Through the application of the Rietveld method, X-ray diffraction analysis has developed into a fully quantitative method for phase analysis of metallurgical products. The Rietveld method itself has progressed from an unstable method that required constant operator intervention to a stable and robust method suited even for routine process control._x000D_
Knowledge of the crystal structures of the major phases is essential for Rietveld analysis, and these are well known for most minerals and major phases in metallurgical products. It provides the basic structural information necessary for the determination of mineral stoichiometry and for elucidating solid solution behaviour. Modern methods, such as simulated annealing and charge flipping, permits the determination of crystal structures from powder data._x000D_
Unit cell data can be used where conventional microchemical analysis is unable to provide an answer to the extent of solid solution in ilmenite roasting. Unit cell data (by XRD) is used to determine the amount of roasting necessary for the development of magnetisation to be able to separate chromite from an ilmenite concentrate._x000D_
Phase quantification is probably the most widely used application of XRD analysis. It is used for materials balance in the minerals and cement industries, and it is finding novel applications in the iron and steel industry._x000D_
Applications of XRD in high-temperature metallurgical processes are increasing. In this paper the phase chemistry of iron ore sinters, the evaluation of subsolidus reactions in titania slags and the identification of furnace accretions are discussed._x000D_
Despite the success of the Rietveld method in phase quantification, the method still needs further development in the quantification of closely related or polytypic phases. The quantification of pyrrhotite phases using various Rietveld programs still gives ambiguous results. This is also true for the different SFCA phases in iron ore sinters. Clearly the analysis of similar phases, differing only in the presence of weak superlattice reflections is still problematic.