprayed (PS) TBCs was investigated. Spallation lifetimes of TBC specimens sprayed onto alumina substrates were measured. A simple fracture mechanics approach was employed in order to deduce a value for the strain energy release rate. The critical strain energy release rate was found to be constant, and if this value had been known beforehand, then the rationale presented here could be used for prediction of coating lifetime. The effect of vermiculite (VM) and volcanic ash (VA) contamination on the sintering-induced spallation lifetime of PS TBCs was also investigated. The presence of both VM and VA was found to accelerate the rise in their Young’s modulus with sintering. Spallation results show that coating lifetime may be significantly reduced, even at relative low addition levels, due to the loss of strain tolerance caused by the penetration of glassy deposits. This result gives a clear insight into the role CMAS plays in destabilizing TBCs. Finally, the adhesion characteristics of ingested volcanic ash were studied using a small jet engine. The effects of engine speed and particle size were investigated. Deposition on turbine surfaces was assessed using a borescope. Deposition mainly occurred on the nozzle guide vane and blade platform. A numerical model was used to predict particle acceleration and heating in flight. It was observed that larger particles are more likely to adhere because they have greater inertia, and thus are more likely to impact surfaces. The temperature of the larger particles at the end of its flight was predicted to be below its softening point. However, since the component surface temperatures are expected to be hotter, adhesion of such particles is probable, by softening/melting straight after impact.

Les barrières thermiques (BT) élaborées par projection plasma sous air (APS) sont utilisées par l’industrie aéronautique pour protéger les pièces fixes des parties chaudes des turbines à gaz. Les BT consistent en un système bicouche composé d'une couche de liaison NiCrAlY de 200 µm d'épaisseur et d’un revêtement céramique de ZrO2-8%Y2O3 (YSZ) de 1 mm d'épaisseur, déposés sur le substrat métallique à protéger. Les principaux objectifs de cette thèse sont d’une part de comparer la tenue en oxydation cyclique de deux microstructures de barrières thermiques élaborées par APS et d’autre part de caractériser le comportement mécanique de celles-ci, afin de comprendre et de modéliser les mécanismes d’endommagement de ces dépôts afin d’en améliorer la conception. Tout d’abord, l’élaboration par projection plasma des différentes BT a été réalisée. Pour évaluer les performances de ces BT en termes de durée de vie et identifier les mécanismes d’endommagement, elles ont ensuite été testées en oxydation cyclique sous gradient, pour reproduire les conditions réelles d’utilisation en service. Ensuite une caractérisation exhaustive des propriétés physiques et mécaniques des différents matériaux a été menée. Ainsi, les - substrat seul, sous-couche NiCrAlY, les deux revêtements de YSZ à microstructures différents et les deux systèmes BT complets - ont été testés en flexion 3 points (F3P) et en flexion biaxiale Small Punch Test (SPT). A partir des propriétés obtenues et de ces résultats, des modélisations éléments finis ont été proposées : les modes d’endommagement observés pendant les essais de F3P et SPT ont été reproduits. La compréhension de des phénomènes d'endommagement et la prédiction de la durée de vie des BT sont des enjeux majeurs pour les motoristes qui souhaitent élaborer un modèle pertinent de durée de vie. / Thermal barriers coatings (TBC) developed by air plasma spraying (APS) are used by the aviation industry to protect the fixed parts of hot sections of gas turbines. The TBC system consists of a bilayer system composed of a 200 m thick NiCrAlY bondcoat and a 1 mm thick ZrO2-8% Y2O3 (YSZ) ceramic coating, deposited on the metal substrate to be protected. The main objectives of this PhD thesis are, on the one hand, to compare the cyclic oxidation behavior of two microstructures of TBC developed by APS and, on the other hand, to characterize the mechanical behavior of these TBC, in order to understand, model the damage mechanisms. and improve their design. Firstly, the plasma projection of the different TBCs was carried out. To evaluate their performance in terms of lifetime and identify the mechanisms of damage, they were then tested in cyclic oxidation with gradient to reproduce the actual conditions of use in service. Then, an exhaustive characterization of the physical and mechanical properties of the different materials was conducted. Thus, the - substrate alone, NiCrAlY sublayer, the two YSZ coatings with different microstructures, and the two complete TBC systems - were tested in 3-point bending (F3P) and biaxial flexion Small Punch Test (SPT). From the properties obtained and these results, finite element modelisations were proposed: the modes of damage observed during the F3P and SPT tests were reproduced. The understanding of damage phenomenon and the prediction of life of TBCs are major issues for engine makers who wish to develop a relevant model of service life.

