Universally autonomous self-healing elastomer with high stretchability

Developing autonomous self-healing materials for applications in harsh conditions is challenging because the reconstruction of interaction in material for self-healing will experience significant resistance and fail. Herein, a universally self-healing and highly stretchable supramolecular elastomer is designed by synergistically incorporating multi-strength H-bonds and disulfide metathesis in polydimethylsiloxane polymers. The resultant elastomer exhibits high stretchability for both unnotched (14000%) and notched (1300%) samples. It achieves fast autonomous self-healing under universal conditions, including at room temperature (10 min for healing), ultralow temperature (−40 °C), underwater (93% healing efficiency), supercooled high-concentrated saltwater (30% NaCl solution at −10 °C, 89% efficiency), and strong acid/alkali environment (pH = 0 or 14, 88% or 84% efficiency). These properties are attributable to synergistic interaction of the dynamic strong and weak H-bonds and stronger disulfide bonds. A self-healing and stretchable conducting device built with the developed elastomer is demonstrated, thereby providing a direction for future e-skin applications. Developing autonomous self-healing materials for application under extreme conditions is challenging. Here, the authors design a highly stretchable elastomer by incorporation of H-bonds and disulphide methathesis, which shows efficient self-healing under extreme conditions.

[1]  Zhenan Bao,et al.  Skin-Inspired Electronics: An Emerging Paradigm. , 2018, Accounts of chemical research.

[2]  Aaron M Kushner,et al.  A biomimetic modular polymer with tough and adaptive properties. , 2009, Journal of the American Chemical Society.

[3]  Wei Cao,et al.  Dynamic diselenide bonds: exchange reaction induced by visible light without catalysis. , 2014, Angewandte Chemie.

[4]  S. Nutt,et al.  A Thermally Re-mendable Cross-Linked Polymeric Material , 2002, Science.

[5]  P. Liu,et al.  Multiphase-Assembly of Siloxane Oligomers with Improved Mechanical Strength and Water-Enhanced Healing. , 2018, Angewandte Chemie.

[6]  Germán Cabañero,et al.  Catalyst-free room-temperature self-healing elastomers based on aromatic disulfide metathesis , 2014 .

[7]  Yifan Guo,et al.  A Highly Efficient Self‐Healing Elastomer with Unprecedented Mechanical Properties , 2019, Advanced materials.

[8]  Fan Zhang,et al.  A Rapid and Efficient Self‐Healing Thermo‐Reversible Elastomer Crosslinked with Graphene Oxide , 2013, Advanced materials.

[9]  Joanna Aizenberg,et al.  Extremely Stretchable and Fast Self‐Healing Hydrogels , 2016, Advanced materials.

[10]  E. W. Meijer,et al.  Tough stimuli-responsive supramolecular hydrogels with hydrogen-bonding network junctions. , 2014, Journal of the American Chemical Society.

[11]  Albert P H J Schenning,et al.  Supramolecular polymerization. , 2009, Chemical reviews.

[12]  M. Urban,et al.  Self-Repairing Oxetane-Substituted Chitosan Polyurethane Networks , 2009, Science.

[13]  Benjamin C. K. Tee,et al.  An electrically and mechanically self-healing composite with pressure- and flexion-sensitive properties for electronic skin applications. , 2012, Nature nanotechnology.

[14]  D. Weitz,et al.  Tough Self‐Healing Elastomers by Molecular Enforced Integration of Covalent and Reversible Networks , 2017, Advanced materials.

[15]  Francisco Molina-Lopez,et al.  An integrated self-healable electronic skin system fabricated via dynamic reconstruction of a nanostructured conducting network , 2018, Nature Nanotechnology.

[16]  Jing Liu,et al.  Ultra-compliant liquid metal electrodes with in-plane self-healing capability for dielectric elastomer actuators , 2013 .

[17]  Jong Won Chung,et al.  Stretchable Self-Healing Polymeric Dielectrics Cross-Linked Through Metal-Ligand Coordination. , 2016, Journal of the American Chemical Society.

[18]  C. Keplinger,et al.  A highly stretchable autonomous self-healing elastomer. , 2016, Nature chemistry.

[19]  Zhenan Bao,et al.  Self-healing chemistry enables the stable operation of silicon microparticle anodes for high-energy lithium-ion batteries. , 2013, Nature chemistry.

[20]  Z. Guan,et al.  Enhancing mechanical performance of a covalent self-healing material by sacrificial noncovalent bonds. , 2015, Journal of the American Chemical Society.

