Flotation is an important separation process used in the mining industry. The process is based on hydrophobizing a selected mineral using an appropriate surfactant, so that an air bubble can spontaneously adhere on the mineral surface. The bubble-particle adhesion is possible only when the thin film of water between the bubble and particle ruptures, just like when two colloidal particles or air bubbles adhere with each other. Under most flotation conditions, however, both the double-layer and dispersion forces are repulsive, which makes it difficult to model the rupture of the wetting films using the DLVO theory. In the present work, we have measured the kinetics of film thinning between air bubble and flat surfaces of gold and silica. The former was hydrophobized by ex-site potassium amyl xanthate, while the latter by in-site Octadecyltrimetylammonium chlroride. The kinetics curves obtained with and without theses hydrophobizing agents were fitted to the Reynolds lubrication theory by assuming that the driving force for film thinning was the sum of capillary pressure and the disjoining pressure in a thin film. It was found that the kinetics curves obtained with hydrophilic surfaces can be fitted to the theory with the disjoining pressure calculated from the DLVO theory. With hydrophobized surfaces, however, the kinetics curves can be fitted only by assuming the presence of a non-DLVO attractive force (or hydrophobic force) in the wetting films. The results obtained in the present work shows that long-range hydrophobic forces is responsible for the faster drainage of wetting film. It is shown that the changes in hydrophobic forces upon the thin water film between air bubble and hydrophobic surface is dependent on hydrophobizing agent concentration, immersion time and the electrolyte concentration in solution. The obtained hydrophobic forces constant in wetting film K132 is compared with the hydrophobic forces constant between two solid surfaces K131 to verify the combining rule for flotation. / Master of Science

Flotation is regarded as the best available separation method for the recovery of valuable minerals such as chalcopyrite (CuFeS2), sphalerite (ZnS), etc., from mined ores. Practically all metals humans use today are produced by flotation. The process relies on controlling the stability of the thin liquid films (TLFs) of water formed between minerals and air bubbles (wetting film), air bubbles (foam film), and mineral particles (colloid films). In flotation, a desired mineral is rendered hydrophobic by surfactant coating as a means to destabilize the TLFs, so that they can be attached to the hydrophobic air bubbles. A TLF ruptures when the disjoining pressure (or surface forces per unit area) of the film becomes negative, i.e., Π < 0. Thermodynamically, a wetting film can rupture when the contact angle (θ) of a mineral surface is larger than zero. It would, therefore, be reasonable to consider the roles of the surface forces to better understand the fundamental mechanisms involved in flotation. The surface forces considered in the present work included the electric double layer (EDL), van der Waals (vdW), and attractive hydrophobic (HP) forces. A flotation model has been developed by using the hydrophobic force as a kinetic parameter, which made it possible to track the fates of mineral particles of different of size, surface liberation, and contact angle to predict both recovery and grades for the first time. The model has been validated against the plant survey data obtained from an operating copper flotation plant. The simulation results obtained using the first principles model have been utilized to address the limitations of current flotation practices. One such limitation is the presence of slow-floating target minerals present in the cleaner-scavenger tails (CST) that are routinely recycled back to the rougher flotation bank as circulating loads (CLs) to allow longer retention times for the slow-floating particles for additional recovery. The simulation results show also that opening a flotation circuit by treating the CST streams separately in an advanced circuit can substantially improve the plant performance. One of the major limitations of flotation is that the coarse particles in a feed stream are difficult to recover due to the low hydrophobicity associated with poor surface liberation. A new flotation model developed in the present work suggests various ways to address the problem. One is to increase the hydrophobicity of the composite (poorly liberated) particles using the Super Collectors that can increase the contact angles to 150 -170o. Simulation results obtained using the model developed in the present work show significant financial benefits of using Super Collectors. Flotation is controlled by surface forces as noted above. As particle size becomes larger than 150 µm, however, the gravitational force comes into the picture and can override the surface forces. A new flotation cell has been developed to mitigate the effects of the extraneous force by decreasing the effective specific gravity (SG) by attaching air bubbles to facilitate levitation and by creating a pulsation to allow particles to move according to SGs independent of particle size, which should help increase the upper particle