Influence of Interfacial Gas Enrichment on Controlled Coalescence of Oil Droplets in Water in Microfluidics.

Interfacial gas enrichment (IGE) of dissolved gases in water is shown to govern the strong attraction between solid hydrophobic surfaces of an atomic force microscopy (AFM) colloidal probe and solid substrate. However, the role of IGE in controlling the attraction between fluid-fluid interfaces of foam films and emulsion films is difficult to establish by AFM techniques because of the extremely fast coalescence. Here, we applied droplet-based microfluidics to capture the fast coalescence event under the creeping flow condition and quantify the effect of IGE on the drainage and stability of water films between coalescing oil droplets. The amount of dissolved gases is controlled by partially degassing the oil phase. When the amount of dissolved gases (oxygen) in oil decreases (from 7.89 to 4.59 mg/L), the average drainage time of coalescence significantly increases (from 19 to 50 ms). Our theoretical quantification of the coalescence by incorporating IGE into the multilayer van der Waals attraction theory confirms the acceleration of film drainage dynamics by the van der Waals attractive force generated by IGE. The thickness of the IGE layer decreases from 5.5 to 4.9 nm when the amount of dissolved gas decreases from 7.89 to 4.59 mg/L. All these results establish the universal role of dissolved gases in governing the strong attraction between particulate hydrophobic interfaces.

Evaporation of Ethanol-Water Binary Mixture Sessile Liquid Marbles.

Liquid marble is a liquid droplet coated with particles. Recently, the evaporation process of a sessile liquid marble using geometric measurements has attracted great attention from the research community. However, the lack of gravimetric measurement limits further insights into the physical changes of a liquid marble during the evaporation process. Moreover, the evaporation process of a marble containing a liquid binary mixture has not been reported before. The present paper investigates the effective density and the effective surface tension of an evaporating liquid marble that contains aqueous ethanol at relatively low concentrations. The effective density of an evaporating liquid marble is determined from the concurrent measurement of instantaneous mass and volume. Density measurements combined with surface profile fitting provide the effective surface tension of the marble. We found that the density and surface tension of an evaporating marble are significantly affected by the particle coating.

A Microfluidic Method for Investigating Ion-Specific Bubble Coalescence in Salt Solutions.

This paper reports the direct and precise measurement of bubble coalescence in salt solutions using microfluidics. We directly visualized the bubble coalescence process in a microchannel using high-speed imaging and evaluated the shortest coalescence time to determine the transition concentration of sodium halide solutions. We found the transition concentration is ion-specific, and the capacity of sodium halide salts to inhibit bubble coalescence follows the order of NaF > NaCl > NaBr > NaI. The microfluidic method overcomes the inherent uncertainties in conventional large-scale devices and methods.

Influence of microwaves on the water surface tension.

In this study, microwave irradiation was applied to hanging droplets of both water and ethylene glycol. Once the irradiation had ceased and the droplet was allowed to return to its original temperature, it was found that the surface tension of ethylene glycol returned to its original value. In contrast, the water surface tension remained well below its original value for an extended period of time. Similar observations have been reported for magnetically treated water, but this is the first time that such a lasting effect has been reported for microwave irradiation. The effect can be attributed to the unique hydrogen bonds of interfacial water molecules. While the irradiation intensities used in this study are well above those in household devices, there is certainly the potential to apply the methodology to industrial applications where the manipulation of surface tension is required without the use of chemical addition.

Interactions between halide anions and interfacial water molecules in relation to the Jones-Ray effect.

The Jones-Ray effect is shown to be governed by a different mechanism to enhanced anion adsorption. Halide ions at sub-molar concentrations are not exposed to the vapour phase; instead their first-solvating shell intimately interacts with the outmost water layer. Our novel proposal opens challenges for predicting related interfacial phenomena consistently.

Effect of environmental humidity on static foam stability.

