Titanium dioxide (TiO₂) pigments, subjected to different coating processes, have been characterized by microelectrophoresis (MEP), high-resolution transmission electron microscopy (HRTEM) and Fourier-transform infrared spectroscopy (FTIR). MEP and HRTEM measurements are in excellent agreement with the FTIR data, to which they add useful complementary information. Among the FTIR measurements, the adsorption of pyridine yields vital information on the composition and thermal stability of the surface layer. The coating overlayer complete in all cases examined, and none of the ions introduced in the TiO₂ phase (e.g. the photostabilizing Zn²⁺) is present in the surface layer after the coating process.

Pre-coating with TiO₂ from titanyl sulfate produces a porous overlayer of scale-like anatase crystallites. The vacuum thermal stability of the TiO₂ overlayer is quite low. Coating with alumina yields a thick, homogeneous, and amorphous overlayer, whose chemical nature depends on the coating procedure. When derived from Na aluminate, it is an amorphous Al hydrate (similar to boehmite), but contains some Al³⁺ surface ions in a quasi-tetrahedral co-ordination. However, when derived from aluminium sulfate, it is an amorphous aluminium basic sulfate, ionic and highly hydrated. The alumina overlayers of both types are quite unstable towards vacuum thermal treatments. Coating with silica yields an amorphous overlayer of variable thickness of regular hydrated silica, with no mixed TiO₂–SiO₂ phases. The SiO₂ layer is chemically stable towards vacuum thermal treatments at high temperatures, whereas the hydration degree and the texture (surface area and porosity) are irreversibly modified.