Formation of porous anodic titanium oxide films in hot phosphate/glycerol electrolyte

The present study reveals the formation of porous anodic films on titanium at an increased growth rate in hot phosphate/glycerol electrolyte by reducing the water content. A porous titanium oxide film of 12 μm thickness, with a relatively low content of phosphorus species, is developed after anodizing at 5 V for 3.6 ks in 0.6 mol dm⁻³ K₂HPO₄ + 0.2 mol dm⁻³ K₃PO₄/glycerol electrolyte containing only 0.04% water at 433 K. The growth efficiency is reduced by increasing the formation voltage to 20 V, due to formation of crystalline oxide, which induces gas generation during anodizing. The film formed at 20 V consists of two layers, with an increased concentration of phosphorus species in the inner layer. The outer layer, comprising approximately 25% of the film thickness, is developed at low formation voltages, of less than 10 V, during the initial anodizing at a constant current density of 250 A m⁻². The pore diameter is not significantly dependent upon the formation voltage, being ∼10 nm.     

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.     

Effects of a magnetic field on growth of porous alumina films on aluminum

The effects induced by a magnetic field on the oxide film growth on aluminum in sulfuric, oxalic, phosphoric and sulfamic acid, and on current transients during re-anodizing of porous alumina films in the barrier-type electrolyte, were studied. Aluminum films of 100 nm thickness were prepared by thermal evaporation on Si wafer substrates. We could show that the duration of the anodizing process increased by 33% during anodizing in sulfuric acid when a magnetic field was applied (0.7 T), compared to the process without a magnetic field. Interestingly, such a magnetic field effect was not found during anodizing in oxalic and sulfamic acid. The pore intervals were decreased by ca. 17% in oxalic acid. These findings were attributed to variations in electronic properties of the anodic oxide films formed in various electrolytes and interpreted on the basis of the influence of trapped electrons on the mobility of ions migrating during the film growth. The spin dependent tunneling of electrons into the surface layer of the oxide under the magnetic field could be responsible for the shifts of the current transients to lower potentials during re-anodizing of heat-treated oxalic and phosphoric acid alumina films.     

Fast anodization fabrication of AAO and barrier perforation process on ITO glass

Thin films of porous anodic aluminum oxide (AAO) on tin-doped indium oxide (ITO) substrates were fabricated through evaporation of a 1,000- to 2,000-nm-thick Al, followed by anodization with different durations, electrolytes, and pore widening. A faster method to obtain AAO on ITO substrates has been developed, which with 2.5 vol.% phosphoric acid at a voltage of 195 V at 269 K. It was found that the height of AAO films increased initially and then decreased with the increase of the anodizing time. Especially, the barrier layers can be removed by extending the anodizing duration, which is very useful for obtaining perforation AAO and will broaden the application of AAO on ITO substrates.     

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.     

Porous Alumina Films with Width-Controllable Alumina Stripes

Porous alumina films had been fabricated by anodizing from aluminum films after an electropolishing procedure. Alumina stripes without pores can be distinguished on the surface of the porous alumina films. The width of the alumina stripes increases proportionally with the anodizing voltage. And the pores tend to be initiated close to the alumina stripes. These phenomena can be ascribed to the electric field distribution in the alumina barrier layer caused by the geometric structure of the aluminum surface.     

Cyclic oxidation processes during anodizing of Al-Cu alloys

The influence of copper on the morphologies of porous anodic alumina has been investigated under current and voltage control using a sputtering-deposited Al-2.7 at.% Cu alloy and a commercial AA 2024-T3 aluminium alloy anodized in either sulphuric acid electrolyte or the same electrolyte but with addition of tartaric acid. The findings indicate that film development involves repeated formation of embryo cells of anodic alumina at the metal/film interface. During the initial stages of anodizing at constant voltage, cell formation is accompanied by current peaks in the current-time response. The porosity of the resultant films has a lateral aspect due to the layering of embryo cells. The thickness of individual layers is proportional to the formation voltage, with a ratio of the order 1 nm V⁻¹. The cell formation is accompanied by enrichment of copper in the alloy, incorporation of copper species into the anodic film, in low amounts relative to the alloy, and evolution of oxygen. These processes disrupt the formation of the classical pore morphology, characteristic of high purity aluminium, due to continuous formation of fresh embryo cells and re-direction of pores. The main effect of the tartaric acid addition to the sulphuric acid was to reduce the rate of anodizing of the alloys at constant voltage by about 10-20%.     

