Oxygen evolution and porous anodic alumina formation

A new formation mechanism of porous anodic alumina (PAA) is proposed, which emphasizes the close relationship between pore generation and oxygen evolution during aluminum anodization. Two special experiments were designed to confirm the formation mechanism: (1) to introduce a reducing agent in anodization for oxygen suppression, and (2) to perform anodization under a reduced pressure for easy oxygen release. The results showed that both reducing agent and atmospheric pressure had a great effect on the morphology of the resultant film. This can be expected on the basis of our hypothesis about the formation mechanism of PAA, but cannot be easily explained by the existing theories.     

Effects of anodizing conditions on anodic alumina structure

In this paper, two-step anodization was used to obtain porous anodic alumina (PAA) films, which are widely used as the temples to fabricate nanomaterials. Effects of anodizing conditions such as anodizing voltage and the concentration of electrolyte on steady current density (I _s) and anodic alumina structure were investigated for oxalic acid as an electrolyte. The result shows that I _s is dependent on anodizing voltage exponentially. The relationship between the concentration of electrolyte and the pore diameter is almost linear, while there is no effect on inner-pore distance. At different anodizing voltage, the effect degree of the concentration of oxalic acid on the pore diameter is various. In oxalic acid electrolyte with given concentration matching with a specifically anodizing voltage, optimal nano-pores arrangements can be obtained. The higher voltage induces the collapse of thin inner wall and disordered alumina nanowires (ANWs) were formed.     

Preparation of h-BN nano-tubes, -bamboos, and -fibers from borazine oligomer with alumina porous template

h-BN nano-tubes, -bamboos, and -fibers were prepared separately from borazine oligomers using an alumina porous template at different wetting times of 20 h, 40 h and 2 weeks at room temperature, respectively. The borazine oligomer in the template was transformed to the h-BN nano-materials by two-step heat-treatment at 600 and 1200 °C in flowing N₂. The FT-IR result confirmed the formation of BN. TEM and SEM images showed the formation of the nano-tubes in diameters 200-300 nm with thin walls about 10-20 nm thick, nano-bamboos 200-300 nm wide with knots at the separations of 0.5-1 μm, and the nano-fibers 15-20 μm long with fine crystallized BN particles. The mechanism for the formation of h-BN nano-tubes, -bamboos and -fibers is proposed.     

Influence of secondary anodization voltage on free-standing crystallized TiO2 nanotube array membrane

Vertically aligned, free-standing crystallized TiO₂ nanotube arrays with a length of 32 μm have been fabricated by a two-step anodization method. The TiO₂ nanotube membrane can be detached from the Ti substrate through the secondary anodization process. The influence of the secondary anodization voltage on the morphology, crystalline phase and photovoltaic performance of the as-fabricated samples has been investigated. Results show that the side wall of TiO₂ nanotubes becomes obviously thin as the secondary anodization voltage increases and leads to crack when the voltage reaches 25 V. The mass fraction of the anatase reduces by the increase of the voltage. Furthermore, the dye-sensitized solar cells (DSSCs) based on TiO₂ nanotube arrays have been assembled. The energy conversion efficiency decreases with the increase of secondary anodization voltage, and a highest energy conversion efficiency of 10.6 % under UV illumination (368.1 nm) is obtained from the cell with TiO₂ nanotube membrane re-anodizad at 15 V.     

From alumina nanopores to nanotubes: dependence on the geometry of anodization system

The Conventional anodization of commercial aluminum sheets with a phosphoric acid electrolyte was employed for the preparation of alumina nanopore and/or nanotube structures. Modifying the system geometry (the ratio of platinum to aluminum electrode areas) controlled the nature of the anodization process (mild to hard). Nanotube formation was observed after low temperature preferential chemical etching of the defective corners of the hexagonal alumina cells using the same solution from the anodization process. Electrode geometry can be used to combine mild and hard anodization with low temperature etching to tune the alumina morphology from 100% nanopores to 100% nanotubos coverage.     

