On the factors controlling the mechanical properties of nanotube films

We have studied the mechanical and morphological properties of carbon nanotube films prepared from tubes produced by a range of commercial suppliers. We find significant correlations between mechanical parameters (modulus, strength, toughness and ductility) and morphological parameters (porosity and bundle diameter). Both strength and toughness scale linearly with the number of inter-bundle junctions per unit volume as calculated from the porosity and bundle size. Applying a simple model, we can use this data to find the average force and energy required to break a junction to be ∼113 pN and 0.7 eV, respectively. This latter value agrees well with the value of 0.9 eV estimated from the nanotube surface energy, indicating that adjacent bundles are bound predominately by van der Waals interactions.     

Complex dielectric functions of anodic bi-layer tantalum oxide

The optical properties and structure of anodic oxides are dependent on the anodization conditions. For tantalum oxide formed in dilute phosphoric acid, the anodic oxide forms as two chemically distinct layers, referred to as a bi-layer, where the inner layer is pure tantalum oxide and the outer layer contains incorporated phosphate. The complex dielectric functions of the individual inner and outer layers are determined using spectroscopic ellipsometry. The dielectric functions of the bi-layers are compared to mono-layer oxides formed in sodium sulfate, and the effects of hydrothermal sealing are explored. For bi-layer oxides formed to 70 V in phosphoric acid, the inner layer band gap is 4.37 ± 0.02 eV and the outer layer band gap is 3.86 ± 0.06 eV. Thin anodic oxides (∼6-15 nm) are best described by a mono-layer oxide model and exhibit higher optical absorption with a band gap of 3.98 ± 0.08 eV. This study shows that spectroscopic ellipsometry is a valuable tool in assessing processing-property relationships of multi-layer anodic films.     

Enhanced visible light photocurrent generation at surface-modified TiO2 nanotubes

Photoelectrodes consisting of TiO₂ nanotube layers with different thicknesses (0.5 μm, 1.7 μm, 3 μm, 6 μm, 9 μm, and 18 μm) were prepared by anodization of titanium substrates and subsequent surface modification by a heat treatment at 400 °C in the presence of urea pyrolysis products. In contrast to unmodified TiO₂ nanotubes, the modified photoelectrodes exhibit photocurrents under visible light irradiation down to 750 nm. Photocurrent transients indicate enhanced recombination unless a suitable hole-scavenger, like iodide, is present since the photogenerated holes do not oxidize water efficiently. In the visible light the photoconversion efficiency increases significantly with nanotube length. The maximum incident photon-to-current efficiency (IPCE) was observed for tubes with the length of 6-9 μm (IPCE ∼4.5% and 1.4% at 450 nm and 550 nm, respectively) and the photocurrent enhancement with increasing tube length is found to be stronger at longer irradiations wavelengths.     

Porous niobium oxide films prepared by anodization in HF/H3PO4

Ordered porous niobium oxide with the diameter of less than 10 nm and the aspect ratio of more than 20 is prepared by anodization of niobium foils at 2.5 V in the mixture of 1 wt% HF and 1 M H₃PO₄ for 1 h. In this study, the effects of the mixed electrolytes, anodic potential and anodization time on the preparation of porous niobium oxide are described based on the current-time transients during anodization and morphological observations. It is founded that a single HF electrolyte leads to the formation of pores as well as the fast dissolution of formed pores at the surface. The dissolution of the formed oxide is significantly retarded by the addition of appropriate amount of H₃PO₄.     

