Polymorphic transformation of titanium dioxide by mechanical grinding

Abstract

The effect of mechanical grinding on the structural transformation of titanium dioxide was studied by using several anatase samples prepared from different starting materials and with various particle sizes. Three anatase samples were prepared by hydrolysis of Ti(O·i-C₃H₇)₄, TiCl₄, and TiOSO₄·2H₂O and one is commercial reagent grade anatase. Each of the as-prepared or heat-treated samples (1.0 g) was ground in a mortar of sintered alumina for up to 96 h in air. The stability of brookite synthesized by grinding was examined by heating in air and under hydrothermal pressure. From the relative amount of the phases estimated by the measurement of the integrated intensity of X-ray line profile and of X-ray crystallite size, DTA and TG, IR spectra, and observation by electron microscope, it is concluded that: 1. the transformation proceeds by a consecutive process from anatase to rutile through brookite by grinding; 2. the smaller the initial particle size of anatase, the more stable the intermediate phase of brookite; 3. the very fine crystals of 5∼20 nm of anatase can be grown to 50∼150 nm of rutile by grinding for 96 h; 4. the rate process of the transformation depends on the initial particle size and is independent of the difference in starting materials or of surface adsorbants; 5. an appropriate lattice distortion introduced by grinding is considered to stabilize the brookite phase; and 6. the lattice constant and the density of brookite synthesized by grinding,a ₀=0.5447±0.005 nm,b ₀=0.9150±0.0005 nm,c ₀=0.5141±0.0005 nm, andD _x =4.14 g cm⁻³ agree with those in natural brookite.