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A thermally remendable multiwalled carbon nanotube/epoxy composites via Diels-Alder bonding

  • Junali Handique
  • Swapan Kumar DoluiEmail author
ORIGINAL PAPER
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Abstract

Mechanically robust and self-healing epoxy composites are highly desired to satisfy the increasing demand of high-performance smart materials. Herein, a dual functionalized epoxy composite (EpF-MWCNT-PA-BM) with self-healing performance based on Diels-Alder chemistry has been investigated. The furfuryl grafted epoxy (EpF) and furfuryl modified MWCNTs (MWCNT-F) are reacted with bifunctional maleimide (BM) and normal anhydride curing agent (PA) to form a covalently bonded and reversibly crosslinked epoxy composite with two types of intermonomer linkage. That is, thermally reversible Diels-alder bonds between the furan groups of both epoxy and MWNCTs with malemide and thermally stable bonds of epoxide and anhydride groups. MWCNTs act as both reinforcer and a healant in the epoxy composite. In this way, the cured epoxy composite possessed not only enhanced mechanical properties but also thermal remendability that enabled elimination of cracks. The latter function took effect as a result of successive retro-DA and DA reactions, which led to crack healing upto 79.82% healing efficiency in a controlled manner through chain reconnection.

Keywords

Epoxy Multiwalled carbon nanotubes Diels-Alder ATRP Self-healing 

Notes

Acknowledgements

This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors.

Supplementary material

10965_2019_1804_MOESM1_ESM.docx (1.7 mb)
ESM 1 (DOCX 1691 kb)

