litosphereЛитосфераLITHOSPHERE (Russia)1681-90042500-302XA.N. Zavaritsky Institute of Geology and Geochemistry10.24930/1681-9004-2024-24-2-226-239litosphere-2057Research ArticleСтатьиArticlesОксобораты группы людвигита: минералы и перспективные материалы на их основеOxoborates of the ludwigite group: Natural and mineral-like compounds as prospective materialsБирюковЯ. П.BiryukovYa. P.

199034, г. Санкт-Петербург, наб. Макарова, 2

Yaroslav P. Biryukov

2 Makarova emb., Saint Petersburg 199034

y.p.biryukov@gmail.comЗиннатуллинА. Л.ZinnatullinA. L.

420008, г. Казань, ул. Кремлевская, 18

Almaz L. Zinnatullin

18 Kremlyovskaya st., Kazan 420008

БубноваР. С.BubnovaR. S.

199034, г. Санкт-Петербург, наб. Макарова, 2

Rimma S. Bubnova

2 Makarova emb., Saint Petersburg 199034

ВагизовФ. Г.VagizovF. G.

420008, г. Казань, ул. Кремлевская, 18

Farit G. Vagizov

18 Kremlyovskaya st., Kazan 420008

ШаблинскийА. П.ShablinskiiA. P.

199034, г. Санкт-Петербург, наб. Макарова, 2

Andrey P. Shablinskii

2 Makarova emb., Saint Petersburg 199034

ФилатовС. К.FilatovS. K.

199034, г. Санкт-Петербург, Университетская наб., 7/9

Stanislav K. Filatov

7/9 Universitetskaya emb., Saint Petersburg 199034

ПековИ. В.PekovI. V.

геологический факультет

119991, г. Москва, Ленинские горы, 1

Igor V. Pekov

Faculty of Geology

1 Leninskie Gory, Moscow 119991

Институт химии силикатов им. И.В. Гребенщикова РАНРоссияI.V. Grebenschikov Institute of Silicate Chemistry of the Russian Academy of Sciences (ISC RAS)Russian FederationКазанский федеральный университет, Институт физикиРоссияKazan Federal University, Institute of PhysicsRussian FederationСанкт-Петербургский государственный университет, Институт наук о ЗемлеРоссияSaint Petersburg State University, Institute of Earth SciencesRussian FederationМосковский государственный университет им. М.В. ЛомоносоваРоссияMoscow State UniversityRussian Federation202403052024242226239Copyright © Бирюков Я.П., Зиннатуллин А.Л., Бубнова Р.С., Вагизов Ф.Г., Шаблинский А.П., Филатов С.К., Пеков И.В., 20242024Бирюков Я.П., Зиннатуллин А.Л., Бубнова Р.С., Вагизов Ф.Г., Шаблинский А.П., Филатов С.К., Пеков И.В.Biryukov Y.P., Zinnatullin A.L., Bubnova R.S., Vagizov F.G., Shablinskii A.P., Filatov S.K., Pekov I.V.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://www.lithosphere.ru/jour/article/view/2057

