Investigation of momentum and heat transfer between the fluid and solid phase is critical to the study of fluid-particle systems. Dense suspensions are characterized by the solid fraction (ratio of solid volume to total volume), the particle Reynolds number, and the shape of the particle. The behavior of non-spherical particles deviates considerably from spherical particle shapes which have been studied extensively in the literature. Momentum transfer, to first-order, is driven by drag forces experienced by the particles in suspension, followed by lift and lateral forces, and also through the transmission of fluid torque to the particles. The subject of this thesis is a family of prolate ellipsoidal particle geometries of aspect ratios (AR) 2.5, 5.0 and 10.0 at nominal solid fractions (φ) between 0.1 and 0.3, and suspensions of cylinders of AR=0.25. The nominal particle Reynolds number (Re) is varied between 10 to 200, representative of fluidized beds. Fluid forces and heat transfer coefficients are obtained numerically by Particle Resolved Simulations (PRS) using the Immersed Boundary Method (IBM). The method enables the calculation of the interstitial flow and pressure field surrounding each particle in suspension leading to the direct integration of fluid forces acting on each particle in the suspension. A substantial outcome of the research is the development of a new drag force correlation for random suspensions of prolate ellipsoids over the full range of geometries and conditioned studied. In many practical applications, especially as the deviation from the spherical shape increases, particles are not oriented randomly to the flow direction, resulting in suspensions which have a mean preferential orientation. It is shown that the mean suspension drag varies linearly with the orientation parameter, which varies from -2.0 for particles oriented parallel to the flow direction to 1.0 for particles normal to the flow direction. This result is significant as it allows easy calculation of drag force for suspension with any preferential orientation. The heat transfer coefficient or Nusselt number is investigated for prolate ellipsoid suspensions. Significantly, two methods of calculating the heat transfer coefficient in the literature are reconciled and it is established that one asymptotes to the other. It is also established that unlike the drag force, at low Reynolds number the suspension mean heat transfer coefficient is very sensitive to the spatial distribution of particles or local-to-particle solid fractions. For the same mean solid fraction, suspensions dominated by particle clusters or high local solid fractions can exhibit Nusselt numbers which are lower than the minimum Nusselt number imposed by pure conduction on a single particle in isolation. This results from the dominant effect of thermal wakes at low Reynolds numbers. As the Reynolds number increases, the effect of particle clusters on heat transfer becomes less consequential. For the 0.25 aspect ratio cylinder, it was found that while existing correlations under predicted the drag forces, a sinusoidal function F_(d,θ)=F_(d,θ=0°)+(F_(d,θ=90°)-F_(d,θ=0°) )sin⁡(θ) captured the variation of normalized drag with respect to inclination angle over the range 10≤Re≤300 and 0≤φ≤0.3. Further the mean ensemble drag followed F_d=F_(d,θ=0°)+1/2(F_(d,θ=90°)-F_(d,θ=0°)). It was shown that lift forces were between 20% to 80% of drag forces and could not be neglected in models of fluid-particle interaction forces. Comparing the pitching fluid torque to collision torque during an elastic collision showed that as the particle equivalent diameter, density, and collision velocities decreased, fluid torque could be of the same order of magnitude as collisional torque and it too could not be neglected from models of particle transport in suspensions. / Doctor of Philosophy / Momentum and heat exchange between the fluids (air, water…) and suspensions of solid particles plays a critical role in power generation, chemical processing plants, pharmaceuticals, in the environment, and many other applications. One of the key components in momentum exchange are the forces felt by the particles in the suspension due to the flow of the fluid around them and the amount of heat the fluid can transfer to or from the particles. The fluid forces and heat transfer depend on many factors, chief among them being the properties of the fluid (density, viscosity, thermal properties) and the properties of the particles in the suspension (size, shape, density, thermal properties, concentration). This introduces a wide range of parameters that have the potential to affect the way the fluid and particles behave and move. Experimental measurements are very difficult and expensive to conduct in these systems and computational modeling can play a key role in characterization. For accuracy, computational models have to have the correct physical laws encoded in the software. The objective of this thesis is to use very high-fidelity computer models to characterize the forces and heat transfer under different conditions to develop general formulas or correlations which can then be used in less expensive computer models. Three basic particle shapes are considered in this study, a sphere, a disk like cylindrical particles, and particles of ellipsoidal shapes. More specifically, Particle Resolved Simulations of flow through suspensions of ellipsoids with aspect ratio of 2.5, 5, 10 and cylinders with aspect ratio of 0.25 are performed. The Reynolds number range covered is [10, 200] for ellipsoids and [10, 300] for cylinders with solid fraction range of [0.1, 0.3]. New fluid drag force correlations are proposed for the ellipsoid and cylinder suspensions, respectively, and heat transfer behavior is also investigated.

