Microstructure and melting behavior of a solution‐cast polylactide stereocomplex: Effect of annealing

The effect of annealing on the microstructure and melting behavior of a solution‐cast polylactide (PLA) stereocomplex (sc) was systematically investigated by differential scanning calorimetry and small‐angle X‐ray scattering. A preorder state, an intermediate form between the amorphous and crystalline states, was found in the solution‐cast poly( l ‐lactide)–poly( d ‐lactide) blend. When the annealing temperature ( T a ) was below 220 °C, a part of the preorder state directly formed thicker sc crystallites; these corresponded to the second melting peak, which appeared around 250 °C during the heating process. Although the rest melted and became the amorphous phase, it formed a thinner lamella under the restriction of the unmelted initial sc crystallites during annealing; the melting process of this lamella was parallel to that of the new melting peak, which appeared around 220 °C. The melting of the initial crystal formed as the solvent volatilized corresponded to the range of the first melting temperature around 230 °C. When T a was above 220 °C, the preorder state melted completely, and the initial crystal experienced perfection process. Furthermore, the highest melting temperature of PLA sc (254.1 °C, with a fusion enthalpy of 125.5 J/g) was obtained when T a was 235 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44626.