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The use of colloidal quantum dots (QDs) for photovoltaic energy conversion is a nascent field that has been dominated for well over a decade by the use of 3-mercaptopropionic acid (3-MPA) capped PbS QDs. These QDs are routinely deposited via an in situ solid state ligand exchange process that displaces the native oleate ligand on the PbS QD surface. This ligand exchange procedure is wasteful of material and has been demonstrated to leave numerous impurities that limit electronic performance of the as-deposited QD devices. Until the last few years there was very little understanding in chemical literature as to many important aspects of QD chemistry for this material pairing outside the framework of a QD solid. In this work, a colloidal suspension of 3-MPA capped PbS QDs in DMSO was formulated and investigated to probe ligand dynamics and optical properties of the suspended colloid. QD bound 3-MPA was found to be in dynamic exchange with "free" ligand in solution by 1H-NMR spectroscopy. Optical properties and colloidal stability were found to be heavily dependent on the presence of a significant excess of free ligand. PbS QDs were also found to be highly photo-catalytic towards oxidative dimerization of 3-MPA to its dimer, dithiodipropionic acid (dTdPA). After an initial colloidal suspension was achieved, attempts were made to directly deposit the colloid as a QD "ink" to form optoelectronic devices. While photo-switchable devices were obtained, ultimately it was determined that DMSO was a largely incompatible solvent choice for solution processing methodologies. Subsequently, 3-MPA capped PbS QD colloids were obtained in volatile organic solvents amenable to solution processing by the addition of a stabilizing ammonium salt. These QD colloids maintained excellently resolved optical properties and were able to form conformal coatings from simple evaporative deposition. The ligand chemistry of this colloid was extensively investigated via NMR and optical spectroscopy. These QDs were also found to be highly photo-catalytic towards conversion of monomer 3-MPA to dTdPA.

The objective of this Thesis is to devise a system for the "rheology-based design" of non-settling (homogeneous) slurry pipelines that is more conducive to application by practicing engineers without impairing its accuracy or utility for research purposes. The cornerstone is the development of a new rheological model and constitutive equation for homogeneous slurry based on the aggregation/deaggregation of the suspended mineral particles. This “yield plastic” model is shown to describe a family of models that includes the Newtonian, Bingham plastic and Casson models as special cases. It also closely approximates the results of many consistency models, including power law, yield power law, Cross and Carreau-Yasuda. The yield plastic model is then used to develop design equations to determine the pressure-gradient of laminar and turbulent pipe flow. A relative energy dissipation criterion is proposed for the laminar-turbulent transition and shown to be consistent with currently used transition models for Newtonian and Bingham fluids. Finally, a new dimensionless group (the “stress number”) is proposed that is directly proportional to the pressure-gradient and independent of the velocity. When the design equations are presented graphically in terms of the stress number and the plastic Reynolds number, the resulting “design curve diagram” is shown to be a dimensionless (pressure-gradient vs. velocity) pipe flow curve. The net result is that the hydraulic design of homogeneous slurry systems only requires the use of a single constitutive equation and three engineering design equations. The results are presented in a conceptually easy form that will foster an intuitive understanding of non-Newtonian pipe flow. This will assist engineers to understand the impact of slurry rheology when designing, operating and troubleshooting slurry pipelines and, in the future, other slurry related processes. / Applied Science, Faculty of / Mining Engineering, Keevil Institute of / Graduate

