화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.120, No.27, 6882-6889, 2016
Glass Transition and Dynamics of the Polymer and Water in the Poly(vinylpyrrolidone)-Water Mixtures Studied by Dielectric Relaxation Spectroscopy
In this study, broadband dielectric spectroscopy and differential scanning calorimetry (DSC) measurements are performed to study the dynamics of water and polymers in an aqueous solution of poly(vinylpyrrolidone) (PVP) with concentrations of 60, 65, and 70 wt % PVP in a temperature range of 123-298 K. Two distinct relaxation processes, l- and h-processes, which originate from the segmental chain motion of PVP and the primary relaxation process of water, respectively, are observed simultaneously. The relationship between l- and h-processes and their temperature dependences mimic those of the alpha-process and Johari-Goldstein beta-process, which are observed in ordinal glass formers. The relaxation time of the l-process, tau(l), obeys the Vogel-Fulcher (VF)-type temperature dependence, and the glass-transition temperature of the l-process, T-g,T-l, which is defined by the temperature that is reached in a tau(l) of 100-1000 s, shows good agreement with the calorimetric T-g obtained by DSC. The temperature dependence of the relaxation time of the h-process, tau(h), exhibits a crossover from VF to Arrhenius behavior at the so-called fragile-to-strong transition (FST) of water at T-g,T-l. The temperature dependence of the relaxation strength of the h-process, Delta epsilon(h), increases with a decrease in temperature from 298 K to T-g,T-l. Below T-g,T-l, Delta epsilon(h) is nearly constant or slightly decreases with decreasing temperature. According to previous studies on aqueous solutions of sugars and alcohols, the Delta epsilon of the nu-process, which originates from local motion of water, decreases with decreasing temperature above the T-g of the alpha-process, which originates from the cooperative motion of the solute and water. Therefore, the l-process in the PVP-water mixture is not a result of the cooperative motion of PVP and water but rather a result of the polymer-polymer cooperative motion of PVP. In addition, agreement among T-g,T-l, the temperature of the FST of water, and calorimetric T-g suggests that the FST of water occurs at T-g.