Anomalous Surface Relaxations of Branched-Polymer Melts

Abstract

The dynamics of thermally stimulated surface fluctuations of 100 nm thick films of long-branched polymers are measured for the first time. In contrast to comparable films of linear or cyclic chains that show no change in viscosity upon confinement, films of 6-pom, 6-star, and 6-end end-branched stars show viscosities, inferred from x-ray photon correlation spectroscopy, as much as 100 times higher than in the bulk. This difference varies in magnitude with chain architecture. Branching has a profound effect on confinement, even for these unentangled chains.