Temperature and Thickness Dependence of the Time Scale of Crystallization of Polymers under 1D Confinement.

Confined in nanodomains, polymers crystallize much slower than in bulk due to both finite size and interfacial effects. These two factors are successfully disentangled in our phenomenological framework, which provides a measurement of the time scale of crystallization via a product of probabilities involving nucleation and of chain diffusion. In this Letter, we demonstrate that our model allows determining the Gibbs free energy of the formation of a critical size nucleus indicated by the classical nucleation theory for bulk polymer melts. In addition to that, by means of segmental mobility data and one single set of isothermal crystallization measurements at different confinement degrees, our model predicts the right temperature and thickness dependence of the crystallization time.