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Abstract Nanoporous metal‐oxide films formed on some metals and their alloys during anodization are crucial for both basic research and commercial applications. They are used as important materials for various types of device fabrication due to their distinctive solid‐state shapes, such as nanopores and nanotubes. However, preparing nanoporous films using anodization, which is a surface treatment for plate‐like specimens, requires a direct electrical connection to the workpiece. Developing new materials independent of the specimen's shape and size will vary if the need for direct energization is eliminated. Here, bipolar electrochemistry is employed to fabricate two‐phase (insulator–conductor) and three‐phase (insulator–conductor–insulator) aluminum balls by controlling the redox reaction region in an electric field. The aluminum balls are site‐selectively anodized employing a wireless and maskless operation. The multiphase aluminum balls’ versatility is demonstrated in the site‐selective electroless deposition of copper on their exposed regions. Additionally, it is demonstrated that various types of materials, including aluminum and titanium, can be oxidized simultaneously in the same cell.

Although anodization is an essential technology that has supported the aluminum industry for nearly a century, the atomistic structure of the formed alumina films has not completely understood. Here we used NMR spectroscopy to clarify the factors affecting local structure of anodic porous alumina films prepared under various electrolytic conditions. For anion-free amorphous alumina films prepared using chromic acid, the local structure does not depend on electrolytic factors. For films prepared using phosphoric acid, the average coordination number was lower than that of anion-free alumina. On the other hand, films prepared using oxalic and sulfuric acids showed the average coordination numbers higher than that of anion-free alumina. We reveal that aluminum coordination number of anodic porous alumina are affected by anion species and anion content. In addition, the depth of anion incorporation into cell walls, or compositional uniformity, is quite important for accurate interpretation of NMR spectra.

Abstract The effects of the size and position of an aluminum bipolar electrode (BPE) on the uniformity of formation of anodic porous alumina in an alternating current electric field were investigated. Anodized specimens were dyed, and the resistance was measured after the specimens were anodized again. Phenomena observed during film formation indicated that the BPEs had unique potential distributions that strongly depended on their length and width. The color variations and electrical resistance of the BPEs were symmetrical and varied from the centers of the BPEs to their ends. When multiple BPEs were processed at the same time, their position in the non-uniform electric field was demonstrated to be an important factor for controlling the uniformity of film formation. The best results were obtained when the BPE was placed at the center of the defined space.

In this study, titanium (Ti) with two chemically distinct faces was formed using two-step direct current (DC) bipolar anodization. A Ti sheet was positioned vertically in the center of an electrolytic cell as a bipolar electrode (BPE). The oxidation area on the BPE was visualized using an interference color caused by the formation of a barrier-type oxide film on the Ti BPE in phosphoric acid under a DC electric field. When different voltages were applied between the driving electrodes for the first and second steps, the front and back sides of the BPE showed different colors because of differences in film thickness. Even in the case of a ball-shaped Ti BPE, site-selective film formation could be demonstrated using a wireless and maskless operation, regardless of the shape of the BPE.

A drawback of acid cleaning as surface finishing of magnesium (Mg) surface is the absence of a protective oxide film on its surface. Acid–alkaline treatment is proposed to enhance the surface corrosion resistance of AMX601 Mg alloy. Acid–alkaline treatment was conducted by first dipping the alloy in HNO3–H3PO4 solution and then immersing the al-loy in NaOH solution. The potentiodynamic polarization test in 0.9% NaCl solution at 37 °C revealed a nobler corro-sion potential of −1.36 VAg/AgCl and a lower corrosion current density of 36.0 µA•cm−2 of the acid–alkaline-treated spec-imen than the acid-treated (−1.44 VAg/AgCl, 89.7 µA•cm−2) and untreated (−1.52 VAg/AgCl, 40.0 µA•cm−2) specimens. Acid treatment induced a significantly higher surface roughness (20 µm) than acid–alkaline (10 µm) and grinding (0.5 µm) treatments because of the selective dissolution of the Mg matrix and the accumulation of intermetallic precipitates. The film formed on the acid–alkaline-treated specimen was thick and free of cracks, whereas that formed on the acid-treated specimen was thin and cleaved. The formation of a protective oxide film and the enrichment of cathodic intermetallic particles on the acid–alkaline-treated specimen enhanced the corrosion resistance of the surface.

