Polyaniline-modified graphene oxide nanocomposites in epoxy coatings for enhancing the anticorrosion and antifouling properties

  • Sara Fazli-Shokouhi
  • Farzad NasirpouriEmail author
  • Maasoumeh Khatamian


We report on the anticorrosion and antifouling properties of epoxy-based polyaniline (PANI)–graphene oxide nanosheets (GONs) paint coatings. PANI-based nanocomposites with different fractions of GONs were synthesized by an in situ polymerization process. Well-dispersed GONs were prepared using a modified Hummers’ method in the presence of (NH4)2S2O8 as an effective oxidant. We employed a spontaneous in situ polymerization at a constant temperature of 0°C using an ultrasonic bath to produce homogenous PANI-GON nanocomposites as characterized by X-ray diffraction (XRD), Fourier transfer infrared spectroscopy (FTIR), and field-emission scanning electron microscopy (FESEM) techniques. The nanocomposites were incorporated into an epoxy resin with different fractions to form epoxy/PANI-GON paint coatings. The epoxy/PANI-GON dip coated on a carbon steel (grade St-37) substrate exhibited significant improvement of the anticorrosion and antifouling properties. Epoxy-12 wt% PANI-GON coating revealed the highest corrosion resistance of 2.70 × 106 Ω cm2 after 192-h immersion in saline water measured by electrochemical impedance spectroscopy (EIS) technique. Such high corrosion resistance was attainable by inhibiting the diffusion process against the corrosive environment. Furthermore, higher protection against fouling was observed for epoxy 6 and 12 wt% PANI/GON as the most efficient antifouling composite coatings.


Graphene oxide nanosheet (GON) Polyaniline (PANI) Epoxy Anticorrosion Antifouling 



The authors would like to thank the Sahand University of Technology of Tabriz and University of Tabriz and Iranian Nanotechnology Initiative Council for the financial support of this project.


