Interfacial Assembly of Tunable Anisotropic Nanoparticle Architectures.
We propose a strategy for assembling spherical nanoparticles (NPs) into anisotropic architectures in a polymer matrix. The approach takes advantage of the interfacial tension between two mutually immiscible polymers forming a bilayer and differences in the compatibility of the two polymer layers with polymer grafts on particles to trap NPs within two-dimensional planes parallel to the interface. The ability to precisely tune the location of the entrapment planes via the NP grafting density, and to trap multiple interacting particles within distinct planes, can then be used to assemble NPs into unconventional arrangements near the interface. We carry out molecular dynamics simulations of polymer-grafted NPs in a polymer bilayer to demonstrate the viability of the proposed approach in both trapping NPs at tunable distances from the interface and assembling them into a variety of unusual nanostructures. We illustrate the assembly of NP clusters, such as dimers with tunable tilt relative to the interface and trimers with tunable bending angle, as well as anisotropic macroscopic phases, including serpentine and branched structures, ridged hexagonal monolayers, and square-ordered bilayers. We also develop a theoretical model to predict the preferred positions and free energies of NPs trapped at or near the interface that could help guide the design of polymer-grafted NPs for achieving target NP architectures. Overall, this work suggests that interfacial assembly of NPs could be a promising approach for fabricating next-generation polymer nanocomposites with potential applications in plasmonics, electronics, optics, and catalysis where precise arrangement of polymer-embedded NPs is required for function.
Tang, T-Y; Zhou, Y; Arya, G
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