Journal Of Metallurgical and Materials Engineering

Journal Of Metallurgical and Materials Engineering

Surface Engineering of Titanium via a Two-Step Electrochemical Anodization Process: Mechanism of Nucleation and Growth of Titanium Oxide Nanotubes

Document Type : Original Articles

Authors
Faezeh Darvishian Haghighi
Nazanin Yazdan Parast
Sahar Mollazadeh Beidokhti
Mohsen Haddad Sabzevar
Department of Materials Science and Metallurgical Engineering, Faculty of Engineering, Ferdowsi University of Mashhad, Mashhad, Iran
10.22067/jmme.2026.95575.1224
Abstract
In recent years, titanium oxide nanotubes (TiO₂ NTs) grown on titanium metallic substrates have attracted significant attention due to their wide applications in biomedical and energy-related fields. Electrochemical anodization is considered one of the most effective methods for producing these nanotubular structures. The present study aims to investigate the influence of a two-step electrochemical anodization process on the physicochemical properties of titanium oxide nanotubes. Following anodization, the fabricated coatings were characterized using various metallurgical techniques. Raman spectroscopy confirmed the presence of characteristic peaks of titanium oxide in the developed layer. Phase analysis using X-ray diffraction (XRD) revealed that the formed nanotubes consisted of TiO₂ nanocrystallites with anatase as the dominant phase. Moreover, field-emission scanning electron microscopy (FESEM) observations demonstrated that two-step anodization remarkably improves the nanotube structural order compared to single-step anodization, as the nanotubes grow during the second stage based on a pre-formed template, resulting in highly parallel and well-aligned structures. Contact angle measurements indicated a 38.78% reduction in wettability angle, signifying enhanced surface hydrophilicity after two-step anodization. Additionally, atomic force microscopy (AFM) analyses revealed an increase in surface roughness from 69.8 to 285.3 nm, which improves the specific surface area. Such enhancement in surface roughness is considered beneficial for biomedical applications, particularly in implant technology. Therefore, it can be concluded that two-step anodization is a key process for engineering and optimizing titanium-based nanotubular structures.
Keywords
Titanium Oxide Nanotubes
Electrochemical Anodization Process
Nucleation Mechanism
Subjects
[1] M. Geetha, A. K. Singh, R. Asokamani, and A. K. Gogia, “Ti based biomaterials, the ultimate choice for orthopaedic implants – A review,” Progress in Materials Science, vol. 54, no. 3, pp. 397–425, 2009. https://doi.org/10.1016/j.pmatsci.2008.06.004
[2] J. M. Macak, H. Tsuchiya, A. Ghicov, et al., “TiO₂ nanotubes: self-organized electrochemical formation, properties and applications,” Current Opinion in Solid State and Materials Science, vol. 11, no. 1–2, pp. 3–18, 2007. https://doi.org/10.1016/j.cossms.2007.03.001
[3] P. Roy, S. Berger, and P. Schmuki, “TiO₂ nanotubes: synthesis and applications,” Angewandte Chemie International Edition, vol. 50, no. 13, pp. 2904–2939, 2011. https://doi.org/10.1002/anie.201001374
[4] X. Chen and S. S. Mao, “Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications,” Chemical Reviews, vol. 107, no. 7, pp. 2891–2959, 2007. https://doi.org/10.1021/cr0500535
[5] K. Lee, A. Mazare, and P. Schmuki, “One-dimensional titanium dioxide nanomaterials: nanotubes,” Chemical Reviews, vol. 114, no. 19, pp. 9385–9454, 2014. https://doi.org/10.1021/cr5000891
