Reductions of the glass transition temperature in thin polymer films: probing the length scale of cooperative dynamics

Abstract

We report measurements of the glass transition temperature, T(g), in free standing polymer films in a low M(n) limit where chain confinement effects are not observed. The measured T(g) values are accurately described by a layer model incorporating a mobile surface layer with a size determined by the length scale of cooperative dynamics. The analysis leads to a surface T(g) value and length scale of cooperative motion near bulk T(g) which quantitatively agree with independently determined values. The model and parameters provide a framework within which all previous measurements of T(g) values in thin supported films may be understood and provides values for the length scale of cooperative motion over an extended range of temperatures below the bulk T(g) value.