Classification of interfacial water governed by water-polymer interactions in hydrated polymers: A molecular dynamics simulation study of ethylene-based and acrylate polymers

TL;DR

This study uses molecular dynamics simulations to classify interfacial water in polymers based on hydration structure, dynamics, and polymer-water interactions, revealing three distinct hydration types.

Contribution

It provides a molecular-level framework for understanding interfacial water behavior in hydrated polymers, integrating hydration structure, dynamics, and polymer fluctuations.

Findings

Hydroxyl polymers show high $T_g$ and pronounced hydration effects.

Hydrophobic polymers exhibit low water content and aggregation-driven hydration.

Flexible polymers display loosely bound water with super-Arrhenius hydrogen-bond dynamics.

Abstract

We perform molecular dynamics simulations to investigate hydration structures and dynamics in seven water-containing polymers: PVA, PHEA, PHEMA, PBA, PMEMA, PEG, and PMEA. The analysis integrates four perspectives: the water-content dependence of the glass transition temperature $T_g$, polymer chain fluctuations characterized by dihedral angle distributions, hydrogen-bond lifetimes $\tau_{\mathrm{HB}}$ between water and polymer functional groups, and the localization and exchange dynamics of confined water quantified by the distinct part of van Hove correlation function. Hydroxyl-containing polymers (PVA, PHEA, and PHEMA) exhibit relatively high dry-state $T_g$ values and its pronounced depression upon hydration. Chain fluctuations are limited, and $\tau_{\mathrm{HB}}$ follows Arrhenius behavior, forming localized hydration shells. In contrast, PMEMA and PBA show low equilibrium water contents and hydrophobic character; although their dry-state $T_g$ values are moderately lower and less sensitive to water content, chain fluctuations remain small, and $\tau_{\mathrm{HB}}$ also obeys Arrhenius behavior, with hydrophobic aggregation promoting water localization. PEG and PMEA display low dry-state $T_g$ values and weak water-content dependence. Greater rotational freedom around ether or methoxy oxygen atoms leads to larger chain fluctuations and loosely bound water. Below $T_g$, $\tau_{\mathrm{HB}}$ between water and ether or methoxy oxygen atoms exhibits super-Arrhenius behavior. These results clarify three hydration types: highly hydrated (PVA, PHEA, and PHEMA), hydrophobic (PMEMA and PBA), and flexibly hydrated (PEG and PMEA), and provide a molecular-level framework for interpreting interfacial water governed by water-polymer interactions.