Correlation of surface and bulk order in low surface energy polymers

Perfluoroalkyl-substituted polymethacrylates (PFPM) are known to exhibit various ordered bulk phases (crystalline, smectic A, smectic B, nematic and isotropic), depending on the number of CF2 units in the side groups. A link between the surface energy and the structural order in the surface region which is found to be limited by the bulk phase behavior was established. It was clear that the surface energies are determined by the structures present in the top layer (1 nm or less from the air surface).