References

  1. 1.
    White SR, Sottos NR, Geubelle PH, Moore JS, Kessler MR, Sriram SR, Brown EN, Viswanathan S (2001) Autonomic healing of polymer composites. Nature 409:794–797CrossRefGoogle Scholar
  2. 2.
    Ghosh B, Urban MW (2009) Self-repairing oxetane-substituted chitosan polyurethane networks. Science 323:1458–1460CrossRefGoogle Scholar
  3. 3.
    Cordier P, Tournilhac F, Soulie-Ziakovic C, Leibler L (2008) Self-healing and thermoreversible rubber from supramolecular assembly. Nature 451:977–980CrossRefGoogle Scholar
  4. 4.
    Pathak AK, Garg H, Singh M, Yokozeki T, Dhakate SR (2019) Enhanced interfacial properties of graphene oxide incorporated carbon fiber reinforced epoxy nanocomposite: a systematic thermal properties investigation. J Polym Res 26:23CrossRefGoogle Scholar
  5. 5.
    Haase MF, Grigoriev DO, Mohwald H, Shchukin DG (2012) Development of nanoparticle stabilized polymer Nanocontainers with high content of the encapsulated active agent and their application in water-borne anticorrosive coatings. Adv Mater 24:2429–2435CrossRefGoogle Scholar
  6. 6.
    Wu G, An JL, Tang XZ, Yang JL, Xiang YA (2014) A versatile approach towards multifunctional robust microcapsules with tunable, restorable, and solvent-proof Superhydrophobicity for self-healing and self-cleaning coatings. Adv Funct Mater 24:6751–6761CrossRefGoogle Scholar
  7. 7.
    Yuan YC, Ye XJ, Rong MZ, Zhang MQ, Yang GC, Zhao JQ (2011) Self-healing epoxy composite with heat-resistant healant. ACS Appl Mater Interfaces 3:4487–4495CrossRefGoogle Scholar
  8. 8.
    Tang XL, Zhou Y, Peng M (2016) Green preparation of epoxy/graphene oxide nanocomposites using a glycidylamine epoxy resin as the surface modifier and phase transfer agent of graphene oxide. ACS Appl Mater Interfaces 8:1854–1866CrossRefGoogle Scholar
  9. 9.
    Jin HH, Mangun CL, Stradley DS, Moore JS, Sottos NR, White SR (2012) Self-healing thermoset using encapsulated epoxy-amine healing chemistry. Polymer 53:581–587CrossRefGoogle Scholar
  10. 10.
    Hillewaere XKD, Teixeira RFA, Nguyen LT, Ramos JA, Rahier H, Du Prez FE (2014) Autonomous self-healing of epoxy thermosets with thiol-isocyanate chemistry. Adv Funct Mater 24:5575–5583CrossRefGoogle Scholar
  11. 11.
    Gao L, He J, Hu J, Wang C (2015) Photoresponsive self-healing polymer composite with photoabsorbing hybrid microcapsules. ACS Appl Mater Interfaces 7:25546–25552CrossRefGoogle Scholar
  12. 12.
    Guo W, Jia Y, Tian K, Xu Z, Jiao J, Li R, Wu Y, Cao L, Wang H (2016) UV-triggered self-healing of a single robust SiO2 microcapsule based on cationic polymerization for potential application in aerospace coatings. ACS Appl Mater Interfaces 8:21046–21054CrossRefGoogle Scholar
  13. 13.
    Luterbacher R, Trask RS, Bond IP (2016) Static and fatigue tensile properties of cross-ply laminates containing vascules for self-healing applications. Smart Mater Struct 25:015003CrossRefGoogle Scholar
  14. 14.
    Hart KR, Sottos NR, White SR (2015) Repeatable self-healing of an epoxy matrix using imidazole initiated polymerization. Polymer 67:174–184CrossRefGoogle Scholar
  15. 15.
    Ghazi A, Ghasemi E, Mahdavian M, Ramezanzadeh B, Rostami M (2015) The application of benzimidazole and zinc cations intercalated sodium montmorillonite as smart ion exchange inhibiting pigments in the epoxy ester coating. Corros Sci 94:207–217CrossRefGoogle Scholar
  16. 16.
    Altuna FI, Pettarin V, Williams RJJ (2013) Self-healable polymer networks based on the cross-linking of epoxidised soybean oil by an aqueous citric acid solution. Green Chem 15:3360–3366CrossRefGoogle Scholar
  17. 17.
    Long R, Qi HJ, Dunn ML (2013) Modeling the mechanics of covalently adaptable polymer networks with temperature-dependent bond exchange reactions. Soft Matter 9:4083–4096CrossRefGoogle Scholar
  18. 18.
    Lafont U, Van Zeijl H, Van der Zwaag S (2012) Influence of cross-linkers on the cohesive and adhesive self-healing ability of polysulfide-based thermosets. ACS Appl Mater Interfaces 4:6280–6288CrossRefGoogle Scholar
  19. 19.
    Hernandez M, Grande AM, Dierkes W, Bijleveld J, Van der Zwaag S, Garcia SJ (2016) Turning vulcanized natural rubber into a self-healing polymer: effect of the disulfide/polysulfide ratio. ACS Sustain Chem Eng 4:5776–5784CrossRefGoogle Scholar
  20. 20.
