Irreversible Adsorption Erases the Free Surface Effect on the Tg of Supported Films of Poly(4-tert-butylstyrene).

When cooled at constant rate, a 25 nm thin film of poly(4-tert-butylstyrene) vitrifies 50 K lower than in bulk. This record sets the largest depression in thermal glass transition temperature (Tg) ever observed upon confinement at the nanoscale level. Same as for other supported polymer layers, this reduction in Tg has been attributed to the presence of a free surface, the ensemble of molecules at the interface with air remaining in the liquid state also at temperatures well below bulk Tg. Here, we verify that such tremendous shifts can be erased upon prolonged annealing in the liquid state, hinting at a metastable nature of confinement effects. We demonstrate that the recovery of bulk behavior and the manifestation of the free surface are enslaved to the kinetics of irreversible adsorption of chains on the supporting substrate.