Investigation of thermal behavior of mixed-valent iron borates vonsenite and hulsite containing [OM4]n+and [OM 5] n+oxocentred polyhedra by in situ high-temperature Mössbauer spectroscopy, X-ray diffraction and thermal analysis

Standard

Investigation of thermal behavior of mixed-valent iron borates vonsenite and hulsite containing [OM₄]ⁿ⁺and [OM ₅] ⁿ⁺oxocentred polyhedra by in situ high-temperature Mössbauer spectroscopy, X-ray diffraction and thermal analysis. / Biryukov, Yaroslav P.; Zinnatullin, Almaz L.; Bubnova, Rimma S.; Vagizov, Farit G.; Shablinskii, Andrey P.; Filatov, Stanislav K.; Shilovskikh, Vladimir V.; Pekov, Igor V.

In: Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials, Vol. 76, 01.08.2020, p. 543-553.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{9ffb3624450342d583eaa87263ddb3a9,

title = "Investigation of thermal behavior of mixed-valent iron borates vonsenite and hulsite containing [OM4]n+and [OM 5] n+oxocentred polyhedra by in situ high-temperature M{\"o}ssbauer spectroscopy, X-ray diffraction and thermal analysis",

abstract = "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 M{\"o}ssbauer spectroscopy and compared with EDX and X-ray diffraction data (XRD). According to results obtained from high-temperature M{\"o}ssbauer 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. ",

keywords = "high-temperature M{\"o}ssbauer spectroscopy, high-temperature X-ray diffraction, oxidation, oxoborate, thermal expansion",

author = "Biryukov, {Yaroslav P.} and Zinnatullin, {Almaz L.} and Bubnova, {Rimma S.} and Vagizov, {Farit G.} and Shablinskii, {Andrey P.} and Filatov, {Stanislav K.} and Shilovskikh, {Vladimir V.} and Pekov, {Igor V.}",

note = "Funding Information: The X-ray diffraction experiments were performed at The Centre for X-ray Diffraction Studies (Saint Petersburg State University). The authors are grateful to Dr M. G. Krzhizha-novskaya (Institute of Earth Sciences, Department of Crystallography, Saint Petersburg State University) for conducting the high-temperature X-ray powder diffraction experiments and Dr V. L. Ugolkov (Institute of Silicate Chemistry, Russian Academy of Sciences) for conducting the thermal analysis experiments. Dr Farit G. Vagizov acknowledges the Program of Competitive Growth of Kazan Federal University funded by the Russian Government. Funding Information: The following funding is acknowledged: Russian Foundation for Basic Research (RFBR) (grant No. 18-33-00644 to Yaro-slav P. Biryukov, Almaz L. Zinnatullin, Institute of Silicate Chemistry of the Russian Academy of Sciences). Publisher Copyright: {\textcopyright} 2020 International Union of Crystallography. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.",

year = "2020",

month = aug,

day = "1",

doi = "10.1107/S2052520620006538",

language = "English",

volume = "76",

pages = "543--553",

journal = "Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials",

issn = "2052-5192",

publisher = "International Union of Crystallography",

}

RIS

TY - JOUR

T1 - Investigation of thermal behavior of mixed-valent iron borates vonsenite and hulsite containing [OM4]n+and [OM 5] n+oxocentred polyhedra by in situ high-temperature Mössbauer spectroscopy, X-ray diffraction and thermal analysis

AU - Biryukov, Yaroslav P.

AU - Zinnatullin, Almaz L.

AU - Bubnova, Rimma S.

AU - Vagizov, Farit G.

AU - Shablinskii, Andrey P.

AU - Filatov, Stanislav K.

AU - Shilovskikh, Vladimir V.

AU - Pekov, Igor V.

N1 - Funding Information: The X-ray diffraction experiments were performed at The Centre for X-ray Diffraction Studies (Saint Petersburg State University). The authors are grateful to Dr M. G. Krzhizha-novskaya (Institute of Earth Sciences, Department of Crystallography, Saint Petersburg State University) for conducting the high-temperature X-ray powder diffraction experiments and Dr V. L. Ugolkov (Institute of Silicate Chemistry, Russian Academy of Sciences) for conducting the thermal analysis experiments. Dr Farit G. Vagizov acknowledges the Program of Competitive Growth of Kazan Federal University funded by the Russian Government. Funding Information: The following funding is acknowledged: Russian Foundation for Basic Research (RFBR) (grant No. 18-33-00644 to Yaro-slav P. Biryukov, Almaz L. Zinnatullin, Institute of Silicate Chemistry of the Russian Academy of Sciences). Publisher Copyright: © 2020 International Union of Crystallography. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/8/1

Y1 - 2020/8/1

N2 - 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.

AB - 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.

KW - high-temperature Mössbauer spectroscopy

KW - high-temperature X-ray diffraction

KW - oxidation

KW - oxoborate

KW - thermal expansion

UR - http://www.scopus.com/inward/record.url?scp=85090072384&partnerID=8YFLogxK

U2 - 10.1107/S2052520620006538

DO - 10.1107/S2052520620006538

M3 - Article

C2 - 32831273

AN - SCOPUS:85090072384

VL - 76

SP - 543

EP - 553

JO - Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials

JF - Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials

SN - 2052-5192

ER -

ID: 74714719