Implicit Chain Particle Model for Polymer Grafted Nanoparticles

TL;DR

This paper introduces the implicit chain particle model (ICPM), a coarse-grained simulation framework that significantly accelerates the study of polymer grafted nanoparticles, enabling efficient exploration of their interfacial interactions and mechanical properties.

Contribution

The paper presents a new modeling paradigm for PGNs using a strain-energy mapping framework with implicit chains, vastly improving computational efficiency over traditional molecular dynamics.

Findings

ICPM increases simulation speed by 5-6 orders of magnitude.

Effective interactions derived from strain energy matching.

Model captures strain-rate dependence of mechanical work.

Abstract

Matrix-free nanocomposites made from polymer grafted nanoparticles (PGN) represent a paradigm shift in materials science because they greatly improve nanoparticle dispersion and offer greater tunability over rheological and mechanical properties in comparison to neat polymers. Utilizing the full potential of PGNs requires a deeper understanding of how polymer graft length, density, and chemistry influence interfacial interactions between particles. There has been great progress in describing these effects with molecular dynamics (MD). However, the limitations of the length and time scales of MD make it prohibitively costly to study systems involving more than a few PGNs. Here, we address some of these challenges by proposing a new modeling paradigm for PGNs using a strain-energy mapping framework involving potential of mean force (PMF) calculations. In this approach, each nanoparticle is coarse-grained into a representative particle with chains treated implicitly, namely, the implicit chain particle model (ICPM). Using a chemistry-specific CG-MD model of PMMA as a testbed, we derive the effective interaction between particles arranged in a closed-packed lattice configuration by matching bulk dilation/compression strain energy densities. The strain-rate dependence of the mechanical work in ICPM is also discussed. Overall, the ICPM model increases the computational speed by approximately 5-6 orders of magnitude compared to the CG-MD models. This novel framework is foundational for particle-based simulations of PGNs and their blends and accelerates the understanding and predictions of emergent properties of PGN materials.