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.

La projection plasma de suspensions (SPS) est un procédé de revêtement de surface qui consiste à injecter une suspension (particules solides d’environ 1 μm ou moins, dispersées dans une phase liquide) dans un jet de plasma énergétique. Les particules sont chauffées, accélérées en direction d’un substrat, écrasées et soumises à une solidification très rapide (de l’ordre de 106 K.s-1). Couche après couche, un dépôt se forme en surface du substrat et lui apporte de nouvelles propriétés fonctionnelles. Cette variante de la projection plasma conventionnelle permet la fabrication de revêtements avec des épaisseurs plus fines de quelques dizaines de μm et une échelle microstructurale réduite, pouvant conduire à améliorer, par exemple, les performances de dureté ou de conductivité thermique des dépôts. Bien que ce procédé soit étudié depuis le milieu des années 1990 et connaisse un intérêt grandissant, les applications industrielles ne sont pas finalisées et leur développement nécessite d’être poursuivi. En effet, l’injection d’une suspension dans un jet thermique conduit à des phénomènes complexes tels que la fragmentation des gouttes de suspension ou encore l’évaporation de la phase liquide. A ce jour, ces mécanismes ne sont pas parfaitement compris et maîtrisés et méritent d’être étudiés pour comprendre les interactions de ces fines particules avec le plasma. Les travaux décrits dans ce mémoire s’intéressent au cas de la projection SPS de céramiques avec un atomiseur bi-fluide comme système d’injection. Deux matériaux ont été choisis : l’alumine, connue pour sa difficulté à être projetée conventionnellement et dont la formation de phases cristallines particulières constitue une source d’informations sur l’histoire thermique des particules, ainsi que l’yttrine, qui permet de confirmer les tendances observées pour l’alumine. Dans un premier temps, l’optimisation de l’injection de la suspension a été effectuée en travaillant sur deux axes. Le premier axe concerne la formulation des suspensions, qui a conduit à l’obtention, avec différentes phases liquides, de suspensions stables et dispersées, de propriétés parfaitement connues. De telles suspensions assurent une reproductibilité du procédé à ce niveau et limitent le bouchage du système d’injection. Le deuxième axe porte sur la conception mécanique en trois étapes d’un atomiseur pneumatique approprié au procédé SPS. Cette étude a commencé par la caractérisation d’une buse commerciale notamment par des tests d’injection de suspension dans le plasma. Les tests étant peu concluants, l’étude s’est poursuivie par la mise au point d’une nouvelle géométrie d’atomiseur inspirée du modèle commercial. Les essais ont conduit à la réalisation de cordons et de dépôts satisfaisants. Cette étude s’est terminée enfin par l’optimisation de sa géométrie grâce à la mise en évidence de l’influence de plusieurs paramètres-clé sur les caractéristiques du jet atomisé. Dans un second temps, des outils de diagnostic ont été mis en oeuvre pour mesurer la qualité de l’injection. Le jet de suspension a été caractérisé en termes de géométrie et de tailles de gouttes, respectivement par ombroscopie et diffraction laser. L’ombroscopie a été réutilisée pour l’optimisation de l’injection de la suspension dans le plasma en permettant le réglage en temps réel des pressions d’entrée de l’atomiseur. Les propriétés des particules en vol ont ensuite été étudiées grâce à des collectes de particules sur substrat et à la vélocimétrie par images de particules (PIV). Cet outil a apporté des informations complémentaires sur l’injection de la suspension. Enfin, les revêtements obtenus ont été caractérisés en termes de morphologie (MEB), taux de porosité (analyse d’images MEB et USAXS) et de phases cristallines (DRX et EBSD). Le