Observation of the nearly constant loss in super rigid saccharides: in search of a hidden crossover in dynamics deep in the glassy state

Abstract

The molecular dynamics of three saccharides: D-glucose, 1,6-anhydro-D-glucose (levoglucosan) and 1,6:2,3-dianhydro-β-D-mannopyranose of various degrees of freedom, number of hydroxyl groups and internal structures was investigated over a wide range of temperatures and frequencies by means of Broadband Dielectric Spectroscopy (BDS). Despite the pronounced variety in the physicochemical properties of the carbohydrates, no change in the shape of the structural relaxation process was observed in the vicinity of the glass transition temperature (β_KWW = 0.5). On the other hand further studies of the Debye–Stokes–Einstein relationship between dc conductivity and structural dynamics revealed some significant changes connected with the ability to form strong H-bonded structures. Moreover the presence of nearly constant loss (NCL) at moderate frequencies and just below the T_g in the glassy state of levoglucosan and 1,6:2,3-dianhydro-β-D-mannopyranose was noticeable. We followed the temperature evolution of ε′′ located at frequencies f = 0.1 kHz and f = 1 kHz, where the NCL is detected. Interestingly, a clear change in the dynamics far below the glass transition was observed in both compounds. This crossover (T_c), found in different materials, and studied by various experimental techniques, is usually interpreted as being caused by the freezing of the Johari–Goldstein (JG) relaxation process. Alternatively it can also be due to the increasing anharmonicity in the density of vibrational states. Interestingly, it was shown that the slope of ε′′(T) measured above the T_c slightly changes while below the T_c stays constant after physical aging. This is related to the densification of the sample that might result in steric hindrance and suppression of some kind of motion occurring in the glassy state, involving the larger parts of the molecules.