Aggregation in a high internal phase emulsion observed by SANS and USANS

As part of a wider study into high internal phase emulsions, we have prepared and studied by SANS and USANS the structure of an unstable emulsion consisting of 90% by volume saturated ammonium nitrate dispersed as micron-scale droplets in hexadecane, stabilised by the surfactant Pluronic L92. Similar emulsions produced using polyisobutylene-based surfactants, reported earlier, are highly stabilised by a significant number of surfactant rich reverse micelles a few nanometres in diameter in the oil phase. The aqueous-oil droplet interfaces are coated with a monolayer of surfactant, while a very small amount of surfactant is aggregated into micron-scale surfactant-rich objects. In contrast, the Pluronic emulsion contains an insignificant number of reverse micelles and a complex multilayered interface between oil and aqueous phases. Now, the great majority of added surfactant is in the form of micron scale, fractally linked, blocks of lamellar phase at the aqueous-oil droplet interfaces. The lamellar phase can be characterised by the Bragg peaks observed in three different isotopic contrasts by SANS. We attribute the shear instability of the Pluronic emulsion to the more hydrophilic nature of the surfactant which causes both depletion of reverse micelles in the oil phase, and aggregation into the blocks of lamellar phase.