Periodic Expansion and Contraction Phenomena in a Pendant Droplet Associated with Marangoni Effect

A spontaneous oscillation between the expansion and contraction of a nitrobenzene pendant droplet containing di-(2-ethylhexyl)phosphoric acid (DEHPA) was observed in an aqueous phase under alkaline conditions. We described this phenomenon as the spontaneous oscillation of the oil–water interfacial tension. The oscillation characteristics such as the induction period and the interfacial-tension oscillation frequency were investigated under different temperatures and aqueous phase polarities. The effects of the interfacial tension of the biphasic pendant-droplet, the surface excess of the surfactant molecules, and the amount of nitrobenzene elution from the droplet to the aqueous phase on the oscillation characteristics were investigated. Consequently, the periodic expansion–contraction oscillation mechanism was explained through the adsorption–desorption cycle of DEHPA with respect to the aggregate formation of the inverted micelle of DEHPA. This study was based on a simple vibration phenomenon of interfacial tension, and is extremely important for clarifying the predominant factors that cause fluctuations in the free interface energy, which has been ambiguous.