Research was performed on the development of relationships between the microstructure of nickel and yttria-stabilized zirconia (YSZ) coatings and the processing parameters used for their deposition by atmospheric plasma spraying (APS). Research was also performed on the development of relationships between the microstructure of plasma sprayed Ni-YSZ coatings and the electrochemical performance of metal-supported solid oxide fuel cells (SOFCs) incorporating these coatings as anodes. Three APS processes were used to deposit Ni-YSZ coatings: dry-powder plasma spraying (DPPS), suspension plasma spraying (SPS), and solution precursor plasma spraying (SPPS). These processes differ in the form of the feedstock injected into the plasma. The composition of the Ni-YSZ coatings deposited with each spray process could be controlled through adjustment of the plasma gas composition and stand-off distance, as well as adjustment of feedstock properties including agglomerate size fraction for DPPS, NiO particle size and suspension feed rate in SPS, and the enthalpy of decomposition of the precursors used in SPPS. The porosity of the Ni-YSZ coatings could be controlled through the addition of a sacrificial pore forming material to each feedstock, with coating porosities up to approximately 35% being achieved for each coating type. Metal-supported SOFCs were fabricated to each have anodes deposited with a different plasma spray process, where all anodes had nominally identical composition. The microstructures obtained for each anode type were distinctly different. SPPS led to the most uniform mixing of the smallest Ni and YSZ particles. These anodes most resembled typical structures from anodes fabricated using conventional methods. It was found that the polarization resistance, Rp, associated with the high frequency (> 1 kHz) range of the impedance spectrum correlated to the three phase boundary length (TPBL) density of each anode, with lower Rp values corresponding to higher TPBL densities. It was also found that the Knudsen diffusion coefficient and effective ordinary diffusion coefficient of the porous anodes correlated with the Rp associated with the low frequency (< 1 kHz) range of the impedance spectrum. Therefore, the impedance spectrum can be used to compare microstructural differences among plasma sprayed Ni-YSZ anodes.

Research was performed on the development of relationships between the microstructure of nickel and yttria-stabilized zirconia (YSZ) coatings and the processing parameters used for their deposition by atmospheric plasma spraying (APS). Research was also performed on the development of relationships between the microstructure of plasma sprayed Ni-YSZ coatings and the electrochemical performance of metal-supported solid oxide fuel cells (SOFCs) incorporating these coatings as anodes. Three APS processes were used to deposit Ni-YSZ coatings: dry-powder plasma spraying (DPPS), suspension plasma spraying (SPS), and solution precursor plasma spraying (SPPS). These processes differ in the form of the feedstock injected into the plasma. The composition of the Ni-YSZ coatings deposited with each spray process could be controlled through adjustment of the plasma gas composition and stand-off distance, as well as adjustment of feedstock properties including agglomerate size fraction for DPPS, NiO particle size and suspension feed rate in SPS, and the enthalpy of decomposition of the precursors used in SPPS. The porosity of the Ni-YSZ coatings could be controlled through the addition of a sacrificial pore forming material to each feedstock, with coating porosities up to approximately 35% being achieved for each coating type. Metal-supported SOFCs were fabricated to each have anodes deposited with a different plasma spray process, where all anodes had nominally identical composition. The microstructures obtained for each anode type were distinctly different. SPPS led to the most uniform mixing of the smallest Ni and YSZ particles. These anodes most resembled typical structures from anodes fabricated using conventional methods. It was found that the polarization resistance, Rp, associated with the high frequency (> 1 kHz) range of the impedance spectrum correlated to the three phase boundary length (TPBL) density of each anode, with lower Rp values corresponding to higher TPBL densities. It was also found that the Knudsen diffusion coefficient and effective ordinary diffusion coefficient of the porous anodes correlated with the Rp associated with the low frequency (< 1 kHz) range of the impedance spectrum. Therefore, the impedance spectrum can be used to compare microstructural differences among plasma sprayed Ni-YSZ anodes.

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.

