vuzbiochemiИзвестия вузов. Прикладная химия и биотехнологияProceedings of Universities. Applied Chemistry and Biotechnology2227-29252500-1558ИРНИТУ10.21285/2227-2925-2020-10-1-6-13vuzbiochemi-322Research ArticleХИМИЧЕСКИЕ НАУКИCHEMICAL SCIENCESОсобенности синтеза три- и тетрабората лития в субсолидусной областиAspects of lithium tri- and tetraborate synthesis in the subsolidus regionМамонтоваС. Г.MamontovaS. G.

Мамонтова Светлана Григорьевна - кандидат геолого-минералогических наук, научный сотрудник.

664033, Иркутск, ул. Фаворского, 1а.

Svetlana G. Mamontova - Сand. Sci. (Geology and Mineralogy), Researcher, A.P. Vinogradov Institute of Geochemistry SB RAS.

1а Favorsky St., Irkutsk 664033.

svelta@igc.irk.ruДергинA. А.DerginA. A.

Дергин Александр Александрович – аспирант.

664033, Иркутск, ул. Фаворского, 1а.

Alexander A. Dergin - Postgraduate Student, A.P. Vinogradov Institute of Geochemistry SB RAS.

1а Favorsky St., Irkutsk 664033.

dergin@igc.irk.ruНепомнящихА. И.NepomnyashchikhA. I.

Непомнящих Александр Иосифович - доктор физико-математических наук, профессор, главный научный сотрудник.

664033, Иркутск, ул. Фаворского, 1а.

Alexander I. Nepomnyashchikh - Dr. Sci. (Physics and Mathematics), Chief Researcher A.P. Vinogradov Institute of Geochemistry SB RAS.

1а Favorsky St., Irkutsk 664033.

ainep@igc.irk.ruКаневаЕ. В.KanevaE. V.

Канева Екатерина Владимировна - кандидат геолого-минералогических наук, старший научный сотрудник.

664033, Иркутск, ул. Фаворского, 1а.

Ekaterina V. Kaneva - Сand. Sci. (Geology and Mineralogy), Senior Researcher, A.P. Vinogradov Institute of Geochemistry SB RAS.

1а Favorsky St., Irkutsk 664033.

kaneva@igc.irk.ruИнститут геохимии им. А.П. Виноградова СО РАНРоссияA.P. Vinogradov Institute of Geochemistry SB RASRussian Federation202031032020101613Copyright © Мамонтова С.Г., Дергин A.А., Непомнящих А.И., Канева Е.В., 20202020Мамонтова С.Г., Дергин A.А., Непомнящих А.И., Канева Е.В.Mamontova S.G., Dergin A.A., Nepomnyashchikh A.I., Kaneva E.V.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://vuzbiochemi.elpub.ru/jour/article/view/322

Целью работы являлось исследование закономерностей преобразования кристаллической структуры фаз, образующихся в процессе синтеза поликристаллических три- и тетрабората лития. В области существования трибората лития (LiB3O5) и тетрабората лития (Li2B4O7) системы Li2O – B2O3 синтезированы поликристаллические порошки LiB3O5 и Li2B4O7. В качестве исходных реактивов выбраны карбонат лития (Li2CO3) и борная кислота (H3BO3). Опробованы два способа синтеза: осаждение из раствора и твердофазный синтез. Показано, что оптимальным вариантом кристаллизации LiB3O5 и Li2B4O7 является непосредственное спекание механически измельченной стехиометрической смеси исходных веществ. Специфика кристаллизации боратов лития исследовалась в температурном интервале от 500 до 850 °C. Пробоотбор проводился через каждые 50 °C.

