Thermally Activated Processes in Polymer Glasses

A derivation is given for the Vogel-Fulcher-Tammann thermal activation law for the glassy state of a bulk polymer. Our microscopic considerations involve the entropy of closed polymermolecular chains (i.e. polymerclosed strings). For thin film polymerglasses, one obtains open polymerstrings in that the boundary surfaces serve as possible string endpoint locations. The Vogel-Fulcher-Tammann thermal activation law thereby holds true for a bulk polymerglass but is modified in the neighborhood of the boundaries of thin film polymers.