Understanding the role of grafted polystyrene chain conformation in assembly of magnetic nanoparticles

Polystyrene-grafted iron oxide nanoparticles have been shown to phase separate into ordered morphologies of strings, well-dispersed particles, and spherical aggregates at low graft densities in polymer matrices. In this work, small-angle neutron scattering experiments are performed to reveal the role of grafted chain conformation on nanoparticle assemblies. We demonstrate that chains grafted at low densities follow Gaussian statistics at any dispersion states. These results suggest that grafted chains are not distorted but remain Gaussian when particles are aggregated into strings. Small-angle x-ray and neutron scattering results show that matrix chains do not influence the formation of strings, but have a significant impact on the size and internal structure of aggregated particles. We conclude that spherical aggregates of nanoparticles with low polymer graft densities are akin to interpenetrating networks in which free matrix chains bridge the fractals of particles and control the cluster density.