Установлены частные фазовые портреты, то есть совокупность характеристик процесса в зависимости от уровня организации частиц вещества, субсолидусной кристаллизации из исходной смеси реагентов три- и тетрабората лития на фазовом, локальном и структурном уровнях. На фазовом уровне в смеси со стехиометрией трибората лития максимум преобразования кристаллических фаз наблюдается в области 500–600 °C, для тетрабората лития температурный максимум находится в диапазоне 600–700 °C. Последовательность фазовых преобразований при этом остается практически неизменной и происходит по схеме: исходные вещества – промежуточные мета-стабильные фазы – конечные бораты. Локальный уровень фазовых портретов характеризует взаимодействие координационных полиэдров, образующих кристаллическую решетку исследованных фаз: твердофазный синтез кристаллического LiB3O5 из исходных Li2CO3 и H3BO3 происходит за счет перехода (BO3)3- → (B3O7)5-, а при получении Li2B4O7 реализуется схема (BO3)3- → (B4O9)6-. На уровне кристаллической структуры таким переходам соответствуют преобразования моноклинной решетки первичных фаз Li2CO3 и H3BO3 в ромбическую и тетрагональную структуру LiB3O5 и Li2B4O7 соответственно. Промежуточной ступенью такого преобразования являются тригональный цепочечный метаборат LiBO2 и метастабильный Li2B8O13.

The present work is focused at studying the transformation patterns for the crystalline structure of phases formed during the synthesis of polycrystalline lithium tri- and tetraborate. In the field of lithium triborate (LiB3O5) and tetraborate (Li2B4O7) of the Li2O – B2O3 system, LiB3O5 and Li2B4O7 polycrystalline powders were synthesised.

In terms of precursors, lithium carbonate (Li2CO3) and boric acid (H3BO3) were selected. Two synthesis methods were tested including precipitation from solution and solid-phase synthesis. As a result, the direct sintering of a mechanically-grinded stoichiometric precursor mixture is shown to be the optimal method for crystallising LiB3O5 and Li2B4O7. The crystallisation patterns of lithium borates were studied in a temperature range of 500-850 °C with sampling carried out every 50 °C. Individual phase portraits were established presenting a set of process character-istics depending on the level of substance particle organisation and subsolidus crystallisation from the initial reagent mixture of lithium tri- and tetraborate at the phase, local and structural levels. In a lithium triborate stoichiometric mixture, the maximum conversion of crystalline phases is observed in the region of 500–600 °C, while, for lithium tetraborate, the temperature maximum is in the range of 600–700 °C. The sequence of phase transformations re-mains almost unchanged and occurs according to the following scheme: starting reagents > intermediate metastable phases > final borates. The local level of phase portraits characterises the interaction of coordination polyhedra forming the crystal lattice of the studied phases. Solid-phase synthesis of crystalline LiB3O5 from the Li2CO3 and H3BO3 takes place as a result of (BO3)3- → (B3O7)5- transition with the (BO3)3- → (B4O9)6- scheme realised in obtaining Li2B4O7. At the crystal structure level, such transitions correspond to transformations of the monoclinic lattice of the Li2CO3 and H3BO3 primary phases into the LiB3O5 and Li2B4O7 rhombic and tetragonal structure, respectively.

In this case, an intermediate step of this transformation consists in formation of the LiBO2 trigonal chain metaborate and metastable Li2B8O13.