Permeability of anodic alumina membranes with branched channels

Mass-transport properties of anodic alumina membranes exploited in a number of technological areas are strongly affected by the real pore structure and arrangement of channels that can split or terminate during the anodization process. This paper focuses on the investigation of pore branching and rearrangement caused by voltage variation in the course of the anodic oxidation of aluminum. Gas-transport measurements were utilized for the quantitative determination of an effective through porosity of multilayer anodic alumina membranes with branched channels obtained by variation of anodization voltage. It was shown that on decrease of anodization voltage a branching of pores occurs, while an increase of anodization voltage leads to the termination of some of the pores with an increase in the diameter of others. Gas permeance measurements combined with electron microscopy unambiguously prove dead-end pore formation on voltage increase, while no pore merging appears. This generally affects any mass-transport properties and applications of anodic alumina membranes as the delivery of any species (e.g.?ions, gas molecules, etc) through the blocked channels is impossible.     

Nanoporous anodic alumina obtained without protective oxide layer by hard anodization

In this study, a fast and cost-effective approach is applied for fabricating nanoporous anodic alumina membranes under hard conditions without a protective oxide layer. This structural characteristic is a result of using a two-step anodization strategy under specific hard conditions during the second anodization step (i.e. high stirring rate, low acid electrolyte temperature and concentration). Notice that, after the anodization process, the membrane is detached from the aluminium substrate at the same time that pores are opened. So, after the fabrication process, no additional stages are required for removing both the protective oxide layer and the oxide barrier layer from the top and the bottom of the membrane, respectively. The resulting nanostructures obtained by this approach are defect-free nanoporous anodic alumina membranes with well-defined pores from the top to the bottom. This makes it possible to directly use those membranes in later applications (e.g. templates for replicating nanostructures, filters, optoelectronic devices and so forth) without additional processes and costs.     

Nanopatterned silicon emitters of a solar cell fabricated by anodic aluminum oxide masks

We investigated the nanopattern transferring process by a template of anodic aluminum oxide and the formation of a nanoporous aluminum oxide layer on a Si solar cell by the anodization process of Al thin films. The anodization process provided a template to transfer the nanopattern onto the Si surface. The small-sized nanoporous alumina template was attached to be covered on the textured surface and played the role of etching mask in the F-based dry etching process. Furthermore, we deposited an Al thin film onto the Si surface and the subsequent anodization process was performed. The alumina formulated on the deposited Al thin film did not show the array of nanoporous structure and no nanopatterns were transferred onto the surface. The large-areal alumina deposited on the Si surface showed enhanced photo-absorption in the ultraviolet spectral region of 243 nm, but increased the photo-reflectance in the visible and infrared spectral regions when compared to the Si-bare sample.     

Alternating nanopore diameters in anodic alumina grown within aluminium tubes

In a two-step anodization process within sulphuric acid, aluminium tubes were anodized from inside to outside. The formed nanoporous alumina layers appear stacked since the pore diameters alternate between (15 ± 7) nm and (30 ± 10) nm. During the anodization process the current was measured and it was found that it oscillates. The oscillation rate (approximately 1 per hour) corresponds to the alternating rate of the pore diameter. During the alumina growth within the tubular substrate, the area of the alumina/aluminium interface increases continuously. Therefore, it can be supposed that the switching between two pore diameters allows the system to reduce the internal stress, which would otherwise continuously increase. Other or additional reasons for the alternating nanopore sizes could be fluctuations of concentration gradients in the electrolyte within the tubes or the formation of oxygen bubbles.     

Constitutive modeling of alumina sintering: grain-size effect on dominant densification mechanism

In the present work, alumina powders with the initial grain sizes of 0.9 and 7.0 μm, respectively, were sintered at different temperatures. Constitutive laws for densification were employed to model the sintering process of alumina ceramics. Based on the constitutive laws employed and the experimental results obtained, the dominant densification mechanism was identified and the effect of grain size on dominant densification mechanism was discussed. The activation energy for densification was also evaluated. In the investigated sintering temperature range, interface reaction was identified as the controlling process in sintering of alumina powders with the initial grain size of 0.9 μm, while grain-boundary diffusion was identified as the dominant process in sintering of alumina powders with the initial grain size of 7.0 μm. The activation energies for densification of the finer and coarser grain size alumina ceramics were determined as 342 and 384 kJ mol⁻¹, respectively, which provided a strong support on the densification mechanism investigation.     

