Polymer loaded microemulsions: Changeover from finite size effects to interfacial interactions

Form fluctuations of microemulsion droplets are observed in experiments using dielectric spectroscopy (DS) and neutron spin echo spectroscopy (NSE). Previous work on dioctyl sodium sulfosuccinate based water in oil microemulsions in the droplet phase has shown that adding a water soluble polymer (Polyethylene glycol M = 1500 g mol^-1) modifies these fluctuations. While for small droplet sizes (water core radius r_c < 37 Å) compared to the size of the polymer both methods consistently showed a reduction in the bending modulus of the surfactant shell as a result of polymer addition, dielectric spectroscopy suggests the opposite behaviour for large droplets. This observation is now confirmed by NSE experiments on large droplets. Structural changes due to polymer addition are qualitatively independent of droplet size. Dynamical properties, however, display a clear variation with the number of polymer chains per droplet, leading to the observed changes in the bending modulus. Furthermore, the contribution of structural and dynamical properties on the changes in bending modulus shifts in weight. With increasing droplet size, we initially find dominating finite size effects and a changeover to a system, where interactions between the confined polymer and the surfactant shell dominate the bending modulus.