Skip to main content
SpringerLink
Log in

Fabrication of graphene-coated poly(glycidyl methacrylate) microspheres by electrostatic interaction and their application in epoxy anticorrosion coatings

  • Published:
Journal of Coatings Technology and Research Aims and scope Submit manuscript

Abstract

The uneven dispersion of graphene in the resin matrix hinders its application in anticorrosion coatings. This study reports a new method where graphene oxide (GO) is coated on the surface of the poly(glycidyl methacrylate) (PGMA) microspheres to promote the dispersion of GO in epoxy resin (EP) to improve the anticorrosion performance of EP. GO-coated PGMA microspheres (PGMA@GO) were successfully fabricated by electrostatic interaction, which was confirmed by Fourier transform infrared spectroscopy, X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and zeta potential analysis. The scanning electron microscopy results showed that the PGMA microspheres were uniformly coated with GO, when the weight ratio of PGMA@GO was 1:2 (PGMA: GO). Electrochemical impedance spectroscopy and salt immersion experiments were performed to evaluate the corrosion resistance of the EP composite coatings. Comparing with pure EP and GO/EP coatings, the mechanical properties and anticorrosion properties of coatings were improved after adding PGMA@GO. When the addition amount of PGMA@GO (of 50 g EP) was 1.0 wt% and about 0.67 wt% GO was only needed, the PGMA@GO/EP composite coating possessed a high impedance of 5.68 × 108 Ω cm2 and a low breakpoint frequency of 0.39 Hz for 21-day immersion in 3.5 wt% NaCl solution. The anticorrosion mechanism of PGMA@GO/EP composite coating was also discussed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Boukhvalov, DW, Katsnelson, MI, Lichtenstein, AI, “Hydrogen on Graphene: Electronic Structure, Total Energy, Structural Distortions and Magnetism from First-Principles Calculations.” Phys. Rev. B, 77 (3) 035427 (2008)

    Google Scholar 

  2. DeAndres, PL, Ramirez, R, Verges, JA, “Strong Covalent Bonding Between Two Graphene Layers.” Phys. Rev. B, 77 (4) 045403 (2008)

    Google Scholar 

  3. Reddy, CD, Rajendran, S, Liew, KM, “Equilibrium Configuration and Continuum Elastic Properties of Finite Sized Graphene.” Nanotechnology, 17 (3) 864–870 (2006)

    CAS  Google Scholar 

  4. Nemes-Incze, P, Osvath, Z, Kamaras, K, Biro, LP, “Anomalies in Thickness Measurements of Graphene and Few Layer Graphite Crystals by Tapping Mode Atomic Force Microscopy.” Carbon, 46 (11) 1435–1442 (2008)

    CAS  Google Scholar 

  5. Li, YY, Xu, YT, Wang, SC, Wang, HC, Li, M, Dai, LZ, “Preparation of Graphene/Polyaniline Nanocomposite by In Situ Intercalation Polymerization and Their Application in Anti-corrosion Coatings.” High Perform. Polym., 31 (9–10) 1226–1237 (2019)

    CAS  Google Scholar 

  6. Chen, D, Feng, HB, Li, JH, “Graphene Oxide: Preparation, Functionalization, and Electrochemical Applications.” Chem. Rev., 112 (11) 6027–6053 (2012)

    CAS  Google Scholar 

  7. Atif, R, Inam, F, “Modeling and Simulation of Graphene Based Polymer Nanocomposites: Advances in the Last Decade.” Graphene, 5 96–142 (2016)

    CAS  Google Scholar 

  8. Nikpour, B, Ramezanzadeh, B, Bahlakeh, G, Mahdavian, M, “Synthesis of Graphene Oxide Nanosheets Functionalized by Green Corrosion Inhibitive Compounds to Fabricate a Protective System.” Corros. Sci., 127 240–259 (2017)