This thesis is concerned with the use of semi-active suspensions in heavy vehicles to improve ride and reduce road damage. An introduction into the subject is given in chapter 1 and a review of the relevant literature is presented at the beginning of each main chapter. The development and modelling of a prototype, continuously variable semi-active damper for heavy vehicles is described in chapter 2. A proportional valve is used to generate the variable damping coefficient and the detrimental effects of the oil flow forces acting on the valve spool are studied. The force tracking performance of the damper is then examined for simple input conditions and the compliance of the hydraulic fluid is found to have a strong influence upon the response of the damper. The different vehicle and road models used in the thesis are described in chapter 3. In chapter 4, the performance of the prototype damper is investigated under realistic operating condition using a Hardware-in-the-Loop (HiL) test rig, with a single wheel station vehicle model. The prototype damper displays a phase lag of approximately 20ms between the demanded and achieved damping force. The semi-active suspension is found to be most effective in reducing the body accelerations relative to an optimum non-linear passive suspension. A theoretical investigation into the reduction of road damage through the use of active and semi-active suspensions is described in chapter 5. The relative performance of four linear state feedback control strategies is examined. The potential for reducing road damage by using a controller which directly regulates various measures of road damage is also studied. Significant improvements are predicted for the three controllers which assume the road inputs to the vehicle are correlated. However, these benefits are shown to diminish as the vehicle speed is reduced. It is concluded that the control of the dynamic tyre forces is an effective means by which to regulate road damage. Theoretical predictions of the benefits from wheelbase preview control are measured experimentally in chapter 6, using the prototype semi-active damper in a half-car HiL rig with a planar two axled heavy vehicle model. The benefits of preview control using the prototype semi-active damper are found to be less than theoretically possible due to the phase lag between the demanded and achieved damping force of the prototype damper. The final section of chapter 6 shows that the performance of the prototype damper can be improved further by having a theoretical simulation running ahead of the HiL vehicle. The theoretical simulation is used to predict the demanded damper force for the HiL vehicle and thereby compensate for the phase lag in the prototype damper. Conclusions and recommendations for further work are presented in chapter 7.

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No description available.

No description available.

Following successful implementation of inerters for passive mechanical control in racing cars, this research studies potential innovative solutions for railway vehicle suspensions by bringing the inerter concept to the design of mechatronic systems. The inerter is a kinetic energy storage device which reacts to relative accelerations; together with springs and dampers, it can implement a range of mechanical networks distinguished by their frequency characteristics. This thesis investigates advantages of inerter-based novel devices to simplify the design of active solutions. Most of the research work is devoted to the enhancement of vertical ride quality; integrated active-plus-novel-passive solutions are proposed for the secondary suspensions. These are defined by different active control strategies and passive configurations including inerters. By optimisation of the suspension parameters, a synergy between passive and active configurations is demonstrated for a range of ride quality conditions. The evidence of cooperative work is found in the reduction of the required active forces and suspension travelling. This reveals a potential for reducing the actuator size. Benefits on power requirements and actuator dynamic compensation were also identified. One of the strategies features a nonlinear control law proposed here to compensate for 'sky-hook' damping effects on suspension deflection; this, together with inerter-based devices attains up to 50% in active force reduction for a setting providing 30% of ride quality enhancement. The study is developed from both, an analytical and an engineering perspective. Validation of the results with a more sophisticated model is performed. The lateral stability problem was briefly considered towards the end of the investigation. A potential use of inerter-based devices to replace the static yaw stiffness by dynamic characteristics was identified. This leads to a synergy with 'absolute stiffness', an active stability solution for controlling the wheelset 'hunting' problem, for reducing the creep forces developed during curve negotiation.

