Particle-stabilized emulsions comprised of solid droplets.

We kinetically stabilize oil-in-water emulsions comprising paraffin crystals by adsorbing solid particles (silica) of colloidal size at the oil/water interface. We obtain a set of emulsions that are quiescently stable for a long period of time (months), while the same emulsions are destabilized after only a few hours in the presence of surfactant molecules alone. The emulsions are submitted to a shear stress in order to probe their stability under flow conditions. Partial coalescence and gelation occur when the shear is applied for a sufficiently long period of time. The experiments reveal the existence of a critical droplet mass fraction, phi*, that defines a sharp transition between slow and fast gelation. The process of gelation is rather slow for phi < phi*, occurring at the scale of hours, and becomes almost instantaneous above phi*.

Solid colloidal particles inducing coalescence in bitumen-in-water emulsions.

Silica particles are dispersed in the continuous phase of bitumen-in-water emulsions. The mixture remains dispersed in quiescent storage conditions. However, rapid destabilization occurs once a shear is applied. Observations under the microscope reveal that the bitumen droplets form a colloidal gel and coalesce upon application of a shear. We follow the kinetic evolution of the emulsions viscosity, eta, at constant shear rate: eta remains initially constant and exhibits a dramatic increase after a finite time, tau. We study the influence of various parameters on the evolution of tau: bitumen droplet size and volume fraction, silica diameter and concentration, shear rate, etc.

Coarsening of alkane-in-water emulsions stabilized by nonionic poly(oxyethylene) surfactants: the role of molecular permeation and coalescence.

We produce different alkane-in-water concentrated emulsions stabilized by the same nonionic surfactant, and we follow their kinetic evolution by granulometry. The size distribution becomes remarkably narrow during the first stages of coarsening and progressively turns to a wide function as time passes. We get evidence that the size evolution occurs under the effect of molecular permeation and coalescence. A second hydrophobic species of large molecular size is dissolved in the dispersed phase. This latter is expected to inhibit the permeation mechanism, and coalescence should act alone. Surprisingly, coalescence is also suppressed, even at a very low concentration of the second component (approximately 1% w/w). We vary the chemical nature and concentration of the second species, and we propose a simple mechanism to explain the stabilizing effect with respect to coalescence.

Some general features of limited coalescence in solid-stabilized emulsions.

We produce direct and inverse emulsions stabilized by solid mineral particles. If the total amount of particles is initially insufficient to fully cover the oil-water interfaces, the emulsion droplets coalesce such that the total interfacial area between oil and water is progressively reduced. Since it is likely that the particles are irreversibly adsorbed, the degree of surface coverage by them increases until coalescence is halted. We follow the rate of droplet coalescence from the initial fragmented state to the saturated situation. Unlike surfactant-stabilized emulsions, the coalescence frequency depends on time and particle concentration. Both the transient and final droplet size distributions are relatively narrow and we obtain a linear relation between the inverse average droplet diameter and the total amount of solid particles, with a slope that depends on the mixing intensity. The phenomenology is independent of the mixing type and of the droplet volume fraction allowing the fabrication of both direct and inverse emulsion with average droplet sizes ranging from micron to millimetre.

Double emulsions: how does release occur?

Water-in-oil-in-water double emulsions (W/O/W) consist of dispersed oil globules containing smaller aqueous droplets. These materials offer interesting possibilities for the controlled release of chemical species initially entrapped in the internal droplets. A better understanding of the stability conditions and release properties in double emulsions requires the use of model systems with a well-defined droplet size. In this paper, we use quasi-monodisperse double emulsions made of calibrated water droplets and oil globules to investigate the two mechanisms that are responsible for the release of a chemical substance (NaCl). (i) One is due to the coalescence of the thin liquid film separating the internal droplets and the globule surfaces. (ii) The other mechanism termed as 'compositional ripening' occurs without film rupturing; instead it occurs by diffusion and/or permeation of the chemical substance across the oil phase. By varying the proportions and/or the chemical nature of the surface active species it is possible to shift from one mechanism to the other one. We therefore study separately both mechanisms and we establish some basic rules that govern the behavior of W/O/W double emulsions.

Double emulsions: a tool for probing thin-film metastability.

We study the kinetics of the release of monodisperse water-in-oil-in-water double emulsions in the regime dominated by coalescence of the internal aqueous droplets onto the globule interface. By measuring the rate of release of adsorbed droplets, we directly determine the average lifetime of the thin film that forms between the small internal droplets and the globule surface. Therefore, the activation energy and the natural frequency of the hole nucleation process within the adhesive thin liquid films are unambiguously deduced.

Viscous sintering phenomena in liquid-liquid dispersions.

We present experimental evidence for viscous sintering phenomena in a gel formed by highly viscous emulsion droplets. When a rupturing agent is added to the initially stable emulsion, a gel forms, which further contracts by preserving the geometry of the container. The initial stages of densification (up to 60%) follow very well the "cylindrical model" for viscous sintering, but deviate at the final stages of densification. The observed inverse dependence of the contraction rate on viscosity is consistent with the viscous sintering theory.