MARTINI Coarse-grained Force Field for Thermoplastic Starch Nanocomposites

TL;DR

This paper develops a MARTINI coarse-grained force field for thermoplastic starch (TPS) and its nanocomposites with TMA-MMT clay, validated against all-atom simulations to enable efficient modeling of their properties.

Contribution

The paper introduces a novel MARTINI coarse-grained force field for TPS and its nanocomposites, calibrated with all-atom simulations, facilitating large-scale modeling of these materials.

Findings

The CG model accurately predicts thermodynamic and structural properties.

The force field captures polymer-clay interactions and conformational behavior.

The model is robust for simulating TPS nanocomposites.

Abstract

Thermoplastic starch (TPS) is an excellent film-forming material, and adding fillers such as tetramethylammonium-montmorillonite (TMA-MMT) clay has significantly expanded its use in packaging applications. We first used all-atom (AA) simulation to predict several macroscopic (Young modulus, glass transition temperature, density) and microscopic (conformation along 1-4 and 1-6 glycosidic linkages, composite morphology) properties of TPS melt and TPS-TMA-MMT composite. The interplay of polymer-surface, plasticizer-surface, and polymer-plasticizer interactions leads to conformational and dynamic properties distinct from those in systems with either attractive or repulsive polymer-surface interactions. A subset of AA properties was used to parameterize the MARTINI coarse-grained (CG) force field (FF) for the melt and composite systems. Specifically, we determined the missing bonded parameters of amylose and amylopectin and rationalized the bead types for 1-4 and 1-6 linked alpha-D glucose using two-body excess entropy, density, and bond and angle distributions in AA TPS melt. The MARTINI CG model for TPS was combined with an existing parameter set for TMA-MMT. The liquid-liquid partitioning-based MARTINI-2 FF shows freezing and compaction of polymer chains near the sheet surface, further accentuated by lowering of dispersive interactions between pairs of high covalent coordination ring units of TPS polymers and MMT sheet. A rescaling of the dispersive component of TPS MMT cross-interactions was used to optimize the FF for the composite system, with structural, thermodynamic, and dynamic properties obtained from long AA simulations forming the constraints for optimization. The obtained CG FF parameters provided excellent estimates for several other properties of the melt and composite systems not used in parameter estimation, thus establishing the robustness of the developed model.