Molecular dynamics of hyperbranched polyesters in the confinement of thin films

Broadband Dielectric Spectroscopy is employed to investigate the molecular dynamics in thin films of hyperbranched polyesters (type AB(1)B(2), with -OH and -OCOCH3 as terminal groups). Three relaxation processes are detected: alpha, beta and gamma. While the latter two are not influenced by the confinement, a pronounced effect is observed on the alpha relaxation: with decreasing film thickness the slower relaxation modes of the dynamic glass transition are gradually suppressed, resulting in an increase of the average relaxation rate and in a linear decrease of the dielectric strength. This is attributed to an immobilization in confinement of the polymeric segments located at the periphery of the hyperbranched macromolecular structures.