Dynamics of Supramolecular Self-Healing Recovery in Extension

Self-healing materials are prized for their ability to recover mechanical properties after damage. Supramolecular polymer networks have been demonstrated to have the ability to recover without the need for extraneous material components or the use of external stimuli. Surprisingly, there is little quantitative measure of self-healing dynamics and recovery. In this work, we develop a tool using a filament stretching rheometer to probe self-healing dynamics in creep and constant rate of extension. We experimentally determine the effect of process time scales, τH and τW, on the degree of recovery for two distinct supramolecular architectures. These results are put into the context of molecular time scales such as disengagement time, the Rouse time, and bond lifetime. We find that entangled polymers undergo sequential healing, whereby at short times, dynamics are dominated by entanglement recovery followed by recovery of associations. For an unentangled polymer, recovery is seemingly dominated by association dynamics. Our experimental results are put into the context of leading theoretical models. We also introduce the importance of the measurement flow time scale on perceived material recovery. These initial results and reliable experimental tools begin to construct a framework for measuring, understanding, and predicting recovery of self-healing soft materials.