Poor indoor air quality is a source of adverse health effects. TiO2 coatings deposited on well-illuminated surfaces, such as window panes, can be used to fully mineralize indoor air pollutants by photocatalysis. In such applications it is important to ensure stable photocatalytic activity for a wide range of operating conditions, such as relative humidity and temperature, and to avoid deactivation of the catalyst. In this thesis photocatalytic removal of the indoor-pollutant acetaldehyde (CH3CHO) on nanostructured TiO2 films is investigated, and in particular it is proposed how such films can be modified and operated for maximum performance. Catalyst deactivation can be reduced by purposefully changing the surface acidity of TiO2 by covalently attaching SO4 to the surface. Moreover, the overall photocatalytic activity on anatase TiO2 films can be improved by increasing the fraction of exposed reactive {001} surfaces, which otherwise are dominated by {101} surfaces. In the first part of the thesis mode-resolved in-situ FTIR is used to elucidate the reaction kinetics of CH3CHO adsorption and photo-oxidation on the TiO2 and SO4 – modified TiO2 surfaces. Surface concentrations of main products and corresponding reaction rates were determined. Formate is the major reaction product, whose further oxidation limits the complete oxidation to gaseous species, and is responsible for photocatalyst deactivation by site inhibition. The oxidation reaction is characterized by two reaction pathways, which are associated with two types of surface reaction sites. On the sulfate modified TiO2 catalyst fewer intermediates are accumulated, and this catalyst resists deactivation much better than pure TiO2. A hitherto unknown intermediate – surface-bound acetaldehyde dimer with an adsorption band at 1643 cm−1 was discovered, using interplay between FTIR spectroscopy and DFT calculations. The second part of the thesis treats the effect of increasing the relative abundance of exposed {001} facets on the photocatalytic activity of anatase TiO2 films prepared by DC magnetron sputtering. A positive effect was observed both for liquid-phase photo-oxidation of methylene blue, and for gas-phase photocatalytic removal of CH3CHO. In both cases it was found that the exposed {001} surfaces were an order of magnitude more reactive, compared to the {101} ones. Furthermore, it was found that the reactive films were more resilient towards deactivation, and exhibited almost unchanged activity under varying reaction conditions. Finally, a synergetic effect of SO4 – modification and high fraction of exposed {001} surfaces was found, yielding photocatalysts with sustained high activity. The results presented here for facet controlled and chemically modified TiO2 films are of interest for applications in the built environment for indoor air purification and as self-cleaning surfaces. / GRINDOOR

Cette étude a pour but la mise au point d'un procédé de dépôt en vue de réaliser des fibres piézoélectriques. Ces fibres pourront être utilisées soit comme jauge de déformation (extensomètre) soit comme système de récupération d'énergie liée au mouvement d'un utilisateur (tissu) pour alimenter un dispositif d'électronique embarqué. Une fibre piézoélectrique constituée d'un dépôt cylindrique d'oxyde de zinc sur un fil d'acier inoxydable a été réalisée par pulvérisation magnétron à impulsion de haute puissance (HiPIMS) à l'aide d'un prototype de traitement au défilé conçu, réalisé et décrit lors de cette étude. Une caractérisation précise des échantillons réalisés dans différentes conditions expérimentales a permis de décrire et comprendre en partie les mécanismes de croissance des dépôts, ceci de manière, en particulier, à déterminer les conditions de fonctionnement optimum pour l'élaboration de dépôts possédant une orientation cristalline préférentielle hors plan. Pour envisager le traitement de fibres ne supportant pas les hautes températures nous avons montré qu'il était possible de contrôler cette température en ajustant certains paramètres du procédé, tel que la pression et la puissance moyenne. Un mécanisme de germination préférentielle suivi d'une croissance par auto-épitaxie a été proposé afin d'expliquer la très forte orientation préférentielle des films réalisés à faible température. Pour des fortes valeurs de courant crête, le phénomène de germination préférentielle associé à la croissance évolutionnaire pourrait favoriser l'orientation (101)*. Pour les plus fortes valeurs de courant, aucune orientation préférentielle n'est observée et les fortes contraintes mesurées ont été attribuées à l'excès d'oxygène détecté dans les couches / A piezoelectric fiber constituted of ZnO cylindrical coating on a stainless steel wire has been achieved by High Power Impulse Magnetron Sputtering (HiPIMS) by using a prototype designed and assembled during this PhD work. The piezoelectric fiber can be used as a strain probe or as a vibration harvesting generator for embedded electronics. The analyses of deposited layer allow to understand ZnO growth mechanism in order to optimize to deposition process. A special emphasis has been placed on the selection of preferential orientation during the growth. The low volume of steel wire, allow to control his temperature by adjusting some process parameters, like the pressure and the average power. Temperature sensitive wires (e.g. polymer) can be treated in the mildest conditions. Preferential nucleation followed by self-epitaxy have been proposed to explain the very strong preferential orientation identified in coatings deposited at low temperature. At high peak current, preferential nucleation and evolutionary growth can promote the (101)* orientation. At highest peak currents no preferential orientation was identified and the high residual stress has been attributed to the excess of oxygen in the coating