Galvanostatic anodization of pure Al in some aqueous acid solutions Part I: Growth kinetics, composition and morphological structure of porous and barrier-type anodic alumina films

The growth kinetics of anodic films formed on the surface of high purity Al by anodization under galvanostatic conditions at current densities in the range 5–75 mA cm^–2 in thermostatically controlled and vigorously stirred solutions of chromic, sulfuric, phosphoric, citric, tartaric and oxalic acids at different temperatures, were studied. It has been shown that chromic acid solution produces a typical barrier type oxide growth at any given temperature, while the specific kinetic curve representing the combined barrier/porous type film growth is observed when the anodization process is carried out in a nonstirred chromic acid solution. The oxide growth in the rest of the anodizing solutions occurs in different ways depending on the bath temperature. Barrier oxide growth is observed at temperatures lower than 30 °C. Above this temperature, combined barrier/porous oxide growth is observed. In all cases, the slope of the linear part of the potential against time curves, and therefore the rate of barrier oxide growth, increases with increasing anodizing current density and acid concentration, while it decreases with increase in temperature. The composition and surface morphology of the anodic films have been studied by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and atomic force microscopy (AFM).     

Importance of water content in formation of porous anodic niobium oxide films in hot phosphate-glycerol electrolyte

Niobium has been anodized at a constant current density to 10 V with a current decay in 0.8 mol dm⁻³ K₂HPO₄-glycerol electrolyte containing 0.08-0.65 mass% water at 433 K to develop porous anodic oxide films. The film growth rate is markedly increased when the water content is reduced to 0.08 mass%; a 28 μm-thick porous film is developed in this electrolyte by anodizing for 3.6 ks, while the thickness is 4.6 and 2.6 μm in the electrolytes containing 0.16 and 0.65 mass% water respectively. For all the electrolytes, the film thickness changes approximately linearly with the charge passed during anodizing, indicating that chemical dissolution of the developing oxide is negligible. SIMS depth profiling analysis was carried for anodic films formed in electrolyte containing ∼0.4 mass% water with and without enrichment of H₂¹⁸O. Findings disclose that water in the electrolyte is a predominant source of oxygen in the anodic oxide films. The anodic films formed in the electrolyte containing 0.65 mass% water are practically free from phosphorus species. Reduction in water content increased the incorporation of phosphorus species.     

Electrochemical behaviour of ZrO2 sol-gel pre-treatments on AA6060 aluminium alloy

ZrO₂ pre-treatments applied with the sol-gel technique are a possible replacement of chromium based pre-treatments on aluminium alloys. The thickness and homogeneity of the films deposited on AA6060 alloy are strongly related to the process parameters like preparation of the surface, number of dips and thermal treatment of the film.ZrO₂ films were prepared using the dip-coating technique in sol obtained from metal-organic precursors in an organic solvent (0.1 M Zr(OBuⁿ)₄ in anhydrous n-butanol with addition of acetic acid as complexing agent). Different layers were applied on AA6060 changing number of dips and thermal treatment (150 °C for 1 h or 250 °C for 4 min). The typical thickness of the deposited layers was in the range 70-180 nm depending on process parameters. The electrochemical behaviour of the pre-treated alloy in diluted Harrison solution (0.05 wt% NaCl + 0.35 wt% (NH₄)₂SO₄) was investigated by means of potentiodynamic polarization, open circuit potential measurements, and electrochemical impedance spectroscopy. In addition, the electrochemical behaviour of ZrO₂ sol-gel films was compared with that of chromatized AA6060 and fluotitanated/fluozirconated AA6060. In order to evaluate the adhesion properties of the films, ZrO₂ pre-treated AA6060, chromatized AA6060 and fluotitanated/fluozirconated AA6060 were painted with a polyester resin and subjected to thermal cycles in 0.05 wt% NaCl. Each thermal cycle consisted of heating the samples at 90 °C, permanence at 90 °C for 6 h, cooling at room temperature and permanence at room temperature for 18 h. Impedance measurements were performed at the end of each cycle.Potentiodynamic polarization curves and impedance spectra indicate that ZrO₂ pre-treatments have similar barrier properties to those of chromatized AA6060. However, no self-healing ability is observed for ZrO₂ films.The barrier properties of ZrO₂ films are strongly dependent on process parameters. In particular, the number of dips determines the amount of defects in the film and its homogeneity. The electrochemical behaviour strongly improves increasing the number of dips in the deposition bath. Thermal aging cycles evidence good adhesion properties for ZrO₂ pre-treatments.     

