Nanoparticle assembly modulated by polymer chain conformation in composite materials

Abstract

Mixing nanoparticles into a strategically selected polymer matrix yields nanocomposites with well-controlled microstructures and unique properties and functions. The modulation of nanoparticle assembly by polymer chain conformation can play a dominant role in determining nanocomposite structures, yet such a physical mechanism remains largely unexplored. We hypothesize that highly ordered microdomains of rigid linear polymers provide a template for nanoparticle assembly into open fractal structures. We conducted mesoscopic computer simulations and physical experiments to elucidate how polymer chain conformation regulates the dynamic evolution of nanoparticle structures during the drying processing of polymer nanocomposite films. The evaporation of polymer–nanoparticle mixtures with varying chain stiffnesses was simulated using dissipative particle dynamics. The formation of distinguished nanoparticle assemblies as a result of matrix selection was further corroborated by probing nanoparticle aggregation in different polymer nanocomposite coatings. The results show that polymer conformation not only influences the dispersion states of individual particles (dispersed vs. aggregated), but also modulates the morphologies of large-scale assembly (globular vs. fractal). The emergence of nematically ordered polymer clusters when the chain rigidity is increased creates local solvent-rich “voids” that promote anisotropic particle aggregates, which then percolate into open fractal structures upon solvent evaporation. The nanoparticle dynamics also exhibits an intriguing non-monotonic behavior attributed to the transitions between the coupling and decoupling with polymer dynamics. The nanoparticle assembly morphologies obtained in simulations match well with the electron microscopy images taken in physical experiments.