Dynamics of tetrahydrofuran as minority component in a mixture with poly(2-(dimethylamino)ethyl methacrylate): A neutron scattering and dielectric spectroscopy investigation.
We have investigated a mixture of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and tetrahydrofuran (THF) (70 wt. % PDMAEMA/30 wt. % THF) by combining dielectric spectroscopy and quasielastic neutron scattering (QENS) on a labelled sample, focusing on the dynamics of the THF molecules. Two independent processes have been identified. The "fast" one has been qualified as due to an internal motion of the THF ring leading to hydrogen displacements of about 3 Å with rather broadly distributed activation energies. The "slow" process is characterized by an Arrhenius-like temperature dependence of the characteristic time which persists over more than 9 orders of magnitude in time. The QENS results evidence the confined nature of this process, determining a size of about 8 Å for the volume within which THF hydrogens' motions are restricted. In a complementary way, we have also investigated the structural features of the sample. This study suggests that THF molecules are well dispersed among side-groups nano-domains in the polymer matrix, ruling out a significant presence of clusters of solvent. Such a good dispersion, together with a rich mobility of the local environment, would prevent cooperativity effects to develop for the structural relaxation of solvent molecules, frustrating thereby the emergence of Vogel-Fulcher-like behavior, at least in the whole temperature interval investigated.
Centro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizabal 5, 20018 San Sebastián, Spain.
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Goracci
Centro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizabal 5, 20018 San Sebastián, Spain.
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Arbe
Centro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizabal 5, 20018 San Sebastián, Spain.
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Alegría
Heinz Maier-Leibnitz Zentrum, Technische Universität München, Lichtenbergstraße 1, D-85748 Garching, Germany.
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Lohstroh
Jülich Centre for Neutron Science JCNS, Forschungszentrum Jülich GmbH, Outstation at MLZ, Lichtenbergstraße 1, 85747 Garching, Germany.
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Su
Centro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizabal 5, 20018 San Sebastián, Spain.
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Colmenero