Fast fabrication of long-range ordered porous alumina membranes by hard anodization

Nanoporous anodic aluminium oxide has been widely used for the development of various functional nanostructures. So far these self-organized pore structures could only be prepared within narrow processing conditions. Here we report a new oxalic-acid-based anodization process for long-range ordered alumina membranes. This process is a new generation of the so-called "hard anodization" approach that has been widely used in industry for high-speed fabrication of mechanically robust, very thick (>100 microm) and low-porosity alumina films since the 1960s. This hard anodization approach establishes a new self-ordering regime with interpore distances, (D(int))=200-300 nm, which have not been achieved by mild anodization processes so far. It offers substantial advantages over conventional anodization processes in terms of processing time, allowing 2,500-3,500% faster oxide growth with improved ordering of the nanopores. Perfectly ordered alumina membranes with high aspect ratios (>1,000) of uniform nanopores with periodically modulated diameters have been realized.     

Reduction of nanoparticle deposition during fabrication of porous anodic alumina

In this paper, we present evidences of nanoparticle deposition on porous anodic alumina (PAA) surface under different anodizing conditions, and discuss the formation mechanism of precipitations. Low-temperature anodization, vigorous stirring and ultrasound-assisted anodization are proposed to reduce the hydrolysis product or hinder its deposition on the surface as well as inside nanopores of PAA. It is discovered that the ultrasound is very efficient to prevent the deposition of Al³⁺ hydrolysis product on PAA. This study is of great value for realizing ordered PAAs with clean surface.     

Highly ordered hexagonally arranged nanostructures on silicon through a self-assembled silicon-integrated porous anodic alumina masking layer

A combined process of electrochemical formation of self-assembled porous anodic alumina thin films on a Si substrate and Si etching through the pores was used to fabricate ideally ordered nanostructures on the silicon surface with a long-range, two-dimensional arrangement in a hexagonal close-packed lattice. Pore arrangement in the alumina film was achieved without any pre-patterning of the film surface before anodization. Perfect pattern transfer was achieved by an initial dry etching step, followed by wet or electrochemical etching of Si at the pore bottoms. Anisotropic wet etching using tetramethyl ammonium hydroxide (TMAH) solution resulted in pits in the form of inverted pyramids, while electrochemical etching using a hydrofluoric acid (HF) solution resulted in concave nanopits in the form of semi-spheres. Nanopatterns with lateral size in the range 12-200?nm, depth in the range 50-300?nm and periodicity in the range 30-200?nm were achieved either on large Si areas or on pre-selected confined areas on the Si substrate. The pore size and periodicity were tuned by changing the electrolyte for porous anodic alumina formation and the alumina pore widening time. This parallel large-area nanopatterning technique shows significant potential for use in Si technology and devices.     

Er-doped alumina crystalline films deposited by radiofrequency magnetron co-sputtering

Er-doped dielectric films are materials characterized by the emission of an intense photoluminescence signal at λ = 1.54 μm. The shape and intensity of the radiative emission of Er³⁺ ions may depend on the compositional and structural characteristics of the host dielectric matrix. With a suitable choice of the preparation parameters, we were able to synthesize luminescence dielectric thin films of crystalline alumina doped with erbium atoms by means of radiofrequency magnetron co-sputtering deposition. The samples were mainly characterized by X-ray diffraction, photoluminescence spectroscopy, and Rutherford backscattering spectrometry. The films show interesting changes of the 1.54 μm emission band shape as a function of the optical activation annealing temperature.     

Structural study of very thin anodic alumina films on silicon by anodization in citric acid aqueous solution

The formation of thin alumina films on a silicon substrate by anodization in a mild acid, specifically in 1% wt citric acid aqueous solution, is investigated by transmission electron microscopy (TEM). We present a comparative study between two cases of starting material: pure aluminum and an alloy of aluminum with 1% silicon. In both cases the thickness of the Al layer was less than 50 nm. It was observed that under exactly the same conditions, in the first case the anodization was stopping before anodizing the whole film and a remaining non-anodized Al layer was always present, while in the second case, the Al layer was fully anodized, resulting in an alumina matrix with a very high density of silicon nanocrystals of uniform sizes embedded in it. In both cases the alumina film was compact and amorphous.     

