Influence of Process Parameters on the Kinetics of the Micelle-to-Vesicle Transition and Ripening of Polystyrene-Block-Polyacrylic Acid.

Due to their ability to self-assemble into complex structures, block copolymers are of great interest for use in a wide range of future applications, such as self-healing materials. Therefore, it is important to understand the mechanisms of their structure formation. In particular, the process engineering of the formation and transition of the polymer structures is required for ensuring reproducibility and scalability, but this has received little attention in the literature. In this article, the influence of the addition rate of the selective solvent on the homogeneity of self-assembled vesicles of polystyrene-block-polyacrylic acid is demonstrated, as well as the influence of the reaction time and the mixing intensity on the morphology of the polymer structures. For example, it was demonstrated that the higher the mixing intensity, the faster the transition from micelle to vesicle. The experimental results are further supported by CFD simulations, which visually and graphically show an increase in shear rate and narrower shear rate distributions at higher stirring rates. Furthermore, it was demonstrated that the vesicle size is not only kinetically determined, since flow forces above a critical size lead to the deformation and fission of the vesicles.