Langmuir, Vol.19, No.19, 7911-7918, 2003
Optically profiling a draining aqueous film confined between an oil droplet and a solid surface: Effect of nonionic surfactant
We have profiled the deformation of an oil droplet during its approach to a silica surface, monitoring the drainage of the intervening aqueous film in real time, using imaging ellipsometry/reflectometry. Specifically, we investigated how film drainage and droplet deformation are affected by the addition of the nonionic surfactant C12E8. The droplet dimples at the beginning of film drainage at its center. At low surfactant concentrations (< 10% of the cmc)we observe film recovery, due to the Marangoni effect reversing the direction of fluid flow. High surfactant concentrations minimize interfacial tension gradients, thereby hindering Marangoni flow. Lowering of the oil-water interfacial tension promotes spreading at the barrier ring and nonuniform film drainage; i.e., the dimple "sweeps" across the film profile. The rate of drainage can be explained in terms of the Hagen-Poiseuille law and, as such, is dependent on the extent to which spreading occurs and the hydrostatic pressure difference between the bulk solution and the dimple, where the reverse curvature of the droplet sets up a Laplace pressure. This positive Laplace pressure drives film drainage to equilibrium, where a thin aqueous film of uniform thickness is stabilized by double-layer repulsion between the similarly charged oil droplet and the silica surface. The equilibrium film thickness is proportional to the range of the double-layer repulsion and decreases with more added C12E8 as a result of partitioning of surfactant at the oil-water interface.