Electropolymerized Poly(4-amino-1,2,4-triazole) with Inorganic Oxides as Advanced Corrosion-Inhibitive Coatings for Cu–Ni (90/10) Alloy
J. Environ. Nanotechnol., Volume 15, No 1 (March 2026) pp. 565-575
Abstract
The present study focuses on the electrochemical synthesis and characterization of poly(4-amino-1,2,4-triazole) (poly-4-ATA) and its composites incorporating various metal oxides. Metal oxides such as CeO₂, ZnO, and TiO₂, along with SiO₂, were integrated into the polymer matrix to enhance the structural, morphological, and electrochemical performance of the coatings. The prepared materials were examined by FT-IR, XRD, SEM, EDAX, and electrochemical analyses, confirming successful polymerization and the uniform distribution of metal oxide particles within the polymer network. Electrochemical investigations, including potentiodynamic polarization (PP) and electrochemical impedance spectroscopy (EIS), revealed that The incorporation of TiO₂ of metal oxides significantly improved corrosion resistance compared with that of the bare alloy and the pure polymer film. Among the tested composites, the poly-4-ATA/TiO₂ coating exhibited the highest charge-transfer resistance and an inhibition efficiency of 97.8%, indicating superior protective performance. These findings suggest that poly-4-ATA/metal oxide composites are promising corrosion-inhibitive coatings, with the synergistic effect of the polymer and the metal oxide contributing to the enhanced durability and stability of metallic substrates in aggressive chloride environments.
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Reference
Abilash, R., Muraliraja R. and Shasisundaram V. S.,Electroless Ni-P-TiO2 nanocomposite coatings for enhanced durability and saltwater corrosion protection of jet ski engine components, J.Enviorn. Nanotechnol., 14(3), 685-691(2025),
https://doi.org/10.13074/jent.2025.09.2531734
Akpan, E. D., Singh, A. K., Lgaz, H., Quadri, T. W., Shukla, S. K., Mangla, B., Dwivedi, A., Dagdag, O., Sheetal, Inyang, E. E. and Ebenso, E. E., Coordination compounds as corrosion inhibitors of metals: A review, Coord. Chem. Rev., 499, 215503 (2024).
https://doi.org/10.1016/j.ccr.2023.215503
Aslam, R., Mobin, M., Zehra, S. and Aslam, J., A comprehensive review of corrosion inhibitors employed to mitigate stainless steel corrosion in different environments, J. Mol. Liq., 364, 119992 (2022).
https://doi.org/10.1016/j.molliq.2022.119992
Ates, M., Kalender, O., Topkaya, E. and Kamer, L., Polyaniline and polypyrrole/TiO₂ nanocomposite coatings on Al1050: electrosynthesis, characterization and their corrosion protection ability in saltwater media, Iran. Polym. J., 24(7), 607–619 (2015).
https://doi.org/10.1007/s13726-015-0352-1
Aydın, F., A review of recent developments in the corrosion performance of aluminium matrix composites, J. Alloys Compd., 949, 169508 (2023).
https://doi.org/10.1016/j.jallcom.2023.169508
Choudhury, B. and Choudhury, A., Ce³⁺ and oxygen vacancy mediated tuning of structural and optical properties of CeO₂ nanoparticles, Mater. Chem. Phys., 131, 666–671 (2012).
https://doi.org/10.1016/j.matchemphys.2011.10.032
Edison, T. N. J. I., Atchudan, R., Pugazhendhi, A., Lee, Y. R. and Sethuraman, M. G., Corrosion inhibition performance of spermidine on mild steel in acid media, J. Mol. Liq., 264, 483–489 (2018).
https://doi.org/10.1016/j.molliq.2018.05.087
Elangovan, N., Srinivasan, A., Pugalmani, S., Kalaiyarasan, M., Rajendran, N., Seikh, A. H. and Rajendiran, N., Development and electrochemical investigations of enhanced corrosion-resistant polyvinylcarbazole-TiO₂ hybrid nanocomposite coatings on 316L SS for marine applications, Surf. Coatings Technol., 481, 130628 (2024).