    CAS  Google Scholar 

  9. Kasaeian, M, Ghasemi, E, Ramezanzadeh, B, Mahdavian, M, Bahlakeh, G, “Construction of a Highly Effective Self-repair Corrosion-Resistant Epoxy Composite Through Impregnation of 1H-Benzimidazole Corrosion Inhibitor Modified Graphene Oxide Nanosheets (GO-BIM).” Corros. Sci., 145 119–134 (2018)

    CAS  Google Scholar 

  10. Krishnamoorthy, K, Jeyasubramanian, K, Premanathan, M, Subbiah, G, Shin, HS, Kim, SJ, “Graphene Oxide Nanopaint.” Carbon, 72 328–337 (2014)

    CAS  Google Scholar 

  11. Yu, YH, Lin, YY, Lin, CH, Chan, CC, Huang, YC, “High-Performance Polystyrene/Graphene-Based Nanocomposites with Excellent Anti-corrosion Properties.” Polym. Chem., 5 (2) 535–550 (2014)

    CAS  Google Scholar 

  12. Ramezanzadeh, B, Niroumandrad, S, Ahmadi, A, Mahdavian, M, Moghadam, MHM, “Enhancement of Barrier and Corrosion Protection Performance of an Epoxy Coating Through Wet Transfer of Amino Functionalized Graphene Oxide.” Corros. Sci., 103 283–304 (2016)

    CAS  Google Scholar 

  13. Yu, ZX, Di, HH, Ma, Y, et al., “Fabrication of Graphene Oxide-Alumina Hybrids to Reinforce the Anti-corrosion Performance of Composite Epoxy Coatings.” Appl. Surf. Sci., 351 986–996 (2015)

    CAS  Google Scholar 

  14. Muzammil Ezzah, M, Khan, A, Stuparu, MC, “Post-polymerization Modification Reactions of Poly(glycidyl methacrylate)s.” RSC Adv., 7 (88) 55874–55884 (2017)

    Google Scholar 

  15. Li, QL, Gu, WX, Gao, H, Yang, YW, “Self-assembly and Applications of Poly(glycidyl methacrylate)s and Their Derivatives.” Chem. Commun., 50 (87) 13201–13215 (2014)

    CAS  Google Scholar 

  16. Sun, XT, Yang, LR, Xing, HF, et al., “High Capacity Adsorption of Cr(VI) from Aqueous Solution Using Polyethylenimine-Functionalized Poly(glycidyl methacrylate) Microspheres.” Colloid Surf. A, 457 160–168 (2014)

    CAS  Google Scholar 

  17. Zhang, HW, Zhao, R, Chen, ZY, Shangguan, DH, Liu, GQ, “QCM-FIA with PGMA Coating for Dynamic Interaction Study of Heparin and Antithrombin III.” Biosens. Bioelectron., 21 (1) 121–127 (2005)

    Google Scholar 

  18. Koysuren, O, Karaman, M, Ozyurt, D, “Effect of Noncovalent Chemical Modification on the Electrical Conductivity and Tensile Properties of Poly(methyl methacrylate)/Carbon Nanotube Composites.” J. Appl. Polym. Sci., 127 (6) 4557–4563 (2013)

    CAS  Google Scholar 

  19. Canamero, PF, de la Fuente, JL, Madruga, EL, Fernandez-Garcia, M, “Atom Transfer Radical Polymerization of Glycidyl Methacrylate: A Functional Monomer.” Macromol. Chem. Phys., 205 (16) 2221–2228 (2004)

    CAS  Google Scholar 

  20. Mrlik, M, Ilcikova, M, Plachy, T, Moucka, R, Pavlinek, V, Mosnacek, J, “Tunable Electrorheological Performance of Silicone Oil Suspensions Based on Controllably Reduced Graphene Oxide by Surface Initiated Atom Transfer Radical Polymerization of Poly(glycidyl methacrylate).” J. Ind. Eng. Chem., 57 104–112 (2018)

