In the oil sand industry, bitumen is separated from sands by aerating the heavy oil so that it can float out of a flotation vessel, leaving the unaerated sands behind. A bubble-against-plate apparatus equipped with a high-speed camera has been developed to record the optical interference patterns of the wetting films formed on a flat surface and subsequently obtain the temporal and spatial profiles of the films offline using the Reynolds lubrication theory. The technique has been used to study the interaction mechanisms between air bubbles and bitumen. It has been found that the film thinning kinetics increases in the order of asphaltene, bitumen, and maltene, and that the kinetics increases sharply with increasing temperature. In addition to obtaining kinetic information, the temporal and spatial profiles of the wetting films have been used to derive appropriate hydrodynamic information that can be used to determine the disjoining pressures (∏) in the wetting films. The results obtained in the present work show that ∏ < 0 for maltene and bitumen, while ∏ > 0 for asphaltene at temperatures in the range of 22 to 80 °C. The disjoining pressure data have been analyzed by considering the contributions from the hydrophobic and steric forces in addition to the classical DLVO forces. It has been found that the hydrophobic force increases with increasing temperature, which corroborates well with contact angle data. Dynamic contact angle measurements show that air bubbles attach on bitumen with relatively small contact angles initially but increase sharply to >90° . The extent and the kinetics of contact angle change increase sharply with increasing temperature. These findings suggest that the primary role of temperature may be to increase iii bitumen hydrophobicity and hence hydrophobic force, which is the driving force for bubblebitumen interaction. A thermodynamic analysis carried out on the basis of the Frumkin-Derjaguin isotherm suggests that the disjoining pressure will remain positive (and hence no flotation) until the hydrophobic force becomes strong enough (due to temperature increase) to overcome the positive disjoining pressure created during the course of bitumen liberation. / Ph. D.

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

Hydrophobic interaction plays an important role in biology, daily lives, and a variety of industrial processes such as flotation. While the mechanisms of hydrophobic interactions at molecular scale, as in self-assembly and micellization, is relatively well understood, the mechanisms of macroscopic hydrophobic interactions have been controversial. It is, therefore, the objective of the present work to study the mechanisms of interactions between macroscopic hydrophobic surfaces in H-bonding liquids, including water, ethanol, and water-ethanol mixtures. The first part of the present study involves the measurement of the hydrophobic forces in the thin liquid films (TLFs) confined between two identical hydrophobic surfaces of contact angle 95.3o using an atomic force microscope (AFM). The measurements are conducted in pure water, pure ethanol, and ethanol-water mixtures of varying mole fractions. The results show that strong attractive forces, not considered in the classical DLVO theory, are present in the colloid films formed with all of the H-bonding liquids tested. When an H-bonding liquid is confined between two hydrophobic surfaces, the vicinal liquid molecules form clusters in the TLFs and give rise to an attractive force. The cluster formation is a way to minimize free energy for the molecules denied of H-bonding with the substrates. Thus, solvophobic forces are the result of the antipathy between the CH2- and CH3-coated surface and H-bonding liquid confined in the film. A thermodynamic analysis of the solvophobic forces measured at different temperatures support this mechanism, in which solvophobic interactions entail decreases in the excess film enthalpy and entropy. The former represents the energy gained by building clusters, while the latter represents loss of entropy due to structure building. Thus, hydrophobic interaction may be a subset of solvophobic interaction. The solvophobic forces are strongest in pure water and pure ethanol, and decrease when one is added to the other. Adding a very small amount of ethanol to water sharply reduced the solvophobic force due to the adsorption of the former with an inverse orientation. An exposure of the OH-group toward the aqueous phase decreases the antipathy between the surface and H-bonding liquid and hence causes the hydrophobic (or solvophobic) forces to decrease. The second part of the study involves the measurement of the hydrophobic forces in the wetting films of water using the force apparatus for deformable surfaces (FADS). This new instrument recently developed at Virginia Tech is designed to monitor the deformation of bubbles to determine the surface forces in wetting films. In effect, an air bubble is used a force sensor. The measurements have been conducted with gold, chalcopyrite, and galena as substrates. The results obtained with all three minerals show that hydrophobic force increases with increasing water contact angle, suggesting that hydrophobic forces are inherent properties of hydrophobic surfaces rather than created from artifacts such as preexisting nanobubbles and/or cavitation. A utility of the intrinsic relationship between hydrophobic force and contact angle is to predict flotation kinetics from the hydrophobicity of the minerals of interest. / Ph. D.

