Surface dilatational elasticity of poly(oxy ethylene)-based surfactants by oscillation and relaxation measurements of sessile bubbles.

Surface dilatational elasticities and viscosities have been measured by means of the axisymmetric bubble shape method. Two different techniques using sinusoidal oscillations and step relaxations have been used, and the results are treated by means of the bulk/surface diffusional exchange model. Three different nonionic surfactants based on poly(oxy ethylene) as the hydrophilic group have been used: one simple surfactant, Brij 35, and two block copolymers, Pluronic F68 and P9400. Step relaxation and oscillation give mostly the same limiting surface dilatational elasticities, but step relaxation is a more model-dependent method. In the cases where the bulk/surface diffusion model is correct, the two methods give the same results, but otherwise step relaxation gives average values of the limiting elasticity E0 and the typical relaxation frequency omega0. Limiting elasticities up to ca. 25 mN m(-1)have been found for these substances. The surface/bulk diffusion model describes quite well the two relatively hydrophilic substances Brij 35 and F68, especially at low concentrations, but less so for the more hydrophobic P9400. The surface dilatational elasticity as a function of the surface pressure of the surface-active polymers goes through at least one maximum as a result of surface conformational changes.