    CAS  Google Scholar 

  21. Chuo, T-W, Yeh, J-M, Liu, Y-L, “A Reactive Blend of Electroactive Polymers Exhibiting Synergistic Effects on Self-healing and Anticorrosion Properties.” RSC Adv., 6 (60) 55593–55598 (2016)

    CAS  Google Scholar 

  22. EI-Sawy, SM, Abu-Ayana, YM, Abdel-Mohdy, FA, “Preparation of Some Nitrogen Containing Polymers/Copolymers for Corrosion Protection.” J. Appl. Sci. Res., 4 (5) 534–544 (2008)

    Google Scholar 

  23. Zhang, WC, Sun, Y, Zhang, L, “In Situ Synthesis of Monodisperse Silver Nanoparticles on Sulfhydryl-Functionalized Poly(glycidyl methacrylate) Microspheres for Catalytic Reduction of 4-Nitrophenol.” Ind. Eng. Chem. Res., 54 (25) 6480–6488 (2015)

    CAS  Google Scholar 

  24. Chen, GF, Lu, JR, Lam, C, Yu, Y, “A Novel Green Synthesis Approach for Polymer Nanocomposites Decorated with Silver Nanoparticles and Their Antibacterial Activity.” Analyst, 139 (22) 5793–5799 (2014)

    CAS  Google Scholar 

  25. Jin, HJ, Choi, HJ, Yoon, SH, Myung, SJ, Shim, SE, “Carbon Nanotube-Adsorbed Polystyrene and Poly(methyl methacrylate) Microspheres.” Chem. Mater., 17 (16) 4034–4037 (2005)

    CAS  Google Scholar 

  26. Cho, MS, Cho, YH, Choi, HJ, Jhon, MS, “Synthesis and Electrorheological Characteristics of Polyaniline-Coated Poly(methyl methacrylate) Microsphere: Size Effect.” Langmuir, 19 (14) 5875–5881 (2003)

    CAS  Google Scholar 

  27. Krizova, J, Spanova, A, Rittich, B, Horak, D, “Magnetic Hydrophilic Methacrylate-Based Polymer Microspheres for Genomic DNA Isolation.” J. Chromatogr. A, 1064 (2) 247–253 (2005)

    CAS  Google Scholar 

  28. Yu, Y, Wu, X-L, Li, Y, et al., “Preparation of Mixed-Mode Chromatography Supports Based on Gigaporous Polymer Microspheres.” Chin. J. Anal. Chem., 44 (12) 1874–1879 (2016)

    CAS  Google Scholar 

  29. Oh, H, Kim, Y, Kim, J, “Co-curable Poly(glycidyl methacrylate)-Grafted Graphene/Epoxy Composite for Thermal Conductivity Enhancement.” Polymer, 183 121834 (2019)

    CAS  Google Scholar 

  30. Kakaei, K, Hasanpour, K, “Synthesis of Graphene Oxide Nanosheets by Electrochemical Exfoliation of Graphite in Cetyltrimethylammonium Bromide and Its Application for Oxygen Reduction.” J. Mater. Chem. A., 2 (37) 15428–15436 (2014)

    CAS  Google Scholar 

  31. Meng, W, Gall, E, Ke, FY, et al., “Structure and Interaction of Graphene Oxide-Cetyltrimethylammonium Bromide Complexation.” J. Phys. Chem. C, 119 (36) 21135–21140 (2015)

    CAS  Google Scholar 

  32. Oh, J, Lee, JH, Koo, JC, et al., “Graphene Oxide Porous Paper from Amine-Functionalized Poly(glycidyl methacrylate)/Graphene Oxide Core-Shell Microspheres.” J. Mater. Chem., 20 (41) 9200–9204 (2010)

