Abstract
The development of self-healing polymeric materials was inspired by biological systems wherein damage initiates an autonomic healing response and can automatically repair the internal cracks/ damages without the need for external intervention. This is a new and fascinating field of research that has the potential to improve service life of the materials. These have attracted the attention of many scientists/researchers due to their wide range of applications. The self-healing materials have been broadly classified in to two categories: (1) extrinsic self-healing materials, wherein, the repairing agent is pre-embedded in to the resin matrix and no human involvement is needed to start the healing process, and (2) intrinsic self-healing materials, which do not have an embedded healing agent and an external-stimuli is essential to initiate the healing process. The current review article summarizes a state-of-art in terms of self-healing ability of the polymeric materials. It also provides comprehensive comparison of healing efficiencies, advantages and challenges for the future development, and potential applications of such materials in numerous fields, such as aerospace, coatings and paints, electronics energy, etc.
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References
van Benthem RATM, Ming W (Marshall), de With G (eds) (2007) (Bert) Self Healing Polymer Coatings. In: Springer Series in Materials Science. pp 139–159
Dry C (1996) Procedures developed for self-repair of polymer matrix composite materials. Compos Struct 35:263–269. https://doi.org/10.1016/0263-8223(96)00033-5
Chen Y, Kushner AM, Williams GA, Guan Z (2012) Multiphase design of autonomic self-healing thermoplastic elastomers. Nat Chem 4:467–472. https://doi.org/10.1038/nchem.1314
Zhang Y, Yu Y, Zhao X et al (2021) A high strength but fast fracture-self-healing thermoplastic elastomer. Macromol Rapid Commun 42:1–6. https://doi.org/10.1002/marc.202100135
Yu K, Xin A, Feng Z et al (2020) Mechanics of self-healing thermoplastic elastomers. J Mech Phys Solids 137. https://doi.org/10.1016/j.jmps.2019.103831
Jones AR, Watkins CA, White SR, Sottos NR (2015) Self-healing thermoplastic-toughened epoxy. Polym (Guildf) 74:254–261. https://doi.org/10.1016/j.polymer.2015.07.028
Subramanian V, Varade D (2017) Self-healed materials from thermoplastic polymer composites. 153–180. https://doi.org/10.1007/978-3-319-50424-7_6
Eom Y, Kim SM, Lee M et al (2021) Mechano-responsive hydrogen-bonding array of thermoplastic polyurethane elastomer captures both strength and self-healing. Nat Commun 12:1–11. https://doi.org/10.1038/s41467-021-20931-z
Zhu DY, Wetzel B, Noll A et al (2013) Thermo-molded self-healing thermoplastics containing multilayer microreactors. J Mater Chem A 1:7191–7198. https://doi.org/10.1039/c3ta11008g
Wang HP, Yuan YC, Rong MZ, Zhang MQ (2010) Self-healing of thermoplastics via living polymerization. Macromolecules 43:595–598. https://doi.org/10.1021/ma902021v
Karami Z, Zolghadr M, Zohuriaan-Mehr MJ (2020) Self-healing diels–alder engineered thermosets. Self-Healing polymer-based Systems. INC, pp 209–233
Li G, Meng H (2015) Overview of crack self-healing. In: Recent advances in smart self-healing polymers and composites, pp 1–19
Kahar NNFNMN, Osman AF, Alosime E et al (2021) The versatility of polymeric materials as self-healing agents for various types of applications: a review. Polym (Basel) 13:1–34. https://doi.org/10.3390/polym13081194
Radl S, Kreimer M, Griesser T et al (2015) New strategies towards reversible and mendable epoxy based materials employing [4πs + 4πs] photocycloaddition and thermal cycloreversion of pendant anthracene groups. Polym (Guildf) 80:76–87. https://doi.org/10.1016/j.polymer.2015.10.043
Yuan D, Solouki Bonab V, Patel A, Yilmaz T, Gross RA, Manas-Zloczower I (2020) Design strategy for self‐healing epoxy coatings.pdf. Coatings 10