The quality of foaming products (such as beer and shampoo) and the performance of industrial processes that harness foam (such as the froth flotation of minerals or the foam fractionation of proteins) depend upon foam stability. In this study, experiments are performed to study the effect of environmental humidity on the collapse of static foams. The dependency of the rate at which a foam collapses upon humidity is demonstrated, and we propose a hypothesis for bubble bursting due to Marangoni instability induced by nonuniform evaporation to help explain the dependency. This hypothesis is supported by direct experimental observations of the bursting process of isolated bubbles by high speed video recording and the thinning of isolated foam films under different values of humidity and temperature by microinterferometric methods.

Manipulation of a floating liquid marble using dielectrophoresis.

A liquid marble is a microliter-sized droplet coated with hydrophobic powder. The porous coating prevents the liquid content from being in direct physical contact with its surroundings, making the liquid marble perfectly non-wetting. On the one hand, the non-wetting ability allows the liquid marble to float and move across a liquid surface with little resistance. On the other hand, the porosity enables gas exchange between the liquid marble and its surroundings. These properties allow the liquid marble to serve as a bioreactor platform for important applications such as cell culture. Liquid marbles floating on a free liquid surface prevent evaporation due to the high humidity near the liquid surface. Moving a floating liquid marble allows for stirring and mixing inside the liquid marble. This paper reports a novel technique for manipulating a floating liquid marble using dielectrophoresis. A relatively simple setup can move liquid marbles of various sizes across the water surface at high speeds. We also present an analytical model to model and accurately predict the motion of the floating liquid marble. The technique reported here potentially allows for high-throughput and efficient handling of floating liquid marbles as a digital microfluidics platform.

Effect of aluminium sulphate on interactions between silica surfaces studied by atomic force microscopy.

Surface interaction forces between different types of silica surfaces (pure silica beads, borosilicate glass beads, polished silicon wafers and fused silica slides) were measured by atomic force microscopy (AFM) in solutions of aluminium sulphate (alum) in order to understand the role of hydrated aluminium species on the coagulation of negatively charged oxide colloids in drinking water treatment. The alum coagulant concentration used in this study was 150 microM aluminium. The alum solutions were prepared from analytical grade Al2(SO4)3.16H2O. It was found that the presence of aluminium sulphate at a concentration close to the values typically used in industrial scale water treatment applications generally induced strong, long-range repulsive forces between the various types of surfaces studied. At this alum concentration streaming potential measurements indicated reversal in the sign of the surface charge. It was also found that whenever borosilicate glass beads were used, the interaction force became strongly attractive when the AFM cell was flushed with deionised water. It was argued that this attraction occurred because of the charge nonuniformity of the aluminium hydrates adsorbed at the glass surface. A mechanism was proposed to explain the observed interaction phenomena based on the deduced microstructure of the adsorbed surface layers and to rationalise the new findings for applications in drinking water treatment.

Combining hydrodynamics and molecular kinetics to predict dewetting between a small bubble and a solid surface.

This paper examined the dewetting between a small air bubble and a solid surface in deionised water. Hydrodynamics was used in conjunction with surface molecular kinetics to model and predict the velocity of the moving contact line as a function of the dynamic macroscopic contact angle. The dewetting hydrodynamics was modelled following the approach developed specifically for drops and bubbles using the (absolute) coordinate system with the origin located at the centre of the contact area, which does not move with the moving contact line. The model provides accurate corrections unavailable in the generic hydrodynamic theories developed by Voinov and Cox, and removes the need for a macroscopic length scale employed in their generic theories. Molecular kinetics was used to determine the contact angle of the inner region close to the contact line, where the hydrodynamic approach breaks down due to the singularity. Unlike the generic hydrodynamic theories, the inner (microscopic) angle in our combined model is not a constant (a fitting parameter) but is a function of the moving contact line velocity and other molecular properties of the interfaces. The combined model agreed with the experimental data and produced physically consistent values for the slip length, molecular jumping distance and frequency. The dissolved gases accumulated at the non-wetting solid-liquid interface may influence the slip length.

Measuring the Coefficient of Friction of a Small Floating Liquid Marble.

