Anodic Titania Nanotube Research Articles

Hydroxyapatite based and anodic Titania nanotube biocomposite coatings: Fabrication, characterization and electrochemical behavior

The main challenges of biological implants are suitable strength, adhesion, biocompatibility and corrosion resistance. This paper discusses fabrication, characterization and electrochemical investigation of anodized Ti6Al4V without and with a hydroxyapatite (HA) layer, HA/TiO2 nanoparticles (NPs) and HA/TiO2 nanotubes (HA/anodized). X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and energy dispersive spectroscopy (EDS) were used to characterize and compare properties of different samples. Dense HA with uniform distribution and 12.8 ± 2 MPa adhesive strength enhanced to 19.2 ± 4 MPa by the addition of TiO2 nanoparticles and enhanced to 23.1 ± 4 MPa by the deposition of a TNT interlayer was fabricated by an anodic oxidation process. EIS analysis divulged the polarization behavior of various layers formed on a Ti6Al4V substrate. Electrochemical measurements indicated polarization passivation due to incorporation of TiO2 nanoparticles to HA. Hydroxyapatite on a TNT layer revealed lower corrosion resistance than a HA/TiO2 nanoparticle sample due to the vacuolar nature of TNT conformation. The passivation current density of the Ti6Al4V alloy coated with a HA/TiO2 nanocomposite (0.125 μA/cm2) was less than 1% of the bare substrate.

Tube-Super Dielectric Materials: Electrostatic Capacitors with Energy Density Greater than 200 J·cm-3.

The construction and performance of a second generation of super dielectric material based electrostatic capacitors (EC), with energy density greater than 200 J·cm−3, which rival the best reported energy density of electric double layer capacitors (EDLC), also known as supercapacitors, are reported. The first generation super dielectric materials (SDM) are multi-material mixtures with dielectric constants greater than 1.0 × 105, composed of a porous, electrically insulating powder filled with a polarizable, ion-containing liquid. Second-generation SDMs (TSDM), introduced here, are anodic titania nanotube arrays filled with concentrated aqueous salt solutions. Capacitors using TiO2 based TSDM were found to have dielectric constants at ~0 Hz greater than 107 in all cases, a maximum operating voltage of greater than 2 volts and remarkable energy density that surpasses the highest previously reported for EC capacitors by approximately one order of magnitude. A simple model based on the classic ponderable media model was shown to be largely consistent with data from nine EC type capacitors employing TSDM.

Comparison of platelet adhesion behavior on pure titanium surfaces modified by different techniques

To evaluate the platelet adhesion ability on pure titanium surfaces modified with different techniques. Pure titanium specimens were treated with 5 different surface modification techniques, including machine polish (MP), dual acid-etch (DAE), sand blast-large grit and acid-etch (SLA), micro-arc oxidation (MAO) and anodized titania nanotube (TNT). The surface topographies of specimens were observed by scanning electron microscopy (SEM). Chemical compositions, surface roughness and static water contact angle of specimens were detected by energy dispersive spectrometer (EDS), laser scanning confocal microscope (LSCM) and contact angle analyzer respectively. Platelets were cultured on specimen surfaces for 30 min. The amount and viability of adhered platelets adhered were evaluated. Platelet distribution and morphology were observed by LSCM and SEM. Surface topographies of the five groups of specimens differed significantly. MP, DAE, SLA and MAO surfaces showed micro-scale topographies, while TNT surfaces showed nano-scale topography with nanotubes at the diameter of (80.46 ± 0.35) nm. The surface roughness of MAO was the highest among the 5 groups. TNT surfaces demonstrated the lowest roughness as well as the lowest static water contact angle as 13.55° ± 0.96°. The amount of platelets adhered on TNT surface was the greatest as (300 729 ± 8 325) platelet/µl and the viability was the highest (A450 value 2.14 ± 0.05). Platelet adhered intensively on TNT surfaces, forming pseudopodia, extending and connecting with each other. Surface properties of pure titanium affect platelet adhesion ability. Nano-scale topography can greatly improve platelet adhesion. Increased surface roughness and hydrophilicity can improve platelet adhesion ability.

The Synthesis and Structure of Anodized Titania Nanotubes for Energy Conversion Materials

Titania nanotubes (TiO2 NTs) photoanodes were synthesized by anodization method. The electrolytes were the mixtures of ethylene glycol (EG), ammonium fluoride (0.3 wt % NH4F) and deionized water (2 Vol % H2O) with different concentrations of dopant Fe (NO3)3∙9H2O. A constant dc power supply at 50 V was used as anodic voltage. The samples were annealed at 450 °C for 2 hours. The resultant products were characterized by Scanning Electron Microscopy (SEM) and X-ray diffraction (XRD) to determine their microstructure when TiO2 NTs were doped with different amounts of Fe atoms. The diameters of TiO2 NTs were about60-120 nm. The highest density of TiO2 NTs was obtained when the nanotubes were doped with 0.01 M of Fe.