Silicon-based ceramics and ceramic matrix composites (CMCs), such as silicon carbide (SiC) fiber reinforced SiC, are promising candidates for hot section components in next generation turbine engines. Environmental barrier coatings (EBCs) are essential for implementing these components as they insulate and protect the substrate from reaction with water vapor in the engine environment. EBCs are typically deposited via atmospheric plasma spraying (APS) and preparing the component surfaces through cleaning and roughening prior to coating is a vital step to ensure sufficient coating adhesion. The adhesion of a plasma sprayed coating to the underlying component is one of the most important properties as the component will not be protected if the coating is not well adhered. Surface roughening of metallic components via grit blasting is well documented and understood, but much less is known about preparing ceramic and ceramic composite surfaces for thermal spray coating. Silicon coatings are often used as a bond coating between SiC-based components and EBC top layers, but the adhesion strength of plasma sprayed Si on these substrates, Si splat formation and the factors that affect coating formation and adhesion have not been well studied. The effects of automated grit blasting process parameters on surface roughness and material loss of a reaction bonded SiC (rb SiC) composite were evaluated. Surface roughness before and after grit blasting was evaluated with a confocal laser scanning microscope. The differences and advantages of automated grit blasting compared to manual grit blasting were observed. Most notably was the level of control at high nozzle traverse speeds resulting in reduction of material loss and consistency of roughening. At high nozzle traverse speeds, the amount of material loss decreased greatly with a small effect on induced surface roughness. The degree of grit blasting induced roughness and material loss was found to be largely dependent on the nature of the composite matrix and reinforcement, as well as blast nozzle traverse speed. A statistical model was developed to predict the substrate thickness loss and induced average roughness based on nozzle traverse speed and blast pressure for automated grit blasting. Additionally, laser ablation was used to create controlled, regularly patterned surface texture on rb SiC substrates to further investigate the role of texture parameters in Si coating adhesion. Si was plasma sprayed onto rb SiC substrates to deposit both thick coatings to evaluate adhesion strength and single splats to study splat formation. Surface roughness/texture, substrate preheat temperature and mean Si particle size were varied in plasma spray coating experiments to observe their role in coating adhesion strength. Si adhesion strength was found to be related to all three factors and a statistical model was developed to predict adhesion strength based on them. Substrate preheat temperature had a significant effect on both Si adhesion strength and Si splat formation on rb SiC. Single splat formation during plasma spraying of Si on SiC was simulated with software called SimDrop. Simulations of Si droplet impact, spreading and solidification during plasma spraying on smooth and textured SiC surfaces were used to investigate the effects of relevant process parameters on splat formation. Experimentally observed Si splats on smooth substrates at different temperatures during deposition were matched with simulated splats with the same spraying parameters. A change in thermal contact resistance with changing substrate preheat temperature was confirmed by the simulation results. The role of surface texture parameters for a regularly patterned surface texture in splat formation was demonstrated through simulation. This dissertation investigates methods of roughening and preparing a SiC composite substrate for plasma spray coating, as well as factors which affect the adhesion strength and splat formation of plasma sprayed Si through experiments and simulation. The observations made provide valuable insight for understanding and optimizing the manufacturing processes utilized to deposit strongly adhered coatings onto SiC-based composites. In addition, areas of interest in this field for future study and further investigation are introduced and suggested. / Doctor of Philosophy / Silicon-based ceramics and ceramic matrix composites (CMCs), such as silicon carbide (SiC) fiber reinforced SiC, are promising candidates for hot section components in next generation turbine engines. Environmental barrier coatings (EBCs) are essential for implementing these components as they insulate and protect the substrate from reaction with water vapor in the engine environment. EBCs are typically deposited via atmospheric plasma spraying (APS) and preparing the component surfaces through cleaning and roughening prior to coating is a vital step to ensure sufficient coating adhesion. The adhesion of a plasma sprayed coating to the underlying component is one of the most important properties as the component will not be protected if the coating is not well adhered. Silicon coatings are often used as a bond coating between SiC-based components and EBC top layers, but the adhesion strength of plasma sprayed Si on these substrates, Si splat formation and the factors that affect coating formation and adhesion have not been well studied. This dissertation investigates methods of roughening and preparing a SiC composite substrate for plasma spray coating, as well as factors which affect the adhesion strength and splat formation of plasma sprayed Si through experiments and simulation. The observations made provide valuable insight for understanding and optimizing the manufacturing processes utilized to deposit strongly adhered coatings onto SiC-based composites. In addition, areas of interest in this field for future study and further investigation are introduced and suggested.

