Empowering self-reporting polymer blends with orthogonal optical properties responsive in a broader force range

Abstract

Self-reporting polymers, which can indicate damage with perceptible optical signals in a tailored force range, are useful as stress-sensitive sensors. We demonstrate a simple approach to realize this function by embedding two distinct mechanophores - rhodamine (<b>Rh</b>) and bis(adamantyl)-1,2-dioxetane (<b>Ad</b>), in polyurethane/polylactic acid blends. The deformed blends generate red coloration and red chemiluminescence. Such a unique dual-responsive behavior was evaluated by solid-state UV-vis spectroscopy, macroscopic tensile tests with <i>in situ</i> RGB and light intensity analyses, which supported a stress-correlated occurrence of the ring-opening of <b>Rh</b>, the scission of <b>Ad</b> and the fluorescence resonance energy transfer process between the respective mechanochemical species. Complementarity stemming from the difference in properties and manifestations of the two mechanophores is essential. That is, the more labile <b>Rh</b> allows shifting the appreciable optical changes to a much lower force threshold; the transient nature and high dynamic range of mechanochemiluminescence from <b>Ad</b> map in real time where and when many of the covalently incorporated dioxetane bonds break; besides, the disrupted yet non-scissile structure of <b>Rh</b> acts as a fluorescent acceptor to effectively harvest chemiluminescence from ruptured <b>Ad</b>. The current strategy is thus empowering multi-functional mechano-responsive polymers with greatly improved sensitivity and resolution for multimodal stress reporting.