In this study, the electrical potential distributions on aluminum bipolar electrodes (BPEs) subjected to bipolar anodization in a direct current (DC) electric field were investigated. Aluminum sheets were used as BPEs, suspended in an electrolyte solution, and positioned either vertically or horizontally at the center of a cell. The results of reflective interference measurements, depth-profiling analysis, and re-anodization clearly revealed that the thicknesses of the porous alumina films and barrier layers near the aluminum substrates can be taken to represent the potential distributions on the horizontally located BPEs; the thickest anodic alumina was formed at the edge of the anodic pole of the BPE, and its thickness continuously decreased in the direction of the cathodic pole. Furthermore, the area of the anodic reaction was much larger than expected, accounting for 90% of the BPE.

In this study, we use advanced analysis techniques to examine the nanostructures of anodic films formed on aluminum in various electrolytes, including oxalic acid and sulfuric acid, in the original state (without being chemically dissolved) and reveal that pores grow with radially branched nanopores. Nanopores are generated in the main pores for the same reason that initial small pores are generated on the film surface: nanopores are created when the electric field is reduced due to the presence of a thick barrier layer. These radially branched nanopores appear in a form characteristic of a film formed in chromic acid, producing a feather-like pore wall. As a representative model, the atypical porous structures created in the film formed in chromic acid were classified into five categories: initial small pores, branched pores, side holes, spherical voids, and radially branched nanopores. We demonstrate that these structures are not unique to chromic acid films but are a universal phenomenon, particularly radial nanobranching, which occurs naturally during the anodizing of most electrolytes.

The electrical potential gradients on aluminum bipolar electrodes (BPEs) subjected to bipolar anodization in an alternating current (AC) electric field were investigated by performing scanning electron microscopy, dyeing the anodized specimens, and measuring the resistance in the alumina films after re-anodizing the samples. The thickness and morphology of each alumina film varied, which reflected the unique potential distributions on the BPEs in the AC electric field. The electrical resistance was symmetrical and increased linearly from the centers of the BPEs to their extremities. This synthetic approach should lead to the development of various functional materials using bipolar electrochemistry.

The characteristics of coatings formed by Plasma Electrolytic Oxidation (PEO) are affected by the composition of metal substrates. In this work, the effect of alloying element Ca (0, 1 and 2 wt%) on the degradation behavior and apatite-forming ability of PEO coated AZ61 magnesium alloys was clarified by means of polarization measurements in 0.9% NaCl solution and an in-vitro test in Simulated Body Fluid (SBF), respectively. The AZ61 alloys were subjected to plasma electrolytic oxidation at a constant current of 200 A/m2 at 25°C for 8 min in 0.5 M Na3PO4 solution. The surface investigation suggested no significant effect of Ca content on the morphology of the PEO coating formed on the AZ61 specimens. The coatings exhibited an eruption-like structure decorated with micropores and microcracks. Their average thicknesses were 13.2, 17.4 and 14.3 µm for AZ61, AZ61-1Ca and AZ61-2Ca, respectively. The polarization measurements showed no significant difference in the corrosion potentials (-1.60 VAg/AgCl) and corrosion current densities (1.61×10-5 A cm-2) of all the coated specimens. Similarly, there was no significant effect of Ca on the apatite-forming ability in SBF, as indicated by the lack of apatite deposition on all the coated specimens after 14 days of immersion. Further sealing of the PEO coatings by chemical treatment in NaOH solution is suggested to enhance the corrosion resistance.

Abstract GaAs nanopillar arrays were successfully fabricated by metal-assisted chemical etching using Au nanodot arrays. The nanodot arrays were formed on substrates by vacuum deposition through a porous alumina mask with an ordered array of openings. By using an etchant with a high acid concentration and low oxidant concentration at a relatively low temperature, the area surrounding the Au/GaAs interface could be etched selectively. Under the optimum conditions, Au-capped GaAs nanopillar arrays were formed with an ordered periodicity of 100 nm and pillar heights of 50 nm.

The electrochemical exfoliation of graphite has attracted considerable attention as a method for large-scale, rapid production of graphene and graphene oxide (GO). As exfoliation typically requires direct electrical contact, and is limited by the shape and/or size of the starting graphite, treatment of small graphite particles and powders, the typical form available commercially, is extremely difficult. In this study, GO nanosheets were successfully prepared from small graphite particles and powders by a bipolar electrochemical process. Graphite samples were placed between two platinum feeder electrodes, and a constant current was applied between the feeder electrodes using dilute sulfuric acid as the electrolyte. Optical microscopy, atomic force microscopy, X-ray diffractometry, Raman spectroscopy, and X-ray photoelectron spectroscopy were employed to examine the samples obtained after electrolysis. The results obtained from these analyses confirmed that anodic electrochemical exfoliation occurs in the graphite samples, and the exfoliated samples are basically highly crystalline GO nanosheets with a low degree of oxidation (C/O = 3.6–5.3). This simple electrochemical method is extremely useful for preparing large amounts of graphene and GO from small particles of graphite. Keywords: Graphite, Graphene, Graphene oxide, Electrochemical exfoliation, Anode, Bipolar electrochemistry

