Dielectric secondary relaxations in polypropylene glycols

Broadband dielectric measurements of polypropylene glycol of molecular weight M w = 400 g ∕ mol (PPG 400) were carried out at ambient pressure over the wide temperature range from 123 to 353 K . Three relaxation processes were observed. Besides the structural α relaxation, two secondary relaxations, β and γ , were found. The β process was identified as the true Johari-Goldstein relaxation by using a criterion based on the coupling model prediction. The faster γ relaxation, well separated from the primary process, undoubtedly exhibits the anomalous behavior near the glass transition temperature ( T g ) which is reflected in the presence of a minimum of the temperature dependence of the γ -relaxation time. We successfully applied the minimal model [ Dyre and Olsen , Phys. Rev. Lett. 91 , 155703 ( 2003 ) ] to describe the entire temperature dependence of the γ -relaxation time. The asymmetric double-well potential parameters obtained by Dyre and Olsen for the secondary relaxation of tripropylene glycol at ambient pressure were modified by fitting to the minimal model at lower temperatures. Moreover, we showed that the effect of the molecular weight of polypropylene glycol on the minimal model parameters is significantly larger than that of the high pressure. Such results can be explained by the smaller degree of hydrogen bonds formed by longer chain molecules of PPG at ambient pressure than that created by shorter chains of PPG at high pressure.