Non-exponential relaxation, fictive temperatures, and dispersive kinetics in the liquid-glass-liquid transition range of acetaminophen, sulfathiazole, and their mixtures
- Additional Document Info
- View All
To investigate the effects of added molecular heterogeneity on the hysteretic features of liquid-glass-liquid transition, we studied acetaminophen, sulfathiazole, and three of their mixtures by calorimetry, and determined the T(g) and the fictive temperature, T(f), from changes in the enthalpy and entropy on the cooling and heating paths, as well as the non-exponential parameter, β(cal). We find that, (i) T(f) for cooling is within 1-3 K of T(f) for heating and both are close to T(g), (ii) the closed loop entropy change in the liquid-glass-liquid range is negligibly small, (iii) T(g) and T(f) increase on increasing sulfathiazole in the mixture, (iv) β(cal) first slightly increases when the second component is added and then decreases, and (v) ageing causes deviations from a non-exponential, nonlinear behavior of the glass. In terms of fluctuations in a potential energy landscape, adding a solute heterogeneity would shift the state point to another part of the landscape with a different distribution of barrier heights and a different number of minima accessible to the state point. Part of the change in β(cal) is attributed to hydrogen-bond formation between the two components. Ageing changes the relaxation times distribution, more at short relaxation times than at long relaxation times, and multiplicity of relaxation modes implied by β(cal) < 1 indicates that each mode contributing to the enthalpy has its own T(g) or T(f). β(cal) differs from β(age) determined from isothermal ageing, and the distribution parameter of α-relaxation times would differ from both β(cal) and β(age).
has subject area