Crystallization of Poly(l-lactic acid) on Water Surfaces via Controlled Solvent Evaporation and Langmuir-Blodgett Films.

Solvent evaporation is one of the most fundamental processes in soft matter. Structures formed via solvent evaporation are often complex yet tunable via the competition between solute diffusion and solvent evaporation time scales. This work concerns the polymer evaporative crystallization on the water surface (ECWS). The dynamic and two-dimensional (2D) nature of the water surface offers a unique way to control the crystallization pathway of polymeric materials. Using poly(l-lactic acid) (PLLA) as the model polymer, we demonstrate that both one-dimensional (1D) crystalline filaments and two-dimensional (2D) lamellae are formed via ECWS, in stark contrast to the 2D Langmuir-Blodgett monolayer systems as well as polymer solution crystallization. Results show that this filament-lamella biphasic structure is tunable via chemical structures such as molecular weight and processing conditions such as temperature and evaporation rate.