Fabrication and characterization of anodic oxide nanotubes on TiNb alloys

Titanium and its alloys have been extensively used as implant materials owing to their high specific strength, good biocompatibility and excellent corrosion resistance. Oxide nanotubular array layer can be formed on Ti alloy surface by electrochemical anodization treatment. In this work, the morphology of nanotubes formed on Ti–Nb alloys(Nb content of 5 wt%, 10 wt%, 20 wt%, 30 wt% and40 wt%) was investigated using an electrolyte containing ethylene glycol and NH_4 F. Oxide layers consisting of highly ordered nanotubes with a range of diameters(approximately40–55 nm for the inner diameter and 100–120 nm for the outer diameter) and lengths(approximately 10–20 lm) can be formed on alloys in the Ti–x Nb system, independent on the Nb content. The nanotubes formed on the Ti–Nb alloy surface were transformed from the anatase to rutile structure of titanium oxide. The oxide nanotubular surface is highly hydrophilic compared with the intact Ti Nb foil. The surface wettability varies with the nanotube diameter. As the nanotube diameter increases while the nanotube layer thickness remains constant, the capillary wetting of the nanotube surface decreases and the surface becomes less hydrophilic.Annealing changes the nanotubular surface wettability further and establishes less hydrophilic surface conditions due to the removal of hydroxyl groups and residue fluoridecontaining species. It is believed that the surface wettability is changed due to the decreasing content of hydroxyl groups in ambient atmosphere. This work can provide guidelines for improving structural and environmental conditions responsible for changing surface wettability of Ti Nb surfaces for biomedical applications.     

Rapid anodic oxidation of highly ordered TiO2 nanotube arrays

Highly ordered TiO₂ nanotube arrays prepared by anodic oxidation have attracted increasing research interests due to their promising applications in many scientific areas. To the best of our knowledge, a factor limiting the application of TiO₂ nanotube arrays was their long sustaining reaction time by anodic oxidation, usually lasting 6-12 h and even longer when synthesizing thicker nanotubular layers. In the present paper, we reported for the first time a facile but effective approach to accelerate the anodic formation of TiO₂ nanotube arrays by proper addition of sodium carbonate (Na₂CO₃) into the anodization electrolyte. We adopted the 0.3 M NH₄F + 0.03 M Na₂CO₃ + EG (ethylene glycol) + 3.0 vol.% H₂O electrolyte and the average growth rate of the nanotubes achieved in our experiments could be accelerated to 1100 nm/min. The possible mechanism of the rapid electrochemical process was also presented.     

钛表面纳米管处理后在含白蛋白模拟唾液中的电化学性质(英文)

探讨了白蛋白对表面纳米管处理后的纯钛( nanotubular Ti,NT)中模拟唾液中电化学行为的影响,白蛋白浓度为5 g/L.与机械抛光的纯钛(mechanically polished Ti,MPT)相比,白蛋白导致NT的开路腐蚀电位向正方向偏移,而且更加有效地导致其阳极极化行为的变化与腐蚀电流密度的降低.取决于纳米管层性质的表面电容随着浸泡时间的增加而增大.结果表明,纯钛表面的纳米管有利于白蛋白的吸附.     

Effects of heat treatment scheme on the photocatalytic activity of TiO2 nanotube powders derived by a facile electrochemical process

TiO₂ nanotubes (NTs) in powder form were synthesized by a facile electrochemical process in a perchlorate-containing electrolyte. Transmission electron microscopy results indicate that the TiO₂ NT-powder is in an amorphous structure and has outer diameter of 20 nm and tube-wall thickness of 5 nm. X-ray diffraction analysis reveals that phase composition of the annealed TiO₂ NT-powders is related to the heat treatment scheme. Methyl orange was employed as a representative dye pollutant to evaluate the ultraviolet photocatalytic activity of the TiO₂ NT-powders. It was found that different post heat treatment schemes affect greatly the photocatalytic activities of the TiO₂ NT-powders, which should be ascribed to the changes in phase structural and morphological properties of the TiO₂ NT-powders. These results indicate that there should be a balance between crystal phase and nanotubular configuration for achieving the best photocatalytic activity of the TiO₂ nanotube powders.     

