Structural features of self-organized nanopore arrays formed by anodization of aluminum in oxalic acid at relatively high temperatures

Anodic aluminum oxide (AAO) membranes with a highly ordered nanopore arrangement typically serve as ideal templates for the formation of various nanostructured materials. A typical procedure of the template preparation is based on a two-step self-organized anodization of aluminum carried out at the temperature of about 1-3 °C. In the current study, AAO templates were fabricated in 0.3 M oxalic acid under the anodizing potential range of 30-65 V at a relatively high electrolyte temperature ranging from 20 to 30 °C. Due to a high rate of porous oxide growth, about 5-10-fold higher than in low-temperature anodizing, the process of the template fabrication can be shorten significantly. Similarly to the low-temperature anodization, the best hexagonal pore arrangement is observed for samples anodized at 40 V. With a prolonged duration of the first anodizing step the order degree of triangular nanoporous lattice, observed after the second anodization, improves considerably. The effects of the anodizing potential and the process duration on the structural features of porous anodic alumina such as: pore diameter (D_p), interpore distance (D_c), porosity (P), pore density (n) and anodizing ratio (B_U) were investigated in details at various temperatures. The obtained results were compared with theoretical predictions and data reported in the literature.     

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.     

Temperature influence on well-ordered nanopore structures grown by anodization of aluminium in sulphuric acid

The nanostructure dimensions and regularity of the hexagonal arrangement of nanopores formed by self-organized anodization of aluminium in a 20 wt.% sulphuric acid was investigated at various cell potentials and temperatures. The quantitative analyses of defects and Fourier transforms (FFT) performed from SEM images showed that regularity of nanopores arrangement can be improved by increasing anodizing potential, independently of the anodizing temperature. The best result in controlled anodization of aluminium can be obtained at 25 V and the temperature of 1 °C. The pore size and interpore distance distribution diagrams constructed for 1000 independent measurements showed that increasing uniformity of pore diameter and interpore distance is directly responsible for improvement of the regularity of hexagonal arrangement of nanopores observed with increasing anodizing potential at temperatures of −8 or 1 °C. At 25 V and independently of the anodizing temperature, the reduced number of generated defects is predominant factor improving regularity of the nanopore arrangement. The temperature influence on the lattice data, porosity of the nanostructure and real current density at the bottom of nanopores have been demonstrated.     

Fabrication and structural control of anodic alumina films with inverted cone porous structure using multi-step anodizing

Porous anodic alumina (PAA) film has recently attracted much attention as a key material for the fabrication of various nanostructures. In this study, a multi-step anodization and leaching process was employed to produce three-dimensional nanometer scale structured film. During the leaching process, the porous alumina film was dipped in phosphoric acid solution for pore widening. Each anodization process was followed by this leaching process. This method produced alumina film with multi-step structure. Meanwhile, with five-step film production, the structure showed inverted cone structure. We produced the low aspect ratio pores of this structure, which would be applicable for fabrications of nanomaterials. In addition, the aspect ratio was controlled by changing the anodization duration.     

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.     

Through-hole membranes of nanoporous alumina formed by anodizing in oxalic acid and their applications in fabrication of nanowire arrays

The nanopore arrays were fabricated by two-step self-organized anodization of aluminum carried out in 0.3 M oxalic acid at the temperature of 20 °C. This relatively high temperature shortens significantly the anodizing time and allows to fabricate quickly thick through-hole membranes without the additional operating cost of a cooling circuit. The structural features of anodic porous alumina such as pore diameter, interpore distance, porosity, pore density and pore circularity were investigated at various durations of pore opening/widening process carried out in 5% H₃PO₄. An excellent agreement of AAO structural features measured in FE-SEM images of the studied samples with results from software calculations was observed. The pore shape can be monitored qualitatively by fast Fourier transforms (FFTs) and quantitatively by calculation the percentage of pore circularity. Additionally, the regularity of the hexagonal arrangement of nanopores in through-hole AAO membranes was compared for various opening/widening time ranging from 40 to 100 min. It was shown that three-dimensional (3D) representations of FE-SEM images and their surface-height distribution diagrams provide interesting information about the surface roughness evolution during the pore opening/widening process. A template-assisted fabrication of Ag and Sn nanowire arrays by electrochemical deposition into the pores of the prepared AAO templates was also successfully demonstrated.     

