Fabrication of nanoporous TiO2 by electrochemical anodization

The formation of self-organized porous titania is achieved by electrochemical anodization under a potentiostatic regime. Anodic titanium oxide (ATO) was fabricated by a three-step self-organized anodization of the Ti foil in an ethylene glycol electrolyte containing 0.38 wt% of NH₄F and 1.79 wt% of H₂O. Anodizing was carried out at the constant cell potential ranging from 30 to 70 V at the temperature of 20 °C. It was found that nanoporous TiO₂ arrays can be obtain only after a short duration of the third step (10 min). The influence of anodizing potential on the structural parameters of porous anodic titania including pore diameter, interpore distance, wall thickness, porosity and pore density was extensively studied. The linear dependencies between interpore distance, pore diameter and wall thickness upon the anodizing potential were found. The regularity of pore arrangement was monitored qualitatively by fast Fourier transforms (FFTs) of top-view FE-SEM images. It was found that the best arrangement of nanopores is observed at 40 V. This finding was confirmed by the analysis of pore circularity. The highest circularity of pores was observed once again at 40 V.     

Preparation of nanoporous tin oxide by electrochemical anodization in alkaline electrolytes

This paper reports the creation of a porous tin oxide structure by means of anodization of pure tin foil in alkaline NaOH solutions. The tin oxide film formed is polycrystalline and possesses an irregular nanoporous structure with a porosity of ∼50%. The average pore size is ∼37 nm with a size distribution from 10 to 60 nm irrespective of anodization conditions, including the applied voltage (5–15 V) and NaOH concentration (0.125–1 M). The BET specific surface area of this porous structure is 79.6 m²/g. Linear relationships are observed for the dependence of tin oxide layer thickness on anodization time, applied voltage, and NaOH concentration. A thermodynamic model is established to explain the pore growth mechanism in the anodization process.     

Effect of the solvent on growth of titania nanotubes prepared by anodization of Ti in HCl

The effect of the solvent on the anodic growth of titania nanotubes in HCl dissolved in water, ethylene glycol and 2-propanol was studied. These nanotubes grow with locally rapid breakdown of the passive TiO₂ film forming a forest of nanotubes-bearing microtowers with the background of passive TiO₂ Film. These bundles of assembled-groups of titania nanotubes look like Pillars corals. The low relative permittivity of the 2-propanol led to lowering of dissociation of HCl and hence lowering the activity of H⁺ and Cl⁻ ions which in turn led to suppress of dissolution of titania and increasing the growth rate of the titania nanotubes. The X-ray diffraction pattern showed that the titania nanotubes after annealing change to the crystalline anatase phase. The anodic films showed characteristic coloration with intensity and color that changes (qualitatively) with time of anodization.     

A study on the formation of titania nanopillars during porous anodic alumina through-mask anodization of Ti substrates

The formation of anodic titania during porous anodic alumina (PAA) through-mask anodization has been analysed for varying anodization conditions on mechanically polished bulk Ti surfaces. Titania nanopillars were formed through the porous masks in both oxalic and phosphoric acid electrolytes. For applied potentials above 40 V the titania formed along narrow channels through the alumina pore bottoms resulting in root-like attachments of the titania pillars to the Ti substrate. We further demonstrated that high-field anodization can be used for PAA through-mask anodization. The formation of titania changed with increased current density which resulted in more efficient oxide growth through the alumina pores. When the Al/Ti samples were immersed in the electrolyte without exclusively exposing the Al surface to the electrolyte the titania formed solely on top of the alumina pore bottoms which resulted in that the titania structures were detached from the Ti substrates during selective removal of the PAA templates.     

Fabrication of Ti–Al–Zr alloy oxide nanotube arrays in organic electrolytes by anodization

We report the formation of self-organized Ti–Al–Zr alloy oxide nanotube arrays at different fluoride concentrations in formamide and glycerol electrolytes. The nanotube morphology is strongly influenced by the fluoride concentration, applied potential and reaction time. Titanium alloy (Ti–Al–Zr) oxide nanotube arrays with a length of about 6.13 μm, a pore diameter of 116 nm and wall thickness of 55 nm were prepared at 50 V for 24 h in formamide and glycerol mixtures (volume ratio 1:1) with addition of 1.0 wt% NH₄F. The as-prepared nanotubes were amorphous and alloy oxide crystals appeared after annealing in air at 400 and 600 °C for 3 h.     

