Abstract 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.

中文翻译：

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含多糖和多元醇的三元体系中的相分离、抗塑化和吸湿

摘要 在本文中，我们研究了 Flory-Huggins-Free-Volume (FHFV) 理论是否可以描述淀粉、多元醇和水三元混合物的丰富热力学。这些系统表现出 1) 随着增塑剂浓度增加的非单调吸湿，2) 相分离，和 3) 抗增塑作用。在将 FHFV 理论扩展为 1) 水和多元醇的化学势的适当公式，以及 2) 淀粉和水之间相互作用参数的适当组成依赖性之后，该理论能够很好地描述上述复杂的热力学行为，与实验数据显示出良好的一致性。此外，我们的分析表明，当三元混合物仍处于玻璃态时，相分离已经发生。全面的，相分离发生在抗塑化/塑化转变之后，这可能与水分吸附的最小值有关，当在相同的水分活度下增加多元醇浓度时。我们认为扩展理论将成为分析和设计复杂食品材料、药物系统和以碳水化合物为增塑剂的生物聚合物薄膜的重要工具。