Nonsolvent-induced morphological changes and nanoporosity in poly(l-lactide) films.

The role of a nonsolvent in controlling the crystallization and morphology of solvent-crystallized poly(l-lactide) (PLLA) films was investigated using various microscopy techniques and small- and wide-angle X-ray scattering (SAXS/WAXS). PLLA films crystallized in THF and acetone had 40-80 μm spherulites. When water was present in the solvent, a completely different morphology was observed with nanosized voids and the surfaces of the films were smooth. In contrast, SEM studies revealed that the films crystallized in acetone and THF which had macroporous structures, had larger voids and film surfaces were rough because of the presence of globular structures. Voids appeared within the spherulites in the THF/water treated film, whereas crystals nucleated at the surface of the nanosized voids in acetone/water treated PLLA films. The formation of such voids is attributed to the interface-enhanced crystal nucleation in a solvent/nonsolvent system where the nonsolvent increases the polymer crystal nucleation and the subsequent evaporation of the nonsolvent. The method described in this work can be extended to other polymers to control the morphologies of polymer films during solvent-induced crystallization.