Объект исследования. Природные оксобораты группы людвигита – азопроит, людвигит и вонсенит. Эмпирические формулы минералов, рассчитанные на пять атомов кислорода, имеют следующий вид: азопроит (Mg1.81Fe2+0.19)∑2.00(Fe3+0.36Ti0.26Mg0.26Al0.12)∑1.00O2(BO3), людвигит (Mg1.69Fe2+0.30Mn2+0.01)Σ2.00(Fe3+0.90Al0.07Mg0.02Sn0.01)Σ1.00O2(BO3) и вонсенит (Fe2+1.86Mg0.13)∑1.99(Fe3+0.92Mn2+0.05Sn4+0.02Al0.02)∑1.01O2(BO3). Цель. Установление взаимосвязи между составом, структурой и термическим поведением (293–1373 K) указанных минералов. Материалы и методы. Людвигит отобран из Итеньюргинского скарнового месторождения олова, вонсенит – из Титовского магнезиальноскарнового месторождения бора, азопроит – из магнезиальных скарнов щелочного массива Тажеран. Для достижения указанной цели использовались данные рентгеноструктурного анализа, энергодисперсионной рентгеновской спектроскопии, терморентгенографии, термомёссбауэровской спектроскопии и термического анализа. Результаты. Во всех исследуемых минералах прослеживается тенденция заселения позиций M(1)–M(3) низкозарядными катионами (Fe2+, Fe2.5+, Mg2+), позиции M(4) – главным образом высокозарядными (Fe3+, Al3+, Ti4+, Sn4+). Азопроит является самым тугоплавким среди исследованных минералов с Tпл > 1650 K; ввиду малого содержания Fe2+ не претерпевает твердофазного разложения во всем интервале температур исследования. Температура плавления людвигита превышает 1582 K, что обусловлено высоким содержанием Mg; в результате окисления Fe2+ → Fe3+ поэтапно разлагается на гематит, варвикит и магнетит. В Fe2+-обогащенном вонсените температуры процессов окисления и твердофазного разложения примерно на 100 K ниже, чем в людвигите. Температура плавления вонсенита – 1571 K. Для всех минералов характерна слабая степень анизотропии расширения. Основной вклад в анизотропию расширения обусловлен предпочтительной ориентировкой треугольников [BO3]3–. Выводы. Термические свойства исследованных оксоборатов коррелируют с их химическим составом. Выявлена тенденция возрастания с увеличением содержания Mg и Ti4+ и уменьшения Tпл с увеличением содержания Fe2+. Окисление Fe2+ → Fe3+ в случае содержания FeO-компоненты в минералах более 10 мас. % приводит к поэтапному твердофазному разложению, начинающемуся при температурах 500–600 K. Значения объемного коэффициента термического расширения 293KαV людвигита и азопроита сопоставимы, вонсенита – наибольшие, что связано с наибольшими значениями средних длин связей, главным образом <Fe2+–O>6. 

Research subject. Natural oxoborates of the ludwigite group, including azoproite, ludwigite, and vonsenite. Their empirical formulas based on five oxygen atoms have the following form: azoproite (Mg1.81Fe2+0.19)∑2.00(Fe3+0.36Ti0.26Mg0.26Al0.12)∑1.00 O2(BO3), ludwigite (Mg1.69Fe2+0.30Mn2+0.01)Σ2.00(Fe3+0.90Al0.07Mg0.02Sn0.01)Σ1.00O2(BO3) and vonsenite (Fe2+1.86Mg0.13)∑1.99 (Fe3+0.92Mn2+0.05Sn4+0.02Al0.02)∑1.01O2(BO3). Aim. To establish the relationship between the composition, crystal structure, and thermal behavior (293–1373 K) of the minerals. Materials and methods. Ludwigite was collected at the Iten’yurginskoe tin skarn deposit; vonsenite was collected at the Titovskoe magnesium-skarn boron deposit; azoproite was collected at magnesian skarns of the Tazheran alkaline massif. The methods of single crystal X-ray diffraction, energy dispersive X-ray spectroscopy, high-temperature X-ray diffraction, Mössbauer spectroscopy, and thermal analysis were used. Results. Low-charge cations (Fe2+, Fe2.5+, Mg2+) tend to occupy the M(1)–M(3) sites, and high-charge cations (Fe3+, Al3+, Ti4+, Sn4+) generally occupy the M(4) site. Azoproite is characterized by the highest melting temperature Tm > 1650 K. Due to the low Fe2+ content, azoproite does not undergo solid-phase decomposition across the investigated temperature range. The melting point of ludwigite exceeds 1582 K, which is due to the high Mg content; as a result of the Fe2+ → Fe3+ oxidation, it gradually decomposes with the formation of hematite, warwickite, and magnetite. The temperatures of oxidation and solid-phase decomposition in the Fe2+-rich vonsenite are approximately 100 K lower than those in ludwigite. The melting point of vonsenite is 1571 K. All the minerals are characterized by a weak degree of thermal expansion anisotropy. The main contribution to the thermal expansion anisotropy is due to the preferred orientation of the [BO3]3– triangles. Conclusions. The thermal properties of the oxoborates depend on their chemical composition. It was established that Tm increases with an increase in the Mg and Ti4+ content, and decreases with an increase in the Fe2+ content. The Fe2+ → Fe3+ oxidation is observed when the FeO component in the minerals exceeds 10 wt %, which leads to the solid-phase decomposition starting at temperatures of about 500–600 K. The values of the 293KαV volume thermal expansion of ludwigite and azoproite are comparable, while the largest values were observed for vonsenite. This is associated with the largest average bond lengths, primarily those of <Fe2+–O>6.

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The authors declare that there are no conflicts of interest present.