Porous WO3 formed by anodization in oxalic acid

This work reports the investigation of the anodic growth of porous tungsten oxide (WO₃) in oxalic acid. It was found that pore diameter increases from approximately 50 to 90 nm while the layer thickness of porous structures increases from approximately 100 to 400 nm as the voltage varies from 40 to 100 V. Extended anodization duration improves the homogeneity of the porous structure at 40 V but it has no effect on the pore layer thickness. During the pore formation process, nucleation of small pores in the existing pore is observed while several layers of pores with voids underneath the surface layer are formed especially at high anodization voltage. A possible growth mechanism of the pores is proposed.     

Kinetics of the electrolytic coloring process on anodized aluminum

The kinetics of tin electrodeposition during the electrolytic coloring of porous anodic oxide films on aluminum is studied as a function of the oxide properties, e.g., the thickness of the porous oxide layer, and the surface resistance offered by the barrier oxide layer. While the thickness of the porous oxide layer is controlled by the anodization time, the surface resistance is controlled by the anodization voltage, and the anodization bath temperature. Steady-state polarization measurements are employed to characterize the dependence of the coloring kinetics on the oxide properties. Measurements indicate that the kinetics of the electrolytic coloring process can be accelerated by: (i) reducing the surface resistance of the oxide film (primarily offered by the barrier oxide layer) by growing the oxide at a lower anodization voltage, and/or a higher bath temperature, or (ii) growing a thinner porous oxide layer by decreasing the anodization time. The electrochemical measurements are supported by gravimetric analysis of electrolytically colored alumina samples (using calibrated wavelength-dispersive X-ray fluorescence spectroscopy), and by optical spectrophotometry.     

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.     

Modeling of the Current Distribution in Aluminum Anodization

The growth of porous anodic Al₂O₃ films, formed potentiostatically in continuously stirred 15 wt.% H₂SO₄ electrolyte was studied as a function of the anodization voltage (14–18 V), bath temperature (15–25 °C) and anodization time (15–35 min). The variation of the anodic surface overpotential with the current density was measured experimentally. The film thickness at the more accessible portions of the anode was observed to increase with the anodization voltage and the bath temperature. However, the film thickness on the less accessible portions of the anode did not significantly change with the voltage or the bath temperature. This indicates that the anodization process at the more accessible regions is more strongly influenced by the surface processes than by the electric migration within the electrolyte. Furthermore, analysis confirms that the major portion of the film resistivity resides within a thin sub-layer that does not vary with the anodization time, and the growing anodic layer contributes only marginally to the overall film resistance. Computer aided design software was employed to simulate the current density distribution. For the range of process parameters studied, the electrochemical CAD software predicts accurately the measured thickness distribution along the anode.     

Tantalum Oxide Films Prepared by Oxygen Plasma Anodization and Reactive Sputtering

Anodic tantalum oxide thin-film capacitors have proved quite satisfactory for circuit applications, although some minor limitations exist in the maximum usable dielectric thickness, current asymmetry, and allowable counterelectrode materials. For this reason, two processes of glow discharge anodization and dc diode reactive sputtering were investigated for the formation of tantalum oxide films. Dielectrics up to a maximum thickness of 3000 A could be prepared by these methods with equal or larger than anticipated capacitance per unit area and dielectric strengths of about one third of anodically formed tantalum oxide. The dc diode reactive sputtering process produces thickness variations over 50 cm² of 4 to 20% compared with 4 and 1%, respectively, for glow discharge anodization and aqueous anodization. At the present time, the all-vacuum methods are limited in applicability because of lower dielectric strength and lower formation rates.     

