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

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.

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Titanium oxide nanotube arrays prepared by anodic oxidation

Journal of Materials Research ◽

10.1557/jmr.2001.0457 ◽

2001 ◽

Vol 16 (12) ◽

pp. 3331-3334 ◽

Cited By ~ 1548

Author(s):

Dawei Gong ◽

Craig A. Grimes ◽

Oomman K. Varghese ◽

Wenchong Hu ◽

R. S. Singh ◽

...

Keyword(s):

Titanium Oxide ◽

Anodic Oxidation ◽

Hydrofluoric Acid ◽

Layer Structure ◽

Porous Alumina ◽

Pure Titanium ◽

Nanotube Arrays ◽

Titanium Sheet ◽

Anodization Time ◽

Titanium Oxide Nanotubes

Titanium oxide nanotubes were fabricated by anodic oxidation of a pure titanium sheet in an aqueous solution containing 0.5 to 3.5 wt% hydrofluoric acid. These tubes are well aligned and organized into high-density uniform arrays. While the tops of the tubes are open, the bottoms of the tubes are closed, forming a barrier layer structure similar to that of porous alumina. The average tube diameter, ranging in size from 25 to 65 nm, was found to increase with increasing anodizing voltage, while the length of the tube was found independent of anodization time. A possible growth mechanism is presented.

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Crystallization and high-temperature structural stability of titanium oxide nanotube arrays

Journal of Materials Research ◽

10.1557/jmr.2003.0022 ◽

2003 ◽

Vol 18 (1) ◽

pp. 156-165 ◽

Cited By ~ 532

Author(s):

Oomman K. Varghese ◽

Dawei Gong ◽

Maggie Paulose ◽

Craig A. Grimes ◽

Elizabeth C. Dickey

Keyword(s):

Heat Treatment ◽

High Temperature ◽

Titanium Oxide ◽

Elevated Temperatures ◽

Anatase Phase ◽

Argon Atmosphere ◽

Nanotube Arrays ◽

Nanotube Array ◽

Inner Diameter ◽

The Stability

The stability of titanium oxide nanotube arrays at elevated temperatures was studied in dry oxygen as well as dry and humid argon environments. The tubes crystallized in the anatase phase at a temperature of about 280 °C irrespective of the ambient. Anatase crystallites formed inside the tube walls and transformed completely to rutile at about 620 °C in dry environments and 570 °C in humid argon. No discernible changes in the dimensions of the tubes were found when the heat treatment was performed in oxygen. However, variations of 10% and 20% in average inner diameter and wall thickness, respectively, were observed when annealing in a dry argon atmosphere at 580 °C for 3 h. Pore shrinkage was even more pronounced in humid argon environments. In all cases the nanotube architecture was found to be stable up to approximately 580 °C, above which oxidation and grain growth in the titanium support disrupted the overlying nanotube array.

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PREPARATION OF HIGH-ORDERLY TIO2 NANOTUBES IN DIFFERENT CONDITIONS AND ELECTROLYTE SOLUTIONS

International Journal of Modern Physics B ◽

10.1142/s0217979207044858 ◽

2007 ◽

Vol 21 (18n19) ◽

pp. 3506-3510 ◽

Cited By ~ 1

Author(s):

YUNHUAI ZHANG ◽

FU HU ◽

PENG XIAO ◽

XIAOYAN FAN

Keyword(s):

Titanium Oxide ◽

Structural Properties ◽

Anodic Oxidation ◽

Tio2 Nanotubes ◽

Ph Value ◽

Pure Titanium ◽

Titanium Substrate ◽

Electrolyte Solutions ◽

Organic Solutions ◽

Better Than

High-orderly nanotubes of titania were fabricated by anodic oxidation of pure titanium substrate in different electrolytes containing fluoride. Different morphological nanotubes of titania were obtained through controlling the different pH value of inorganic electrolytes, and it was found that nanotubes of titanium oxide would not formed when pH value was above 6. The morphological and structural properties of nanotublar products were characterized by SEM. The synthesized nanotubes of titania in organic electrolytic solutions containing fluoride was of 60 μm in length. The experiments demonstrated the length and orderliness of nanotubes of titanium oxide in organic solutions were much better than those in inorganic solutions.

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The Effect of Preparation Temperature of Electrolytes on Undoped and Ag-Doped TiO2 Nanotube Structures

Materials Science Forum ◽

10.4028/www.scientific.net/msf.860.7 ◽

2016 ◽

Vol 860 ◽

pp. 7-11 ◽

Cited By ~ 2

Author(s):

Somkuan Photharin ◽

Buagun Samran ◽

Rinnatha Vongwatthaporn ◽

Narongsak Kodtharin ◽

Ramida Chaiyarat ◽

...