Mechanism of Formation of Faceted Titania Nanoparticles from Anodized Titania Nanotubes

Though researchers worldwide have attempted to fabricate faceted titania nanoparticles with a higher fraction of {001} facets, which have high surface energy, the approaches have focused on use of either a very aggressive heating schedule or highly corrosive chemicals like HF. The current article reports a simple method for the transformation of the titania nanotubes to faceted nanoparticles (size varying from 15–120 nm) at relatively low temperatures and heating rates, without the use of any other corrosive chemicals, utilizing only the electrolyte inside the titania nanotubes remnant from the anodization of the titanium substrate. The formation of faceted nanoparticles was found to be strongly dependent on fluorine concentration and on initial state of titania nanotubes (amorphous/crystalline) and annealing temperature. The formation of the unique “nanorod in nanoporous” structures has been reported for the first time. The current article deals with a detailed study of the formation of these unique nanostructures and proposes a mechanism for the same.

Synthesis and Characterization Anodized Titania Nanotubes for Enhancing Hydrogen Production

Pure and doped Titania nanotubes (TiO2 NTs) photoanodes were fabricated by means of anodization method. The anodization was carried out in electrolytes prepared by mixing ethylene glycol (EG), ammonium fluoride (0.3 wt % NH4F) and deionized water (2 Vol % H2O) with different concentrations of dopant Fe (NO3)3∙9H2O. A constant dc power supply of 50 V was used as anodic voltage. The samples were annealed at 450 °C for 2 hours. The resultant products were characterized by Scanning Electron Microscopy (SEM) and X-ray diffraction (XRD) to determine their microstructures when TiO2 NTs were doped with different amounts of Fe atoms. The diameters of TiO2 NTs were about 60-120 nm. The highest density of TiO2 NTs was obtained when the nanotubes were doped with 0.01 M of Fe. The photocatalytic activity was examined without external applied potential. The maximum photocurrent density was 3.0 mA/cm2 under illumination of 100 mW/cm2.

GISAXS and TOF-GISANS studies on surface and depth morphology of self-organized TiO2nanotube arrays: model anode material in Li-ion batteries

Self-organized anodic titania (TiO2) nanotube arrays are an interesting model anode material for use in Li-ion batteries owing to their excellent rate capability, their cycling stability and their enhanced safety compared to graphite. A composite material where carbothermally treated conductive TiO2nanotubes are used as support for a thin silicon film has been shown to have the additional advantage of high lithium storage capacity. This article presents a detailed comparison of the structure, surface and bulk morphology of self-organized conductive TiO2nanotube arrays, with and without silicon coating, using a combination of X-ray diffraction, X-ray reflectivity, grazing-incidence small-angle X-ray scattering (GISAXS) and time-of-flight grazing-incidence small-angle neutron scattering (TOF-GISANS) techniques. X-ray diffraction shows that the nanotubes crystallize in the anatase structure with a preferred (004) orientation. GISAXS and TOF-GISANS are used to study the morphology of the nanotube arrays, delivering values for the inner nanotube radius and intertubular distances with high statistical relevance because of the large probed volume. The analyses reveal the distinct signatures of a prominent lateral correlation of the TiO2nanotubes of ∼94 nm and a nanotube radius of ∼46 nm. The porosity averaged over the entire film using TOF-GISANS is 46%. The inner nanotube radius is reduced to half (∼23 nm) through the silicon coating, but the prominent lateral structure is preserved. Such in-depth morphological investigations over large sample volumes are useful towards development of more efficient battery electrode morphologies.

Anodized titania nanotube array microfluidic device for photocatalytic application: Experiment and simulation

Microfluidic photocatalytic reactors have advantages over conventional bulk reactors such as large surface-area-to-volume ratio and high control of fluid flow. Although titania nanotubular arrays (TNA) have shown enhanced photocatalytic degradation compared to nanoparticle films in a batch reactor configuration, their application in a microfluidic format has yet to be explored. The photocatalytic performance of a microfluidic reactor with TNA catalyst was compared with the performance of microfluidic format with TiO2 nanoparticulate (commercial P25) catalyst. The microfluidic device was fabricated using non-cleanroom based soft lithography, making it suitable for economical large scale manufacturing. The photocatalytic performance was evaluated at different flow rates ranging from 25 to 200μL/min. The TNA microfluidic system demonstrated enhanced photocatalytic performance over microfluidic TiO2 nanoparticulate layers, especially at higher flow rates (50–200μL/min). For instance, 12μm long TNA was able to achieve 82% fractional conversion of 18mM methylene blue in comparison to 55% conversion in case of the TiO2 nanoparticulate layer at a flow rate of 200μL/min. A computational model of the microfluidic format was developed to evaluate the effect of diffusion coefficient and rate constant on the photocatalytic performance. The improved performance of the TNA photocatalyst over the nanoparticle film can be attributed to higher generation of oxidizing species.

