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The effect of confinement in the segmental relaxation of polymers is considered. On the basis of a thermodynamic model we discuss the emerging relevance of the fast degrees of freedom in stimulating the much slower segmental relaxation, as an effect of the constraints at the walls of the amorphous regions. In the case that confinement is due to the presence of crystalline domains, a quasi-Poissonian distribution of local constraining conditions is derived as a result of thermodynamic equilibrium. This implies that the average free-energy barrier F for conformational rearrangement is of the same order of the dispersion of the barrier heights, ( F) , around F . As an example, we apply the results to the analysis of the -relaxation as observed by dielectric broad-band spectroscopy in semicrystalline poly(ethylene terephthalate) cold-crystallized from either an …
Publication date: 
1 Jun 2009

Marco Pieruccini, Tiberio A Ezquerra

Biblio References: 
Volume: 29 Issue: 2 Pages: 163-171
The European Physical Journal E