Characterization and Quantification of Immiscible Polymer Blend Compatibilization by Phyllosilicate Clays

Abstract

Phyllosilicate clays are widely used in polymer nanocomposites owing to their high anisotropy and tunable surface polarity. Their distribution and interface localization in polymer blends can be used to tune the properties of polymer-clay nanocomposites (PCNCs). A coarse-grained (CG) force field for clays can aid molecular simulations in PCNC development. Here, we developed MARTINI-3 parameters, a CG force field with high chemical specificity, for phyllosilicate clays with diverse surface polarities. Initial interactions for the clay functional groups were determined from hydration free energies, obtained by applying the Lifshitz theory to experimental surface tension data. These were fine-tuned using the structural, thermodynamic, and dynamic properties of thermoplastic starch (TPS)-clay composites from all-atom (AA) molecular dynamics (MD) simulations. The radial distribution function and two-body excess entropy of TPS components, not used in CG parameterization, were accurately estimated, establishing the robustness of the parameters. We investigated the effect of clay surface polarity on polymer segmental dynamics and structure-property relationships. The CG parameters were then used to study the effect of dodecyltrimethylammonium (C12TAB)-modified montmorillonite (MMT), an organically-modified MMT, on TPS-polyethylene (PE) blend morphology using large time- and length-scale MD simulations. We observed compatibilization of the TPS-PE interphase by the amphiphilic clay particle, reducing the TPS-PE interfacial tension from 45 mN/m to 13.06 mN/m. We found good agreement between MARTINI-3 estimates for properties of model MMT-based PCNCs and those from AA simulations and experimental data, establishing grounds for the transferability of the parameters to other systems.