Viscous Liquids and the Glass Transition. II. Secondary Relaxations in Glasses of Rigid Molecules

The dielectric loss factor and dielectric permittivity of 8–16 mol% solutions of chlorobenzene, o‐dichlorobenzene, and 1‐chloronaphthalene in cis‐decalin; 50–60 mol% mixtures of pyridine with chlorobenzene, bromobenzene, 1‐chloronaphthalene, and toluene; 50–60 mol% mixtures of tetrahydrofuran with bromobenzene and 1‐chloronaphthalene; the pure liquids cis‐decalin, o‐terphenyl, iso‐propylbenzene, propylene carbonate; and two fused salt systems, 45 mol% Ca(NO₃)₂–KNO₃ mixture and Ca(NO₃)₂·4H₂O have been measured from 50 Hz to 1 × 10⁵ Hz from − 196° in the vitreous state to about 30° above their respective glass transition temperatures. The $Tg's$ of the organic glasses have been measured by DTA. With the exception of propylene carbonate, all glasses show the presence of one secondary relaxation between − 196° and their respective $Tg's$ either as a peak or shoulder in a tanδ–temperature plot at a single frequency, or in the dielectric loss spectrum. Arrhenius plots of the frequency of maximum loss against temperature in the main relaxation region for all systems are nonlinear, with the activation energy at the lowest temperature of our measurements ranging from 55 kcal/mol to 70 kcal/mol. The Arrhenius plots in the secondary relaxation region are linear and have activation energies between 5 and 12 kcal/mol. These glasses, most of which are composed of rigid molecules, show a remarkable similarity in their dielectric behavior to amorphous polymers. The results confirm the prediction made by one of the authors that the occurence of secondary relaxations is an intrinsic property of the glassy state.