Tuning nanoporous anodic alumina distributed-Bragg reflectors with the number of anodization cycles and the anodization temperature

The influence of the anodization temperature and of the number of applied voltage cycles on the photonic properties of nanoporous anodic alumina-based distributed-Bragg reflectors obtained by cyclic voltage anodization is analyzed. Furthermore, the possibility of tuning the stop band central wavelength with a pore-widening treatment after anodization and its combined effect with temperature has been studied by means of scanning electron microscopy and spectroscopic transmittance measurements. The spectra for samples measured right after anodization show irregular stop bands, which become better defined with the pore widening process. The results show that with 50 applied voltage cycles, stop bands are obtained and that increasing the number of cycles contributes to enhancing the photonic stop bands (specially for the case of the as-produced samples) but at the expense of increased scattering losses. The anodization temperature is a crucial factor in the tuning of the photonic stop bands, with a linear rate of 42 nm/°C. The pore widening permits further tuning to reach stop bands with central wavelengths as low as 500 nm. Furthermore, the results also show that applying different anodization temperatures does not have a great influence in the pore-widening rate or in the photonic stop band width.     

Fabrication of high aspect ratio and open‐ended TiO2 nanotube photocatalytic arrays through electrochemical anodization

Well‐aligned, high aspect‐ratio and open‐ended TiO₂ nanotube arrays secured within a Ti foil (TiO₂ nanotubes cartridge) were successfully prepared through the double‐sided anodization method. With ～210 µm of nanotube length, the anodic growth of TiO₂ was accelerated and stabilized by the lactic acid‐containing ethylene glycol electrolyte. In the absence of lactic acid, the anodization led to detachment of nanotubes from the Ti foil after 5–6 h of high voltage (80 V) anodization. Transmission electron microscope image and Raman spectrum revealed that the as‐anodized TiO₂ nanotube arrays without annealing treatment were partially crystalline anatase and demonstrated photocatalytic activity in the mineralization of formic acid. © 2015 American Institute of Chemical Engineers AIChE J, 62: 415–420, 2016     

Fabrication of porous titania sheet via tape casting: Microstructure and water permeability study

In this article, we report the effects of slurry formulation and sintering conditions on the microstructure and permeability of porous titania sheets prepared by tape casting. It was found that solid concentration and binder content in the titania slurry play a vital role in the porosity and microstructure of the sintered titania sheets. Solid concentration and binder content were optimized based on the green tape quality and open porosity of the sintered titania sheets. The optimum solid concentration with the lowest surface roughness was obtained at 0.61 g/cm³. The effects of temperature and sintering time on the open porosity and crystal structure of the final product were also investigated. Increasing the sintering temperature from 1000 to 1100 °C resulted in increasing the pore size from 170 to 264 nm and decreasing the open porosity. Finally, water permeability of the porous titania sheets was studied to evaluate the permeation flux and maximum operating pressure. The results revealed that the permeability of the porous titania sheet is increased not only by increasing the open porosity but also by increasing the pore size.     

Corrosion behavior of electrochemically assembled nanoporous titania for biomedical applications

Corrosion resistance of nanoporous titania was investigated in Hank’s solution using potentiodynamic polarization and electrochemical impedance spectroscopic techniques. The phase structure, surface morphology and elemental composition of the untreated, anodized heat treated and anodized heat treated titanium specimens immersed in Hank’s solution for seven days were characterized using X-ray diffraction, atomic force microscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy techniques, respectively. The X-ray diffraction technique revealed that the anodized heat treated titanium exhibited anatase structure. The atomic force microscopic and scanning electron microscopic results showed that the titanium surface has transformed from a smooth to nanoporous surface depending on the anodization conditions. The energy dispersive X-ray spectroscopy results confirmed the formation of hydroxyapatite over the anodized titanium after immersion for seven days in Hank’s solution. The electrochemical results revealed that the anodized heat treated titanium after seven day immersion in Hank’s solution showed nobler shift in corrosion potential compared to untreated and anodized titanium. Hence, the results suggested that the nanoporous titania layer developed on titanium is a promising material for application as orthopaedic implants.     

