Influence of polymer bidispersity on the effective particle-particle interactions in polymer nanocomposites

TL;DR

This study explores how polymer bidispersity influences nanoparticle interactions in polymer nanocomposites, revealing that bidispersity can be tuned to control material structure and stability.

Contribution

It introduces a hybrid particle-field molecular dynamics method to analyze the effects of bidispersity on nanoparticle interactions in polymer melts, providing new insights into material design.

Findings

Bidispersity increases attraction between ungrafted nanoparticles.

Grafted chain bidispersity affects nanoparticle interactions differently based on grafting density.

Proper modeling of multi-body interactions improves predictions of composite stability.

Abstract

We investigate the role played by the bidispersity of polymer chains on the local structure and the potential of mean force (PMF) between silica nanoparticles (NPs) in a polystyrene melt. We use the hybrid particle-field molecular dynamics technique which allows to efficiently relax polymer nanocomposites even with high molecular weights.The NPs we investigate are either bare or grafted with polystyrene chains immersed in a melt of free polystyrene chains, whereas the grafted and the free polystyrene chains are either monodisperse or bidisperse. The two-body PMF shows that a bidisperse distribution of free polymer chains increases the strength of attraction between a pair of ungrafted NPs. If the NPs are grafted by polymer chains, the effective interaction crucially depends on bidispersity and grafting density of the polymer chains: for low grafting densities, the bidispersity of both free and grafted chains increases the repulsion between the NPs, whereas for high grafting densities we observe two different effects. An increase of bidispersity in free chains causes the rise of the repulsion between the NPs, while an increase of bidispersity in grafted chains promotes the rise of attraction. Additionally, a proper treatment of multi-body interactions improves the simpler two-body PMF calculations, in both unimodal and bimodal cases. We found that, by properly tuning the bidispersity of both free and grafted chains, we can control the structure of the composite materials, which can be confirmed by experimental observations. As a result, the hybrid particle-field approach is confirmed to be a valid tool for reproducing and predicting microscopic interactions, which determine the stability of the microscopic structure of the composite in a wide range of conditions.