[21]  M. Watanabe,et al.  Self‐Healing Micellar Ion Gels Based on Multiple Hydrogen Bonding , 2018, Advanced materials.

[22]  Ying Yang,et al.  Self-healing polymeric materials. , 2013, Chemical Society reviews.

[23]  Stephanie J. Benight,et al.  Stretchable and self-healing polymers and devices for electronic skin , 2013 .

[24]  Yue Cao,et al.  Self-healing electronic skins for aquatic environments , 2019, Nature Electronics.

[25]  Jincai Li,et al.  Seawater-Assisted Self-Healing of Catechol Polymers via Hydrogen Bonding and Coordination Interactions. , 2016, ACS applied materials & interfaces.

[26]  Masaru Yoshida,et al.  High-water-content mouldable hydrogels by mixing clay and a dendritic molecular binder , 2010, Nature.

[27]  N. Sottos,et al.  Autonomic healing of polymer composites , 2001, Nature.

[28]  Guoping Zhang,et al.  Ultrafast Self-Healing Nanocomposites via Infrared Laser and Their Application in Flexible Electronics. , 2017, ACS applied materials & interfaces.

[29]  Zhibin Guan,et al.  Malleable and Self-Healing Covalent Polymer Networks through Tunable Dynamic Boronic Ester Bonds. , 2015, Journal of the American Chemical Society.

[30]  Michael D. Dickey,et al.  Self‐Healing Stretchable Wires for Reconfigurable Circuit Wiring and 3D Microfluidics , 2013, Advanced materials.

[31]  Jianjun Cheng,et al.  Dynamic urea bond for the design of reversible and self-healing polymers , 2014, Nature Communications.

[32]  S. Thayumanavan,et al.  Smart Organic Two-Dimensional Materials Based on a Rational Combination of Non-covalent Interactions. , 2016, Angewandte Chemie.

[33]  P. Cordier,et al.  Self-healing and thermoreversible rubber from supramolecular assembly , 2008, Nature.

[34]  Joanna Aizenberg,et al.  Dynamic polymer systems with self-regulated secretion for the control of surface properties and material healing. , 2015, Nature materials.

[35]  Zhenan Bao,et al.  Thermodynamically stable whilst kinetically labile coordination bonds lead to strong and tough self-healing polymers , 2019, Nature Communications.

[36]  Yifan Guo,et al.  Biomimetic Materials with Multiple Protective Functionalities , 2019, Advanced Functional Materials.

[37]  M. Dickey.  Stretchable and Soft Electronics using Liquid Metals , 2017, Advanced materials.

[38]  Olivia R. Cromwell,et al.  Self-healing multiphase polymers via dynamic metal-ligand interactions. , 2014, Journal of the American Chemical Society.

[39]  Takuzo Aida,et al.  Mechanically robust, readily repairable polymers via tailored noncovalent cross-linking , 2018, Science.

[40]  N. Sugimoto,et al.  Artificial G-wire switch with 2,2'-bipyridine units responsive to divalent metal ions. , 2007, Journal of the American Chemical Society.

[41]  Honglei Guo,et al.  Oppositely Charged Polyelectrolytes Form Tough, Self‐Healing, and Rebuildable Hydrogels , 2015, Advanced materials.

[42]  Bryan M. Wong,et al.  A Transparent, Self‐Healing, Highly Stretchable Ionic Conductor , 2016, Advanced materials.

[43]  Pengxu Wang,et al.  Ultrastretchable, Self-Healable Hydrogels Based on Dynamic Covalent Bonding and Triblock Copolymer Micellization , 2017 .

[44]  Jian Ping Gong,et al.  Physical hydrogels composed of polyampholytes demonstrate high toughness and viscoelasticity. , 2013, Nature materials.

[45]  Christoph Weder,et al.  Light-Healable Supramolecular Nanocomposites Based on Modified Cellulose Nanocrystals. , 2013, ACS macro letters.

[46]  Jianhua Xu,et al.  Transparent, Mechanically Strong, Extremely Tough, Self‐Recoverable, Healable Supramolecular Elastomers Facilely Fabricated via Dynamic Hard Domains Design for Multifunctional Applications , 2019, Advanced Functional Materials.

[47]  Pingao Huang,et al.  Quadruple H-Bonding Cross-Linked Supramolecular Polymeric Materials as Substrates for Stretchable, Antitearing, and Self-Healable Thin Film Electrodes. , 2018, Journal of the American Chemical Society.

