The dynamics of ultra-thin polymer films Alberto D’Amore and Luigi Grassia Department of Aerospace and Mechanical Engineering The Second University of Naples - SUN, Aversa (CE), 81031, Campania, Italy

Ultra thin films (thickness h < REE) of glassy polymers such as polystyrene (PS) can show: a) anomalously large thickness changes b) unexpected dewetting properties c) large shifts in the glass temperature Tg. The present discussion focuses mainly on point a). de Gennes picture the first term describes cohesion, and is minimal for θ = 0. The second term describes the Leibler-Sekimoto network and is minimal for θ = ψc

Reiter 1994 Macromolecules Film thickness 52.8 nm 29.0 nm Mukherjee et al. 2002 PRE Orts 1993 PRL Kanaya 2004 PRE Reiter 1994 Macromolecules

Modeling the interplay between structural relaxation and viscoelasticity reduced time: time-temperature-stress-volume superposition Grassia & D’Amore PRE 2006

McKenna et al. 2005 Science Forrest et al. 2005 PRL NTE ZTE