Facile synthesis of size- and shape-controlled freestanding Au nanohole arrays by sputter deposition using anodic porous alumina templates.

To fabricate a freestanding through-hole Au membrane using an anodic porous alumina template, Au was deposited on the outermost surface of an anodic film followed by the removal of the template. Alumina templates with different dimensions (e.g. diameters and number of pores) were prepared by two-step anodization in the range of 40-80 V and pore-widening. The Au thin films were deposited onto alumina templates with well-controlled surface morphologies by sputter deposition using a commercially available ion sputter coater. After the removal of the alumina template, a variety of Au membranes with nanoholes, nanotubes, or branched pores were obtained, which reflect the morphology of the alumina template. When the sputtered Au penetrates the pores of the alumina film, Au nanotube arrays with an aspect ratio of ∼3 can be fabricated. The present method is much simpler than the traditional template process involving multi-step replication because there is no need to separate the alumina template from the aluminum substrate before Au deposition.

Detection of the Oxidation Area by Spectrophotometry: Regional and Temporal Changes in Anodic Oxidation on Titanium in Bipolar Electrochemistry.

This study investigated the temporal change in the oxidation area on a titanium (Ti) bipolar electrode (BPE) subjected to bipolar anodization in a direct current (DC) electric field using a spectrophotometer. The rectangular Ti sheet used as a BPE was horizontally positioned at the center of a cell. After the DC bipolar anodization, the oxidized area was detected nondestructively and visually using a specific interference color that depends on the thickness of the barrier-type oxide film formed on the Ti BPE. The change in the L*a*b* color space corresponding to each interference color revealed that the oxidation area increased along the longitudinal axis of the BPE with the increasing electrolysis time by reflecting the change in the potential distributions on the BPE. As visually demonstrated, the area where the anodic reaction proceeded reached saturation at 90% of the BPE surface area.

Hexagonal geometric patterns formed by radial pore growth of InP based on Voronoi tessellation.

To fabricate ordered geometric patterns consisting of InP nanoporous structures, a photoresist mask with periodic opening arrays was prepared by sphere photolithography. The diameter and interval of the openings of the photoresist mask could be controlled independently by adjusting the diameter of silica spheres used as a lens and the exposure time. Through this resist mask with a two-dimensional (2D) hexagonal array of openings, the pore growth of InP during anodic etching was investigated. The isolated openings could act as initiation sites for the radial growth of pores, resulting in the formation of hexagonal geometric patterns based on Voronoi tessellation in 2D space. With further anodic etching, inside the substrate, the growth direction of the pores changed from radial to perpendicular relative to the substrate. Moreover, by removing domains consisting of nanopores by anisotropic chemical etching, the fabrication of InP microhole arrays with circular and triangular cross sections was also achieved.

Effects of size and position of an unconnected aluminum electrode on bipolar anodization in an AC electric field.

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.

Effect of alcohol addition on the structure and corrosion resistance of plasma electrolytic oxidation films formed on AZ31B magnesium alloy.

The effect of the addition of alcohol to a Na3PO4-based electrolyte on plasma electrolytic oxidation (PEO) of AZ31B magnesium alloy was investigated. Anodization with spark discharge was conducted in Na3PO4-based electrolyte containing various alcohols (e.g., ethanol, ethylene glycol, and glycerol) at a constant current density of 200 A m-2 and a constant temperature of 25 °C. Voltage-time curves during the PEO process, the film structure, surface roughness, crystallographic structure, composition, corrosion resistance, and withstand voltage were investigated using various analytical equipment and electrochemical measurements. When the electrolyte containing alcohol was used, the initial bending voltage was higher than that observed using the basic electrolyte without alcohol addition, as was the oscillation voltage during the PEO process. For a given amount of electricity supplied, the addition of alcohol into the basic electrolyte tended to increase the thickness and corrosion resistance of PEO films formed while effectively reducing surface roughness. In particular, the addition of a polyhydric alcohol (i.e., ethylene glycol and glycerol) could act not only as a leveler for the formation of compact film but also as an enhancer for film qualities, such as corrosion resistance and withstand voltage. The patterns observed for Na3PO4-based electrolyte containing alcohol also hold for Na2SiO3-based electrolyte containing alcohol.

Bright Yellowish-Red Pigment Based on Hematite/Alumina Composites with a Unique Porous Disk-like Structure.

