Glycerol is a well-known plasticizer for starch-based materials, but it easily migrates during starch retrogradation, thereby deteriorating the films' properties. We hypothesized that the performance of high-content starch/poly(butylene adipate-co-terephthalate) (PBAT) films could be enhanced by using sugar/sugar alcohol (glucose, sucrose and sorbitol) as natural, green and edible co-plasticizers with glycerol. The employment of co-plasticizers reduced the melt fluidity of the blends, established intermolecular hydrogen bonds with starch and resulted in a brittle film structure. The presence of sucrose contributed to the formation of more B-type starch crystals. Glucose and sucrose promoted the conversion of bound water to entrapped water, while sorbitol contributed to more bound water. The co-plasticizers enhanced films' thermal stability, moisture permeability (from 3.61 to 3.72 × 10-11 g m m-2 s-1 Pa-1), and oxygen barrier (from 12.84 to 8.74 × 10-13 cm3 cm cm-2 s-1 Pa-1). Glucose/glycerol co-plasticized film had the maximum tensile strength (10.12 MPa), and sucrose/glycerol co-plasticized film showed the highest Young's modulus (380.31 MPa). Sorbitol with linear structure and the lowest melting point exhibited a plasticizing capacity similar to glycerol. The molecular structure (linear or cyclic), hydroxyl group proportion and melting point of the sugar/sugar alcohol were the key factors to regulate the fine structure and properties of starch/PBAT films. © 2024 Society of Chemical Industry.
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