Journal of Physical Chemistry, Vol.100, No.20, 8508-8517, 1996
Dielectric-Relaxation in Monohydroxy Alcohols and Its Connection to the Glass-Transition Process
The nature of dielectric relaxation is studied in a number of supercooled monohydroxy alcohols in the frequency range (10(6)-10(-3) Hz) at temperatures above 77 K. Differential scanning calorimeter (DSC) measurements are also carried out on all the alcohols above 100 K. The temperature dependence of the relaxation rates and the spectral characteristic of the main relaxation process are critically examined both above and near the glass transition temperature T-g. The measurements clearly indicate that the relaxation rates in the high-viscosity regime are non-Arrhenius down to T-g in all the samples and also in most of the cases the dielectric relaxation rate is found to approach the structural relaxation rate in the vicinity of T-g. In the monohydroxy alcohols where the -OH group is easily accessible for hydrogen bonding, the spectral character is nearly Debye down to T-g. In alcohols, where the -OH group is relatively inaccessible for hydrogen bonding, the spectral half-width is significantly higher than that of Debye behavior and this group of liquids is found to be more fragile than the former group of alcohols. Use of scaling law fits (Dixon et al., 1990) indicates that the spectral data over the entire frequency range is perhaps governed by one single mechanism which cannot be described by any of the conventional equations and, hence, the often observed high-frequency deviation of the data from the conventional equations cannot be taken as evidence for one or more processes operative on the higher frequency side. It is also noticed that the monohydroxy systems studied here do not follow the general pattern when the fragility is plotted against the stretching exponential parameter beta(WW). An attempt has been made to explain this as due to the "decoupling" of dielectric modes in terms of the model suggested by Hassion and Cole (1955). The origin of sub-T-g processes is also briefly discussed.
Keywords:SECONDARY RELAXATIONS;LIQUIDS