Deformation behavior of titanate nanotubes subjected to high pressure

Nano-sized titania (anatase) and sodium and potassium titanate nanotubes were studied via in situ Raman spectroscopy at hydrostatic pressures up to 6 GPa. Analysis by scanning electron microscopy shows a uniform dispersion of sodium and potassium cations in the nanotubes. The effect of the pressure was observed by significant shifts in the Raman band structure of nano-sized anatase crystals and nanotube titanate. In nano-particulate anatase, the phonon frequencies (143, 395, 517, and 639 cm⁻¹) increase linearly with pressure. In contrast, the upward frequency shifts in the sodium titanate nanotubes (NaTNT) and potassium-modified nanotubes (NaTNT+K) occur in a stepwise fashion. These stepwise changes occur in the nanotube samples between 2 and 4 GPa (ambient pressure phonon bands in NaTNT at 274, 444, 650, and 906 cm⁻¹) and between 4.5 and 5.5 GPa, (phonons 273 cm⁻¹ and 436 cm⁻¹ in NaTNT+K at an ambient pressure). Post-pressure high-resolution transmission electron microscopy analysis shows evidence of nanotube distortions and a 5% contraction in the interlaminar spacing of both NaTNT and NaTNT+K.