The effect of anodizing parameters in anodizing process of pure titanium on morphology of titanium‌ dioxide nanotubes

Document Type : Original Articles

Authors

Nazanin Yazdanparast

Faezeh Darvishian Haghiggi

Mohsen Haddad sabzevar

Sahar Mollazadeh Beidokhti

Department of Materials and Metallurgical Engineering, Faculty of Engineering, Ferdowsi University of mashhad, mashhad, Iran

10.22067/jmme.2025.92562.1196

Abstract

Nanoscale structures have recently attracted considerable attention due to their unique properties, particularly their excellent biocompatibility. Among these, titania nanotubes (TiO₂ NTs) are notable for their wide-ranging applications in fields such as biomedicine, catalysis, and energy. A highly effective method for fabricating these nanostructures is electrochemical anodization, which enables the direct in-situ formation of TiO₂ nanotubes on the titanium substrate. This technique offers the advantage of controlling nanotube morphology, including length and diameter, through simple adjustments of anodization parameters, making it both cost-effective and time-efficient. In this study, commercially pure titanium (Grade 2) was anodized using a standard two-electrode setup to investigate the influence of various parameters on nanotube formation. The effects of temperature, anodization time, surface preparation, cathode material, and electrolyte composition were systematically examined. Morphological analysis was performed using field emission scanning electron microscopy (FESEM), while elemental composition was determined using energy-dispersive X-ray spectroscopy (EDS). Results indicate that anodization conditions significantly impact the final morphology of the TiO₂ nanotubes. At 60 V, increasing the temperature accelerated nanotube dissolution, with severe degradation observed at 50 °C after 270 minutes. Fluoride ions in the electrolyte were identified as essential for nanotube formation. Additionally, extending the anodization time from 60 to 360 minutes increased the nanotube length from 12 μm to 47 μm and diameter from 50 nm to 120 nm. Overall, understanding the influence of these parameters provides a pathway for optimizing the anodization process to tailor TiO₂ nanotube structures for specific applications.

Keywords

Electrochemical anodizing

effect of temperature and time

type of cathode and electrolyte

pure titanium (grade2)

effect of voltage

morphology

Subjects

• Nanomaterials

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References

[1] 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.2013.10.001 

[2] C. M. Taylor, D. Mattia, and J. Wenk, “Photocatalytic immobilised TiO₂ nanostructures via fluoride-free anodisation,” Journal of Environmental Chemical Engineering, vol. 8, p. 103798, 2020. https://doi.org/10.1016/j.jece.2020.103798

[3] M. Sarraf, E. R. Ghomi, and S. Alipour, “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, no. 2, pp. 371–395, 2022. https://doi.org/10.1007/s42242-021-00170-3

[4] M. Mansoorianfar, R. Rahighi, and A. Hojjati-Najafabadi, “Amorphous/crystalline phase control of nanotubular TiO₂ membranes via pressure-engineered anodizing,” Materials & Design, vol. 198, p. 109314, 2021. https://doi.org/10.1016/j.matdes.2020.109314

[5] J. Wang and Z. Lin, “Anodic formation of ordered TiO₂ nanotube arrays: Effects of electrolyte temperature and anodization potential,” Journal of Physical Chemistry C, vol. 113, no. 10, pp. 4026–4030, 2009. https://doi.org/10.1021/jp811201x

[6] A. F. Cipriano, C. Miller, and H. Liu, “Anodic growth and biomedical applications of TiO₂ nanotubes,” Journal of Biomedical Nanotechnology, vol. 10, pp. 2977–3003, 2014. https://doi.org/10.1166/jbn.2014.1927

[7] 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. 157–162, 2014. https://doi.org/10.1016/j.elecom.2014.06.021

[8] 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. 521–529, 2016. https://doi.org/10.1016/j.electacta.2016.01.088

[9] D. Khudhair, A. Bhatti, and Y. Li, “Anodization parameters influencing the morphology and electrical properties of TiO₂ nanotubes for living cell interfacing and investigations,” Materials Science and Engineering: C, vol. 59, pp. 1125–1142, 2016. https://doi.org/10.1016/j.msec.2015.10.042

[10] J. A. Chacón and A. Cerdán-Pasarán, “Anodized TiO₂ nanotubes sensitized with selenium doped CdS nanoparticles for solar water splitting,” Energies, vol. 17, no. 7, p. 1592, 2024. https://doi.org/10.3390/en17071592

[11] S. Simbolon and Mahesa, “Fabrication of TiO₂ nanotubes on a Ti6Al4V substrate by anodisation under high voltage,” Ceramics-Silikáty, vol. 68, no. 1, pp. 88–95, 2024. https://doi.org/10.13168/cs.2024.0008

[12] P. Nakpan and A. Aeimbhu, “Fabrication of titanium dioxide nanotubes by difference the anodization voltage and time,” Materials Today: Proceedings, vol. 47, pp. 3436–3440, 2021. https://doi.org/10.1016/j.matpr.2021.03.290

