Multi-scale characterization of thermoplastic starch structure using Second Harmonic Generation imaging and NMR

•SHG imaging can be used to differentiate crystalline spatial organization in TPS.•Combining SHG and NMR sheds new light on extrusion-induced modifications of starch.•The maximum swelling rate makes it possible to discriminate the microstructure of TPS.•Native starch granular structure in TPS does not necessarily impair functionality. Starch granules can be extruded to obtain a thermoplastic material. Thermoplastic starch (TPS) usually requires a significant break down of the starch granular organization to form a continuous polysaccharide matrix. In this work, we extrude potato starch with and without a plasticizer and store samples at high humidity to generate recrystallization. A multi-scale investigation of the microstructure is performed by combining different techniques: WAXS and solid-state NMR to describe macromolecule organization and Second Harmonic Generation (SHG) imaging to provide spatial information. Finally, the ability of the material to swell and remain sound in water is assessed. Glycerol-plasticized samples swell the least despite many granules with native-like structure embedded in the starch matrix. Glycerol limits the fragmentation and melting of the granules and crystallites during extrusion but also reduces the proportion of starch molecules in constrained conformations, enabling the formation of a polymer network that can sustain the penetration of water.