Gray–blue Al 2O 3–MoO x ceramic pigments: Crystal structure, colouring mechanism and performance

Abstract

Grayish-blue coloured alumina–molybdena was synthesized by high temperature reducing firing and experimented as ceramic pigment. Synchrotron light and conventional X-ray diffraction powder, ICP-OES and BET analyses proved that molybdenum spreads over alumina surface, without entering the corundum lattice, with a high superficial concentration (i.e. 27–99 Mo atoms nm −2) implying a prevailing octahedral coordination and a certain long-range order, eventually resulting in the formation of crystalline MoO 2. XPS and DRS suggested the occurrence of different valences, Mo(VI) being predominant over Mo(V) and Mo(IV). The colouring mechanism is mainly due to electronic absorption of Mo(V) in the red–orange region of the visible spectrum, giving rise to a characteristic blue shade; the gray cast is caused by extensive light absorption by Mo(IV) crystal field transitions and particularly Mo–O charge transfer. The colouring performance of Al 2O 3–MoO x in ceramic glazes and porcelain stoneware bodies for wall and floor tiles is excellent, being equivalent to the pigment coloration. Thermal stability in these matrices seems to be mostly affected by Na 2O and MgO. However, the distinctly blue shade of these pigments is much less intense than that of the most performant ceramic colorants. At all events, alumina–molybdena system develops a peculiar colour that cannot be reproduced unless utilising the most expensive blue and black cobalt-bearing ceramic pigments.