Broadband dielectric spectroscopy in the frequency range from 10-1 to 109 Hz in combination with specific heat spectroscopy are employed to revisit the segmental dynamics of the miscible blend system poly(vinyl methyl ether)/polystyrene (PVME/PS) in dependence on the composition firstly in the bulk state. Here especially the case of high polystyrene concentrations is considered. It is important to note that only the molecular dynamics of PVME segments as affected by PS is observed by dielectric spectroscopy because the dipole moment of polystyrene is negligible. Three relaxation processes are found which are due to fluctuations of differently constrained or confined PVME segments. The degree of the confinement of PVME segments due to PS is discussed in dependence on the composition. Further a nanometer spatial confinement is considered by investigating thin films of the PVME/PS blend where the film thickness was varied from 100 nm down to 5 nm. Two concentrations of PVME/PS (50/50 wt% and 25/75 wt%) are considered. To measure nanometer thick films by dielectric spectroscopy a novel electrode system based on nanostructured electrodes was employed. Nanostructured electrodes are a cut-edge technology in dielectric spectroscopy. The relaxation spectra of the films showed multiple processes like the dielectric spectra of the bulk. The dielectric data are compared in detail with that obtained by specific heat spectroscopy. Both set of results are discussed in dependence on film thickness where the mobile free surface and the at the substrate irreversible adsorbed layer are considered.

Investigations on miscible polymer blends in the bulk and in nanometer thin films: Comparison of the different confinement situations

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.