синтез боратовтриборат литиятетраборат литиясистема Li2O – B2O3твердофазный синтезфазовый портрет кристаллизацииborate synthesislithium triboratelithium tetraborateLi2O – B2O3 systemsolid-phase synthesisphase portrait of crystallizationПриведенные в работе данные получены на оборудовании ЦКП «Изотопно-геохимических исследований» Института геохимии им. А.П. Виноградова СО РАН. Исследование проведено в рамках выполнения государственного задания по проекту IX.25.3.2. «Кристаллические и аморфные функциональные материалы с прогнозируемыми свойствами» (0350-2019-0002).The data presented were obtained using the equipment of the Centre for Collective Use “Isotope Geochemical Research”, SB RAS. The study was carried out as a part of the State assignment IX.25.3.2 “Crystal and amorphous functional materials with predictable properties” (0350-2019-0002).ReferencesAnjaiah J., Laxmikanth C., Veeraiah N., Kristaiah P. Luminescence properties of Pr3+ doped Li2O– MO–B2O3 glasses // Journal of Luminescence. 2015. Vol. 161. P. 147–153. https://doi.org/10.1016/j.jlumin.2015.01.007Anjaiah J, Laxmikanth C, Veeraiah N, Kristaiah P. Luminescence properties of Pr3+ doped Li2O–MO– B2O3 glasses. Journal of Luminescence. 2015; 161:147–153. https://doi.org/10.1016/j.jlumin.2015.01.007Pawar P.P., Munishwar S.R., Gedam R.S. Intense white light luminescent Dy3+ doped lithium borate glasses for W-LED: A correlation between physical, thermal, structural and optical properties // Solid State Sciences. 2017. Vol. 64. P. 41–50. https://doi.org/10.1016/j.solidstatesciences.2016.12.009Pawar PP, Munishwar SR, Gedam RS. Intense white light luminescent Dy3+ doped lithium borate glasses for W-LED: A correlation between physical, thermal, structural and optical properties. Solid State Sciences. 2017;64:41–50. https://doi.org/10.1016/j.solidstatesciences.2016.12.009Laorodphan N., Kidkhunthod P., Khajonrit J., Montreeuppathum A., Chanlek N., Pinitsoontorn S., et al. Effect of B2O3 content on structure-function of vanadium‑lithium-borate glasses probed by synchrotron-based XAS and vibrating sample magnetrometry technique // Journal of Non-Crystalline Solids. 2018. Vol. 497. P. 56–62. https://doi.org/10.1016/j.jnoncrysol.2018.04.045Laorodphan N, Kidkhunthod P, Khajonrit J, Montreeuppathum A, Chanlek N, Pinitsoontorn S, et al. Effect of B2O3 content on structure-function of vanadium‑lithium-borate glasses probed by synchrotron-based XAS and vibrating sample magnetrometry technique. Journal of Non-Crystalline Solids. 2018; 497:56–62. https://doi.org/10.1016/j.jnoncrysol.2018.04.045Saidu A., Wagiran H., Saeed M.A., Obayes H.K., Bala A., Usman F. Thermoluminescence response of rare earth activated zinc lithium borate glass // Radiation Physics and Chemistry. 2018. Vol. 144. P. 413–418. https://doi.org/10.1016/j.radphyschem.2017.10.004Saidu A, Wagiran H, Saeed MA, Obayes HK, Bala A, Usman F. Thermoluminescence response of rare earth activated zinc lithium borate glass. Radiation Physics and Chemistry. 2018;144:413–418. https://doi.org/10.1016/j.radphyschem.2017.10.004Neumair S.C., Vanicek S., Wurst K., Huppertz H., Kaindl R., Többens D.M. High-pressure synthesis and crystal structure of the lithium borate HP-LiB3O5 // Journal of Solid State Chemistry. 2011. Vol. 184. Issue 9. P. 2490–2497. https://doi.org/10.1016/j.jssc.2011.07.011Neumair SC, Vanicek S, Wurst K, Huppertz H, Kaindl R, Többens DM. High-pressure synthesis and crystal structure of the lithium borate HP-LiB3O5. Journal of Solid State Chemistry. 2011; Vol. 184(9):2490–2497. https://doi.org/10.1016/j.jssc.2011.07.011Sanyal B., Goswami M., Shobha S., Prakasan V., Chawla S.P., Krishnan M., et al. Synthesis and characterization of Dy3+ doped lithium borate glass for thermoluminescence dosimetry // Journal of Non-Crystalline Solids. 2017. Vol. 475. P. 184– 189. https://doi.org/10.1016/j.jnoncrysol.2017.09.016Sanyal B, Goswami M, Shobha S, Prakasan V, Chawla SP, Krishnan M, et al. Synthesis and characterization of Dy3+ doped lithium borate glass for thermoluminescence dosimetry. Journal of Non-Crystalline Solids. 