Comparison between thermal sampling and numerical analysis of thermally stimulated depolarization current peaks

Thermal sampling peaks recorded after windowing polarization are studied for the segmental mode in poly(ε-caprolactone). Also, numerical decompositions of the global thermally stimulated depolarization current peak into pure Debye contributions are performed with direct signal analysis (DSA) and simulated annealing direct signal analysis procedures for Arrhenius and Vogel–Tammann–Fulcher (VTF) temperature dependences, respectively. It is found that the results between the experimental and the numerical procedures agree very well and the approximations made in the analysis of the experimental curves are thus validated, despite the unphysical values for the relaxation parameters found by both methods when using Arrhenius relaxation times. On the contrary, when VTF relaxation times are used for the numerical decomposition, agreement is found with the results of isothermal dielectric absorption as a function of frequency, together with reasonable values for reorientation energies, pre-exponential factors and VTF temperature. Thermal sampling and DSA also compare well when studying the departure from the zero-entropy line which indicates the onset of a cooperative character in the dynamics of molecular motion. Compensation is found whenever the primary relaxation is analyzed with Arrhenius or Eyring relaxation times and does not appear when VTF relaxation times are used in the numerical decomposition.