Is the Reduction in Tracer Diffusivity under Nanoscopic Confinement Related to a Frustrated Segmental Mobility?

We developed an experimental method for the determination of the tracer diffusivity D-tr in ultrathin polymer films, and the changes in the segmental mobility of tracer molecules while they diffuse through matrices of different thickness and get adsorbed onto a target substrate. D-tr starts decreasing already at 120-150 nm and drops to 1% of its bulk value in films as thin as 7.5 nm. We discuss the results highlighting a strong decoupling between the reduction in mass transport at the nanoscale and the increase in the glass transition temperature determined via capacitive dilatometry together with a breakdown of the Stokes-Einstein relation between orientational and translational degrees of freedom.