Dynamics of polymer thin films and surfaces
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The dynamics of thin polymer films display many differences from the bulk dynamics. Different modes of motions in polymers are affected by confinement in different ways. The enhancement in the dynamics of some modes of motion can cause anomalies in the glass transition temperature (Tg) of thin films, while other modes of motion such as diffusion can be substantially slowed down due to the confinement effects. In this thesis, different modes of dynamics are probed using different techniques. The interface healing of two identical polymer surfaces is used as a probe of segmental motion in the direction normal to the plane of the films and it is shown that this mode of motion is slowed down at temperatures above bulk glass transition, while the glass transition itself is decreased indicating that the type of motion responsible for the glass transition is enhanced. The glass transition measurements at different cooling rates indicate that this enhancement only happens at temperatures close to or below bulk glass transition temperature and it is not expected to be detected at higher temperatures where the system is in the melt state. It is shown that the sample preparation technique is not a factor in observing this enhanced dynamics, while the existence of the free surface can be important in observed reductions in the glass transition temperature. The dynamics near the free surface is further studied using a novel nano-deformation technique, and it is shown that the dynamics near the free surface is in fact enhanced compared to the bulk dynamics and this enhancement is increased as the temperature is decreased further below Tg. It is also shown that this mode of relaxation is much different from the bulk modes of relaxations, and a direct relationship between this enhanced motion and Tg reduction in thin films can be established. The results presented in this thesis can lead to a possib le universal picture that can resolve the behavior of different modes of motions in thin polymer films.