size limit of flotation. Surface forces in foam and oil-in-water emulsion films have been measured at different temperatures to determine the changes in thermodynamic properties of the thin liquid films (TLFs) of water confined between two bubbles and two oil drops. The results show that the films are destabilized by the attractive hydrophobic forces created during the course of building H-bonded structures in confined spaces, which entails decreases in enthalpy (H < 0) and entropy (TS < 0), the second term representing the thermodynamic cost of building the structures. / Doctor of Philosophy / Flotation is a kinetic process designed to separate valuable minerals from mined ores. This process depends on several hydrodynamic and surface chemistry parameters making it hard to model. A U.S. patent was awarded to Sulman and Picard in 1905 for using air bubbles to selectively collect hydrophobic particles from the aqueous phase, leaving hydrophilic particles behind. Since then, the separation process known as flotation has been used to produce practically all metals humans use. Many investigators developed flotation models using hydrodynamic parameters, e.g., particle size, bubble size, energy dissipation rate, etc., but without a reference to particle hydrophobicity. Therefore, the models were successful in predicting recoveries but not product grades. Derjaguin and Dukhin (1961) were the first to model flotation using surface forces but without due consideration of the role of hydrophobic force in flotation. Therefore, it also failed to predict product grades. In the current work, a new flotation model has been developed using the hydrophobic force as a kinetic parameter. This approach made it possible to predict both recoveries and grades for the first time. The model has been reduced to a simple form mimicking the Arrhenius equation so that it can be used to delineate the different conditions required for optimizing coarse and fine particle flotation. The model has been derived by considering the surface forces in the thin liquid films (TLFs) of water confined between bubbles, and bubbles and particles. It has been found that the hydrophobic force plays a decisive role in destabilizing a wetting film and inducing bubble-particle attachment. The surface forces measured in the present work show that the hydrophobic interactions in macroscopic scales are controlled by enthalpy rather than entropy, which is contrary to the nanoscale hydrophobic interactions. The model has been validated against a full-scale plant operation and demonstrated predictive capabilities. The simulation results have been analyzed to determine the limitations of the current flotation practices. It was found that coarse particle flotation is difficult either due to the presence of composite particles reducing the particle contact angle or due to their poor hydrodynamic properties. Utilizing the insights from the model, various methods of alleviating these limitations have been developed and presented in the current work. References Derjaguin, B.V., Dukhin, S.S., 1961. Theory of flotation of small and medium-size particles. Inst. Min. Metall. 241–267. Sulman, H.L., and Kirkpatrick-Picard (1905). U.S. Patent No. 793,808.

La compréhension du transport et du dépôt bio-colloïdal dans un milieu poreux présente un grand intérêt dans les applications environnementales, en particulier pour le contrôle de la bio-remédiation des sols et la protection des ressources en eau souterraine. Afin de mieux évaluer et prévenir les risques de contamination de la nappe phréatique et de proposer des solutions adéquates de remédiation, il est nécessaire d’avoir une bonne compréhension des mécanismes qui contrôlent le transport et le dépôt des bactéries dans les milieux poreux saturés et non saturés. L’objectif des ces travaux de thèse est d’étudier le rôle de l’hétérogénéité physique du milieu poreux (distribution granulométrique, porosité…) et de l’hydrodynamique du milieu sur les mécanismes de transport et de dépôt de particules bio-colloïdales, tout en prenant en compte l’impact des propriétés de cellules bactériennes sur ces mécanismes. Des expériences de traçage et d’injection de suspensions bactériennes ont été menées à l’échelle de colonnes de laboratoire dans trois milieux poreux avec une porosité et une distribution de taille de pore distincte. Afin de caractériser l’écoulement dans les milieux poreux, un soluté non-réactif a été utilisé comme traceur de l’eau. Trois souches bactériennes ont été utilisées pour préparer les suspensions bactériennes : une bactérie mobile (Escherichia coli), et deux non mobiles (Klebsiella sp. et R. rhodochrous). La caractérisation des propriétés cellulaires (telles que la taille et la forme des cellules, le potentiel zêta, la motilité et l'hydrophobicité) a été effectuée pour chaque souche. Des simulations numériques ont été réalisées en utilisant le code de calcul HYDRUS-1D afin de modéliser l’écoulement et d’estimer les paramètres de transport et de dépôt des bactéries. Ces derniers ont été explorés afin d'identifier le mode de transport bactérien et les mécanismes physico-chimiques ou physiques impliqués dans le dépôt des bactéries. Des expériences supplémentaires à l'échelle des pores ont été réalisées à l'aide de dispositifs