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.     

Asymmetric alumina membranes electrochemically formed in oxalic acid solution

Alumina membranes were fabricated by anodizing aluminium metal in 0.15 M oxalic acid. The growth kinetics of the porous layer were investigated in the temperature range –1 to 16 °C using linear potential scans up to 70 V. The faradaic efficiencies of metal oxidation and of porous layer formation, determined by applying Faraday's law, were found to be independent of both temperature and electrical charge. SEM analysis of the metal-side and solution-side surfaces revealed different morphologies. After dissolution of the barrier layer in phosphoric acid, the metal-side surface showed circular pores whose size of about 90 nm was found to be uniform and independent of temperature. The pore population was also practically independent of temperature and a value of about 4 × 10¹³ pores m^–2 was determined. On the solution-side surface the presence of a deposit partially occluding the mouths of pores was observed. This coating could be removed by chemical etching in NaOH or thermal treatment at 870 °C, where decomposition of oxalate occurs. This supports the hypothesis that the deposit consists of an aluminium salt containing oxalate anions precipitated from the solution. The results show that it is possible to control the morphological characteristics of the anodic alumina membranes by careful choice of experimental conditions.     

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.     

Mechanism of one-step voltage pulse detachment of porous anodic alumina membranes

The mechanism for one-step detachment of porous anodic alumina (PAA) membranes by using an electrochemical voltage pulse technique is systematically studied. Electrochemical oxidation of pretreated aluminum foil results in a thin oxide layer called barrier layer alumina (BLA) between the formed PAA and the Al substrate. Achievement of through-hole PAA membranes requires electrolytes of highly concentrated perchloric acid containing biacetyl and a short detaching pulse voltage of 5-10 V higher than the film forming potential. The influence of the PAA forming potential, voltage pulse height (0-10 V), and the nature of electrolytes on the efficiency of detachment have been systematically investigated. The successful detachment of the PAA could only be achieved with systems giving appropriate transient current upon application of an optimal voltage pulse. Based on the experimental results and the electropolishing mechanism of aluminum, a two-step detachment process of PAA freestanding films is proposed. In this mechanism, the detachment of PAA film from the aluminum substrate upon application of a short voltage pulse is followed by a pores-opening process. The present mechanism is promising for preparation of freestanding PAA films with various pores sizes, which are important for nanomaterial synthesis.     

应用多孔阳极氧化电流—时间曲线比较壁垒膜厚

在有壁垒膜存在的表面,多孔膜的生长在氧化初期受到延迟阻碍,这一现象在直流恒压多孔阳极氧化电流一时间曲线上反映出来。电流达到稳态氧化的时间愈长,壁垒膜愈厚。文中应用此法判断了0.5MH_3BO_3介质的pH值、温度对壁垒阳极氧化膜厚的影响,并应用记录同一介质环境壁垒恒流阳极氧化的槽压一时间曲线得到验证。     

Growth of anodic oxide films on oxygen-containing niobium

The present study is directed at understanding of the influence of oxygen in the metal on anodic film growth on niobium, using sputter-deposited niobium containing from about 0-52 at.% oxygen, with anodizing carried out at high efficiency in phosphoric acid electrolyte. The findings reveal amorphous anodic niobia films, with no significant effect of oxygen on the field strength, transport numbers, mobility of impurity species and capacitance. However, since niobium is partially oxidized due to presence of oxygen in the substrate, less charge is required to form the films, hence reducing the time to reach a particular film thickness and anodizing voltage. Further, the relative thickness of film material formed at the metal/film interface is increased by the incorporation of oxygen species into the films from the substrate, with an associated altered depth of incorporation of phosphorus species into the films.     

