The nanobubble inflation method is the only experimental technique that can measure the viscoelastic creep compliance of unsupported ultrathin films of polymers over the glass–rubber transition zone as well as the dependence of the glass transition temperature (Tg) on film thickness. Sizeable reduction of Tg was observed in polystyrene (PS) and bisphenol A polycarbonate by the shift of the creep compliance to shorter times. The dependence of Tg on film thickness is consistent with the published data of free-standing PS ultrathin films. However, accompanying the shift of the compliance to shorter times, a decrease in the rubbery plateau compliance is observed. The decrease becomes more dramatic in thinner films and at lower temperatures. This anomalous viscoelastic behavior was also observed in poly(vinyl acetate) and poly (n-butyl methacrylate), but with large variation in the change of either the Tg or the plateau compliance. By now, well established in bulk polymers is the presence of three different viscoelastic mechanisms in the glass–rubber transition zone, namely, the Rouse modes, the sub-Rouse modes, and the segmental α-relaxation. Based on the thermorheological complexity of the three mechanisms, the viscoelastic anomaly observed in ultrathin polymer films and its dependence on chemical structure are explained in the framework of the Coupling Model. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013
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