Nanoporous and single phase α-alumina membranes with pore diameters tunable over a wide range of approximately 60–350 nm were successfully fabricated by optimizing the conditions for anodizing, subsequent detachment, and heat treatment. The pore diameter increased and the cell diameter shrunk upon crystallization to α-alumina by approximately 20% and 3%, respectively, in accordance with the 23% volume shrinkage resulting from the change in density associated with the transformation from the amorphous state to α-alumina. Nevertheless, flat α-alumina membranes, each with a diameter of 25 mm and a thickness of 50 μm, were obtained without thermal deformation. The α-alumina membranes exhibited high chemical resistance in various concentrated acidic and alkaline solutions as well as when exposed to high temperature steam under pressure. The Young’s modulus and hardness of the single phase α-alumina membranes formed by heat treatment at 1250 °C were notably decreased compared to the corresponding amorphous membranes, presumably because of the nodular crystallite structure of the cell walls and the substantial increase in porosity. Furthermore, when used for filtration, the α-alumina membrane exhibited a level of flux higher than that of the commercial ceramic membrane.

The properties of composite coatings formed by plasma electrolytic oxidation (PEO) were affected by the alloy composition. The corrosion resistance and apatite-forming ability of PEO coatings formed on Mg−6Al−1Zn−xCa alloys with a variation of Ca content were investigated. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements showed an order magnitude improvement of corrosion resistance in the AZ61 alloy as a result of the coating. A higher enhancement in polarization resistance was obtained in the Mg−6Al−1Zn−1Ca and Mg−6Al−1Zn−2Ca alloys due to thicker coatings were formed as a result of the incorporation of calcium oxide/hydroxide. However, the underlying substrates were more prone to localized corrosion with increasing Ca content. The microstructure investigation revealed an enlargement in precipitates (Al2Ca, Mg2Ca) sizes with increasing Ca content in the alloys. The growth of larger size precipitates increased the danger to micro galvanic corrosion. Apatite layers were formed on all of the coatings indicating high apatite-forming ability, but the layers formed on the Mg−6Al−1Zn−1Ca and Mg−6Al−1Zn−2Ca alloys contained higher Mg, possibly due to the accumulation of corrosion product, than that on the Mg−6Al−1Zn alloy. The alloying element Ca should be limited to 1 wt.% as the excess tended to degrade the corrosion resistance and apatite-forming ability of the PEO coating.

Effects of alloying element Ca on the corrosion behavior and bioactivity of films formed by plasma electrolytic oxidation (PEO) on AM60 alloys were investigated. The corrosion behavior was studied by conducting electrochemical tests in 0.9% NaCl solution while the bioactivity was evaluated by soaking the specimens in simulated body fluid (SBF). Under identical anodization conditions, the PEO film thicknesses increased with increasing Ca content in the alloys, which enhanced the corrosion resistance in NaCl solution. Thicker apatite layers grew on the PEO films of Ca-containing alloys because Ca was incorporated into the PEO film and because Ca was present in the alloys. Improvement of corrosion resistance and bioactivity of the PEO-coated AM60 by alloying with Ca may be beneficial for biodegradable implant applications.

In this study, the effects of the nanoporous structure of anodic films on adhesive strength between aluminum alloys and polyamide resin were systematically investigated. Alumina films with different dimensions (such as pore density, diameter, and depth) were formed on A6063 aluminum alloys by various anodizing conditions to compare the anchoring effect. The adhesive strength at the interface between the adherend (anodized aluminum) and adhesive (thermoplastic elastomer resin) was evaluated by a method for determining the tensile lap-shear strength of rigid-to-rigid bonded assemblies. The higher pore density and larger pores in anodic films were important factors for improving the adhesive strength and increasing the adhesion interface area and the amount of adhesive impregnated into the pores. After anodizing in phosphoric acid at 60V and subsequent pore widening, the adhesive strength of aluminum was 17.4 MPa, which was -3.5 times higher than that of an aluminum substrate without surface treatment. [ABSTRACT FROM AUTHOR]