Journal of Materials Science

, Volume 53, Issue 10, pp 7793–7808 | Cite as

Novel self-healing anticorrosion coating based on L-valine and MBT-loaded halloysite nanotubes

  • Chundong Dong
  • Manxin Zhang
  • Tengfei Xiang
  • Ling Yang
  • Wenming Chan
  • Cheng LiEmail author


This work creatively utilized the pH-dependent electrostatic interactions between L-valine (L-Val) and halloysite nanotubes (HNTs) to fabricate pH-responsive anticorrosion materials and compared with 2-mercaptobenzothiazole (MBT)-loaded HNTs, which were assembled via layer-by-layer (LbL) self-assembly. These two methods can achieve controlled release of inhibitors and self-healing performance. However, the loading capacity of L-Val-loaded HNTs is higher than that of MBT’s. There are 12 and 7 wt%, respectively. The pH-responsive release property was systematically evaluated by ultraviolet–visible (UV/Vis) spectrophotometry measurement. It demonstrates that 98% of adsorbed L-Val molecules released from HNTs within 300 min at pH 10 while the loaded MBT needs 120 h to achieve the equal ratio. Moreover, the difference of the release rate has a significant impact on the artificial crossed scratch experiment and shows a great performance gap in photographs. By comparing electrochemical impedance spectroscopy (EIS) data of three epoxy coatings, it can be seen that the epoxy coating, which was mixed with L-Val-loaded HNTs, shows a better anticorrosion ability than the epoxy coating contains MBT-loaded HNTs after immersion in 3.5 wt% sodium chloride solution for 96 h. Crucially, the pH-responsive anticorrosion material we fabricated can offer a rapid self-healing performance when the coating damaged by mechanical scratch via visual test and atomic absorption spectroscopy.



The authors would like to thank the project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.

Compliance with ethical standards

Conflict of interest

All authors agree to submit this paper to “Journal of Materials Science.” We confirm that there is no conflict of interest in this paper.


