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Hydrothermal crystallization in the KOH-ZrO2-GeO2-H2O system under 0.1 GPa pressure at 500°C: Phase relationships for Zr germanates and modeling of K2ZrGe2O7 crystal structure

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Abstract

Formation of germanium dioxide of the composition R-GeO2 (rutile structure type), Zr germanate of the composition Zr[8]Ge[4]O4 (scheelite structure type), K,Zr[6] germanates of the compositions K2Zr[6]Ge [4]3 O9 (wadeite structure type) and K2Zr[6]Ge [4]2 O7, K,Ge[6] germanate of the composition K2Ge[6]Ge [4]3 O9, and the K,Ge[6] hydroxo germanate of the composition K3HGe [6]4 Ge [4]3 O16 · 4H2O is established in the KOH-ZrO2(nanocrystalline)-GeO2 (quartz structure type)-H2O system under the pressure 0.1 GPa at the temperature 500°C (the superscripts indicate the coordination numbers of Zr and Ge atoms with respect to oxygen). It is shown that crystallization of K,Zr germanates under hydrothermal conditions depends on the molar ZrO2/GeO2 ratio and KOH concentration. The phases synthesized are subjected to crystallochemical analysis. The specific characteristics of the matrix assembly of the K2ZrGe2O7 structure from suprapolyhedral structural units (SSU) are considered. The K2ZrGe2O7 structure having the MT 2 framework built by M octahedra of the composition ZrO6 and T tetrahedra of the composition GeO4 is considered as a packing of SSU precursors of the composition K2 M 2 T 4. The chemical composition of the SSU precursor of the composition K2 M 2 T 4 with M: T = 1: 2 determines the lower boundary of germanium content in the three-dimensional framework structures of K,Zr germanates as Ge/Zr = 2.

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  1. Shubnikov Institute of Crystallography, Russian Academy of Sciences, Leninskii pr. 59, Moscow, 119333, Russia

    G. D. Ilyushin

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__________

Translated from Kristallografiya, Vol. 50, No. 3, 2005, pp. 550–558.

Original Russian Text Copyright © 2005 by Ilyushin.

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Ilyushin, G.D. Hydrothermal crystallization in the KOH-ZrO2-GeO2-H2O system under 0.1 GPa pressure at 500°C: Phase relationships for Zr germanates and modeling of K2ZrGe2O7 crystal structure. Crystallogr. Rep. 50, 504–512 (2005). https://doi.org/10.1134/1.1927617

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