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High-aspect ratio ordered nanomaterial arrays exhibit several unique physicochemical and optical properties. Porous anodic aluminum oxide (AAO) is one of the most typical ordered porous structures and can be easily fabricated by applying an electrochemical anodizing process to Al. However, the dimensional and structural controllability of conventional porous AAOs is limited to a narrow range because there are only a few electrolytes that work in this process. Here, we provide a novel anodizing method using an alkaline electrolyte, sodium tetraborate (Na 2 B 4 O 7 ), for the fabrication of a high-aspect ratio, self-ordered nanospike porous AAO structure. This self-ordered porous AAO structure possesses a wide range of the interpore distance under a new anodizing regime, and highly ordered porous AAO structures can be fabricated using pre-nanotexturing of Al. The vertical pore walls of porous AAOs have unique nanospikes measuring several tens of nanometers in periodicity, and we demonstrate that AAO can be used as a template for the fabrication of nanomaterials with a large surface area. We also reveal that stable anodizing without the occurrence of oxide burning and the subsequent formation of uniform self-ordered AAO structures can be achieved on complicated three-dimensional substrates.

A superhydrophilic aluminum surface with fast water evaporation based on nanostructured aluminum oxide was fabricated via anodizing in pyrophosphoric acid. Anodizing aluminum in pyrophosphoric acid caused the successive formation of a barrier oxide film, a porous oxide film, pyramidal bundle structures with alumina nanofibers, and completely bent nanofibers. During the water contact angle measurements at 1 s after the water droplet was placed on the anodized surface, the contact angle rapidly decreased to less than 10°, and superhydrophilic behavior with the lowest contact angle measuring 2.0° was exhibited on the surface covered with the pyramidal bundle structures. As the measurement time of the contact angle decreased to 200-33 ms after the water placement, although the contact angle slightly increased in the initial stage due to the formation of porous alumina, at 33 ms after the water placement, the contact angle was 9.8°, indicating that superhydrophilicity with fast water evaporation was successfully obtained on the surface covered with the pyramidal bundle structures. We found that the shape of the pyramidal bundle structures was maintained in water without separation by in situ high-speed atomic force microscopy measurements.

The fabrication of sticky and slippery superhydrophobic aluminum was achieved by anodizing in pyrophosphoric acid and modification with self-assembled monolayers (SAMs). In addition, the corresponding sliding behaviors of a water droplet were investigated by contact angle measurements and direct observations. For the formation of anodic alumina nanofibers, 4N aluminum plates were anodized in a concentrated pyrophosphoric acid solution at 25-75 V. The morphology of the anodic oxide successively changed to barrier oxide, porous oxide, nanofibers, bundle structures with many nanofibers, and then weak nanofibers during anodizing. The anodized specimens were immersed in a fluorinated phosphonic acid/ethanol solution to form SAMs on the surface of the anodic oxide. The contact angle hysteresis drastically changed with anodizing time: it increased with the formation of porous oxide, decreased for the nanofibers and bundle structures, and then increased once again for the weak nanofibers. Correspondingly, the adhesion interaction between the water droplet and the aluminum surface also drastically changed to show sticky, slippery, and sticky behaviors with anodizing time. More sticky and slippery aluminum surfaces can be obtained by anodizing at higher voltages. The slippery behavior was further improved through two distinct anodizing processes with the formation of ordered alumina nanofibers. A superhydrophobic aluminum surface with coexisting sticky and slippery properties was fabricated by the selective anodizing method., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The molten salt-based direct reduction process for reactive solid metal outperforms traditional pyrometallurgical methods in energy efficiency. However, the simplity and rapidity of this process require a deeper understanding of the interfacial morphology in the vicinity of liquid metal deposited at the cathode. For the first time, here we report the time change of electrode surface on the sub-millisecond/micrometre scale in molten LiCl-CaCl 2 at 823 K. When the potential was applied, liquid Li-Ca alloy droplets grew on the electrode, and the black colloidal metal moved on the electrode surface to form a network structure. The unit cell size of the network and the number density of droplets were found to depend on the applied potential. These results will provide important information about the microscale mixing action near the electrode, and accelerate the development of metallothermic reduction of oxides.

We investigated the transient behavior of immiscible two-liquid interfaces initiated by a single rising gas bubble and characterized by liquid "column" and "film" morphologies. To analyze the effect of the buoyancy force, viscosity, and interfacial tension on these morphologies, the single-solution density was controlled continuously by association with the rising velocity of the bubble. It was observed that the extension of the liquid column further into the upper liquid phase owing to the wake flow under the bubble is driven by the buoyancy force, with the velocity decreasing gradually with the distance between the bubble and the liquid-liquid interface. Based on this mechanism, we determined that a strong dimensionless correlation exists between the lifetime of the column and the physical properties of the two liquid phases. On the other hand, gravitational drainage does not affect the film lifetime. However, marginal pinching is dominant, probably owing to the existence of a surface tension gradient between the film and the meniscus.

Anodic oxide fabricated by anodizing has been widely used for nanostructural engineering, but the nanomorphology is limited to only two oxides: anodic barrier and porous oxides. Therefore, the discovery of an additional anodic oxide with a unique nanofeature would expand the applicability of anodizing. Here we demonstrate the fabrication of a third-generation anodic oxide, specifically, anodic alumina nanofibers, by anodizing in a new electrolyte, pyrophosphoric acid. Ultra-high density single nanometer-scale anodic alumina nanofibers (10(10) nanofibers/cm(2)) consisting of an amorphous, pure aluminum oxide were successfully fabricated via pyrophosphoric acid anodizing. The nanomorphologies of the anodic nanofibers can be controlled by the electrochemical conditions. Anodic tungsten oxide nanofibers can also be fabricated by pyrophosphoric acid anodizing. The aluminum surface covered by the anodic alumina nanofibers exhibited ultra-fast superhydrophilic behavior, with a contact angle of less than 1°, within 1 second. Such ultra-narrow nanofibers can be used for various nanoapplications including catalysts, wettability control, and electronic devices.

Anodic porous alumina has been widely investigated and used as a nanostructure template in various nanoapplications. The porous structure consists of numerous hexagonal cells perpendicular to the aluminum substrate and each cell has several tens or hundreds of nanoscale pores at its center. Because the nanomorphology of anodic porous alumina is limited by the electrolyte during anodizing, the discovery of additional electrolytes would expand the applicability of porous alumina. In this study, we report a new self-ordered nanoporous alumina formed by selenic acid (H2SeO4) anodizing. By optimizing the anodizing conditions, anodic alumina possessing 10-nm-scale pores was rapidly assembled (within 1 h) during selenic acid anodizing without any special electrochemical equipment. Novel sub-10-nm-scale spacing can also be achieved by selenic acid anodizing and metal sputter deposition. Our new nanoporous alumina can be used as a nanotemplate for various nanostructures in 10-/sub-10-nm-scale manufacturing.