多孔质铝阳极氧化膜表面与界面研究

铝质材料阳极氧化作为铝质材料最重要的表面改性技术已有几十年历程，并在现代工业中获得了广泛应用［1，’］．前人对铝阳极氧化股的结构、组成及生成机理等进行了大量的研究工作［3－6］，研究结果表明铝阳极氧化膜具有多孔型和壁垒型二种，其中多孔型铝阳极氧化膜是由非晶态     

Properties of composite nickel-cobalt-aluminum oxide coating deposited from chloride electrolyte

Effect of the cathodic current density, pH value, electrolyte temperature, and concentration of aluminum oxide introduced into the electrolyte on the wear, microhardness, and internal stresses in nickel-cobalt-aluminum oxide composite electrolytic coatings was studied. It is shown that the coatings under consideration can be used instead of chromium coatings.     

Study of the Microarc Oxidation of Aluminum Modified with Silicon Carbide Particles

Methods for obtaining aluminum materials modified with silicon carbide particles were studied. The oxidation resistance of silicon carbide in an aluminum matrix was examined under microarc oxidation in an electrolyte based on boric acid. A protective composite-based silicon-containing oxide coating was obtained with low porosity and microhardness of up to 9.0 GPa.     

The influence of electrolyte on photocatalytic activity of PEO coatings with incorporated Ce-ZSM5 formed on aluminum

Journal of Solid State Electrochemistry - The preparation and characterization of oxide coatings made by plasma electrolytic oxidation (PEO) process on aluminum in two different electrolyte...     

Development of the local proton concentration during pulse anodizing

The literature describes various beneficial effects of the pulse anodizing of aluminum related to the corrosion resistance, hardness, and electronic properties of the oxide layer, the thermal impact during the anodizing process as well as reduced energy consumption. In spite of the considerable improvements, the understanding of basic mechanisms and the specific impact of the applied pulse parameters are still under discussion. Herein, the local development of the electrolyte concentration during pulse anodizing in sulfuric acid is investigated by means of finite element computations. The impact of the thickness of the porous oxide, the applied current density, and the pulse frequency are examined systematically. The results suggest that the electrolyte concentration at the oxide/electrolyte interface can be effectively controlled by applying tailored pulse parameters.     

Electrodeposition and physicomechanical properties of coatings and foil of copper reinforced with nanosize aluminum oxide

Method of electrosynthesis of composite coatings and foil composed of copper reinforced with nanosize aluminum oxide is described. A method for chemical dispersion of aluminum oxide by the top-down principle and an electrolyte composition are suggested, which provide synthesis of composite materials with varied content of the modifying phase. The results of mechanical tests indicate that the plasticity, strength, and a number of other physicomechanical properties of thus synthesized composite materials are improved.     

Chemiluminescence of luminol induced by dissolution of oxide-covered aluminum in alkaline aqueous solution

One-electron reduction of oxygen, hydrogen peroxide, potassium peroxodisulphate and potassium peroxodiphosphate was studied during the dissolution of oxide-covered aluminum in alkaline aqueous solution. The production of free oxidizing radicals was monitored by luminol chemiluminescence (CL). It was observed superoxide, hydroxyl, sulphate and phosphate radicals can be generated by the present method. In addition, luminol can be detected below nanomolar level, the linear logarithmic calibration range covering several orders of magnitude of concentration. The metallic aluminum and low-valent aluminum ions are the primary reductants of the system. The electron transfer to the solution is proposed to occur by tunneling through a thin insulating aluminum oxide film at the solid/electrolyte interface in moderately alkaline solutions with simultaneous dissolution of the forming oxide film. In a highly alkaline solution, it is more probable that the oxidation of aluminum species occurs in direct contact of the metallic aluminum with the aqueous solution. In the latter case, short-lived solvated low-valent aluminum ions, hydrogen atom and its deprotonated form, the hydrated electron, can exist as reducing mediators in the chemical reactions in the close vicinity of the dissolving solid/electrolyte interface. Luminol was also observed to exhibit CL under purely reducing conditions produced by a presently unknown excitation pathway.     

Formation of Protective Coatings on Graphite by a Microspark Oxidation Method

Models, mechanisms, and criteria of formation of protective coatings on graphite by a microspark oxidation method (MSO) are considered. It is established that a prerequisite for the graphite MSO is the deposition of a barrier film of a valve metal oxide at the graphite surface. Optimum regimes of the graphite MSO in aqueous solutions of sodium aluminate are determined. Protective coatings on graphite comprising α-phase aluminum oxide are obtained. It is concluded that the graphite MSO should be viewed as a version of MSO of metals, which involves the electrochemical deposition (at high voltages that cause the anode to microspark) of oxide films consisting of electrolyte components on graphite, as opposed to a version of MSO of metals, which involves the formation of an anodic film consisting of electrolyte components and the intrinsic oxide.     

