Is the chain dynamics in thin polymer films isotropic ?

The dynamics of molten polymer chains (polydimethylsiloxane) confined between air and a solid, wettable and non-adsorbing surface, is investigated using NMR. The basic approach used here consists in studying how nuclear interactions are time-averaged by rapid molecular motions. Chain segments in such molten films undergo uniaxial reorientations around the normal to the surfaces. The influence of the film thickness ( 50 ≤ h ≤ 3500 Å ) proves this dynamic uniaxiality involves rapid segment diffusion between both surfaces which impose a high degree of planar orientation. Thus the segmental ordering is observed over a thickness range which depends on the degree of chain entanglements