The thermo-mechanical effects on the strain evolution within an EB-PVD thermal barrier coating (TBC) is presented in this work using in-situ characterization. Synchrotron X-ray diffraction at sector 1-ID at the Argonne National Laboratory provided both qualitative and quantitative in-situ data on the strain evolution under a thermal cycle with mechanical loading. The results show that at a critical combination of temperature and load, the stress in the thermally grown oxide (TGO) layer in the TBC reaches a tensile region. These significant findings enhance existing literature showing purely compressive strains within the TGO where mechanical loads have been neglected. The results have important implications on the effects on the overall life of the coating. Depth resolved quantitative strain is presented as contour plots over a thermal cycle highlighting the complementary strains in the adjacent layers including the bond coat and the TBC with time and temperature. Systematic identification of the appropriate peaks within the multi-layer TBC system provides guidelines for future strain studies using high energy X-rays. Piezospectroscopic studies with applied mechanical loading are further presented as verification of the room temperature XRD data for future development of the method as an operational technique to be used outside the laboratory environment.

There has been an urge for increasing the efficiency in advanced gas turbine engines. To fulfill these needs the inlet gas temperatures should be increased in the gas turbine engines, thermal barrier coatings (TBCs) have gained significant applications in increasing the gas inlet temperatures. Insulating characteristics of ceramic TBCs allow the operation at up to 150~250 ˚C higher gas temperatures. Because of the severe turbine engine operating conditions that include high temperature, steep temperature gradient, thermal cycling, oxidation and hot-corrosion, TBCs can fail by spallation at the interface between the metal and ceramic. The lack of understanding in failure mechanisms and their prediction warrant a development of non-destructive evaluation technique that can monitor the quality and degradation of TBCs. In addition, the development of NDE technique must be based on a robust correlation to the characteristics of TBC failure. The objective of this study is to develop electrochemical impedance spectroscopy (EIS) as a Non-destructive evaluation (NDE) technology for application to TBCs. To have a better understanding of the multilayer TBCs using EIS they were divided into individual layers and EIS were performed on them. The individual layers included polycrystalline ZrO2-7~8 wt.%Y2O3 (YSZ) (topcoat) of two different densities were subjected to sintering by varying the sintering temperature and holding time for three different thickness and hot extruded NiAl alloy buttons which were subjected to isothermal oxidation with varying temperature and time. NiAl is as similar to the available commercial bondcoats used in TBCs. Then degradation monitoring with electrolyte penetration was carried out on electron beam physical vapor deposited (EB PVD) TBCs as a function of isothermal exposure. Quality control for air plasma sprayed TBCs were carried out as a function of density, thickness and microstructure. Dense vertically cracked TBCs were tested as a function of vertical crack density and thickness. Electrochemical impedance response was acquired from all specimens at room temperature and analyzed with an AC equivalent circuit based on the impedance response as well as multi-layered structure and micro-constituents of specimens. Physical and microstructural features of these specimens were also examined by optical and electron microscopy. The EIS measurement was carried out in a three-electrode system using a standard Flat Cell (K0235) from Princeton Applied Research™ and IM6e BAS ZAHNER™ frequency response analyzer. The electrolyte employed in this investigation was 0.01M (molar) potassium Ferri/Ferro Cyanide {(K3Fe(CN)6/K4Fe(CN)6·3H2O)}. The thickness and density were directly related to the resistance and capacitance of the polycrystalline YSZ with varying thickness and open pores. As the effective thickness of the YSZ increased with sintering time and temperature, the resistance of the YSZ (RYSZ) increased proportionally. The variation in capacitance of YSZ (CYSZ) with respect to the change in porosity/density and thickness was clearly detected by EIS. The samples with high porosity (less dense) exhibited large capacitance, CYSZ, compared to those with less porosity (high density), given similar thickness. Cracking in the YSZ monoliths resulted in decrease