Supramolecular Adhesives with Tunable Crystallinity for Extreme Environments

ABSTRACT

Developing high‐performance adhesives capable of withstanding harsh environments‐specifically ultralow temperatures, water, acid, base and organic solvents‐via low‐cost, scalable manufacturing remains a significant challenge. Inspired by the architecture of spider silk, we report a facile strategy to fabricate a solvent‐free supramolecular adhesive composed of tannic acid (TA) and poly(ε‐caprolactone) (PCL). Integrated theoretical and experimental investigations uncover the critical role of crystallinity modulation in governing adhesion performance. The resulting adhesive achieves an exceptional strength of up to 8.5 MPa at ambient temperature (25°C) and 6.6 MPa at cryogenic temperature (−196°C), outperforming existing commercial hot‐melt adhesives. Furthermore, it exhibits remarkable stability in corrosive underwater environments (acidic, alkaline, and saline) and organic solvents. This work not only establishes a novel bioinspired design paradigm for adhesives operating under extreme conditions but also paves the way for the scalable production and practical applications of supramolecular materials.