Interfacial Instability of Emulsion Droplets Containing a Polymer and a Fatty Alcohol

We investigated the interfacial instability of emulsion droplets via in situ measuring the oil/water interfacial tension (IFT) using the capillary suction method. The discrete phase of the oil-in-water emulsion contains a hydrophobic polymer (polystyrene, PS) and a fatty alcohol cosurfactant n-cetyl alcohol (CA) or n-octadecanol (OD), both of which were dissolved in an organic solvent (chloroform). The continuous phase is an aqueous solution of surfactant (sodium dodecyl sulfate, SDS). Upon removal of the organic solvent, the concentrations of CA and PS increase gradually, which induce a continual decrease of the IFT until the occurrence of interfacial instability. Micropipette tensiometry performed on an evaporating emulsion droplet reveals that interfacial instability is triggered when the IFT decreases close to ∼0.17 mN/m. As a result, micron particles with wrinkled surfaces can be obtained after the complete removal of the organic solvent. The effect of the initial concentration and alkyl chain length of the cosurfactant on the interfacial instability and surface roughness of the formed particles was studied. This study provides theoretical guidance for the preparation of micrometer-sized polymer particles with diverse morphologies via the interfacial instability of emulsion droplets.