[6] G. Li, H. Haneda, S. Hishita, and N. Ohashi, “Photocatalytic activity and photoinduced hydrophilicity of various crystalline TiO₂,” The Journal of Physical Chemistry B, vol. 107, no. 3, pp. 438–444, 2003. https://doi.org/10.1021/jp0269009
[7] A. Ghicov and P. Schmuki, “Self-organized TiO₂ nanotube arrays: synthesis and applications,” Chemical Communications, vol. 20, pp. 2791–2808, 2009. https://doi.org/10.1039/b822556h
[8] H. Zhang and J. F. Banfield, “Understanding polymorphic phase transformation behavior during growth of nanocrystalline aggregates: insights from TiO₂,” The Journal of Physical Chemistry B, vol. 104, no. 15, pp. 3481–3487, 2000. https://doi.org/10.1021/jp9938823
[9] J. M. Macak, H. Tsuchiya, and A. Ghicov, “Self-organized nanotubular oxide layers on Ti–6Al–4V and Ti–6Al–7Nb alloys,” Electrochimica Acta, vol. 50, no. 18–19, pp. 3679–3684, 2005. https://doi.org/10.1016/j.electacta.2005.02.019
[10] K. C. Popat, L. Leoni, C. A. Grimes, and T. A. Desai, “Influence of engineered titania nanotubular surfaces on bone cells,” Biomaterials, vol. 28, no. 21, pp. 3188–3197, 2007. https://doi.org/10.1016/j.biomaterials.2007.03.003
[11] Y. Yang, Y. Chen, and L. Shi, “Titanium dioxide nanotubes as selective photocatalysts for oxidative degradation of organic pollutants,” The Journal of Physical Chemistry C, vol. 114, no. 1, pp. 487–493, 2010. https://doi.org/10.1021/jp9092106
[12] Y. Choi, H. Yang, and Y. Kim, “Effect of electrolyte composition on the formation of self-organized TiO₂ nanotube arrays via anodization,” Electrochimica Acta, vol. 115, pp. 250–257, 2014. https://doi.org/10.1016/j.electacta.2013.10.004
[13] Z. Huang, N. Geyer, and P. Werner, “TiO₂ nanotube arrays: synthesis, properties, and applications,” Angewandte Chemie International Edition, vol. 50, no. 13, pp. 2904–2939, 2011. https://doi.org/10.1002/anie.201001374
[14] K. Shankar, D. Bera, and H. Y. Kim, “Growth and characterization of anodic titanium oxide nanotube arrays prepared by single-step and two-step anodization,” Materials Chemistry and Physics, vol. 132, no. 2–3, pp. 658–666. https://doi.org/10.1016/j.matchemphys.2011.10.026
[15] H. Masuda and K. Fukuda, “Ordered metal nanohole arrays made by a two-step replication of honeycomb structures of anodic alumina,” Science, vol. 268, no. 5216, pp. 1466–1468, 1995. https://doi.org/10.1126/science.268.5216.1466
[16] S. P. Albu, A. Ghicov, J. M. Macak, et al., “Formation of double-walled TiO₂ nanotubes and robust anatase membranes,” Advanced Materials, vol. 20, no. 23, pp. 4135–4139, 2008. https://doi.org/10.1002/adma.200801308
[17] J. M. Macak, M. Zlamal, J. Krysa, and P. Schmuki, “Self-organized TiO₂ nanotube layers as highly efficient photocatalysts,” Small, vol. 3, no. 2, pp. 300–304, 2007. https://doi.org/10.1002/smll.200600574
[18] Das, S. Dasgupta, and R. Maric, “Characterization and properties of anodic titanium oxide nanotube arrays prepared by one-step and two-step anodization processes,” Electrochimica Acta, vol. 245, pp. 473–485, 2017. https://doi.org/10.1016/j.electacta.2017.04.019
[19] P. Roy, O. K. Varghese, M. Paulose, and C. A. Grimes, “Toward solar fuels: photocatalytic hydrogen generation using titania nanotube arrays,” ACS Nano, vol. 4, no. 3, pp. 1259–1279, 2010. https://doi.org/10.1021/nn901525r
[20] H. Tsuchiya, A. Ghicov, and J. M. Macak, “Enhanced photocatalytic activity of TiO₂ nanotubes prepared by anodic oxidation,” Chemical Physics Letters, vol. 429, nos. 4–6, pp. 606–610, 2006. https://doi.org/10.1016/j.cplett.2006.07.014
[21] H. Masuda, K. Yada, and A. Osaka, “Highly ordered nanochannel-array architecture in anodic alumina,” Applied Physics Letters, vol. 74, no. 6, pp. 851–853, 1999. https://doi.org/10.1063/1.123507