Modelling and simulation of self-ordering in anodic porous alumina

Real-time evolution of pre-textured anodic porous alumina growth during anodization is numerically simulated in two-dimensional cases based on a kinetic model involving the Laplacian electric field potential distribution and a continuity equation for current density within the oxide body. Ion current densities governed by the Cabrera–Mott equation in high electric field theory are formed by ion migration within the oxide as well as across the metal/oxide (m/o) and oxide/electrolyte (o/e) interfaces, and the movements of the m/o and o/e interfaces due to oxidation and electric field assisted oxide decomposition, respectively, are governed by Faraday's law. Typical experimental results, such as linear voltage dependence of the barrier layer thickness and pore diameter, time evolution of the current density, scalloped shape of the barrier layer, and the extreme difference in the reaction rates between pore bottoms and pore walls, are successfully predicted. Our simulations revealed the existence of a domain of model parameters within which pre-textured porous structures which do not satisfy self-ordering configurations are driven into self-ordering configurations through a self-adjustment process. Our experimental results also verify the existence of the self-adjustment process during anodization.     

Fabrication of self-ordered nanoporous alumina with 500–750 nm interpore distances using hard anodization in phosphoric/oxalic acid mixtures

A hard anodization (HA) technique is employed using different mixtures of phosphoric/oxalic acid for fast fabrication of alumina nanopore arrays in voltages higher than 200 V. The mixtures enable to avoid the breakdown of porous anodic alumina (PAA) in the high voltages. It is revealed for the first time that continuously tunable pore intervals (D_int) from 500 to 750 nm can be controlled by varying the concentrations of oxalic acid at anodization voltages (U_anod) from 230 to 360 V, far beyond the U_anod in the single electrolyte of phosphoric acid or oxalic acid. The ratios of interpore distance, pore diameter and barrier layer thickness to anodization voltage are in the range of conventional HA process for each acid mixture. In this approach, the PAA film growth rate is 26 µm/h, being 7 times larger than that in typical mild anodization.     

Preparation of anodic aluminum oxide (AAO) nano-template on silicon and its application to one-dimensional copper nano-pillar array formation

Anodized aluminum oxide (AAO) nanotemplates were prepared using the Al/Si substrates with an aluminum layer thickness of about 300 nm. A two-step anodization process was used to prepare an ordered porous alumina nanotemplate, and the pores of various sizes and depths were constructed electrochemically through anodic oxidation. The optimum morphological structure for large area application was constructed by adjusting the applied potential, temperature, time, and electrolyte concentration. SEM investigations showed that hexagonal-close-packed alumina nano-pore arrays were nicely constructed on Si substrate, having smooth wall morphologies and well-defined diameters. It is also reported that one dimensional copper nanopillars can be fabricated using the tunable nanopore sized AAO/Si template, by controlling the copper deposition process.     

电压施加方式在阳极氧化钛薄膜形成过程中的作用

采用阳极氧化的方法,通过改变电压的施加方式制备了具有不同形貌的氧化钛薄膜。使用扫描电子显微镜考察了氧化钛薄膜的形貌,结合实验现象探讨了阳极氧化钛薄膜纳米孔的形成机制。研究结果表明,采用一步施加电压和连续施加电压的方法,氧化钛薄膜纳米孔的形成过程由电压、阻挡层的厚度决定;采用两步施加电压的方法,氧化钛薄膜纳米孔的形成过程由放电电压、阻挡层的厚度和阻挡层/电解液的边界条件协同控制。在相同工艺条件下,采用两步施加电压法能够扩展阳极氧化钛薄膜纳米孔孔径和孔密度的范围。     

Controlling the thickness of electrochemically produced porous alumina membranes: the role of the current density during the anodization

A study of the thickness growth rate of anodized porous alumina membranes (PAMs) and its connection to the current density during the anodization process is presented. Several samples of PAMs were prepared in a hydrate solution of 0.3 M oxalic acid, under applied voltages of 40 and 50 V with varying solution temperatures in a purpose-built electrochemical cell. The thickness of the PAMs produced under these conditions was measured using cross section images taken by scanning electron microscopy (SEM). From these measurements, a linear expression between the growth rate of PAMs and the current density during the anodization is deduced, giving an efficiency value of 53 and 65 % for applied voltages 40 and 50 V, respectively. In steady state conditions, i.e., after the stabilization of the anodization current, this linear dependence is very conveniently transformed into linear dependence of thickness versus total anodization time, providing thus a simple method for controlling the thickness of the produced membranes. Finally, from the Arrhenius-type plot of the thickness growth rate versus temperature and the anodization current density vs temperature a mean value of 48.5 kJ mol^?1 for the aluminum oxide formation activation energy E _a is deduced.     