This paper investigates the friction coefficient of a moving liquid marble, a small liquid droplet coated with hydrophobic powder and floating on another liquid surface. A floating marble can easily move across water surface due to the low friction, allowing for the transport of aqueous solutions with minimal energy input. However, the motion of a floating marble has yet to be systematically characterised due to the lack of insight into key parameters such as the coefficient of friction between the floating marble and the carrier liquid. We measured the coefficient of friction of a small floating marble using a novel experimental setup that exploits the non-wetting properties of a liquid marble. A floating liquid marble pair containing a minute amount magnetite particles were immobilised and then released in a controlled manner using permanent magnets. The capillarity-driven motion was analysed to determine the coefficient of friction of the liquid marbles. The "capillary charge" model was used to fit the experimental results. We varied the marble content and carrier liquid to establish a relationship between the friction correction factor and the meniscus angle.

Heterocoagulation of chalcopyrite and pyrite minerals in flotation separation.

Heterocoagulation between various fine mineral particles contained within a mineral suspension with different structural and surface chemistry can interfere with the ability of the flotation processes to selectively separate the minerals involved. This paper examines the interactions between chalcopyrite (a copper mineral) and pyrite (an iron mineral often bearing gold) as they approach each other in suspensions with added chemicals, and relates the results to the experimental data for the flotation recovery and selectivity. The heterocoagulation was experimentally studied using the electrophoretic light scattering (ELS) technique and was modelled by incorporating colloidal forces, including the van der Waals, electrostatic double layer and hydrophobic forces. The ELS results indicated that pyrite has a positive zeta potential (zeta) up to its isoelectric point (IEP) at approximately pH 2.2, while chalcopyrite has a positive zeta up to its IEP at approximately pH 5.5. This produces heterocoagulation of chalcopyrite with pyrite between pH 2.2 and pH 5.5. The heterocoagulation was confirmed by the ELS spectra measured with a ZetaPlus instrument from Brookhaven and by small-scale flotation experiments.

Exact and global rational approximate expressions for resistance coefficients for a colloidal solid sphere moving in a quiescent liquid parallel to a slip gas-liquid interface.

In this paper mathematical expressions have been developed to describe the hydrodynamic resistance force on a colloidal particle as it slides along a slip surface of a gas bubble held stationary in a quiescent liquid. The particle size was considered to be sufficiently small relative to the bubble size so that the bubble surface could be locally approximated to a planar interface. The modeling incorporated a bispherical coordinate transformation to solve the equations governing the liquid creeping flow disturbed by the particle. Exact numerical solutions for the resistance coefficients of the particle-shearing motion parallel to the slip bubble surface were obtained as a function of the separation distance from the bubble surface. Finally, simplified analytical rational approximations for the whole range of the separation distance were presented, which were in good agreement with the exact numerical result. Importantly, the approximations for the modeling and simulation of the bubble-particle interactions are mathematically tractable.

Movement of fine particles on an air bubble surface studied using high-speed video microscopy.

A CCD high-speed video microscopy system operating at 1000 frames per second was used to obtain direct quantitative measurements of the trajectories of fine glass spheres on the surface of air bubbles. The glass spheres were rendered hydrophobic by a methylation process. Rupture of the intervening water film between a hydrophobic particle and an air bubble with the consequent formation of a three-phase contact was observed. The bubble-particle sliding attachment interaction is not satisfactorily described by the available theories. Surface forces had little effect on the particle sliding with a water film, which ruptured probably due to the submicrometer-sized gas bubbles existing at the hydrophobic particle-water interface.

The liquid flow force on a particle in the bubble-particle interaction in flotation.

In this paper the problem of calculating the liquid flow force on a particle in interaction with an air bubble with a mobile surface in flotation as a function of the separation distance was solved. The force equation was obtained by first deriving the disturbed flow confined between the surfaces. The model for the force includes the separation distance between the bubble and the particle, the particle size, the bubble's Reynolds number, the bubble rise velocity, and the polar position of the particle on the bubble surface. The proposed equations provide an exact solution to the situation where the particle and the bubble are very close together. The attractive flow force and the surface forces are of similar orders of magnitude. Consequently, the models presented in this paper should provide a better estimate for calculating the forces on particles interacting with air bubbles in mineral flotation and other separation operations involving colloidal interactions.