Du Y, Li D, Liu L, Gai G (2018) Recent achievements of self-healing graphene/polymer composites. Polym (Basel) 10. https://doi.org/10.3390/polym10020114
Lin C, Ge H, Wang T et al (2020) A self-healing and recyclable polyurethane/halloysite nanocomposite based on thermoreversible Diels-Alder reaction. Polym (Guildf) 206:122894. https://doi.org/10.1016/j.polymer.2020.122894
Yuan YC, Ye XJ, Rong MZ et al (2011) Self-healing epoxy composite with heat-resistant healant. ACS Appl Mater Interfaces 3:4487–4495. https://doi.org/10.1021/am201182j
Lee JY, Buxton GA, Balazs AC et al (2014) Using nanoparticles to create self-healing composites Using nanoparticles to create self-healing composites. 5531. https://doi.org/10.1063/1.1784432
Frei R, McWilliam R, Derrick B et al (2013) Self-healing and self-repairing technologies. Int J Adv Manuf Technol 69:1033–1061. https://doi.org/10.1007/s00170-013-5070-2
Gurumurthy BM, Shivaprakash YM, Hiremath A et al (2016) Self healing materials: a new era in material technology: a review. Int J Appl Eng Res 11:1373–1378
Zwaag SV, Der, Grande AM, Post W et al (2014) Review of current strategies to induce self-healing behaviour in fibre reinforced polymer based composites. 30:1633–1641. https://doi.org/10.1179/1743284714Y.0000000624
Urdl K, Kandelbauer A, Kern W et al (2017) Self-healing of densely crosslinked thermoset polymers—a critical review. Prog Org Coatings 104:232–249. https://doi.org/10.1016/j.porgcoat.2016.11.010
Hu H, Zhang L, Zhang Y et al (2020) Microencapsulation of tris(dimethylaminomethyl)phenol using polystyrene shell for self-healing materials. Sci Rep 10:1–14. https://doi.org/10.1038/s41598-020-69168-8
Kessler MR, White SR (2001) Self-activated healing of delamination damage in woven composites. Compos Part A Appl Sci Manuf 32:683–699
Brown EN, White SR, Sottos NR (2004) Microcapsule induced toughening in a self-healing polymer composite. J Mater Sci 39:1703–1710. https://doi.org/10.1023/B:JMSC.0000016173.73733.dc
White SR, Sottos NR, Geubelle PH et al (2002) Erratum: correction: autonomic healing of polymer composites. Nature 415:817–817. https://doi.org/10.1038/415817a
Lee JK, Hong SJ, Liu X (2004) Characterization of dicyclopentadiene and 5-ethylidene-2-norbornene as self-healing agents for polymer composite and its microcapsules. 12:478–483
Thakur T, Gaur B, Singha AS (2021) Bio-based epoxy/imidoamine encapsulated microcapsules and their application for high performance self-healing coatings. Prog Org Coatings 159:106436. https://doi.org/10.1016/j.porgcoat.2021.106436
Rodriguez R, Bekas DG, Flórez S et al (2020) Development of self-contained microcapsules for optimised catalyst position in self-healing materials. Polym (Guildf) 187:122084. https://doi.org/10.1016/j.polymer.2019.122084
Tang H, Fang ZP (2008) Preparation of glass fiber-supported platinum complex catalyst for hydrosilylation reactions. 9:1092–1095. https://doi.org/10.1016/j.catcom.2007.10.017
Cho SH, Andersson HM, White SR et al (2006) Polydiniethylsiloxane-based self-healing materials. Adv Mater 18:997–1000. https://doi.org/10.1002/adma.200501814
Ullah H, Azizli K, Man ZB, Ismail MBC (2016) Synthesis and characterization of urea-formaldehyde Microcapsules containing functionalized polydimethylsiloxanes. Procedia Eng 148:168–175. https://doi.org/10.1016/j.proeng.2016.06.519
Dohler D, Michael P, Binder W (2013) Part one design of self-healing materials. In: Self-healing polymers: from principles to applications, pp 5–60
Wang R, Hu H, Liu W, Guo Q (2011) Preparation and characterization of self-healing polymeric materials with microencapsulated epoxy and imidazoline derivatives curing agent. 19:279–288. https://doi.org/10.1177/0967391111019004-505
Yuan YC, Rong MZ, Zhang MQ et al (2008) Self-healing polymeric materials using epoxy / mercaptan as the healant. 5197–5202
Jin H, Mangun CL, Stradley DS et al (2012) Self-healing thermoset using encapsulated epoxy-amine healing chemistry. Polym (Guildf) 1–7. https://doi.org/10.1016/j.polymer.2011.12.005