Electrochemical detection of methyl nicotinate biomarker using functionalized anodized titania nanotube arrays

Sensing and detection of volatile organic compounds (VOCs) from exhaled breath is a possible method for early diagnosis of several pulmonary diseases. The use of solid-state TiO2 nanotube array sensors for VOC sensing applications has been of great interest. In this study, titania nanotubular arrays (TNAs) were synthesized through electrochemical anodization and used for the electrochemical detection of methyl nicotinate biomarker vapor. Functionalization of the TNA with cobalt was found to be necessary for methyl nicotinate detection. Titanium dioxide films synthesized through high temperature oxidation and functionalized with cobalt were also compared with cobalt functionalized TNA. The ordered TNA demonstrated itself to be an effective substrate for cobalt deposition and subsequent biomarker detection over thin titanium dioxide films. Surface analysis of the cobalt functionalized TNA by x-ray photoelectron spectroscopy (XPS) studies observed cobalt deposits exist as cobalt hydroxide on the surface. Exposure of the sensor surface to methyl nicotinate vapor results in the reduction of cobalt hydroxide to cobalt metal on the surface. Two mechanisms have been proposed to describe the binding of the nicotinate biomarker to cobalt functionalized TNA consistent with the XPS studies and band theory.

Rutile phase n- and p-type anodic titania nanotube arrays with square-shaped pore morphologies.

Rutile-phase TiO2 nanotube arrays without broken walls were formed by annealing of anodically formed nanotubes in a propane flame at 650 °C and in air at 750 °C. An unusual morphological transformation was observed from the ellipsoidal pore-shapes of titania nanotubes grown in aqueous electrolyte to a square-shaped pore structure subsequent to the anneals. 750 °C annealed nanotubes were found to be lightly p-type, rare in TiO2.

Effects of anodic titanium dioxide nanotubes of different diameters on macrophage secretion and expression of cytokines and chemokines.

To investigate effects of TiO2 nanotubes of different diameters on J744A.1 macrophage behaviour, secretion and expression of pro-inflammatory cytokines and chemokines. Macrophage-like J744A.1 cells were cultured on three types of Ti surface: mechanically polished titanium plus 30 and 80 nm TiO2 nanotube surfaces, for 4, 24 and 48 h. Macrophage adhesion and proliferation were assessed using CCK-8 assay. Levels of pro-inflammatory cytokines (TNF-α, IL-1β and IL-6) and chemokines (MCP-1 and MIP-1α) secreted into the supernatant were measured using the Cytometric Bead Arrays kit. TNF-α, MCP-1 and MIP-1α gene expression were quantitatively analysed by real-time PCR. These show that TiO2 nanotube surfaces, especially of 80 nm TiO2 nanotube, benefited macrophage adhesion and proliferation, and reduced protein secretion and mRNA expression of TNF-α, MCP-1 and MIP-1α. IL-1β and IL-6 were undetectable on all the surfaces at all times. TiO2 nanotube surfaces, especially of 80 nm TiO2 nanotube, reduced inflammatory response in vitro, which might be part of a basis for rapid osseointegration in implants with TiO2 nanotube surfaces in animal studies.

Enhanced photoelectrochemical water splitting performance of anodic TiO(2) nanotube arrays by surface passivation.

One-dimensional anodic titanium oxide nanotube (TONT) arrays provide a direct pathway for charge transport, and thus hold great potential as working electrodes for electrochemical energy conversion and storage devices. However, the prominent surface recombination due to the large amount surface defects hinders the performance improvement. In this work, the surface states of TONTs were passivated by conformal coating of high-quality Al2O3 onto the tubular structures using atomic layer deposition (ALD). The modified TONT films were subsequently employed as anodes for photoelectrochemical (PEC) water splitting. The photocurrent (0.5 V vs Ag/AgCl) recorded under air mass 1.5 global illumination presented 0.8 times enhancement on the electrode with passivation coating. The reduction of surface recombination rate is responsible for the substantially improved performance, which is proposed to have originated from a decreased interface defect density in combination with a field-effect passivation induced by a negative fixed charge in the Al2O3 shells. These results not only provide a physical insight into the passivation effect, but also can be utilized as a guideline to design other energy conversion devices.