Multifunctional,environmental coatings on AA2024 by combining anodization with sol-gel process

The present work proposes the development of multifunctional composite coatings on AA 2024 by combining anodization and sol-gel process. To render the surface of AA 2024 with maximum corrosion resistance, eco-friendly citric-sulfuric acid (CSA) electrolyte with low sulphur content was used for anodization at 20 V for a duration of 30 min. The obtained anodized layer was porous. Ambient curable hybrid sol-gel coating with 8-hydroxy quinoline (8-HQ) as corrosion inhibitor was used as a sealant for the porous anodized layer to enhance the corrosion resistance with self-healing properties. Surface pre-treatments were carried out using sand blasting and alkaline etching to ensure high surface activity prior to anodization. The surface morphology and chemical composition of samples with and without coatings were characterized by field emission scanning electron microscopy (FESEM) and energy dispersive X-ray spectroscopic analysis (EDX). Adhesion strength and wettability of the coatings were measured by tape adhesion test and water contact angle analysis respectively, which revealed excellent binding strength and hydrophobic nature. The corrosion resistance of the coatings was evaluated using electrochemical impedance spectroscopic (EIS), potentiodynamic polarization and salt spray tests. The results revealed improved corrosion resistance of anodized + 8-HQ sealed AA2024. Moreover, when the coated samples were scribed and exposed to the corrosive medium, the SEM/EDX mapping confirmed presence of corrosion inhibitors at the location of the defect, thereby confirming the self-healing property. Hence, the proposed system is a chromium-free, environment friendly multifunctional system exhibiting excellent self-healing corrosion protection and can be a promising substitute for chromic acid anodization.     

Kinetics and mechanism of the silver (I) oxide to silver (II) oxide layer electrooxidation reaction

The electroformation of Ag(II) oxide layer during the anodization of silver in 0.1 M NaOH is investigated under potentiostatic and potentiodynamic conditions. Results are discussed in terms of nucleation and growth models and statistical analysis of induction times related to the nucleation kinetics of Ag(II) oxide crystals. The best fitting of results comes out from the application of a progressive nucleation and 3-D growth model under mass transfer control where diffusion of species from the electrode to growing sites is essential for further expansion.     

A kinetic model of diamond nucleation and silicon carbide interlayer formation during chemical vapor deposition

The presence of thin silicon carbide intermediate layers on silicon substrates during nucleation and the early stages of diamond deposition have been frequently reported. It is generally accepted that the intermediate layer is formed by the bulk diffusion of carbon atoms into the silicon carbide layer and the morphology and orientation of the diamond film subsequently grown on the intermediate layer are strongly affected by that layer. While there have been considerable attempts to explain the mechanism for intermediate layer formation, limited quantitative data are available for the layer formation under the operating conditions conducive to diamond nucleation.This study employs a kinetic model to predict the time evolution of a β-SiC intermediate layer under the operating conditions typical of diamond nucleation in hot filament chemical vapor deposition reactors. The evolution of the layer is calculated by accounting for gas-phase and surface reactions, surface and bulk diffusions, the mechanism for intermediate layer formation, and heterogeneous diamond nucleation kinetics and of its dependence on the operating conditions such as substrate temperature and inlet gas composition. A comparison between the time scales for intermediate layer growth and diamond nuclei growth is also performed. Discrepancies in published adsorption energies of gaseous hydrocarbon precursors on the intermediate layer—ranging from 1.43 to 4.61 eV—are examined to determine the most reasonable value of the adsorption energy consistent with observed saturated thicknesses, 1–10 nm, of the intermediate layer reported in the literature. The operating conditions that lead to intermediate layer growth followed by diamond deposition vs. those that yield heteroepitaxial diamond nucleation without intermediate layer formation are discerned quantitatively. The calculations show that higher adsorption energies, 3.45 and 4.61 eV, lead to larger surface number densities of carbon atoms, lower saturated nucleation densities, and larger intermediate layer thicknesses. The observed saturated thicknesses of the intermediate layer may be reproduced if the true adsorption energy is in the range of 3.7–4.5 eV. The intermediate layer thickness increases by increasing substrate temperature and inlet hydrocarbon concentration and the dependence of the thickness on substrate temperature is especially significant. Heteroepitaxial diamond nucleation without intermediate layer formation reported in experimental results can be readily explained by the significant decrease of the intermediate layer thickness at lower substrate temperatures and at higher diamond nucleation densities. Further, the present model results indicate that the intermediate layer thickness becomes saturated when growing diamond nuclei cover a very small surface area of that layer.     

