The lifetime of the deviations from bulk behaviour in polymers confined at the nanoscale

Monitoring the impact of annealing on the dynamic glass transition of nanometres-thick polymer layers provides new insights into the mechanisms behind the tremendous changes in the performance of macromolecular materials in close proximity to an interface. Here we present results revealing a correlation between deviations from bulk behaviour, manifesting in changes to the glass transition temperature, the reduction of dielectric strength and the growth of an irreversibly adsorbed layer (Guiselin brushes). The non-universal behaviour of polymers under confinement could be explained in terms of a dimensionless number given by the ratio between the timescale of adsorption and the annealing time. In particular, in the case of slow adsorption kinetics, such as for polystyrene on aluminium, deviations from bulk behaviour correspond to metastable states with an extremely long lifetime.