Plasma spray coatings are vital to the capabilities of jet engines. They allow engines to operate at combustion temperatures that would otherwise melt the superalloy components. Coatings tighten clearance between rotating components, increasing engine compression. They prevent chemical attack and physical erosion. Plasma spray coatings are imperative to the durability and efficient operation of the modern jet engine. In this application coating material property variation has a significant cost. In addition to the variation inherent in the process, some of the biggest contributors to coating property variation have been traced to spray gun nozzle wear and powder feed variation[3, 4]. Presented here are multiple methods utilizing flow induced acoustic signals to quantify noise parameters, measure component wear, diagnose the plasma spray process and detect coating property deviation. Methods have been developed for offline and online analysis of components in addition to online process analysis. These include characterization of nozzle wear by throat roughness measurements and nozzle casting, offline detection of nozzle wear by attenuation of discrete tone generation and broadband signal variation, and offline measurement of powder port wear by jet screech frequency variation. Online methods include pre-ignition nozzle degree of wear measurement by discrete frequency changes; online parameter change detection, process deviation detection with potential source identification, as well as variation in coating property detection by broadband acoustic signal changes. Offline methods allow for 100% accurate new nozzle manufacturer identification. By the same test nozzle wear state can be predicted with over 95% accuracy with the potential for a degree of wear determination. Internal diameter changes of less than 10 microns can similarly be detected. Analysis of online plasma spray acoustic signals as described here can distinguish nozzle state and powder feed variation with over 90% accuracy. The capabilities developed here will aid in plasma spray process variation detection and contribute to identifying the source of this variation. This will improve coating quality and consistency, reduce failures, lower operational costs and ultimately make jet engines more economical, safer, and more fuel efficient with significant environmental and financial cost reduction. / Ph. D.

Thermal Barrier Coatings (TBCs), and plasma spray coatings in general, require critical control over the deposited thickness to achieve reliable coating performance. Currently, the plasma spray industry quantifies thickness by sampling the part before and after TBC deposition. Approximate thickness is thus inferred from previous runs. However, process variability can allow errors to propagate in this result that leads to wasted time and resources, and can ultimately lead to non-reliant coatings. To this end, an in situ optical fringe profilometer is developed that enables coating thickness measurements across a 2-dimensional surface. The initial profilometer concept is explored through requirements and trade studies, leading to a hardware and algorithm design family and prototype build to capture and compare real-world data to simulation and model predictions. This initial result shows a viable path-forward and the ability to achieve micrometer-scale depth resolution. Modifications and alterations to the in situ profilometer are then explored to improve the performance limits achievable. In specific, industrial spray coatings operate by dropping fine-grain media into a high pressure gas line aimed through a plasma torch to impart enough thermal and kinetic energy to stick to the part surface. This presents a challenging operational environment for an optical depth measurement sensor, working with a variable high-temperature blackbody stray light source; constant part rotation and plasma gun movement; and a non-isolated vibration environment. As such, the concept of the profilometer is further adapted specific to this end-purpose, by developing and reviewing both dual-fringe projection and plenoptic imaging. These techniques allow an improvement to both the system micro- and macroscopic depth retrieval limits, allowing a method to solve for an extended range of phase ambiguities and relax object focus requirements (respectively). The end result is a system concept and algorithm design that presents a feasible manner for automated in situ geometry and depth measurements in the plasma spray industry. The in situ fringe profilometer work described herein allows a flexible path to recover object depth information remotely, and is especially relevant for asymmetric and complex non-planar geometries, which are experiencing renewed interest with additive manufacturing processes and generally quite common to the thermal spray industry.

