Physically crosslinked poly (vinyl alcohol) (PVA) hydrogels obtained by the repeated freezing/thawing (F/T) technique have been investigated by termomechanical analysis and dielectric relaxation spectroscopy (DRS). The crosslinked polymer was produced by the clustering of chains caused by the association of a polar group of the dissolved polymer followed by polymer crystallization. The dielectric spectra obtained from -50 C to 200 C shows two relaxation processes associated to local mobility and conductivity. These processes are strongly affected by the freezing/thawing cycles. Parameters associated to activation energy and dielectric relaxation strength were crosslinked dependent, fig. 1. Dielectric and modulus formalism was used to analysis the behavior of samples, according to the result, Cole-Cole approach is the best fitted to the experimental points of 8C and 12C samples, and Havriliak-Negami approach is best fitting to the experimental point of the WC, 4C and 6C samples.