couplage des informations obtenues entre ces différentes techniques a permis de faire ressortir le rôle de la phase liquide et de la charge massique sur la microstructure... / Suspension plasma spray (SPS) is a surface coating process that consists in injecting a suspension (solid particles of about 1 μm or less, dispersed in a liquid phase) in a high-energy plasma flow. Particles are heated, accelerated towards a substrate, flattened and submitted to a rapid solidification (order of 106 K.s-1). Layer after layer, a coating is formed on the substrate surface and brings new functional properties. This variation of the conventional plasma spray process allows the manufacturing of coatings with finer thickness of few tens of μm and a reduced structural scale that can lead to improved coating properties, like hardness or thermal conductivity. Even though this process has been studied since the middle of the 1990’S and known a fast-growing interest, industrial applications are not finalized and their development needs to be pursued. Indeed, the suspension injection in a thermal jet leads to complex phenomena such as suspension droplet fragmentation or liquid phase evaporation. Up to now, these mechanisms are not perfectly understood and controlled and deserve to be further studied to understand interactions between these fine particles and the plasma. This thesis focuses on the SPS process with ceramic suspensions and a twin-fluid nozzle as injection system. Two materials were chosen: alumina, known for its difficulty to be conventionally sprayed and whose crystalline phase formation represents a source of information about particle thermal history, and also yttria, in order to confirm the tendencies observed for alumina. Firstly, the suspension injection was optimized by working on two areas. The first area concerns suspension formulation. This led to obtain, with different liquid phases, stable and dispersed suspensions, whose properties are perfectly known. Such suspensions ensure reproducibility of the process at this level and limit the risk of injection system clogging. The second area is about the three-step mechanical conception of a pneumatic atomizer, adapted to the SPS process. This study began with the characterization of a commercial nozzle, in particular by testing the suspension injection into a plasma flow. Tests being little convincing, the study was carried on with the development of a new atomizer geometry, inspired from the commercial model. Trials drove to the manufacturing of satisfying spray beads and coatings. This study was finally completed with the optimization of this new geometry by highlighting the influence of several key parameters on the atomized jet features. Secondly, diagnostic tools were implemented to qualify the injection. Suspension jet was characterized in terms of geometry and droplet sizes, using respectively shadowgraphy and laser diffraction. Shadowgraphy was used again for optimizing the suspension injection into plasma by allowing the adjustment in real time of inlet atomizer pressures. In-flight particle properties were then studied thanks to particle collection onto a substrate and particle image velocimetry (PIV). This tool also provided additional information on the suspension injection. Finally, the resulting coatings were characterized in terms of morphology (SEM), porosity rate (SEM image analysis and USAXS) and crystalline phases (DRX and EBSD). The cross-checking of the information obtained with all these techniques brought out the role of the suspension liquid phase and of the mass load on the coating microstructure. These works contributed to enhance the knowledge about the SPS process and justified the use of a twin-fluid nozzle to obtain specific microstructures of coatings, whose functional characterizations have still to be done.

