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.     

Local deposition of polypyrrole on aluminum by anodizing, laser irradiation, and electrolytic polymerization and its application to the fabrication of micro-actuators

Polypyrrole was deposited at selected areas on aluminum by anodizing, laser irradiation, and electrolytic polymerization, and the application of the technique for fabricating micro-actuators was attempted. Aluminum specimens covered with porous type anodic oxide films were irradiated with a pulsed Nd-YAG laser to remove the oxide films locally, and then thin Ni layers were deposited at areas where film had been removed. Polypyrrole could be successfully deposited only on the Ni layer by anodic polarization of the specimens in pyrrole monomer solution, and a polypyrrole/Ni bilayer structure could be obtained by dissolution of the aluminum substrate and anodic oxide film in NaOH solutions. The bilayer structure was found to be inactive to doping and dedoping of ions during anodic and cathodic polarization. A three-layer structure, nitrocellulose/Ni/polypyrrole, fabricated by electrolytic polymerization after nitrocellulose coating on a Ni layer detached from the aluminum substrate, showed ion-doping and -dedoping activity, suggesting the possibility of fabricating micro-actuators in this manner.     

汽车用2024铝合金阳极氧化膜性能的研究

对汽车用2024铝合金板材进行酒石酸阳极氧化处理,并研究了阳极氧化对铝合金的成分、结构、表面形貌及耐蚀性的影响。研究发现,铝合金阳极氧化膜是由表面多孔层和内部无孔层构成的。铝合金阳极氧化过程是一个氧化铝生成和溶解的动态过程。阳极氧化膜由刚玉结构的α-Al_2O_3和八面结构的γ-Al_2O_3构成,α相和γ相大大提高了阳极氧化膜的硬度和耐蚀性。阳极氧化膜为典型的多孔结构,孔洞分布均匀,孔径为50nm左右。     

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.     

电压对7N01铝合金阳极氧化膜结构及耐蚀性的影响

采用160 g/L硫酸溶液在17℃下对7N01铝合金阳极氧化30 min,氧化电压分别选取14、15、16、17和18 V。用扫描电镜观察所得阳极氧化膜的形貌,用能谱仪和电化学测量分析了它的成分、厚度和耐蚀性。结果表明,7N01铝合金经过不同电压下的阳极氧化处理后,表面均能形成凹凸不平并有孔洞的阳极氧化膜,电压为17 V时所制膜层致密、均匀,厚度约为7.6μm,耐蚀性最佳,在3.5%NaCl溶液中浸泡1 440 h后没有明显的腐蚀。     

Alkaline Corrosion Resistance of Anodized Aluminum Coated with Zirconium Oxide by a Sol-Gel Process

To improve the alkaline corrosion resistance of aluminum, composite films were prepared that consisted of a porous layer of anodically grown aluminum oxide filled with zirconium oxide, with a zirconium oxide coating layer that was deposited thereon via the sol—gel process, using a dip-coating technique. The alkaline corrosion resistance of these composite films was extremely improved when this coating layer was placed on an anodic oxide film. Comparisons of the composite film and conventional anodic oxide film showed that the alkaline corrosion resistance of the composite film was increased by a factor of 24–50. Because these composite films, which have high corrosion resistance, indicated a vibration phenomenon of voltage in the duration time curve of the electromotive force measurement, the composite film had a self-repairing action for alkaline corrosion.     

Surface analyses of anodic oxides films formed on Fe-3% Ti alloy

Surface analyses of the anodic oxide films formed on Fe—3% Ti alloy in deaerated pH 3.0 phosphate solution were performed with Auger electron spectroscopy (AES) and ellipsometry to evaluate the role of allying titanium in the corrosion resistance of iron.The 3%-addition of titanium reduced significantly the passivity-maintaining current density of iron as well as the maximum-active current density. Auger analysis revealed that titanium was enriched markedly in the anodic oxide films formed on Fe—3% Ti alloy and that a significant amount of phosphorus was distributed in the whole range of film thickness. Both the amount of titanium enriched in the film and the film thickness (20–40 nm) ellipsometrically obtained were proportional to the amount of electric charge required for passivation. Atomic absorption analysis of the solution indicated that the formation of a titanium-enriched film resulted from a preferential dissolution of iron as ferrous ions.From the measurement of the potential decay curves of the Fe—3% Ti alloy and pure iron electrodes passivated for different hours, it was concluded that the titanium-enriched layer promoted the passivity by suppressing, though incompletely, the active dissolution, whereas the substantial passivity of the alloy was attributed to the iron oxide film of barrier type formed at the interface of titanium-enriched layer/alloy substrate.     

