Evolution of Pristine Emulsions and Hypothesis Explaining Their Existence

The term “pristine emulsion” is used for differentiating emulsions that consist of only water and oil with no surfactant from the Pickering emulsions, which are also surfactant-free but stabilized with colloidal particles. We review 22 papers dedicated to such emulsions prepared from a wide variety of liquids. We studied here the evolution of one such emulsion, hexadecane-in-water at 4% vl, over a long period of time, from days to weeks. We discovered that the droplet size grows with time, with a rate that depends on mixing conditions, which supports a coalescence hypothesis. However, this coalescence is unusual because the size reaches a certain constant value, which contradicts typical coalescence behavior. To explain this peculiarity and such emulsification in general, we employ a theoretical model that was developed for explaining pristine nano-bubble stability. We hypothesize the existence of a layer of structured water molecules at the interface, following Eastoe and Ellis (Adv in Colloid and Interface Sci., 134–135, 89–95, 2007) and others. We point out that the Electric Double Layer exerts a force on the water dipole moments in this layer (dielectrostatic force) that compensates Kelvin’s pressure. The droplet size calculated using this model is close to the measured size. The second factor associated with this layer is the repulsion of the water dipole moments, which we show can compensate for the surface tension tangential to the interface. After ruling out alternative hypotheses with our data, we conclude that the model suggested for explaining the stability of nano-bubbles is also consistent with our results for these “pristine emulsions”.