Relaxation processes of PGPR at the water/oil interface inferred by oscillatory or transient viscoelasticity measurements.

The rheological properties of PolyGlycerol PolyRicinoleate (PGPR) at the oil/water interface were studied using a drop-shaped tensiometer. Small deformation oscillations of the drop area allow the measurement of the interfacial viscoelasticity spectrum, that is, the elastic and viscous moduli as a function of frequency. Another way to obtain such a spectrum is to perform a transient relaxation measurement from which the relaxation modulus as a function of time is deduced and interpreted. Several models containing one or more relaxation times were considered, and their resulting spectra were compared to the oscillatory ones. Similar results suggest that one could in principle use oscillatory or transient relaxations indifferently. However, the transient relaxation technique proved to be more adapted for the determination of the relaxation times. At low PGPR concentrations in oil, the behavior is controlled by long relaxation times, whereas short ones take over when approaching and exceeding the saturation interfacial concentration. This was understood as a shift from a diffusion-dominated regime to a rearrangements-dominated regime.