Organization and mixing properties of semi-ordered chains at interfaces

The author has developed mean-field theory for chain organization in these systems. Chains are assumed to adopt their configurations of maximum entropy, subject to the constraint that planar layers parallel to the interface are fully filled by chain segments. One property calculated with this model is the relative incidence of different types of chain foldbacks in semicrystalline polymers. The authors find that for freely-flexible chains, the preponderance of foldbacks is adjacent whereas for chains with more realistic bending energies, it is predicted that there will be relatively few adjacent re-entrants of the chains. In addition to the chain configurations, the theory also permits calculation of the distribution of small- molecule solutes within these interfacial phases.