Mechanical constraint and release generates long, ordered horizontal pores in anodic alumina templates

We describe the formation of long, highly ordered arrays of planar oriented anodic aluminum oxide (AAO) pores during plane parallel anodization of thin aluminum 'finger' microstructures fabricated on thermally oxidized silicon substrates and capped with a silicon oxide layer. The pore morphology was found to be strongly influenced by mechanical constraint imposed by the oxide layers surrounding the Al fingers. Tractions induced by the SiO(2) substrate and capping layer led to frustrated volume expansion and restricted oxide flow along the interface, with extrusion of oxide into the primary pore volume, leading to the formation of dendritic pore structures and meandering pore growth. However, partial relief of the constraint by a delaminating interfacial fracture, with its tip closely following the anodization front, led to pore growth that was highly ordered with regular, hexagonally packed arrays of straight horizontal pores up to 3 μm long. Detailed characterization of both straight and dendritic planar pores over a range of formation conditions using advanced microscopy techniques is reported, including volume reconstruction, enabling high quality 3D visualization of pore formation.     

高度有序多孔阳极氧化铝模板的制备

为了得到纳米孔排列高度有序的多孔阳极氧化铝模板,以0.3 mol·L-1的草酸为电解液研究了模板的制备工艺.采用场发射扫描电子显微镜(FE-SEM)对多孔氧化铝模板的表面形貌进行表征,X射线衍射分析高纯铝及氧化膜的结构.实验结果表明,铝基体不经过高温退火处理,同样能够得到高度有序的氧化铝膜,简化了多孔氧化铝膜的制备工艺.分别讨论了阳极氧化电压和电解液温度对多孔阳极氧化铝膜的形貌及孔径的影响,并对一步法和两步法制得的多孔氧化铝膜进行比较,结果表明,两步阳极氧化法制备的多孔氧化铝模板的有序性优于一步氧化法.XRD分析证实,多孔氧化铝膜由非晶态的Al2O3组成.     

Distributed Bragg reflector made of anodic alumina membrane

A new kind of distributed Bragg reflector is made of layer-by-layer anodic alumina membrane using electrochemical anodization, which is consisted of periodically stacked main stem channel layers and branched channel layers with the period comparable to the optical wavelength. The first Bragg condition peak, which is characterized for main inhibition of incident light perpendicular to the surface of anodic alumina membrane, could be modulated from 727 to 1200 nm by modifying the anodizing voltage waveform. It possibly provides a plan to fabricate light filters in large area, which have very low transmissivity within stop band but high transmissivity in other ranges.     

Which tool to distinguish transient alumina from alpha alumina in thermally grown alumina scales?

Abstract

Alumina scales constitute excellent protective barriers when they form on alumina-forming steels. If they keep tightly adherent to the underlying substrate, they isolate it from the surrounding aggressive atmosphere at high temperature. The protectiveness of the alumina scale is highly dependant upon its growth mechanism. The nucleation and transformation of transient alumina (mainly γ-Al₂O₃ and θ-Al₂O₃) is known to play an important role on alumina scale formation. It is therefore fundamental to characterise these transient alumina especially during the early stages of the oxidation process. The morphology of the transient alumina was observed by scanning electron microscopy (SEM), their crystallographic phases determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). X-ray photoelectron spectrometry (XPS) analyses were performed on reference samples and then compared to the alloys oxidised 5 and 30 minutes at 850, 900 and 950°C.     

Inside Front Cover: Fabrication of Ideally Ordered Nanoporous Alumina Films and Integrated Alumina Nanotubule Arrays by High‐Field Anodization (Adv. Mater. 17/2005)

A simple, low‐cost approach to fabricating large‐area highly ordered nanoporous alumina films in sulfuric acid solutions through a single‐step high‐field anodization, without the assistance of any additional process, is reported on p. 2115 by Chu and co‐workers. The critical high anodizing potential in the adopted electrolyte system increases with the ageing of solutions after a long period of anodization. Correspondingly, the applicable current density for stable anodization rises significantly, thus leading to high‐speed film growth. Uniform porous anodic alumina films in sulfuric acid solutions under a high electric field of 40–70 V and 1600–2000 A m^–2 are achieved.