Keyword(s):

Heat Treatment ◽

Electrolyte Solution ◽

Pure Titanium ◽

Silver Ions ◽

Ammonium Fluoride ◽

Electrolyte Solutions ◽

Nanotube Arrays ◽

X Ray Diffraction ◽

Preparation Temperature ◽

X Ray

In this work, we present the effect of preparation temperature of electrolytes for fabricating undoped and silver (Ag) doped titanium dioxide (TiO2) nanotubes by the electrochemical anodic oxidation of pure titanium sheets in electrolytes, mixtures of ethylene glycol (EG), ammonium fluoride (NH4F) and deionized water, that contain with different of silver ions. Heat treatment of electrolytes was carried out at 100 °C during preparation process. The morphology and structure of prepared nanotubes were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The structures of TiO2 nanotubes obtained from heat treatment and non-heat treatment of electrolyte solutions and adding silver ions in electrolyte solution are similar. The nanotubes appear in arrays and the diameters of nanotubes were about 92 nm for non-heat treatment electrolyte solution and undoped TiO2 and about 102 nm for heat treatment electrolyte solution and all Ag-doped TiO2 nanotube arrays. When the concentration of silver nitrate (AgNO3) increases, the TiO2 nanotube arrays cracked and are not well arranged.

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Fabrication of self-organised highly ordered titanium oxide nanotube arrays by anodic oxidation and characterisation

International Journal of Nanomanufacturing ◽

10.1504/ijnm.2010.033872 ◽

2010 ◽

Vol 5 (3/4) ◽

pp. 297

Author(s):

Raheleh Mohammadpour ◽

Mohammad Mahdi Ahadian ◽

Azam Iraji zad ◽

Nima Taghavinia ◽

Abol Ghasem Dolati

Keyword(s):

Titanium Oxide ◽

Anodic Oxidation ◽

Nanotube Arrays

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Self-Organized Nitrogen and Fluorine Co-doped Titanium Oxide Nanotube Arrays with Enhanced Visible Light Photocatalytic Performance

Environmental Science & Technology ◽

10.1021/es902214s ◽

2009 ◽

Vol 43 (23) ◽

pp. 8923-8929 ◽

Cited By ~ 70

Author(s):

Qi Li ◽

Jian Ku Shang

Keyword(s):

Visible Light ◽

Titanium Oxide ◽

Photocatalytic Performance ◽

Nanotube Arrays ◽

Self Organized ◽

Co Doped ◽

Visible Light Photocatalytic

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Investigation of wear behavior of titanium oxide films, produced by anodic oxidation, on commercially pure titanium in vacuum conditions

Surface and Coatings Technology ◽

10.1016/j.surfcoat.2010.08.079 ◽

2010 ◽

Vol 205 (6) ◽

pp. 1757-1763 ◽

Cited By ~ 101

Author(s):

A.F. Yetim

Keyword(s):

Titanium Oxide ◽

Anodic Oxidation ◽

Wear Behavior ◽

Oxide Films ◽

Pure Titanium ◽

Commercially Pure Titanium ◽

Commercially Pure ◽

Titanium Oxide Films

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Preparation and Optical Properties of TiO2 Nanotube Arrays by Anodic Oxidation Method

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.105-106.363 ◽

2010 ◽

Vol 105-106 ◽

pp. 363-366

Author(s):

Zhu Mei Wang ◽

Yun Xia Chen ◽

Yue Ming Li ◽

Jian Lin Zuo

Keyword(s):

Optical Properties ◽

Anodic Oxidation ◽

Pure Titanium ◽

Tio2 Nanotube Arrays ◽

Tio2 Nanotube ◽

Nanotube Arrays ◽

Titania Nanotube Arrays ◽

Titania Nanotube ◽

Anodic Oxidation Method ◽

Oxidation Parameters

Titania nanotube arrays were fabricated by anodic oxidation of a pure titanium foil. The morphology, structure and optical properties of the nanotube arrays were characterized by SEM, XRD and UV-Vis spectrum. The effect of anodic oxidation parameters on the morphology was investigated. The growth mechanism of the titania nanotube arrays was discussed. The results show that the vertical oriented TiO2 nanotube arrays can be obtained at 20V for 60min in 0.5wt%HF+1mol/L H3PO4 solution. The aperture size of nanotube is 60nm~80nm and the thickness of tube wall is about 10nm. The spectral absorptivity of TiO2 nanotube arrays membrane calcined at 600°C towards ultravlolet light 349.7nm and visible light 443.9nm was relatively higher. It is also found that the crystal structure is greatly affected by calcining temperature.

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