The Influence of Ti-6AI-4V Chromic Acid Anodization Conditions Upon Anodic Oxide Thickness and Topography

Chromic acid (CA) anodization of Ti-6A1-4V (6% Al, 4% V by weight) produced an anodic oxide on the alloy surface. The influence of specific CA anodization conditions upon anodic oxide thickness was determined. Each CA anodization condition tested was defined by setting five variables: (1) solution composition; (2) anodization time; (3) solution temperature; (4) initial current density; and, (5) anodization potential.

The results confirmed observations by previous workers about oxide thickness and structure. Data indicated an inverse relationship between film thickness and temperature, and that film growth rate decreases with time.     

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.     

规整填料型加氢脱硫催化剂的制备及性能评价

用电化学方法制备多孔氧化铝膜,并负载Mo-Co活性组分制得了金属支撑-多孔层规整填料型加氢催化剂。采用BET和SEM技术表征了多孔性氧化铝膜的物理结构,并考察了电解及后处理条件的影响。结果表明,电解液浓度、氧化时间、水封时间、水封温度等对多孔氧化铝膜的比表面积影响显著。采用二次氧化的方法,在质量分数为4%的草酸电解液、氧化时间1 h、80℃水封3 h条件下,所制备的多孔氧化铝膜具有相对较大的比表面积。汽油重馏分加氢反应结果表明该类催化剂具有较高的催化活性和选择性。     

Plasma-deposited fluoropolymer film mask for local porous silicon formation

ABSTRACT: The study of an innovative fluoropolymer masking layer for silicon anodization is proposed. Due to its high chemical resistance to hydrofluoric acid even under anodic bias, this thin film deposited by plasma has allowed the formation of deep porous silicon regions patterned on the silicon wafer. Unlike most of other masks, fluoropolymer removal after electrochemical etching is rapid and does not alter the porous layer. Local porous regions were thus fabricated both in p+-type and low-doped n-type silicon substrates.     

Porous anodic alumina formed by anodization of aluminum alloy (AA1050) and high purity aluminum

A two-step anodization process performed at 0 °C was used to prepare highly ordered porous anodic alumina on the AA1050 alloy and high purity aluminum foil. The anodizing of both substrates was carried out in 0.3 M sulfuric acid and 0.3 M oxalic acid baths at 25 V and 40 V, respectively. The effect of the extended duration of the second anodizing step on pore order degree and structural features of AAO membranes was studied. The presence of alloying elements affects not only the rate of oxide growth but also the microstructure of the anodic film. It was found that pore circularity and regularity of pore arrangement in AAO membranes formed on the AA1050 alloy were always worse than those observed on the pure Al substrate. The structural features, such as pore diameter, interpore distance, wall thickness, barrier layer thickness, porosity and pore density of porous anodic alumina formed on AA1050 are a little different from those obtained for high purity Al. The extended time of the second anodizing step, up to 16 h does not affect significantly the regularity of pore order and all structural features of AAO membranes, independently of the anodizing electrolyte.     

未抛光多晶硅表面阳极氧化后的可见光发射

用制备发光多孔硅的常规电化学方法。在未抛光多晶硅表面备了均匀发射可见光的样品。光致发光实验表明：多晶硅表面上的样品可以产生多孔硅特征光致发光。用扫描电镜对此样品及常规多孔硅的微结构做了研究，结果表明：两种样品的微结构有很大差别，多晶硅表面上的样品只有两层结构，即表面层和多晶硅衬底，而没有形成多孔层。