microfluidiques conçus à cet effet. Un calcul théorique des différentes interactions entre les bactéries et le milieu poreux aux interfaces air/eau/solide a été effectué pour compléter les résultats expérimentaux ainsi que ceux issus de la modélisation numérique. Ainsi, les énergies d’interactions telles que les forces de van der Waals, électrostatiques de double couche, hydrophobes, stériques, capillaires et hydrodynamiques, impliquées dans le dépôt de bactéries ont été calculées pour décrire les interactions bactéries-interfaces afin d'identifier leur impact relatif sur le dépôt physico-chimique et physique des bactéries. Les résultats expérimentaux et la modélisation numérique ont mis en évidence un écoulement non uniforme, dépendant de la taille des grains ainsi que de la distribution de la taille des pores du milieu poreux. Pour un milieu poreux donné, l’écoulement devient plus dispersif quand la teneur en eau du milieu diminue. Ceci est dû à l’augmentation de la tortuosité du milieu, du fait de la présence de l’air dans les pores. Le transport des bactéries diffère de celui du traceur de l’eau. Le dépôt bactérien a été fortement influencé par la géométrie du réseau poral du milieu, les propriétés cellulaires et le degré de saturation en eau. Le piégeage physique et physico-chimique sont des mécanismes qui doivent être pris en compte pour bien décrire le dépôt bactérien, mais leur importance sur les mécanismes de dépôt est étroitement liée aux propriétés du milieu poreux et des cellules. Ces travaux mettent en évidence l’effet simultané des propriétés cellulaires, des propriétés physiques (granulométrie et distribution de taille de pores) et de l'hydrodynamique du milieu poreux sur les mécanismes de transport et de dépôt bactérien. Le calcul des différentes énergies d’interaction a permis d’identifier leur importance sur les mécanismes de dépôt bactérien. / The investigation of the transport and retention of bacteria in porous media has a great practical importance in environmental applications, such as protection of the surface and groundwater supplies from contamination, risk assessment from microorganisms in groundwater, and soil bioremediation. The aim of this study is to gain a fundamental understanding of the mechanisms that control bacteria transport and deposition in saturated and unsaturated porous media. Laboratory tracer and bacteria transport experiments at Darcy scale were performed in three porous media with distinct pore size distribution in order to investigate and quantify water and bacteria transport process under steady state flow conditions. A conservative solute was used as water tracer to characterize water flow pathways through porous media. A gram negative, motile Escherichia coli, a gram negative, non-motile Klebsiella sp. and a gram positive, non-motile R. rhodochrous were selected for the transport experiments. Characterization of cell properties (such as cell size and shape, zeta potential, motility and hydrophobicity) was performed for each strain. Numerical simulations with HYDRUS-1D code were performed to characterize water flow and to estimate bacteria transport and deposition parameters. The later were explored to identify bacteria flow patterns and physicochemical or physical mechanisms involved in bacteria deposition. To provide a better understanding of the mechanisms involved on bacteria transport and deposition, pore scale experiments were carried out by using microfluidic devices, designed for this purpose. The information obtained from laboratory experiments and numerical modeling was improved by theoretical calculation of different interactions between bacteria and porous media at air/water/solid interfaces. DLVO and non-DLVO interactions such as hydrophobic, steric, capillary and hydrodynamic forces involved in bacteria deposition were considered to describe bacteria-interface interactions in order to identify their relative impact on physicochemical and physical deposition of bacteria. Results obtained through both laboratory experiments and numerical simulationsoutlined non-uniform flow pathways, which were dependent on both grain/pore size as well as pore size distribution of the porous media. For a given porous medium, water flow patterns became more non-uniform and dispersive with decreasing water saturation due to the presence of air phase, which lead to an increase of the tortuosity of the flow pathways under unsaturated conditions. Bacteria transport pathways were different from the tracer transport, due to size exclusion of bacteria from smaller pore spaces and bacteria motility. Bacteria deposition was greatly influenced by pore network geometry, cell properties and water saturation degree. Both physical straining and physicochemical attachment should be taken into account to well describe bacteria deposition, but their importance on bacteria deposition is closely linked to porous media and cell properties. The results obtained in this work highlighted the simultaneous role of cell properties, pore size distribution and hydrodynamics of the porous media on bacteria transport and deposition mechanisms. The calculation of DLVO and non-DLVO interactions showed that bacteria deposition in saturated and unsaturated porous media was influenced by both kinds of interactions.