Synthesis and thermal behavior of Fe3O2(BO4) oxoborate

Biryukov, Yaroslav P.; Бубнова, Р. С.; Филатов, С. К.; Goncharov, Alexey

doi:10.1134/s1087659616020048

Cited by 11 publications

(4 citation statements)

References 9 publications

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“…Co 3 BO 5 demonstrates the largest anisotropy of the thermal expansion among the parent compounds studied until now, for example, iron borate FeBO 3 , 28 hulsite (Fe 2+ ,Mg,Fe 3+ ,Sn) 3 (BO 3 )O 2 , 29 iron vonsenite (Fe,Mg) 3 BO 5 , 29 and oxoborate Fe 3 O 2 (BO 4 ). 30 The volume thermal expansion demonstrates two well-resolved anomalies, whose positions coincide with those observed in the temperature dependencies of heat capacity 15 and resistivity (see the text below).…”

Section: Resultssupporting

confidence: 61%

Anisotropic thermal expansion and electronic transitions in the Co₃BO₅ ludwigite

et al. 2022

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Section: Resultssupporting

confidence: 61%

Anisotropic thermal expansion and electronic transitions in the Co₃BO₅ ludwigite

et al. 2022

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“…Our recent works were aimed at a complex investigation of the chemical composition, crystal structure, magnetic and thermal properties of synthetic calcite-type FeBO 3 (Biryukov et al, 2018), norbergite-type Fe 3 O 2 (BO 4 ) (Biryukov et al, 2016(Biryukov et al, , 2018, natural ludwigite-type vonsenite (Fe 2+ ,Mg) 2 -(Fe 3+ ,Mn,Sn,Al)O 2 (BO 3 ) (Biryukov et al, 2020(Biryukov et al, , 2021, azoproite (Mg,Fe 2+ ) 2 (Fe 3+ ,Ti,Mg,Al)O 2 (BO 3 ) (Biryukov et al, 2022), pinakiolite-type hulsite (Fe 2+ ,Mg) 2 (Fe 3+ ,Mn,Sn,-Al)O 2 (BO 3 ) (Biryukov et al, 2020(Biryukov et al, , 2021. Because of the absence of data for these compounds, investigation of the lowand high-temperature behavior of the iron-containing borates is of particular interest.…”

Section: Introductionmentioning

confidence: 99%

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

Biryukov,

Zinnatullin,

Levashova

et al. 2023

Acta Crystallogr Sect B

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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, the M1 site is occupied by Mg, M2 and M3 by Mg and Fe2+, M4 by Fe3+, Mg and Al. There are also oxo-centered [O4M 4] n+ and [O2M 5] 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 (α c = 9.1 × 10−6 K−1) and minimum expansion is in the ab plane (α a = 8.6 × 10−6, α 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.

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“…It should be noted that there is a lack of high-temperature crystal-chemical investigations of iron borates in general. There are a few works known devoted to such investigations (Shimomura et al, 2007;Biryukov et al, 2016Biryukov et al, , 2018. A combination of in situ high-temperature Mö ssbauer spectroscopy and high-temperature X-ray diffraction (HTXRD) works well to reveal magnetic phase transitions in iron borates (Biryukov et al, 2016(Biryukov et al, , 2018.…”

Section: Introductionmentioning

confidence: 99%

“…There are a few works known devoted to such investigations (Shimomura et al, 2007;Biryukov et al, 2016Biryukov et al, , 2018. A combination of in situ high-temperature Mö ssbauer spectroscopy and high-temperature X-ray diffraction (HTXRD) works well to reveal magnetic phase transitions in iron borates (Biryukov et al, 2016(Biryukov et al, , 2018. The investigation of Fe 2+ to Fe 3+ oxidation, which should occur in vonsenite and hulsite with an increase in temperature using data of these methods, is of special interest too.…”

Section: Introductionmentioning

confidence: 99%

Investigation of thermal behavior of mixed-valent iron borates vonsenite and hulsite containing [OM₄]ⁿ⁺and [OM₅]ⁿ⁺oxocentred polyhedra byin situhigh-temperature Mössbauer spectroscopy, X-ray diffraction and thermal analysis

Biryukov

Zinnatullin

Бубнова

et al. 2020

Acta Crystallogr B Struct Sci Cryst Eng Mater

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The investigation of elemental composition, crystal structure and thermal behavior of vonsenite and hulsite from the Titovskoe boron deposit in Russia is reported. The structures of the borates are described in terms of cation-centered and oxocentred polyhedra. There are different sequences of double chains and layers consisting of oxocentred [OM 4] n + tetrahedra and [OM 5] n + tetragonal pyramids forming a framework. Elemental composition was determined by energy-dispersive X-ray spectroscopy (EDX). Oxidation states and coordination sites of iron and tin in the oxoborates are determined using Mössbauer spectroscopy and compared with EDX and X-ray diffraction data (XRD). According to results obtained from high-temperature Mössbauer spectroscopy, the Fe2+ to Fe3+ oxidation in vonsenite and hulsite occurs at approximately 500 and 600 K, respectively. According to the high-temperature XRD data, this process is accompanied by an assumed deformation of crystal structures and subsequent solid-phase decomposition to hematite and warwickite. It is seen as a monotonic decrease of volume thermal expansion coefficients with an increase in temperature. A partial magnetic ordering in hulsite is observed for the first time with T c ≃ 383 K. Near this temperature, an unusual change of thermal expansion coefficients is revealed. Vonsenite starts to melt at 1571 K and hulsite melts at 1504 K. Eigenvalues of thermal expansion tensor are calculated for the oxoborates as well as anisotropy of the expansion is described in comparison with their crystal structures.

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Synthesis and thermal behavior of Fe3O2(BO4) oxoborate

Cited by 11 publications

References 9 publications

Anisotropic thermal expansion and electronic transitions in the Co₃BO₅ ludwigite

Anisotropic thermal expansion and electronic transitions in the Co₃BO₅ ludwigite

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

Investigation of thermal behavior of mixed-valent iron borates vonsenite and hulsite containing [OM₄]ⁿ⁺and [OM₅]ⁿ⁺oxocentred polyhedra byin situhigh-temperature Mössbauer spectroscopy, X-ray diffraction and thermal analysis

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Synthesis and thermal behavior of Fe3O2(BO4) oxoborate

Cited by 11 publications

References 9 publications

Anisotropic thermal expansion and electronic transitions in the Co3BO5 ludwigite

Anisotropic thermal expansion and electronic transitions in the Co3BO5 ludwigite

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

Investigation of thermal behavior of mixed-valent iron borates vonsenite and hulsite containing [OM4]n+and [OM5]n+oxocentred polyhedra byin situhigh-temperature Mössbauer spectroscopy, X-ray diffraction and thermal analysis

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Anisotropic thermal expansion and electronic transitions in the Co₃BO₅ ludwigite

Anisotropic thermal expansion and electronic transitions in the Co₃BO₅ ludwigite

Investigation of thermal behavior of mixed-valent iron borates vonsenite and hulsite containing [OM₄]ⁿ⁺and [OM₅]ⁿ⁺oxocentred polyhedra byin situhigh-temperature Mössbauer spectroscopy, X-ray diffraction and thermal analysis