Scaled down glass transition temperature in confined polymer nanofibers

Arrays of polymer nanostructures have been widely used in many novel devices and nanofabrication methods. The glass transition temperature, which is a key parameter influencing the long-term stability of polymer nanostructures, has not yet been systematically studied and well understood. Here we study this technological and fundamental issue with polymers of different values of molar mass M confined in nanocylinders of a varying diameter D. The glass transition temperature Tg loses its dependence on the molar mass for D ≲ 100 nm, a range in which the relative depression of Tg varies as D(-0.44). For higher cylinder diameters, Tg progressively recovers its dependence on the molar mass. This is quantitatively reproduced by a model based on an equilibrium interfacial excess of free volume, which needs to be created unless provided by the chain ends. Our findings suggest that the structural perturbations during nanofabrication may strongly affect the long-term stability of arrays of polymer nanostructures.