In this work, the influence of polyvinyl acetate (PVAc) and conductive polyaniline (PAni) composite formation on its conduction mechanism was investigated. To achieve this goal, different concentrations of PAni were prepared in PVAc miniemulsions. Dynamic relaxation and conductivity were assessed using broadband dielectric spectroscopy techniques. The relaxation rate for acetate charge the local reorientation (β-process) of the ester group follows an Arrhenius relationship with an activation energy of 39 kJ/mol. The coupling of segmental dynamics (α process) and terminal fluctuations (β' process) occurs above the calorimetric glass transition temperature Tg of pure PVAc. This is reasonable because below Tg the alpha processes resulting from structural rearrangements become very slow, leading the polymer towards an equilibrium state. If one considers ion motion at T  Tg, there is also a decoupling of carrier transport and segmental motion, a concept summarized in this manuscript that sounds reasonable. This conclusion is directly deduced from the experimental data, as explained in more detail. The study also confirmed that the conduction mechanism of PAni is conserved.
The decoupling of mass and charge transport at the microscopic scale in polymer and polymer composite systems is a challenge to be clarified and understood. This phenomenon manifests itself as a transition from the Vogel-Fulcher-Tammann (VFT) thermally activated behavior of DC conductivity at high temperatures (Tc  Tg, where Tg is the glass transition temperature) to the Arrhenius behavior at lower temperatures , in many polymer systems according to Kremer et al. , this phenomenon is attributed to the gigantic demodulation of the so-called backbone and attached ionic groups. However, free charge carriers (counter ions) are still transported through the polymer, resulting in a direct current conductivity σdc. In other words, at this characteristic temperature Tc, there is a decoupling between the α-process originating from the dynamics of the glassy state and the charge carrier transport as a contribution to the dc conductivity.