Exploring unconventional hydrocarbon reservoirs and enhancing the recovery of hydrocarbon from conventional reservoirs are necessary for meeting the society's ever-increasing energy demand and requires a thorough understanding of the multiphase interfacial and transport phenomena in these reservoirs. This dissertation performs pore-scale studies of interfacial thermodynamics and multiphase hydrodynamics in shale reservoirs and conventional oil-brine-rock (OBR) systems. In shale gas reservoirs, the imbibition of water through surface hydration into gas-filled mica pores was found to follow the diffusive scaling law, but with an effective diffusivity much larger than the self-diffusivity of water molecules. The invasion of gas into water-filled pores with width down to 2nm occurs at a critical invasion pressure similar to that predicted by the classical capillary theories if effects of disjoining pressure and diffusiveness of water-gas interfaces are considered. The invasion of oil droplets into water-filled pores can face a free energy barrier if the pressure difference along pore is small. The computed free energy profiles are quantitatively captured by continuum theories if capillary and disjoining pressure effects are considered. Small droplets can invade a pore through thermal activation even if an energy barrier exists for its invasion. In conventional oil reservoirs, low-salinity waterflooding is an enhanced oil recovery method that relies on the modification of thin brine films in OBR systems by salinity change. A systematic study of the structure, disjoining pressure, and dynamic properties of these thin brine films was performed. As brine films are squeezed down to sub-nanometer scale, the structure of water-rock and water-oil interfaces changes marginally, but that of the electrical double layers in the films changes greatly. The disjoining pressure in the film and its response to salinity change follow the trend predicted by the DLVO theory, although the hydration and double layer forces are not simple additive as commonly assumed. A notable slip between the brine film and the oil phase can occur. The role of thin liquid films in multiphase transport in hydrocarbon reservoirs revealed here helps lay foundation for manipulating and leveraging these films to enhance hydrocarbon production and to minimize environmental damage during such extraction. / Doctor of Philosophy / Meeting the ever-increasing energy demand requires efficient extraction of hydrocarbons from unconventional reservoirs and enhanced recovery from conventional reservoirs, which necessitate a thorough understanding of the interfacial and transport phenomena involved in the extraction process. Abundant water is found in both conventional oil reservoirs and emerging hydrocarbon reservoirs such as shales. The interfacial behavior and transport of water and hydrocarbon in these systems can largely affect the oil and gas recovery process, but are not well understood, especially at pore scale. To fill in the knowledge gap on these important problems, this dissertation focuses on the pore-scale multiphase interfacial and transport phenomena in hydrocarbon reservoirs. In shales, water is found to imbibe into strongly hydrophilic nanopores even though the pore is filled with highly pressurized methane. Methane gas can invade into water-filled nanopores if its pressure exceeds a threshold value, and the thin residual water films on the pore walls significantly affect the threshold pressure. Oil droplet can invade pores narrower than their diameter, and the energy cost for their invasion can only be computed accurately if the surface forces in the thin film formed between the droplet and pore surface are considered. In conventional reservoirs, thin brine films between oil droplet and rock greatly affect the wettability of oil droplets on the rock surface and thus the effectiveness of low-salinity waterflooding. In brine films with sub-nanometer thickness, the ion distribution differs from that near isolated rock surfaces but the structure of water-brine/rock interfaces is similar to their unconfined counterparts. The disjoining pressure in thin brine films and its response to the salinity change follow the trend predicted by classical theories, but new features are also found. A notable slip between the brine film and the oil phase can occur, which can facilitate the recovery of oil from reservoirs.

Two-phase heat transfer techniques such a boiling make use of the high latent heat of fluids to enable dissipation of higher heat fluxes from surfaces compared to conventional single-phase cooling methods. To meet the increasing heat flux dissipation requirements of high-power electronic devices, modifications to the surface properties and roughness are often considered as a means to enhance two-phase heat transfer processes. Although surface roughness of varying length scales has been observed experimentally to enhance boiling heat transfer performance, the physical mechanisms that govern this improvement are not widely accepted. Correlations can be developed to map the behavior of specific surface structure geometries, but a broader investigation of the fundamental forces affecting evaporation at the three-phase contact line, which is critically important to the two-phase heat transfer process, may provide more widely applicable insights. In this thesis, an experimental setup was developed to investigate the effect of small scale surface roughness, with feature sizes below 1 micron, on the liquid film profile of a meniscus formed on a surface. This physical film profile can provide insight into how the surface roughness affects disjoining pressure, an important force that affects the phase change heat transfer process at the contact line. Using an interferometry technique to measure the liquid film profile for a model system of octane on silicon substrate with varying roughness, the change in disjoining pressure in the liquid film was observed. We found that the strength of disjoining pressure in the liquid film increases with increasing surface roughness feature depth.<br>

No description available.

