Pseudobrookite pigments were synthesised by the conventional ceramic route, calcining at 1300 ?C four mixtures, with a Fe2O3:TiO2 ratio ranging from 47:53 to 40:60, and were characterised by XRPD, DRS and colouring performance in several ceramic matrices. Titania in moderate excess of the Fe2TiO5 stoichiometry, necessary to minimise the occurrence of unreacted precursors, induced lattice parameters smaller than ideal pseudobrookite, in agreement with the different radii of Ti4+ and Fe3+ ions. These pigments exhibit a peculiar, intensely brown coloration originated by several light absorptions in the visible spectrum due to both d5 electronic transitions and a magnetically-coupled paired transition between iron ions in adjacent lattice sites. A doubling of the 6A1 → 4T1 and 4T2 bands is related to the occurrence of Fe3+ in both octahedral sites of pseudobrookite. Besides, distinct metal-oxygen distances imply different energy absorptions in good accordance with the crystal field theory, despite the strongly covalent character of the Fe-O bonding. Although an entropy-stabilised phase, pseudobrookite persists dispersed in glazes and glassy coatings even after fast firing at 1200 ?C, so being suitable as ceramic pigment. However, its colouring performance depends on the chemico-physical properties of ceramic matrices: saturated brown shades achieved in low temperature glasses shift to a lighter brown in opacified glazes and fade to a light gray in wall tile glazes, where the high CaO and ZnO content contributes to rapidly dissolve pseudobrookite
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