    Lei ZQ, Xiang HP, Yuan YJ, Rong MZ, Zhang MQ (2014) Room-temperature self-healable and remoldable cross-linked polymer based on the dynamic exchange of disulfide bonds. Chem Mater 26:2038–2046CrossRefGoogle Scholar
  21. 21.
    Nguyen LTT, Nguyen HT, Truong TT (2015) Thermally mendable material based on a furyl-telechelic semicrystalline polymer and a maleimide crosslinker. J Polym Res 22:186CrossRefGoogle Scholar
  22. 22.
    Chen XX, Dam MA, Ono K, Mal A, Shen HB, Nutt SR, Sheran K, Wudl FA (2002) A thermally re-mendable cross-linked polymeric material. Science 295:1698–1702CrossRefGoogle Scholar
  23. 23.
    Chen XX, Wudl F, Mal AK, Shen HB, Nutt SR (2003) New thermally remendable highly cross-linked polymeric materials. Macromolecules 36:1802–1807CrossRefGoogle Scholar
  24. 24.
    Liu YL, Hsieh CY (2006) Crosslinked epoxy materials exhibiting thermal remendablility and removability from multifunctional maleimide and furan compounds. J Polym Sci Part A: Polym Chem 44:905–913CrossRefGoogle Scholar
  25. 25.
    Tian Q, Yuan YC, Rong MZ, Zhang MQ (2009) A thermally remendable epoxy resin. J Mater Chem 19:1289–1296CrossRefGoogle Scholar
  26. 26.
    Tian Q, Rong MZ, Zhang MQ, Yuan YC (2010) Synthesis and characterization of epoxy with improved thermal remendability based on Diels-Alder reaction. Polym Int 59:1339–1345CrossRefGoogle Scholar
  27. 27.
    Bai N, Simon GP, Saito K (2013) Investigation of the thermal self-healing mechanism in a cross-linked epoxy system. RSC Adv 3:20699–20707CrossRefGoogle Scholar
  28. 28.
    Bai N, Saito K, Simon GP (2013) Synthesis of a diamine cross-linker containing Diels–Alder adducts to produce self-healing thermosetting epoxy polymer from a widely used epoxy monomer. Polym Chem 4:724–730CrossRefGoogle Scholar
  29. 29.
    Kuang X, Liu GM, Dong X, Liu XXG, Xu JJ, Wang DJ (2015) Facile fabrication of fast recyclable and multiple self-healing epoxy materials through diels-alder adduct cross-linker. J Polym Sci Part A: Polym Chem 53:2094–2103CrossRefGoogle Scholar
  30. 30.
    Turkenburg DH, Fischer HR (2015) Diels-Alder based, thermo-reversible cross-linked epoxies for use in self-healing composites. Polymer 79:187–194CrossRefGoogle Scholar
  31. 31.
    Guo YK, Li H, Zhao PX, Wang XF, Astruc D, Shuai MB (2017) Thermo-reversible MWCNTs/epoxy polymer for use in self-healing and recyclable epoxy adhesive. Chin J Polym Sci 35:728–738CrossRefGoogle Scholar
  32. 32.
    Rivero G, Nguyen LTT, Hillewaere XK, Du Prez FE (2014) One-pot thermo-remendable shape memory polyurethanes. Macromolecules 47:2010–2018CrossRefGoogle Scholar
  33. 33.
    Heo Y, Sodano HA (2014) Self-healing polyurethanes with shape recovery. Adv Funct Mater 24:5261–5268CrossRefGoogle Scholar
  34. 34.
    Zeng C, Seino H, Ren J, Hatanaka K, Yoshie N (2013) Bio-based furan polymers with self-healing ability. Macromolecules 46:1794–1802CrossRefGoogle Scholar
  35. 35.
    Barthel MJ, Rudolph T, Teichler A, Paulus RM, Vitz J, Hoeppener S, Schubert US (2013) Self-healing materials via reversible crosslinking of poly (ethylene oxide)-block-poly (furfuryl glycidyl ether)(peo-b-pfge) block copolymer films. Adv Funct Mater 23:4921–4932CrossRefGoogle Scholar
  36. 36.
    Liu YL, Chen YW (2007) Thermally-reversible cross-linked polyamides with high toughness and self-repairing ability from maleimide- and furan-functionalized aromatic polyamides. Macromol Chem Phys 208:224–232CrossRefGoogle Scholar
  37. 37.
    Zhang JJ, Niu Y, Huang CL, Xiao LP, Chen ZT, Yang KK, Wang YZ (2012) Self-healable and recyclable triple-shape PPDO-PTMEG co-network constructed through Thermoreversible Diels-Alder reaction. Polym Chem 3:1390–1393CrossRefGoogle Scholar
  38. 38.
    Yang S, Chen JS, Korner H, Breiner T, Ober CK (1998) Reworkable epoxies: thermosets with thermally cleavable groups for controlled network breakdown. Chem Mater 10:1475–1482CrossRefGoogle Scholar
  39. 39.
    Chen JS, Ober CK, Poliks MD (2002) Characterization of thermally reworkable thermosets: materials for environmentally friendly processing and reuse. Polymer 43:131–139CrossRefGoogle Scholar
  40. 40.
    Small JH, Loy DA, Wheeler DR, McElhanon JR, Saunders RS, Method of making thermally removable polymeric encapsulants. U.S. Patent No. 6,271,335. 7 Aug. 2001Google Scholar
  41. 41.
    Shen X, Liu X, Wang J, Dai J, Zhu J (2017) Synthesis of an epoxy monomer from bio-based 2, 5-Furandimethanol and its toughening via Diels–Alder reaction. Ind Eng Chem Res 56:8508–8516CrossRefGoogle Scholar