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.

The aim of this thesis work was to investigate theadsorption of surfactants to different nonpolar interfaces.Particularly, the effects of the polar group and the nature ofthe hydrophobic interface were elucidated. The interfacialbehavior of the liquid-vapor interface was investigated bymeans of surface tension measurements. Here the effect of thepolar group and the hydrocarbon chain length was investigatedin a systematic manner. It was found that the shorter of thetwo chains examined, decyl, generated a larger surface pressurecontribution than the longer, dodecyl. Furthermore, the sugarbased surfactants behaved differently as compared to theethylene oxide based ones. The former could be modelled byassuming a hard disc behavior of the head group while thelatter displayed polymeric behavior. The influence of saltconcentration on the surface tension behavior of an ionicsurfactant, sodium dodecyl sulphate, was investigated. Theresult could be rationalized by employing the Gouy- Chapmanmodel to the polar region. Furthermore, mixtures of two sugarbased surfactants were investigated by surface tensionmeasurements and the adsorbed amount of the two components atthe interface atdifferent concentrations and fractions in thebulk were obtained by applying the Gibbs surface tensionequation. It was found that the molecule with the smaller headgroup adsorbed preferentially, and more so as the totalsurfactant concentration was increased. These findings could beexplained by considering the interactions generated by thedifferent head groups. The adsorption of sugar surfactants toan isolated hydrophobic surface was studied by means of wettingmeasurements and the behavior was similar to that at theliquid-vapor interface. Wetting isotherms were measured on twodifferent hydrophobic surfaces where the covalently attachedhydrophobic layers were in a crystalline and fluid state,respectively. The wetting results revealed that the sugarsurfactants anchored in the fluid hydrophobic layer. This had asignificant influence on the force profile. For example, at thecrystalline surface the surfactant monolayers were easilyremoved as the surface came into contact at relatively lowapplied loads. This was not the case when the hydrophobic layerwas in a fluid state. Here a significant fraction of thesurfactants remained between the surfaces. Disjoining pressureisotherms were measured using a sugar based surfactant thatwere thoroughly purified and compared to the as receivedsample. Even the purified sample showed a double-layer forcealthough lower as compared to the as received, one. Asignificant difference in foam stability was also observed. / <p>NR 20140805</p>

No description available.

<p>The aim of this thesis work was to investigate theadsorption of surfactants to different nonpolar interfaces.Particularly, the effects of the polar group and the nature ofthe hydrophobic interface were elucidated. The interfacialbehavior of the liquid-vapor interface was investigated bymeans of surface tension measurements. Here the effect of thepolar group and the hydrocarbon chain length was investigatedin a systematic manner. It was found that the shorter of thetwo chains examined, decyl, generated a larger surface pressurecontribution than the longer, dodecyl. Furthermore, the sugarbased surfactants behaved differently as compared to theethylene oxide based ones. The former could be modelled byassuming a hard disc behavior of the head group while thelatter displayed polymeric behavior. The influence of saltconcentration on the surface tension behavior of an ionicsurfactant, sodium dodecyl sulphate, was investigated. Theresult could be rationalized by employing the Gouy- Chapmanmodel to the polar region. Furthermore, mixtures of two sugarbased surfactants were investigated by surface tensionmeasurements and the adsorbed amount of the two components atthe interface atdifferent concentrations and fractions in thebulk were obtained by applying the Gibbs surface tensionequation. It was found that the molecule with the smaller headgroup adsorbed preferentially, and more so as the totalsurfactant concentration was increased. These findings could beexplained by considering the interactions generated by thedifferent head groups. The adsorption of sugar surfactants toan isolated hydrophobic surface was studied by means of wettingmeasurements and the behavior was similar to that at theliquid-vapor interface. Wetting isotherms were measured on twodifferent hydrophobic surfaces where the covalently attachedhydrophobic layers were in a crystalline and fluid state,respectively. The wetting results revealed that the sugarsurfactants anchored in the fluid hydrophobic layer. This had asignificant influence on the force profile. For example, at thecrystalline surface the surfactant monolayers were easilyremoved as the surface came into contact at relatively lowapplied loads. This was not the case when the hydrophobic layerwas in a fluid state. Here a significant fraction of thesurfactants remained between the surfaces. Disjoining pressureisotherms were measured using a sugar based surfactant thatwere thoroughly purified and compared to the as receivedsample. Even the purified sample showed a double-layer forcealthough lower as compared to the as received, one. Asignificant difference in foam stability was also observed.</p>

The ascent of liquids with low dielectric constant on straight cylinders are obtained.

