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@ARTICLE{Goracci:827713,
      author       = {Goracci, G. and Arbe, A. and Alegría, A. and Su, Y. and
                      Gasser, U. and Colmenero, J.},
      title        = {{S}tructure and component dynamics in binary mixtures of
                      poly(2-(dimethylamino)ethyl methacrylate) with water and
                      tetrahydrofuran: {A} diffraction, calorimetric, and
                      dielectric spectroscopy study},
      journal      = {The journal of chemical physics},
      volume       = {144},
      number       = {15},
      issn         = {1089-7690},
      address      = {Melville, NY},
      publisher    = {American Institute of Physics},
      reportid     = {FZJ-2017-01821},
      pages        = {154903 -},
      year         = {2016},
      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
                      structural relaxation 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.},
      cin          = {JCNS (München) ; Jülich Centre for Neutron Science JCNS
                      (München) ; JCNS-FRM-II / JCNS-2},
      ddc          = {540},
      cid          = {I:(DE-Juel1)JCNS-FRM-II-20110218 /
                      I:(DE-Juel1)JCNS-2-20110106},
      pnm          = {6G15 - FRM II / MLZ (POF3-6G15) / 6G4 - Jülich Centre for
                      Neutron Research (JCNS) (POF3-623)},
      pid          = {G:(DE-HGF)POF3-6G15 / G:(DE-HGF)POF3-6G4},
      experiment   = {EXP:(DE-MLZ)DNS-20140101},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000375786000040},
      doi          = {10.1063/1.4946004},
      url          = {https://juser.fz-juelich.de/record/827713},
}