Rapid, puncture-initiated healing via oxygen-mediated polymerization

Autonomously healing materials that utilize thiol-ene polymerization initiated by an environmentally borne reaction stimulus are demonstrated by puncturing trilayered panels, fabricated by sandwiching thiol-ene-trialkylborane resin formulations between solid polymer panels, with high velocity projectiles; as the reactive liquid layer flows into the entrance hole, contact with atmospheric oxygen initiates polymerization, converting the liquid into a solid plug. Using infrared spectroscopy, we find that formulated resins polymerize rapidly, forming a solid polymer within seconds of atmospheric contact. During high-velocity ballistics experiments, additional evidence for rapid polymerization is provided by high-speed video, demonstrating the immediate viscosity increase when the thiol-ene-trialkylborane resins contact atmospheric oxygen, and thermal imaging, where surface temperature measurements reveal the thiol-ene reaction exotherm, confirming polymerization begins immediately upon oxygen exposure. While other approaches for materials self-repair have utilized similar liquid-to-solid transitions, our approach permits the development of materials capable of sealing a breach within seconds, far faster than previously described methods.