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.

No description available.

The aerospace industry strives to develop new methods of refining gas turbine engines by increasing power and thermal efficiencies while simultaneously reducing cost. Turbine engines operate under high temperatures and therefore thermal barrier coatings (TBCs) composed of yttria-stabilized zirconia (YSZ) play an important role in improving the performance of the components that make up the engine. Failure of the TBC could lead to catastrophic events, thus requiring consistent and accurate characterization for supplier qualification and production quality assurance. However, due to porosity and the anisotropic behavior of the coating and variability in processing of TBCs, consistent characterization has proven to be extremely challenging. One of the reoccurring issues is the inconsistency in measuring percent porosity, which stems from the difficulty in distinguishing filled pores from damaged, unfilled voids. Sample preparation of TBCs involves sectioning, mounting, grinding, polishing, and characterization. Eliminating variability in characterization begins with mounting which is a critical step to protect the surface integrity and edge retention of the coating during grinding and polishing. The curing kinetics of a slow cure two part epoxy was investigated and the TBC samples were mounted and cured at heating rates of 2, 5, and 10°C/min to 55°C and 70°C. Grinding and polishing procedures simulated industry practices followed by characterization with optical microscopy. Results showed that heating rates of 2°C/min to 55°C and 70°C have the best impregnation properties while uncontrolled or high heating rates of 10°C/min had an increase in the amount of pullouts and lack of infiltration from the epoxy. The curing kinetics of the epoxy needs to be controlled to eliminate the ambiguity of filled and unfilled pores. / Master of Science

The main objective of this work was to design a suitable composition of a protective coatings, made of several different layers of specific materials - with respect to residual stress, induced due to a mismatch in thermal expansion coefficients of each layer. Protective coating in this work means both the thermal and the environmental barrier. These coatings protect components against high temperatures and harsh environment. In this work, necessary theoretical background in the field of the thermal and environmental barrier coatings is introduced. There are mentioned some basic design approaches, commonly used materials and processing methods for the coating structure. The literature review gives an overview of modeling of such coated structures, in particular it is devoted to the thermal barrier coatings deposited by air plasma spray process. The next chapter closely describes classical laminate theory used for calculation of residual stresses in the coating. One of the assumptions of this theory is homogenous temperature field through the coating’s thickness. However, in this work was revealed a way to extend the classical lamination theory of such cases, in which the temperatures vary along the thickness of the coating. In the practical part, the analytical model was used for designing suitable properties of some coatings, which were consists of two, three and four layers. The calculations were performed both for constant temperature and for the temperature gradient. All results obtained from analytical approach were verified by numerical calculations.

The research work performed in this thesis has been carried out at the Production Tech-nology Centre where the Thermal Spray research group of University West has its work-shop and labs. This research work has been performed in collaboration with the International Advanced Research Centre for Powder Metallurgy and New Materials (ARCI), Hyderabad, India. First of all, I would like to express my sincere thanks and gratitude to my supervisors Dr. Nicolaie Markocsan and Dr. Nicholas Curry for their guidance, great support and valuable suggestions without which this work could not have been possible. I would also like to thanks Prof. Per Nylén for keeping faith in me and providing me an opportunity to work at PTC, which is a great place to perform research. It is my pleasure being their student and I wish I would keep learning from all of them, both on academic and personal grounds. I would also like to thank my colleagues at PTC Mr. Mohit Gupta and Mr. Stefan Björklund, for their help and support during this work. I would like to acknowledge the H.C. Starck Company for its financial support for the pro-ject; Dr. Filofteia-Laura TOMA at Fraunhofer IWS, Dresden to help us in spraying suspen-sion sprayed YSZ top coats, G Shivkumar from ARCI to help us in spraying solution pre-cursor sprayed top coats and Toni Bogdanoff, Jönköping University to help us in conduct-ing the LFA experiment

Atmospheric plasma sprayed (APS) thermal barrier coatings (TBCs) are commonly used for thermal protection of components in modern gas turbine application such as power generation, marine and aero engines. TBC is a duplex material system consisting of an insulating ceramic topcoat layer and an intermetallic bondcoat layer. TBC microstructures are highly heterogeneous, consisting of defects such as pores and cracks of different sizes which determine the coating's final thermal and mechanical properties, and the service lives of the coatings. Failure in APS TBCs is mainly associated with the thermo-mechanical stresses developing due to the thermally grown oxide (TGO) layer growth at the topcoat-bondcoat interface and thermal expansion mismatch during thermal cycling. The interface roughness has been shown to play a major role in the development of these induced stresses and lifetime of TBCs.The objective of this thesis work was two-fold for one purpose: to design an optimised TBC to be used for next generation gas turbines. The first objective was to investigate the relationships between coating microstructure and thermal-mechanical properties of topcoats, and to utilise these relationships to design an optimised morphology of the topcoat microstructure. The second objective was to investigate the relationships between topcoat-bondcoat interface roughness, TGO growth and lifetime of TBCs, and to utilise these relationships to design an optimal interface. Simulation technique was used to achieve these objectives. Important microstructural parameters influencing the performance of topcoats were identified and coatings with the feasible identified microstructural parameters were designed, modelled and experimentally verified. It was shown that large globular pores with connected cracks inherited within the topcoat microstructure significantly enhanced TBC performance. Real topcoat-bondcoat interface topographies were used to calculate the induced stresses and a diffusion based TGO growth model was developed to assess the lifetime. The modelling results were compared with existing theories published in previous works and experiments. It was shown that the modelling approach developed in this work could be used as a powerful tool to design new coatings and interfaces as well as to achieve high performance optimised morphologies.