Characterization of electronic properties of TiO2 nanotube films

By anodization of titanium, TiO₂ nanotube layers were grown that consist of arrays of individual tubes with a length of ≈2.5 μm, a diameter of ≈100 nm and a wall thickness of ≈15 nm. The electronic properties of TiO₂ nanotube layers were characterized using photoelectrochemical and impedance measurements. Photocurrents for as-anodized tubes are dominated by their amorphous state and a high number of defects. Conversion to anatase by annealing decreases the defect density drastically which results in an enhanced photocurrent.     

Electrochemical corrosion behaviour of nanotubular Ti-13Nb-13Zr alloy in Ringer’s solution

Nanotubular oxide layer formation was achieved on biomedical grade Ti-13Nb-13Zr alloy using anodization technique in 1 M H₃PO₄ + 0.5 wt.% NaF. The as-formed and heat treated nanotubes were characterized using SEM, XRD and TEM. Corrosion behaviour of the nanotubular alloy was investigated employing potentiodynamic and potentiostatic polarization. The alloy after nanotubular oxide layer formation exhibited significantly higher corrosion current density than the bare alloy. The lower corrosion resistance of the nanotubular alloy was suggested to be associated with the distinctly separated barrier oxide/concave shaped tube bottom interface. A heat treatment at 150 °C appreciably enhanced the corrosion resistance property.     

Formation behavior of anodic TiO2 nanombes in fluoride containing electrolytes

TiO₂ nanotube layers can be formed with titanium in the electrolytes containing fluoride by electrochemical method. The role of fluoride ion, the crystallinity of the anodic oxide, and the chemical state were investigated. The results show the anodic film is composed of oxide and a little amount of hydroxide. The presence of F⁻ ions leads to chemical dissolution of Ti oxide layer and prevents hydroxide precipitation. Consequently, chemical dissolution rate increases with increasing the fluoride content in the range of 0–2% (in mass fraction) because F⁻ ions in electrolyte attack the interface and allow the ions of the electrolyte to easily penetrate into the interface. The as-anodized TiO₂ nanotubes exhibit an amorphous structure. Thermally treated nanotubes are composed of mixtures of the anatase and rutile phases.     

Self-organized porous TiO2 and ZrO2 produced by anodization

The present work investigates the electrochemical formation of self-organized high aspect ratio TiO₂ and ZrO₂ nanotube layers. The formation and growth of a self-organized porous layer can be achieved directly by anodization without any templates in fluoride containing electrolytes. The morphology of the porous layers is affected by the electrochemical conditions such as the electrolyte composition, the pH and the exact polarization treatment (such as the potential sweep rate from the open-circuit potential to the anodizing potential). For Ti, nanotube layers are formed with diameters varying from approx. 20 nm to 100 nm and lengths from approx. 0.25 μm to 2.5 μm depending on the electrolytes and pH. On the other hand, for Zr, tubes of 50 nm in diameter and up to approx. 17 μm in length can be grown—a key parameter in this case is the potential sweep rate. The large difference between Ti and Zr in the achievable thickness of nanotube layers indicates a difference in the growth mechanism which may be based on the different chemical dissolution rates of electrochemically formed oxides.     

Amphiphilic and photocatalytic behaviors of TiO2 nanotube arrays on Ti prepared via electrochemical oxidation

Amphiphilic TiO₂ nanotube arrays (TiO₂ NTs) were fabricated through electrochemical oxidation of Ti in solution containing H₃PO₄ and NaF. Scanning electron microscopic analysis shows that the as-prepared TiO₂ NTs have an average pore diameter of 100 nm and a wall thickness of 15 nm. The electrochemical oxidation of Ti can be divided into four stages. In the first stage, when the potential is very low, oxygen formation and Ti dissolution are the major reactions. The second stage corresponds to a slightly higher potential, but less than 2.5 V. In this stage, the formation of TiO₂ film occurs. When the potential is increased to the even higher range from 2.5 V to 6 V, the TiO₂ film dissolves and nanoporous surface structure is generated. This is the third stage. Further increase of the potential enters stage four. The high potentials cause the self-organization of the nanostructure and allow the formation of well-aligned TiO₂ NTs. We also found that the change in surface condition of Ti by annealing heat treatment affects the film dissolution kinetics. As compared with TiO₂ thin film, the TiO2 NTs show higher photocatalytic activity on decomposing Rhodamine B. The surface of the TiO₂ NTs can be wetted by both water and oil. Such an amphiphilic property comes from the capillary effect of the nanochannel structure of the TiO₂ NTs. Because of the amphiphilic property and the photocatalytic activity, we conclude that the TiO₂ NTs have the capability of self-cleaning.     