La microfluidique utilisant les gouttes a connu un essor remarquable ces dix dernières années. Pourtant, la dynamique de ces objets reste largement inexplorée et incomprise. Une question aussi simple que déterminer la vitesse d’une goutte poussée par une phase porteuse à vitesse imposée, ne possède à ce jour toujours pas de réponse. Comprendre et modéliser la vitesse d’une goutte nécessite dans un premier temps de caractériser les mécanismes de dissipation intervenant dans la goutte, dans le ménisque dynamique et dans le film de lubrification.Ce manuscrit présente une étude de la dynamique de films de lubrification en utilisant une technique interférométrique (RICM) qui a dû être adaptée à notre système. Nous montrons dans un premier temps que, dans un cas statique, cette outil permet de mesurer l’épaisseur de ce film nanométrique avec une très grande précision, et que celle-ci est fixée par la pression de disjonction dont la composante principale est électrostatique. Puis, le film de lubrification est étudié dans un cas dynamique. Aux faibles vitesses, l’épaisseur du film est fixée par la pression de disjonction, tandis qu’aux nombres capillaires plus élevés nous montrons qu’un modèle visqueux permet de reproduire nos résultats expérimentaux. Pour une solution micellaire,nous observons une décomposition spinodale permettant d’extraire des propriétés interfaciales (vitesse, contrainte de Marangoni). Enfin, nous avons pu dans un projet fédératif développer une laboratoire sur puce permettant des opérations de manipulation sur des gouttes en utilisant l’intégration de systèmes de chauffage au niveau micrométrique. / Digital microfluidics is a growing field of research. However, droplet dynamics remains largely unknown. As an example, a question as simple as predicting the droplet velocity while pushed by an external fluid at fixed velocity is still not answered. Understanding and thus modelizing it requires the identification of dissipation mechanisms in the droplet, in the dynamical meniscus and in the flat film. This thesis presents a study on the dynamical properties of lubrication films using an interferometric method (RICM) that has been adapted to microfluidics. We first show that, in a static case, we are able to measure nanometric film thicknesses with very accurate precision and that it is set by the disjoining pressure, especially the electrostatic part. Then the film is studied when the droplets flow. At low speeds, the film thickness is set by the disjoining pressure, while at higher capilarry numbers we identify a viscous model in agreement with our experimental results. For a micellar solution, we observe spinodal decomposition allowing us to recover interfacial properties (velocity, Marangoni stress). Finally, in a collaborative project, we were able to develop a lab on a chip allowing droplets manipulations taking advantage of micro-heaters integration.