The process of froth flotation relies on using air bubbles to collect desired mineral particles dispersed in aqueous media on the surface, while leaving undesirous mineral particles behind. For a particle to be collected on the surface of a bubble, the thin liquid films (or wetting films) of water formed in between must rupture. According to the Frumkin-Derjaguin isotherm, it is necessary that wetting films can rupture when the disjoining pressures are negative. However, the negative disjoining pressures are difficult to measure due to the instability and short lifetimes of the films. In the present work, two new methods of determining negative disjoining pressures have been developed. One is to use the modified thin film pressure balance (TFPB) technique, and the other is to directly determine the interaction forces using the force apparatus for deformable surfaces (FADS) developed in the present work. The former is designed to obtain spatiotemporal profiles of unstable wetting films by recording the optical interference patterns. The kinetic information derived from the spatiotemporal profiles were then used to determine the disjoining pressures using an analytical expression derived in the present work on the basis of the Reynolds lubrication theory. The technique has been used to study the effects of surface hydrophobicity, electrolyte (Al3+ ions) concentration, and bubble size on the stability of wetting films. Further, the geometric mean combining rule has been tested to see if the disjoining pressures of the wetting films can be predicted from the disjoining pressures of the colloid films formed between two hydrophobic surfaces and the disjoining pressures of the foam films formed between two air bubbles. The FADS is capable of directly measuring the interaction forces between air bubble and solid surface, and simultaneously monitoring the bubble deformation. The results were analyzed using the Reynolds lubrication theory and the extended DLVO theory to determine both the hydrodynamic and disjoining pressures. The FADS was used to study the effects of surface hydrophobicity and approach speeds. The results show that hydrophobic force is the major driving force for the bubble-particle interactions occurring in flotation. / Ph. D.

Il existe de nombreuses technologies de décontamination, néanmoins les spores et les biofilms bactériens demeurent une préoccupation majeure dans de nombreux domaines, tels que le secteur hospitalier, alimentaire et de la biodéfense car elles sont résistantes. Une mousse novatrice contenant un biocide (l’hypochlorite de sodium ou le peroxyde d’hydrogène) et un agent stabilisant (le Xanthane) a été étudiée pour répondre à ce besoin. Cette mousse a la capacité d’être mise en oeuvre de différentes façons sur le terrain par : pulvérisation au sol ; talochage et pulvérisation sur les murs ; remplissage de pièces entières (murs et sols). Le travail de thèse est d’évaluer les modes d’action biocide de ces mousses sur les spores et les biofilms. Afin d’étudier le mode d’action de ces mousses des protocoles expérimentaux ont été mis au point sur les spores et les biofilms suivant leurs futures mises en oeuvre (horizontale, verticale et remplissage) et suivant différents facteurs environnementaux pouvant influencer leur efficacité de décontamination (températures, salissures, matériaux, …). L’ensemble de ce travail de thèse a permis de distinguer l’intérêt de la mousse au Xanthane contenant NaOCl 5% par rapport à celle H2O2 12% pour répondre aux besoins spécifiques de la décontamination des agents de la menace biologique. Cette mousse permet une décontamination rapide de 7 logs de spores en 30 minutes pour chacune des trois voies de mise en oeuvre à 20°C. De plus, elle permet la destruction de biofilms contenant 107 de bactéries/cm² en 1 heure maximum sur un support horizontal et par remplissage. Cette mousse NaOCl est suffisamment mature pour pouvoir réaliser un futur transfert industriel. / Several decontamination technologies exist, however bacterial spores and biofilms remain a concern in a lot of fields, like hospital, alimentary and military. A new foam containing a biocide (sodium hypochlorite or hydrogen peroxide) and a stabilizing agent (Xanthan) has been studied to answer this problematic. This foam can be used in different ways on the field following contaminations: grounds’ spraying, walls’ covering and spraying, full pieces’ filling (walls and ground). The goal of this thesis is to evaluate the biocide efficiency of these foams on spores and biofilms. We optimized experimental protocols in order to study mechanisms of foams’ action on spores and biofilms based on theirs future applications (horizontal, vertical and filling) and depending on different environmental factors which may impact foam decontamination efficiencies (materials, temperatures, soil, …). This thesis work enabled to highlight the Xanthan foam containing 5% NaOCl from the one including 12% H2O2 in military sector. This foam allows a rapid decontamination, about 7 logs of spores in 30 minutes, for each of the three ways of use at 20°C. Moreover, the destruction of biofilms containing 107 logs of bacteria/cm² was achieved in 1 hour on a horizontal support by filling. This NaOCl foam is ready to be used for industrials.