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 diameter-modulated and ultrathin porous nanowires in anodic aluminum oxide templates

Anodic aluminum oxide (AAO) membranes with modulated pore diameter were synthesized by pulse anodization in 0.3 M sulfuric acid at 1 °C. For AAO growth, a typical combination of alternating mild anodizing (MA) and hard anodizing (HA) pulses with applied potential pulses of 25 V and 35 V was applied. The control of the duration of HA pulses will provide an interesting way to tune the shape of pores and the structure of AAO channels. It was found that a non-uniform length of HA segments in cross section of AAO is usually observed when the HA pulse duration is shorter than 1.2 s. The pulse anodization performed with longer HA pulses leads to the formation of AAO templates with periodically modulated pore diameter and nearly uniform length of segments. Various diameter-modulated metallic nanowires (Au, Ag, Ni and Ag–Au) were fabricated by electrodeposition in the pores of anodic alumina membranes. A typical average nanowire diameter was about 30 nm and 48 nm for MA and HA nanowire segments, respectively. After a successful dealloying silver from Ag–Au nanowires, porous ultrathin Au nanowires were obtained.     

铝阳极氧化法制备Al2O3纳米线

采用二次铝阳极氧化法在草酸体系中制备多孔铝阳极氧化膜,用逆电剥离技术将氧化膜从铝基体上剥离：经超声清洗后,放入磷酸溶液中去除阻挡层,使纳米孔贯通。再将膜放入c=1mol／L的NaOH溶液和w=6％的铬酸、w=1．8％的磷酸混合溶液中进行溶解,可获得Al2O3纳米线。纳米线长度为40μm,与模板厚度一致,直径为10～20nm.通孔前后铝阳极氧化膜的形貌由SEM进行表征,纳米线的形貌由SEM和TEM表征．此外,本文还结合模板在溶解过程中的实验现象,对Al2O3纳米线的形成机理进行了初步分析。     

Fabrication of enhanced anodic aluminum oxide performance at room temperatures using hybrid pulse anodization with effective cooling

Conventional anodic aluminum oxide (AAO) template was performed using potentiostatic method of direct-current anodization (DCA) on costly high-purity (99.997%) aluminum foils at low temperatures of 0–10 °C to avoid dissolution effects which occurred frequently at room temperatures (RT) of 20–30 °C. In this paper, we show the hybrid pulse anodization (HPA) method with pulsing normal-positive and small-negative potential differences at RT for enhancing performance of AAO structure for both the cheap low-purity (99%) and costly high-purity (99.997%) aluminum foils. The HPA mainly takes advantages of effective cooling that arise from the nearly zero cathodic current and high-thermal-conductivity liquid electrolyte on the foils. The HPA is different from the traditional pulse anodization with alternating both high and low positive potential differences (/currents) or both one-positive and one-zero potential differences. The HPA not only merits manufacturing convenience and cost reduction but also promotes pore distribution uniformity of AAO at severe conditions of cheap low-purity Al foils and relatively high room temperature. The pore distribution uniformity can be improved by HPA in a suitable duration compared with the DCA. Very good AAO distribution uniformity (91%) was achieved in high-purity aluminum foil by HPA because it can suppress the Joule's heat to diminish the dissolution reaction. The evolution of AAO distribution uniformity for both the HPA and DCA on Al foil purities and process durations were comparatively investigated.     

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.).     

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.     

Nanotube oxide coating on Ti-29Nb-13Ta-4.6Zr alloy prepared by self-organizing anodization

The present paper reports on the formation of self-organized nanotube oxide layers on β-type Ti-29Nb-13Ta-4.6Zr alloy in (NH₄)₂SO₄ containing a small amount of NH₄F. Highly ordered nanotube layers can be formed on the alloy under a wide range of applied potentials. Initiation and self-organization of pores is a potential and time dependent process. Layers removed from the electrolyte in an early growth state consist of two different morphologies—an outer nanoporous structure and an underneath ordered nanotube layer. For extended anodization, the outer nanoporous layer is completely dissolved. Within subsequent growth stages multi-scale ordering of the nanotube arrays with two discrete geometries can be observed. The different stages and morphologies depend significantly on the anodizing potentials. Clearly - compared with anodic tubes on pure Ti - a much broader range of nanotube geometries i.e. “structural flexibility” can be achieved with the Ti-29Nb-13Ta-4.6Zr alloy.     

Well-defined meso- to macro-porous film of tin oxides formed by an anodization process

Anodically formed tin oxide typically displays a self-ordered porous structure with a large degree of cracking. In addition, its surface pores are frequently closed, especially in the case where the deposited tin film is anodized. Herein, we report a simple way of eliminating virtually all the inner cracks and ensuring that the surface pores are totally open, leading to well-defined one-dimensional anodic tin oxide. The current efficiency ratio of oxygen gas generation to tin oxide formation and the amount of charge allocated for pore initiation are suggested to be the key factors affecting the internal crack development and pore opening, respectively. Pulsed anodization proved to be quite an effective way to create a well-defined structure with few inner cracks and completely open pores.     

