Crystal structure refinement, low- and hightemperature X-ray diffraction and Mössbauer spectroscopy study of the oxoborate ludwigite from the Iten'yurginskoe deposit

Abstract

This paper reports an investigation of the chemistry, crystal structure refinement and thermal behavior (80-1650 K) of ludwigite from the Iten'yurginskoe deposit (Eastern Chukotka, Russia). Its chemical composition was determined by electron microprobe analysis, giving an empirical formula (Mg1.70Fe2+ 0.29Mn0.01)Σ2.00(Fe3+ 0.90Al0.08Mg0.02)Σ1.00O2(BO3). A refinement of the crystal structure from single-crystal X-ray diffraction data (SCXRD) was provided for the first time for ludwigite from this deposit (R = 0.047). The structure can be described as a framework composed of [MO6]n- octahedra and isolated [BO3]3- triangles located in triangular interstices of the framework. Based on a comprehensive analysis of SCXRD and Mössbauer spectroscopy data, theM1 site is occupied by Mg,M2 andM3 byMg and Fe2+,M4 by Fe3+, Mg and Al. There are also oxo-centered [O4M4]n+ and [O2M5]n+ polyhedra building up a framework with the [BO3]3_ triangles located in its hexagonal interstices. No indications of magnetic ordering are found in the temperature range investigated. The Fe2+ → Fe3+ oxidation occurs above 600 K, and is accompanied by a decrease of the unit-cell parameters and subsequent incomplete solid-phase decomposition with the formation of hematite, warwickite and magnetite. The mineral melts at temperatures above 1582 K. The thermal expansion of ludwigite is slightly anisotropic, which is explained by a dense packing of the [MO6]n_ octahedra as well as a virtually perpendicular orientation of the oxo-centered double chains to each other. At room temperature, maximum expansion is along the c axis (αc = 9.1 × 10-6 K-1) and minimum expansion is in the ab plane (αa = 8.6 × 10-6, -b = 7.6 × 10-6 K-1), which is due to the preferred orientation of the [BO3]3- triangles. A comparison of the thermal behavior of three oxoborates of the ludwigite group, namely azoproite (Mg,Fe2+)2(Fe3+,Ti,Mg,Al)O2(BO3), vonsenite (Fe2+,Mg)2- (Fe3+,Mn2+,Sn,Al)O2(BO3) and ludwigite (Mg,Fe2+ ,Mn)2(Fe3+ ,Al,Mg)O2(BO3), is provided.