Blaiszik BJ, Caruso MM, Mcilroy DA et al (2009) Microcapsules filled with reactive solutions for self-healing materials. Polym (Guildf) 50:990–997. https://doi.org/10.1016/j.polymer.2008.12.040
Song Y, Jo Y, Lim Y et al (2013) Sunlight-Induced Self-Healing of a Microcapsule-Type Protective Coating. ACS Appl Mater Interfaces 5:1378–1384
Trask RS, Williams GJ, Bond IP et al (2007) Bioinspired self-healing of advanced composite structures using hollow glass fibres Bioinspired self-healing of advanced composite structures using hollow glass fibres. 363–371. https://doi.org/10.1098/rsif.2006.0194
Dry CM, Sottos NR (1993) Passive smart self-repair in polymer matrix composite materials — University of Illinois Urbana-Champaign. Proc SPIE - Int Soc Opt Eng 1916:438–444
Toohey KS, Sottos NR, Lewis JA et al (2007) Self-healing materials with microvascular networks. 581–585. https://doi.org/10.1038/nmat1934
Toohey BKS, Hansen CJ, Lewis JA et al (2009) Delivery of two-part self-healing chemistry via microvascular networks.1399–1405. https://doi.org/10.1002/adfm.200801824
Hansen BCJ, Wu W, Toohey KS et al (2009) Self-healing materials with interpenetrating microvascular networks. 4143–4147. https://doi.org/10.1002/adma.200900588
Hansen CJ, White SR, Sottos NR, Lewis JA (2011) Accelerated self-healing via ternary interpenetrating microvascular networks. 4320–4326. https://doi.org/10.1002/adfm.201101553
Postiglione G, Alberini M, Leigh SJ et al (2017) Effect of 3D-printed microvascular network design on the self-healing behaviour of crosslinked polymers. https://doi.org/10.1021/acsami.7b01830
Hamilton BAR, Sottos NR, White SR (2010) Self-healing of internal damage in synthetic vascular materials. 61801:5159–5163. https://doi.org/10.1002/adma.201002561
Trask RS, Norris CJ, Bond IP (2014) Stimuli-triggered self-healing functionality in advanced fibre-reinforced composites. 25:87–97. https://doi.org/10.1177/1045389X13505006
Bekas DG, Baltzis D, Paipetis AS (2017) Nano-reinforced polymeric healing agents for vascular self-repairing composites. JMADE 116:538–544. https://doi.org/10.1016/j.matdes.2016.12.049
Zhu Y, Ji X, Zhi M, Qiu M (2016) Self-healing glass fi ber / epoxy composites with polypropylene tubes containing self-pressurized epoxy and mercaptan healing agents. Compos Sci Technol 135:146–152. https://doi.org/10.1016/j.compscitech.2016.09.020
Al-maadeed PPV MASA (2016) TiO 2 nanotubes and mesoporous silica as containers in self-healing epoxy coatings. Nat Publ Gr 1–9. https://doi.org/10.1038/srep38812
Bleay SM, Loader CB, Hawyes VJ et al (2001) A smart repair system for polymer matrix composites. Compos Part A Appl Sci Manuf 32:1767–1776. https://doi.org/10.1016/S1359-835X(01)00020-3
Williams G, Trask R, Bond I (2007) A self-healing carbon fibre reinforced polymer for aerospace applications. Compos Part A Appl Sci Manuf 38:1525–1532. https://doi.org/10.1016/j.compositesa.2007.01.013
Pang JWC, Bond IP (2005) ‘ Bleeding composites ’— damage detection and self-repair using a biomimetic approach. 36:183–188. https://doi.org/10.1016/j.compositesa.2004.06.016
Silva ACM, Moghadam AD, Singh P, Rohatgi PK (2017) Self-healing composite coatings based on in situ micro–nanoencapsulation process for corrosion protection. J Coat Technol Res 1–29. https://doi.org/10.1007/s11998-016-9879-0
Nevejans S, Ballard N, Miranda JI et al (2016) The underlying mechanisms for self-healing of poly(disulfide)s. Phys Chem Chem Phys 18:27577–27583. https://doi.org/10.1039/c6cp04028d
Garcia SJ (2014) Effect of polymer architecture on the intrinsic self-healing character of polymers. Eur Polym J 53:118–125. https://doi.org/10.1016/j.eurpolymj.2014.01.026
Zhou J, Guimard NK, Inglis AJ et al (2012) Thermally reversible Diels-Alder-based polymerization: an experimental and theoretical assessment. Polym Chem 3:628–639. https://doi.org/10.1039/c1py00356a