  1. 1.
    Koch, GH, Brongers, MP, Thompson, NG, Virmani, YP, Payer, JH, “Corrosion Cost and Preventive Strategies in the United States.” (2002)Google Scholar
  2. 2.
    Ramón, JE, Gandía-Romero, JM, Valcuende, M, Bataller, R, “Integrated Sensor Network for Monitoring Steel Corrosion in Concrete Structures.” VITRUVIO-Int. J. Archit. Technol. Sustain., 1 (1) 65–79 (2016)Google Scholar
  3. 3.
    Böhm, S, “Graphene Against Corrosion.” Nat. Nanotechnol., 9 (10) 741–742 (2014)Google Scholar
  4. 4.
    Rathish, RJ, Dorothy, R, Joany, R, Pandiarajan, M, “Corrosion Resistance of Nanoparticle-Incorporated Nano Coatings.” Eur. Chem. Bull., 2 (12) 965–970 (2013)Google Scholar
  5. 5.
    Zvonkina, I, Soucek, M, “Inorganic–Organic Hybrid Coatings: Common and New Approaches.” Curr. Opin. Chem. Eng., 11 123–127 (2016)Google Scholar
  6. 6.
    Montemor, M, “Functional and Smart Coatings for Corrosion Protection: A Review of Recent Advances.” Surf. Coat. Technol., 258 17–37 (2014)Google Scholar
  7. 7.
    Nine, MJ, Cole, MA, Tran, DN, Losic, D, “Graphene: A Multipurpose Material for Protective Coatings.” J. Mater. Chem. A, 3 (24) 12580–12602 (2015)Google Scholar
  8. 8.
    Hellio, C, Yebra, D, Advances in Marine Antifouling Coatings and Technologies. Elsevier, Amsterdam, 2009Google Scholar
  9. 9.
    Nurioglu, AG, Esteves, ACC, “Non-Toxic, Non-Biocide-Release Antifouling Coatings Based on Molecular Structure Design for Marine Applications.” J. Mater. Chem. B, 3 (32) 6547–6570 (2015)Google Scholar
  10. 10.
    Sørensen, PA, Kiil, S, Dam-Johansen, K, Weinell, CE, “Anticorrosive Coatings: A Review.” J. Coat. Technol. Res., 6 (2) 135–176 (2009)Google Scholar
  11. 11.
    Novoselov, KS, Geim, AK, Morozov, SV, Jiang, D, Zhang, Y, Dubonos, SV, Grigorieva, IV, Firsov, AA, “Electric Field Effect in Atomically Thin Carbon Films.” Science, 306 (5696) 666–669 (2004)Google Scholar
  12. 12.
    Martin-Gallego, M, Verdejo, R, Lopez-Manchado, M, Sangermano, M, “Epoxy-Graphene UV-Cured Nanocomposites.” Polymer, 52 (21) 4664–4669 (2011)Google Scholar
  13. 13.
    Wang, H, Hao, Q, Yang, X, Lu, L, Wang, X, “Effect of Graphene Oxide on the Properties of its Composite with Polyaniline.” ACS Appl. Mater. Interfaces, 2 (3) 821–828 (2010)Google Scholar
  14. 14.
    Zhang, WL, Liu, YD, Choi, HJ, “Fabrication of Semiconducting Graphene Oxide/Polyaniline Composite Particles and their Electrorheological Response Under an Applied Electric Field.” Carbon, 50 (1) 290–296 (2012)Google Scholar
  15. 15.
    Nasrollahzadeh, M, Babaei, F, Fakhri, P, Jaleh, B, “Synthesis, Characterization, Structural, Optical Properties and Catalytic Activity of Reduced Graphene Oxide/Copper Nanocomposites.” RSC Adv., 5 (14) 10782–10789 (2015)Google Scholar
  16. 16.
    Huang, Y, Lin, C, “Polyaniline-Intercalated Graphene Oxide Sheet and its Transition to a Nanotube Through a Self-curling Process.” Polymer, 53 (5) 1079–1085 (2012)Google Scholar
  17. 17.
    Huang, X, Qi, X, Boey, F, Zhang, H, “Graphene-Based Composites.” Chemical Society Reviews, 41 (2) 666–686 (2012)Google Scholar
  18. 18.
    Zhu, Y, Murali, S, Cai, W, Li, X, Suk, JW, Potts, JR, Ruoff, RS, “Graphene and Graphene Oxide: Synthesis, Properties, and Applications.” Advanced Materials, 22 (35) 3906–3924 (2010)Google Scholar
  19. 19.
    Pumera, M, “Electrochemistry of Graphene: New Horizons for Sensing and Energy Storage.” The Chemical Record, 9 (4) 211–223 (2009)Google Scholar
  20. 20.
    Wei, J, Vo, T, Inam, F, “Epoxy/Graphene Nanocomposites–Processing and Properties: A Review.” RSC Advances, 5 (90) 73510–73524 (2015)Google Scholar
  21. 21.
    Shi, X, Nguyen, TA, Suo, Z, Liu, Y, Avci, R, “Effect of Nanoparticles on the Anticorrosion and Mechanical Properties of Epoxy Coating.” Surface and Coatings Technology, 204 (3) 237–245 (2009)Google Scholar
  22. 22.
    Dominis, AJ, Spinks, GM, Wallace, GG, “Comparison of Polyaniline Primers Prepared with Different Dopants for Corrosion Protection of Steel.” Prog. Org. Coat., 48 (1) 43–49 (2003)Google Scholar
  23. 23.
