Well-Tunable, 3D-printable, and Fast Autonomous Self-Healing Elastomers

Li, Bingrui; Ge, Sirui; Zhao, Xiao; Chen, Qiyi; Tian, Jia; Hun, Diana; Sokolov, Alexei P.; Saito, Tomonori; Cao, Peng-Fei

doi:10.1016/j.supmat.2023.100042

Title: Well-Tunable, 3D-printable, and Fast Autonomous Self-Healing Elastomers

Journal Article · 11 October 2023 · Supramolecular Materials

DOI: https://doi.org/10.1016/j.supmat.2023.100042 · OSTI ID:2283852

^[1];

^[1]; Zhao, Xiao ^[2]; Chen, Qiyi ^[2]; Tian, Jia ^[3];

^[2];

^[4]; Saito, Tomonori ^[5];

^[3]

University of Tennessee, Knoxville, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Beijing University of Chemical Technology (China)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); University of Tennessee, Knoxville, TN (United States)
University of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Self-healing elastomers provide extended longevity of functional materials, due to their unique adaptability and durability. However, a major scientific challenge remains in developing materials with a rapid healing process combined with decent mechanical properties, that can be prepared by a relatively simple synthesis approach. Herein, we report a versatile design approach on self-healing elastomers by incorporating two different hydrogen bonding containing monomers, i.e., 2-[[(butylamino)carbonyl]oxy]ethyl acrylate (BCOE) and 2-ureido-4[1H]pyrimidinone (UPy) functionalized ethyl methacrylate. Poly(BCOE-r-UPy)s are synthesized by reversible addition-fragmentation chain-transfer (RAFT) polymerization, and controlling the ratio of two monomers enables well-tunable mechanical properties with tensile strength ranging from 0.04 to 6.3 MPa and tensile strain up to 3,000 %. The characteristic dissociation energy is calculated from a temperature dependence of terminal relaxation followed by subtracting the segmental relaxation. The rapid autonomous self-healing is achieved when the molar composition of Poly(BCOE-r-UPy) is tailored to BCOE/UPy = 99/1. The self-healing process is monitored in situ by a helium-ion microscope, and its macroscopic study using tensile tests indicates that Poly(BCOE-r-UPy1) with 1 % molar ratio of UPy recovers 70 % of its original toughness at ambient temperature within 10 mins. 3D printing of Poly(BCOE-r-UPy) affords a self-healable 3D structure, demonstrating the adaptability of Poly(BCOE-r-UPy) for on-demand fabrication. The simplicity of synthesis, well-tunable mechanical properties, unique self-healability, and 3D printing capability of Poly(BCOE-r-UPy)s indicate their potential for a range of applications.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Building Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); Natural Science Foundation of China (NSFC); National Science Foundation (NSF)

Grant/Contract Number:: AC05-00OR22725; 52373275; DMR-1904657

OSTI ID:: 2283852

Journal Information:: Supramolecular Materials, Vol. 2, Issue 1; ISSN 2667-2405

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (66)

