Evaporation rates of water from concentrated oil-in-water emulsions

We have investigated the rate of water evaporation from concentrated oil-in-water (o/w) emulsions containing an involatile oil. Evaporation of the water continuous phase causes compression of the emulsion with progressive distortion of the oil drops and thinning of the water films separating them. Theoretically, the vapor pressure of water is sensitive to the interdroplet interactions, which are a function of the film thickness. Three main possible situations are considered. First, under conditions when the evaporation rate is controlled by mass transfer across the stagnant vapor phase, model calculations show that evaporation can, in principle, be slowed by repulsive interdroplet interactions. However, significant retardation requires very strong repulsive forces acting over large separations for typical emulsion drop sizes. Second, water evaporation may be limited by diffusion in the network of water films within the emulsion. In this situation, water loss by evaporation from the emulsion surface leads to a gradient in the water concentration (and in the water film thickness). Third, compression of the drops may lead to coalescence of the emulsion drops and the formation of a macroscopic oil film at the emulsion surface, which serves to prevent further water evaporation. Water mass-loss curves have been measured for silicone o/w emulsions stabilized by the anionic surfactant SDS as a function of the water content, the thickness of the stagnant vapor-phase layer, and the concentration of electrolyte in the aqueous phase, and the results are discussed in terms of the three possible scenarios just described. In systems with added salt, water evaporation virtually ceases before all the water present is lost, probably as a result of oil-drop coalescence resulting in the formation of a water-impermeable oil film at the emulsion surface.