    Fang, J, Xu, K, Zhu, L, Zhou, Z, Tang, H, “A Study on Mechanism of Corrosion Protection of Polyaniline Coating and its Failure.” Corros. Sci., 49 (11) 4232–4242 (2007)Google Scholar
  24. 24.
    Schauer, T, Joos, A, Dulog, L, Eisenbach, C, “Protection of Iron Against Corrosion with Polyaniline Primers.” Prog. Org. Coat., 33 (1) 20–27 (1998)Google Scholar
  25. 25.
    Hartwig, A, Sebald, M, Pütz, D, Aberle, L, “Preparation, Characterisation and Properties of Nanocomposites Based on Epoxy Resins—An Overview.” Proc. Macromolecular Symposia (2005)Google Scholar
  26. 26.
    Becker, O, Varley, R, Simon, G, “Morphology, Thermal Relaxations and Mechanical Properties of Layered Silicate Nanocomposites Based upon High-Functionality Epoxy Resins.” Polymer, 43 (16) 4365–4373 (2002)Google Scholar
  27. 27.
    Yang, L, Liu, F, Han, E, “Effects of P/B on the Properties of Anticorrosive Coatings with Different Particle Size.” Prog. Org. Coat., 53 (2) 91–98 (2005)Google Scholar
  28. 28.
    Lamaka, SV, Zheludkevich, ML, Yasakau, KA, Serra, R, Poznyak, S, Ferreira, M, “Nanoporous Titania Interlayer as Reservoir of Corrosion Inhibitors for Coatings with Self-healing Ability.” Prog. Org. Coat., 58 (2) 127–135 (2007)Google Scholar
  29. 29.
    Shi, H, Liu, F, Yang, L, Han, E, “Characterization of Protective Performance of Epoxy Reinforced with Nanometer-Sized TiO2 and SiO2.” Prog. Org. Coat., 62 (4) 359–368 (2008)Google Scholar
  30. 30.
    Pourhashem, S, Vaezi, MR, Rashidi, A, “Investigating the Effect of SiO2-Graphene Oxide Hybrid as Inorganic Nanofiller on Corrosion Protection Properties of Epoxy Coatings.” Surf. Coat. Technol., 311 282–294 (2017)Google Scholar
  31. 31.
    Yu, Z, Di, H, Ma, Y, He, Y, Liang, L, Lv, L, Ran, X, Pan, Y, Luo, Z, “Preparation of Graphene Oxide Modified by Titanium Dioxide to Enhance the Anti-Corrosion Performance of Epoxy Coatings.” Surf. Coat. Technol., 276 471–478 (2015)Google Scholar
  32. 32.
    Mostafaei, A, Nasirpouri, F, “Electrochemical Study of Epoxy Coating Containing Novel Conducting Nanocomposite Comprising Polyaniline–ZnO Nanorods on Low Carbon Steel.” J. Coat. Technol. Res., 10 (5) 679–694 (2013)Google Scholar
  33. 33.
    Mostafaei, A, Nasirpouri, F, “Preparation and Characterization of a Novel Conducting Nanocomposite Blended with Epoxy Coating for Antifouling and Antibacterial Applications.” Corros. Eng. Sci. Technol., 48 (7) 513–524 (2014)Google Scholar
  34. 34.
    Mostafaei, A, Nasirpouri, F, “Epoxy/Polyaniline–ZnO Nanorods Hybrid Nanocomposite Coatings: Synthesis, Characterization and Corrosion Protection Performance of Conducting Paints.” Prog. Org. Coat., 77 (1) 146–159 (2014)Google Scholar
  35. 35.
    Jafari, Y, Ghoreishi, SM, Shabani-Nooshabadi, M, “Electrochemical Deposition and Characterization of Polyaniline–Graphene Nanocomposite Films and its Corrosion Protection Properties.” J. Polym. Res., 23 (5) 91 (2016)Google Scholar
  36. 36.
    Mooss, VA, Bhopale, AA, Deshpande, PP, Athawale, AA, “Graphene Oxide-Modified Polyaniline Pigment for Epoxy Based Anti-Corrosion Coatings.” Chem. Pap., 71 (8) 1515–1528 (2017)Google Scholar
  37. 37.
    Zhang, K, Zhang, LL, Zhao, X, Wu, J, “Graphene/Polyaniline Nanofiber Composites as supercapacitor Electrodes.” Chem. Mater., 22 (4) 1392–1401 (2010)Google Scholar
  38. 38.
    Nasirpouri, F, Pourmahmoudi, H, Abbasi, F, Littlejohn, S, Chauhan, AS, Nogaret, A, “Modification of Chemically Exfoliated Graphene to Produce Efficient Piezoresistive Polystyrene-Graphene Composites.” J. Electron. Mater., 44 (10) 3512 (2015)Google Scholar
  39. 39.
    Huang, Y, Lin, C, “Facile Synthesis and Morphology Control of Graphene Oxide/Polyaniline Nanocomposites Via In Situ Polymerization Process.” Polymer, 53 (13) 2574–2582 (2012)Google Scholar
  40. 40.
    Yin, Q, Shu, R, Xing, H, Tan, D, Gan, Y, Xu, G, “Rheological Behavior and Electrical Properties of Graphene Oxide/Polyaniline Nanocomposites.” Nano, 11 (02) 1650020 (2016)Google Scholar
  41. 41.
    Li, M, Yin, W, Han, X, Chang, X, “Hierarchical Nanocomposites of Polyaniline Scales Coated on Graphene Oxide Sheets for Enhanced Supercapacitors.” J. Solid State Electrochem., 20 (7) 1941–1948 (2016)Google Scholar
  42. 42.
