Self-Assembly of Polymer Blends and Nanoparticles through Rapid Solvent Exchange

Molecular dynamics simulations were performed to study the fabrication of polymeric colloids containing inorganic nanoparticles (NPs) via the flash nanoprecipitation (FNP) technique. During this process, a binary polymer blend, initially in a good solvent for the polymers, is rapidly mixed with NPs and a poor solvent for the polymers that is miscible with the good solvent. The simulations reveal that the polymers formed Janus particles with NPs distributed either on the surface of the aggregates, throughout their interior, or aligned at the interface between the two polymer domains, depending on the NP-polymer and NP-solvent interactions. The loading and surface density of NPs can be controlled by the polymer feed concentration, the NP feed concentration, and their ratio in the feed streams. Selective localization of NPs by incorporating electrostatic interactions between polymers and NPs has also been investigated, and was shown to be an effective way to enhance NP loading and surface density as compared to the case with only van der Waals attractions. This work demonstrates that the FNP process is promising for the production of structured and hybrid nanocolloids in a continuous and scalable way, with independent control over particle properties such as size, NP location, loading, and surface density. Our results provide useful guidelines for experimental fabrication of such hybrid nanoparticles.