Effect of the anodization voltage on the pore-widening rate of nanoporous anodic alumina

ABSTRACT: A detailed study of the pore-widening rate of nanoporous anodic alumina layers as a function of the anodization voltage was carried out. The study focuses on samples produced under the same electrolyte and concentration but different anodization voltages within the self-ordering regime. By means of ellipsometry-based optical characterization, it is shown that in the pore-widening process, the porosity increases at a faster rate for lower anodization voltages. This opens the possibility of obtaining three-dimensional nanostructured nanoporous anodic alumina with controlled thickness and refractive index of each layer, and with a refractive index difference of up to 0.24 between layers, for samples produced with oxalic acid electrolytes.     

Effects of anodization parameters on the formation of titania nanotubes in ethylene glycol

The effects of fluoride concentration, anodization temperature, and anodization applied potential difference on the formation and dimensions of the titania nanotubes in ethylene glycol/water systems were investigated. It was found that fluoride concentration and anodization temperature were the two critical parameters for controlling the nanotube formation whilst anodization applied potential difference mainly contributes to tuning the dimension of the nanotubes. Electrolytes containing a low fluoride concentration are beneficial for initiating nanotube formation, whilst a higher anodization temperature is helpful to the rapid growth of the nanotubes. It is shown that the current-time curve obtained during the anodization can be used as an effective tool to predict the morphology of titania nanotubes. A model based on the competition between electrochemical oxidation of the titanium and chemical dissolution by fluoride ions is developed to explain the experimental observations.     

Fabrication of corrosion resistant, bioactive and antibacterial silver substituted hydroxyapatite/titania composite coating on Cp Ti

The present work is aimed at developing a bioactive, corrosion resistant and anti bacterial nanostructured silver substituted hydroxyapatite/titania (AgHA/TiO₂) composite coating in a single step on commercially pure titanium (Cp Ti) by plasma electrolytic processing (PEP) technique. For this purpose 2.5 wt% silver substituted hydroxyapatite (AgHA) nanoparticles were prepared by microwave processing technique and were characterized by X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy and transmission electron microscopy (TEM) methods. The as-synthesized AgHA particles with particle length ranging from 60 to 70 nm and width ranging from 15 to 20 nm were used for the subsequent development of coating on Cp Ti. The PEP treated Cp Ti showed both titania and AgHA in its coating and exhibited an improved corrosion resistance in 7.4 pH simulated body fluid (SBF) and 4.5 pH osteoclast bioresorbable conditions compared to untreated Cp Ti. The in vitro bioactivity test conducted under Kokubo SBF conditions indicated an enhanced apatite forming ability of PEP treated Cp Ti surface compared to that of the untreated Cp Ti. The Kirby-Bauer disc diffusion method or antibiotic sensitivity test conducted with the test organisms of Escherichia coli (E. coli) for 24 h showed a significant zone of inhibition for PEP treated Cp Ti compared to untreated Cp Ti.     

Optical and electrochemical properties of titania pillared clays

The silicate layers of clay were pillared with TiO₂ sol particles. The sol particles were stabilized between the layers against aggregation on heating up to 500°C, and exhibited a wide optical absorption edge tailing to shorter wavelengths compared with bulk anatase-type TiO₂. This indicates the existence of small TiO₂ sol particles with size quantization effects. The silicate layer used as host matrix was almost transparent in UV-visible region. The TiO₂ sol particles between the silicate layers were electrochemically lithiated, and the pillared clay was used as cathode for a rechargeable lithium cell. Transmission electron micrograph of the section perpendicular to the basal planes showed that the pillared clays have a wide distribution in the interlayer spacing. This wide distribution in interlayer spacings apparently leads to the poor crystallinity and the wide observed pore size distribution of the pillared clays.     

