Studies of polymer thin films using atomic force microscopy
MetadataShow full item record
This thesis focuses on how the properties of polymer thin films depend on the film thickness and molecular weight (Mw). Previous studies of polystyrene (PS) films coated on silica with Mw of 2.4 and 212 kg/mol found that the viscosity of the films decreases with decreasing film thickness. A two-layer model assuming a 3 nm thick mobile layer situated at the top surface of the film and hydrodynamically coupled to a bulklike inner layer is able to describe the viscosity of the films. To better understand the dynamics exhibited by the surface mobile layer, this work extends the measurement to various other Mw up to 2316 kg/mol. The result shows that the viscosity of the films also decreases with decreasing film thickness and can be described by the same two-layer model. But there are exceptional findings as well. Specifically, the viscosity of the high-Mw films (> 60 kg/mol) exhibit a Mw^0 dependence, distinctly different from the Mw^3.4 dependence exhibited by the viscosity of the bulk polymer. Moreover, the surface chains in the high-Mw films, as inferred from the two-layer model, are in an unphysically stretched state. These observations led to the conjecture that the viscosity reduction in the high-Mw films is due to a different mechanism from that in the lower Mw films which is directly tied to the surface mobile layer as in the two-layer model. To scrutinize this conjecture, viscosity measurement is extended to PS films doped with Dioctyl phthalate (DOP). A previous experiment showed that the influence of the surface on the overall dynamics in this system is likely to be much smaller than in the undoped films. The measurement results are examined to determine, among other things, whether the viscosity reduction relative to that in the undoped films is weaker in the low-Mw than in the high-Mw regime.