Molecular dynamics in thin grafted and spin-coated polymer layers.

Broadband Dielectric Spectroscopy is employed to study the molecular dynamics in thin layers of grafted and spin-coated polydimethylsiloxane (PDMS) and of the type-A polymer cis-1,4-polyisoprene (PI). Strong resemblance with low-molecular-weight systems is found but additionally the conformation of the chain and its extension becomes important. For PI a confinement-induced relaxation is found. It is observable if the layer thickness is comparable to the end-to-end vector of the chain and it depends strongly on the separation between interfaces. In contrast, the dynamic (and hence the calorimetric) glass transition is not affected by the geometrical confinement.