Les interactions entre les interfaces liquide/liquide et liquide/solide interviennent dans de nombreux domaines et procédés industriels. Cependant, ces interactions ont été très peu étudiées par le passé. Nous nous concentrons ici sur le drainage spontané de solutions aqueuses de sel ou de tensio-actifs pressées entre une goutte d'huile et une surface en verre. Expérimentalement, une goutte d'huile est immergée dans de l'eau et approchée d'une surface solide ; le film d'eau pressé résultant draine et adopte une forme “dimple” due au gradient de pression. Par la suite, le film d'eau relaxe vers son épaisseur uniforme d'équilibre.Les profils d'épaisseur spatio-temporels du film sont mesurés par microscopie d'interférences en réflexion. Nous avons étudié la dynamique de drainage ainsi que l'état d'équilibre du système en présence de sel et/ou de tensio-actifs. Tout d'abord, nous réalisons une description quantitative de l'ensemble de la dynamique de drainage. Trois régimes sont identifiés pour une solution aqueuse d'électrolyte : un régime dominé par la pression capillaire, un second mixte décrit par les pressions capillaire et de disjonction, et un troisième dominé par la pression de disjonction. Ces régimes sont modélisés dans le cadre de l'approximation de lubrification. En particulier, le rôle de la pression de disjonction est étudié avec précision dans la limite de la portée des interactions électrostatiques. Nous déduisons des lois analytiques simples permettant de décrire la dynamique de drainage, découplant ainsi les effets des pressions des effets géométriques. Par ailleurs, nous montrons que l'ajout de tensio-actifs ne modifie pas qualitativement les régimes de drainage, à l'exception de concentrations supérieures à la concentration micellaire critique. En effet, à de très faibles épaisseurs, l'huile mouille alors partiellement le solide, ralentissant ainsi le drainage de l'eau piégée au centre du dimple.Nous mesurons la condition aux limites à l'interface eau/huile. Nous confirmons ainsi l'effet Marangoni, mentionné dans la littérature, résultant du gradient de concentration d'espèces (impuretés ou tensio-actifs) adsorbés à l'interface. Nous montrons que l'interface eau/huile est en général de type solide et donc que la vitesse tangentielle est nulle à l'interface. Cependant, pour des concentrations faibles en espèces adsorbées, nous mettons en évidence pour la première fois un contre-courant à l'interface eau/huile résultant de l'approche de la goutte et d'une cinétique lente d'adsorption des tensio-actifs.Par la suite, nous nous concentrons sur l'état d'équilibre du système, soit par mouillage de l'huile sur le solide, soit par formation d'un film d'eau homogène stable. Dans le cas d'un film d'eau stable, l'équilibre résulte d'une égalité entre la surpression dans la goutte et la pression de disjonction du film. En variant le rayon de la goutte, nous montrons qu'il est possible de mesurer l'évolution de la pression de disjonction avec l'épaisseur du film. Cette évolution peut être entièrement décrite par les interactions entre les interfacées chargées. Pour de grandes surpressions de goutte, ou de petites longueurs de Debye, l'huile mouille le solide. Nous montrons que la dynamique de mouillage dépend fortement de la concentration en tensio-actif lorsqu'elle est inférieure à la concentration micellaire critique. La vitesse de la triple ligne de contact peut varier de quatre décades. Nous attribuons ces comportements à l'adsorption du tensio-actif aux interfaces eau/huile et eau/verre, et en particulier à la possible formation de monocouches ou bicouches sur le solide. / The interactions between liquid/liquid and solid/liquid interfaces are involved in many industrial processes and fields. However, they have been poorly studied in the past. We focus here on the spontaneous drainage of aqueous solutions of salt or surfactants squeezed between an oil drop and a glass surface. Experimentally, an oil drop immersed in water is driven towards a solid surface; the resulting squeezed water film drains and adopts a dimple shape due to the pressure gradient, and further relaxes to its equilibrium uniform thickness. The thickness profile of the film is measured in space and time by reflection interference microscopy. We have studied both the drainage dynamics and the final equilibrium state reached by the system in presence of salt and/or surfactants. First, we quantify and provide a full description of the drainage dynamics. Three regimes are identified in an aqueous electrolyte: a capillary dominated regime, a mixed capillary and disjoining pressure regime, and a disjoining pressure dominated regime. These regimes are modeled within the lubrication approximation, and the role of the disjoining pressure is precisely investigated in the limit of thicknesses smaller than the range of electrostatic interactions. We derive simple analytical laws describing the drainage dynamics, thus providing tools to uncouple the effect of the film geometry from the effects of the disjoining or capillary pressures. We show that the addition of surfactants does not qualitatively modify the drainage regimes, except at concentrations larger than the critical micellar concentration and very small film thicknesses in which the oil can partially wet the solid, thus slowing down the drainage of the remaining trapped water. In addition, we provide measurements of the boundary condition at the oil/water interface. We confirm the role of Marangoni flows, suggested in the literature and resulting from concentration gradients of species (impurities or surfactants) adsorbed at the interface. We thus show that a solid-like, no-slip boundary condition is generally met at the oil/water interface. However, for low concentrations in adsorbed species, we evidence for the first time a reverse flow at the interface resulting from the approach of the drop and the slow adsorption kinetics of surfactants. In a second part, we focus on the equilibrium state reached by the water film, i.e. either wetting of the solid surface by the oil drop or formation of a stable water film between the drop and the solid. In the latter case, equilibrium results from the balance of the capillary pressure in the drop and the disjoining pressure. By varying the droplet radius, we show it is possible to measure the variations of the disjoining pressure with the film thickness, and that they can be fully described by taking into account the interactions between the charged interfaces. For large capillary pressures or short Debye lengths, the oil wets the solid surface and we show the wetting dynamics is strongly modified depending on surfactant concentration below the cmc: the velocity of the oil/water/solid triple line varied over four decades. We ascribe the observed behaviors to surfactant adsorption at the oil/water and solid/water interfaces, and in particular to the possible formation of surfactant mono or bi-layers on the solid.