Tailored Morphology in Polystyrene/Poly(lactic acid) Blend Particles: Solvent's Effect on Controlled Janus/Core-Shell Structures.

Abstract

Controlling the morphology of polymeric particles is vital for their diverse applications. In this study, we explored how solvent composition influences the morphology of poly(styrene)/poly(lactic acid) (PS/PLA) particles prepared via the emulsion solvent evaporation method. We used toluene, dichloromethane (DCM), and various mixtures to prepare these particles. We investigated phase separation within the PS/PLA/solvent system using the Flory-Huggins ternary phase diagram and MesoDyn simulation, revealing pronounced immiscibility and phase separation in both PS/PLA/DCM and PS/PLA/toluene systems. We employed scanning electron microscopy (SEM) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) to characterize the resulting morphologies. Our study unveiled the substantial impact of solvent composition on particle structure. Using pure toluene resulted in acorn-shaped Janus particles. However, incorporating DCM into the solvent induced a transition from Janus to core-shell morphology. Remarkably, core-shell particles exhibited a single-core structure in a mixed toluene/DCM solvent, indicating thermodynamic stability. In contrast, pure DCM favored kinetically controlled multicore morphology, leading to lower PLA crystallinity due to increased PS-PLA interfaces. Samples with high Janus balance formed a self-assembled, two-dimensional (2-D) monolayer film, demonstrating the interfacial activity of the Janus particles. This 2-D monolayer film exhibits desirable emulsification properties with potential applications in various fields. Our study combines theoretical and experimental analyses, shedding light on the profound impact of solvent composition on the PS/PLA particle morphology. We observed transitions from Janus to core-shell structures, highlighted the influence of solvent viscosity on particle size, and uncovered the formation of self-assembled 2-D monolayer films. These insights are pivotal for tailoring polymeric particle structures. Furthermore, our findings advance macromolecular science in interface design, offering promising prospects for innovative materials development.