Supramolecular Polymer Networks Made by Solvent-Free Copolymerization of a Liquid 2-Ureido-4[1 H ]-pyrimidinone Methacrylamide Heinzmann, Christian; Lamparth, Iris; Rist, Kai Macromolecules, Vol. 48, Issue 22 https://doi.org/10.1021/acs.macromol.5b02081	journal	October 2015
50th Anniversary Perspective : RAFT Polymerization—A User Guide Perrier, Sébastien Macromolecules, Vol. 50, Issue 19 https://doi.org/10.1021/acs.macromol.7b00767	journal	September 2017
Self-healing supramolecular bioelastomers with shape memory property as a multifunctional platform for biomedical applications via modular assembly Wu, Yaobin; Wang, Ling; Zhao, Xin Biomaterials, Vol. 104 https://doi.org/10.1016/j.biomaterials.2016.07.011	journal	October 2016
Highly Recyclable, Mechanically Isotropic and Healable 3D-Printed Elastomers via Polyurea Vitrimers Niu, Wei; Zhang, Zhen; Chen, Qiyi ACS Materials Letters, Vol. 3, Issue 8 https://doi.org/10.1021/acsmaterialslett.1c00132	journal	June 2021
Reprocessable thermosets for sustainable three-dimensional printing Zhang, Biao; Kowsari, Kavin; Serjouei, Ahmad Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04292-8	journal	May 2018
Self‐Healing Supramolecular Polymers In Action van Gemert, Gaby M. L.; Peeters, Joris W.; Söntjens, Serge H. M. Macromolecular Chemistry and Physics, Vol. 213, Issue 2 https://doi.org/10.1002/macp.201100559	journal	December 2011
Healable, memorizable, and transformable lattice structures made of stiff polymers Yu, Kunhao; Du, Haixu; Xin, An NPG Asia Materials, Vol. 12, Issue 1 https://doi.org/10.1038/s41427-020-0208-9	journal	March 2020
Stability and Lifetime of Quadruply Hydrogen Bonded 2-Ureido-4[1 H ]-pyrimidinone Dimers Söntjens, Serge H. M.; Sijbesma, Rint P.; van Genderen, Marcel H. P. Journal of the American Chemical Society, Vol. 122, Issue 31 https://doi.org/10.1021/ja000435m	journal	August 2000
Thermoresponsive and Self-Healing Hydrogel Based on Chitosan Derivatives and Polyoxometalate as an Antibacterial Coating Fan, Baoer; Cui, Naifu; Xu, Zhewei Biomacromolecules, Vol. 23, Issue 3 https://doi.org/10.1021/acs.biomac.1c01368	journal	January 2022
Room-Temperature Self-Healing Polymers Based on Dynamic-Covalent Boronic Esters Cash, Jessica J.; Kubo, Tomohiro; Bapat, Abhijeet P. Macromolecules, Vol. 48, Issue 7 https://doi.org/10.1021/acs.macromol.5b00210	journal	March 2015
Dual-action smart coatings with a self-healing superhydrophobic surface and anti-corrosion properties Qian, Hongchang; Xu, Dake; Du, Cuiwei Journal of Materials Chemistry A, Vol. 5, Issue 5 https://doi.org/10.1039/C6TA10903A	journal	January 2017
Polymers with Dynamic Bonds: Adaptive Functional Materials for a Sustainable Future Samanta, Subarna; Kim, Sungjin; Saito, Tomonori The Journal of Physical Chemistry B, Vol. 125, Issue 33 https://doi.org/10.1021/acs.jpcb.1c03511	journal	July 2021
Tough, adhesive, self-healing, fully physical crosslinked κ-CG-K+/pHEAA double-network ionic conductive hydrogels for wearable sensors Xu, Jianxiong; Guo, Ziyu; Chen, Yin Polymer, Vol. 236 https://doi.org/10.1016/j.polymer.2021.124321	journal	November 2021
Rheological properties of linear and crosslinked polymer blends: Relation between crosslink density and enhancement of elongational viscosity Yamaguchi, Masayuki Journal of Polymer Science Part B: Polymer Physics, Vol. 39, Issue 2 https://doi.org/10.1002/1099-0488(20010115)39:2<228::AID-POLB50>3.0.CO;2-Z	journal	January 2000
Self-Healable Silicone Elastomer Based on the Synergistic Effect of the Coordination and Ionic Bonds Yu, Shui; Zuo, Hongli; Xu, Xiaowei ACS Applied Polymer Materials, Vol. 3, Issue 5 https://doi.org/10.1021/acsapm.1c00236	journal	May 2021
Linear Viscoelastic and Dielectric Relaxation Response of Unentangled UPy-Based Supramolecular Networks Shabbir, Aamir; Javakhishvili, Irakli; Cerveny, Silvina Macromolecules, Vol. 49, Issue 10 https://doi.org/10.1021/acs.macromol.6b00122	journal	May 2016