[48]  Huan Zhang,et al.  Mechanoresponsive Healable Metallosupramolecular Polymers , 2013 .

[49]  Bowen Zhu,et al.  A Mechanically and Electrically Self‐Healing Supercapacitor , 2014, Advanced materials.

[50]  Xuanhe Zhao,et al.  Mechanochemical Activation of Covalent Bonds in Polymers with Full and Repeatable Macroscopic Shape Recovery. , 2014, ACS macro letters.

[51]  Ying‐Ling Liu,et al.  Self-healing polymers based on thermally reversible Diels–Alder chemistry , 2013 .

[52]  Sung-Ho Shin,et al.  Superior Toughness and Fast Self‐Healing at Room Temperature Engineered by Transparent Elastomers , 2018, Advanced materials.

[53]  Z. Suo,et al.  Highly stretchable and tough hydrogels , 2012, Nature.

[54]  Krzysztof Matyjaszewski,et al.  Self‐Healing of Covalently Cross‐Linked Polymers by Reshuffling Thiuram Disulfide Moieties in Air under Visible Light , 2012, Advanced materials.

[55]  M. Rong,et al.  Stabilization of catechol–boronic ester bonds for underwater self-healing and recycling of lipophilic bulk polymer in wider pH range , 2016 .

[56]  Z. Guan,et al.  Olefin metathesis for effective polymer healing via dynamic exchange of strong carbon-carbon double bonds. , 2012, Journal of the American Chemical Society.

[57]  Jessica J. Cash,et al.  Room-Temperature Self-Healing Polymers Based on Dynamic-Covalent Boronic Esters , 2015 .

[58]  J. B. Tok,et al.  An Elastic Autonomous Self‐Healing Capacitive Sensor Based on a Dynamic Dual Crosslinked Chemical System , 2018, Advanced materials.

[59]  Jianhua Xu,et al.  Extremely Stretchable, Self-Healable Elastomers with Tunable Mechanical Properties: Synthesis and Applications , 2018, Chemistry of Materials.

[60]  Scott R White,et al.  Biomimetic Self-Healing. , 2015, Angewandte Chemie.

[61]  Michael D. Dickey,et al.  Emerging Applications of Liquid Metals Featuring Surface Oxides , 2014, ACS applied materials & interfaces.

[62]  Bryan M. Wong,et al.  A Highly Stretchy, Transparent Elastomer with the Capability to Automatically Self‐Heal Underwater , 2018, Advanced materials.

[63]  Aaron M Kushner,et al.  Multiphase design of autonomic self-healing thermoplastic elastomers. , 2012, Nature chemistry.

[64]  Costantino Creton,et al.  Toughening Elastomers with Sacrificial Bonds and Watching Them Break , 2014, Science.

[65]  M. Rong,et al.  Polymer engineering based on reversible covalent chemistry: A promising innovative pathway towards new materials and new functionalities , 2018 .

[66]  Nan Li,et al.  Tough Supramolecular Polymer Networks with Extreme Stretchability and Fast Room‐Temperature Self‐Healing , 2017, Advanced materials.

[67]  Zhenan Bao,et al.  Tough and Water‐Insensitive Self‐Healing Elastomer for Robust Electronic Skin , 2018, Advanced materials.

[68]  M. Rong,et al.  A seawater triggered dynamic coordinate bond and its application for underwater self-healing and reclaiming of lipophilic polymer , 2016, Chemical science.

[69]  Takao Someya,et al.  The rise of plastic bioelectronics , 2016, Nature.

[70]  Guangji Li,et al.  An intermolecular quadruple hydrogen-bonding strategy to fabricate self-healing and highly deformable polyurethane hydrogels. , 2014, Journal of materials chemistry. B.

[71]  Qingchuan Tao,et al.  Multiple Hydrogen Bonding Enables the Self-Healing of Sensors for Human-Machine Interactions. , 2017, Angewandte Chemie.

[72]  Justin R. Kumpfer,et al.  Optically healable supramolecular polymers , 2011, Nature.

[73]  C. Abell,et al.  Biomimetic Supramolecular Polymer Networks Exhibiting both Toughness and Self‐Recovery , 2017, Advanced materials.

[74]  Lan Li,et al.  A rigid and healable polymer cross-linked by weak but abundant Zn(II)-carboxylate interactions , 2018, Nature Communications.

[75]  N. Chen,et al.  Mussel-inspired healing of a strong and stiff polymer , 2018 .