Enhanced inactivation of E. coli bacteria using immobilized porous TiO2 photoelectrocatalysis

Immobilized TiO₂ nanotube electrodes with high surface areas were grown via electrochemical anodization in aqueous solution containing fluoride ions for photocatalysis applications. The photoelectrochemical properties of the grown immobilized TiO₂ film were studied by potentiodynamic measurements (linear sweep voltammetry), in addition to the calculation of the photocurrent response. The nanotube electrode properties were compared to mesoporous TiO₂ electrodes grown by anodization in sulfuric acid at high potentials (above the microsparking potential) and to 1 g/l P-25 TiO₂ powder. Photocatalyst films were evaluated by high resolution SEM and XRD for surface and crystallographic characterization. Finally, photoelectrocatalytic application of TiO₂ was studied via inactivation of E. coli. The use of the high surface area TiO₂ nanotubes resulted in a high photocurrent and an extremely rapid E. coli inactivation rate of ∼10⁶ CFU/ml bacteria within 10 min. The immobilized nanotube system is proven to be the most potent electrode for water purification.     

Stable TiO2 nanotube arrays with high UV photoconversion efficiency

This work is intended to define an optimal methodology for preparing highly ordered TiO₂ nanotube arrays by a 60-V anodization in a glycol ethylene solution. In order to obtain a mechanically stable structure with a high UV photoconversion efficiency, it is necessary to carefully control the growth mechanism through the anodization process. For this reason, the nanotube arrays have to be formed upon a compact titanium dioxide layer with well-defined thickness. Besides, both the fluoride concentration and anodization time are strictly correlated, because elevated concentrations and/or a long anodization time produce unstable structure with low photoconversion efficiency. The best result in the terms of reproducibility has been obtained previously for a three-minute galvanostatic oxide growth on the pickled titanium sheet, and anodic growth in ethylene glycol solution containing 1 wt.% H₂O and 0.20 wt.% NH₄F for a period lower than 4.5 h. The UV photoconversion efficiency was measured and a maximum value of 28.3% has been obtained, which is the highest result in the literature.     

Electrochemically multi-anodized TiO2 nanotube arrays for enhancing hydrogen generation by photoelectrocatalytic water splitting

An enhanced hydrogen production by photoelectrocatalytic water splitting was obtained using extremely highly ordered nanotubular TiO₂ arrays in this work. Highly ordered TiO₂ nanotube arrays with a regular top porous morphology were grown by a facile and green three-step electrochemical anodization. The well ordered hexagonal concaves were uniformly distributed on titanium substrate by the first anodization, served as a template for further growth of TiO₂ nanotubes. As a result, the TiO₂ nanotube arrays constructed through the third anodization showed appreciably more regular architecture than that of the sample by conventional single anodization under the same conditions. The enhanced photoelectrochemical activity was demonstrated through the hydrogen generation by photoelectrocatalytic water splitting, with an exact H₂ evolution rate up to 420 μmol h⁻¹ cm⁻² (10 mL h⁻¹ cm⁻²) in 2 M Na₂CO₃ + 0.5 M ethylene glycol. The photocurrent density of the third-step anodic TiO₂ nanotubes is about 24 mA cm⁻² in 0.5 M KOH, which is 2.2 times higher than that of the normal TiO₂ nanotubes (∼11 mA cm⁻²) by a single electrochemical anodization.     

Effect of a galvanostatic treatment on the preparation of highly ordered TiO2 nanotubes

This work is intended to define an optimal methodology of preparation of highly ordered TiO₂ nanotube arrays by a 60 V anodization in a glycol ethylene solution. The effect of the presence of an initial superficial oxide on the sample, before operating the anodization growth, has been analysed. The best result has been obtained by a galvanostatic oxide growth on the titanium sheet, before the anodization process. The photoconversion efficiency was measured and we have obtained a maximum value of 12.97%, strictly in line with the literature. We have also underlined the necessity to operate a heat treatment using only dry atmosphere.     

