Fabrication of titanium oxide nanotube arrays by anodic oxidation

The formation of titanium oxide nanotube arrays on titanium substrates was investigated in HF electrolytes. Under optimized electrolyte and oxidation conditions, well-ordered nanotubes of titania were fabricated. Topologies of the anodized titanium change remarkably along with the changing of applied voltages, electrolyte concentration and oxidation time. Electrochemical determination and scanning electron microscope indicate the nanotubes are formed due to the competition of titania formation and dissolution under the assistance of electric field. A possible growth mechanism has also been presented.     

Analysis of chemical dissolution of the barrier layer of porous oxide on aluminum thin films using a re-anodizing technique

Chemical dissolution of the barrier layer of porous oxide formed on thin aluminum films (99.9% purity) in the 4% oxalic acid after immersion in 2 mol dm⁻³ sulphuric acid at 50 °C has been studied. The barrier layer thickness before and after dissolution was calculated using a re-anodizing technique. It has been shown that above 57 V the change in the growth mechanism of porous alumina films takes place. As a result, the change in the amount of regions in the barrier oxide with different dissolution rates is observed. The barrier oxide contains two layers at 50 V: the outer layer with the highest dissolution rate and the inner layer with a low dissolution rate. Above 60 V the barrier oxide contains three layers: the outer layer with a high dissolution rate, the middle layer with the highest dissolution rate and the inner layer with a low dissolution rate. We suggest that the formation of the outer layer of barrier oxide with a high dissolution rate is linked with the injection of protons or H₃O⁺ ions from the electrolyte into the oxide film at the anodizing voltages above 57 V.     

New route to form micro-pores on 316L stainless steel surface

In order to seek an effective way for preventing restenosis after coronary stent implantation, a proposal of increasing the amount of loaded drug without changing the size of struts was given. Thereafter, a process of fabricating in-situ formed sub-micro-pores on 316L stainless steel (316L SS) was demonstrated. An aluminum thin film was deposited by magnetron sputtering on a 316L substrate. The aluminum film was then anodized in different acids (0.3 M oxalic and 10 vol.% sulfuric) by regulating direct current power supply. Through an appropriate chemical dissolution, the anodic alumina film was removed and the underlying porous 316L was obtained. The morphology of the porous 316L surface was examined by scanning electron microscope and the composition of the pores was investigated by energy dispersive X-ray analysis. The corrosion behavior of the porous 316L was evaluated by the polarization measurement. The results indicate that the shape and size of pores could be affected evidently by the acids used in anodization. The pores density is found to change with variation of the applied voltage in anodization. The corrosion current of the anodized specimens decrease and the corrosion voltage increase, compared with the untreated specimens.     

Microstructured horizontal alumina pore arrays as growth templates for large area few and single nanowire devices

We demonstrate the fabrication of horizontally aligned and well‐defined nanopore structures by anodic oxidation of aluminum thin films and micro stripes on a Si substrate. We are able to control both, the pore diameters and interpore distances from 10 nm to 130 nm and from 30 nm to 275 nm, respectively. The anisotropy of the system induces some deviations in the pore configuration from the typical honeycomb structure. By decreasing the dimensions of the Al structures, the final pore diameter and interpore distance remains constant, enabling the transition from multiple to a few nanowire porous structures. Finally, we successfully filled the nanopores by pulsed electroplating, as demonstrated both by Scanning Electron Microscopy and by current–voltage measurements. Having full control over the size, the density, the position and the orientation of the porous structure, our approach is promising for many exciting applications, including nanoelectronics and sensing. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of Y-junction carbon nanotubes within porous anodic aluminum oxide template

Y-junction carbon nanotubes with the average diameter about 200 nm were successfully synthesized within porous anodic aluminum oxide template, which was prepared by anodic anodizing aluminum sheet in 1.0 mol/l H₃PO₄ solution at a constant anodization voltage 90 V.     