Quantum-chemical study on the effect of Lewis acid centers in a poly(ethylene oxide)-based solid electrolyte

Quantum-chemical calculations on borate and aluminate esters have been performed to study the effect of a Lewis acid center on the ion complexation in a poly(ethylene oxide)-based solid electrolyte. The preferred conformations of the investigated model molecules have been determined. Stabilization energies for Li+ and ClO4- ions complexed at the boron or aluminum center have been calculated. The results reveal that the stabilization of the perchlorate ion at the boron center is mainly due to the interactions with CH2 and CH3 groups and suggest much stronger binding of the anion to the aluminum atom.     

Luminescence of aluminum oxide films in aqueous electrolytes

Luminescence of oxide films on aluminum, emerging upon their immersion in aqueous electrolytes, is studied. The volt-brightness and temperature curves of the luminescence are measured. The luminescence is shown to be induced not only by protons and hydroxyl ions, as assumed earlier, but by other ions present in electrolyte as well.     

Effect of ac electrodeposition conditions on the growth of high aspect ratio copper nanowires in porous aluminum oxide templates

The effect of several deposition parameters on the uniformity of copper electrodeposition through the alumina barrier layer into porous aluminum oxide templates grown in sulfuric or oxalic acid was systematically investigated. A fractional factorial design of experiment was conducted to find suitable deposition conditions among the variables: frequency, voltage, pulsed or continuous deposition, electrolyte concentration, and barrier layer thinning voltage. Continuous ac sine wave deposition conditions yielded excellent uniformity of pore-filling but damaged the porous aluminum oxide templates when deposition was continued to grow bulk copper on the surface. Pulsed electrodeposition yielded comparable uniformity of pore-filling and no damage to the porous aluminum oxide templates, even when bulk copper was deposited on them. Further optimization of pulsed deposition conditions was accomplished by comparing square and sine waveforms and pulse polarity. Pulsed square waveforms produced better pore-filling than pulsed sine waveforms. For sine wave depositions, the oxidative/reductive pulse polarity was more efficient than the commonly used reductive/oxidative pulse polarity. For square wave depositions into sulfuric acid grown pores, the reductive/oxidative pulse polarity produces more uniform pore-filling, likely as a result of enhanced resonant tunneling through the barrier layer and reoxidation of copper in faster filling pores.     

Anodic oxidation of complex shaped items of aluminum and aluminum alloys with subsequent electrodeposition of copper coatings

It was shown that the method of anodization of aluminum and aluminum alloys can be applied for subsequent plating of highly adherent copper coating instead of the known zincate treatment with additional annealing. Fluorine-containing additives in anodizing electrolyte were proposed as activator of oxide film. The parameters of the anodic film (thickness, porosity, and microroughness) were calculated. The plated quality copper coatings have high adhesion to the aluminum support, and no additional heat treatment is required. This considerably reduces the processing time for deposition of multilayer coatings and decreases the material costs.     

Correlation between formation conditions and breakdown voltage of anodic oxide films on aluminum

Two series of samples were investigated: a) aluminum films with a sublayer of tantalum; b) industrial aluminum alloys AMg-2m; D16; AMc; AD-1n. The optimum composition of re-anodizing electrolyte was chosen on the basis of a solution of citric acid and ethylene glycol. The results of investigations of the sparking voltage at re-anodizing for various aluminum alloys and thicknesses of primary porous oxide are presented. The analytical dependence of breakdown voltage value on forming voltage value for alloy AD-1n was obtained. The original design of re-anodizing cell allowing increase of the sparking voltage was developed.     

Formation and dielectric properties of anodic oxide films on Zr–Al alloys

Zr–Al alloys containing up to 26 at.% aluminum, prepared by magnetron sputtering, have been anodized in 0.1 mol dm⁻³ ammonium pentaborate electrolyte, and the structure and dielectric properties of the resultant anodic oxide films have been examined by grazing incidence X-ray diffraction, transmission electron microscopy, Rutherford backscattering spectroscopy, and AC impedance spectroscopy. The anodic oxide film formed on zirconium consists of monoclinic and tetragonal ZrO₂ with the former being a major phase. Two-layered anodic oxide films, comprising an outer thin amorphous layer and an inner main layer of crystalline tetragonal ZrO₂ phase, are formed on the Zr–Al alloys containing 5 to 16 at.% aluminum. Further increase in the aluminum content to 26 at.% results in the formation of amorphous oxide layer throughout the thickness. The anodic oxide films become thin with increasing aluminum content, while the relative permittivity of anodic oxide shows a maximum at the aluminum content of 11 at.%. Due to major contribution of permittivity enhancement, the maximum capacitance of the anodic oxide films is obtained on the Zr–11 at.% Al alloy, being 1.7 times than on zirconium at the formation voltage of 100 V.     