    CAS  Google Scholar 

  33. Oh, JS, Luong, ND, Hwang, TS, Hong, JP, Lee, YK, Nam, JD, “In Situ Fabrication of Platinum/Graphene Composite Shell on Polymer Microspheres Through Reactive Self-assembly and In Situ Reduction.” J. Mater. Sci., 48 (3) 1127–1133 (2013)

    CAS  Google Scholar 

  34. Fang, R, Ge, XP, Du, M, et al., “Preparation of Silver/Graphene/Polymer Hybrid Microspheres and the Study of Photocatalytic Degradation.” Colloid Polym. Sci., 292 (4) 985–990 (2014)

    CAS  Google Scholar 

  35. Sari, MG, Ramezanzadeh, B, “Epoxy Composite Coating Corrosion Protection Properties Reinforcement Through the Addition of Hydroxyl-Terminated Hyperbranched Polyamide Non-covalently Assembled Graphene Oxide Platforms.” Constr. Build. Mater., 234 117421 (2020)

    CAS  Google Scholar 

  36. Long, GC, Tang, CY, Wong, KW, et al., “Resolving the Dilemma of Gaining Conductivity but Losing Environmental Friendliness in Producing Polystyrene/Graphene Composites via Optimizing the Matrix-Filler Structure.” Green Chem., 15 (3) 821–828 (2013)

    CAS  Google Scholar 

  37. Akbarzadeh, S, Ramezanzadeh, M, Ramezanzadeh, B, Bahlakeh, G, “A Green Assisted Route for the Fabrication of a High-Efficiency Self-healing Anti-corrosion Coating Through Graphene Oxide Nanoplatform Reduction by Tamarindus indiaca Extract.” J. Hazard. Mater., 390 122147 (2020)

    CAS  Google Scholar 

  38. Liu, Y, Zhang, YH, Duan, LL, et al., “Polystyrene/Graphene Oxide Nanocomposites Synthesized via Pickering Polymerization.” Prog. Org. Coat., 99 23–31 (2016)

    CAS  Google Scholar 

  39. Zhang, WL, Liu, YD, Choi, HJ, “Graphene Oxide Coated Core-Shell Structured Polystyrene Microspheres and Their Electrorheological Characteristics Under Applied Electric Field.” J. Mater. Chem., 21 (19) 6916–6921 (2011)

    CAS  Google Scholar 

  40. Xu, J, Wang, L, Zhu, YF, “Decontamination of Bisphenol A from Aqueous Solution by Graphene Adsorption.” Langmuir, 28 (22) 8418–8425 (2012)

    CAS  Google Scholar 

  41. Zhao, JP, Ren, WC, Cheng, HM, “Graphene Sponge for Efficient and Repeatable Adsorption and Desorption of Water Contaminations.” J. Mater. Chem., 22 (38) 20197–20202 (2012)

    CAS  Google Scholar 

  42. Konkena, B, Vasudevan, S, “Understanding Aqueous Dispersibility of Graphene Oxide and Reduced Graphene Oxide Through pKa Measurements.” J. Phys. Chem. Lett., 3 (7) 867–872 (2012)

    CAS  Google Scholar 

  43. Li, D, Muller, MB, Gilje, S, Kaner, RB, Wallace, GG, “Processable Aqueous Dispersions of Graphene Nanosheets.” Nat. Nanotechnol., 3 (2) 101–105 (2008)

    CAS  Google Scholar 

  44. Chen, C, Qiu, SH, Cui, MJ, et al., “Achieving High Performance Corrosion and Wear Resistant Epoxy Coatings via Incorporation of Noncovalent Functionalized Graphene.” Carbon, 114 356–366 (2017)

    CAS  Google Scholar 

  45. Chen, Y, Wang, XH, Li, J, Lu, JL, Wang, FS, “Long-Term Anticorrosion Behaviour of Polyaniline on Mild Steel.” Corros. Sci., 49 (7) 3052–3063 (2007)

