The properties of polymeric materials close to interfaces are different from the bulk. Much of this behavior stems from the fact that at interfaces the local structure, or “packing” of monomers, differs from the bulk, due to polymer-substrate interactions. Understanding the role of packing and of interfacial interactions will enable the design of polymer interfaces with controlled physical properties (wettability, adhesion, aging, viscosity, glass temperature and associated dynamics) suitable for applications (coatings, membranes, organic electronic devices). Herein we explore the effect of 2-D confinement on the segmental and chain dynamics of the type-A polymer cis-1,4-polyisoprene (PI). For low molecular weight unentangled PI the main effect of confinement was the broadening of both segmental and chain modes. Entangled chains on the other hand mitigate polymer/surface interactions further away from the interface. For the higher molecular weights the segmental dynamics of PI obtained on cooling consistently speed-up under confinement resulting to a lower glass temperature, Tg. This effect is discussed in view of the proposed relation of the glass temperature to the interfacial energy. Under confinement a new process is evidenced with an Arrhenius temperature dependence. This mode is attributed to the adsorption/desorption kinetics of segments in vicinity to the pore walls. Moreover, by employing several thermal protocols in temperature-modulated differential scanning calorimetry and dielectric spectroscopy we address the origin of the dual glass temperature, Tg, found on the heating traces. The results suggest that the lower Tg is closer to equilibrium under confinement. In addition, we report on the in situ monitoring of the imbibition process by nano-dielectric spectroscopy.

Polymers under 2D confinement: In situ monitoring of the imbibition of polymers in nanopores by nanodielectric spectroscopy

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.