Interaction forces between a deformable air bubble and a spherical particle of tuneable hydrophobicity and surface charge in aqueous solutions.

Interaction forces between an air bubble and a spherical particle of moderate and tuneable surface charge density and hydrophobicity in aqueous solutions were measured using atomic force microscopy. Bitumen coated silica spheres were used as model particles of tuneable charge density and hydrophobicity due to pH-dependent ionisation of carboxylic acids at bitumen-water interfaces. The measured force profiles showed a long-range repulsion prior to jump into contact, indicating the rupture of intervening liquid film between the bitumen and bubble surfaces. The long-range repulsive force increased with increasing pH. The measured force profiles were analysed by adopting the model originally developed by White and co-workers to account for deformation and change in shape of bubbles before rupture of the intervening liquid film. Satisfactory agreement between the theory and measured force profiles was obtained, showing the suitability of the model to describe the measured interaction forces. The model was then used to study the physical parameters on the particle-bubble interaction forces prior to three phase contact line (TPCL) formation. The hydrophobic decay length, surface potential and size of bubble and probe particles, and ionic strength of the medium (KCl concentration) were found to have a strong influence on the predicted force profiles.

Probing colloidal forces between a Si3N4 AFM tip and single nanoparticles of silica and alumina.

The atomic force microscope (AFM) has been used to measure surface forces between silicon nitride AFM tips and individual nanoparticles deposited on substrates in 10(-4) and 10(-2) M KCl solutions. Silica nanoparticles (10 nm diameter) were deposited on an alumina substrate and alumina particles (5 to 80 nm diameter) were deposited on a mica substrate using aqueous suspensions. Ionic concentrations and pH were used to manage attractive substrate-particle electrostatic forces. The AFM tip was located on deposited nanoparticles using an operator controlled offset to achieve stepwise tip movements. Nanoparticles were found to have a negligible effect on long-range tip-substrate interactions, however, the forces between the tip and nanoparticle were detectable at small separations. Exponentially increasing short-range repulsive forces, attributed to the hydration forces, were observed for silica nanoparticles. The effective range of hydration forces was found to be 2-3 nm with the decay length of 0.8-1.3 nm. These parameters are in a good agreement with the results reported for macroscopic surfaces of silica obtained using the surface force apparatus suggesting that hydration forces for the silica nanoparticles are similar to those for flat silica surfaces. Hydration forces were not observed for either alumina substrates or alumina nanoparticles in both 10(-4) M KCl solution at pH 6.5 and 10(-2) M KCl at pH 10.2. Instead, strong attractive forces between the silicon nitride tip and the alumina (nanoparticles and substrate) were observed.

AFM colloidal forces measured between microscopic probes and flat substrates in nanoparticle suspensions.

Colloidal forces between atomic force microscopy probes of 0.12 and 0.58 N/m spring constant and flat substrates in nanoparticle suspensions were measured. Silicon nitride tips and glass spheres with a diameter of 5 and 15 mum were used as the probes whereas mica and silicon wafer were used as substrates. Aqueous suspensions were made of 5-80 nm alumina and 10 nm silica particles. Oscillatory force profiles were obtained using atomic force microscope. This finding indicates that the nanoparticles remain to be stratified in the intervening liquid films between the probe and substrate during the force measurements. Such structural effects were manifested for systems featuring attractive and weak repulsive interactions of nanoparticles with the probe and substrate. Oscillation of the structural forces shows a periodicity close to the size of nanoparticles in the suspension. When the nanoparticles are oppositely charged to the probes, they tend to coat the probes and hinder probe-substrate contact.

Frequency-dependent laminar electroosmotic flow in a closed-end rectangular microchannel.

This article presents an analysis of the frequency- and time-dependent electroosmotic flow in a closed-end rectangular microchannel. An exact solution to the modified Navier-Stokes equation governing the ac electroosmotic flow field is obtained by using the Green's function formulation in combination with a complex variable approach. An analytical expression for the induced backpressure gradient is derived. With the Debye-Hückel approximation, the electrical double-layer potential distribution in the channel is obtained by analytically solving the linearized two-dimensional Poisson-Boltzmann equation. Since the counterparts of the flow rate and the electrical current are shown to be linearly proportional to the applied electric field and the pressure gradient, Onsager's principle of reciprocity is demonstrated for transient and ac electroosmotic flows. The time evolution of the electroosmotic flow and the effect of a frequency-dependent ac electric field on the oscillating electroosmotic flow in a closed-end rectangular microchannel are examined. Specifically, the induced pressure gradient is analyzed under effects of the channel dimension and the frequency of electric field. In addition, based on the Stokes second problem, the solution of the slip velocity approximation is presented for comparison with the results obtained from the analytical scheme developed in this study.