  1. 1.
    Radovanović MB, Antonijević MM (2016) Protection of copper surface in acidic chloride solution by non-toxic thiadiazole derivative. J Adhes Sci Technol 31:369–387CrossRefGoogle Scholar
  2. 2.
    Fan Y, Chen Z, Liang J, Wang Y, Chen H (2014) Preparation of superhydrophobic films on copper substrate for corrosion protection. Surf Coat Technol 244:1–8CrossRefGoogle Scholar
  3. 3.
    Peng S, Zhao W, Li H, Zeng Z, Xue Q, Wu X (2013) The enhancement of benzotriazole on epoxy functionalized silica sol–gel coating for copper protection. Appl Surf Sci 276:284–290CrossRefGoogle Scholar
  4. 4.
    Yu Y, Yang D, Zhang D, Wang Y, Gao L (2017) Anti-corrosion film formed on HAl77-2 copper alloy surface by aliphatic polyamine in 3 wt% NaCl solution. Appl Surf Sci 392:768–776CrossRefGoogle Scholar
  5. 5.
    Liang J, Deng A, Xie R, Gomez M, Hu J, Zhang J, Ong CN, Adin A (2013) Impact of flow rate on corrosion of cast iron and quality of re-mineralized seawater reverse osmosis (SWRO) membrane product water. Desalination 322:76–83CrossRefGoogle Scholar
  6. 6.
    Zheludkevich ML, Tedim J, Ferreira MGS (2012) “Smart” coatings for active corrosion protection based on multi-functional micro and nanocontainers. Electrochim Acta 82:314–323CrossRefGoogle Scholar
  7. 7.
    Tian H, Li W, Cao K, Hou B (2013) Potent inhibition of copper corrosion in neutral chloride media by novel non-toxic thiadiazole derivatives. Corros Sci 73:281–291CrossRefGoogle Scholar
  8. 8.
    El-Haddad MN (2013) Chitosan as a green inhibitor for copper corrosion in acidic medium. Int J Biol Macromol 55:142–149CrossRefGoogle Scholar
  9. 9.
    Kartsonakis IA, Balaskas AC, Kordas GC (2011) Influence of cerium molybdate containers on the corrosion performance of epoxy coated aluminium alloys 2024-T3. Corros Sci 53:3771–3779CrossRefGoogle Scholar
  10. 10.
    Snihirova D, Lamaka SV, Cardoso MM, Condeço JAD, Ferreira HECS, Montemor MD (2014) pH-sensitive polymeric particles with increased inhibitor-loading capacity as smart additives for corrosion protective coatings for AA2024. Electrochim Acta 145:123–131CrossRefGoogle Scholar
  11. 11.
    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
  12. 12.
    Snihirova D, Lamaka SV, Montemor MF (2012) “SMART” protective ability of water based epoxy coatings loaded with CaCO3 microbeads impregnated with corrosion inhibitors applied on AA2024 substrates. Electrochim Acta 83:439–447CrossRefGoogle Scholar
  13. 13.
    Kartsonakis I, Daniilidis I, Kordas G (2008) Encapsulation of the corrosion inhibitor 8-hydroxyquinoline into ceria nanocontainers. J Sol Gel Sci Technol 48:24–31CrossRefGoogle Scholar
  14. 14.
    Fix D, Andreeva DV, Lvov YM, Shchukin DG, Möhwald H (2009) Application of inhibitor-loaded halloysite nanotubes in active anti-corrosive coatings. Adv Funct Mater 19:1720–1727CrossRefGoogle Scholar
  15. 15.
    Kartsonakis IA, Athanasopoulou E, Snihirova D, Martins B, Koklioti MA, Montemor MF, Kordas G, Charitidis CA (2014) Multifunctional epoxy coatings combining a mixture of traps and inhibitor loaded nanocontainers for corrosion protection of AA2024-T3. Corros Sci 85:147–159CrossRefGoogle Scholar
  16. 16.
    Tedim J, Kuznetsova A, Salak AN, Montemor F, Snihirova D, Pilz M, Zheludkevich ML, Ferreira MGS (2012) Zn–Al layered double hydroxides as chloride nanotraps in active protective coatings. Corros Sci 55:1–4CrossRefGoogle Scholar
  17. 17.
    Shchukin DG, Zheludkevich M, Yasakau K, Lamaka S, Ferreira MGS, Möhwald H (2006) Layer-by-layer assembled nanocontainers for self-healing corrosion protection. Adv Mater 18:1672–1678CrossRefGoogle Scholar
  18. 18.
    Snihirova D, Lamaka SV, Taryba M, Salak AN, Kallip S, Zheludkevich ML, Ferreira MG, Montemor MF (2010) Hydroxyapatite microparticles as feedback-active reservoirs of corrosion inhibitors. ACS Appl Mater Interfaces 2:3011–3022CrossRefGoogle Scholar
  19. 19.
    Skorb EV, Skirtach AG, Sviridov DV, Shchukin DG, Möhwald H (2009) Laser controllable coatings for corrosion protection. ACS Nano 3:1753–1760CrossRefGoogle Scholar
  20. 20.
    Choi H, Song YK, Kim KY, Park JM (2012) Encapsulation of triethanolamine as organic corrosion inhibitor into nanoparticles and its active corrosion protection for steel sheets. Surf Coat Technol 206:2354–2362CrossRefGoogle Scholar
  21. 21.
    Zheng Z, Huang X, Schenderlein M, Borisova D, Cao R, Möhwald H, Shchukin D (2013) Self-healing and antifouling multifunctional coatings based on pH and sulfide ion sensitive nanocontainers. Adv Funct Mater 23:3307–3314CrossRefGoogle Scholar
