Characterizing the shear response of polymer-grafted nanoparticles

Abstract

Grafting polymer chains to the surface of nanoparticles overcomes the challenge of nanoparticle dispersion within nanocomposites and establishes high-volume fractions that are found to enable enhanced material mechanical properties. This study utilizes coarse-grained molecular dynamics simulations to quantify how the shear modulus of polymer-grafted nanoparticle (PGN) systems in their glassy state depends on parameters such as strain rate, nanoparticle size, grafting density, and chain length. The results are interpreted through further analysis of the dynamics of chain conformations and volume fraction arguments. The volume fraction of nanoparticles is found to be the most influential variable in deciding the shear modulus of PGN systems. A simple rule of mixture is utilized to express the monotonic dependence of shear modulus on the volume fraction of nanoparticles. Due to the reinforcing effect of nanoparticles, shortening the grafted chains results in a higher shear modulus in PGNs, which is not seen in linear systems. These results offer timely insight into calibrating molecular design parameters for achieving the desired mechanical properties in PGNs.