Phase separation, antiplasticization and moisture sorption in ternary systems containing polysaccharides and polyols

In this paper, we investigate whether the Flory-Huggins-Free-Volume (FHFV) theory can describe the rich thermodynamics of the ternary mixtures of starch, polyol, and water. These systems exhibit 1) non-monotonic moisture sorption with increasing plasticizer concentration, 2) phase separation, and 3) antiplasticization. After extending the FHFV theory with 1) the proper formulation of the chemical potential of water and polyol, and 2) the proper composition dependency of the interaction parameter between starch and water, the theory is well able to describe the above described complex thermodynamic behavior, showing good agreement with experimental data. Furthermore, our analysis shows that phase separation can already occur when the ternary mixture is still in the glassy state. Overall, the phase separation happens after the antiplasticization/plasticization transition, which can be linked to the minimum in moisture sorption, when increasing the polyol concentration at equal water activity. We think that the extended theory will become an important tool for analysis and design of complex food materials, pharmaceutical systems, and biopolymeric films having carbohydrates as plasticizers.