X-ray Photon Correlation Spectroscopy Study on Dynamics of the Free Surface in Entangled Polystyrene Melt Films

The dynamics of polymer chains near the surface of a melt and within thin films remains a subject of inquiry along with the nature of the glass transition in these systems. Recent studies show that the properties of the free surface region are crucial in determining the anomalous glass transition temperature (Tg) reduction of polymer thin films. In this study, by embedding 'dilute' gold nanoparticles in polystyrene (PS) thin films as 'markers', we could successfully probe the diffusive Brownian motion which tracks the local viscosity both at the free surface and within the rest of the single PS thin film far above bulk Tg. The technique used was X-ray photon correlation spectroscopy with resonance-enhanced X-rays that allows us to independently measure the motion in the regions of interest at the nanometer scale. We found the presence of the surface reduced viscosity layer in entangled PS thin films at T>>Tg.