Zirconium titanate ceramic pigments: Crystal structure, spectroscopy and technological properties

Srilankite-type zirconium titanate, a promising structure for ceramic pigments, was synthesized at 1400 1C following three main doping strategies: (a) ZrTi1-xAxO4, (b) ZrTi1-x-yAxByO4 and (c) Zr1-xCxTiO4 where A = Co, Cr, Fe, Mn, Ni or V (chromophores), B = Sb or W (counterions) and C = Pr (chromophore); x = y = 0.05. Powders were characterized by XRD with Rietveld refinements and DRS in the UV-visible-NIR range; technological properties were appraised in several ceramic matrices (frits, glazes and body). Zirconium titanate can be usefully coloured with first row transition elements, giving green and greenish yellow (Co and Ni); orange-buff (Cr and V); tan-brown hues (Mn and Fe). In industrial-like synthesis conditions, a disordered structure as (Zr,Ti)O2, with both Zr and Ti randomly distributed in the octahedral site, is achieved. Doping with chromophores and counterions induces unit cell dimensions variation and causes an oversaturation in zirconium oxide. Optical spectroscopy reveals the occurrence of Co2+, Cr3+, Fe3+, Mn2+, Mn3+, Ni2+, V3+ and V4+. The zirconium titanate pigments fulfil current technological requirements for low-temperature applications, but exhibit a limited chemico-physical stability for higher firing temperature and in chemically aggressive media.