Thermo-elastic properties of hydrated epoxy-graphene nanocomposites from ensemble-based molecular dynamics simulations

Abstract

Epoxy-based materials are inherently hygroscopic, absorbing moisture from the environment, which can significantly alter their short and long-term performance. The presence of graphene is often considered as a potential candidate to act as a microscopic barrier, mitigating the adverse effects of hydration on the matrix. This study investigates the impact of hydration on the glass transition and elastic mechanical properties of epoxy resins and their graphene nanocomposites, focusing on water content up to 5 wt%. Using large-ensemble molecular dynamics simulations, we analyze the temperature-driven glass transition and mechanical response of both neat epoxy and epoxy-graphene systems under varying hydration levels. Our results reveal a distinct threshold at 3 wt% water content: below this, hydration primarily reduces the glass transition temperature, while mechanical properties remain unaffected. Beyond 3 wt%, however, the mechanical properties deteriorate, highlighting a non-linear sensitivity to water uptake. Furthermore, we emphasize the critical role of ensemble size in ensuring the reliability of molecular dynamics predictions for such heterogeneous systems. Our simulations demonstrate that ensembles substantially larger than current state-of-the-art standards are necessary to achieve converged distributions of the predicted mechanical properties, particularly in highly heterogeneous hydrated epoxy-graphene nanocomposites. These findings provide novel insights into the hydration behavior of epoxy-based materials and underscore the potential of graphene to enhance their environmental resistance. This work also advances the understanding of structure-property relationships in polymer nanocomposites, offering guidance for the design of more robust materials in humid environments.