Topotactic transformation of gadolinite‐ to melilite‐type structure revisited

• Published in: Journal of the American Ceramic Society 2024-05, Vol.107 (5), p.3534-3549
• Main Authors: Gorelova, Liudmila A., Vereshchagin, Oleg S., Shagova, Anastasia K., Krzhizhanovskaya, Maria G., Pankin, Dmitrii V., Bocharov, Vladimir N., Kasatkin, Anatoly V., Pekov, Igor V.
• Format: Article
• Language: English
• Subjects: datolite; Density functional theory; High temperature; homilite; Iron; Low temperature; okayamalite; Oxidation; Raman spectra; Raman spectroscopy; Single crystals; Spectrum analysis; Substitution reactions; Temperature; Thermal expansion; Thermodynamic properties; topotactic reaction
• ISSN: 0002-7820; 1551-2916
• DOI: 10.1111/jace.19656

Topotactic reactions can lead to the formation of new phases, which cannot be obtained via classical synthesis methods. The high‐temperature topotactic transformation of gadolinite‐type compounds, homilite Ca2Fe2+B2Si2O8O2 and datolite Ca2□B2Si2O8(OH)2, into a melilite‐type compound, okayamalite Ca2B2SiO7, was studied by in situ high‐temperature single‐crystal X‐ray diffraction and ex situ Raman spectroscopy. Furthermore, the density functional theory was used to calculate the electronic structures and Raman spectra of datolite, homilite, and okayamalite. At low temperatures (250–500°C), homilite undergoes the Fe oxidation process, whereas at high temperatures, both homilite and datolite transform into okayamalite (750 and 780°C, respectively). The transformation of datolite into okayamalite is a conversion of a single crystal to a polycrystalline aggregate, while the transformation of homilite into okayamalite is a transformation of a single crystal to a single crystal. Datolite derived from okayamalite is similar to natural okayamalite, whereas homilite derived from okayamalite shows Fe3+ for Si/B substitution. The existence of tetrahedrally coordinated Fe3+ leads to a stabilizing effect, resulting in the formation of a single crystal of okayamalite. In addition, the incorporation of iron into the structure of okaymalite leads to a change in the thermal behavior of the compound (α11 = 22 and 15×10−6°C–1 for datolite‐derived and homilite‐derived okayamalites, respectively). However, the thermal expansion of okayamalites is almost isotropic, which is typical for melilite‐type compounds. datolite, high‐temperature, homilite, okayamalite, topotactic reaction