Ce travail se compose de deux parties : la première partie traite de la formation de dépôts épais du composé YBa2Cu3O7-x par la technique électrophorétique (EPD) tandis que la seconde décrit la réalisation de dépôts par la technique de projection plasma. Dans le cadre de la méthode EPD, des suspensions aqueuses et non-aqueuses ont été étudiées. Plus particulièrement, des suspensions à base dacétone en présence ou non diode ont été caractérisées de manière approfondie. A laide de ces résultats, un mécanisme de charge des particules a été proposé. La cinétique de dépôt de lYBa2Cu3O7-x par EPD a également été étudiée. Les dépôts formés ont montré des propriétés supraconductrices sur substrat dAg. Une densité de courant critique Jc (77 K, H=0) de lordre de 103 A/cm² a été obtenue. Finalement, une méthode de texturation sous champ magnétique appliquée à lEPD a été explorée. Pour la technique de projection plasma, différents paramètres opératoires ont été étudiés. Par un traitement thermique adéquat du dépôt sur substrat de Ni, la phase supraconductrice a été obtenue.

Solid oxide fuel cells (SOFCs) that operate directly on hydrocarbon fuels eliminate the requirement for costly and complex external reforming systems. Atmospheric plasma spraying (APS) is an established manufacturing method that offers the potential to fabricate direct oxidation SOFC anodes in a single step, instead of the multiple steps currently required. Manufacturing by APS also allows the use of metal supports, which improve thermal shock resistance, allow rapid cell heat-up, and reduce total cost. In this study, direct oxidation SOFC anodes based on Cu and samaria-doped ceria (SDC) in combination with Co and/or Ni were investigated for their stability and performance in H2 and CH4 when plasma sprayed on ferritic stainless steel supports. Several different APS techniques were investigated. Two of these techniques were hybrid methods involving a combination of dry powder plasma spray and suspension plasma spray (SPS) processes. These techniques were proposed to help balance the degree of melting of the lower melting temperature oxides of the metals Cu, Co, and Ni with that of the higher melting temperature SDC. The use of a single suspension containing all of the anode component feedstocks was also investigated. Multi-component aqueous suspensions of CuO, Co3O4, and NiO were developed with or without the addition of carbon black and SDC. It was found that the use of a hybrid plasma spray technique can help to improve deposition efficiency (D.E.) and enhance partial melting of the low melting temperature feedstocks. However, plasma spraying all of the components in a single suspension can lead to more homogeneous mixing and greater resistance to metal coarsening at SOFC operating temperatures. In electrochemical tests of plasma-sprayed metal-supported cells containing these anodes, peak power densities as high as 0.6 W/cm2 were achieved at 750 deg C in humidified H2. In CH4, power density was limited by the activity of the anodes. Stability in CH4 was poor because of oxidation of the metal support and enhanced coking behaviour resulting from interactions between Fe in the support and Co and Ni in the anodes. When separated from the supports, the anodes demonstrated very low coking rates in thermogravimetric analysis experiments in CH4.

Solid oxide fuel cells (SOFCs) that operate directly on hydrocarbon fuels eliminate the requirement for costly and complex external reforming systems. Atmospheric plasma spraying (APS) is an established manufacturing method that offers the potential to fabricate direct oxidation SOFC anodes in a single step, instead of the multiple steps currently required. Manufacturing by APS also allows the use of metal supports, which improve thermal shock resistance, allow rapid cell heat-up, and reduce total cost. In this study, direct oxidation SOFC anodes based on Cu and samaria-doped ceria (SDC) in combination with Co and/or Ni were investigated for their stability and performance in H2 and CH4 when plasma sprayed on ferritic stainless steel supports. Several different APS techniques were investigated. Two of these techniques were hybrid methods involving a combination of dry powder plasma spray and suspension plasma spray (SPS) processes. These techniques were proposed to help balance the degree of melting of the lower melting temperature oxides of the metals Cu, Co, and Ni with that of the higher melting temperature SDC. The use of a single suspension containing all of the anode component feedstocks was also investigated. Multi-component aqueous suspensions of CuO, Co3O4, and NiO were developed with or without the addition of carbon black and SDC. It was found that the use of a hybrid plasma spray technique can help to improve deposition efficiency (D.E.) and enhance partial melting of the low melting temperature feedstocks. However, plasma spraying all of the components in a single suspension can lead to more homogeneous mixing and greater resistance to metal coarsening at SOFC operating temperatures. In electrochemical tests of plasma-sprayed metal-supported cells containing these anodes, peak power densities as high as 0.6 W/cm2 were achieved at 750 deg C in humidified H2. In CH4, power density was limited by the activity of the anodes. Stability in CH4 was poor because of oxidation of the metal support and enhanced coking behaviour resulting from interactions between Fe in the support and Co and Ni in the anodes. When separated from the supports, the anodes demonstrated very low coking rates in thermogravimetric analysis experiments in CH4.

