Crystal structure change of katoite, CaAl(OD), with temperature at high pressure

Kyono, Atsushi*; Kato, Masato*; Sano, Asami   ; Machida, Shinichi*; Hattori, Takanori   

To reveal the decomposition mechanism with temperature under high-pressure, crystal structure of a hydrogrossular, katoite CaAl(OD) has been studied by in-situ neutron diffraction at 8 GPa. Although unusual expansion behavior was discerned at 200-400C, the unit cell was continuously expanded up to 850C. At 900C, katoite was decomposed, indicating that pressure strongly increases dehydration temperature from 300C to 900C. On release of pressure, the katoite reappear together with corundum and portlandite. At 8 GPa, CaO and AlO polyhedra expand with temperature up to 850C by about 8% and 13%, respectively. On the other hand, tetrahedral interstices are isotopically squeezed by about 10%: due to the expansion of above polyhedra. The neighboring D-D distance remains almost unchanged in this temperature range, while the O-D bond distance shrinks drastically just before decomposition. This finding suggests that the shortening of O-D distance caused by the D-D repulsion destabilizes the O-D bond, which induces the thermal decomposition of katoite.