Gradient control of the adhesive force between Ti/TiO2 nanotubular arrays fabricated by anodization.

The poor control of the adhesion of TiO2 nanotubes (TNTs) layers to a non-anodized titanium (Ti) substrate has limited their widespread application, because the stripping mechanism has not yet been revealed. Here, we report a novel method to control the detachment of TNTs by post-treatment of the as-fabricated samples in protic and aprotic solvents with different polarities. Post-treatment using an organic solvent of lower polarity increases the adhesion of the tube layer, in contrast to the spontaneous detachment of the TNT layer after treatment using a solvent of higher polarity. The structure and the composition at the rupture interface were studied to explore the mechanism of the stripping behavior. Based on our experimental results and previous studies, a hypothesis of a hydrogen-assisted cracking (HAC) mechanism was proposed to explain the mechanism of TNTs' natural detachment and the control over of TNTs' stripping behaviors by post-treatment, in which the presence of protons at the interface between the TNT layer and the Ti substrate play an important role in controlling the two layers' cohesion. In summary, this method and mechanism hold promise to be used as a tool for the design and fabrication of TNT-related materials in future.