Dielectric and mechanical relaxation behavior in poly(butyl methacrylate) isomers

Dielectric and mechanical spectroscopies have been used to study the dynamics in poly(butyl methacrylate) isomers (namely PnBMA, PiBMA and PtBMA). This analysis has revealed four relaxation processes: δ, γ, β and α and has allowed the observation of the evolution of molecular relaxation phenomena with the lateral chain steric hindrance. The α relaxation is associated with the glass transition of the isomers and depends strongly on the lateral chain structure. The secondary relaxation phenomena are very similar for the three isomers. Arrhenius diagrams have been plotted for the three isomers. The activation parameters have been calculated from Arrhenius equation for the sub-glass processes δ and γ whereas the dynamics are characterized by a Vogel-Fulcher-Tamman law for the α relaxations. With a deconvolution procedure for the α and β processes, a departure from the Arrhenius law of the β process in the vicinity of the merging between the α and β phenomena is observed for each isomer.