Recent measurements have suggested that the antiplasticizing effect of glycerol on trehalose can significantly increase the preservation times of proteins stored in this type of preservative formulation. In order to better understand the physical origin of this phenomenon, we examine the nature of antiplasticization in trehalose-glycerol mixtures by dielectric spectroscopy. These measurements cover a broad frequency range between $40\mathrm{Hz}\text{to}18\mathrm{GHz}$ (covering the secondary relaxation range of the fragile glass-former trehalose and the primary relaxation range of the strong glass-former glycerol) and a temperature $\left(T\right)$ range bracketing room temperature $\left(220\mathrm{K}\text{to}350\mathrm{K}\right)$. The Havriliak-Negami function precisely fits our relaxation data and allows us to determine the temperature and composition dependence of the relaxation time $\tau$ describing a relative fast dielectric relaxation process appropriate to the characterization of antiplasticization. We observe that increasing the glycerol concentration at fixed $T$ increases $\tau$ (i.e., the extent of antiplasticization) until a temperature dependent critical “plasticization concentration” $x_{wp}$ is reached. At a fixed concentration, we find a temperature at which antiplasticization first occurs upon cooling and we designate this as the “antiplasticization temperature,” $T_{\mathit{ant}}$. The ratio of the $\tau$ values for the mixture and pure trehalose is found to provide a useful measure of the extent of antiplasticization, and we explore other potential measures of antiplasticization relating to the dielectric strength.

• Received 27 January 2006

DOI:https://doi.org/10.1103/PhysRevE.74.031501