    CAS  Google Scholar 

  46. Qiu, SH, Liu, G, Li, W, Zhao, HC, Wang, LP, “Noncovalent Exfoliation of Graphene and Its Multifunctional Composite Coating with Enhanced Anticorrosion and Tribological Performance.” J. Alloy. Compd., 747 60–70 (2018)

    CAS  Google Scholar 

  47. Sakhri, A, Perrin, FX, Aragon, E, Lamouric, S, Benaboura, A, “Chlorinated Rubber Paints for Corrosion Prevention of Mild Steel: A Comparison Between Zinc Phosphate and Polyaniline Pigments.” Corros. Sci., 52 (3) 901–909 (2010)

    CAS  Google Scholar 

  48. Ramezanzadeh, B, Ghasemi, E, Mahdavian, M, Changizi, E, Moghadam, MHM, “Covalently-Grafted Graphene Oxide Nanosheets to Improve Barrier and Corrosion Protection Properties of Polyurethane Coatings.” Carbon, 93 555–573 (2015)

    CAS  Google Scholar 

  49. Liu, S, Gu, L, Zhao, HC, Chen, JM, Yu, HB, “Corrosion Resistance of Graphene-Reinforced Waterborne Epoxy Coatings.” J. Mater. Sci. Technol., 32 (5) 425–431 (2016)

    CAS  Google Scholar 

  50. Parhizkar, N, Shahrabi, T, Ramezanzadeh, B, “A New Approach for Enhancement of the Corrosion Protection Properties and Interfacial Adhesion Bonds Between the Epoxy Coating and Steel Substrate Through Surface Treatment by Covalently Modified Amino Functionalized Graphene Oxide Film.” Corros. Sci., 123 55–75 (2017)

    CAS  Google Scholar 

  51. Zheng, HP, Shao, YW, Wang, YQ, Meng, GZ, Liu, B, “Reinforcing the Corrosion Protection Property of Epoxy Coating by Using Graphene Oxide–Poly(urea–formaldehyde) Composites.” Corros. Sci., 123 267–277 (2017)

    CAS  Google Scholar 

  52. Liu, X, Xiong, J, Lv, Y, Zuo, Y, “Study on Corrosion Electrochemical Behavior of Several Different Coating Systems by EIS.” Prog. Org. Coat., 64 (4) 497–503 (2009)

    CAS  Google Scholar 

  53. Ramezanzadeh, B, Bahlakeh, G, Ramezanzadeh, M, “Polyaniline-Cerium Oxide (PAni-CeO2) Coated Graphene Oxide for Enhancement of Epoxy Coating Corrosion Protection Performance on Mild Steel.” Corros. Sci., 137 111–126 (2018)

    CAS  Google Scholar 

Download references

Acknowledgments

This study was supported by Science and Technology Major Project of the Fujian Province (2018HZ0001-1) and the National Natural Science Foundation of China (U1805253).

Author information

Authors and Affiliations

  1. Fujian Provincial Key Laboratory of Fire-Retardant Materials, College of Materials, Xiamen University, Xiamen, 361005, People’s Republic of China

    Meng Li, Yiyi Li, Jiatian Zhang, Dandan Zhang, Kaibin He, Yiting Xu, Birong Zeng & Lizong Dai

  2. Fujian Inspection and Research Institute for Product Quality, Fuzhou, 350002, People’s Republic of China

    Jie Li

Authors
  1. Meng Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yiyi Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jiatian Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Dandan Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jie Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Kaibin He
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yiting Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Birong Zeng
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Lizong Dai
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yiting Xu.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 160 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Li, M., Li, Y., Zhang, J. et al. Fabrication of graphene-coated poly(glycidyl methacrylate) microspheres by electrostatic interaction and their application in epoxy anticorrosion coatings. J Coat Technol Res 18, 383–396 (2021). https://doi.org/10.1007/s11998-020-00409-1

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11998-020-00409-1

Keywords

Search

Navigation