Do You Get What You See? Understanding Molecular Self‐Healing

The self-healing ability of self-healing materials is often analyzed using morphologic microscopy images. Here it was possible to show that morphologic information alone is not sufficient to judge the status of a self-healing process and molecular information is required as well. When comparing molecular coherent anti-Stokes Raman scattering (CARS) and morphological laser reflection images during a standard scratch healing test of an intrinsic self-healing polymer network, it was found that the morphologic closing of the scratch and the molecular crosslinking of the material do not take place simultaneously. This important observation can be explained by the fact that the self-healing process of the thiol-ene based polymer network is limited by the mobility of alkene-containing compounds, which can only be monitored by molecular CARS microscopy and not by standard morphological imaging. Additionally, the recorded CARS images indicate a mechanochemical activation of the self-healing material by the scratching/damaging process, which leads to an enhanced self-healing behavior in the vicinity of the scratch.