Inspired by a bacteriogenic, iron-based oxide material and a traditional Japanese red pigment, a bright yellowish-red pigment was prepared by heating an Al-containing iron oxyhydroxide precursor. The obtained red pigment had a unique porous disk-like structure, comprising Al-substituted hematite particles and crystalline alumina nanoparticles. Although these disk-like structures loosely gathered to form an aggregate in powder, they can be easily dispersed into a single, disk-like structure by simple ultrasonic irradiation. The powder exhibited a bright yellowish-red color and high thermostability, making it attractive as a coloring material for various industrial products needing a bright-red color, high weather resistance, and durability. Quantitative color measurements revealed extremely high L*, a*, and b* values that are much greater than those of commercially available hematite. The thermostability test showed that even after exposure to high temperatures, the pigment retained the red color, indicating its high thermostability. The unique microstructure should be strongly related to the bright yellowish-red color and the high thermostability of the developed red pigment.

Corrosion Resistance and Apatite-Forming Ability of Composite Coatings formed on Mg-Al-Zn-Ca Alloys.

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.

Metal patterning on silicon surface by site-selective electroless deposition through colloidal crystal templating.

Site-selective Cu deposition on a Si substrate was achieved by a combination of colloidal crystal templating, hydrophobic treatment, and electroless plating. Uniformly sized nano/microstructures were produced on the substrate using a monolayer coating of colloidal spheres instead of a conventional resist. The Cu patterns obtained were of two different types: networklike honeycomb and isolated-island patterns with a minimum period of 200 nm. Each ordered pattern with the desired intervals was composed of clusters of Cu nanoparticles with a size range of 50-100 nm. By the present method, it is possible to control the periodicity of metal arrays by changing the diameter of the colloidal spheres used as an initial mask and to adjust the shape of the metal patterns by changing the mask structure for electroless plating.

Au-Capped GaAs Nanopillar Arrays Fabricated by Metal-Assisted Chemical Etching.

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.

Effects of Alloying Element Ca on the Corrosion Behavior and Bioactivity of Anodic Films Formed on AM60 Mg Alloys.

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.

Well-Dispersed α-Fe2O3 Particles for Lead-Free Red Overglaze Enamels through Hydrothermal Treatment.

The traditional Japanese overglaze ceramic, akae porcelain, typically known for Kakiemon-style wares, has been prized around the world for over 400 years. The red color of akae porcelain provides an attractive contrast to white porcelain. In recent years, because the use of leaded frit in making akae has been restricted by law owing to the effects of lead on human health and the environment, lead-free glass frit mixtures for overglaze ceramic wares have been developed in various porcelain production areas throughout Japan. However, current lead-free frit for red overglaze enamels produces a color that is duller than that of conventional leaded frit. Therefore, the development of red pigments that are suitable for use with lead-free frit is strongly desired. In this study, we used a hydrothermal process to prepare nanosized iron oxide and oxyhydroxide powders, which showed good particle dispersion in molten lead-free frit. The precursor paste was prepared by reacting iron nitrate with ammonium hydrogen carbonate and heated in a sealed vessel at 80-150 °C. The sample powder prepared at 90 °C was almost monophasic α-Fe2O3 (hematite) and exhibited the brightest red color (highest L*, a*, and b* values). This powder featured primary particles of ∼15 nm in diameter that aggregated to form secondary spherical particles of ∼100 nm in diameter. This powder was mixed with lead-free frit and applied as a red paint to a porcelain test piece. The resultant akae showed a bright red color with high L*, a*, and b* values that exceeded the values of akae prepared using conventional hematite powder. Microscopic analysis revealed that the hematite particles were well dispersed in the resultant glass layer, indicating that the hematite powders have good dispersibility in molten frit.

Fabrication and Characterization of Single Phase α-Alumina Membranes with Tunable Pore Diameters.

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.

Sub-100-nm ordered silicon hole arrays by metal-assisted chemical etching.

Sub-100-nm silicon nanohole arrays were fabricated by a combination of the site-selective electroless deposition of noble metals through anodic porous alumina and the subsequent metal-assisted chemical etching. Under optimum conditions, the formation of deep straight holes with an ordered periodicity (e.g., 100 nm interval, 40 nm diameter, and high aspect ratio of 50) was successfully achieved. By using the present method, the fabrication of silicon nanohole arrays with 60-nm periodicity was also achieved.

Triangle pore arrays fabricated on Si (111) substrate by sphere lithography combined with metal-assisted chemical etching and anisotropic chemical etching.

The morphological change of silicon macropore arrays formed by metal-assisted chemical etching using shape-controlled Au thin film arrays was investigated during anisotropic chemical etching in tetramethylammonium hydroxide (TMAH) aqueous solution. After the deposition of Au as the etching catalyst on (111) silicon through a honeycomb mask prepared by sphere lithography, the specimens were etched in a mixed solution of HF and H2O2 at room temperature, resulting in the formation of ordered macropores in silicon along the [111] direction, which is not achievable by conventional chemical etching without a catalyst. In the anisotropic etching in TMAH, the macropores changed from being circular to being hexagonal and finally to being triangular, owing to the difference in etching rate between the crystal planes.