Effect of Interphase Properties on Isothermal and Non-isothermal Crystallization Behavior of Poly(lactic acid)/Acetylated Starch Blends

The effect of interphase properties on the crystallization behavior of blends of poly(lactic acid) (PLA)/acetylated starch (AS) with different degrees of substitution (DSs) was investigated. Under isothermal crystallization conditions, the rate of crystallization was higher for PLA/DS0.5 and lower for PLA/DS1.5 and PLA/DS2.5 when compared to PLA. In contrast, non-isothermal crystallization behavior indicated a slower rate of crystallization of PLA/DS0.5 and a faster rate of crystallization of PLA/DS1.5 and PLA/DS2.5 compared to PLA at the highest cooling rate (5 °C/min). The potential relationship between crystallization behavior and interphase properties and interphase thickness and formation of rigid amorphous fraction in the interphase, was investigated. The formation of a rigid amorphous fraction in PLA/DS1.5 and a thick interphase in PLA/DS2.5 prevented the formation of crystals on the dispersed phase and interrupted the crystallization under isothermal conditions. Hydrogen bonding in the PLA/DS1.5 blend and hydrophobic interactions in the PLA/DS2.5 blend may facilitate the crystallization at high cooling rates under non-isothermal conditions. Small-angle X-ray scattering analysis revealed the presence of a smaller lamellar structure in PLA/AS blends. The largest amorphous phase among blends was observed for the PLA/DS1.5 blend, which can be attributed to the hydrogen bonding in the interphase region of this blend. © 2022 American Chemical Society. All rights reserved.