Pratama PA, Shari M, Peterson AM, Palmese GR (2013) Room temperature self-healing Thermoset based on the Diels – AlderAm403459E.Pdf. ACS Appl Mater Interfaces 12425–12431
Chen X, Dam MA, Ono K et al (2002) A thermally re-mendable cross-linked polymeric material. Sci (80-) 295:1698–1702. https://doi.org/10.1126/science.1065879
Scheltjens G, Diaz MM, Brancart J et al (2013) A self-healing polymer network based on reversible covalent bonding. React Funct Polym 73:413–420. https://doi.org/10.1016/j.reactfunctpolym.2012.06.017
Turkenburg DH, Durant Y, Fischer HR (2017) Bio-based self-healing coatings based on thermo-reversible Diels-Alder reaction. Prog Org Coatings 111:38–46. https://doi.org/10.1016/j.porgcoat.2017.05.006
Coope TS, Turkenburg DH, Fischer HR et al (2016) Novel Diels-Alder based self-healing epoxies for aerospace composites. Smart materials and structures. Springer, Singapore, Singapore, pp 15–39
Toncelli C, De Reus DC, Picchioni F, Broekhuis AA (2012) Properties of reversible diels-alder furan/maleimide polymer networks as function of crosslink density. Macromol Chem Phys 213:157–165. https://doi.org/10.1002/macp.201100405
Liu Y, Hsieh C (2005) Crosslinked epoxy materials exhibiting thermal remendablility and removability from multifunctional maleimide and furan compounds. 905–913. https://doi.org/10.1002/pola.21184
Tian Q, Yuan C, Rong Z, Qiu M (2009) A thermally remendable epoxy resin. 1289–1296. https://doi.org/10.1039/b811938d
Parihar S, Gaur B (2022) Thermo-reversible self-healing polymeric coatings derived from gum rosin. Prog Org Coatings 168:106889. https://doi.org/10.1016/j.porgcoat.2022.106889
Liu Y, Chen Y (2007) Thermally reversible cross-linked polyamides with high toughness and self-repairing ability from maleimide- and furan-functionalized aromatic polyamides. 224–232. https://doi.org/10.1002/macp.200600445
Kavitha AA, Singha NK (2007) A tailor-made polymethacrylate bearing a reactive diene in reversible diels – alder reaction. 4441–4449. https://doi.org/10.1002/pola
Peterson AM, Jensen RE, Palmese GR (2011) Thermoreversible and remendable glass-polymer interface for fiber-reinforced composites. Compos Sci Technol 71:586–592. https://doi.org/10.1016/j.compscitech.2010.11.022
Du P, Liu X, Zheng Z et al (2013) Synthesis and characterization of linear self-healing polyurethane based on thermally reversible Diels-Alder reaction. RSC Adv 3:15475–15482. https://doi.org/10.1039/c3ra42278j
Zeng C, Seino H, Ren J et al (2013) Bio-based furan polymers with self-healing ability. Polym (Guildf) 54:5351–5357. https://doi.org/10.1016/j.polymer.2013.07.059
Bai N, Simon GP, Saito K (2015) Characterisation of the thermal self-healing of a high crosslink density epoxy thermoset. New J Chem 39:3497–3506. https://doi.org/10.1039/c5nj00066a
Okhay N, Mignard N, Jegat C, Taha M (2013) Diels-Alder thermoresponsive networks based on high maleimide- functionalized urethane prepolymers. Des Monomers Polym 16:475–487. https://doi.org/10.1080/15685551.2012.747166
Xu M, Liu N, Mo H et al (2022) Synthesis and properties of thermally self-healing PET based Linear polyurethane containing diels–alder bonds. Polym (Basel) 14:1–13. https://doi.org/10.3390/polym14163334
Lee WJ, Cha SH (2020) Improvement of mechanical and self-healing properties for polymethacrylate derivatives containing maleimide modified graphene oxide. Polym (Basel) 12. https://doi.org/10.3390/polym12030603
Canadell J, Goossens H, Klumperman B (2011) Self-healing materials based on disulfide links. Macromolecules 44:2536–2541. https://doi.org/10.1021/ma2001492
Xu Y, Chen D (2016) A novel self-healing polyurethane based on disulfide bonds. Macromol Chem Phys 217:1191–1196. https://doi.org/10.1002/macp.201600011
Ortiz RA, Berlanga OA, Valdez AEG et al (2016) Self-healing photocurable epoxy/thiol-ene systems using an aromatic epoxy resin. Adv Mater Sci Eng. https://doi.org/10.1155/2016/8245972
