Correlating thermodynamics, morphology, mechanics and thermal transport in PMMA-PLA blends

TL;DR

This study uses molecular dynamics simulations and Kirkwood-Buff theory to connect thermodynamics, morphology, mechanics, and thermal transport in PMMA-PLA polymer blends, aiding the design of advanced lightweight materials.

Contribution

It introduces a microscopic understanding of phase behavior and mechanical properties in PMMA-PLA blends through KB theory and simulations, linking thermodynamics to physical properties.

Findings

Proper entropic accounting influences phase morphology.

Microscopic interactions control mechanical behavior.

Thermodynamics correlates with thermal transport properties.

Abstract

Thermodynamics controls structure, function, stability and morphology of polymer blends. However, obtaining the precise information about their mixing thermodynamics is a challenging task, especially when dealing with complex macromolecules. This is partially because of a delicate balance between the local concentration/composition fluctuations and the monomer level (multi-body) interactions. In this context, the Kirkwood-Buff (KB) theory serves as a useful tool that connects the local pairwise fluid structure to the mixing thermodynamics. Using larger scale molecular dynamics simulations, within the framework of KB theory, we investigate a set of technologically relevant poly(methyl methacrylate)-poly(lactic acid) (PMMA-PLA) blends with the aim to elucidate the underlying microscopic picture of their phase behavior. Consistent with these experiments, we emphasize the importance of properly accounting for the entropic contribution, to the mixing Gibbs free energy change $\Delta {\mathcal G}_{\rm mix}$, that controls the phase morphology. We further show how the relative microscopic interaction details and the molecular level structures between different mixing species can control the non-linear mechanics and ductility. As a direct consequence, we provide a correlation that links thermodynamics, phase behavior, mechanics, and thus also thermal transport in polymer blends. Therefore, this study provides a guiding principle for the design of light weight functional materials with extraordinary physical properties.