https://doi.org/10.1016/j.surfcoat.2024.130628
Hosseini, M. G. and Aboutalebi, K., Enhancement of anticorrosive resistance of epoxy coatings by incorporation of CeO₂@polyaniline@2-mercaptobenzothiazole nanocomposite, Synth. Met., 250, 63–72 (2019).
https://doi.org/10.1016/j.synthmet.2019.03.001
Jalal, R., Goharshadi, E. K., Abareshi, M., Moosavi, M., Yousefi, A. and Nancarrow, P., ZnO nanofluids: Green synthesis, characterization, and antibacterial activity, Mater. Chem. Phys., 121, 198–201 (2010).
https://doi.org/10.1016/j.matchemphys.2010.01.020
Li, L., Liu, L., Li, Z., Hu, D., Gao, C., Xiong, J. and Li, W., The synthesis of CB[8]/ZnO composite materials with enhanced photocatalytic activities, Heliyon, 5(5), e01714 (2019).
https://doi.org/10.1016/j.heliyon.2019.e01714
Madhuvilakku, R. and Piraman, S., Biodiesel synthesis by TiO₂–ZnO mixed oxide nanocatalyst catalyzed palm oil transesterification process, Bioresour. Technol., 150, 55–59 (2013).
https://doi.org/10.1016/j.biortech.2013.09.087
Mohanty, A., Kumar, S. and Tiwari, S. K., Assessment of N-(4H-1,2,4-triazol-4-yl) octanamide as hydrochloric acid corrosion inhibitor for mild steel, Mater. Today Commun., 27, 102439 (2021).
https://doi.org/10.1016/j.mtcomm.2021.102439
Phadke, S. N., Alva, V. D. P. and Samshuddin, S., A Review on 1,2,4-Triazole Derivatives as Corrosion Inhibitors, J. Bio-Tribo-Corrosion, 3, 1–12 (2017).
https://doi.org/10.1007/s40735-017-0102-3
Rajkumar, G. and Sethuraman, M. G., Electrochemical synthesis of poly-3-amino-5-mercapto-1,2,4-triazole on copper and its protective effect in 3.5 % NaCl medium, Res. Chem. Intermed., 41, 8041–8055 (2015).
https://doi.org/10.1007/s11164-014-1876-2
Rajkumar, G. and Sethuraman, M. G., Synthesis, characterization and corrosion protection of poly-4-methyl-3-mercapto-1,2,4-triazole/TiO₂ composite on copper, Polym. Bull., 71(12), 3249–3260 (2014).
https://doi.org/10.1007/s00289-014-1248-5
Saravanan, S. and Dubey, R. S., Synthesis of SiO₂ nanoparticles by sol–gel method and their optical and structural properties, Rom. J. Inf. Sci. Technol., 23(1), 105–112 (2020).
Singh, J., Sahu, K., Satpati, B. and Mohapatra, S., Facile synthesis, structural, optical and photocatalytic properties of anatase/rutile mixed-phase TiO₂ ball-like sub-micron structures, Optik (Stuttg)., 188, 270–276 (2019).
https://doi.org/10.1016/j.ijleo.2019.05.053
Vinothkumar, K. and Sethuraman, M. G., A robust method of enhancement of corrosion inhibitive ability of electrodeposited poly-3-amino-5-mercapto-1,2,4-triazole films over copper surface using graphene oxide, J. Adhes. Sci. Technol., 34(6), 651–669 (2020).
https://doi.org/10.1080/01694243.2019.1674599
Vinothkumar, K. and Sethuraman, M. G., Corrosion inhibition ability of electropolymerised composite film of 2-amino-5-mercapto-1,3,4-thiadiazole/TiO₂ deposited over the copper electrode in neutral medium, Mater. Today Commun., 14, 27–39 (2018).
https://doi.org/10.1016/j.mtcomm.2017.12.007
Winkler, D. A., Hughes, A. E., Özkan, C., Mol, A., Würger, T., Feiler, C., Zhang, D. and Lamaka, S. V., Impact of inhibition mechanisms, automation, and computational models on the discovery of organic corrosion inhibitors, Prog. Mater. Sci., 149, 101392 (2025).
