Gelatinization and retrogradation phenomena in starch/montmorillonite nanocomposites plasticized with different glycerol/water ratios

• Glycerol/water ratio alters TPS/MMT gelatinization, retrogradation and morphology.
• MMT preferentially interact with glycerol molecules rather than starch macromolecules.
• For glycerol-only MMT addition increase starch gelatinization temperature over 100 °C.
• For glycerol-only amylose leaching occurs simultaneously with amylopectin melting.

This study aims to gain insights into the intermolecular interactions present in thermoplastic starch (TPS)/montmorillonite (MMT) nanocomposites prepared using water and/or glycerol as plasticizers. Specifically, the impact of using different glycerol/water proportions on the nature of gelatinization and retrogradation processes is studied. Nanocomposites were characterized by rheometry, scanning electron microscopy (SEM) and X-rays diffraction (XRD). It is shown that clay tactoids preferentially interact with glycerol molecules rather than starch macromolecules. Consequently, the effects of MMT incorporation strongly depend on the glycerol/water ratio; when a ratio of 0.5 is used minor variations were observed on the starch gelatinization process—although stronger clays–starch interactions were evident—whereas at higher ratios the addition of clays significantly increased the gelatinization temperature, up to values over 100 °C. In the gelatinization process of starch in TPS samples having only glycerol as a plasticizer, the leaching of amylose and the melting of amylopectin crystalline domains seem to occur simultaneously. This different gelatinization mechanism produces a TPS having a substantially different morphology, which exhibited reduced retrogradation characteristics.