Fabrication of integrated arrays of ultrahigh density magnetic nanowires on glass by anodization and electrodeposition

Integrated nanowire arrays of Fe-Pt, Co-Pt, and Ni-Pt alloys were successfully fabricated on glass substrates by successive anodization and electrodeposition. Porous alumina films, which were formed from an aluminum layers sputter-deposited on glass substrates covered with transparent oxide conductive films, were used as template-electrodes to deposit various magnetic alloys (Fe-Pt, Co-Pt, and Ni-Pt) in the nanopores by a cathodic electrodeposition, thus leading to integrated nanowire arrays with ultrahigh densities of (0.6-2.1) × 10¹⁵ wire m⁻². The as-deposited nanowires of Fe-Pt, Co-Pt, and Ni-Pt alloys are polycrystalline and composed of fine crystals (4-7 nm across) of chemically ordered tetragonal FePt, CoPt, or NiPt phase. The integrated nanowire arrays may be the promising candidate materials for ultrahigh density perpendicular magnetic recording media in terabits per square inch regime, due to the predictable enhanced perpendicular magnetic performance after appropriate annealing.     

Polishing effect on anodic titania nanotube formation

Titania nanotubes represent exciting opportunities in solar cell, sensing, and catalytic applications. In this work, four different surface polishing conditions: as-received, chemical polishing, mechanical polishing, and electropolishing, are studied in order to understand the effect of different surface conditions on the anodization process and nanotube morphology. At the same anodization condition of 100 V in 0.1 M NH₄F ethylene glycol at 0 °C for 3 min, the as-received and mechanically polished samples show nano-tubular surfaces while the chemically polished and electropolished samples have oxide layers on the top of the nanotubes. The nanotube morphologies, anodization current vs. time curves, and the bottom barrier layers are all related to the Ti surface conditions. The electropolished surface leads to the most homogeneous TiO₂ nanotube formation.     

Raman spectroscopy and nitrogen vapour adsorption for the study of structural changes during purification of single-wall carbon nanotubes

Raman spectroscopy and nitrogen adsorption measurements were combined to study the surface features of semi-conducting and metallic single-wall nanotubes (SWNTs). The nanotubes were treated chemically and with heat under moderate conditions that more than doubled the mesopore volume of the tested samples, which consistently led to a significant rise in the total surface area of up to 1550 m²/g. The large increase in the number of micropores of less than 1 nm in diameter was associated with the loosening of nanotube bundles as well as the creation of structural flaws on the surface of individual SWNTs due to chemical treatment. Micropores in the 1.0-1.8 nm range were associated with the holes created on the surface of individual tubes. Heating at 1000 °C was shown to restore nanotube diameter to their initial pre-chemical treatment levels with the change in the chirality of SWNTs and diminish the porosity by closing small holes. It was assumed that the intermediate frequency range (500-1100 cm⁻¹) was associated with the degree of imperfection of HiPco SWNTs crystalline structures, and therefore provided information about the degree of tube surface damage due to the presence of functional groups. A hypothesis explaining the transformation of SWNT porous structure during heat treatment is proposed.     

Metallurgical aspects on the formation of self-organized anodic oxide nanotube layers

The present work reports how metallurgical factors such as grain size and chemical composition of substrate affect the current behavior during anodization and the morphology of resulting formed oxide layers. The grain size of pure Ti sheet is controlled by the accumulative roll-bonding (ARB) process. Tubular oxide layers are formed on the ARB-processed Ti sheets with different grain sizes, but grain size does not affect the length, diameter of tubes and the degree of tube arrangement. The effect of chemical composition is examined using Ti-Zr alloys (Ti-20Zr, Ti-50Zr, Ti-80Zr) that can consist of a single phase, meaning that homogeneous tube formation can be achieved. With increasing Zr content in the alloys, tube diameter decreases while tube length increases. For the Ti-50Zr and Ti-80Zr, self-organization is achieved on two size scales, that is, nanotube arrays with two distinct diameters are observed. TEM observation revealed that anodic oxide layers are in crystalline state only in the case of pure Zr.     

