Alkali treatment is used for melt extrusion film formation with corn starch, but optimal conditions for this procedure are still unknown. In this study, the changes in properties and structure of high amylose corn starch (70%) films with different concentrations of sodium hydroxide (NaOH), prepared by melting extrusion, were investigated. With increasing sodium hydroxide concentrations, the tensile strength of the high-amylose starch film decreased gradually, while the elongation at break increased. The tensile strength of the high amylose starch (HAS) film with 2% NaOH-treatment was 10.03 MPa and its elongation at break was 40%. A 2% NaOH-treatment promoted the orderly rearrangement of starch molecules and formed an Eh
-type crystal structure, which enlarged the spacing of the single helix structure, increased the molecular mobility of the starch, and slowed down the process of recrystallization; a 10% NaOH-treatment oxidized the hydroxyl groups of the high amylose corn starch during extrusion, formed a poly-carbonyl structure, and initiated the degradation and cross-linking of starch molecule chains.
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