Abstract
The extensive polygonization of 200 nm rutile crystals in high-energy dry milling allowed to study the spectral properties of grain boundaries and adjacent microstrained crystalline matter. Changes in UV, VIS, NIR, IR and FIR spectra during milling were followed. For the UV absorption edge the value of unstrained rutile was retained while residual traces of anatase, intergrown with the rutile phase, continued to act as traps for photoinduced charges. The evolving broad absorption in VIS and NIR could be attributed to electrons weakly bound to defects in the packing of oxygen anions at the grain boundaries, which may relax to face-sharing Ti 3+ –O octahedra. Among the IR-active lattice vibrations, the narrow E u (2) band showed a shift to higher frequencies by 15 cm −1 which is definitively not due to phonon confinement or Fröhlich surface modes but probably to coupling of the bulk phonon to a plasmon at the grain boundary. At the external surface of the polygonized primary particle, the regular atomic order is destroyed by milling so that hydroxylation is replaced by physisorption of H 2 O, as shown by IR and TG.
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