A mechanism for the corrodability of hafnium and the anodic oxide film thereon in HCl solutions

A study is made to account for the corrodability of each of the naturally developed and anodically formed oxide films on hafnium in HCl solutions. The behaviour of these oxide films was investigated by capacitance and potential measurements. The naturally developed oxide film grows spontaneously according to a direct logarithmic law. In diluted HCl (< 1 N), the rate of growth is small but the resultant film has better electrochemical insulating properties than that rapidly grown in the more concentrated solutions. On the other hand, the anodic oxide film is more liable to chemical (currentless) dissolution in HCl as the initial thickness increases. The rate determining step in the dissolution process is determined mainly by the oxide and is almost independent of the acid concentration. The behaviour of each of the two films has been correlated to changes in the fine structure of the parent oxide during its growth.     

汽车用6063铝合金硬质阳极氧化工艺的研究

使用硬质阳极氧化工艺对汽车用6063铝合金进行阳极氧化处理。通过实验发现,电流密度影响氧化膜多孔层的形成过程。氧化初期,提高电流密度有利于促进成膜过程,获得性能较好的氧化膜。当电流密度大于2.0A/dm2时,氧化膜的溶解速率加快,表面孔径增大,使得氧化膜的硬度和耐蚀性有所下降。     

Fabrication of three-dimensional platinum microstructures with laser irradiation and electrochemical technique

Three-dimensional (3D) platinum microstructures were fabricated by successive procedures: aluminum anodizing, laser irradiation, nickel/platinum electroplating, and removal of the aluminum substrate, the oxide films, and the nickel metal layer. Aluminum plates and rods were anodized in an oxalic acid solution to form porous type oxide films. The anodized specimens were immersed in a nickel electroplating solution, and then irradiated with a pulsed Nd-yttrium aluminum garnet (YAG) laser beam to remove the anodic oxide film with a three-dimensional XYZθ stage. The specimens were cathodically polarized in the nickel and a platinum electroplating solution to form the metal micropattern at the laser-irradiated area. The electroplated specimens were immersed in NaOH solution to dissolve the aluminum substrate and the oxide films, and then immersed in HCl solution to dissolve the nickel deposits. A platinum grid-shaped microstructure, a microspring, and a cylindrical network microstructure with 50-100 μm line width were obtained successfully.     

Dissolution electrochimique des films anodiques du titane dans l''acide sulfurique

Electrochemical dissolution of anodic oxide films on Ti in H₂SO₄ is studied by the use of an optical—electrolytic cell adapted for in situ ellipsometric and electrochemical measurements. Films were grown on electropolished Ti surfaces by anodic oxidation in 0.5 mol dm⁻³ H₂SO₄ for duration of 30 s, in the potential range from 0 to 100 V. Electrochemical dissolution of these films was performed in the potential range between −0.4 and −0.9 V sce. The potential at which electrochemical dissolution is fastest and homogeneous is determined. In addition it is shown that for potentials more cathodic than −0.8 V, TiH₂ is formed on the electrode surface, if polarization lasts sufficiently long. THe commencement of formation and dissolution of anodic films was monitored by potentiostatic j-E curves and variations of ellipsometric azimuths P and A. by potentiostatic and ellipsometric measurements it was confirmed that complete reduction of anodic films is possible. A possibility is indicated for calculating the refractive index of anodic film during its dissolution by observing the time of successive diminution of film thickness and using the variations of ellipsometric azimuths P and A.     

Effect of surface pretreatment on the galvanostatic oxidation of nickel

The open-circuit, cathodic reduction and anodic charging characteristics of oxide films on both electropolished and electropolished + HNO₃ etched nickel electrodes have been studied in aqueous Na₂SO₄ solutions. While the oxide film thicknesses are approximately the same, the film on etched nickel dissolves much more rapidly than that on electropolished nickel. To galvanostatically passivate etched nickel at charging rates in the range 20–200 μA cm^?2 in pH 2.8 Na₂SO₄, the rate of oxide chemical dissolution has to be substantially decreased and this is achieved by lowering the electrolyte temperature from 25°C to 5°C. The transient anodic passivation charge thus observed for etched nickel is ～ 2x larger than that for electropolished nickel. With either pretreatment, the current efficiency for oxide formation is low (～ 20%), the majority of the transient charge (～ 80%) accounted for by Ni²⁺ in solution. Chemical dissolution of the oxide alone cannot explain the observed charging differences between etched and electropolished nickel since the individual charges and oxide formation current efficiencies are not influenced by anodic charging rate or solution aggressiveness. The results are best explained in terms of a continual breakdown and repair of the oxide film at defect areas during anodic charging, with most of the charge consumed by inefficient film repair. The influence of the oxide defects and the reason for the differences in behaviour between electropolished and etched nickel are discussed.     

Anodization of hafnium in phosphoric acid solutions

The kinetics of formation of anodic oxide films on hafnium electrodes either under open circuit conditions or constant current density were investigated using polarization and impedance measurements. Under open circuit conditions the oxide film was found to thicken with time following a direct logarithmic law, whereas it thickens linearly with time under galvanostatic polarization and obeys the exponential law due to Güntherschulze and Betz. An increase in phosphoric acid concentration was found to increase the rate of oxide formation and the field strength owing to incorporation of electrolyte species into the oxide during the anodization process. The break-down voltage was found to increase linearly with the logarithm of phosphoric acid resistivity and was independent of the anodizing current density. The impedance behaviour of the hafnium oxide film/solution interface was found to be purely capacitive and the impedance increases with increase in the film thickness. The film thickness was found to decrease linearly with the logarithm of time probably owing to partial dissolution of the oxide film.     

