Systematic Investigation on the Glass Transition Temperature of Binary and Ternary Sugar Mixtures and the Applicability of Gordon–Taylor and Couchman–Karasz Equation

Glass transition temperatures (T_g ) of carbohydrate mixtures consisting of only one monomer and glycosidic binding type (aldohexose glucose, α1-4-glycosidic bonded) were studied by differential scanning calorimetry (DSC). The aim of this work was to systematically assess the predictability of T_g of anhydrous binary and ternary sugar mixtures focusing on the components T_g, molecular chain length, and shape. Binary systems were investigated with glucose as a monosaccharide and its linear di-, tri-, tetra-, penta-, hexa-, and heptasaccharides. Additionally, the T_g of ternary carbohydrate systems prepared with different glucose/maltose/maltotriose mass fractions were studied to evaluate the behavior of more complex mixtures. An experimental method to prepare fully amorphized, anhydrous mixtures were developed which allows the analysis of mixtures with strongly different thermodynamic pure-component properties (T_g, melting temperature, and degradation). The mixtures’ T_g is systematically underestimated by means of the Couchman–Karasz model. A systematic, sigmoidal deviation behavior from the Gordon–Taylor model could be found, which we concluded is specific for the investigated glucopolymer mixtures. At low concentrations of small molecules, the model underestimates T_g, meeting the experimental values at about equimolarity, and overestimates T_g at higher concentrations. These deviations become more pronounced with increasing T_g differences and were explained by a polymer mixture-specific, nonlinear plasticizing/thermal volume expansion effect.