Influence of electrical double-layer interaction on coal flotation.

In the early 1930s it was first reported that inorganic electrolytes enhance the floatability of coal and naturally hydrophobic minerals. To date, explanations of coal flotation in electrolytes have not been entirely clear. This research investigated the floatability of coal in NaCl and MgCl2 solutions using a modified Hallimond tube to examine the role of the electrical double-layer interaction between bubbles and particles. Flotation of coal was highly dependent on changes in solution pH, type of electrolyte, and electrolyte concentration. Floatability of coal in electrolyte solutions was seen not to be entirely controlled by the electrical double-layer interaction. Coal flotation in low electrolyte concentration solutions decreases with increase in concentration, not expected from the theory since the electrical double layer is compressed, resulting in diminishing the (electrical double layer) repulsion between the bubble and the coal particles. Unlike in low electrolyte concentration solutions, coal flotation in high electrolyte concentration solutions increases with increase in electrolyte concentration. Again, this behavior of coal flotation in high electrolyte concentration solutions cannot be quantitatively explained using the electrical double-layer interaction. Possible mechanisms are discussed in terms of the bubston (i.e., bubble stabilized by ions) phenomenon, which explains the existence of the submicron gas bubbles on the hydrophobic coal surface.

Spontaneous formation of an "antidrop".

We have observed, with great surprise, the spontaneous formation of a quite unusual drop. Because of its similarity to the antibubble [(a) Hughes, W.; Hughes, A. R. Nature 1932, 129 (3245), 59. (b) Skogen, N. Am. J. Phys. 1956, 24, 239. (c) Strong, C. L. Sci. Am. 1974, 230 (4), 116.], we describe our find as an "antidrop", a thin spherical shell of an aqueous salt solution, surrounded by an inner and outer organic liquid phase. Two of these antidrops, about 8 mm in diameter, are shown in the present paper resting on a bed of smaller conventional drops. Drops of this size do not normally appear so spherical, however the antidrop is a mere shell, and hence its geometry is dominated by the interfacial tension. We found these drops to be remarkably stable, given it was possible to reversibly deform the drops and even slice through a drop with a glass rod to produce two antidrops. Ultimately, after some finite time period, the antidrops simply disintegrated into clouds of tiny droplets of the aqueous salt solution because of the drainage and concomitant rupturing of the liquid comprising their thin spherical shells.

Influence of surfactant on gas bubble stability.

Gas-bubble stability is achieved either by a reduction in the Laplace pressure or by a reduction in the permeability of the gas-liquid interface. Although insoluble surfactants have been shown definitively in many studies to lower the permeability of the gas-liquid interface and hence increase the resistance to interfacial mass transfer, remarkably little work has been done on the effects of soluble surfactants. An experimental system was developed to measure the effect of the soluble surfactant dodecyl trimethylammonium bromide on the desorption and absorption of carbon dioxide gas through a quiescent planar interface. The desorption experiments conformed to the model of non-steady-state molecular diffusion. The absorption experiments, however, produced an unexpected mass transfer mechanism, with surface renewal, probably because of instability in the density gradient formed by the carbon dioxide. In general, the soluble surfactant produced no measurable reduction in the rate of interfacial mass transfer for desorption or absorption. This finding is consistent with the conclusion of Caskey and Barlage that soluble surfactants produce a significantly lower resistance to interfacial mass transfer than do insoluble surfactants. The dynamic adsorption and desorption of the surfactant molecules at the gas-liquid interface creates short-term vacancies, which presumably permit the unrestricted transfer of the gas molecules through the interface. This surfactant exchange does not occur for insoluble surfactants. Gas bubbles formed in the presence of a high concentration of soluble surfactant were observed to dissolve completely, while those formed in the presence of the insoluble surfactant stearic acid did not dissolve easily, and persisted for very long periods. The interfacial concentration of stearic acid rises during bubble dissolution, as it is insoluble, and must eventually achieve full monolayer coverage and a state of compression, lowering the permeability of the interface. Thus, insoluble surfactants or hydrophobic impurities from solid surfaces may account for increased bubble stability.