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The Effect of Electrolyte Composition on the Fabrication of Self-Organized Titanium Oxide Nanotube Arrays by Anodic Oxidation

Published online by Cambridge University Press:  03 March 2011

Qingyun Cai ,
Maggie Paulose ,
Oomman K. Varghese  and
Craig A. Grimes
Qingyun Cai
Affiliation:
Department of Electrical Engineering, Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802; and Department of Chemistry, Hunan University, Changsha 410082, People’s Republic of China, 410082
Maggie Paulose
Affiliation:
Sentechbiomed Corporation, State College, Pennsylvania 16803
Oomman K. Varghese
Affiliation:
Department of Electrical Engineering, Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802
Craig A. Grimes
Affiliation:
Department of Electrical Engineering, Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802
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Abstract

We report on the fabrication of self-organized titanium oxide nanotube arrays of enhanced surface area prepared by anodic oxidation of a pure titanium sheet in electrolyte solutions containing potassium fluoride (KF) or sodium fluoride (NaF). The effects of electrolyte composition and concentration, solution pH, and the anodic potential on the formation of nanotubes and dimensions of the resulting nanotubes are detailed. Although nanotube arrays of length greater than 500 nm are not possible with hydrofluoric acid containing electrolytes [G.K. Mor, O.K. Varghese, M. Paulose,N. Mukherjee, C.A. Grimes, J. Mater. Res. 18, 2588 (2003)], by adjusting the pH of a KF containing electrolyte to 4.5 using additives such as sulfuric acid, sodium hydroxide, sodium hydrogen sulfate, and/or citric acid, we could increase the length of the nanotube-array to approximately 4.4 μm, an order of magnitude increase in length. The as-prepared nanotubes are composed of amorphous titanium oxide. Independent of the electrolyte composition, crystallization of the nanotubes to anatase phase occurred at temperatures ⩾280 °C. Rutile formation occurred at the nanotube-Ti substrate interface at temperatures near 480 °C. It appears geometry constraints imposed by the nanotube walls inhibit anatase to rutile transformation. No disintegration of the nanotube array structure is observed at temperatures as high as 580 °C. The excellent structural and crystal phase stability of these nanotubes make them promising for both low- and high-temperature applications.

Keywords

CeramicElectrochemical synthesisNanoscale
Type
Articles
Information
Journal of Materials Research , Volume 20 , Issue 1 , January 2005 , pp. 230 - 236
Copyright
Copyright © Materials Research Society 2004