Fabrication and Mossbauer Study of FeCo Alloy Nanotube Array

Arrays of FeCo nanotubes are fabricated in the pores of porous anodic aluminium oxide templates. Transmission electron microscopic result shows that the nanotubes are regular and uniform. Magnetic hysteresis loops measured at room temperature are different from those of nanowires with the same composition, which are caused by the unique shape of nanotubes. The M6ssbauer spectra show that the hyperfine field is smaller than that of the bulk＇s and increases with decrease of measuring temperature. However, the areas of the doublets appeared in M6ssbauer spectra decrease with decrease of measuring temperature.     

Extremely high-aspect-ratio patterns in macroporous substrate by focused-ion-beam etching: the realization of three-dimensional lattices

We show the very particular behavior of focused-ion-beam etching in macroporous silicon. We demonstrate that, contrary to bulk samples, a porous substrate allows extremely high-aspect-ratio patterns to be etched at submicrometer scales. Thanks to the pre-introduced porosity, the secondary effects that limit the pattern depth in bulk-sample etching, namely the sputtered material redeposition as well as the beam ‘self-focusing’ effects, are strongly reduced in a porous sample. In this case the walls between the pores are sputtered in an almost independent way. The etching of deep and straight patterns is feasible. Combined with photoelectrochemical etching that generates the initial macropores, three-dimensional (3D) lattices can be obtained, as demonstrated by 3D photonic crystal fabrication. Received: 21 August 2002 / Accepted: 21 August 2002 / Published online: 12 February 2003 RID="*" ID="*"Corresponding author. Fax: +33-1/6915-6086, E-mail: wang@lps.u-psud.fr     

On the compressive response of carbon nanotube tangles

The nonlinear bulk compressibility of entangled multiwalled carbon nanotubes is studied. The analogy with textile fibre assemblies is explored by means of the well established van Wyk model. In view of the small diameter of the nanotubes, the possible effect of adhesive van der Waals interactions at tube-tube contacts is analysed. It is found, however, that the contribution of adhesive contacts to the bulk stress should be negligible. Compression experiments are performed on multi-walled carbon nanotubes and show that van Wyk's model is able to describe the response, although the values of the dimensionless parameter k of van Wyk's model were lower than expected. There is indeed no indication that van der Waals interactions play any significant role.     

Environmentally friendly approach for nonlithographic nanostructuring of materials

Self‐organized quasi‐ordered two‐dimensional hexagonal arrays of pores with diameters as low as 70 nm in n‐InP substrates subjected to anodic etching in aqueous solution of NaCl are reported. We show that proper periodic modulation of the applied potential with time allows one to reach 3D nanostructuring of the material. Anodization in salty water proves to be a cost‐effective and environmentally‐friendly tool for spatial nanostructuring of materials and nonlithographic manufacturing of semiconductor nanotemplates for nanofabrication. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of structural and optical properties of nanoporous GaN film

The structural and optical characteristics of porous GaN prepared by Pt-assisted electroless etching under different etching durations are reported. The porous GaN samples were investigated by scanning electron microscopy (SEM), high-resolution X-ray diffraction (HR-XRD), photoluminescence (PL) and Raman scattering. SEM images indicated that the density of the pores increased with the etching duration; however, the etching duration has no significant effect on the size and shape of the pores. XRD measurements showed that the (0 0 0 2) diffraction plane peak width of porous samples was slightly broader than the as-grown sample, and it increased with the etching duration. PL measurements revealed that the near band edge peak of all the porous samples were red-shifted; however, the porosity-induced PL intensity enhancement was only observed in the porous samples; apart from that, two additional strain-induced structural defect-related PL peaks observed in as-grown sample were absent in porous samples. Raman spectra showed that the shift of E₂ (high) to lower frequency was only found in samples with high density of pores. On the contrary, the absence of two forbidden TO modes in the as-grown sample was observed in some of porous samples.     

