Alkaline Corrosion-Resistant Anodic Aluminum Oxide Formed By Etidronic Acid Anodizing

Abstract

A newly discovered electrolyte for anodizing aluminum, etidronic acid (CH3C(OH)[PO(OH)2]2), operates at high voltages of more than 200 V, and ordered porous alumina measuring 400-670 nm in cell diameter (interpore distance) can be fabricated via constant voltage anodizing. Because such porous alumina film formed at high voltages possesses a thick barrier layer, etidronic acid anodizing may be useful for corrosion protection of aluminum. Here, we describe the alkaline corrosion-resistant porous alumina formed by high voltage anodizing in an etidronic acid solution, and its hydration behavior in boiling water was investigated. Highly pure aluminum plates (99.999 wt%) were anodized in 0.3 M sulfuric acid, 0.3 M oxalic acid, 0.3 M citric acid, and 0.3 M etidronic acid solutions (293 K) at a constant current density of 30 Am-2 or a constant voltage of 250 V. The anodized specimens were immersed in a 2.5 M NaOH solution (293 K). The nanostructural changes were examined by electrochemical impedance spectroscopy (EIS). The anodized specimens were immersed in boiling water to seal the pores in the porous alumina film. The surface and cross-section of the specimens were characterized by field-emission scanning electron microscopy (FE-SEM) The plateau voltages during anodizing aluminum at a constant current density of 30 Am-2 in sulfuric and etidronic acid solutions exhibited approximately 16 V and 197 V, respectively. As the specimen anodized in sulfuric acid was immersed in a 2.5 M sodium hydroxide solution, H2 gas evolution was observed from the surface at the beginning of immersion, and the amount increased with the immersion time. In contrast, the specimen anodized in etidronic acid did not result in hydrogen gas evolution during immersion until 8 min. Here, the capacitance (Cb ) is inversely proportional to the thickness of the barrier layer. Figure 1 shows the changes in the reciprocal Cb with the immersion time, ti . Complete dissolution of porous alumina formed in etidronic acid takes 15 times longer than dissolution of the alumina formed by sulfuric acid anodizing due to the formation of a thick barrier layer. As the porous alumina formed by etidronic acid anodizing is immersed in boiling water, plate-like hydroxides were formed at the bottom of the pores in the initial immersion stage. The thickness of the hydroxide layer increased with the immersion time, and the nanopores are completely sealed by long-term immersion. Figure 1