On the cooperative nature of the β-process in neat and binary glasses: A dielectric and nuclear magnetic resonance spectroscopy study

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By means of dielectric as well as 2H and 31P nuclear magnetic resonance spectroscopy (NMR) the component dynamics of the binary glass tripropyl phosphate (TPP)/polystyrene (PS/PS-d3) is selectively investigated for concentrations distributed over the full range. We study the secondary (β-) relaxation below Tg, which is found in all investigated samples containing TPP, but not in neat polystyrene. The dielectric spectrum of the β-process is described by an asymmetric distribution of activation energies, essentially not changing in the entire concentration regime; its most probable value is E/k ≅ 24 Tg. Persistence of the β-process is confirmed by 31P NMR Hahn-echo and spinlattice relaxation experiments on TPP, which identify the nature of the β-process as being highly spatially hindered as found for other (neat) glasses studied previously, or re-investigated within this work. The corresponding 2H NMR experiments on PS-d3 confirm the absence of a β-process in neat PS-d3, but reveal a clear signature of a β-process in the mixture, i.e., polystyrene monomers perform essentially the same type of secondary relaxation as the TPP molecules. Yet, there are indications that some fractions of PS-d3 as well as TPP molecules become immobilized in the mixture in contrast to the case of neat glasses. We conclude that in a binary glass the β-process introduced by one component induces a highly similar motion in the second component, and this may be taken as an indication of its cooperative nature. © 2013 AIP Publishing LLC.

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Journal of Chemical Physics

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