  22. 22.
    Jafari AH, Hosseini SMA, Jamalizadeh E (2010) Investigation of smart nanocapsules containing inhibitors for corrosion protection of copper. Electrochim Acta 55:9004–9009CrossRefGoogle Scholar
  23. 23.
    Lvov YM, Shchukin DG, Mohwald H, Price RR (2008) Halloysite clay nanotubes for controlled release of protective agents. ACS Nano 2:814–820CrossRefGoogle Scholar
  24. 24.
    Abdullayev E, Abbasov V, Tursunbayeva A, Portnov V, Ibrahimov H, Mukhtarova G, Lvov Y (2013) Self-healing coatings based on halloysite clay polymer composites for protection of copper alloys. ACS Appl Mater Interfaces 5:4464–4471CrossRefGoogle Scholar
  25. 25.
    Abdullayev E, Joshi A, Wei W, Zhao Y, Lvov Y (2012) Enlargement of halloysite clay nanotube lumen by selective etching of aluminum oxide. ACS Nano 6:7216–7226CrossRefGoogle Scholar
  26. 26.
    Abdullayev E, Lvov Y (2010) Clay nanotubes for corrosion inhibitor encapsulation: release control with end stoppers. J Mater Chem 20:6681–6687CrossRefGoogle Scholar
  27. 27.
    Abdullayev E, Sakakibara K, Okamoto K, Wei W, Ariga K, Lvov Y (2011) Natural tubule clay template synthesis of silver nanorods for antibacterial composite coating. ACS Appl Mater Interfaces 3:4040–4046CrossRefGoogle Scholar
  28. 28.
    Wang MD, Liu MY, Fu JJ (2015) An intelligent anticorrosion coating based on pH-responsive smart nanocontainers fabricated via a facile method for protection of carbon steel. J Mater Chem A 3:6423–6431CrossRefGoogle Scholar
  29. 29.
    Huang H, Yao J, Chen H, Zeng X, Chen C, She X, Li L (2016) Facile preparation of halloysite/polyaniline nanocomposites via in situ polymerization and layer-by-layer assembly with good supercapacitor performance. J Mater Sci 51:4047–4054. CrossRefGoogle Scholar
  30. 30.
    Itano K, Choi J, Rubner MF (2005) Mechanism of the pH-induced discontinuous swelling/deswelling transitions of poly (allylamine hydrochloride)-containing polyelectrolyte multilayer films. Macromolecules 38:3450–3460CrossRefGoogle Scholar
  31. 31.
    Guimarães L, Enyashin AN, Seifert G, Duarte HA (2010) Structural, electronic, and mechanical properties of single-walled halloysite nanotube models. J Phys Chem C 114:11358–11363CrossRefGoogle Scholar
  32. 32.
    Mauser T, Déjugnat C, Möhwald H, Sukhorukov GB (2006) Microcapsules made of weak polyelectrolytes: templating and stimuli-responsive properties. Langmuir 22:5888–5893CrossRefGoogle Scholar
  33. 33.
    Ouyang L, Malaisamy R, Bruening ML (2008) Multilayer polyelectrolyte films as nanofiltration membranes for separating monovalent and divalent cations. J Membr Sci 310:76–84CrossRefGoogle Scholar
  34. 34.
    Chen T, Fu JJ (2012) An intelligent anticorrosion coating based on pH-responsive supramolecular nanocontainers. Nanotechnology 23:505705CrossRefGoogle Scholar
  35. 35.
    Oguzie EE, Li Y, Wang SG, Wang F (2011) Understanding corrosion inhibition mechanisms—experimental and theoretical approach. RSC Adv 1:866–873CrossRefGoogle Scholar
  36. 36.
    Zor S, Kandemirli F, Bingul M (2009) Inhibition effects of methionine and tyrosine on corrosion of iron in HCl solution: electrochemical, FTIR, and quantum-chemical study. Prot Met Phys Chem Surf 45:46–53CrossRefGoogle Scholar
  37. 37.
    Cordeiro GGO, Barcia OE, Mattos OR (1993) Copper electrodissolution mechanism in a 1 M sulphate medium. Electrochim Acta 38:319–324CrossRefGoogle Scholar
  38. 38.
    Zhang DQ, Gao LX, Zhou GD (2005) Inhibition of copper corrosion in aerated hydrochloric acid solution by amino-acid compounds. J Appl Electrochem 35:1081–1085CrossRefGoogle Scholar
  39. 39.
    Fu JJ, Li SN, Cao LH, Wang Y, Yan LH, Lu LD (2009) L-tryptophan as green corrosion inhibitor for low carbon steel in hydrochloric acid solution. J Mater Sci 45:979–986. CrossRefGoogle Scholar
  40. 40.
    Abdel-Fatah HTM, Rashwan SAM, Wahaab SMAE, Hassan AAM (2016) Effect of Tryptophan on the corrosion behavior of low alloy steel in sulfamic acid. Arab J Chem 9:S1069–S1076CrossRefGoogle Scholar
  41. 41.
    Subramanian R, Lakshminarayanan V (2002) Effect of adsorption of some azoles on copper passivation in alkaline medium. Corros Sci 44:535–554CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • Chundong Dong
    • 1
  • Manxin Zhang
    • 1
  • Tengfei Xiang
    • 1
  • Ling Yang
    • 1
  • Wenming Chan
    • 1
  • Cheng Li
    • 1
    Email author
  1. 1.College of Materials Science and TechnologyNanjing University of Aeronautics & AstronauticsNanjingPeople’s Republic of China

Personalised recommendations