Martini coarse-grained model for clay-polymer nanocomposites

TL;DR

This paper introduces a MARTINI coarse-grained model for clay-polymer nanocomposites, accurately capturing structural and thermodynamic properties and demonstrating transferability across different polymers and conditions.

Contribution

A novel MARTINI-based coarse-grained model for organically modified montmorillonite clay in polymer nanocomposites, validated against all-atom simulations and applicable to multiple polymer types.

Findings

Model accurately reproduces mechanical and thermodynamic properties.

Transferability demonstrated across polyethylene, polypropylene, and polystyrene.

Clay influences structure-property relationships captured by excess entropy scaling.

Abstract

We have developed a coarse-grained (CG) model of a polymer-clay system consisting of organically modified montmorillonite nanoclay as the nanoparticle in accordance with the MARTINI forcefield. We have used mechanical properties and cleavage free energy of clay particle to respectively parameterize bonded and nonbonded interaction parameters for an organically modified montmorillonite (oMMT) clay particle where intergallery Na+ ions are replaced by tetramethylammonium (TMA) ions. The mechanical properties were determined from the slope of stress-strain curve and cleavage free energy was determined by allowing for full surface reconstruction corresponding to a slow equilibrium cleavage process. Individual dispersive and polar contributions to oMMT cleavage energy were used for determination of appropriate MARTINI bead types for CG oMMT sheet. The self-consistency of developed MARTINIFF parameters for TMA-MMT-polymer system was verified by comparing estimates for select structural, thermodynamic, and dynamic properties obtained in all-atomistic simulations with that obtained in coarse-grained simulations. We have determined the influence of clay particle on properties of three polymer melts (polyethylene, polypropylene, and polystyrene) at two temperatures to establish transferability of the developed parameters. We have also shown that the effect of clay-polymer interactions on structure-property relationships in this nanocomposite system is well captured by Rosenfeld's excess entropy scaling.