On the bridge hypothesis in the glass transition of freestanding polymer films

TL;DR

This paper critically examines the bridge hypothesis for the glass transition in freestanding polymer films, demonstrating through statistical analysis that the proposed sliding mechanism cannot account for experimental observations.

Contribution

The study provides a detailed statistical analysis showing the bridge hypothesis is insufficient to explain the glass transition behavior in thin polymer films.

Findings

Sliding mechanism cannot reproduce experimental T_g thickness dependence

Fundamental reasons why the bridge hypothesis fails are identified

Analysis challenges the validity of the bridge hypothesis in this context

Abstract

Freestanding thin polymer films with high molecular weights exhibit an anomalous decrease in the glass-transition temperature with film thickness. Specifically, in such materials, the measured glass-transition temperature evolves in an affine way with the film thickness, with a slope that weakly depends on the molecular weight. De Gennes proposed a sliding mechanism as the hypothetical dominant relaxation process in these systems, where stress kinks could propagate in a reptation-like fashion through so called bridges, i.e. from one free interface to the other along the backbones of polymer macromolecules. Here, by considering the exact statistics of finite-sized random walks within a confined box, we investigate in details the bridge hypothesis. We show that the sliding mechanism cannot reproduce the basic features appearing in the experiments, and we exhibit the fundamental reasons behind such a fact.