Effects of nanoscopic-confinement on polymer dynamics

The static and dynamic behavior of polymers in confinement close to interfaces can be very different from that in the bulk. Among the various geometries, intercalated nanocomposites, in which polymer films of ∼1 nm thickness reside between the parallel inorganic surfaces of layered silicates in a well-ordered multilayer, offer a unique avenue for the investigation of the effects of nanoconfinement on polymer structure and dynamics by utilizing conventional analytical techniques and macroscopic specimens. In this article, we provide a review of research activities mainly in our laboratory on polymer dynamics under severe confinement utilizing different polymer systems: polar and non-polar polymers were mixed with hydrophilic or organophilic silicates, respectively, whereas hyperbranched polymers were studied in an attempt to probe the effect of polymer-surface interactions by altering the number and the kinds of functional groups in the periphery of the branched polymers. The polymer dynamics was probed by quasielastic neutron scattering and dielectric relaxation spectroscopy and was compared with that of the polymers in the bulk. In all cases, very local sub-Tg processes related to the motion of side and/or end groups as well as the segmental α-relaxation were identified with distinct differences recorded between the bulk and the confined systems. Confinement was found not to affect the very local motion in the case of the linear chains whereas it made it easier for hyperbranched polymers due to modifications of the hydrogen bond network. The segmental relaxation in confinement becomes faster than that in the bulk, exhibits Arrhenius temperature dependence and is observed even below the bulk Tg due to reduced cooperativity in the confined systems.