Preparation and capacitive properties of cobalt-nickel oxides/carbon nanotube composites

In this paper, nickel-cobalt oxides/carbon nanotube (CNT) composites were prepared by adding and thermally decomposing nickel and cobalt nitrates directly onto the surface of carbon nanotube/graphite electrode to form nickel and cobalt oxides. Carbon nanotubes used in this paper were grown directly on graphite substrate by chemical vapor deposition technique. The capacitive behavior of nickel-cobalt oxides/CNT electrode was investigated by cyclic voltammetry and galvanostatic charge-discharge method in 1 M KOH aqueous solutions. The results show that nickel-cobalt oxides/CNT composite electrode has excellent charge-discharge cycle stability (0.2% and 3.6% losses of the specific capacitance are found at the 1000th and 2000th charge-discharge cycles, respectively) and good charge-discharge properties at high currrent density. Additionally, the effect of Ni/Co molar ratio on specific capacitance of the composite electrode was investigated and the highest specific capacitance (569 F g⁻¹ at 10 mA cm⁻²) is obtained at Ni/Co molar ratio = 1:1.     

Transfer-matrix simulations of electronic transport in single-wall and multi-wall carbon nanotubes

We present simulations of electronic transport in single-wall and multi-wall carbon nanotubes, which are placed between two metallic contacts. We consider situations where the electrons first encounter a singe-wall nanotube (corresponding to either the inner or the outer shell of the (10, 10)@(15, 15)@(20, 20) and (10, 10)@(20, 10)@(20, 20) nanotubes), before encountering the multi-wall structures. The role of this two-step procedure is to enforce the electrons to enter a single shell of the multi-wall nanotubes, and we study how from that point they get redistributed amongst the other tubes. Because of reflections at the metallic contacts, the conductance of finite armchair nanotubes is found to depend on the length of the tubes, with values that alternate between three separate functions. Regarding the transport in multi-wall nanotubes, it is found that the electrons keep essentially propagating in the shell in which they are initially injected, with transfers to the other tubes hardly exceeding one percent of the whole current. In the case where the three tubes are conducting, these transfers are already completed after four nanometers. The conductance and repartition of the current present then oscillations, which are traced to the band structure of the nanotube. The transfers between the shells and the amplitude of these oscillations are significantly reduced when the intermediate tube is semiconducting.     

Synthesis of close-packed multi-walled carbon nanotube bundles using Mo as catalyst

A simple mixture of porous magnesium oxide and commercial molybdenum oxide shows high efficiency for the synthesis of carbon nanotubes through the catalytic decomposition of methane at 900 °C. Field emission scanning electron microscopy (FE-SEM), Raman spectroscopy, and transmission electron microscopy (TEM) were used to characterize the products. The results indicate that close-packed multi-walled carbon nanotube (MWCNT) bundles were synthesized and the carbon nanotubes restricted within the bundles were about 5-7 nm in diameter. A growth mechanism for the bundles was suggested based on the FE-SEM images of bundles produced using different reaction times, and the X-ray diffractions of the raw products grown at the initial stage. Raman spectroscopy and FE-SEM results on the bundles grown using different methane flow rates confirmed the growth mechanism of close-packed MWCNT bundles.     

Control of morphology and composition of self-organized zirconium titanate nanotubes formed in (NH4)2SO4/NH4F electrolytes

We investigated the formation of self-organized zirconium titanate nanotubes by anodizing a Ti-35Zr alloy in 1 M (NH₄)₂SO₄ + 0.1-2.0 wt.% NH₄F electrolytes. The morphology and composition of the zirconium titanate nanotube are controlled by the applied electrochemical conditions. The outer diameter of nanotubes is controlled by the anodization potential in the range between 1 and 100 V (versus Ag/AgCl). Tubes with diameters from 14 to 470 nm can be grown. The nanotube length correlates with the anodic charge up to a length where significant dissolution of the nanotube layer is observed. The wall thickness, composition of the nanotubes and porosity of the nanotube layer are significantly affected by the fluoride ion concentration. The length limiting factor of the nanotube growth is found to be the diffusion of ionic species in the electrolyte.     