Streaming potential and electroosmotic flow in heterogeneous circular microchannels with nonuniform zeta potentials: requirements of flow rate and current continuities.

Real surfaces are typically heterogeneous, and microchannels with heterogeneous surfaces are commonly found due to fabrication defects, material impurities, and chemical adsorption from solution. Such surface heterogeneity causes a nonuniform surface potential along the microchannel. Other than surface heterogeneity, one could also pattern the various surface potentials along the microchannels. To understand how such variations affect electrokinetic flow, we proposed a model to describe its behavior in circular microchannels with nonuniform surface potentials. Unlike other models, we considered the continuities of flow rate and electric current simultaneously. These requirements cause a nonuniform electric field distribution and pressure gradient along the channel for both pressure-driven flow (streaming potential) and electric-field-driven flow (electroosmosis). The induced nonuniform pressure and electric field influence the electrokinetic flow in terms of the velocity profile, the flow rate, and the streaming potential.

Shape relaxation of an elongated viscous drop.

The shape relaxation of a distorted viscous drop suspended in a quiescent immiscible liquid is analyzed in the creeping flow limit. The shape of the drop is axisymmetric, but otherwise arbitrary. The relaxation process is assumed to be driven by a constant interfacial tension and rate-limited by the Newtonian viscosities of the dispersed and continuous phases. For analysis, a least squares technique is developed which, compared to the more common boundary integral methods, is simpler to implement and especially suited for systems where one liquid is much more viscous than the other (i.e., when the viscosity ratio lambda, defined as the ratio of the dispersed to continuous phase viscosities, approaches either zero or infinity). To demonstrate the validity of the proposed least squares technique, its results are shown to agree well with boundary integral calculations for moderate values of lambda, and with experimental data when lambda is much larger than unity (approximately 10(6)). Predictions at infinite viscosity ratio--the regime in which the least squares technique is most useful--are then used to evaluate interfacial tensions associated with a system of practical importance, namely, the dispersion of heavy crude oil in an aqueous environment. This amounts to a novel and accurate technique for determining interfacial tensions--especially those of low values (1 mN/m or less)--between density-matched liquids where at least one of the phases is highly viscous. The experimental part of this study involves the use of suction pipettes to manipulate the shapes of individual micrometer-sized droplets, thus avoiding the need for complex flow-generating devices to create drop deformations.

Shear-induced coalescence of emulsified oil drops.

Crude oil droplets, when suspended in water, possess negative surface charges which give rise to double-layer repulsive forces between the drops. According to conventional DLVO theory, the magnitude of this repulsion (based on the measured zeta potential) is more than sufficient to prevent coalescence of the droplets. Indeed, when two such droplets were brought together on direct (i.e., "head-on") approach, coalescence was rarely observed. Upon oblique approach, however, the same droplets were seen to coalesce readily. An oblique encounter must necessarily give rise to lateral relative motion-or shearing-between the droplet surfaces. It is speculated that, if the charge distributions at the droplet surfaces were heterogeneous, lateral shearing would facilitate many encounters between surface patches of different zeta potentials across the intervening water film. If the repulsion across any local region were sufficiently weak to allow formation of an oil bridge across the water film, coalescence of the drops would follow inevitably. With the hypothesis of surface heterogeneity, it is not necessary to invoke any additional colloidal interactions (such as "hydrophobic forces") to account for the observed droplet-droplet coalescence. This finding may have important implications for the underlying mechanisms of emulsion stability in general and the commercial extraction of bitumen from oil sands in particular.

Oscillating laminar electrokinetic flow in infinitely extended circular microchannels.

This article addresses the problem of oscillating laminar electrokinetic liquid flow in an infinitely extended circular microchannel. Based on the Debye-Huckel approximation for low surface potential at the channel wall, a complex variable approach is used to obtain an analytical solution for the flow. The complex counterparts of the flow rate and the current are linearly dependent on the pressure gradient and the external electric field. This property is used to show that Onsager's principle of reciprocity continues to be valid (involving the complex quantities) for the stated problem. During oscillating pressure-driven flow, the electroviscous effect for a given value of the normalized reciprocal electrical double-layer (EDL) thickness is observed to attain a maximum at a certain normalized frequency. In general, an increasing normalized frequency results in a reduction of EDL effects, leading to (i). a volumetric flow rate in the case of streaming potential approaching that predicted by the theory without EDL effects, and (ii). a reduction in the volumetric flow rate in the case of electroosmosis.

