Activated Physical Properties at Air-Polymer Interface

Molecular motion at the surface of monodisperse polystyrene (PS) films with various chain end groups was studied by scanning probe microscopy. Surface glass transition temperature ($T_{g^s}$) of the PS films was much lower than the corresponding bulk value. And, the magnitude of $T_{g^s}$ was strongly dependent on chain end chemistry. This result can be explained in terms of the chain end concentration at the surface. Time-temperature superposition principle was applied to rheological analysis at the surface. The apparent activation energy of the surface ${\alpha}_{a}$-relaxation process was approximately a half of that for the bulk sample. This result clearly indicates that the cooperativity for the surface segmental motion was reduced in comparison with that in the bulk region.