Pour construire le lien entre l'organisation structurale des milieux dispersés concentrés et leurs propriétés mécaniques, il est nécessaire de pourvoir identifier leur structure à l'échelle microscopique. En particulier, il faut être capable mesurer la taille des particules ou des amas de particules, leur concentration et les éventuelles anisotropies liées à une déformation ou une orientation (globale ou partielle) dans le cas de particules anisotropes (fibres par exemple) ou déformables (émulsions, globules rouges,...). La difficulté majeure est que ces systèmes composés de particules micrométriques sont généralement opaques à la lumière visible (produits agroalimentaires tels que les laitages, fluides biologiques tels que le sang, matériaux liés au bâtiment tels que les ciments, les argiles ou les peintures,...). Nous avons ainsi mis au point une technique optique basée sur la diffusion multiple de la lumière. Dans le cadre de cette thèse, nous nous intéressons plus particulièrement à la caractérisation des milieux constitués d'objets anisotropes. Sous l'action d'un champ de cisaillement, on observe une orientation privilégiée ou une déformation globale des particules. L'objectif de cette thèse est donc à la fois d'étudier les mécanismes qui sont à l'origine de la déformation et/ou l'orientation des particules et également de mesurer ces anisotropies à l'échelle microscopique. On s'appuie pour mener cette étude sur un dispositif développé au laboratoire basé sur le transport incohérent de lumière couplé à un rhéomètre. Il s'agit d'un dispositif constitué d'une source laser focalisée à la surface d'un échantillon et d'une caméra CCD permettant l'acquisition d'une image rétrodiffusée loin du point d'impacte du laser. Parallèlement, une base de données de simulation de Monte Carlo est en cours de réalisation permettant par analyse des images rétrodiffusées anisotropes, de remonter à l'information sur l'anisotropie réelle des particules (facteur de forme) leur champ d'orientation (paramètre d'ordre). En effet, en confrontant les données expérimentales aux données numériques, nous sommes en mesure de déterminer le taux d'orientation moyen de particules très anisotropes ou de caractériser la déformation des particules. Une application à la déformation des rouges sous cisaillement pour du sang en concentration physiologique (40 à 50% en volume) sera présentée. D'autres applications, notamment à l'endommagement des plastiques et à l'orientation de suspensions de fibres seront discutées / To build the link between the structural organization between concentrated dispersions and their mechanical properties, you have to be able to identify their microscopic structure. In particular, for anisotropic particles (fibbers for example) or deformable particles (emulsions, red blood cells...), the knowledge of the particle size, the concentration, the deformation or the orientation of particles (partial or global) are very important. Most of concentrated dispersions are generally opaque to visible light (biological fluids as blood, clays...). An optical diffusing method based on multiple diffusion light has been developed in the laboratory to study this kind of materials. In this thesis, we are interested in the general problem of characterizing concentrated dispersions with anisotropic objects. Under shear rate, a preferential orientation or a global deformation of particles has been observed. The objective of this thesis is to study the mechanisms which involve deformation and/or orientation of anisotropic particles. An experimental device based on the incoherent light transport has been developed at the laboratory in order to determine the orientation or the deformation. The experimental device is composed of a focused laser diode and a CCD camera to acquire the backscattered images. A data base of Monte Carlo simulation has been created in order to get the form factor or the orientation of particles by analyse of anisotropic backscattered images. By comparing the numerical data with the experimental data, we are able to determine the average rate of orientated particles. Thanks to this optical diffusing method, the deformation of red blood cells in physiological concentration (40 to 50% volume fraction) and the orientation of fibbers dispersion has been study