Oscillating laminar electrokinetic flow in infinitely extended rectangular microchannels.

This paper has addressed analytically the problem of laminar flow in microchannels with rectangular cross-section subjected to a time-dependent sinusoidal pressure gradient and a sinusoidal electric field. The analytical solution has been determined based on the Debye-Hückel approximation of a low surface potential at the channel wall. We have demonstrated that Onsager's principle of reciprocity is valid for this problem. Parametric studies of streaming potential have shown the dependence of the electroviscous effect not only on the Debye length, but also on the oscillation frequency and the microchannel width. Parametric studies of electroosmosis demonstrate that the flow rate decreases due to an increase in frequency. The obtained solutions for both the streaming potential and electroosmotic flows become those for flow between two parallel plates in the limit of a large aspect ratio.

Dynamic and static interactions between bitumen droplets in water.

In the commercial bitumen extraction operation, dynamic and static interaction forces between bitumen drops in water determine the likelihood of desirable bitumen coalescence at different process stages. These dynamic and static forces were measured using colloidal particle scattering and hydrodynamic force balance techniques, respectively. In the former technique, dynamic interactions are studied through droplet-droplet collision trajectory measurement. In the latter technique, the static attractive forces between droplets are determined when a doublet is separated with a known and adjustable hydrodynamic force. The dynamic force measurement implies the presence of rigid chains on bitumen surfaces. The mean chain lengths for deasphalted bitumen at pH 7, whole bitumen at pH 7, and whole bitumen at pH 8.5 are 50, 78, and 41 nm, respectively. However, the static force measurement indicates much shorter mean chain lengths (<9 nm) in these three bitumen systems. Shorter chain length indicates weaker repulsive force. This finding of a much weaker repulsion between bitumen droplets under static conditions has important implications on the commercial bitumen extraction operation.

Bitumen-clay interactions in aqueous media studied by zeta potential distribution measurement.

A novel technique to investigate the interactions between bitumen and clays in an aqueous solution from the measurement of zeta potential distributions is described. For a single component suspension (i.e., clay or bitumen), a single modal zeta potential distribution was obtained under a given solution condition. In the case of a two-component (i.e., bitumen and clay) mixture system, the measured zeta potential distribution showed either one or two distribution peaks, depending on the chemical condition of the suspension and the type/amount of clays present. In the absence of added calcium ions, a mixture of bitumen emulsion and clay suspension exhibited two distinct zeta potential distribution peaks, corresponding to the peaks measured individually for the bitumen and clays, respectively. With the addition of 1 mM calcium ions, however, only one zeta potential distribution peak was obtained for the mixture of bitumen emulsion and montmorillonite clay suspension. Depending on the montmorillonite clay to bitumen ratio, the peak position in this case shifted toward the value for montmorillonite clay suspension alone. For kaolinite, the addition of 1 mM calcium ions did not cause a substantial change in the bimodal zeta potential distribution. The results suggest qualitatively a stronger interaction of bitumen with montmorillonite clay than with kaolinite clay, when calcium ions were present. The slime coating of montmorillonite clay on bitumen droplets in the presence of 1 mM calcium was validated. The conclusions obtained from this study further justified our mechanistic hypothesis for the observed depression of bitumen flotation by montmorillonite but not by kaolinite clay addition when calcium ions were added. This study demonstrated that zeta potential distribution measurement could be a powerful tool to study slime coating phenomena in a complex colloidal system.

Emulsification through Area Contraction.

Emulsification requiring very little input energy can be induced at an oil-water interface that is initially in a state of equilibrium. The process involves destabilization, through contraction, of local interfacial regions. For emulsification to occur, it is necessary for the interfacial structure to have no resistance to surface shearing. Such a mechanism of emulsification may have important implications for the approach to solving emulsion problems in the petroleum industry. Copyright 1999 Academic Press.

Does Equilibrium Interfacial Tension Depend on Method of Measurement?

In the presence of surfactants, the equilibrium interfacial tension (IFT) between two immiscible fluids can be very dependent on the particular technique used for measurement. This is because the partitioning of surfactants between the two bulk phases and the interface, which ultimately determines IFT, depends on geometric factors such as the volume fractions and specific interfacial areas (i.e., interfacial areas per unit volume) of the two fluids. In this work, the effect of surfactant partitioning on equilibrium IFT is demonstrated both theoretically and experimentally. A novel technique which enables direct measurement of IFT at macroemulsion droplet surfaces, with direct application to emulsion research, is demonstrated. Copyright 1998 Academic Press.