Formation of TiO2 Nanotube Layer by Anodization of Titanium in Ethylene Glycol-H2O Electrolyte


In orthopaedics and orthodontics, the growth of nanotubes of titanium oxide on titanium implants is a promising route for improving the osseointegration. Among the fabrication routes to produce nanotubes, anodization was generally preferred due to its simplicity and low cost. TiO2 nanotubes are formed by the simultaneous anodic reaction and chemical dissolution due to the fluoride species present in the anodization bath. In this work, the formation of TiO2 nanotubes was studied in stirred ethylene glycol-H2O electrolyte (90 - 10 v/v) containing NH4F at room temperature. In order to study the effect of NH4F concentration, voltage and anodization time, and to reduce the number of experiments, a design of experiments (DOE) based on a 2k factorial design with four replicates at the center point was used. The analysis of variance (ANOVA) was used to evaluate the effects of the factors of control and their interactions on the percentage of the titanium surface coated by nanotubes. The dimensions of nanotubes (length and diameter) were also evaluated using field emission gun scanning electron microscopy. The cristallinity and phase composition of the oxide layers was investigated by X-ray diffractometry. The electrochemical behavior of as-received and anodized titanium specimens was studied in Ringer’s solution. The statistical analysis showed that fluoride concentration is the most significant factor. The best condition according to the response surface analysis is the center point (1% NH4F, 20 V, 2 h). The nanotubular oxide layers presented an amorphous structure. Electrochemical tests showed that TiO2 nanotubes coated titanium is less corrosion resistant than as-received titanium.

Share and Cite:

Robin, A. , Bernardes de Almeida Ribeiro, M. , Luiz Rosa, J. , Zenhei Nakazato, R. and Borges Silva, M. (2014) Formation of TiO2 Nanotube Layer by Anodization of Titanium in Ethylene Glycol-H2O Electrolyte. Journal of Surface Engineered Materials and Advanced Technology, 4, 123-130. doi: 10.4236/jsemat.2014.43016.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] Jones, F.H. (2001) Teeth and Bones: Applications of Surface Science to Dental Materials and Related Biomaterials. Surface Science Reports, 42, 75-205.
[2] Narayanan, R., Lee, H.-J., Kwon, T.-Y. and Kim, K.-H. (2011) Anodic TiO2 Nanotubes from Stirred Baths: Hydroxyapatite Growth & Osteoblast Responses. Materials Chemistry and Physics, 125, 510-517.
[3] Kaneco, S., Chen, Y., Westerhoff, P. and Crittenden, J.C. (2007) Fabrication of Uniform Size Titanium Oxide Nanotubes: Impact of Current Density and Solution Conditions. Scripta Materialia, 56, 373-376.
[4] Prida, V.M., Manova, E., Veja, V., Hernandez-Velez, M., Aranda, P., Pirota, K.R., Vázquez, M. and Ruiz-Hitzky, E. (2007) Temperature Influence on the Anodic Growth of Self-Aligned Titanium Dioxide Nanotubes Arrays. Journal of Magnetism and Magnetic Materials, 316, 110-113.
[5] Bauer, S., Pittrof, A., Tsuchiya, H. andSchmuki, P. (2011) Size-Effects in TiO2 Nanotubes: Diameter Dependent Anatase/Rutile Stabilization. Electrochemistry Communications, 13, 538-541.
[6] Liu, R., Hsieh, C.-S., Yang, W.D., Qiang, L.-S. and Wu, J.-F. (2011) Applying the Statistical Experimental Method to Evaluate the Process Conditions of TiO2 Nanotube Arrays by Anodization Method. Current Applied Physics, 11, 1294-1298.
[7] Pittrof, A., Bauer, S. and Schmuki, P. (2011) Micropatterned TiO2 Nanotube Surfaces for Site-Selective Nucleation of Hydroxyapatite from Simulated Body Fluid. Acta Biomaterialia, 7, 424-431.
[8] Kafi, A.K.M., Wu, G., Benvenuto, P. and Chen, A. (2011) High Sensitive Amperometric H2O2 Biosensor Based on Hemoglobin Modified TiO2 Nanotubes. Journal of Electroanalytical Chemistry, 662, 64-69.
[9] Park, H.H., Park, I.S., Kim, K.S., Jeon, W.Y., Park, B.K., Kim, H.S., Bae, T.S. and Lee, M.H. (2010) Bioactive and Electrochemical Characterization of TiO2 Nanotubes on Titanium via Anodic Oxidation. Electrochimica Acta, 55, 6109-6114.
[10] Cummings, F.R., Le Roux, L.J., Mathe, M.K. and Knoesen, D. (2010) Structure Induced Optical Properties of Anodized TiO2 Nanotubes. Materials Chemistry and Physics, 124, 234-242.
[11] Minagar, S., Berndt, C.C., Wang, J., Ivanova, E. and Wen, C. (2012) A Review of the Application of Anodization for the Fabrication of Nanotubes on Metal Implant Surfaces. Acta Biomaterialia, 8, 2875-2888.
[12] Regonini, D., Bowen, C.R., Jaroenworaluck, A. and Stevens, R. (2013) A Review of Growth Mechanism, Structure and Crystallinity of Anodized TiO2 Nanotubes. Materials Science and Engineering R, 74, 377-406.
[13] Montgomery, D.C. (2009) Introduction to Statistical Quality Control. 6th Edition, John Wiley & Sons, New York.
[14] Ghicov, A. and Schmuki, P. (2009) Self-Ordering Electrochemistry: A Review on Growth and Functionality of TiO2 Nanotubes and Other Self-Aligned MOx Structures. Chemical Communications, 45, 2791-2808.
[15] Shibata, T. and Zhu, Y.-C. (1995) The Effect of Film Formation Conditions on the Structure and Composition of Anodic Oxide Films on Titanium. Corrosion Science, 37, 253-270.
[16] Sul, Y.-T., Johansson, C.B., Jeong, Y. and Albrektsson, T. (2001) The Electrochemical Oxide Growth Behaviour on Titanium in Acid and Alkaline Electrolytes. Medical Engineering & Physics, 23, 329-346.
[17] Pourbaix, M. (1966) Atlas of Electrochemical Equilibria in Aqueous solutions. Pergamon Press, New York.
[18] Liu, C.L., Wang, Y.J., Wang, M., Huang, W.J. and Chu, P.K. (2012) Electrochemical Behavior of TiO2 Nanotube on Titanium in Artificial Saliva Containing Bovine Serum Albumin. Corrosion Engineering, Science and Technology, 47, 167-169.

Copyright © 2023 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.