[13] A. L. Escada and R. Z. Nakazato, “Influence of anodization parameters in the TiO₂ nanotubes formation on Ti-7.5Mo alloy surface for biomedical application,” Materials Research, vol. 20, no. 5, pp. 1282–1290, 2017. https://doi.org/10.1590/1980-5373-MR-2016-0520

[14] Z. Lockman and S. Sreekantan, “Influence of anodisation voltage on the dimension of titania nanotubes,” Journal of Alloys and Compounds, vol. 503, no. 2, pp. 359–364, 2010. https://doi.org/10.1016/j.jallcom.2009.12.093

[15] S. Sreekantana and Z. Lockman, “Influence of electrolyte pH on TiO₂ nanotube formation by Ti anodization,” Journal of Alloys and Compounds, vol. 485, no. 1–2, pp. 478–483, 2009. https://doi.org/10.1016/j.jallcom.2009.05.152

[16] T. Guo, S. Ivanovski, and K. Gulati, “Optimizing titanium implant nano-engineering via anodization,” Materials & Design, vol. 223, p. 111110, 2022. https://doi.org/10.1016/j.matdes.2022.111110

[17] V. Sivaprakash and R. Narayanan, “Synthesis of TiO₂ nanotubes via electrochemical anodization with different water content,” Materials Today: Proceedings, vol. 37, pp. 142–146, 2020. https://doi.org/10.1016/j.matpr.2020.04.657

[18] M. Erol, T. Dikici, M. Toparli, and E. Celik, “The effect of anodization parameters on the formation of nanoporous TiO₂ layers and their photocatalytic activities,” Journal of Alloys and Compounds, vol. 604, pp. 66–72, 2014. https://doi.org/10.1016/j.jallcom.2014.03.105

[19] D. R. Barjaktarević and I. Lj. Cvijović-Alagić, “Anodization of Ti-based materials for biomedical applications: A review,” Metallurgical and Materials Engineering, vol. 22, no. 3, pp. 129–144, 2016. https://doi.org/10.5937/metalmateng1603129B

[20] I. S. Park and T. G. Woo, “Surface characteristics of titanium anodized in the four different types of electrolyte,” Electrochimica Acta, vol. 53, no. 2, pp. 863–870, 2007. https://doi.org/10.1016/j.electacta.2007.07.067

[21] S. Minagar, C. C. Berndt, and J. Wang, “A review of the application of anodization for the fabrication of nanotubes on metal implant surfaces,” Acta Biomaterialia, vol. 8, no. 8, pp. 2875–2888, 2012. https://doi.org/10.1016/j.actbio.2012.04.005

[22] V. Galstyan, A. Vomiero, and E. Comini, “TiO₂ nanotubular and nanoporous arrays by electrochemical anodization on different substrates,” RSC Advances, vol. 1, no. 6, pp. 1038–1044, 2011. https://doi.org/10.1039/C1RA00077B

[23] 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, no. 1, p. C18, 2010. https://doi.org/10.1149/1.3251338

[24] K. Indira, U. K. Mudali, T. Nishimura, and N. Rajendran, “Review on TiO₂ nanotubes: Influence of anodization parameters, formation mechanism, properties, corrosion behavior, and biomedical applications,” Journal of Bio- and Tribo-Corrosion, vol. 1, no. 4, p. 28, 2015. https://doi.org/10.1007/s40735-015-0024-x

[25] B. Li, X. Han, and L. Qin, “Relationship between the growth rate of nanotubes and the current−time curve of the anodizing process,” Journal of Physical Chemistry C, vol. 128, no. 28, p. 18138, 2024. https://doi.org/10.1021/acs.jpcc.4c03809

[26] T. Tian and X.-f. Xiao, “Study on titania nanotube arrays prepared by titanium anodization in NH₄F/H₂SO₄ solution,” Journal of Materials Science, vol. 42, no. 14, pp. 5641–5646, 2007. https://doi.org/10.1007/s10853-006-1104-6

[27] Y. Liu and Y. Wang, “Impact of TiO₂ nanoparticles and nanowires on corrosion protection performance of chemically bonded phosphate ceramic coatings,” Ceramics International, vol. 48, no. 4, pp. 5091–5099, 2022. https://doi.org/10.1016/j.ceramint.2021.11.047

[28] C.-T. Yip and M. Guo, “Open-ended TiO₂ nanotubes formed by two-step anodization and their application in dye-sensitized solar cells,” Nanoscale, vol. 4, no. 2, pp. 448–450, 2012. https://doi.org/10.1039/c2nr11317a

[29] L. Suhadolnik and Ž. Marinko, “Influence of anodization-electrolyte aging on the photocatalytic activity of TiO₂ nanotube arrays,” Journal of Physical Chemistry C, vol. 124, no. 7, pp. 4073–4080, 2020. https://doi.org/10.1021/acs.jpcc.9b09522