Fabrication,characterisation and investigation of zirconium oxide corrosion behaviour on resistance of zirconium oxide nanotubes in artificial saliva as biological environment

Zirconia nanotubes were prepared in glycerol electrolytes containing fluoride ion and water via anodisation. The systematic study of the influence of anodising parameters (applied voltage and electrolyte temperature) on the zirconia nanotube diameter and their corrosion resistance in the artificial saliva solution as biological medium at 37±1°C have been demonstrated. Nanotubes were characterised by field emission scanning electron microscopy (FE-SEM). The FE-SEM results show that zirconia nanotubes have an outer diameter of 40–120 nm and inner diameter of 10–60 nm. The corrosion properties of samples were examined by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarisation tests. The results indicate that zirconium oxide nanotubes that were prepared at 50 V and 5°C demonstrate the best corrosion resistance.     

Chemical state and ultra-fine structure analysis of biocompatible TiO<Subscript>2</Subscript> nanotube-type oxide film formed on titanium substrate

TiO₂ nanotube-type oxide film on Ti substrate has been fabricated using an electrochemical method, and the chemical bonding state, ultra-fine structures, and surface characteristics of the TiO₂ nanotube layer have been investigated. The formation and growth of a self-organized nanotube layer can be achieved directly by anodization in NH₄-containing electrolytes. The diameter, length, and wall thickness of the nanotube are significantly affected by anodizing conditions such as applied voltage, current density, and anodizing time. The length limiting factor of nanotube growth was found to be the diffusion of ionic species in the electrolyte. XRD investigations revealed that annealed nanotubes have anatase and rutile structure, and some Ti-peaks from the Ti substrate were observed. From the compositional analysis of TiO₂ nanotubes layer using Energy Dispersive Spectroscopy (EDS), Ti, O, and P elements were obtained in the wall nanotube layer. For incorporated P-containing in the TiO₂ nanotube layer, various chemical states were presented, which were revealed mostly in the forms of H₂PO₄, HPO₄ ^2-, and PO₄ ^3-.     

Influence of oxygen ion irradiation on the corrosion aspects of Ti-5%Ta-2%Nb alloy and oxide coated titanium

The corrosion resistance of Ti-5%Ta-2%Nb alloy and DOCTOR (double oxide coating on titanium for reconditioning) coated titanium by O⁵⁺ ion irradiation were compared and investigated for their corrosion behaviour. O⁵⁺ ion irradiations were carried out at a dose rate of 1 × 10¹⁷, 1 × 10¹⁸ and 1 × 10¹⁹ ions/m² at 116 MeV. The surface properties and corrosion resistance were evaluated by using scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray (EDX), glancing-angle X-ray diffraction (GXRD) and electrochemical testing methods. The results of electrochemical investigations in 11.5 N HNO₃ indicated that the open circuit potential (OCP) of DOCTOR coated titanium is nobler than Ti-5%Ta-2%Nb alloy. The potentiodynamic polarization study of Ti-5%Ta-2%Nb alloy and DOCTOR coated specimen indicated decrease in passive current density with increase in ion doses (1 × 10¹⁷ to 1 × 10¹⁹ ions/m²) indicating decrease in anodic dissolution. Nyquist arc behaviour in the electrochemical impedance study substantiated the enhancement in oxide layer stability by O⁵⁺ ion irradiation. AFM results revealed that the DOCTOR coated Ti surface was dense without gross voids, and the surface roughness decreased by O⁵⁺ ion irradiation, but increased after corrosion test. EDX and GXRD patterns of DOCTOR coated Ti sample indicated that the coating was mainly composed of rutile TiO₂. Based on the above results, the O⁵⁺ ion irradiation effect on corrosion behavior of Ti-5%Ta-2%Nb alloy and DOCTOR coated titanium are discussed in this paper.     