Recyclable 3D printing of vitrimer epoxy Shi, Qian; Yu, Kai; Kuang, Xiao Materials Horizons, Vol. 4, Issue 4 https://doi.org/10.1039/C7MH00043J	journal	January 2017
Influence of Attractive Functional Groups on the Segmental Dynamics and Glass Transition in Associating Polymers Ghosh, Ashesh; Samanta, Subarna; Ge, Sirui Macromolecules, Vol. 55, Issue 6 https://doi.org/10.1021/acs.macromol.2c00080	journal	March 2022
Advances in self-healing supramolecular soft materials and nanocomposites Thangavel, Gurunathan; Tan, Matthew Wei Ming; Lee, Pooi See Nano Convergence, Vol. 6, Issue 1 https://doi.org/10.1186/s40580-019-0199-9	journal	August 2019
Room-temperature autonomous self-healing glassy polymers with hyperbranched structure Wang, Hao; Liu, Hanchao; Cao, Zhenxing Proceedings of the National Academy of Sciences, Vol. 117, Issue 21 https://doi.org/10.1073/pnas.2000001117	journal	May 2020
Strain-insensitive intrinsically stretchable transistors and circuits Wang, Weichen; Wang, Sihong; Rastak, Reza Nature Electronics, Vol. 4, Issue 2 https://doi.org/10.1038/s41928-020-00525-1	journal	January 2021
Nanowire active-matrix circuitry for low-voltage macroscale artificial skin Takei, Kuniharu; Takahashi, Toshitake; Ho, Johnny C. Nature Materials, Vol. 9, Issue 10, p. 821-826 https://doi.org/10.1038/nmat2835	journal	September 2010
Self-Healing Electrode with High Electrical Conductivity and Mechanical Strength for Artificial Electronic Skin Sim, Hyeon Jun; Kim, Hyunsoo; Jang, Yongwoo ACS Applied Materials & Interfaces, Vol. 11, Issue 49 https://doi.org/10.1021/acsami.9b10100	journal	October 2019
“Flex-Activated” Mechanophores: Using Polymer Mechanochemistry To Direct Bond Bending Activation Larsen, Michael B.; Boydston, Andrew J. Journal of the American Chemical Society, Vol. 135, Issue 22 https://doi.org/10.1021/ja403757p	journal	May 2013
Maskless Lithography and in situ Visualization of Conductivity of Graphene using Helium Ion Microscopy Iberi, Vighter; Vlassiouk, Ivan; Zhang, X. -G. Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep11952	journal	July 2015
Synthesis, swelling behavior, and viscoelastic properties of functional poly(hydroxyethyl methacrylate) with ureidopyrimidinone side-groups Lewis, Christopher L.; Anthamatten, Mitchell Soft Matter, Vol. 9, Issue 15 https://doi.org/10.1039/c3sm27735f	journal	January 2013
In-situ visualization of hydrogen evolution sites on helium ion treated molybdenum dichalcogenides under reaction conditions Mitterreiter, Elmar; Liang, Yunchang; Golibrzuch, Matthias npj 2D Materials and Applications, Vol. 3, Issue 1 https://doi.org/10.1038/s41699-019-0107-5	journal	July 2019
Influence of Selectivity on the Supramolecular Polymerization of AB-Type Polymers Capable of Both A·A and A·B Interactions de Greef, Tom F. A.; Ercolani, Gianfranco; Ligthart, G. B. W. L. Journal of the American Chemical Society, Vol. 130, Issue 41 https://doi.org/10.1021/ja8046409	journal	September 2008
Biomimetic Tough Self-Healing Polymers Enhanced by Crystallization Nanostructures Wan, Dong; Jiang, Qingling; Song, Yan ACS Applied Polymer Materials, Vol. 2, Issue 2 https://doi.org/10.1021/acsapm.9b01094	journal	January 2020
Self-healing chemistry enables the stable operation of silicon microparticle anodes for high-energy lithium-ion batteries Wang, Chao; Wu, Hui; Chen, Zheng Nature Chemistry, Vol. 5, Issue 12 https://doi.org/10.1038/nchem.1802	journal	November 2013
Super Stretchable and Compressible Hydrogels Inspired by Hook-and-Loop Fasteners Ding, Fuchuan; Ding, Hao; Shen, Zhiqiang Langmuir, Vol. 37, Issue 25 https://doi.org/10.1021/acs.langmuir.1c00924	journal	June 2021
Optically healable supramolecular polymers Burnworth, Mark; Tang, Liming; Kumpfer, Justin R. Nature, Vol. 472, Issue 7343, p. 334-337 https://doi.org/10.1038/nature09963	journal	April 2011
Demonstration of self-healing barrier films for vacuum insulation panels Biswas, Kaushik; Gilmer, Dustin; Ghezawi, Natasha Vacuum, Vol. 164 https://doi.org/10.1016/j.vacuum.2019.03.006	journal	June 2019