Soft ZnSe nanobelts: Characterization and feasibility for assembling tubular ZnSe nanostructures

Soft ZnSe nanobelts were synthesized by taking Triton X-100 as the template surfactant in a microemulsion. Orderly alternating grooves and bulges on the surface of the nanobelts were first observed via TEM images, and potentially divide a nanobelt into quantum wire bundles. We found that the as-prepared nanobelts show remarkable varied photon scattering and optical properties. A tubular ZnSe structure was successfully obtained with extra treatment. This is an important phenomenon because that the regular folded nanobelts should help us to understand the plastic mechanical properties in a nanoscale assembled tubular structure of nanomaterials and modulate the optical properties of semiconductors.     

A simple approach for synthesis of TiO2 nanotubes with through‐hole morphology

The present work reports a simple approach for fabrication of self‐standing titania (TiO₂) nanotube membranes with through‐hole morphology. The method is hydrofluoric acid free and the pore opening of TiO₂ nanotubes is performed by electrochemical thinning of the oxide barrier layer. A reduction of anodization voltage was applied at the end of the anodization process to cause a successful removal of the remaining barrier layer from the TiO₂ nanotubes during their detachment from the underlying titanium substrate. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Porous ZnO nanobelts evolved from layered basic zinc acetate nanobelts

Novel porous ZnO nanobelts were successfully synthesized by heating layered basic zinc acetate (LBZA) nanobelts in the air. The precursor of LBZA nanobelts consisted of a lamellar structure with two interlayer distances of 1.325 and 0.99 nm were prepared using a low-temperature, solution-based method. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and infrared spectroscopy are used to characterize the as-products. PL measurements show that the porous ZnO nanobelts have strong ultraviolet emission properties at 380 nm, while no defect-related visible emission is detected. The good performance for photoluminescence emission makes the porous ZnO nanobelts promising candidates for photonic and electronic device applications.     

Fabrication of microrods and microtips of InP by electrochemical etching

Here we presented a simple approach to fabricate the microstructures of InP by electrochemical etching. Microrods were formed while InP etched in 7 M HCl solutions for 30 s, and microtips were obtained while InP etched for 120 s. In addition, with increasing applied potential the surface of the microrods became smoother. The formation mechanism was also discussed in this article.     

Characterization of LaMnAl11O19 by FT-IR spectroscopy of adsorbed NO and NO/O2

The nature of the NO_x species produced during the adsorption of NO at room temperature and during its coadsorption with oxygen on LaMnAl₁₁O₁₉ sample with magnetoplumbite structure obtained by a sol-gel process has been investigated by means of in situ FT-IR spectroscopy. The adsorption of NO leads to formation of anionic nitrosyls and/or cis-hyponitrite ions and reveals the presence of coordinatively unsaturated Mn³⁺ ions. Upon NO/O₂ adsorption at room temperature various nitro-nitrato structures are observed. The nitro-nitrato species produced with the participation of electrophilic oxygen species decompose at 350 °C directly to N₂ and O₂. No NO decomposition is observed in absence of molecular oxygen. The adsorbed nitro-nitrato species are inert towards the interaction with methane and block the active sites (Mn³⁺ ions) for its oxidation. Noticeable oxidation of the methane on the NOx⁻-precovered sample is observed at temperatures higher than 350 °C due to the liberation of the active sites as a result of decomposition of the surface nitro-nitrato species. Mechanism explaining the promoting effect of the molecular oxygen in the NO decomposition is proposed.     

