High-temperature borate crystal chemistry

The paper presents a brief review of the present state of high-temperature borate crystal chemistry. This review summarizes the results of high- and low-temperature single crystal X-ray diffraction studies for more than 10 borate structures and high-temperature powder Xray diffraction data for about 65 borates. Thermal behavior of their crystal structures, thermal expansion, polymorphic transitions and their relationship to borate glasses are presented. These studies allow to formulate the basic principles of high- temperature borate crystal chemistry and to reveal the regularities of thermal behavior of borates. On heating, the BO3 and BO4 polyhedra and rigid groups consisting of these polyhedra, practically maintain their configuration and size, but they are able to rotate like hinges exhibiting highly anisotropic thermal expansion, including linear negative expansion. Based on these results, we generalize the term "rigid group" and render thermal vibrations as the key ingredient for the self-assembly of borate rigid groups.