The glass transition of thin polymer films in relation to the interfacial dynamics

As opposed to measurements on the glass transition of a polymer in the bulk, measurements of thin polymer layers reflect--due to the alterations of the glassy dynamics at the confining interfaces--several contributions acting together to give the net response of a polymer film. This fundamental difference is exemplified in detail for the particular case of broadband dielectric spectroscopy, an experimental tool extensively employed to investigate the glassy dynamics of polymers under condition of geometrical confinement.