[22] J. M. Macak, H. Tsuchiya, and P. Schmuki, “High-aspect-ratio TiO₂ nanotubes by anodization of titanium,” Angewandte Chemie International Edition, vol. 44, no. 14, pp. 2100–2102, 2005. https://doi.org/10.1002/anie.200462132
[23] J. M. Macak, H. Tsuchiya, and A. Ghicov, “Self-organized titanium oxide nanotube arrays as highly efficient photocatalysts,” Small, vol. 1, no. 8–9, pp. 1088–1092, 2005. https://doi.org/10.1002/smll.200500100
[24] Z. Zhang, W. Shen, and W. Chu, “Photocatalytic activity and photoelectrochemical properties of TiO₂ nanotube arrays prepared by anodization,” The Journal of Physical Chemistry C, vol. 116, no. 9, pp. 5443–5450, 2012. https://doi.org/10.1021/jp211344k
[25] P. Roy, S. Berger, and P. Schmuki, “TiO₂ nanotubes: synthesis and applications,” Angewandte Chemie International Edition, vol. 50, no. 13, pp. 2904–2939, 2011. https://doi.org/10.1002/anie.201001374
[26] K. C. Popat, M. L. Eltgroth, T. J. LaTempa, et al., “Titania nanotubes: A novel platform for drug-eluting coatings for medical implants?,” Small, vol. 3, no. 11, pp. 1878–1881, 2007. https://doi.org/10.1002/smll.200700261
[27] C. M. Taylor, D. Mattia, and J. Wenk, “Photocatalytic immobilised TiO₂ nanostructures via fluoride-free anodization,” Environmental Chemistry Engineering, vol. 8, 2020. https://doi.org/10.1016/j.jece.2020.103876
[28] M. Sarraf, E. Rezvani Ghomi, S. Alipour, et al., “A state-of-the-art review of the fabrication and characteristics of titanium and its alloys for biomedical applications,” Bio-Design and Manufacturing, vol. 5, pp. 1–23, 2022. https://doi.org/10.1007/s42242-021-00170-2
[29] D. Regonini, C. R. Bowen, A. Jaroenworaluck, and R. Stevens, “A review of growth mechanism, structure and crystallinity of anodized TiO₂ nanotubes,” Materials Science and Engineering R: Reports, vol. 74, pp. 377–406, 2013. https://doi.org/10.1016/j.mser.2013.04.001
[30] X. Zhou, N. T. Nguyen, S. Özkan, and P. Schmuki, “Anodic TiO₂ nanotube layers: Why does self-organized growth occur—A mini review,” Electrochemistry Communications, vol. 46, pp. 157–161, 2014. https://doi.org/10.1016/j.elecom.2014.06.003
[31] C. Adán, J. Marugán, and E. Sánchez, “Understanding the effect of morphology on the photocatalytic activity of TiO₂ nanotube array electrodes,” Electrochimica Acta, vol. 191, pp. 546–553, 2016. https://doi.org/10.1016/j.electacta.2015.11.092
[32] P. Nakpan and A. Aeimbhu, “Fabrication of titanium dioxide nanotubes by difference the anodization voltage and time,” Materials Today: Proceedings, vol. 44, pp. 1834–1838, 2021. https://doi.org/10.1016/j.matpr.2020.11.682
[33] V. Sivaprakash and R. Narayanan, “Synthesis of TiO₂ nanotubes via electrochemical anodization with different water content,” Materials Today: Proceedings, vol. 33, pp. 3206–3210, 2020. https://doi.org/10.1016/j.matpr.2020.06.514
[34] V. Galstyan, A. Vomiero, and E. Comini, “TiO₂ nanotubular and nanoporous arrays by electrochemical anodization on different substrates,” RSC Advances, vol. 1, pp. 1038–1046, 2011. https://doi.org/10.1039/c1ra00413a
[35] S. Berger, J. Kunze, and P. Schmuki, “Influence of water content on the growth of anodic TiO₂ nanotubes in fluoride-containing ethylene glycol electrolytes,” Journal of The Electrochemical Society, vol. 157, pp. E18–E23, 2010. https://doi.org/10.1149/1.3254167
 
Send comment about this article
Enter Name.
Enter a valid email address.
Enter a vaid affiliation.
Enter comments (At leaset 10 words)
CAPTCHA Image
Enter Security Code Correctly.