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.     

Control of the spatial distribution of porous alumina micro-domes formed during anodic oxidation

We found that micro-domes of porous alumina are self-assembled during anodic oxidation of an aluminum plate. We investigated the effects of the morphology of the initial aluminum surfaces on the formation of these micro-domes and found that the formation of micro-domes depends on the initial surface roughness of the substrate. We have also achieved spatial control over the distribution of these micro-domes through the use of artificial scratches on the initial surface. The origin of this control is the fact that micro-domes are preferentially formed inside hollow areas formed by the scratch. We investigated the inner structure of the micro-dome by separating it from the substrate. Inside the micro-domes, we observed nano-pore arrays similar to a porous alumina membrane, though the regularity of these pores is slightly worse than for the nano-pores around the micro-dome. These results indicate that the porous alumina micro-domes can be used as microscale nanoporous components.     

Optimized nanoporous alumina coating on AA3003-H14 aluminum alloy with enhanced tribo-corrosion performance in palm oil

This study aimed to prepare nanoporous anodic alumina on AA3003-H14 aluminum alloy using a mild anodization process with minimal working voltage and treatment time. The microstructural features, mechanical properties, and tribocorrosion behavior of the coatings were assessed to determine the optimum conditions for the fabrication of nanoporous anodic alumina on AA3003-H14 alloy. The microstructural analysis showed both uniform and nonuniform pore nucleations during anodization in H₂SO₄/C₂H₂O₄, H₂SO₄/H₂CrO₄, and EG/H₂O/NH₄F electrolytes, where the optimal nanoporous structure with an average thickness, porosity, pore diameter, and interpore distance of 382 nm, 19%, 16 nm, and 35 nm, respectively, was developed after a short-time mild anodization for 30 min at constant potential of 12 V using 15 wt% H₂SO₄ electrolyte. The XRD profiles indicated formation of a highly-disordered and amorphous nanoporous anodic alumina. Due to the loss of mechanical properties after heat treatment at 450 °C for 90 min, Vickers microhardness of the samples decreased drastically from 124 to 90.5 HV, respectively. The wear analysis indicated an improved tribological behavior by mild electrochemical anodization owing to the development of nanoporous anodic alumina, which acted as the liquid lubricant reservoir and increased the tribological performance of the workpiece. In addition, the heat treated specimen showed the lowest corrosion rate of 0.079 mm.y^-1 and utmost corrosion protection efficiency of 95.24% following exposure in palm oil methyl ester (B100). This novel nanoporous configuration not only endows excellent tribological performance in the biofuel combustion environment, but also particularly decreases consumption of liquid lubricants through a facilitated multiphase lubrication mechanism.     

Strengthened porous alumina membrane tube prepared by means of internal anodic oxidation

A method for preparing an anodic aluminum oxide tube with a much higher mechanical strength than before was developed, where anodic oxidation was carried out from the inside of an aluminum tube (internal anodizing method). It was considered that the internal stress remaining in the alumina layer, which was formed in the course of the internal anodizing, resulted in a considerable improvement of compressive strength against external pressure. As a matter of fact, the tube could withstand at least up to 0.98 MPa of transmembrane pressure, which corresponded to 32.6 MPa in terms of breaking pressure. The tubular alumina membrane obtained had straight mesopores of 20–25 nm in diameter and, therefore, showed the Knudsen permselectivity for inorganic gases. Such a strengthened alumina tube is expected to be used as a porous membrane or as a support for composite membranes.     

Effects of anodization and electrodeposition conditions on the growth of copper and cobalt nanostructures in aluminum oxide films

Anodic aluminum oxide (AAO) films were prepared by alternative current (ac) oxidation in sulfuric acid and phosphoric acid solution. The porous structure of the AAO templates was probed by ac electrodeposition of copper. AAO templates grown using an applied square waveform signal in cold sulfuric acid solution exhibit a greater pore density and a more homogeneous barrier layer. UV–vis–NIR reflectance spectra of the Cu/AAO assemblies exhibit a plasmon absorption peak centered at 580 nm, consistent with the formation of Cu nanostructures slightly larger than 10 nm in diameter. Spectroscopic data also indicate that there is little or no oxide layer surrounding the Cu nanostructures grown by ac electrodeposition. The effect of pH of the cobalt plating solution on the magnetic properties of the Co/AAO assemblies was also investigated. Co nanowire arrays electrodeposited at pH 5.5 in H₂SO₄-grown AAO templates exhibit a fair coercivity of 1325 Oe, a magnetization squarness of about 72%, and a significant effective anisotropy. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

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.