117 research outputs found
The Glass Transition of Thin Polymer Films: Some Questions, and a Possible Answer
A simple and predictive model is put forward explaining the experimentally
observed substantial shift of the glass transition temperature, Tg, of
sufficiently thin polymer films. It focuses on the limit of small molecular
weight, where geometrical `finite size' effects on the chain conformation can
be ruled out. The model is based on the idea that the polymer freezes due to
memory effects in the viscoelastic eigenmodes of the film, which are affected
by the proximity of the boundaries. The elastic modulus of the polymer at the
glass transition turns out to be the only fitting parameter. Quantitative
agreement is obtained with our experimental results on short chain polystyrene
(Mw = 2 kg/mol), as well as with earlier results obtained with larger
molecules. Furthermore, the model naturally accounts for the weak dependence of
the shift of Tg upon the molecular weight. It furthermore explains why
supported films must be thinner than free standing ones to yield the same
shift, and why the latter depends upon the chemical properties of the
substrate. Generalizations for arbitrary experimental geometries are
straightforward.Comment: 7 pages, 4 figure
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