La microfiltration est largement utilisée pour la clarification, la stabilisation et la concentration de nombreuses suspensions à base de fruits (jus de fruits, agro-déchets, vin, etc.). Malgré ses divers avantages, la microfiltration présente néanmoins un inconvénient majeur qui est le phénomène de colmatage qui s’installe pendant l’opération de filtration et entraîne une diminution de la perméabilité membranaire. Si de nombreux mécanismes de colmatage (adsorption, blocage de pores, etc.) sont observés pendant la filtration de suspensions polydisperses comme les jus de fruits ou certains coproduits liquides, le dépôt de particules sur la membrane est souvent supposé être le mécanisme limitant. La formation de ce dépôt est fortement dépendante de l’équilibre entre forces convectives (imposées par le flux de perméat), qui attirent les particules de la suspension à proximité de la membrane, et forces de rétrotransport, qui éloignent les particules de la surface membranaire. La stratégie la plus employée pour maitriser le colmatage membranaire par dépôt est la filtration tangentielle qui permet d’imposer de forts cisaillements à la surface membranaire qui favorisent les mécanismes de rétrotransport des particules. Si cette stratégie de maîtrise du colmatage est amplement utilisée à l’échelle industrielle pour la microfiltration des suspensions à base de fruits, elle nécessite des coûts d’investissement et de fonctionnement non négligeables qui limitent son implantation aux industries présentant de fortes capacités de production et d’investissement. Au regard de cela, l’utilisation d’une configuration de filtration à membranes immergées pour la microfiltration de suspensions à base de fruits pourrait être une alternative intéressante. Cette configuration repose sur l’immersion de la membrane (modules plans ou fibres creuses) dans la suspension à filtrer, et est associée à un mode de filtration externe-interne, frontal ou quasi-frontale. Si l’absence de conditions hydrodynamiques intenses au voisinage de la membrane est associée à des flux relativement bas, les nombreux avantages de ce mode opératoire (coûts de fonctionnement réduits, simplicité opérationnelle, forte compacité, etc.) pourraient favoriser son emploi par les petits producteurs de jus de fruits et/ou les industries de valorisation des coproduits présentant des capacités limitées d’investissement et enclins à minimiser leurs couts opérationnels. Ce travail a ainsi étudié pour la première fois la possibilité d’utiliser un tel système pour la microfiltration de suspensions à base de fruits variées (jus de fruits et coproduits vinicoles). Ce travail de thèse a ciblé ainsi plusieurs objectifs : (i) caractériser le potentiel et le comportement colmatant de suspensions à base de fruits, en lien avec les caractéristiques physicochimiques propres à chaque suspension et au regard de leur filtration par membranes immergées, (ii) étudier des performances d’un système de microfiltration de suspensions à base de fruits par membranes immergées, performances en termes de productivité et de sélectivité et enfin (iii) dégager des pistes de réflexion qui conduiraient à une choix pertinent de conditions de filtration (mode immergé ou tangentiel) pour un type de suspension ciblé. Ce travail fournit ainsi des résultats d’identification de paramètres physico-chimiques clefs qui pourraient constituer un premier guide pour le choix de la configuration membranaire la plus adaptée au produit, permettant d’assurer une productivité acceptable lors de la microfiltration de suspensions à base de fruits. / Microfiltration is widely used to ensure clarification, stabilization, and concentration of various fruit-based suspensions (e.g. fruit juices, food by-products, wine). However, the performances of membrane filtration remain highly challenged by membrane fouling. During microfiltration of polydisperse suspensions, such as fruit-based suspensions, membrane fouling is generally associated to the deposition of particles on the membrane layer. This type of fouling is mainly governed by the equilibrium between convective forces (permeate flow), leading particles to flow towards the membrane, and back-transport forces, removing particles away from the membrane surface. The filtration performances depend strongly on this equilibrium, which is mostly governed by the hydrodynamic conditions of the filtration process and the particles size distribution of the suspension. In food industries, cross-flow microfiltration is generally used to limit membrane fouling. In this configuration, high cross-flow velocities are applied in order to enhance the back-transport forces limiting the deposition of foulant materials on the membrane surface. However, this working mode is well known to be highly energy consuming and might not always be relevant depending on the suspension characteristics. In the light of this, using immersed membranes configuration for the microfiltration of fruit-based suspensions might be an interesting alternative, especially for small producers with limiting investment capacity. In this configuration, widely used in other fields, the membranes are immersed in the suspension and filtration is performed in operating conditions close to that of dead-end filtration with limited back-transport forces and low operating costs. However, the performances of this filtration configuration remain little studied for the microfiltration of fruit-based suspensions. In this respect, this work investigated for the first time the possibility of using immersed membranes configuration for the microfiltration of various fruit-based suspensions (fruit juices and winery byproducts). Firstly, a characterization of the fouling potential of various suspensions during their microfiltration using immersed membranes filtration was performed in relation with their physicochemical properties (particle size distribution). Then, this work allowed highlighting the promising performances of immersed membranes configuration when used for the microfiltration of fruit-based suspensions, in terms of productivity and in terms of selectivity (clarification, concentration of bioactive compounds). Finally, it allowed drawing preliminary results about the relation between the physicochemical characteristics of a suspension and its fouling behavior while using (i) immersed membranes filtration or (ii) conventional cross-flow filtration. These results might be of great interest for the identification of relevant physicochemical parameters to predict the usefulness of using high cross-flow velocity to prevent membrane fouling during the microfiltration of fruit-based suspensions.