L’ingestion de sables et de cendres volcaniques par les moteurs d’avion conduit à la formation de dépôts silicatés (CMAS) qui s’infiltrent dans la porosité du revêtement barrière thermique (BT) en zircone yttriée des aubes de turbine. De nouvelles compositions de BT issues du système ZrO2-RE2O3 (RE = La-Lu) sont donc envisagées. En effet, leur réactivité chimique au contact des CMAS peut conduire à la formation de phases cristallisées, notamment la phase apatite Ca2RE8(SiO4)6O2, qui bloquent l’infiltration du CMAS. Cependant, divers silicates du système CaO-RE2O3-SiO2 sont susceptibles d’entrer en compétition avec sa formation et de plus, la composition du CMAS varie selon les régions survolées. L’objectif de ces travaux de thèse est de déterminer l’influence de la composition du CMAS et de la terre rare sur les mécanismes réactionnels de dissolution et de précipitation. Divers oxydes RE2O3 à basicité croissante (RE = Yb, Dy, Gd, Sm et Nd) et un CMAS de composition simplifiée du système CaO-Al2O3-SiO2 (CAS) ont été choisis. Des teneurs fixes en MgO et Fe2O3 ont été ensuite ajoutées au CAS en faisant varier le rapport CaO/SiO2 entre 0,4 et 1,6. Les phases apatite et cyclosilicate Ca3RE2(Si3O9)2 ont également été synthétisées afin d’étudier leur dissolution. Il est montré que le mécanisme de dissolution des RE2O3 est indirect, les équilibres locaux établis avec cet oxyde imposant systématiquement la formation de la phase apatite. Sa cristallisation est favorisée par un rayon cationique RE3+ proche de celui de Ca2+. Lorsque l’écart est important, la nucléation de la phase cyclosilicate est rapidement observée dans le CAS avec une répartition préférentielle de ces cations RE3+ dans les sites de coordinence 6. La solubilité en RE dans le liquide silicaté augmente avec la basicité de l’oxyde RE2O3 et en présence de MgO et Fe2O3. La variation de composition du CMAS modifie la nature des phases à l’équilibre. Leurs limites de solubilité en RE sont inférieures à celles de la phase apatite, ce qui réduit d’autant leur vitesse de redissolution dans le liquide silicaté / Fine particles of sand, dust or volcanic ashes ingested by aircraft engines are well-known to damage Thermal Barrier Coatings (TBC) when they infiltrate their porous microstructure as molten silicate (CMAS). They are mainly constituted of CaO-MgO-Al2O3-SiO2 in variable proportions and also contain metallic oxides. RE2Zr2O7 compositions are TBC candidate materials as they have shown efficiency to mitigate CMAS infiltration due to their reactivity with synthetic CMAS. Indeed, the dissolution reaction leads to rapid sealing of the topcoat porosity mainly due to the formation of crystalline Ca2Gd8(SiO4)6O2 apatite. However, many rare-earth silicates are likely to compete with apatite crystallization and little is known on reaction kinetics and thermodynamics involving RE2O3 and multi-component CMAS system. This work aims to determine the influence of CMAS and rare earth composition on dissolution and precipitation mechanisms. A simplified CAS was first selected with eutectic (1170°C), 65SiO2-26CaO-9Al2O3 (mol. %) composition. Dissolution of various RE2O3 with increasing basicity (RE = Yb, Dy, Gd, Sm and Nd) as well as synthetic apatite and cyclosilicate Ca3RE2(Si3O9)2 phases was then performed at 1200°C in CAS-melt. Finally, fixed MgO and Fe2O3 contents were added to CAS melt with an increasing CaO/SiO2 ratio. The results showed that RE2O3 dissolution mechanism is indirect. Apatite formation results from local equilibrium at the interface with solid RE2O3 whatever the rare earth and CMAS composition. Its crystallization is favored when Ca2+ and RE3+ ionic radii are close as they are both distributed within 9-fold coordination sites. Conversely, Ca and RE mismatch leads to rapid nucleation of cyclosilicate phase in CAS as they are preferentially distributed within a 6-fold coordination site. MgO and Fe2O3 addition in CAS as well as RE2O3 basicity tend to increase RE solubility in silicate melt. Phases in thermodynamic equilibrium strongly depend on CMAS composition but generally exhibits lower RE solubility and dissolution rate in melt than apatite