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On the dielectric glass relaxation process of polymers: Ball-like labels in polystyrene

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Ball-like molecules with strong dipoles (labels) were mixed with technical polystyrene (PS168N) in low concentrations (<0.5% wt) and measured dielectrically in the frequency range 10−2–107 Hz, and the temperature range 100°–135°C (glass relaxation region). The measurements showed that these ball-like molecules relax cooperatively with the polymeric segments with relaxation times lying at the high-frequency tail of the glass process. The activation energy of the main label process is found to be very similar to that of the glass process of the polystyrene segments and also has the same temperature dependence. This finding implies the existence of an additional mode of relaxation in the dielectric spectrum of the glass process of polystyrene (compared to polyisoprene). Considering the different behavior of the ball-like molecules in polystyrene and polyisoprene and the temperature dependence of the half-width of dielectric loss peak in different polymers, we suggest that the polymers could be classified into three classes according to the available dielectric relaxation modes in the glass process. In addition, the label molecules showed a high-frequency local relaxation process. The relaxation strength ratio of the local process (X local) to the total relaxation strength of the label was found to be dependent on the volume of the label. This phenomenon could supply a new method for the determination of the mean size of the holes (voids) representing the free volume of the host matrix.

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Mansour, A.A., Stoll, B. On the dielectric glass relaxation process of polymers: Ball-like labels in polystyrene. Colloid Polym Sci 272, 25–35 (1994). https://doi.org/10.1007/BF00653307

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Key words

  • Dielectric relaxation
  • label
  • polystyrene
  • ball-like molecules
  • glass process
  • voids