The fluoride ion is crystal chemically very similar to the hydroxyl ion, substituting for hydroxyl in many minerals in which hydrogen bonding is not important. Fluoride substitutions are particularly common in 2:1 layer silicates, such as micas, illites and smectites. The brick and tile industries, which use naturally occurring clays as their primary raw materials, have devoted considerable effort to understanding fluorine evolution during firing of the raw materials due to increasingly stringent fluorine emission regulations. In order to understand fluorine evolution from ceramic raw materials, we have studied a number of phyllosilicate materials used in making bricks. X-ray powder diffraction and fluorine analyses were combined with heating experiments and thermogravimetric analysis to evaluate the chemical and structural changes taking place on heating. Fluorine remained in 2:1 layer silicates to higher temperatures than did hydroxyl, but it behaved identically to hydroxyl in the kaolinite studied. In all cases, fluorine evolution coincided with structural breakdown of the clay host. These results show that fluorine evolution will consistently occur during firing of clay raw materials, and the problems of fluorine emission cannot be readily solved by simple variations of firing temperatures or times.

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