Enhanced electroactivity at physiological pH for polyaniline in three-dimensional titanium oxide nanotube matrix.

The electroactivity of polyaniline (PANI) can be solely retained in acidic media. However, the acidity requirement greatly limits its potential applications such as biosensors and anticorrosion, where neutral circumstances have to be faced. Herein, PANI is conformally loaded into anodic titanium oxide (ATO) nanotubes by electrodeposition. The prepared PANI-ATO hybrid films exhibited excellent electroactivity and high redox stability in neutral media, which can be ascribed to the intercalation of protons in the ATO layer and the diffusion confinement in three dimensional tubular nanostructures. The results provide a rational design guideline to achieve the electroactivity of PANI in neutral circumstances, which may have immediate impact on bioelectronic applications.

Anodic Titania Nanotube Arrays Sensitized with Mn- or Co-Doped CdS Nanocrystals

The use of doped luminescent nanocrystals or quantum dots have mainly been explored for imaging applications; however, recently they have gained interest in solar energy conversion applications due to long electron lifetimes, tunable band gaps and emission by compositional control. In this study, we have examined the application of Mn or Co doped CdS nanocrystals as a sensitizing layer over titania nanotubular arrays synthesized via electrochemical anodization in photoelectrochemical applications. The doped and undoped CdS nanocrystals were simultaneously synthesized and deposited onto the titania surface by adoption of a successive ion layer adsorption-reaction (SILAR) method. Various characterization methods indicate lattice incorporation of the dopant within CdS. The addition of dopants to CdS was found to improve the photoelectrochemical performance by increasing the depletion width of the CdS nanocrystals and reducing recombination losses of charge carriers.

Preparation and photocatalytic performance of ZrO2 nanotubes fabricated with anodization process

Abstract Anodization process is a facile method to prepare structured nano-material. In this research, anodization process of zirconium in (NH4)2SO4/NH4F solution was studied systematically and the anodized zirconia was applied to degrade methyl orange (MO) solution under UV irradiation and compared with anodized titania nanotubes to determine the photoactivity of zirconia nanotubes. After anodization in aqueous electrolyte containing 1 M (NH4)2SO4 and 0.25 wt% NH4F for 120 min at 20 V, zirconia nanotubes (ZNT) with diameters of about 20 nm and lengths of about 600 nm were formed. The growth mechanism of ZNT was studied with SEM and TEM. The hypothesis of ZNT growth, in which electric etching process started at the pits and further to deepen in situ to form nanotubes, was confirmed by the SEM. The anodization process on the sanded rough Zr foil verified this assumption since the growth of ZNT occurred at the bottom of the ripples on Zr foil and gathered to form bundles at the peaks. The as-grown ZNT is a mixture of monoclinic and tetragonal ZrO2 crystals, which transforms into pure monoclinic structure after annealed at 300 °C. The unannealed ZNT has excellent photocatalytic performance with a MO photo-degradation rate of 94.45% after 4 h, even if contrasting to anodized titania. Reusing experiments confirmed that the decaying of photocatalytic performance of ZNT can be negligible in 6 times recycling.

Anodic Titania Nanotubes Grown on Titanium Tubular Electrodes

In the past decade, research into growth and application of anodic titania nanotubes has been focused on planar titanium electrodes. Although patterned, curved, or cylindrical substrates were also employed in a number of applications, the study of nanotubes grown on a titanium tubular electrode is rather inadequate, despite their expected uses in thermal fluids. In this study, growth of titania nanotubes on tubular electrodes was investigated. It was found that nanotubes are formed at both outer and inner surfaces of the electrode. The nanotube length (or growth rate in the first 30 min) at the outer surface decreases gradually from the side facing the cathode to that at the other side, while the length at the inner surface smears out this trend. This is due to the effect of the electric field emanating from the potential drop in the organic electrolyte. The variation of nanotube diameter just echoes such a tendency of potential drop. The influence of electrode orientation during anodization on the resulting features of nanotubes was also examined and discussed. The nanotube geometry is thus tailorable for particular applications.

