"Magic Numbers" in Self-Faceting of Alcohol-Doped Emulsion Droplets.

ABSTRACT

Oil-in-water emulsion droplets spontaneously adopt, below some temperature Td , counterintuitive faceted and complex non-spherical shapes while remaining liquid. This transition is driven by a crystalline monolayer formed at the droplets' surface. Here, we show that ppm-level doping of the droplet's bulk by long-chain alcohols allows tuning Td by >50 °C, implying formation of drastically different interfacial structures. Furthermore, "magic" alcohol chain lengths maximize Td . This we show to arise from self-assembly of mixed alcoholalkane interfacial structures of stacked alkane layers, co-crystallized with hydrogen-bonded alcohol dimers. These structures are accounted for theoretically and resolved by direct cryogenic transmission electron microscopy (cryoTEM), confirming the proposed structures. The discovered tunability of key properties of commonly-used emulsions by minute concentrations of specific bulk additives should benefit these emulsions' technological applicability.