Growth of porous anodic films on sputtering-deposited aluminium incorporating Al-Hf alloy nanolayers

Formation of porous anodic films on sputtering-deposited aluminium incorporating Al-Hf tracer layers has been examined at constant current in sulphuric and phosphoric acids. Hafnium was selected as the tracer species since the migration rates of Hf⁴⁺ and Al³⁺ ions are similar in barrier-type anodic alumina. The distribution of hafnium in the films was determined using ion beam analysis, scanning electron microscopy and transmission electron microscopy. Increases in the anodizing voltage and barrier layer thickness accompany the oxidation of hafnium and the migration of Hf⁴⁺ ions through the barrier layer region of the porous film. Hf⁴⁺ and Al³⁺ ions that migrate to the pore bases are lost to the electrolyte. Other Hf⁴⁺ ions are incorporated into the cell walls. For films formed in phosphoric acid, with relatively thick barrier layers, channelling of the ion current leads to accelerated outward transport of Hf⁴⁺ ions toward the pore base, while a U-shaped inner edge of the hafnium distribution beneath the pores is associated with more slowly transported hafnium species. The tracer behaviours for films formed in both acids are consistent with the transport of Hf⁴⁺ ions in the barrier layer regions by a combination of flow of film material and ion migration, the flow being a key factor in the development of the pores. The percentage losses of Hf⁴⁺ and Al³⁺ ions from the films to the electrolyte are relatively similar, correlating with their similar migration rates, and contrast with the retention in the film of slow migrating W⁶⁺ ions, found previously, due to a more dominant role of flow.     

A transmission electron microscopy study of hard anodic oxide layers on AlSi(Cu) alloys

Transmission electron microscopy (TEM) has been employed to examine anodic oxide film formation on 99.8 wt.% aluminium, Al-10 wt.%Si and Al-10 wt.%Si-3 wt.%Cu alloys under conditions relevant to hard anodizing. In particular, anodic oxidation of silicon particles proceeded at a significantly reduced rate compared with that of the adjacent aluminium matrix. This gave rise to alumina film encroachment beneath the particles with development of tortuous porosity and, eventually, occlusion of partially anodized particle in the anodic film. Additional effects included the presence of gas-filled cavities above the silicon particles, associated with oxygen generation above the anodizing particle. The presence of such particles and the corresponding gas-filled voids across the anodic film thickness and at the alloy/film interface is considered responsible for the continuous voltage rise during anodizing of the Al-10 wt.%Si alloy, effectively blocking electrolyte access to the pore base and providing local region of high resistance at the alloy/film interface. A direct consequence of the voltage rise was a thickening of the barrier layer at the base of the porous anodic film. For the ternary alloy, with the additional presence of copper and the CuAl₂ particles, the latter appear to have undergone complete oxidation, with copper detected in local film regions.     

Rapid synthesis and dye-sensitized solar cell applications of hexagonal-shaped ZnO nanorods

This paper reports, for the first time, a very rapid and large-scale synthesis and dye-sensitized solar cells (DSSCs) application of well-crystallized hexagonal-shaped ZnO nanorods at very low temperature of about 70 °C in 20 min. The thin films of as-grown nanorods were used as photo-anode materials to fabricate the DSSCs which exhibited an overall light to electricity conversion efficiency (ECE) of 1.86% with a fill factor of 74.4%, short-circuit current of 3.41 mA/cm² and open-circuit voltage of 0.73 V.