of resistance and increase in capacitance and this was related to the electrolyte penetration. Growth and spallation of TGO scale on NiAl alloys during isothermal oxidation at various temperatures and holding time was also correlated with resistance and capacitance of the TGO scale. With an increase in the TGO thickness, the resistance of the TGO (RTGO) increased and capacitance of the TGO (CTGO) decreased. This trend in the resistance and capacitance of the TGO changed after prolonged heat treatment. This is because of the spallation of the TGO scale from the metal surface. The parabolic growth of TGO during high temperature oxidation was inversely proportional to the capacitance of TGO, excluding the abrupt changes associated with the failure. As a function of isothermal exposure for EB-PVD TBCs, initial increase in the resistance of YSZ with thermal exposure was observed perhaps due to the high temperature sintering of YSZ. The parabolic growth of TGO during high temperature oxidation was inversely proportional to the capacitance of TGO. An explanation based on electrolyte penetration into sub-critical damage is proposed for the gradual decrease in the resistances of YSZ and TGO with prolonged thermal exposure. Observation of exposed metallic bond coat surface on the fracture surface, which readily provides conduction, was related to the abrupt and large increase in the capacitance of YSZ and TGO. A direct relation between the resistance of the YSZ (RYSZ) and density of the YSZ was observed for APS TBCs with varying topcoat density. APS TBCs with varying topcoat chemistry and thickness were tested and directly related to resistance of topcoat. With the increase in the topcoat thickness, the capacitance decreased and the resistance increased. The higher values of CCAT and RCAT compared to that of CYSZ and RYSZ were related to the higher dielectric constant and resistivity of CaTiO3. Dense vertically cracked TBCs were tested with varying crack density were tested and the variation in the resistance was related indirectly to the cracks and directly to the difference in the thickness of the topcoat. EB-PVD TBCs with varying density (dense and columnar) were tested and the variation in resistance was attributed to the dense structure and columnar structure of the topcoat with columnar structure having lower resistance because of more electrolyte penetration through the columnar structure. From this study, EIS showed a potential as a NDE technique for quality assurance and lifetime remain assessment of TBCs. Future work should continue on developing a mathematical model to study the impedance curves and come up with a model for individual layers of TBC and then sum them up to get the multilayered TBC response. The flexible instrument probe of EIS needs to be designed and tested for field evaluation of TBCs.

Gas Turbine manufacturers strive for increased operating temperatures of gas turbine engines to improve efficiency and performance. One method of increasing the temperature beyond material limits is by applying thermal barrier coatings (TBCs) to hot section components. TBCs provide a thermal gradient between the hot gases and metallic substrate, and allow an increase in turbine inlet temperatures of 100-150ºC. However, spallation of TBCs can cause catastrophic failure of turbine engines by incipient melting of the substrate. To prevent such an occurrence, non-destructive evaluation (NDE) techniques are critical for quality control, health monitoring, and life assessment of TBCs. Two techniques in development for this purpose are thermal wave imaging (TWI) and photostimulated luminescence (PL) spectroscopy. TWI is a promising NDE technique with the ability to detect integrity and thickness of TBCs. In this study, TWI was employed as an NDE technique to examine as-coated TBCs with varying thicknesses, and thermally-cycled TBCs for initiation and progression of subcritical-subsurface damage as a function of thermal cycling. TWI and thermal response amplitude were correlated to the microstructural characteristics and damage progression of TBCs based on phenomenological expressions of thermal diffusion. The TBC specimens examined consisted of air plasma sprayed ZrO2 - 7wt.