Li ZJ, Zhong J, Liu MC et al (2020) Investigation on self-healing property of epoxy resins based on disulfide dynamic links. Chin J Polym Sci (English Ed) 38:932–940. https://doi.org/10.1007/s10118-020-2406-x
Chang K, Jia H, Gu S (2019) A transparent, highly stretchable, self-healing polyurethane based on disul fi de bonds. Eur Polym J 112:822–831. https://doi.org/10.1016/j.eurpolymj.2018.11.005
Yoon JA, Kamada J, Koynov K et al (2012) Self-healing polymer films based on thiol-disulfide exchange reactions and self-healing kinetics measured using atomic force microscopy. Macromolecules 45:142–149. https://doi.org/10.1021/ma2015134
Zhang L, Qiu T, Sun X et al (2020) Achievement of both mechanical properties and intrinsic self-healing under body temperature in polyurethane elastomers: a synthesis strategy from waterborne polymers. Polym (Basel) 12. https://doi.org/10.3390/POLYM12040989
Huang Y, Yan J, Wang D et al (2021) Construction of self-healing disulfide-linked silicone elastomers by thiol oxidation coupling reaction. Polym (Basel) 13. https://doi.org/10.3390/polym13213729
Chung CM, Roh YS, Cho SY, Kim JG (2004) Crack healing in polymeric materials via photochemical [2 + 2] cycloaddition. Chem Mater 16:3982–3984. https://doi.org/10.1021/cm049394+
Ghosh B, Urban MW (2009) Self-repairing oxetane-substituted chitosan polyurethane networks. Science 323(5920):1458–1460. https://doi.org/10.1126/science.1167391
Froimowicz P, Frey H, Landfester K Towards the generation of self-healing materials by means of a reversible photo-induced approach. https://doi.org/10.1002/marc.201000643
Ling J, Rong MZ, Zhang MQ (2011) Coumarin imparts repeated photochemical remendability to polyurethane. J Mater Chem 14473–14486. https://doi.org/10.1039/c1jm12321a
Dong R, Liu Y, Zhou Y, Yan D, Zhu X (2011) Photo-reversible supramolecular hyperbranched polymer based on host–guest interactions. Polym Chem 2771–2774. https://doi.org/10.1039/c1py00426c
Nishikubo T, Kudo H, Maruyama K (2009) Synthesis and properties of photo-functional hyperbranched polymers. 1–7. https://doi.org/10.1002/pat.1377
Banerjee S, Tripathy R, Cozzens D et al (2015) Photoinduced smart, self-healing polymer sealant for photovoltaics. https://doi.org/10.1021/am508096c
Scott BTF, Draughon RB, Bowman CN (2006) Actuation in crosslinked polymers via photoinduced stress relaxation . 2128–2132. https://doi.org/10.1002/adma.200600379
Ahn D, Zavada SR, Scott TF (2017) Rapid, Photomediated Healing of Hexaarylbiimidazole-Based covalently cross-linked gels. Chem Mater 29:7023–7031. https://doi.org/10.1021/acs.chemmater.7b02640
Leibler L, Cordier P, Soulie C (2008) Self-healing and thermoreversible rubber from supramolecular assembly. 451:977–980. https://doi.org/10.1038/nature06669
Wang C, Liu N, Allen R et al (2013) Communication A rapid and efficient self-healing thermo-reversible elastomer crosslinked with graphene oxide. 5785–5790. https://doi.org/10.1002/adma.201302962
Zeng F, Han Y, Yan Z et al (2013) Supramolecular polymer gel with multi stimuli responsive, self- healing and erasable properties generated by host e guest interactions. Polym (Guildf) 54:6929–6935. https://doi.org/10.1016/j.polymer.2013.10.048
Huang L, Yi N, Wu Y et al (2013) Multichannel and repeatable self-healing of mechanical enhanced graphene-thermoplastic polyurethane composites. 2224–2228. https://doi.org/10.1002/adma.201204768
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The authors are grateful to Ministry of Human Resource Development (MHRD), India as well as the National Institute of Technology Hamirpur, Himachal Pradesh, India, for funding the research.
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Parihar, S., Gaur, B. Self healing approaches in polymeric materials-an overview. J Polym Res 30, 217 (2023). https://doi.org/10.1007/s10965-023-03590-0
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DOI: https://doi.org/10.1007/s10965-023-03590-0