Lattice relaxation in solid solutions: long-range vs. short-range structure around Cr3+ and Co2+ in oxides and silicates

Abstract

This dissertation reports the results derived from the 3-year doctoral thesis project aimed at exploring some oxide and silicate structures as promising ceramic pigments with enhanced colorimetric properties with respect to the traditional colorants. Solid solutions of perovskite, alumoniobite, and melilite compounds were obtained by doping octahedral and tetrahedral coordination sites with transition metal ions (e.g. Cr3+, Co2+, and Zn2) through a solid-state synthesis performed by means of an industrial-like process. The analytical techniques adopted to investigate the synthesized compounds allowed the determination of the "averaged" crystal structure, or the so termed long-range properties, and the short-range properties (i.e. the local structure around the substituting ions) through X-ray powder diffraction and electron absorption spectroscopy (EAS), respectively. As stated by Geiger (2001) "an understanding of the microscopic, mesoscopic and macroscopic properties and of the behaviour of solid solutions under different conditions is a challenge for all disciplines concerned with the solid state". As a matter of fact, the precise determination of a structure around impurities results fundamental to provide detailed information on their incorporation and on physical properties. For instance, in the case of the solid solutions here reported, the lattice incorporation of transition metal ions as impurities is the cause of their gradual coloration. Most of the times, such a coloration is more intense as greater is the impurity amount. The final goal of this work, was attained by calculating the structural relaxation coefficient for each studied solid solution by combining the mean with the local bond distances achieved by XRPD and EAS, respectively.