Electrochemical characteristics of titanium based biomaterials in artificial saliva

In the last decade, new titanium alloys have been developed in different areas of dentistry, such as Ti6Al7Nb, Ti6Al2Nb1Ta1Nb, and Ti5Al2.5Fe. The aim of this study was to compare the Ti6Al7Nb, Ti6Al2Nb1Ta1Nb, Ti5Al2.5Fe, and Ti6Al4V alloys with the commercial titanium, regarding the corrosion resistance in artificial saliva. In the electrochemical estimations the polarization data are converted into instantaneous corrosion rate values (I_corr). The passivation properties were comparable for the four alloys. The EIS spectra are best fitted using an equivalent circuit (EC), which corresponds to the model of a two‐layer structure for the passive film. High impedance values (in the order of 10⁶ Ω cm²) were obtained from medium to low frequencies for all materials suggesting high corrosion resistance in artificial saliva. The electrochemical and corrosion behavior of Ti6Al4V is not affected on substituting vanadium with niobium, iron, molybdenum, and tantalum.     

Electrochemical properties of ordered TiO2 nanotube loaded with Ag nano-particles for lithium anode material

Self-organized TiO₂ nanotube array was grown on titanium (Ti) thin film by anodizing in glycerol solution containing low concentration of NH₄F, and Ag/TiO₂ nanotube was then prepared from TiO₂ nanotube array by thermal decomposition. The physical properties of the synthesized TiO₂ and Ag/TiO₂ nanotubes were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The synthesized two samples were used as negative materials for lithium-ion battery, and their charge–discharge property, cyclic voltammetry, electrochemical impedance spectroscopy, and cycle performance were investigated. The results indicated that the addition of Ag to TiO₂ nanotube could significantly improve the electronic conductivity, charge–discharge capacity, and cycle stability of TiO₂ nanotube.     

Self-aligned TiO2 nanotube arrays produced by air-cathode as electrode

Air-cathodes were used to produce TiO₂ nanotube arrays. The effects of pH, voltage and degradation of air-cathode in tailoring the morphologies of TiO₂ nanotube arrays were investigated. Preliminary results show that TiO₂ nanotubes could be formed and are comparable to those produced by platinum electrodes under similar conditions. The lengths and diameters of TiO₂ nanotube arrays obtained are in the range of 1.0-2.2 μm and 40-150 nm, respectively. It is found that the rate of formation of the nanotubes is closely related to the pH of the solution. Air-cathodes are found to have relative low values of mass loss rates.     

Porous TiO2 film prepared by micro-arc oxidation and its electrochemical behaviors in Hank's solution

Porous titanium oxide film was prepared by micro-arc oxidation (MAO) method on the surface of titanium alloy in electrolyte containing Ca and P. Surface characterizations of the film were carried out using X-ray diffractometer (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS) before and after immersion in Hank's solution. Electrochemical behaviors and corrosion resistance were studied by electrochemical techniques. The film was mainly composed of titania, α-tricalcium phosphate (α-TCP) and amorphous Ca-P compounds. α-TCP and amorphous compounds could transformed into hydroxyapatite (HA) when immersed in Hank's solution. MAO film showed higher corrosion potential and lower corrosion current than the titanium alloy and its chemical stability was slightly changed after formation of HA. Fitted electrochemical impedance spectroscopy (EIS) data indicated that after immersion for 2 weeks the MAO film kept good corrosion resistance. Porous TiO₂ film on titanium alloy by MAO method showed good chemical stability in Hank's solution and the transformation of Ca-P compounds into HA indicated that MAO was an effective method for preparing titanium alloys as bioactive artificial bone substitute even when Ca and P in the tissue environment were not abundant.     

Porous hierarchical TiO2 nanostructures: Processing and microstructure relationships

A dual porous hierarchical coating of TiO₂ nanotubes (～50 nm diameter) on the nanoscale and large (～1 to 20 μm) pores on the micro-scale can be fabricated on the surface of Ti by anodic oxidation. This unique coating may have potential applications as bioactive coatings for Ti bone implants. This paper details several important aspects of the coating microstructure. TiO₂ coatings were fabricated by anodic oxidation in 1 M H₂SO₄ + 0.1 M NaF solution. Microstructure characterization was carried out using scanning electron microscopy. We also report on the observation of precipitates which form as both a continuous surface layer and of a conical geometry. The mechanism for nanotube formation, precipitate layer formation, and microscopic pitting was discussed. The effect of processing variables (i.e. time, temperature, pH) on the TiO₂ microstructure was studied. Anodization time was found to affect nanotube length and also pit size and density. Lowering the electrolyte pH decreased the nanotube length and microscopic pit density. Increasing electrolyte temperature decreased nanotube length and increased pit/pore and precipitate density. Microscopic pitting, in the nanotube coating was found to occur above grain boundaries in the Ti substrate and above Ti grains with (0 0 0 1) orientation.     