Fabrication of metal nano-structures using anodic alumina membranes grown in phosphoric acid solution: Tailoring template morphology

The influence of experimental parameters on the morphology of the porous structure and on the formation kinetics has been investigated for anodic alumina membranes (AAM) grown in aqueous H₃PO₄ at 160 V. It was found that pore aspect ratio and membrane porosity on the solution-side surface are influenced by tensiostatic charge, bath temperature and the presence of Al³⁺ ions in solution. Morphological and kinetic data, recorded in different conditions, give useful information on the growth mechanism of pore channels in phosphoric acid solution.Nickel nano-structures have been fabricated using AAM as template. Electroless deposition, performed by adding the reducing agent to a suitable bath in several steps, resulted in the formation of short metal nanotubes (about 5 μm long) in the upper part of the channels. Long Ni nanowires (up to 25 μm) with aspect ratio higher than 100 were obtained by pulsed unipolar electrodeposition from a Watt bath. In this case, both the influence of some experimental parameters on the nanowires growth and the fast current transients during the electrodeposition steps were analyzed.     

Observation of phase-locking and phase-transition of pores in silicon electrochemistry

In this work, via anodization of n-type silicon specimens pre-textured with different patterns, phase-transition of pores induced by varied HF concentrations and phase-locking of pores imposed by predefined nuclei were evidenced. Based on the analysis of scanning electron microscope (SEM) micrographs and current-voltage curves, the competition between physical and chemical elements was found to be crucial to understand the observations. Not least, our results indicate strongly that pore density can act independently as a function of the initial morphology of sample surface. Electric-field effect as well as current-burst-model (CBM) was employed to interpret the underlying mechanism.     

Preparation of activated carbon from cherry stones by chemical activation with ZnCl2

Cherry stones (CS), an industrial product generated abundantly in the Valle del Jerte (Cáceres province, Spain), were used as precursor in the preparation of activated carbon by chemical activation with ZnCl₂. The influence of process variables such as the carbonisation temperature and the ZnCl₂:CS ratio (impregnation ratio) on textural and chemical-surface properties of the products obtained was studied. Such products were characterised texturally by adsorption of N₂ at −196 °C, mercury porosimetry and density measurements. Information on the surface functional groups and structures of the carbons was provided by FT-IR spectroscopy. Activated carbon with a high development of surface area and porosity is prepared. When using the 4:1 impregnation ratio, the specific surface area (BET) of the resultant carbon is as high as 1971 m² g⁻¹. The effect of the increase in the impregnation ratio on the porous structure of activated carbon is stronger than that of the rise in the carbonisation temperature, whereas the opposite applies to the effect on the surface functional groups and structures.     

Growth mechanisms for single-wall carbon nanotubes in a laser-ablation process

Mechanisms proposed in the literature are compared with a current scenario for the formation of single-wall carbon nanotubes in the laser-ablation process that is based on our spectral emission and laser-induced fluorescence measurements. It is suggested that the carbon which serves as feedstock for nanotube formation not only comes from the direct ablation of the target, but also from carbon particles suspended in the reaction zone. Fullerenes formed in the reaction zone may be photo-dissociated into C₂ and other low molecular weight species, and also may serve as feedstock for nanotube growth. Confinement of the nanotubes in the reaction zone within the laser beam allows the nanotubes to be ‘purified’ and annealed during the formation process by laser heating. Received: 2 November 2000 / Accepted: 3 November 2000 / Published online: 23 March 2001     

Growth process and wear resistance for ceramic coatings formed on Al-Cu-Mg alloy by micro-arc oxidation

The growth process, distribution of chemical elements, phase constitutions and relative wear resistance of the ceramic coatings formed on Al-Cu-Mg alloy by ac micro-arc oxidation are investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscope (EDX), X-ray diffraction (XRD) and reciprocating friction and wear tests. The results indicate that there are three stages with the formation of the ceramic coatings: (1) the formation of ceramic particles, (2) sintering growth in sawtooth structure, (3) the increase of thickness by remolting and sintering. The ceramic coatings are made up of a mixture of α-alumina, γ-alumina and amorphous alumina, whose relative contents varied with the position in the ceramic coatings, respectively. The chemical elements altered in ceramic coatings produced in different electrolytes and varied along the depth in ceramic coatings obtained in phosphate electrolyte. Meanwhile, the results of friction and wear tests against Gr15 after 16 h indicate that the weight loss of ceramic coatings became almost unchanged.