A three-layer zirconia structure composed of nanotubes, dense layer and nanotubes: Evidence against the FADT

Abstract

Porous anodic oxides have become a research hotspot, but their formation mechanisms are still controversial. The classical field-assisted dissolution theory (FADT) is a theory of top-down dissolution to form nanotubes. However, certain key problems such as the three-stage current-time curve in anodizing process cannot be explained by this theory. The oxygen bubble mold (OBM) is a new mechanism of bottom-up growth of nanotubes, which can explain the phenomenon that cannot be explained by the FADT. Compared to the anodic TiO2 nanotubes, ZrO2 nanotubes have a more complex anodizing current-time curve which is not studied sufficiently. Under certain conditions, there are double complete three-stage current-time curves and two-layer nanotubes. In this study, to explore the formation mechanism of anodic ZrO2 nanotubes, the current-time curve and the interesting morphology were analyzed, after zirconium anodizing and SEM characterizing. An interesting three-layer structure composed of upper nanotubes, dense layer and lower nanotubes formed by zirconium anodizing is reported for the first time. The lower nanotubes and the dense layer are tightly bonding, which strongly refutes the FADT. The OBM was used to explain this phenomenon, which promoted the development of the formation mechanism of anodic ZrO2 nanotubes.