Mineralogical evolution of ceramic clays during heating. An ex/in situ X-ray diffraction method comparison study

Abstract The ceramic properties of clay materials heated at high temperature are largely dependent on the mineral reactions, which usually are followed by XRD analysis on pressed pieces that are heated at different temperatures. Nevertheless, the use of “in-situ” high temperature X-ray diffraction (HTXRD) to follow the evolution of the crystalline phases under controlled temperature provides more precision. In this paper, the mineralogical changes produced during firing (RT-1000 °C) of two clay materials of very different mineralogical composition, frequently used in the manufacture of bricks in the SE Spain, have been studied by XRD classical procedure and with HTXRD, and the results obtained were compared. Although the phases identified by both X-ray analyses were the same, temperatures for the mineralogical reactions seem to be different, probably due to the experimental conditions. The patterns obtained by ex-situ XRD were at a higher speed than those by in-situ HTXRD, and probably the equilibrium was not achieved for the most reactions. Because of the expansion of the mineral structure parameters occurred during heating the mineral reflections do not match with those found in the database JPCDS, neither the position nor intensities of some stable phases at high temperature. For the optimization of the interpretation of the HTXRD patterns, and to facilitate the kinetics of the new phases, it is necessary to work at a high integration time per step and a slow heating rate. The in-situ HTXRD investigations of ceramic materials can save time respect to the classical XRD study of test-pieces heated at different temperatures, and lead immediate information of the transformation occurring on heating, which can be useful to improve the most suitable firing temperature in the industry.