  42. 42.
    Byrne MT, Gun’ko YK (2010) Recent advances in research on carbon nanotube-polymer composites. Adv Mater 22:1672–1688CrossRefGoogle Scholar
  43. 43.
    Schwenke AM, Hoeppener S, Ulrich SS, Schubert US (2015) Synthesis and modification of carbon nanomaterials utilizing microwave heating. Adv Mater 27:4113–4141CrossRefGoogle Scholar
  44. 44.
    Kuang X, Liu GM, Dong X, Liu XG, Xu JJ, Wang DJ (2015) Facile fabrication of fast recyclable and multiple self-healing epoxy materials through diels-alder adduct cross-linker. Polym Sci Part A: Polym Chem 53:2094–2103CrossRefGoogle Scholar
  45. 45.
    Li JH, Zhang GP, Deng LB, Zhao SF, Gao YJ, Jiang K, Sun R, Wong CP (2014) In situ polymerization of mechanically reinforced, thermally healable graphene oxide/polyurethane composites based on Diels–Alder chemistry. J Mater Chem A 2:20642–20649CrossRefGoogle Scholar
  46. 46.
    Saikia BJ, Dolui SK (2015) Preparation and characterization of an azide–alkyne cycloaddition based self-healing system via a semiencapsulation method. RSC Adv 5:2480–92489Google Scholar
  47. 47.
    Kong H, Gao C, Yan D (2004) Controlled functionalization of multiwalled carbon nanotubes by in situ atom transfer radical polymerization. J Am Chem Soc 126:412–413CrossRefGoogle Scholar
  48. 48.
    Jones AS, Rule JD, Moore JS, White SR, Sottos NR (2006) Catalyst morphology and dissolution kinetics of self-healing polymers. Chem Mater 18:1312–1317CrossRefGoogle Scholar
  49. 49.
    Chen X, Dam MA, Ono K, Mal AK, Shen H, Nutt SR, Wudl F (2002) A thermally re-mendable cross-linked polymeric material. Science 295:1698–1702CrossRefGoogle Scholar
  50. 50.
    Pratama PA, Sharifi M, Peterson AM, Palmese GR (2013) Room temperature self-healing thermoset based on the Diels–Alder reaction. ACS Appl Mater Interfaces 5:12425–12431CrossRefGoogle Scholar
  51. 51.
    Zhang HB, Lin GD, Zhou ZH, Dong X, Chen T (2002) Raman spectra of MWCNTs and MWCNT-based H2-adsorbing system. Carbon 40:2429–2436CrossRefGoogle Scholar
  52. 52.
    Antunes EF, Lobo AO, Corat EJ, Trava-Airoldi VJ, Martin AA, Veríssimo C (2006) Comparative study of first-and second-order Raman spectra of MWCNT at visible and infrared laser excitation. Carbon 44:2202–2211CrossRefGoogle Scholar
  53. 53.
    Chang CM, Liu YL (2009) Functionalization of multi-walled carbon nanotubes with furan and maleimide compounds through Diels–Alder cycloaddition. Carbon 47:3041–3049CrossRefGoogle Scholar
  54. 54.
    Gojny FH, Wichmann MHG, Köpke U, Fiedler B, Schulte K (2004) Carbon nanotube-reinforced epoxy-composites: enhanced stiffness and fracture toughness at low nanotube content. Compos Sci Technol 64:2363–2371CrossRefGoogle Scholar
  55. 55.
    Abdalla M, Dean D, Robinson P, Nyairo E (2008) Cure behavior of epoxy/MWCNT nanocomposites: the effect of nanotube surface modification. Polymer 49:3310–3317CrossRefGoogle Scholar
  56. 56.
    Sadek EM, El-Nashar DE, Ward AA, Ahmed SM (2018) Study on the properties of multi-walled carbon nanotubes reinforced poly (vinyl alcohol) composites. J Polym Res 25:249CrossRefGoogle Scholar
  57. 57.
    Kuang X, Liu G, Dong X, Wang D (2016) Enhancement of mechanical and self-healing performance in multiwall carbon nanotube/rubber composites via Diels–Alder bonding. Macromol Mater Eng 301:535–541CrossRefGoogle Scholar
  58. 58.
    Li QT, Jiang MJ, Wu G, Chen L, Chen SC, Cao YX, Wang YZ (2017) Photothermal conversion triggered precisely targeted healing of epoxy resin based on thermoreversible diels–alder network and amino-functionalized carbon nanotubes. ACS Appl Mater Interfaces 9:20797–20807CrossRefGoogle Scholar
  59. 59.
    Pramanik NB, Singha NK (2015) Direct functionalization of multi-walled carbon nanotubes (MWCNTs) via grafting of poly (furfuryl methacrylate) using Diels–Alder “click chemistry” and its thermoreversibility. RSC Adv 5:94321–94327CrossRefGoogle Scholar
  60. 60.
    Hirsch A, Backes C (2010) Carbon nanotube science. Synthesis, properties and applications. By Peter JF Harris. Angew Chem Int Ed 49:1722–1723CrossRefGoogle Scholar

Copyright information

© The Polymer Society, Taipei 2019

Authors and Affiliations

  1. 1.Department of Chemical SciencesTezpur UniversityTezpurIndia

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