Glass Transition Behavior in Thin Polymer Films Covered with a Surface Crystalline Layer

Thin amorphous poly(ethylene terephthalate) (PET) films covered with/without a crystallized surface layer were prepared onto silicon wafers. In the former and latter cases, the surface mobility in the film was depressed and enhanced, respectively. The glass transition temperature (T_g) of the amorphous PET film decreased with the reduction of the film thickness, exhibiting a remarkable nanoconfinement effect. However, once the surface region of the thin film was crystallized, or frozen in terms of the segmental motion, T_g of the films recovered to that of the bulk. Concurrently, the apparent activation energy of the segmental motion in the surface-crystallized film was in good accordance with the bulk value as well. These results make it clear that the mobility in the surface region plays an essential role in the glass transition of the thin films.