Nanoparticle–polymer hybrids are becoming increasingly important because seemingly contrasting properties, such as mechanical stability and high elasticity, can be combined into one material. In particular, hybrids made of self-assembled polymers are of growing interest since they exhibit high structural precision and diversity and the subsequent reorganization of the nanoparticles is possible. In this work, we show, for the first time, how hybrids of silica nanoparticles and self-assembled vesicles of polystyrene-block-polyacrylic acid can be prepared using the simple and inexpensive method of co-precipitation, highlighting in particular the challenges of using silica instead of other previously well-researched materials, such as gold. The aim was to investigate the influence of the type of modification and the particle size of the silica nanoparticles on the encapsulation and structure of the polymer vesicles. For this purpose, we first needed to adjust the surface properties of the nanoparticles, which we achieved with a two-step modification procedure using APTES and carboxylic acids of different chain lengths. We found that silica nanoparticles modified only with APTES could be successfully encapsulated, while those modified with APTES and decanoic acid resulted in vesicle agglomeration and poor encapsulation due to their strong hydrophobicity. In contrast, no negative effects were observed when different particle sizes (20 nm and 45 nm) were examined.

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.