Viscoelastic Hydrogels Governed by Molecular Interactions and Mechanochemical Effects

Abstract

Hydrogels, particularly those based on polymer networks, exhibit complex mechanical behaviors arising from the interplay between network architecture, molecular interactions, and external stimuli. In particular, their viscoelasticity, energy dissipation, and nonlinear mechanical responses arise from the dynamic nature of crosslinking and multiscale relaxation processes. This review provides a comprehensive overview of hydrogel mechanics from a multiscale perspective, covering viscoelastic behavior, relaxation dynamics, energy dissipation mechanisms, nonlinear deformation, and fracture properties. We summarize recent advances in experimental characterization, including bulk rheology and single-molecule force spectroscopy, and discuss how molecular-level interactions, bond kinetics and mechanochemical processes contribute to macroscopic mechanical performance. In addition, theoretical models and constitutive frameworks describing transient and dynamic polymer networks are critically evaluated to bridge microscopic dynamics with bulk responses. Emerging strategies that integrate dynamic bonding and force-responsive elements are also discussed in the context of tailoring mechanical adaptability and functionality. Finally, we outline current challenges and future directions toward the rational design of hydrogels with tunable viscoelasticity, enhanced mechanical robustness, and programmable mechanical functions.