Physics and Chemistry of Minerals

, Volume 46, Issue 5, pp 459–469 | Cite as

Crystal structure change of katoite, Ca3Al2(O4D4)3, with temperature at high pressure

  • Atsushi KyonoEmail author
  • Masato Kato
  • Asami Sano-Furukawa
  • Shin-Ichi Machida
  • Takanori Hattori
Original Paper


To reveal the decomposition mechanism with temperature under high pressure, crystal structure of a hydrogrossular, katoite Ca3Al2(O4D4)3 has been studied by high-pressure and high-temperature neutron diffraction technique. The crystal structure was investigated using Rietveld method under a constraint of the space group Ia\(\overline{3}\)d. At pressure of approximately 8 GPa, the unit cell volume of katoite increased as a function of temperature. Although unusual expansion behavior was discerned in a temperature range between 200 and 400 °C, the unit cell was continuously expanded up to 850 °C. At 900 °C, katoite was decomposed and the residuals were dissolved completely in the dehydrated water. The results show that high-pressure strongly affects the increase of the katoite dehydration temperature from 300 to 900 °C. After cooling and decompression to ambient conditions, the peaks of katoite reappear together with those of corundum Al2O3 and portlandite Ca(OH)2. At 8 GPa, the volume of CaO8 dodecahedron and AlO6 octahedron expands with temperature up to 850 °C by about 8% and 13%, respectively. That of tetrahedral interstice, on the other hand, contracts by about 10%: the tetrahedral interstices are squeezed isotopically by the expansion of CaO8 dodecahedra and AlO6 octahedra. The neighboring D–D distance remains almost unchanged in this temperature range, while the O–D bond distance shrinks drastically just before decomposition. It is suggested that the shortening of O–D distance caused by the D–D repulsion destabilizes the O–D bond that results in the thermal decomposition of katoite.


Nominally anhydrous minerals Hydrogrossular High pressure Neutron diffraction Dehydration 



We thank two anonymous reviewers for their detailed constructive comments that helped significantly to improve the manuscript. The high-pressure and high-temperature neutron diffraction experiment was approved by the Neutron Science Proposal Review Committee of J-PARC/MLF (proposal no. 2015A0035). The work was partially supported by a Grant-in-Aid for Scientific Research (C) from the Japan Society for the Promotion of Science (project no. 26400511).

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Division of Earth Evolution Sciences, Faculty of Life and Environmental SciencesUniversity of TsukubaTsukubaJapan
  2. 2.J-PARC CenterJapan Atomic Energy AgencyTokaiJapan
  3. 3.Neutron Science and Technology CenterComprehensive Research Organization for Science and SocietyTokaiJapan

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