Oxidation resistance and corrosion behavior of hot-dip aluminized coatings on commercial-purity titanium

Aluminizing is an effective method to protect alloys from oxidation and corrosion. In this article, the microstructure, morphology, phase composition of the aluminized layers and the oxide films were investigated by SEM, EDS and X-ray diffraction. The high temperature oxidation resistance and electrochemical behavior of hot dip aluminizing coatings on commercial-purity titanium had been studied by cyclic oxidation test and potentiodynamic polarization technique. The results show that the reaction between the titanium and the molten aluminum leads to form an aluminum coating which almost has the composition of the aluminum bath. After diffusion annealing at 950 °C for 6 h, the aluminum coating transformed into a composite layer, which was composed of an inner layer and an outer layer. The inner layer was identified as Ti₃Al or Ti₂Al phase, and the outer layer was TiAl₃ and Al₂O₃ phase. The cyclic oxidation treatment at 1000 °C for 51 h shows that the oxidation resistance of the diffused titanium is 13 times more than the bare titanium. And the formation of TiAl₃, θ-Al₂O₃ and compact α-Al₂O₃ at the outer layer was thought to account for the improvement of the oxidation resistance at high temperature. However, the corrosion resistance of the aluminized titanium and the diffused titanium were reduced in 3.5 wt.% NaCl solution. The corrosion resistance of the aluminized titanium was only one third of bare titanium. Moreover, the corrosion resistance of the diffused titanium was far less than bare titanium.     

Effect of Ti interlayer on corrosion behavior of nanostructured Ti/TiN multilayer coating deposited on TiAl6V4

To improve the corrosion properties of TiAl₆V₄ alloy, TiN monolayer and Ti/TiN multilayer coatings are deposited by reactive magnetron sputtering. The phase, structure, and morphology properties are investigated by grazing‐incidence X‐ray diffraction, field‐emission scanning electron microscopy, and atomic force microscopy, respectively, and the corrosion behavior is evaluated by electrochemical impedance spectroscopy and potentiodynamic polarization. The TiN monolayer and Ti/TiN multilayer with thickness of 1,350 and 1,410 nm have the (111) and (002) preferred orientation and crystallite size of 42.5 and 24.3 nm, respectively. Columnar growth in TiN is hindered by the Ti interlayers and no cracking is observed between the layers indicating strong adhesion. The nanostructured Ti/TiN coating forms stable surface titanium oxide which improves the corrosion resistance by approximately 80 and four times compared with TiAl₆V₄ alloy and TiN coating, respectively. Hindrance of the columnar structure in TiN by the Ti interlayer decreases the local corrosion rate and enhances the galvanic corrosion resistance by forming a layer on the β‐phase enriched with vanadium as well as a TiO₂ stable layer. The nanostructured Ti/TiN coating demonstrates capacitive behavior with phase angles approximately ?50° and high impedance values at low frequency to be the corrosion resistance mechanism.     

Charge transport and recombination in dye-sensitized solar cells based on hybrid films of TiO2 particles/TiO2 nanotubes

In this paper, anodic TiO₂ nanotubes are blended into the TiO₂ mesoporous films based on P25 nanoparticles to assemble a list of dye-sensitized solar cells (DSSCs) with different nanotube concentrations. The electron properties of transport and recombination in the fabricated DSSCs are studied by using electrochemical impedance spectroscopy and the open-circuit voltage decay technique under AM 1.5 illumination. Results indicate that the electron lifetime increases with increasing the concentration of the anodic TiO₂ nanotubes, the electron transport time at a blending level of 10 wt% TiO₂ nanotubes is short as compared to that at 0 wt%, and above 10 wt%, the electron transport time has a trend of becoming large. Due to the combining effects of the electron transport and recombination, the electron collecting efficiency and the electron diffusion length obtain maxima at a blending level of 10 wt% nanotubes, which results in a highest short circuit current and a maximum energy conversion efficiency at this point in the DSSCs. This study gives a clear explanation for the performance enhancement of TiO₂ particle-based DSSCs at a blending level of 10 wt% anodic TiO₂ nanotubes and for the performance decrease at a blending level over 10 wt% anodic TiO₂ nanotubes from the angle of the electron transport and recombination. This study also supplies a feasible and easy way to improve the performance of particle-based DSSCs by restraining electron recombination and accelerating electron transportation.