Andrei Pligovka

The high reactivity of lanthanide metals poses a challenge to the electrochemical anodizing of surfaces for nanostructured coatings. This paper presents the first systematic experimental investigation of anodic oxidation of lanthanide gadolinium in aqueous solutions of citric, boric, oxalic, and tartaric acids. The voltage-current-time responses of anodizing of gadolinium, Al/Gd and Al/Nb/Gd systems were investigated. Anodic thin films were characterized using modern analysis techniques: SEM, FIB, and EDX. Morphology and voltage-current-time response analysis of anodized Al/Nb/Gd systems made it possible to establish the niobia cork-like effect and to develop a growth model.

The paper breaks the general concepts and shows that pore formation is possible in anodic aluminum barrier oxide by anodizing of pure Al, and also presents the results of electrochemical anodizing in boric acid and citrate buffer aqueous solutions of homogeneous binary alloys AlCu (4 wt.%), AlZn (3 wt.%) and AlAg (5.2 wt.% and 16.2 wt.%). Barrier anodizing allowed obtaining Al₂O₃ thin films doped with copper, zinc and silver. The anodizing behavior and the effect of anodic current density on the charge were studied, and scanning electron microscopy, X-ray photoelectron spectroscopy and Auger electron spectroscopy analyses were performed. The doped alumina thin films, which are a mixture of Al₂O₃, Cu₂O, ZnO, Ag₂O, AgO and promising double metal oxides CuAlO₂, AgAlO₂ and ZnAl₂O₄, are promising for use as resistive switching, photoelectron, mechanical, photo-thermoelectric and fluorescence materials; sensors; and transparent conductive and photocatalyst films.

Reanodizing metal underlayers through porous anodic alumina has already been used extensively to fabricate ordered columns of different metal oxides. Here, we present similar 3D multilayered nanostructures with unprecedented complexity. Two-level 3D column-like nanofilms have been synthesized by anodizing an Al/Nb metal layer in aqueous oxalic acid for forming the first level, and an Al/Ta layer in aqueous tartaric acid for forming the second level of the structure. Both levels were then reanodized in aqueous boric acid. The Ta layer deposited on partially dissolved porous anodic alumina of the first level, with protruding tops of niobia columns, acquired a unique hexagonally-packed structure. The morphology of the first and second levels was determined using scanning electron microscopy. Prolonged etching for 24 h in a 50%wt aqueous phosphoric acid was used to remove the porous anodic alumina. The formation mechanism of aluminum phosphates on the second-level columns in the process of long-time cold etching is considered. The model for the growth of columns on a Ta hexagonally-packed structure of the second level is proposed and described. The described approach can be applied to create 3D two- or three-level column-like systems from various valve metals (Ta, Nb, W, Hf, V, Ti), their combinations and alloys, with adjustable column sizes and scaling. The results of optical simulation show a high sensitivity of two-level column-like 3D nanofilms to biomedical objects and liquids. Among potential applications of these two-level column-like 3D nanofilms are photonic crystals for full-color displays, chemical sensors and biosensor, solar cells and thermoresponsive shape memory polymers.

Двухслойная система Al/Nb (1000/200 нм) на кремниевой подложке была проанодирована в 0,2 М водном растворе щавелевой кислоты при постоянном напряжении 53 В. После завершения этапа анодирования алюминия производили замену электролита на 0,5 М водный раствор борной кислоты и затем реанодировали подслой ниобия до напряжения 400 В. Для создания анодной композиционной наноструктуры проводили удаление большей части анодного оксида алюминия методом химического травления в течение 1200 с в 50 % растворе ортофосфорной кислоты при температуре 50 °С. Исследована морфология, фотолюминесценция, оптическое отражение анодной композиционной наноструктуры. Анодная композиционная наноструктура показала эффективное оптическое отражение в диапазоне длин волн от 540 до 1000 нм, а максимальная отражающая эффективность наблюдалась на длине волны 850 нм и составляет 52 %. Пик фотолюминесценции наблюдался на длине волны 453 нм.

The galvanostatic anodizing results of specially prepared high-purity aluminum in aqueous solutions of complex compounds K₃[Co(C₂O_4)_3] and K₂[Zn(edta)] of various concentrations in the current density ranges 1.5-1.10·10² and 1.5-30 mA·cm^-2, respectively. The kinetic features of anodizing have been established, indicating the occurrence of an oscillatory electrochemical process. Morphological features of a flaky and loose nature for K₂[Zn(edta)] and monolithic for K₃[Co(C₂O_4)_3], uncharacteristic for anodic aluminum oxide, were revealed. The elemental composition, IR spectroscopic and photoluminescent characteristics of the formed oxides are shown. Keywords: anodic aluminum oxide, chelated complex compounds, anodizing.