汽车用6061铝合金柠檬酸阳极氧化工艺的研究

对汽车用6061铝合金进行柠檬酸阳极氧化处理。研究发现:铝合金的阳极氧化过程伴随氧化膜的生成和溶解。适当升高氧化温度,有利于增加氧化膜的厚度和硬度。但氧化温度过高,会使得氧化膜的溶解速率加快。铝合金阳极氧化膜呈现典型的多孔结构。40℃下制备的氧化膜表面平整,具有优良的耐蚀性。当氧化温度高于40℃时,氧化膜表面的孔径增大,表面疏松,耐蚀性下降。     

A flow model of porous anodic film growth on aluminium

The development of pores in a classical porous anodic film formed on aluminium in phosphoric acid solution is investigated. The study employs a tungsten tracer layer that is incorporated into the anodic film from the aluminium substrate, followed by detection of the tracer by transmission electron microscopy and Rutherford backscattering spectroscopy. Distortions of the tungsten layer on entry into the film and retention of tungsten species in the film are compatible with porosity arising mainly from flow of anodic oxide beneath the pore bases towards the cell walls. The behaviour is contrary to expectations of a dissolution model of pore formation.     

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.     

Characterisation of titanium oxide film grown in 0.9% NaCl at different sweep rates

The nature of the anodic oxide film that forms on titanium on titanium in 0.9% NaCl has been investigated using a wide range of techniques. A linear relationship was found between the critical current density required for passivation of titanium in 0.9% NaCl and the sweep rate. Anodic oxide films formed on titanium in 0.9% NaCl appear to consist of two layers, an inner compact layer, the growth of which continues to follow a high field growth law, and a porous less protective outer porous layer. XPS and XRD indicated that passive films on titanium consist mainly of TiO₂. However, hydroxides and lower oxides are also present, especially in rapidly grown films. XRD data indicated that in 0.9% NaCl the anodic oxide film is formed through the preferential removal atoms in the plane of (0 0 2) in the course of electrochemical reaction. A model based analysis XPS spectra was proposed to explain the growth rate dependence of the degree of protection offered by anodic oxide films on titanium. XPS clearly demonstrated the present of Ti(III) and Ti(II) cations in the passive film. This is strong evidence that cation migration more likely dominates over anion migration in the growth mechanism of anodic oxide film. XPS data also revealed that the concentrations of Ti(III) and Ti(II) species within the oxide films increased as the oxide/metal interface was approached.     

Preparation and analysis of films on aluminium by high voltage anodization in phosphoric acid and sodium tungstate solution

A high voltage anodic film on aluminium was prepared in a mixed electrolyte of phosphoric acid and sodium tungstate. The properties, structure, morphology and chemical composition of the film were investigated. It was found that the elements in the film were O, Al, P and W and the main chemical compositions of the film were aluminium oxides with some phosphates and tungstates. Compared with conventional anodic films, the high voltage anodic film showed good hardness and excellent corrosion and heat resistance. Scanning electron microscopy indicated that the film could be divided into two layers, a porous surface layer and a compact underlayer. Many cracks were observed in both layers, which are significantly different from those of conventional anodic films.     

A kinetic study on the corrodability of anodic oxide films formed on molybdenum in NaOH solutions

The corrodability of anodic oxide films formed on molybdenum in NaOH solutions was studied using impedance and potential measurements. The corrosion rate was found to increase with increase of alkali concentration, film thickness and temperature and was nearly independent of the rate of oxide formation. The dissolution process was found to involve a valency change from Mo(IV) to Mo(VI) where it seemed, from cathodic polarization, that no electron transfer through the oxide film to/from the metal surface was involved during the dissolution process. In concentrated NaOH solutions ([OH^–]9 M), the dissolution process appeared to follow zero-order kinetics.     

Dissolution kinetics of WO3 in acidic solutions

Potentiostatic polarization and rotating disk electrode techniques were used to obtain the rate constant for the dissolution of electrochemically-formed (at 1 V) WO₃ on tungsten (W) in acidic solutions. The corresponding rate constant for the chemical dissolution of WO₃(s) powder was found by measuring the dissolved tungsten concentration as a function of time and pH. The chemical dissolution experiments supported the view that the rate-determining step in the anodic reaction of W in acidic solution is the chemical dissolution of WO₃(s) formed on the metal surface. Zeta potential measurements gave the isoelectric point (iep) of the WO₃(s) powder as pH 1.5, a value that was somewhat smaller than the point of zero charge (pzc) of WO₃(s) formed on W metal (pH 2.5). This difference was attributed to the highly hydrated nature of the oxide film formed on W metal in aqueous systems.