Cerium oxide (Ceria) at nano scale has gained significant attention due to its numerous technological applications. Ceria in both doped and undoped forms are being explored as oxygen sensor, catalysis, protective coating against UV and corrosion, solid oxide fuel cell (SOFC) electrolyte and newly discovered antioxidant for biomedical applications. Therefore, there is an imminent need of a technology which can provide a cost effective, large scale manufacturing of nanoceria and its subsequent consolidation, specially using thermal spray. This dissertation aims to develop a scientific understanding towards the development of pure and doped ceria- based coating for a variety of technological applications, from SOFC applications to corrosion resistant coating. Atmospheric plasma spray (APS) and solution precursor plasma spray (SPPS) techniques for the fabrication of nano ceria coating were investigated. For feedstock powder preparation, a spray drying technique was used for the agglomeration of cerium oxide nano particles to achieve high density coating. Deposition efficiencies and coating porosity as a function of processing parameters were analyzed and optimized using a statistical design of experiment model. The coating deposition efficiency was dependent on the plasma temperature and vaporization pressure of the ceria nanoparticles. However, low standoff distance and high carrier gas flow rate were responsible for the improved density upto 86 [plus or minus] 3%.An alternative novel SPPS technique was studied for a thin film of cerium oxide deposition from various cerium salt precursors in doped and undoped conditions. The SPPS process allows controlling the chemistry of coating at a molecular level. The deposition mechanism by single scan experiments and the effect of various factors on coating microstructure evolution were studied in terms of splats formation. It was found that the precursor salt (nitrate of cerium) with lower thermal decomposition temperatures was suitable for a high density coating. The high concentration and low spray distance significantly improve the splat morphology and reduced porosity (upto 20%). The feasibility of the trivalent cations (Sm 3+ and Gd 3+) doping into cerium oxide lattice in high temperature plasma was discussed and experimentally studied. XRD analysis revealed the nano crystalline characteristic of the coating and lattice expansion due to doping. The extensive transmission electron microscopy, Scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and thermo gravimetric were conducted to evaluate the precursors, and coating microstructure. Due to facial switching between Ce4+ and Ce3+ oxidation state, the cerium oxide surface becomes catalytically active. Thus, the APS ceria coatings were investigated for their applicability under extreme environmental conditions (high pressure and temperature). The air plasma sprayed coated 17-4PH steel was subjected to high pressure (10 Kpsi) and temperature (300 oF) corrosive environment. The coated steel showed continuous improvement in the corrosion resistance at 3.5 wt% NaCl at ambient temperature for three months study whereas, high pressure did not reveal a significant role in the corrosion process, and however, one needs to do further research. The ceria coated steel also revealed the improvement in corrosion protection (by 4 times) compared to the bare steel at low pH, 300 oF and 4000 Psi environment. This study projects the importance of cerium oxide coatings, their fabrication, optimization and applications.

Three classes of Al-matrix composite were manufactured to combine dissimilar metals and incorporate structural hierarchy, in an attempt to develop unusual combinations of mechanical properties. The first class combined a brittle, nano-quasicrystalline forming Al-3Fe-2Cr-2Ti phase with a ductile Al-4Cu phase into a layered structure using low pressure plasma spraying (LPPS). By using a substrate with multi-scale topological features, an ultra-thick (>2mm) deposit was successfully sprayed, which was subsequently consolidated by hot rolling to reduce residual porosity. The microstructure comprised a 'brick-wall' structure consisting of a convoluted arrangement of inter-leaved discreet droplet splats. Structure-property relationships were studied for four volume fractions of ductile additions and in-situ electron microscopy of beams subjected to 3-point bending suggested the ductile additions were providing additional toughening to the composite by a crack-bridging mechanism. The second class of composite investigated highly deformed microstructures of Al with 20vol% additions of either Sn or Ti. Nano-scale fibrous structures of the minority additions were achieved via an accumulative extrusion method, where extruded rod was abraded, degreased, bundled and re-extruded. This process was repeated to create refined microstructures while retaining a large material section. Fracture properties were studied in three point bending and crack growth monitored using Digital Image Correlation (DIC) to produce strain fields of the deforming beam surface. Modest changes were observed in mechanical properties with weak interfaces between poorly bonded extruded rods dominating fracture behaviour. Whiskers formed on polished surfaces of extruded Al-20vol%Sn and were monitored in real time by electron microscopy. Growth rates of up to 2.8nm/s were measured, which exceeds re- ported values in the literature on electroplated coatings by at least one order of magnitude. This may provide a convenient new means of studying whisker formation and calls into question current growth models. The third class of composite combined heavily rolled sheets of Al-20vol%Sn and Al-20vol%Ti with glass fibre/epoxy sheets to produce a laminate with multi-scale architecture. This laminate was designed as a proof-of-concept hierarchical material with structures ranging from the near millimetre scale of the metal-polymer layers, to the micro-sized glass fibre reinforcement of the epoxy and the nano-scale filamentary/lamellar microstructure of the highly deformed metal sheets. Fracture of such laminates was investigated in 3-point bending with continuous optical monitoring.

