On the Segmental Dynamics and the Glass Transition Behavior of Poly(2-vinylpyridine) in One- and Two-Dimensional Nanometric Confinement

Geometric nanoconfinement, in one and two dimensions, has a fundamental influence on the segmental dynamics of polymer glass-formers and can be markedly different from that observed in the bulk state. In this work, with the use of dielectric spectroscopy, we have investigated the glass transition behavior of poly(2-vinylpyridine) (P2VP) confined within alumina nanopores and prepared as a thin film supported on a silicon substrate. P2VP is known to exhibit strong, attractive interactions with confining surfaces due to the ability to form hydrogen bonds. Obtained results show no changes in the temperature evolution of the a-relaxation time in nanopores down to 20 nm size and 24 nm thin film. There is also no evidence of an out-of-equilibrium behavior observed for other glass-forming systems confined at the nanoscale. Nevertheless, in both cases, the confinement effect is seen as a substantial broadening of the alpha-relaxation time distribution. We discussed the results in terms of the importance of the interfacial energy between the polymer and various substrates, the sensitivity of the glass-transition temperature to density fluctuations, and the density scaling concept.

Automated summary

Geometric nanoconfinement significantly influences the segmental dynamics of polymer glass-formers. When confined within alumina nanopores or prepared as thin films, P2VP showed no changes in glass transition behavior but exhibited a substantial broadening of alpha-relaxation time distribution. This effect was discussed in relation to interfacial energy, glass-transition temperature sensitivity, and density scaling.