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Dynamically crosslinked polymers and their composites have tremendous potential in the development of the next round of advanced materials for aerospace, sensing, and tribological applications. These materials have self-healing properties, or the ability to recover from scratches and cuts. Applied forces can have a significant impact on the mechanical properties of non-dynamic systems. However, the impacts of forces on the self-healing ability of dynamically bonded systems are still poorly understood. Here, we used a combined computational and experimental approach to study the impact of mechanical forces on the self-healing of a model dynamic covalent crosslinked polymer system. Surprisingly, the mechanical history of the materials has a distinct impact on the observed recovery of the mechanical properties after the material is damaged. Higher compressive forces and sustained forces lead to greater self-healing, indicating that mechanical forces can promote dynamic chemistry. The atomistic details provided in molecular dynamics simulations are used to understand the mechanism with both non-covalent and dynamic covalent linkage responses to the external loading. Finite element analysis is performed to bridge the gap between experiments and simulations and to further explore the underlying mechanisms. The self-healing behavior of the crosslinked polymers is explained using reaction rate theory, with the applied force proposed to lower the energy barrier to bond exchange. Overall, our study provides fundamental understanding of how and why the self-healing of cross-linked polymers is affected by a compressive force and the force application time. 

Abstract Dynamically cross‐linked polymer networks have attracted significant interest in recent years due to their unique and improved properties including increased toughness, malleability, shape memory, and self‐healing. Here, a computational study on the mechanical behavior of dynamically cross‐linked polymer networks is presented. Coarse grained models for different polymer network configurations are established and their mechanical properties using molecular dynamics (MD) simulations are predicted. Consistent with the experimental measurements, the simulation results show that interpenetrating networks (IPN) withstand considerably higher stress compared to the single networks (SN). Additionally, the MD results demonstrate that the origin of this variation in mechanical behavior of IPN and SN configurations goes back to the difference in spatial degrees of freedom of the noncovalent cross‐linkers, represented by nonbonded interactions within the two system types. The results of this work provide new insight for future studies on the design of systems with dual dynamic cross‐linkers where one linkage exchanges rapidly and provides autonomic dynamic character, while the other is a stimulus responsive dynamic covalent linkage that provides stability with dynamic exchange on‐demand.