High fuel utilization SOFCs could eliminate emissions from systems that include afterburners and potentially be suitable for carbon sequestration, while producing electricity more efficiently. Current fuel utilization operating points are typically chosen at approximately 85% for Ni-cermet anodes because higher fuel utilization frequently results in the formation of nickel oxide and reduces drastically the performance of the SOFC. In this work the feasibility of an in-plane graded anode architecture with a transition from a material with high catalytic activity to materials more stable under high fuel utilization conditions was evaluated through a steady-state SOFC finite element model. Thereafter, plasma spraying of solution precursor feedstock (SPPS) and suspension feedstock (SPS) was used to fabricate ceramic coatings that could potentially be used as SOFC anodes for high fuel utilization conditions. Microstructural, electrical and electrochemical properties of LST, LSBT and LSFCr coatings with additions of carbon black pore former were investigated.

High fuel utilization SOFCs could eliminate emissions from systems that include afterburners and potentially be suitable for carbon sequestration, while producing electricity more efficiently. Current fuel utilization operating points are typically chosen at approximately 85% for Ni-cermet anodes because higher fuel utilization frequently results in the formation of nickel oxide and reduces drastically the performance of the SOFC. In this work the feasibility of an in-plane graded anode architecture with a transition from a material with high catalytic activity to materials more stable under high fuel utilization conditions was evaluated through a steady-state SOFC finite element model. Thereafter, plasma spraying of solution precursor feedstock (SPPS) and suspension feedstock (SPS) was used to fabricate ceramic coatings that could potentially be used as SOFC anodes for high fuel utilization conditions. Microstructural, electrical and electrochemical properties of LST, LSBT and LSFCr coatings with additions of carbon black pore former were investigated.

Atmospheric plasma spraying is attractive for manufacturing solid oxide fuel cells (SOFCs) because it allows functional layers to be built rapidly with controlled microstructures. The technique allows SOFCs that operate at low temperatures (600 to 750°C) to be fabricated by spraying directly onto robust and inexpensive metallic supports. Processes were developed to manufacture metal-supported SOFC cathodes by axial-injection plasma spraying. Cathodes consisted of LSCF (La0.6Sr0.4Co0.2Fe0.8O3-δ) or SSC (Sm0.5Sr0.5CoO3) as the primary material. Initially, the plasma spray process parameters were varied, and x-ray diffraction analyses were performed on the cathode coatings to detect material decomposition and the formation of undesired phases. These results determined the envelope of plasma spray parameters in which coatings of LSCF and SSC can be manufactured, and the range of conditions in which composite cathode coatings could potentially be manufactured. Subsequently, composite cathodes were fabricated by mixing up to 40 wt. % of the ionic conducting SDC (Ce0.8Sm0.2O1.9) material into the feedstock. The deposition efficiencies of these cathodes were calculated based on the mass of the sprayed cathode. Particle surface temperatures were measured in-flight to enhance understanding of the relationship between spray parameters, microstructure, and deposition efficiency. Electrochemical impedance spectroscopy was performed in symmetrical cells: at 750°C, LSCF-SDC cathodes had polarization resistances as low as 0.101 Ωcm², and SSC cathodes had polarization resistances as low as 0.0056 Ωcm². Finer mixing of the ceramic phases was achieved by using a nano-structured feedstock that contained both LSCF and SDC phases agglomerated together in larger particles. Fuel cells containing a yttria-stabilized zirconia (YSZ) electrolyte and a nickel-YSZ anode were fabricated, and the effect of the cathode microstructure on cell impedance was studied using the analysis of differential impedance spectra. The degradation of composite LSCF-SDC cathodes on porous 430 stainless steel supports was also investigated. To reduce degradation, La2O3 and Y2O3 reactive element oxide coatings were deposited on the internal pore surfaces of the metal supports. As a result, polarization resistance degradation rates as low as 0.00256 Ω·cm2 /1000 h were observed over 100 hours on coated substrates, compared to 0.1 Ω·cm2 /1000 h on uncoated substrates.

