Thermodynamic and Kinetic Pathways to Agitated and Spontaneous Emulsification

Emulsification of an oil (dodecane and diesel fuel) in salinized water was studied under turbulent and agitation-free conditions in the presence of a mixture of an ionic and a nonionic surfactant. The properties of the air-water and the oil-water interfaces were investigated using the methods of du-Nouy ring, drop resonance vibrometry, and Langmuir film balance that allowed pinpointing the relevance of certain interfacial properties in emulsification. Estimation of the droplet size and its distribution from the nanometer-to-micrometer range was carried out with optical microscopy, acoustic attenuation spectroscopy, and continuous hydrodynamic flow fractionation. These measurements provided the platform for the comparison of the emulsion droplet size with those predicted from the fluctuation of the dynamic stress in the turbulent water via a capillary hydrodynamic model. While such a comparison was reasonably meaningful for micron size emulsion droplets, production of nanometer size droplets was beyond such a rudimentary expectation. We thus carried out systematic investigations into other factors that contribute to emulsification under both agitated and agitation-free conditions. An important finding of these studies is that the infusion of air bubbles that profoundly enhance the hydrodynamic fluctuation produces mainly submicroscopic emulsion droplets, while a fluctuation inhibiting water-soluble polymer has the opposite effect. Furthermore, while a hydrophilic polymer dissolved in water enhances the ripening of the droplets with time, hydrophobic polymer in oil thwarts aging, plausibly by osmotic backpressure and interfacial stiffening, which, upon compression, acts against surface tension, thereby decreasing the chemical potential of the trapped oil molecules inside the droplet. These effects are similarly observed in spontaneous emulsifications, that is, when a layer of oil containing the additives is deposited upon the surface of the aqueous phase in the absence of any external work input.