Kinetic viscoelasticity during early polymer-polymer spinodal dewetting

Abstract

The dewetting kinetics of a supported polymer bilayer were measured in situ using coherent grazing-incidence x-ray scattering. X-ray photon correlation spectroscopy provides both the two-time correlation functions and the cross-correlation function which measures the average spatial shift of the speckles produced by the coherent x rays. The stress in the ultrathin top dewetting film can be directly observed due to the exquisite sensitivity to sample curvature changes provided by the x-ray speckle correlation functions. The hole-opening events in the film are found to be associated with significant changes to the stress. These results are interpreted through an analogy between viscoelastic spinodal dewetting and early-stage bulk viscoelastic phase separation. The frequency of hole-initiation events during dewetting decreases with time as a power law, and the power-law exponent can be linked to nonlinear viscoelastic effects, showing similarity in their stress relief dynamics to aftershock decays.