Dynamical heterogeneity in nanoconfined poly(styrene) chains

Fluids in nanoscopic confinements possess a variety of unusual properties, and in particular, remarkable dynamical heterogeneities which vary on length scales as short as a fraction of a nanometer. While the surface forces apparatus provides an experimental probe of macroscopic properties of fluids in contact with atomically smooth solid surfaces, few experimental probes are available which test the microscopic origins of these heterogeneities. In this article we describe our recent efforts to apply nuclear magnetic resonance spectroscopy to nanoscopically confined poly(styrene) (PS) created by intercalation into a surface-modified fluorohectorite. A comparison between surface-sensitive cross polarization experiments with spin–echo experiments which probe the entire organic layer suggests that PS in the center of the nanopores is more mobile than the bulk at comparable temperatures, while chain segments which interact with the surface are dynamically inhibited.