Coanda-assisted Spray Manipulation (CSM) is a means of modifying the direction of a jet. Previous isothermal static vectoring research is expanded to plasma spray. Two- dimensional Particle Image Velocimetry (PIV) was used to determine the vectoring results for small angles between 5-10°. Suitable parameters were determined for use on a plasma spray gun for small angle vectoring. Three-dimensional PIV was used to determine the elect of high speed rotation on a vectored jet. A 2-piece CSM collar was retrotted to a Praxair SG-100 plasma spray gun that replaced the standard faceplate. Two separate collars were tested: one designed for small vector angles and one for larger vector angles. The small-angle device could modify the trajectory of zirconia powder up to several degrees. Doing so could realign the plasma with the powder, resulting in increased powder temperature and velocity. The large-angle device could vector the plasma jet up to 45°; however the powder did not vector as much. Under large-angle vectoring, the powder velocity and temperature decreased steadily with vector angle. Both devices were tested using a supersonic conguration.

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.

Thermal barrier coatings (TBC) with MCrAlY (M=Co and/or Ni) bond coats have been widely used in hot sections of gas turbines to protect underlying superalloys from high temperatures, oxidation, and hot corrosion. Deposition of MCrAlY bond coats using atmospheric plasma spray (APS), as oppose to conventionally employed vacuum/low-pressure plasma spray and high velocity oxy-fuel deposition, allows greater flexibility in ability to coat economically and rapidly for parts with complex geometry including internal surfaces. There were three objectives of this study. First, relationships between APS spray parameters and coating microstructure was examined to determine optimum spray parameters to deposit APS CoNiCrAlY bond coats. Second, free-standing APS CoNiCrAlY coatings were isothermally oxidized at 1124ºC for various periods to examine the evolving microstructure of internal oxidation. Third, as a function of time of isothermal oxidation (i.e., internal oxidation), thermal conductivity and coefficient of thermal expansion were measured for free-standing APS CoNiCrAlY bond coats. Thirteen CoNiCrAlY coatings were deposited on steel substrates by APS using the F4-MB plasma torch. APS CoNiCrAlY bond coats were produced by incremental variation in the flow rate of primary (argon) gas from 85 to 165 SCFH and the flow rate of secondary (hydrogen) gas from 9 to 29 SCFH. Optimum coating microstructure was produced by simultaneously increasing the flow rate of both primary and secondary gas, so that the particle temperature is high enough for sufficient melting and the particle velocity is rapid enough for minimum in-flight oxidation. Optimum spray parameters found in this study were employed to deposit free-standing APS CoNiCrAlY coatings that were isothermally oxidized at 1124ºC for 1, 6, 50,100, and 300 hours. Extent of internal oxidation was examined by scanning electron microscopy and image analysis. Internal oxidation occurred by a thickening of oxide scales segregated at the splat boundaries oriented parallel to the coating surfaces. Thermal conductivity and coefficient of thermal expansion (CTE) of the free-standing APS CoNiCrAlY coatings were measured as a function of internal oxidation (i.e., time of oxidation or extent of internal oxidation). Thermal conductivity of free-standing APS CoNiCrAlY was found to decrease with increasing internal oxidation from 28 to 25 W/m-K. This decrease is due to an increase in the amount of internal oxides with lower thermal conductivity (e.g., Al2O3). CTE of free-standing APS CoNiCrAlY, measured in temperature range of 100°~500°C, was also found to decrease with increasing internal oxidation. Internal oxides have lower CTE than metallic CoNiCrAlY coatings. These evolving properties of APS CoNiCrAlY should be beneficial to the overall performance of TBCs in gas turbine applications.

