Ultra-Strong, Crack-Tolerant Elastomers via Geometrically Confined H-Bonding Semicarbazides

Ultra-Strong, Crack-Tolerant Elastomers via Geometrically Confined H-Bonding Semicarbazides | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Ultra-Strong, Crack-Tolerant Elastomers via Geometrically Confined H-Bonding Semicarbazides Fenfen Wang, Rujuan Li, Shuyao Pan, Zhiming Liu, Shengli Chen, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8257548/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract The development of high-performance elastomers demands a combination of high tensile strength and toughness, yet overcoming the inherent trade-off between them remains a persistent challenge. Herein, inspired by the dense hydrogen-bonding assembly in spider silk, we developed a new generation of semicarbazide chain extender bearing high-density hydrogen-bonding sites for synthesizing poly(urethane-urea) (PUU). The geometric confinement, achieved by employing two specific semicarbazide chain extenders, is key to enhancing the material's properties. The resulting elastomer (PUU-HI) exhibits a nanoscale-ordered phase-separated structure and maximized H-bonding, which collectively amplify the supramolecular interactions and lead to ultra-robust mechanical performance. This material achieved a high tensile strength of 120.2 MPa, with toughness of 400.5 MJ m⁻³ and true fracture stress of 1.3 GPa, even surpassing those of spider silk. Molecular dynamics simulations revealed that geometric confinement effect enhances H-bonding interactions in PUU-HI. Multidimensional solid-state NMR demonstrates that this molecular packing confines chain mobility via augmented steric hindrance, facilitating orderly hard-domain stacking and efficient energy dissipation. The architecture additionally delivers exceptional crack tolerance, fatigue resistance, and recyclability. By designing novel H-bonding motifs and amplifying supramolecular interactions via geometric confinement, this work offers a promising strategy for developing mechanically robust and durable elastomers. Physical sciences/Materials science/Soft materials/Polymers Physical sciences/Chemistry/Polymer chemistry/Mechanical properties Full Text Additional Declarations There is NO Competing Interest. Supplementary Files PUUSI.doc supporting information Cite Share Download PDF Status: Under Review Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8257548","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":562764465,"identity":"59538292-09d0-44d1-8f58-9373aa5c84aa","order_by":0,"name":"Fenfen 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Herein, inspired by the dense hydrogen-bonding assembly in spider silk, we developed a new generation of semicarbazide chain extender bearing high-density hydrogen-bonding sites for synthesizing poly(urethane-urea) (PUU). The geometric confinement, achieved by employing two specific semicarbazide chain extenders, is key to enhancing the material's properties. The resulting elastomer (PUU-HI) exhibits a nanoscale-ordered phase-separated structure and maximized H-bonding, which collectively amplify the supramolecular interactions and lead to ultra-robust mechanical performance. This material achieved a high tensile strength of 120.2 MPa, with toughness of 400.5 MJ m⁻\u0026sup3; and true fracture stress of 1.3 GPa, even surpassing those of spider silk. Molecular dynamics simulations revealed that geometric confinement effect enhances H-bonding interactions in PUU-HI. 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