    Thema, F, Moloto, M, Dikio, E, Nyangiwe, N, Kotsedi, L, Maaza, M, Khenfouch, M, “Synthesis and Characterization of Graphene Thin Films by Chemical Reduction of Exfoliated and Intercalated Graphite Oxide.” J. Chem., 2013 (2012)Google Scholar
  43. 43.
    Sun, J, Bi, H, “Pickering Emulsion Fabrication and Enhanced Supercapacity of Graphene Oxide-Covered Polyaniline Nanoparticles.” Mater. Lett., 81 48–51 (2012)Google Scholar
  44. 44.
    Shunaev, VV, Glukhova, OE, “Topology Influence on the Process of Graphene Functionalization by Epoxy and Hydroxyl Groups.” J. Phys. Chem. C, 120 (7) 4145–4149 (2016)Google Scholar
  45. 45.
    Wei, H, Zhu, J, Wu, S, Wei, S, Guo, Z, “Electrochromic Polyaniline/Graphite Oxide Nanocomposites with Endured Electrochemical Energy Storage.” Polymer, 54 (7) 1820–1831 (2013)Google Scholar
  46. 46.
    Hu, F, Li, W, Zhang, J, Meng, W, “Effect of Graphene Oxide as a Dopant on the Electrochemical Performance of Graphene Oxide/Polyaniline Composite.” J. Mater. Sci. Technol., 30 (4) 321–327 (2014)Google Scholar
  47. 47.
    Marcano, DC, Kosynkin, DV, Berlin, JM, Sinitskii, A, Sun, Z, Slesarev, A, Alemany, LB, Lu, W, Tour, JM, “Improved Synthesis of Graphene Oxide.” ACS Nano, 4 (8) 4806–4814 (2010)Google Scholar
  48. 48.
    Imran, SM, Kim, Y, Shao, GN, Hussain, M, Choa, Y, Kim, HT, “Enhancement of Electroconductivity of Polyaniline/Graphene Oxide Nanocomposites Through In Situ Emulsion Polymerization.” J. Mater. Sci., 49 (3) 1328–1335 (2014)Google Scholar
  49. 49.
    Mohammadi, S, Taromi, FA, Shariatpanahi, H, Neshati, J, Hemmati, M, “Electrochemical and Anticorrosion Behavior of Functionalized Graphite Nanoplatelets Epoxy Coating.” J. Ind. Eng. Chem., 20 (6) 4124–4139 (2014)Google Scholar
  50. 50.
    Liu, C, Bi, Q, Leyland, A, Matthews, A, “An Electrochemical Impedance Spectroscopy Study of the Corrosion Behaviour of PVD Coated Steels in 0.5 N NaCl Aqueous Solution: Part II.: EIS Interpretation of Corrosion Behaviour.” Corros. Sci., 45 (6) 1257–1273 (2003)Google Scholar
  51. 51.
    Hang, TTX, Truc, TA, Nam, TH, Oanh, VK, Jorcin, J-B, Pébère, N, “Corrosion Protection of Carbon Steel by an Epoxy Resin Containing Organically Modified Clay.” Surf. Coat. Technol., 201 (16) 7408–7415 (2007)Google Scholar
  52. 52.
    Pourhashem, S, Rashidi, A, Vaezi, MR, Bagherzadeh, MR, “Excellent Corrosion Protection Performance of Epoxy Composite Coatings Filled with Amino-Silane Functionalized Graphene Oxide.” Surf. Coat. Technol., 317 1–9 (2017)Google Scholar
  53. 53.
    Sun, W, Wang, L, Wu, T, Wang, M, Yang, Z, Pan, Y, Liu, G, “Inhibiting the Corrosion-Promotion Activity of Graphene.” Chem. Mater., 27 (7) 2367–2373 (2015)Google Scholar
  54. 54.
    Di, H, Yu, Z, Ma, Y, Zhang, C, Li, F, Lv, L, Pan, Y, Shi, H, He, Y, “Corrosion-Resistant Hybrid Coatings Based on Graphene Oxide–Zirconia Dioxide/Epoxy System.” J. Taiwan Inst. Chem. Eng., 67 511–520 (2016)Google Scholar
  55. 55.
    Mohammadi, S, Shariatpanahi, H, Taromi, FA, Neshati, J, “Electrochemical and Anticorrosion Behaviors of Hybrid Functionalized Graphite Nano-Platelets/Tripolyphosphate in Epoxy-Coated Carbon Steel.” Mater. Res. Bull., 80 7–22 (2016)Google Scholar
  56. 56.
    Li, M, Ji, X, Cui, L, Liu, J, “In Situ Preparation of Graphene/Polypyrrole Nanocomposite Via Electrochemical Co-Deposition Methodology for Anti-Corrosion Application.” J. Mater. Sci., 52 (20) 12251–12265 (2017)Google Scholar
  57. 57.
    Ramezanzadeh, B, Haeri, Z, Ramezanzadeh, M, “A Facile Route of Making Silica Nanoparticles-Covered Graphene Oxide Nanohybrids (SiO2-GO); Fabrication of SiO2-GO/Epoxy Composite Coating with Superior Barrier and Corrosion Protection Performance.” Chem. Eng. J., 303 511–528 (2016)Google Scholar

Copyright information

© American Coatings Association 2019

Authors and Affiliations

  • Sara Fazli-Shokouhi
    • 1
  • Farzad Nasirpouri
    • 1
    Email author
  • Maasoumeh Khatamian
    • 2
  1. 1.Faculty of Materials EngineeringSahand University of TechnologyTabrizIran
  2. 2.Department of Inorganic Chemistry, Faculty of ChemistryUniversity of TabrizTabrizIran

Personalised recommendations