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2016-12-12T14:44:32Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação - Pedro Henrique Amorim Anjos.pdf: 9970150 bytes, checksum: 29bca81f576fbdecd909c0ab24d68ce5 (MD5) / Made available in DSpace on 2016-12-12T14:44:32Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação - Pedro Henrique Amorim Anjos.pdf: 9970150 bytes, checksum: 29bca81f576fbdecd909c0ab24d68ce5 (MD5) Previous issue date: 2015-02-05 / CNPQ / Consideramos o movimento da interface entre dois fluidos viscosos, imiscíveis e incompressíveis confinados em uma célula de Hele-Shaw radial. Quando o fluido de baixa viscosidade é injetado no centro da célula e desloca radialmente o fluido de alta viscosidade, a instabilidade de Saffman-Taylor entra em ação levando ao crescimento de estruturas em formato de dedos. Dependendo da natureza dos fluidos envolvidos, eles podem molhar as paredes da célula de Hele-Shaw, deixando para trás um filme molhante de espessura finita. Diante disso, investigamos a influência da camada de fluido molhante, deixada pelo fluido deslocado, na dinâmica linear e fracamente não-linear do sistema. Mais especificamente, examinamos como a instabilidade da interface e os mecanismos de formação de padrões (bifurcação e competição de dedos) são afetados pela presença da camada de filme molhante no limite de baixo número de capilaridade. Estudamos também uma variação da instabilidade de Saffman-Taylor usual induzida pela injeção: o problema do levantamento em célula de Hele-Shaw. Nossos resultados analíticos indicam que o molhamento tem um impacto significativo nos padrões não-lineares resultantes. Ele é responsável por uma atenuação na variação do comprimento dos dedos, enquanto que induz o aparecimento de estruturas que apresentam dedos pequenos e largos, provenientes do fluido não molhante, alternados por dedos pequenos e finos pertencentes ao fluido molhante. Durante o processo de levantamento, medidas adquiridas pelo teste de adesão quantificam a força adesiva de um fluido viscoso confinado entre placas paralelas. Experimentos e intensas simulações numéricas indicam que a formação de dedos afeta a força de levantamento, promovendo uma diminuição na magnitude da mesma. Concluímos este trabalho propondo um modelo analítico que forneça a força de adesão considerando não só o efeito de dedos da interface, mas também a ação do molhamento e de estresses viscosos normais. / We consider the interfacial motion between two immiscible, incompressible, viscous fluids in the confined geometry of a radial Hele-Shaw cell. When the less viscous fluid is injected at the center and drives radially the more viscous fluid, the Saffman-Taylor instability takes place leading to the growth of fingerlike shapes. Depending on the nature of the fluids involved, they can wet the walls of the Hele-Shaw cell plates, leaving behind a film of finite thickness. In this framework, we investigate the influence of a thin wetting film trailing behind the displaced fluid on the linear and weakly nonlinear dynamics of the system. More specifically, we examine how the interface instability and the pattern formation mechanisms of finger tip-splitting and finger competition are affected by the presence of such a film in the low capillary number limit. We also examined a variant of the usual injection-driven Saffman-Taylor instability: the lifting Hele-Shaw cell problem. Our analytical results indicate that wettability has a significant impact on the resulting nonlinear patterns. It restrains finger length variability while inducing the development of structures presenting short, blunt penetrating fingers of the nonwetting fluid, alternated by short, sharp fingers of the wetting fluid. During the lifting process, probe-tack measurements evaluate the adhesion strength of viscous fluids confined between parallel plates. Existing meticulous experiments and intensive numerical simulations indicate that fingering formation affects the lifting force, making it to decrease in intensity. We conclude this work by proposing an analytical model that computes the lifting adhesion force by taking into account not only the effect of interfacial fingering, but also the action of wetting, and viscous normal stresses.