Glass transition of miscible binary polymer-polymer thin films.

The average glass transition temperatures, Tg, of thin homopolymer films exhibit a thickness dependence, Tg(h), associated with a confinement effect and with polymer-segment-interface interactions. The Tg's of completely miscible thin film blends of tetramethyl bisphenol-A polycarbonate (TMPC) and deuterated polystyrene (dPS), supported by SiO(x)/Si, decrease with decreasing h for PS weight fractions phi >0.1. This dependence is similar to that of PS and opposite to that of TMPC thin films. Based on an assessment of Tg(h, phi), we suggest that the Tg(h, phi) of miscible blends should be rationalized, additionally, in terms of the notion of a self-concentration and associated heterogeneous component dynamics.