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References

REFERENCES

1Varghese, O.K., Gong, D.W., Paulose, M., Grimes, C.A. and Dickey, E.C.: Crystallization and high-temperature structural stability of titanium oxide nanotube arrays. J. Mater. Res. 18, 156 (2003).CrossRefGoogle Scholar
2Zwilling, V., Darque-Ceretti, E., Boutry-Forveille, A., David, D., Perrin, M.Y. and Aucouturier, M.: Structure and physicochemistry of anodic oxide films on titanium and TA6V alloy. Surf. Interface Anal. 27, 629 (1999).3.0.CO;2-0>CrossRefGoogle Scholar
3Mor, G.K., Carvalho, M.A., Varghese, O.K., Pishko, M.V. and Grimes, C.A.: A room-temperature TiO2-nanotube hydrogen sensor able to self-clean photoactively from environmental contamination. J. Mater. Res. 19, 628 (2004).CrossRefGoogle Scholar
4Varghese, O.K., Gong, D., Paulose, M., Ong, K.G. and Grimes, C.A.: Hydrogen sensing using titania nanotubes. Sens. Actuators B 93, 338 (2003).CrossRefGoogle Scholar
5Varghese, O.K., Gong, D., Paulose, M., Ong, K.G., Dickey, E.C. and Grimes, C.A.: Extreme changes in the electrical resistance of titania nanotubes with hydrogen exposure. Adv. Mater. 15, 624 (2003).CrossRefGoogle Scholar
6Beranek, R., Hildebrand, H. and Schmuki, P.: Self-organized porous titanium oxide prepared in H2SO4/HF electrolytes. Electrochem. Solid State Lett. 6, B12 (2003).CrossRefGoogle Scholar
7Mor, G.K., Varghese, O.K., Paulose, M., Mukherjee, N. and Grimes, C.A.: Fabrication of tapered, conical-shaped titania nanotubes. J. Mater. Res. 18, 2588 (2003).CrossRefGoogle Scholar
8Yang, B.C., Uchida, M., Kim, H.M., Zhang, X.D. and Kokubo, T.: Preparation of bioactive titanium metal via anodic oxidation treatment. Biomaterials 25, 1003 (2004).CrossRefGoogle ScholarPubMed
9Sul, Y.T., Johansson, C.B., Jeong, Y. and Albrektsson, T.: The electrochemical oxide growth behaviour on titanium in acid and alkaline electrolytes. Med. Eng. Phys. 23, 329 (2001).CrossRefGoogle ScholarPubMed
10Gong, D., Grimes, C.A., Varghese, O.K., Hu, W., Singh, R.S., Chen, Z. and Dickey, E.C.: Titanium oxide nanotube arrays prepared by anodic oxidation. J. Mater. Res. 16, 3331 (2001).CrossRefGoogle Scholar
11Varghese, O.K., Mor, G.K., Grimes, C.A., Paulose, M. and Mukherjee, N.: A titania nanotube-array room-temperature sensor for selective detection of hydrogen at low concentrations. J. Nanosci. Nanotech. 4, 733 (2004).CrossRefGoogle ScholarPubMed
12Adachi, M., Murata, Y., Okada, I. and Yoshikawa, S.: Formation of titania nanotubes and applications for dye-sensitized solar cells. J. Electrochem. Soc. 150, G488 (2003).CrossRefGoogle Scholar
13Giavaresi, G., Giardino, R., Ambrosio, L., Battiston, G., Gerbasi, R., Fini, M., Rimondini, L. and Torricelli, R.: In vitro biocompatibility of titanium oxide for prosthetic devices nanostructured by low pressure metal-organic chemical vapor deposition. Int. J. Artif. Organs 26, 774 (2003).CrossRefGoogle ScholarPubMed
14Jang, H.D., Kim, S.K. and Kim, S.J.: Effect of particle size and phase composition of titanium dioxide nanoparticles on the photocatalytic properties. J. Nanopart. Res. 3, 141 (2001).CrossRefGoogle Scholar
15Rodriguez, R., Kim, K. and Ong, J.L.: In vitro osteoblast response to anodized titanium and anodized titanium followed by hydrothermal treatment. J. Biomed. Mater. Res. A 65, 352 (2003).CrossRefGoogle ScholarPubMed
16Zinger, O., Chauvy, P.F. and Landolt, D.: Scale-resolved electrochemical surface structuring of titanium for biological applications. J. Electrochem. Soc. 150, B495 (2003).CrossRefGoogle Scholar
17Gouma, P.I. and Mills, M.J.: Anatase-to-rutile transformation in titania powders. J. Am. Ceram. Soc. 84, 619 (2001).CrossRefGoogle Scholar
18Zhang, H. and Banfield, J.F.: Phase transformation of nanocrystalline anatase-to-rutile via combined interface and surface nucleation. J. Mater. Res. 15, 437 (2000).CrossRefGoogle Scholar
19Kumar, K-N.P., Keizer, K., Burggraaf, A.J., Okubo, T. and Nagamoto, H.: Textural evolution and phase transformation in titania mmbranes: Part 2. Supported membranes. J. Mater. Chem. 3, 1151 (1993).CrossRefGoogle Scholar
20Ohya, Y., Saiki, H., Tanaka, T. and Takahashi, Y.: Microstructure of TiO2 and ZnO films fabricated by sol-gel method. J. Am. Ceram. Soc. 79, 825 (1996).CrossRefGoogle Scholar
21Hoffmann, M.R., Martin, S.T., Choi, W. and Bahnemannt, D.W.: Environmental applications of semiconductor photcatalysis. Chem. Rev. 95, 69 (1995).CrossRefGoogle Scholar
22Fox, M.A. and Dulay, M.T.: Heterogeneous photocatalysis. Chem. Rev. 93, 341 (1993).CrossRefGoogle Scholar
23Gratzel, M.: Photoelectrochemical cells. Nature 414, 338 (2001).CrossRefGoogle ScholarPubMed