Magnetron-sputtered thin films of titanium and zirconium, with a thickness of 150 nm, were hydrogenated at atmospheric pressure and a temperature of 703 K, then anodized in boric, oxalic, and tartaric acid aqueous solutions, in potentiostatic, galvanostatic, potentiodynamic, and combined modes. A study of the thickness distribution of the elements in fully anodized hydrogenated zirconium samples, using Auger electron spectroscopy, indicates the formation of zirconia. The voltage- and current-time responses of hydrogenated titanium anodizing were investigated. In this work, fundamental possibility and some process features of anodizing hydrogenated metals were demonstrated. In the case of potentiodynamic anodizing at 0.6 M tartaric acid, the increase in titanium hydrogenation time, from 30 to 90 min, leads to a decrease in the charge of the oxidizing hydrogenated metal at an anodic voltage sweep rate of 0.2 V·s⁻¹. An anodic voltage sweep rate in the range of 0.05–0.5 V·s⁻¹, with a hydrogenation time of 60 min, increases the anodizing efficiency (charge reduction for the complete oxidation of the hydrogenated metal). The detected radical differences in the time responses and decreased efficiency of the anodic process during the anodizing of the hydrogenated thin films, compared to pure metals, are explained by the presence of hydrogen in the composition of the samples and the increased contribution of side processes, due to the possible features of the formed oxide morphologies.

The influence of arsenazo-I additive on electrochemical anodizing of pure aluminum foil in malonic acid was studied. Aluminum dissolution increased with increasing arsenazo-I concentration. The addition of arsenazo-I also led to an increase in the volume expansion factor up to 2.3 due to the incorporation of organic compounds and an increased number of hydroxyl groups in the porous aluminum oxide film. At a current density of 15 mA·cm⁻² and an arsenazo-I concentration 3.5 g·L⁻¹, the carbon content in the anodic alumina of 49 at. % was achieved. An increase in the current density and concentration of arsenazo-I caused the formation of an arsenic-containing compound with the formula Na_1,5Al₂(OH)_4,5(AsO₄)₃·7H₂O in the porous aluminum oxide film phase. These film modifications cause a higher number of defects and, thus, increase the ionic conductivity, leading to a reduced electric field in galvanostatic anodizing tests. A self-adjusting growth mechanism, which leads to a higher degree of self-ordering in the arsenazo-free electrolyte, is not operative under the same conditions when arsenazo-I is added. Instead, a dielectric breakdown mechanism was observed, which caused the disordered porous aluminum oxide film structure.

Three types of niobia nanostructured films (so-called native, planarized, and column-like) were formed on glass substrates by porous alumina assisted anodizing in a 0.2 M aqueous solution of oxalic acid in a potentiostatic mode at a 53 V and then reanodizing in an electrolyte containing 0.5 M boric acid and 0.05 M sodium tetraborate in a potentiodynamic mode by raising the voltage to 230 V, and chemical post-processing. Anodic behaviors, morphology, and optical properties of the films have been investigated. The interference pattern of native film served as the basis for calculating the effective refractive index which varies within 1.75–1.54 in the wavelength range 190–1100 nm. Refractive index spectral characteristics made it possible to distinguish a number of absorbance bands of the native film. Based on the analysis of literature data, the identified oxide absorbance bands were assigned. The effective refractive index of native film was also calculated using the effective-medium models, and was in the range of 1.63–1.68. The reflectance spectra of all films show peaks in short- and long-wave regions. The presence of these peaks is due to the periodically varying refractive index in the layers of films in two dimensions. FDTD simulation was carried out and the morphology of a potential 2-D photonic crystal with 92% (wavelength 462 nm) reflectance, based on the third type of films, was proposed.

The volumetric growth, composition, and morphology of porous alumina films fabricated by reduced temperature 280 K galvanostatic anodizing of aluminum foil in 0.4, 1.0, and 2.0 M aqueous sulfuric acid with 0.5–10 mA·cm⁻² current densities were investigated. It appeared that an increase in the solution concentration from 0.4 to 2 M has no significant effect on the anodizing rate, but leads to an increase in the porous alumina film growth. The volumetric growth coefficient increases from 1.26 to 1.67 with increasing current density from 0.5 to 10 mA·cm⁻² and decreases with increasing solution concentration from 0.4 to 2.0 M. In addition, in the anodized samples, metallic aluminum phases are identified, and a tendency towards a decrease in the aluminum content with an increase in solution concentration is observed. Anodizing at 0.5 mA·cm⁻² in 2.0 M sulfuric acid leads to formation of a non-typical nanostructured porous alumina film, consisting of ordered hemispheres containing radially diverging pores.