The role of counterions (Mo, Nb, Sb, W) in Cr-, Mn-, Ni- and V-doped rutile ceramic pigments: Part 2. Colour and technological properties

Industrial rutile pigments are manufactured using several chromophores: Cr (giving an orange hue), Mn (tan), Ni (yellow) and V (gray); a second element, the so-called counterion (i.e. Mo, Sb, Nb or W) is always added in order to achieve the desired coloration and/or improve the technological properties (e.g. chemico-physical resistance in ceramic bodies and glazes). The colour of these pigments is determined by both metal–ligand charge transfer (Ti4+ ↔ O2−) and crystal field effects (transition metals substituting Ti4+ in octahedral coordination). Though the absorbance bands are broad and frequently overlapped, the UV–vis–NIR spectra suggest the occurrence of Cr3+, Mn2+, Mn3+, Ni2+, V3+, and V4+ as chromophores. Rutile pigments are suitable for through-body (up to 1250 °C) and glaze applications (up to 1100 °C). The best coloration of porcelain stoneware bodies is achieved with Sb or W as counterions, though the higher stability is ensured by Sb, but in the Ti–Ni–W system. The best glaze colours are accomplished by W-bearing pigments, which however are less stable than Nb- or Sb-containing ones, except than for the V + W coupling. This latter represents a new and very interesting Co-free and Cr-free black pigment for low temperature applications.