Quantifying and Modeling the Crystallinity of Polymers Confined in Nanopores.

We propose a methodology to characterize the crystalline content of interfacial polymer layers in systems confined at the nanoscale level in a 2D geometry. Based on the crystallinity data of a set of polymers, we introduce a simple model to describe the gradient in crystallinity introduced by confining polymer chains in nanopores. Our model underscores the pivotal role that interfaces play in crystallization and unequivocally contradicts the existence of interfacial "dead" layers where crystallization cannot take place. Further, we verified that the organization of crystals near the pore walls resembles the macromolecular architecture of adsorbed layers, hinting at a strong interplay between crystallization and adsorption.