Cathodic electrochemiluminescence at double barrier Al/Al2O3/Al/Al2O3 tunnel emission electrodes

Double insulating barrier tunnel emission electrodes were fabricated by adding a new pure aluminum layer upon oxidized aluminum electrodes by vacuum evaporation and thermally oxidizing the new aluminum layer in air at room temperature. Resulting Al/Al₂O₃/Al/Al₂O₃ electrodes allow the use of various aluminum alloys in the electrode body necessary for hardness or shaping ability of the electrode while obtaining the luminescence properties of pure aluminum oxide. During electrical excitation of luminescent labels by cathodic hot electron injection into aqueous electrolyte solution, the background noise is mainly based on high-field-induced solid-state electroluminescence and F-center luminescence of the outer aluminum oxide film. The more defect states and/or impurity centers the outer oxide film contains, the higher is the background emission intensity. The present electrode fabrication method provides a considerable improvement in signal-to-noise ratio for time-resolved electrochemiluminescence (TR-ECL) measurements when the original native oxide film of the electrode body contains luminescence centers displaying long-lived luminescence. The excellent performance of the present electrodes is demonstrated by extremely low-level detection of Tb(III) chelates, luminol, Pt(II) coproporphyrin and Tb(III) labels in an immunometric immunoassay by time-resolved electrochemiluminescence.     

Anodic alumina membranes with defined pore diameters and thicknesses obtained by adjusting the anodizing duration and pore opening/widening time

The through-hole porous anodic aluminum oxide (AAO) membranes were fabricated by a simple two-step anodization of aluminum in 0.3 M oxalic acid, 0.3 M sulfuric acid, and 2 wt.% phosphoric acid solutions under different operating conditions followed by the removal of the remaining Al substrate and the pore opening/widening process. The effect of duration of the second anodizing step on the thickness of the porous oxide layer and the influence of other anodizing conditions such as applied voltage, type of electrolyte, and purity of the substrate on the rate of porous oxide growth were discussed in detail. The pore opening procedure for all synthesized membranes was optimized, and the influence of the duration of chemical etching on structural features of AAO membranes, especially pore diameter, was studied. The rate of pore widening was established for AAO membranes formed in various anodizing electrolytes and for different temperatures of 5 wt.% H₃PO₄ used for alumina dissolution.

     

The effect of anode surface area on nanoporous oxide formation during anodizing of low purity aluminum (AA1050 alloy)

Porous anodic alumina layers were obtained by a simple two-step anodization of low purity aluminum (99.5 % Al, AA1050 alloy) in a 0.3 M oxalic acid electrolyte at 45 V and 20 °C. The effect of anode surface area on structural features of nanoporous oxide and process of oxide formation was investigated. An ordered structure composed of nanostripes or nanopores was formed on the Al surface during electrochemical polishing in a mixture of perchloric acid and ethanol. This nanopattern is then replicated during the anodic oxide formation. It was found that the pore diameter, interpore distance, and porosity increase slightly with increasing surface area of the aluminum sample exposed to the anodizing electrolyte. On the other hand, a slight decrease in pore density and cell wall thickness was observed with increasing surface area of the sample. The detailed inspection of current density vs. time curves was also performed. The obtained results revealed that the higher surface area of the anode, the local current density minimum, was reached faster during first step of anodization and the increase in current density corresponding to the pore rearrangement process was observed earlier. Finally, a dense array of Pd nanowires (～90 nm in diameter) was synthesized by simple electrodeposition of metal inside the channels of through-hole nanoporous anodic alumina templates with relatively large surface areas (4 cm²).     

Deposition of protective-decorative coatings onto aluminum alloys

Technique for deposition of a nickel coating onto various aluminum alloys was developed. This coating can be used both independently and as a sublayer under multilayer coatings and, in particular, under those of nickel, tin–bismuth, lustrous nickel, and lustrous chromium. The technique includes anodization, chemical treatment, and electrodeposition of nickel in a special solution. The working modes of the anodization electrolyte were chosen and the necessity for a preliminary chemical treatment of the oxide film being formed was substantiated. A composition of the acid electrolyte for the subsequent nickel plating was developed with buffer and improving additives. The thus deposited electroplated nickel coatings exhibit a high adhesion to the aluminum base without additional thermal treatment. This makes it possible not only to reduce the technological time for deposition of the subsequent multilayer coatings, but also to fully automate the whole process.     

铝合金电解加工中的钝化行为及其对加工过程的影响

本文研究与分析了铝合金电解加工过程的钝化行为,探讨了加工电压、电流密度、加工间隙及电解液成分等因素对电解加工性能的影响. 研究表明,在试验温度（23 ± 1）^oC下,铝合金在NaNO₃和NaF复合电解液体系（钝化电解液）存在钝化现象,钝化降低了电解加工的电流效率,并使电流效率随电流密度发生较大变化. 同时,钝化也使间隙特征曲线负移. 而在相同浓度NaCl和NaF复合电解液体系（活化电解液）电解加工,可在很宽的电位范围内保持活性溶解. 在钝化电解液中,电解加工表面更加平整.     

Electrosurface Properties of Hydr(oxides) and Oxide Nanostructures in 1 : 1 Electrolyte Solutions: 1. Adsorption Characteristics of Boehmite, Goethite, and Silicon Dioxide

The adsorption of potential-determining ions on aluminum and iron hydroxides and silicon dioxide was measured in KCl and NaCl background solutions. It was shown that dependences of the adsorption on pH and the concentration of a background 1 : 1 electrolyte (NaCl) have the shape characteristic of oxide surfaces; the of values pH_PZCwere determined. Results of adsorption measurements were used for the determination of constants of surface reactions and adsorption potentials of ions in terms of the 2-pK model.