Strong Dimerization of Ureidopyrimidones via Quadruple Hydrogen Bonding Beijer, Felix H.; Sijbesma, Rint P.; Kooijman, Huub Journal of the American Chemical Society, Vol. 120, Issue 27 https://doi.org/10.1021/ja974112a	journal	July 1998
Polymer Design for 3D Printing Elastomers: Recent Advances in Structure, Properties, and Printing Herzberger, Jana; Sirrine, Justin M.; Williams, Christopher B. Progress in Polymer Science, Vol. 97 https://doi.org/10.1016/j.progpolymsci.2019.101144	journal	October 2019
Quadruple hydrogen bonds of ureido-pyrimidinone moieties investigated in the solid state by ¹H double-quantum MAS NMR spectroscopy Schnell, Ingo; Langer, Benedikt; Söntjens, Serge H. M. Physical Chemistry Chemical Physics, Vol. 4, Issue 15, p. 3750-3758 https://doi.org/10.1039/b203333j	journal	July 2002
Mussel-Inspired Cellulose Nanocomposite Tough Hydrogels with Synergistic Self-Healing, Adhesive, and Strain-Sensitive Properties Shao, Changyou; Wang, Meng; Meng, Lei Chemistry of Materials, Vol. 30, Issue 9 https://doi.org/10.1021/acs.chemmater.8b01172	journal	April 2018
Autonomous self-healing optical sensors for damage intelligent soft-bodied systems Bai, Hedan; Kim, Young Seong; Shepherd, Robert F. Science Advances, Vol. 8, Issue 49 https://doi.org/10.1126/sciadv.abq2104	journal	December 2022
Dynamic and reconfigurable materials from reversible network interactions Webber, Matthew J.; Tibbitt, Mark W. Nature Reviews Materials, Vol. 7, Issue 7 https://doi.org/10.1038/s41578-021-00412-x	journal	January 2022
Highly Selective and Tunable CO₂/N₂ Separation Performance in Ammonium-Based Organic Ionic Plastic Crystal Composite Membranes with Self-Healing Properties Ramos-Saz, Fernando; Kang, Colin S. M.; Forsyth, Maria ACS Applied Polymer Materials, Vol. 4, Issue 2 https://doi.org/10.1021/acsapm.1c01838	journal	January 2022
Self-healing polymers based on thermally reversible Diels–Alder chemistry Liu, Ying-Ling; Chuo, Tsai-Wei Polymer Chemistry, Vol. 4, Issue 7 https://doi.org/10.1039/c2py20957h	journal	January 2013
Self-Healing, Fully Functional, and Multiparametric Flexible Sensing Platform Huynh, Tan-Phat; Haick, Hossam Advanced Materials, Vol. 28, Issue 1 https://doi.org/10.1002/adma.201504104	journal	November 2015
Competitive Intramolecular Hydrogen Bonding in Oligo(ethylene oxide) Substituted Quadruple Hydrogen Bonded Systems de Greef, Tom F. A.; Nieuwenhuizen, Marko M. L.; Sijbesma, Rint P. The Journal of Organic Chemistry, Vol. 75, Issue 3 https://doi.org/10.1021/jo902053t	journal	January 2010
Bio-inspired self-healing polyurethanes with multiple stimulus responsiveness Yang, Zhijun; Wang, Fenfen; Zhang, Chi Polymer Chemistry, Vol. 10, Issue 24 https://doi.org/10.1039/C9PY00383E	journal	January 2019
Order–disorder transition in supramolecular polymer combs/brushes with polymeric side chains Golkaram, Milad; Portale, Giuseppe; Mulder, Pascal Polymer Chemistry, Vol. 11, Issue 15 https://doi.org/10.1039/C9PY01915D	journal	January 2020
A self-healable and highly stretchable supercapacitor based on a dual crosslinked polyelectrolyte Huang, Yan; Zhong, Ming; Huang, Yang Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms10310	journal	December 2015
An electrically and mechanically self-healing composite with pressure- and flexion-sensitive properties for electronic skin applications Tee, Benjamin C-K.; Wang, Chao; Allen, Ranulfo Nature Nanotechnology, Vol. 7, Issue 12 https://doi.org/10.1038/nnano.2012.192	journal	November 2012
Closed-loop additive manufacturing of upcycled commodity plastic through dynamic cross-linking Kim, Sungjin; Rahman, Md Anisur; Arifuzzaman, Md Science Advances, Vol. 8, Issue 22 https://doi.org/10.1126/sciadv.abn6006	journal	June 2022
Self-Healing Materials Based on Disulfide Links Canadell, Judit; Goossens, Han; Klumperman, Bert Macromolecules, Vol. 44, Issue 8 https://doi.org/10.1021/ma2001492	journal	April 2011
Intrinsic self-healing polymers with a high E-modulus based on dynamic reversible urea bonds Zechel, Stefan; Geitner, Robert; Abend, Marcus NPG Asia Materials, Vol. 9, Issue 8 https://doi.org/10.1038/am.2017.125	journal	August 2017