Ferromagnetism at room temperature in Cr-doped anodic titanium dioxide nanotubes

This study reports the room-temperature ferromagnetism in Cr-doped TiO2 nanotubes (NTs) synthesized via the electrochemical method followed by a novel Cr-doping process. Scanning electron microscopy and transmission electron microscopy showed that the TiO2 NTs were highly ordered with length up to 26 μm, outer diameter about 110 nm, and inner diameter about 100 nm. X-ray diffraction results indicated there were no magnetic contaminations of metallic Cr clusters or any other phases except anatase TiO2. The Cr-doped TiO2 NTs were further annealed in oxygen, air and argon, and room-temperature ferromagnetism was observed in all Cr-doped samples. Moreover, saturation magnetizations and coercivities of the Cr-doped under various annealing atmosphere were further analyzed, and results indicate that oxygen content played a critical role in the room-temperature ferromagnetism.

Fabrication and Characterization of Dye-sensitized Solar Cells based on Anodic Titanium Oxide Nanotube Arrays Sensitized with Heteroleptic Ruthenium Dyes

Anodic self-organized titania nanotube (TNT) arrays have a great potential as efficient electron-transport materials for dye-sensitized solar cells (DSSC). Herewith we report the photovoltaic and kinetic investigations for a series of heteroleptic ruthenium complexes (RD16-RD18) sensitized on TNT films for DSSC applications. We found that the RD16 device had an enhanced short-circuit current density (<TEX>$J_{SC}/mAcm^{-2}=15.0$</TEX>) and an efficiency of power conversion (<TEX>${\eta}=7.2%$</TEX>) greater than that of a N719 device (<TEX>${\eta}=7.1%$</TEX>) due to the increasing light-harvesting and the broadened spectral features with thiophene-based ligands. However, the device made of RD17 (adding one more hexyl chain) showed smaller <TEX>$J_{SC}(14.1mAcm^{-2})$</TEX> and poorer <TEX>${\eta}(6.8%)$</TEX> compare to those of RD16 due to smaller amount of dye-loading and less efficient electron injection for the RD17 device than for the RD16 device. For the RD18 dye (adding one more thiophene unit and one more hexyl chain), we found that the device showed even lower <TEX>$J_{SC}(13.2mAcm^{-2}) $</TEX> that led to a poorest device performance (<TEX>${\eta}=6.2%$</TEX>) for the RD18 device. These results are against to those obtained from the same dyes sensitized on <TEX>$TiO_2$</TEX> nanoparticle films and they can be rationalized according to the electron transport kinetics measured using the methods of charge extraction and transient photovoltage decays.

Conformal growth of anodic nanotubes for dye-sensitized solar cells: part II. Nonplanar electrode.

Anodic titania nanotube array features highly ordered alignment as well as porous nature, and exhibits intriguing properties when employed in a variety of applications. All these profit from the continuous efforts on controlling the nanotube configurations. Recently, nonplanar electrodes have also been used to grow the nanotubes besides the conventional planar counterparts. As such, it is of great interest and significance to complete a picture to link the nanotubes grown on planar and various nonplanar electrodes for a comprehensive understanding of nanotube growing manners, in an attempt to boost their future applications. In the first part of this review, planar electrodes are focused with regard to nanotube growth and application in dye-sensitized solar cells. In this part, the nanotubes grown on patterned or curved surfaces are discussed first with reference to a similar structure of alumina nanopores, which are subsequently used to mirror the growth of nanotubes on cylindrical electrodes (i.e., titanium wires or meshes). The last section focuses on titanium tubular electrodes which are attractive for thermal fluids in view of the drastically reduced thermal conductivity in the presence of anodic nanotubes. As a recent hot topic, wire-shaped dye-sensitized solar cells are deliberated in terms of cell structure, efficiency calculation, merits, challenges and outlook.

The correlation between the interference colour and growth procedure of anodic titanium dioxide nanotube arrays

Titanium dioxide nanotube arrays were anodised from titanium foils in an aqueous electrolyte solution of hydrofluoric acid. The formed oxide showed visually different colours owing to light interference in the titanium dioxide layer. The behaviour of interference colour in anodic titanium dioxide film was investigated by varying anodisation parameters such as the applied voltage and the anodisation time. The morphologies and the crystalline phases of anodised samples were studied on a field emission scanning electron microscope and X‐ray diffractometer. The correlation between the interference colour and growth procedure of anodic titanium dioxide nanotube arrays was studied. The anodic films prepared under different conditions consisted of a compact oxide film with a nanoporous/tubular structure upon/beneath it. The crystalline phase of the anodic oxide layer was amorphous. The optical properties of the oxide film were investigated on a spectrophotometer. Optical interference could be detected in compact oxide layers when the thickness of the titanium dioxide was as small as 70 nm. In general, the interferences of the nanoporous/tubular structures were lower than those for compact structures. The empirical colour properties were estimated by the L*a*b* system. The relationships between the interference colour of anodic titanium dioxide film and its thickness and morphology are discussed.