The mechanism for the colour change of iron chromium black pigments in glazes through transmission electron microscopy techniques

Black iron-chromium (Fe-Cr) bearing oxide pigments are generally utilised as effective colourants in a wide variety of applications. However, in the case of their use within ZnO-containing glazes, they yield an undesirable brown colour instead of expected black colour. In order to understand the colour change in this system, we report the use of focused ion beam (FIB) sample preparation technique followed by the use of analytical transmission electron microscopy (TEM) characterisation techniques. According to the results, the formation of a reaction layer between the pigment and glaze was identified with an average composition of Zn_0.48Fe_0.79Cr_1.32O₄. Additionally, the valance of Fe was determined as 3+ in the pigment grain, whereas 2+ in the reaction layer and the glaze, respectively. Therefore, it was concluded that the colour change is occurring as result of the valence variation of Fe, the formation of Zn_0.48Fe_0.79Cr_1.32O₄ compound and the outward diffusion of Fe into the glaze.