The purpose of this study is to characterize the plasma spray deposits used for attaching intrinsic Fabry-Perot interferometric fiber optic strain sensors. The deposits must maintain adhesion at elevated temperatures without distorting the sensors' signals. Two different material systems were tested and modeled, a nickel based alloy and yttria-stabilized zirconia. The material properties of the deposits and the thermal stresses in the system were evaluated to determine attachment lifetime of the sensors. The encapsulated sensors' signals were collected before and after plasma spraying and at elevated temperatures. The material properties of the deposits were evaluated by electron microscopy, energy dispersive x-ray spectroscopy, scratch testing, thermal fatigue testing, and nanoindentation. The thermal stresses were evaluated by Raman spectroscopy and from finite element analysis in COMSOL® Multiphysics®. Several of the sensors broke during encapsulation due to the plasma spray processing conditions and the signals experienced distortion at elevated temperatures. The sensors can be treated to remove this interference to allow for this deposit attachment. The nickel based alloy's ductility and lamellar microstructure allowed for non catastrophic relaxation mechanisms to relieve induced thermal stresses. The yttria stabilized zirconia failed catastrophically at elevated temperatures due its lack of compliance to mismatches in thermal expansion. A high melting point metallic deposit, similar to the nickel based alloy, is desirable for fiber optic sensor attachment due to its ductility, thermal expansion, and dominant relaxation mechanisms. The processing conditions may need to be optimized to allow for the sensors' protection during encapsulation. / Master of Science

Depuis sa création, la projection thermique ne cesse d’étendre son champ d’application en raison de ses potentialités à projeter des matériaux bien différents (métallique, céramique, plastique,...) sous des formes bien différentes aussi (poudre, fil, suspension, solution,...). Plusieurs types de procédés ont été développés afin de satisfaire les applications industrielles, par exemple, le procédé HVOF (High Velocity Oxygen Fuel), le procédé APS (Atmospheric Plasma Spraying), le procédé VLPPS (Very Low Pressure Plasma Spray). Parmi ces procédés, le procédé APS est aujourd’hui bien implanté dans l’industrie et en laboratoire réussissant à élaborer des revêtements de bonne qualité à coût intéressant. Néanmoins, cette technologie pâtit des incidences des instabilités du procédé sur la qualité du produit obtenu et souffre d’un manque de compréhension des relations entre les paramètres opératoires et les caractéristiques des particules en vol.Pour rappel, pendant la projection APS, les phénomènes d’instabilité du pied d’arc, d’érosion des électrodes, d’instabilité des paramètres opératoires ne peuvent pas être complètement éliminés. Et, il est encore aujourd’hui difficile de mesurer et de bien contrôler ces paramètres.Compte tenu des progrès réalisés sur les moyens de diagnostic qui peuvent être utilisés en milieu hostile (comme dans le cas de la projection APS), un contrôle efficace de ce procédé en boucle fermée peut être maintenant envisagé et requiert le développement d’un système expert qui se compose des réseaux de neurones artificiels et de logique floue. Les réseaux de neurones artificiels sont développés dans plusieurs domaines d’application et aussi maintenant au cas de la projection thermique. La logique floue quant à elle est une extension de la logique booléenne basée sur la théorie mathématique des ensembles flous. Nous nous sommes intéressés dans ce travail à bâtir le modèle de contrôle en ligne du procédé de projection basé sur des éléments d’Intelligence Artificielle et à construire un émulateur qui reproduise aussi fidèlement que possible le comportement dynamique du procédé. / Since its creation, the thermal spraying continuously expands its application scope because of its potential to project very different materials (metal, ceramic, plastic ...) as well as different forms (powder, wire, suspension, solution ...). Several types of methods have been developed to meet industrial applications, for example, the process HVOF (High Velocity Oxygen Fuel), the process APS (Atmospheric Plasma Spraying), the process VLPPS (Very Low Pressure Plasma Spray). Among these methods, the APS process is now well established in the industry and laboratory for successfully developing coatings with good quality but low cost. However, this technology suffers from the instability effect of the process on the obtained product quality and endures a lack of understanding of the relationship between the operating parameters and the characteristics of in-flight particles.As a reminder, during the projection APS, the arc foot instability phenomena, the electrode erosion, the instability of the operating parameters cannot be completely eliminated. Further, it is still difficult to measure and control these parameters well. With the developing technology of diagnostic tools that can be used in a hostile environment (as in the case of APS process), an effective control of APS process in closed-loop can be considered and requires the development of an expert system consisting of artificial neural networks and fuzzy logic controlling. The artificial neural networks have been developed in several application fields and now also to plasma spraying process. Fuzzy logic controlling is an extension of Boolean logic based on the mathematical theory of fuzzy sets.We are interested in this work to build an on-line control model for the APS process based on the elements of artificial intelligence and to build an emulator that replicates as closely as possible the dynamic behavior of the process. Further, the artificial neural networks will be combined with the emulator for constituting a big system who can monitor the process and also can automatically carry out modification action. The system then will be tested off-line, the time response will be discussed.