## 3 Results and Discussion
### St-Co-DVB Polymerization in the Presence of Surface-Modified SNps
#### 3.3.1 Hybrid St-DVB Microsphere Preparation Using VBS Surface-Modified SNps  
As mentioned above, we believe that the reaction is initiated onto the SNps, followed by oligomer chains collapsing onto the SNps, which form hydrophobic patches, also called hemimicelles. By analogy to surfactants, patchy nanoparticles or polymer-grafted nanoparticles can self-assemble into anisotropic structures, depending on the grafting density and size, or chain length, of the polymer chains, relative to the nanoparticle size. [PERSON] et al. [59] showed that grafted polymer nanoparticles behave quantitatively like Janus nanoparticles, which can self-assemble into superstructures. The morphologies for self-assembly can be understood with a geometry-based model of surfactants proposed by [PERSON] [65]. In comparison, [PERSON] et al. [60] studied surface-patterning nanoparticles with polymer patches and mentioned that polymer chains uniformly grafted onto inorganic nanoparticles can break up into various hydrophobic patches upon solvent quality reduction. They showed that the patch formation and structure were controlled by the polymer length, nanoparticle diameter, and polymer-grafting density. In contrast, [PERSON] et al. [66] studied the degree of polymerization, bond length, and bond angles of plasmonic polymers. These polymers were prepared by self-assembly of end-tethered gold nano-rods with photoactive macromolecular chains by reducing the solvent quality of end-tethered chains. They photo-crosslinked the polymer chains that resulted in the suppression of the bond-forming ability of the poly(styrene-co-isoprene) chains, a reduction in the inter-nanorods' distance, and an increase in angles between adjacent nanorods. More specifically, the crosslinking effect suppressed the polymer growth and increased the rigidity of copolymer ligands, resulting in a size reduction of the hydrophobic patches at the end of the nano-rods. In addition, crosslinking decreased the effect of the tethered chains' interpenetration, and therefore, weaker hydrophobic interactions between the polymer networks at the nano-rod ends were observed. In all experiments, due to the low VBS concentration and DVB and St low water-solubility, it can be considered that at the early stage of the reactions, sparsely tethered SNps with St-co-DVB chains are formed [37]. As these chains gain length, the solvent quality decreases, causing agglomeration onto the SNp surface at the end, forming pinned micelles or hydrophobic patches. These hydrophobic zones confer the SNps an amphiphilic character. As microspheres are formed at 1 wt% DVB, it is inferred that the amphiphilic patchy SNps aggregate into copolymer-SNp clusters. Ergo, the St-co-DVB chains can interact and interpenetrate among SNps due to van der Waals interactions. Therefore, self-assembled-like surfactant micelles, exhibiting a polymer hydrophobic core surrounded by SNps, explain this mechanism. This aggregation process leads to the formation of copolymer primary particles, which will then further grow by monomer swelling. This nucleation mechanism differs from the one postulated by [PERSON] et al. [28] reporting a heterogenous nucleation coagulative process, where the inorganic nanoparticles are incorporated onto the polymer surface during the primary particles' formation, giving rise to the production of clay-armored latex particles. During the early reaction stage, the incorporation of clay platelets into the polymer matrix was promoted, by the silane functionalization of the clay particles, resulting in a change in the partition behavior within the Pickering emulsion. In contrast, the nucleation process originates from the in situ formation of tethered SNPs, which agglomerate, leading to precursor particles. The interactions between the SNPs and the polymer matrix are promoted by the bifunctional VBS monomer character, which allows pulling the SNPs from the aqueous phase onto the polymer nanoparticles.