Growth mechanisms of multilayered anodic-titanium-oxide nanotube membranes

Anodic titanium oxide TiO2 nanotube membranes with one, two and three layers have been prepared by the anodic oxidation method via adjusting applied bias during the oxidation process in glycol electrolytes containing 0.25wt% or 0.50wt% NH4F. The morphologies of the as-prepared samples were presented in detail using scanning and transmission electron microscopy. The results indicated that the glycol electrolyte containing 0.25wt% NH4F yielded smooth double-walled nanotubes, and their tubes remained open in multilayers; while the glycol electrolyte containing 0.50wt% NH4F yielded single-wall nanotubes with ripples, and most of the nanotubes have closed bottoms. In the case of nanotubes with closed bottoms, it was proposed that the newly grown nanotubes on the succeeding layer formed in the gap between the nanotubes of the previous layer. In order to keep track of the growth of the nanotubes, samples were anodized for different periods of time from 1 to 90min to study their formation process. Growth mechanisms were proposed for different morphologies.