Raman spectroscopy of ball-milled TiO2

Raman spectroscopy was applied to study structural and dimensional changes during high-energy ball milling of TiO2 anatase. Milling was performed for up to 10 h using two different sets of grinding tools (wolfram carbide (WC) and agate), The diminution of the TiO2 particle to nanometric size was monitoring by low-frequency Raman spectroscopy. The nanometric sizes were confirmed by transmission electron microscopy (TEM). After short milling time by WC the bands of high-pressure TiO2 II phase (alpha -PbO2 structure) were detected in Raman spectrum. Prolonged milling time was needed for transformation to rutil. When milling was performed by agate, the time necessary for both phase transitions was longer, presumably because of lower ball-to-powder weight ratio. The low-frequency Raman band of the prolonged milled samples was broad, which suggests the wide dispersion in nanoparticle dimensions. The position of the low-frequency band in longer-milled samples indicated dimensions smaller than 20 nm, since the diameter of the particle is inversely proportional to the low-frequency mode of the spherical particles. These results were in agreement with the TEM results. (C) 2001 Elsevier Science B.V. All rights reserved.