Discontinuous and heterogeneous glass transition behavior of carbohydrate polymer–plasticizer systems

In order to understand the glass transition properties of carbohydrate polymer–plasticizer systems, glass transition temperatures of dextrin–glucose and dextrin–maltose systems were investigated systematically using differential scanning calorimetry. The onset (Tgon) and offset (Tgoff) of the glass transition decreased with increasing plasticizer (glucose or maltose) content, and showed an abrupt depression at certain plasticizer content. The abrupt depression of Tgoff occurred at higher plasticizer content than that of Tgon. The glass transition was much broader for intermediate plasticizer content. From the enthalpy relaxation behavior of samples aged at various temperatures, it was found that two different glass transitions occurred contentiously in the broad glass transition. These results suggested that carbohydrate polymer–plasticizer systems can be classified into three regions: the entrapment of the plasticizer by the polymer, the formations of the polymer–plasticizer and plasticizer-rich domains, and the embedment of polymer into the plasticizer.