Synthesis and crystal structure of LiNbO3-type Mg3Al2Si3O12: A possible indicator of shock conditions of meteorites

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Takayuki Ishii, Ryosuke Sinmyo, Tetsuya Komabayashi, Tiziana Boffa Ballaran, Takaaki Kawazoe, Nobuyoshi Miyajima, Kei Hirose, Tomoo Katsura

American Mineralogist,
v. 102, i. 9, p. 1947-1952
First Published on September 05, 2017
doi:10.2138/am-2017-6027

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“LiNbO3-type Mg2.98(2)Al1.99(2)Si3.02(2)O12 (py-LN) was synthesized by recovering a run product from 2000 K and 45 GPa to ambient conditions using a large volume press. Rietveld structural refinements were carried out using the one-dimensional synchrotron XRD pattern collected at ambient conditions. The unit-cell lattice parameters were determined to be a = 4.8194(3) Å, c = 12.6885(8) Å, V = 255.23(3) Å3, with Z = 6 (hexagonal, R3c). The average A-O and B-O distances of the AO6 and BO6 octahedra have values similar to those that can be obtained from the sum of the ionic radii of the averaged A- and B-site cations and oxygen (2.073 and 1.833 Å, respectively). The present compound has the B-site cations at the octahedral site largely shifted along the c axis compared with other LiNbO3-type phases formed by back-transition from perovskite (Pv)-structure, and as a result, the coordination number of this site is better described as 3+3. It appears therefore that the B-site cation in the octahedral position cannot be completely preserved during the back-transition because of the small size of Si and Al, which occupy usually a tetrahedral site at ambient conditions. The formation of py-LN can be explained by the tilting of BO6 octahedra of the perovskite structure having the pyrope composition and formed at high P-T conditions. The tilting is driven by the decrease in ionic radius ratio between the A-site cation and oxygen during decompression. This also explains why there is no back-transition from the Pv-structure to the ilmenite-structure during decompression, since this is a reconstructive phase transition whose activation energy cannot be overcome at room temperature. Py-LN may be formed in shocked meteorites by the back-transformation after the garnet-bridgmanite transition, and will indicate shock conditions around 45 GPa and 2000 K.”

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