Synthesis and electrochemical study of Pt-based nanoporous materials

In the present work, a variety of Pt-based bimetallic nanostructured materials including nanoporous Pt, Pt-Ru, Pt-Ir, Pt-Pd and Pt-Pb networks have been directly grown on titanium substrates via a facile hydrothermal method. The as-fabricated electrodes were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction and electrochemical methods. The active surface areas of these nanoporous Pt-based alloy catalysts are increased by over 68 (Pt-Pd), 69 (Pt-Ru) and 113 (Pt-Ir) fold compared to a polycrystalline Pt electrode. All these synthesized nanoporous electrodes exhibit superb electrocatalytic performance towards electrochemical oxidation of methanol and formic acid. Among the five nanoporous Pt-based electrodes, the Pt-Ir shows the highest peak current density at +0.50 V, with 68 times of enhancement compared to the polycrystalline Pt for methanol oxidation, and with 86 times of enhancement in formic acid oxidation; whereas the catalytic activity of the nanoporous Pt-Pb electrode outperforms the other materials in formic acid oxidation at the low potential regions, delivering an enhanced current density by 280-fold compared to the polycrystalline Pt at +0.15 V. The new approach described in this study is suitable for synthesizing a wide range of bi-metallic and tri-metallic nanoporous materials, desirable for electrochemical sensor design and potential application in fuel cells.     

Fabrication of nanoporous silicon carbide fibres by thermal treatment

Abstract

Nanoporous silicon carbide fibres were prepared by curing and heat treatment of melt spun polycarbosilane (PCS) fibres. During the curing process, green PCS fibres were thermally oxidised at the temperature between 180 and 220°C and time between 2 and 10 h for cross-linking among the molecule chains in the PCS and controlling the oxygen concentration and distribution. After thermal oxidation, fibres were heat-treated between 1200 and 1600°C for the conversion to SiC phase. About 15–20 wt-% of oxygen was analysed after heat treatment at 1200°C and it can be possible to pyrolyse without melting or deformation of fibre. At a temperature above 1400°C, the uniform distribution of nanopores was observed on the fibre surface, and the size of pores was increased with curing and heating condition. This type of nanoporous SiC fibre is expected to be a good candidate for high temperature catalyst or catalytic supports.     

Review of titania nanotubes: Fabrication and cellular response

Titania (TiO₂) nanotube is gaining prominence as an implantation material due to its unique properties such as high specific surface area and the ability to exhibit positive cellular response. In this paper, we briefly review the current state of fabrication methods to synthesize nanotubular TiO₂ surface topography, and discuss its effect on cellular response of different cells in terms of cell adhesion, proliferation and differentiation. In vitro and in vivo studies by using TiO₂ nanotubes are also presented establishing the potential of nanotubes in biomedical applications. Finally, an outlook of future growth of research in TiO₂ nanostructures beyond the nanotubes is provided     

Fabrication of superhydrophobic titanium surfaces by anodization and surface mechanical attrition treatment

A superhydrophobic surface of titanium was fabricated by anodization in sodium chloride solution followed by immersion in perfluorodecyltriethoxysilane. The surface characteristics of the anodic film (morphology, composition, microstructure, and adhesion) were investigated by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and scratch testing. The anodic film was comprised of TiO₂ and TiCl₃ with a thickness of 50 nm. The anodized titanium surface exhibited a hierarchical structure, which consisted of a microscale horn structure with a nanoscale strip-overlay. This structure provided superhydrophobicity (water contact angle: 151.9° and sliding angle: 3°) following the immersion process. Furthermore, coverage of the hierarchical structure on the anodized titanium surface was improved by performing surface mechanical attrition treatment (SMAT) to grain-refine titanium surface which was then anodized and it enhanced a slightly increased water contact angle. The thickness (200 nm) of the anodic film on the SMAT-pretreated titanium surface was much higher than that on the titanium surface (50 nm). This resulted from a large number of grain boundaries on the surface serving as a fast diffusion path during anodization. However, the adhesion of the SMAT-and-anodized film was worse than that formed by anodization only. This is due to a large number of pores within the SMAT-and-anodized film.     

Structural tuning of photoluminescence in nanoporous anodic alumina by hard anodization in oxalic and malonic acids

ABSTRACT: We report on an exhaustive and systematic study about the photoluminescent properties of nanoporous anodic alumina membranes fabricated by the one-step anodization process under hard conditions in oxalic and malonic acids. This optical property is analysed as a function of several parameters (i.e. hard anodization voltage, pore diameter, membrane thickness, annealing temperature and acid electrolyte). This analysis makes it possible to tune the photoluminescent behaviour at will simply by modifying the structural characteristics of these membranes. This structural tuning ability is of special interest in such fields as optoelectronics, in which an accurate design of the basic nanostructures (e.g. microcavities, resonators, filters, supports, etc.) yields the control over their optical properties and, thus, upon the performance of the nanodevices derived from them (biosensors, interferometers, selective filters, etc.).