Influence of crystallite size and surface morphology on electrochemical properties of annealed TiO2 nanotubes

Abstract

The current study investigates the effect of crystallite size and surface morphology of TiO2 nanotubes on their wettability and electrochemical properties. Self-organized amorphous TiO2 nanotubes were synthesized by anodization process in an acidic (0.5wt% HF) and a neutral electrolyte (1M Na2SO4+0.5wt% NaF). Subsequently, the nanotubes were annealed at 450°C to achieve crystalline phase. Scanning electron microscope micrographs revealed that nanotubes formed from the neutral bath are four times longer (1.2μm) than the ones synthesized from the acidic bath (325nm). The charge consumed during anodization is greater under the acidic conditions implying the severity of the attack on the nanotubes by the electrolyte. X-Ray diffraction analysis showed that after annealing TiO2 crystallizes in the tetragonal lattice as anatase structure. Peak fitting method for line profile analysis was employed to estimate the crystallite size and the micro strain. The oxide nanotubes formed in neutral medium showed smaller crystallite size (28.91nm) than the one formed in acidic medium (43.37nm). Wettability measurements showed wetting angles <60°, indicating hydrophilic nature of the anatase nanotubes. Further, both the dimensional aspect (i.e., length and diameter of nanotubes) and the crystallite size have significant effect on the hydrophilic behavior. Electrochemical impedance spectroscopy in a simulated body fluid environment confirmed that structural changes in the oxide layer influence the electrochemical properties. Polarization studies demonstrated that crystallite size affects the passive behavior of the nanotubes. Smaller crystallite size (28.91nm) lowers the passive current density (0.11μAcm−2), indicating the good protectiveness.