Atmospheric plasma spraying is attractive for manufacturing solid oxide fuel cells (SOFCs) because it allows functional layers to be built rapidly with controlled microstructures. The technique allows SOFCs that operate at low temperatures (600 to 750°C) to be fabricated by spraying directly onto robust and inexpensive metallic supports. Processes were developed to manufacture metal-supported SOFC cathodes by axial-injection plasma spraying. Cathodes consisted of LSCF (La0.6Sr0.4Co0.2Fe0.8O3-δ) or SSC (Sm0.5Sr0.5CoO3) as the primary material. Initially, the plasma spray process parameters were varied, and x-ray diffraction analyses were performed on the cathode coatings to detect material decomposition and the formation of undesired phases. These results determined the envelope of plasma spray parameters in which coatings of LSCF and SSC can be manufactured, and the range of conditions in which composite cathode coatings could potentially be manufactured. Subsequently, composite cathodes were fabricated by mixing up to 40 wt. % of the ionic conducting SDC (Ce0.8Sm0.2O1.9) material into the feedstock. The deposition efficiencies of these cathodes were calculated based on the mass of the sprayed cathode. Particle surface temperatures were measured in-flight to enhance understanding of the relationship between spray parameters, microstructure, and deposition efficiency. Electrochemical impedance spectroscopy was performed in symmetrical cells: at 750°C, LSCF-SDC cathodes had polarization resistances as low as 0.101 Ωcm², and SSC cathodes had polarization resistances as low as 0.0056 Ωcm². Finer mixing of the ceramic phases was achieved by using a nano-structured feedstock that contained both LSCF and SDC phases agglomerated together in larger particles. Fuel cells containing a yttria-stabilized zirconia (YSZ) electrolyte and a nickel-YSZ anode were fabricated, and the effect of the cathode microstructure on cell impedance was studied using the analysis of differential impedance spectra. The degradation of composite LSCF-SDC cathodes on porous 430 stainless steel supports was also investigated. To reduce degradation, La2O3 and Y2O3 reactive element oxide coatings were deposited on the internal pore surfaces of the metal supports. As a result, polarization resistance degradation rates as low as 0.00256 Ω·cm2 /1000 h were observed over 100 hours on coated substrates, compared to 0.1 Ω·cm2 /1000 h on uncoated substrates.

Conventional yttria stabilized zirconia (YSZ) are widely used in the gas turbine to protect the substrate material from high temperature. But the common YSZ top coatings have limitations at higher temperature (above 1200 ℃) due to significant phase transformation and intensified sintering effect. Among the list of pyrochlores, gadolinium zirconate offer very attractive properties like low thermal conductivity, high thermal expansion coefficient and CMAS resistance. However, a lower fracture toughness than YSZ and tendency to react with alumina (thermal grown oxide) can lead to lower lifetime. Therefore, multi-layered thermal barrier coating approach was attempted and compared with single layer system. Single layer (YSZ) was processed by suspension plasma spraying (SPS). Double layer coating system comprising of YSZ as the bottom ceramic layer and gadolinium zir-conate as the top ceramic coat was processed by SPS. Also, a triple layer coating system with denser gadolinium zirconate on top of double layer system, was sprayed. Denser gado-linium zirchonate acts as the sealing layer and arrest the CMAS penetration. Isothermal oxidation performance of the sprayed coating systems including bare substrate and sub-strate with bond coat were investigated for a time period of 10hr, 50hr and 100hr at 1150℃ in air environment. Weight gain was observed in all the systems investigated. Microstruc-tural analysis was carried out using optical microscopy, SEM/EDS. Phase analysis was done using X-ray diffraction (XRD). Porosity measurement was made by water impregna-tion method. It was observed that multi-layered thermal barrier coating systems of YSZ/GZ and YSZ/GZ/GZ(dense) showed lower weight gain and TGO thickness than the single layer YSZ for all exposure time (10hr, 50hr & 100hr). The triple layer system had lower weight gain and TGO thickness compared to double layer system due to lower po-rosity content. Also, from the porosity measurement data, it could be seen that sintering effect is more dominant at 10 hr. of oxidation for all the coatings systems.