Unraveling the Interaction of Water-in-Oil Emulsion Droplets via Molecular Simulations and Surface Force Measurements.

Water-in-oil emulsions widely exist in various chemical and petroleum engineering processes, and their stabilization and destabilization behaviors have attracted much attention. In this work, molecular dynamic (MD) simulations were conducted on the water-in-oil emulsion droplets with the presence of surface-active components, including a polycyclic aromatic compound (VO-79) and two nonionic surfactants: the PEOPPOPEO triblock copolymer and Brij-93. At the surface of water droplets, films were formed by the adsorbate molecules that redistributed during the approaching of the droplets. The redistribution of PEOPPOPEO was more pronounced than that of Brij-93 and VO-79, which contributed to lower repulsion during coalescence. The interaction forces during droplet coalescence were also measured using atomic force microscopy. Jump-in phenomenon and coalescence were observed for systems with VO-79, Brij-93, and a low concentration of Pluronic P123. The critical force before jump-in was lowest for the low concentration of Pluronic P123, consistent with the MD results. Adhesion was measured when separating water droplets with a high concentration of Pluronic P123. By correlating theoretical simulations and experimental force measurements, this work improves the fundamental understanding on the interaction behaviors of water droplets in an oil medium in the presence of interface-active species and provides atomic-level insights into the stabilization and destabilization mechanisms of water-in-oil emulsion.