Corrosion resistance of plasma-anodized AZ91D magnesium alloy by electrochemical methods

Anodic coatings formed on magnesium alloys by plasma anodization process are mainly used as protective coatings against corrosion. The effects of KOH concentration, anodization time and current density on properties of anodic layers formed on AZ91D magnesium alloy were investigated to obtain coatings with improved corrosion behaviour. The coatings were characterized by scanning electron microscopy (SEM), electron dispersion X-ray spectroscopy (EDX), X-ray diffraction (XRD) and micro-Raman spectroscopy. The film is porous and cracked, mainly composed of magnesium oxide (MgO), but contains all the elements present in the electrolyte and alloy. The corrosion behaviour of anodized Mg alloy was examined by using stationary and dynamic electrochemical techniques in corrosive water. The best corrosion resistance measured by electrochemical methods is obtained in the more concentrated electrolyte 3 M KOH + 0.5 M KF + 0.25 M Na₃PO₄·12 H₂O, with a long anodization time and a low current density. A double electrochemical effects of the anodized layer on the magnesium corrosion is observed: a large inhibition of the cathodic process and a stabilization of a large passivation plateau.     

High pressure-high temperature synthesis of diamond from single-wall pristine and iodine doped carbon nanotube bundles

High pressure and high temperature experiments were performed on single-wall carbon nanotube bundles up to 14.5 GPa and 1800 K. Depending on the thermodynamic conditions, we have observed three different behaviors: at ambient temperature and for pressure lower than 24 GPa, minor structural changes are observed. Depending on the loss of hydrostatic conditions or on the combined application of pressure and temperature, partial or total graphitization is observed. For pressures of 14.5 GPa and temperatures of 1800 K the nanotubes are irreversibly transformed into cubic diamond, showing that it is possible to synthesize under high pressure and high temperature pure sp³ carbon structures from single-wall carbon nanotubes. In the case of iodine intercalated nanotubes, the same conditions of 14.5 GPa and 1800 K lead also to the transformation into diamond. No evidence of incorporation of iodine in the sp³ carbon structure was found. On the basis of our results, we discuss possibilities for new carbon-carbon composite engineering from single-wall carbon nanotube bundles.     

Preparation and magnetic properties of iron titanium oxide nanotube arrays

FeTi alloy was prepared by a vacuum smelting method, iron titanium oxide nanotube arrays have been made directly by anodization of the FeTi alloy. Morphologies and microstructures of the samples were characterized by scanning electron microscope, transmission electron microscope, and X-ray diffractometer. Influences of temperature and H₂O concentration on the morphologies of the nanotube arrays have been discussed in detail. Magnetic properties of the samples have also been investigated. The as-prepared samples were amorphous. When annealed at 500 °C and 550 °C, pesudobrookite Fe₂TiO₅ was obtained. At 600 °C, there were mixed Fe₂TiO₅, rutile TiO₂, and α-Fe₂O₃. Magnetic performance of the nanotube arrays exhibited high sensitivity to temperature and changed interestingly upon annealing. The values of the coercivity and remanence were 340 Oe and 0.061 emu/g respectively for the sample annealed at 550 °C.     

Oxidation characteristics of nanodot and nanobump on TiN thin films by atomic force microscopy

The electrochemical oxidation characteristics of TiN thin films by atomic force microscopy (AFM) was investigated. The TiN films were produced on silicon substrate by atomic layer chemical vapor deposition (ALCVD). The anodization parameters, such as the anodized voltages, the oxidation times, and how they affected the creation and growth of the oxide nanostructures were explored. The results showed that the height of the TiN oxide dots grew as a result of either the anodization time or the anodized voltage being increased. The oxide growth rate was dependent on the anodized voltage and the resulting electric field strength. Furthermore, the oxide growth rate decreased immediately when the electric field strength reached (2-3) × 10⁷ V/cm rapidly decrease to a growth rate of 0.