title: Structure and component dynamics in binary mixtures of poly(2-(dimethylamino)ethyl methacrylate) with water and tetrahydrofuran: A diffraction, calorimetric, and dielectric spectroscopy study.
abstract: We have combined X-ray diffraction, neutron diffraction with polarization analysis, small angle neutron scattering,differential scanning calorimetry, and broad band dielectric spectroscopy to investigate the structure and dynamics of binary mixtures of poly(2-(dimethylamino)ethyl methacrylate) with either water or tetrahydrofuran (THF) at different concentrations. Aqueous mixtures are characterized by a highly heterogeneous structure where water clusters coexist with an underlying nano-segregation of main chains and side groups of the polymeric matrix. THF molecules are homogeneously distributed among the polymeric nano-domains for concentrations of one THF molecule/monomer or lower. A more heterogeneous situation is found for higher THF amounts, but without evidences for solvent clusters. In THF-mixtures, we observe a remarkable reduction of the glass-transition temperature which is enhanced with increasing amount of solvent but seems to reach saturation at high THF concentrations. Adding THF markedly reduces the activation energy of the polymer β-relaxation. The presence of THF molecules seemingly hinders a slow component of this process which is active in the dry state. The aqueous mixtures present a strikingly broad glass-transition feature, revealing a highly heterogeneous behavior in agreement with the structural study. Regarding the solvent dynamics, deep in the glassy state all data can be described by an Arrhenius temperature dependence with a rather similar activation energy. However, the values of the characteristic times are about three orders of magnitude smaller for THF than for water. Water dynamics display a crossover toward increasingly higher apparent activation energies in the region of the onset of the glass transition, supporting its interpretation as a consequence of the freezing of the structuralrelaxation of the surrounding matrix. The absence of such a crossover (at least in the wide dynamic window here accessed) in THF is attributed to the lack of cooperativity effects in the relaxation of these molecules within the polymeric matrix.
authors.affiliation: Centro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizabal 5, 20018 San Sebastián, Spain.
authors.forename: G
authors.initials: G
authors.lastname: Goracci
authors.affiliation: Centro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizabal 5, 20018 San Sebastián, Spain.
authors.forename: A
authors.initials: A
authors.lastname: Arbe
authors.affiliation: Centro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizabal 5, 20018 San Sebastián, Spain.
authors.forename: A
authors.initials: A
authors.lastname: Alegría
authors.affiliation: Jülich Centre for Neutron Science JCNS, Forschungszentrum Jülich GmbH, Outstation at MLZ, Lichtenbergstraße 1, 85747 Garching, Germany.
authors.forename: Y
authors.initials: Y
authors.lastname: Su
authors.affiliation: Laboratory for Neutron Scattering, Paul Scherrer Institut, CH-5232 Villigen, Switzerland.
authors.forename: U
authors.initials: U
authors.lastname: Gasser
authors.affiliation: Centro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizabal 5, 20018 San Sebastián, Spain.
authors.forename: J
authors.initials: J
authors.lastname: Colmenero