Optimization is a decision making process to solve problems in a number of fields including engineering mechanics. Bio-inspired optimization algorithms, including genetic algorithm (GA), have been studied for many years. There is a large literature on applying the GA to mechanics problems. However, disadvantages of the GA include the high computational cost and the inability to get the global optimal solution that can be found by using a honeybee-inspired optimization algorithm, called the New Nest-Site Selection (NeSS). We use the NeSS to find optimal parameters for three mechanics problems by following the three processes: screening, identifying relationships, and optimization. The screening process identifies significant parameters from a set of input parameters of interest. Then, relationships between the significant input parameters and responses are established. Finally, the optimization process searches for an optimal solution to achieve objectives of a problem. For the first two problems, we use the NeSS algorithm in conjunction with a third order shear and normal deformable plate theory (TSNDT), the finite element method (FEM), a one-step stress recovery scheme (SRS) and the Tsai-Wu failure criterion to find the stacking sequence of composite laminates and the topology and materials for doubly curved sandwich shells to maximize the first failure load. It is followed by the progressive failure analysis to determine the ultimate failure load. For the sandwich shell, we use the maximum transverse shear stress criterion for delineating failure of the core, and also study simultaneously maximizing the first failure load and minimizing the mass subject to certain constraints. For composite laminates, it is found that the first failure load for an optimally designed stacking sequence exceeds that for the typical [0°/90°]₅ laminate by about 36%. Moreover, the design for the optimal first failure load need not have the maximum ultimate load. For clamped laminates and sandwich shells, the ultimate load is about 50% higher than the first failure load. However, for simply supported edges the ultimate load is generally only about 10% higher than the first failure load. For the atmospheric spray process, we employ the NeSS algorithm to find optimal values of four process input parameters, namely the argon flow rate, the hydrogen flow rate, the powder feed rate and the current, that result in the desired mean particle temperature and the mean particle velocity when they reach the substrate. These optimal values give the desired mean particle temperature and the mean particle velocity within 5% of their target values. / Ph. D. / An optimization process iteratively searches for the best solution from all feasible solutions in the search space that satisfy prespecified criteria. Optimization problems consist of sets of parameters, constraints, and objective functions. Here we use a honeybee-inspired optimization algorithm, called the New Nest-Site Selection (NeSS), to find optimal parameters for three mechanics problems. In the first problem, we optimize the design of an assembly of layers of unidirectional fiber-reinforced materials called composite laminates. Because of their high specific strength and directional-dependent stiffness as compared to those of metals, the composite laminates are being increasingly used in aerospace and automotive industries. After having analyzed deformations of a composite laminate, a failure criterion is used to determine if any point in the structure has failed. The minimum load for which the failure criterion is satisfied at a point is called the first ply failure load. Here we determine the fiber orientation angle in each layer of a rectangular laminate deformed statically by transverse loads applied on the top surface that maximizes the first ply failure load. Subsequently, the load is incrementally increased for the optimally designed laminate and the strength of the failed elements is degraded till the structure cannot support any additional load. The maximum load a structure can support is called the ultimate load. It is found that for a laminate with all edges clamped, the ultimate load can be 40% more than the first ply failure load. We extend the above work to design an optimal geometry and an optimal combination of materials of the facesheets and the core that simultaneously maximizes the first failure load, minimizes the weight of a doubly curved sandwich shell, and satisfies pre-specified constraints. The doubly curved sandwich structure of interest here is comprised of two thin parallel unidirectional fiber-reinforced facesheets bonded to and enclosing a relatively thick mid-layer made of a material softer and lighter than that of the facesheets. The sandwich structures are widely used in aircraft, marine, automobile, and civilian infrastructures. It is found that optimal designs for doubly curved sandwich shells strongly depend upon how the shell edges are supported, and shells designed for the maximum first failure load need not have the maximum ultimate load. An atmospheric plasma spray process (APSP) has been successfully used to coat components for gas turbines, airframe, engines and drive trains, and silicon chips. In the APSP, coating powder is injected into the plasma, which is a mixture of ionized gases such as argon, hydrogen, and helium, through a powder port generally oriented perpendicular to the plasma jet axis. Through interactions with the plasma jet, the particles are accelerated, heated and partially melted before they strike the substrate and are deposited on it to form a coating. It is believed that the coating properties and its quality depend on the particles’ temperature and velocity when they hit the substrate. Here we determine optimum values of four input parameters, namely, the argon flow rate, the hydrogen flow rate, the current, and the powder feed rate to achieve the desirable mean particles’ temperature and the mean particles’ velocity. It is found that the four processes input parameters can be optimized to attain particles’ characteristics within 5% of their prespecified desired values.

Gas turbine engine efficiency needs to be raised in order to decrease fuel consumption, greenhouse gas emissions, and expenses. Efficiency may be improved in two ways: by reducing engine weight and raising intake temperatures. At intake temperature, conventional nickel-based alloys are already on the verge of failure, meaning there is a need and demand of materials which can withstand higher temperatures. Silicon Carbide Ceramic Matrix Composites (SiC CMCs) are being investigated as a potential replacement for superalloys due to their superior physical properties, such as their low weight and high melting point (approximately one-third of superalloys' weight). However, using SiC CMCs has a serious disadvantage. The mass recession of the SiC is caused by the volatilization of silicon hydroxide, which is caused by oxidation and reactivity with water vapor under the working conditions of gas turbine engines. Therefore, a shielding layer is used to prevent oxidation of the SiC CMCs. This protective coating (EBC) goes by the name of Environmental Barrier Coating. Thermal spray techniques such as atmospheric plasma spray and suspension plasma spray, which employ powder as the feedstock, are used to deposit EBC on SiC CMCs. For EBC to perform well, the coating must be crystalline, reasonably thick to sustain harsh environment, and devoid of cracks. EBC was deposited in order to look at how the spray parameters affected the microstructure. SEM pictures were used to quantify the coating's porosity and the severity of the cracks. To investigate the production of thermally grown oxide (TGO) in the coating and substrate and check how EBCs perform under thermal cyclic fatigue loading, a thermal cyclic fatigue test was conducted. The XRD analysis is performed to ascertain the proportion of crystalline and amorphous phases in the coating, which unfortunately is still in the process to be completed. In the as-sprayed coating samples we can see that when there are more amount and larger pores, we see less number of cracks and vice versa. The effect of spray parameters can be seen on the coatings. Comparing to SPS trial 1, the SPS trial 2 coatings are denser with less number of cracks and has good adhesion. Still the SPS trial 2 coating did not achieve better microstructure in terms of density, and cracks compared to the APS coatings but further looking into the parameters, more desirable coatings can be achieved. After TCF testing, a layer of TGO was seen at the bond coat/topcoat interface, and there was no failure of the coating seen.