Self-Healing Coatings Containing Core–Shell Nanofibers with pH-Responsive Performance Wang, Qi; Wang, Wei; Ji, Xiaohong ACS Applied Materials & Interfaces, Vol. 13, Issue 2 https://doi.org/10.1021/acsami.0c18933	journal	January 2021
Self-healing and thermoreversible rubber from supramolecular assembly Cordier, Philippe; Tournilhac, François; Soulié-Ziakovic, Corinne Nature, Vol. 451, Issue 7181, p. 977-980 https://doi.org/10.1038/nature06669	journal	February 2008
Self-Healing of Unentangled Polymer Networks with Reversible Bonds Stukalin, Evgeny B.; Cai, Li-Heng; Kumar, N. Arun Macromolecules, Vol. 46, Issue 18 https://doi.org/10.1021/ma401111n	journal	September 2013
Shape memory effects in self-healing polymers Hornat, Chris C.; Urban, Marek W. Progress in Polymer Science, Vol. 102 https://doi.org/10.1016/j.progpolymsci.2020.101208	journal	March 2020
Artificially innervated self-healing foams as synthetic piezo-impedance sensor skins Guo, Hongchen; Tan, Yu Jun; Chen, Ge Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-19531-0	journal	November 2020
Estimating the Hydrogen Bond Energy Wendler, Katharina; Thar, Jens; Zahn, Stefan The Journal of Physical Chemistry A, Vol. 114, Issue 35 https://doi.org/10.1021/jp103470e	journal	August 2010
Advances in intrinsic self-healing polyurethanes and related composites Willocq, Bertrand; Odent, Jérémy; Dubois, Philippe RSC Advances, Vol. 10, Issue 23 https://doi.org/10.1039/D0RA01394C	journal	January 2020
Highly stretchable, self-adhesive, biocompatible, conductive hydrogels as fully polymeric strain sensors Zhang, Dong; Tang, Yijing; Zhang, Yanxian Journal of Materials Chemistry A, Vol. 8, Issue 39 https://doi.org/10.1039/D0TA07390C	journal	January 2020
Self-healing, highly elastic and amphiphilic silicone-based polyurethane for antifouling coatings Lin, Xiaobin; Xie, Qingyi; Ma, Chunfeng Journal of Materials Chemistry B, Vol. 9, Issue 5 https://doi.org/10.1039/D0TB02465A	journal	January 2021
Dynamic urea bond for the design of reversible and self-healing polymers Ying, Hanze; Zhang, Yanfeng; Cheng, Jianjun Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4218	journal	February 2014
Photoinduced Smart, Self-Healing Polymer Sealant for Photovoltaics Banerjee, Sanjib; Tripathy, Ranjan; Cozzens, David ACS Applied Materials & Interfaces, Vol. 7, Issue 3 https://doi.org/10.1021/am508096c	journal	January 2015
Stress Relaxation, Dynamics, and Plasticity of Transient Polymer Networks Meng, Fanlong; Pritchard, Robyn H.; Terentjev, Eugene M. Macromolecules, Vol. 49, Issue 7 https://doi.org/10.1021/acs.macromol.5b02667	journal	March 2016
An ultrafast self-healing polydimethylsiloxane elastomer with persistent sealing performance Wang, Da-Peng; Zhao, Zi-Han; Li, Cheng-Hui Materials Chemistry Frontiers, Vol. 3, Issue 7 https://doi.org/10.1039/C9QM00115H	journal	January 2019
Self-Healing and Recyclable Hydrogels Reinforced with in Situ-Formed Organic Nanofibrils Exhibit Simultaneously Enhanced Mechanical Strength and Stretchability Yuan, Tao; Qu, Xinxin; Cui, Xinming ACS Applied Materials & Interfaces, Vol. 11, Issue 35 https://doi.org/10.1021/acsami.9b08208	journal	August 2019
Mechanically robust, readily repairable polymers via tailored noncovalent cross-linking Yanagisawa, Yu; Nan, Yiling; Okuro, Kou Science, Vol. 359, Issue 6371 https://doi.org/10.1126/science.aam7588	journal	December 2017
Intrinsically Self-Healing Polymers: From Mechanistic Insight to Current Challenges Li, Bingrui; Cao, Peng-Fei; Saito, Tomonori Chemical Reviews, Vol. 123, Issue 2 https://doi.org/10.1021/acs.chemrev.2c00575	journal	December 2022

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36 MATERIALS SCIENCE
Self-healing
Elastomer
Tunable mechanical properties
Hydrogen bonding
3d printing

Title: Well-Tunable, 3D-printable, and Fast Autonomous Self-Healing Elastomers

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