% Y2O3 on NiCoCrAlY bond coats with Haynes 230 superalloy substrate. As-coated specimens of varying thicknesses were evaluated by TWI to examine its applicability as a thickness measurement tool. It was found that heat dissipation through the TBC following pulsed excitation by xenon flash lamps initially followed the 1-D law of conduction and deviated from it as a function of thickness and time. The deviation resulted from quick dissipation of heat into the conductive metallic substrate. Therefore, with calibration, TWI can be used as a tool for YSZ thickness measurements of APS TBCs in the as-coated condition for quality control measures. Specimens of uniform thickness were evaluated as a function of thermal cyclic oxidation for subcritical-subsurface damage detection. Thermal cycling was carried out in air with 30-minute heat-up, 10-hour dwell at 1150°C, 30-minute air-quench and 1-hour hold at room temperature. During thermal cycling, TBC specimens were evaluated non-destructively by TWI at room temperature every 10 to 20 thermal cycles, and selected specimens were removed from thermal cycling for microstructural analysis by scanning electron microscopy (SEM). Higher thermal response amplitude associated with disrupted heat transfer was observed where localized spallation at or near the YSZ/TGO interface occurred. The health of the TBC was monitored by a rise in thermal response amplitude which may indicate a coalescence of microcracks to a detectable level. PL has been developed to measure stress, and detect subsurface damage and polymorphic transformation within the thermally grown oxide (TGO) of TBCs. PL was employed in this study as an NDE technique for TBCs to correlate subsurface damage as a function of thermal cyclic oxidation. The TBCs consisted of ZrO2 – 7 wt.% Y2O3 applied by electron beam physical vapor deposition with an as-coated (Ni,Pt)Al bond coat on a CMSX-4 superalloy substrate. Specimens were thermally cycled with a 10 minute ramp to a peak temperature of 1121°C, 40 minute hold at peak temperature, and 10 minute forced air quench. The TBCs were periodically removed from thermal cycling for NDE using PL until failure. Two specimens were removed from thermal oxidation after 10% and 70% of the average lifetime for microstructural analysis by SEM. During initial thermal cycling, metastable phases and polymorphic transformations of the Al2O3 scale were examined by PL. The polymorphic transformation from a metastable phase to equilibrium a-Al2O3 was detected. Since metastable phases are thought to be detrimental to coating lifetime, detection of these phases by PL can be used as a quality control tool. Nearing end-of-life, relief of the TGO from the compressive residual stress arising from thermal expansion mismatch was detected with PL and confirmed with microstructural analysis that revealed damage initiation (e.g. microcracking within the TGO scale parallel to the interfaces.) Rise in luminescence near the R-line frequency for polycrystalline a-Al2O3 without any residual stress (i.e. n = 14402 cm-1 and n = 14432 cm-1) corresponded to regions where cracked TGO was adhered to YSZ and not exposed to compressive stresses from thermal expansion mismatch upon cooling.

The durability of thermal barrier coatings (TBCs) affects the life of the hot section engine components on which they are applied. Fatigue is the general failure mechanism for such components and is responsible for most unexpected failures; therefore it is desirable to develop lifetime approximation models to ensure reliability and durability. In this study, we first examined the microstructural degradation of air plasma sprayed ZrO2-8wt.%Y2O3 TBCs with a low-pressure plasma sprayed CoNiCrAlY bond coat on an IN 738LC superalloy substrate. The durability of TBCs were assessed through furnace thermal cyclic tests carried out in air at 1100°C with a 1-, 10-, and 50-hour dwell period, preceded by a 10-minute heat-up and followed by a 10-minute forced-air-quench. Failure mechanisms of the TBCs were thoroughly investigated through materials characterization techniques including: X-Ray Diffraction, Scanning Electron Microscopy, and Energy Dispersive X-Ray Spectroscopy. Quantitative microstructural analyses were then carried out to document the growth of the thermally grown oxide (TGO) scale, the depletion of the Al-rich β-NiAl phase in the bond coat, and the population and growth of micro-cracks near the YSZ/bond coat interface. Trends in the TGO growth and the β-phase depletion in the bond coat followed those of diffusion-controlled processes—parabolic growth of the TGO and exponential depletion of the β-phase. Formation and propagation of cracks within the YSZ resulted in complete spallation of the YSZ topcoat from the bond-coated superalloy substrate. Evolution in these microstructural features was correlated to the lifetime of TBCs, which showed cracking within the YSZ to be the cause of failure; thus a lifetime iv approximation model was developed, via modification of Paris Law, based on the experimental data. The model predicted the TBC lifetime within 10% of the experimental lifetime.