2017;475:184–189. https://doi.org/10.1016/j.jnoncrysol.2017.09.016Ramteke D.D., Ganvira V.Y., Munishwar S.R., Gedam R.S. Concentration Effect of Sm3+ Ions on Structural and Luminescence Properties of Lithium Borate Glasses // Physics Procedia. 2015. Vol. 76. P. 25–30. https://doi.org/10.1016/j.phpro.2015.10.005Ramteke DD, Ganvira VY, Munishwar SR, Gedam RS. Concentration Effect of Sm3+ Ions on Structural and Luminescence Properties of Lithium Borate Glasses. Physics Procedia. 2015;76:25–30. https://doi.org/10.1016/j.phpro.2015.10.005Kindrat I.I., Padlyak B.V., Drzewiecki A. Luminescence properties of the Sm-doped borate glasses // Journal of Luminescence. 2015. Vol. 166. P. 264–275. https://doi.org/10.1016/j.jlumin.2015.05.051Kindrat II, Padlyak BV, Drzewiecki A. Luminescence properties of the Sm-doped borate glass-es. Journal of Luminescence. 2015;166:264–275. https://doi.org/10.1016/j.jlumin.2015.05.051Mhareb M.H.A., Hashim S., Ghoshal S.K., Alajerami Y.S.M., Bqoor M.J., Hamdan A.I., et al. Effect of Dy2O3 impurities on the physical, optical and thermoluminescence properties of lithium borate glass // Journal of Luminescence. 2016. Vol. 177. P. 366–372. https://doi.org/10.1016/j.jlumin.2016.05.002Mhareb MHA, Hashim S, Ghoshal SK, Alajerami YSM, Bqoor MJ, Hamdan AI, et al. Effect of Dy2O3 impurities on the physical, optical and thermoluminescence properties of lithium borate glass. Journal of Luminescence. 2016;177:366–372. https://doi.org/10.1016/j.jlumin.2016.05.002Danilyuk P.S., Volovich P.N., Rizak V.M., Puga P.P., Gomonai A.I., Krasilinets V.N. X-ray luminescence and spectroscopic characteristics of Er3+ ions in a glassy lithium tetraborate matrix // Optics and Spectroscopy. 2015. Vol. 118. Issue 6. P. 924–929. https://doi.org/10.1134/S0030400X15060089Danilyuk PS, Volovich PN, Rizak VM, Puga PP, Gomonai AI, Krasilinets VN. X-ray luminescence and spectroscopic characteristics of Er3+ ions in a glassy lithium tetraborate matrix. Optics and Spectroscopy. 2015;118(6):924–929. https://doi.org/10.1134/S0030400X15060089Rimbach A.C., Steudel F., Ahrens B., Schweizer S. Tb3+, Eu3+, and Dy3+ doped lithium borate and lithium aluminoborate glass: Glass properties and photoluminescence quantum efficiency // Journal of Non-Crystalline Solids. 2018. Vol. 499. P. 380–386. https://doi.org/10.1016/j.jnoncrysol.2018.07.029Rimbach AC, Steudel F, Ahrens B, Schweizer S. Tb3+, Eu3+, and Dy3+ doped lithium borate and lithium aluminoborate glass: Glass properties and photoluminescence quantum efficiency. Journal of Non-Crystalline Solids. 2018;499:380–386. https://doi.org/10.1016/j.jnoncrysol.2018.07.029Bødker M.S., Mauro J.C., Youngman R.E., Smedskjaer M.M. Statistical mechanical modeling of borate glass structure and topology: prediction of superstructural units and glass transition temperature // Journal of physical chemistry b: biophysical chemistry, biomaterials, liquids, and soft matter. 2019. Vol. 123. Issue 5. P. 1206–1213. https://doi.org/10.1021/acs.jpcb.8b11926Bødker MS, Mauro JC, Youngman RE, Smedskjaer MM. Statistical mechanical modeling of borate glass structure and topology: prediction of superstructural units and glass transition temperature. Journal of physical chemistry b: biophysical chemistry, biomaterials, liquids, and soft matter. 2019;123(5):1206–1213. https://doi.org/10.1021/acs.jpcb.8b11926Rollet A.P., Bouaziz R. The binary system: lithium oxide-boric anhydride // Comptes Rendus de l'Académie des Sciences. 1955. Vol. 240. Issue 25. P. 2417–2419.Rollet AP, Bouaziz R. The binary system: lithium oxide-boric anhydride. Comptes Rendus de l'Academie des Sciences. 1955;240(25):2417–2419.Sastry B.S.R., Hummel F.A. Studies in Lithium Oxide Systems: I, Li2O-B2O3 // Journal of the American Ceramic Society. 1958. Vol. 41. Issue 1. P. 7–17. https://doi.org/10.1111/j.11512916.1958.tb13496.xSastry BSR, Hummel FA. Studies in Lithium Oxide Systems: I, Li2O-B2O3. Journal of the American Ceramic Society. 1958;41(1):7–17. https://doi.org/10.1111/j.1151-2916.1958.tb13496.xМешалкин А.Б. Исследование фазовых равновесий и оценка термодинамических свойств расплавов в бинарных боратных системах // Теплофизика и аэромеханика. 2005. Т 12. N 4. С. 669–684.Meshalkin AB. Investigation of phase equilibria and assessment of thermodynamic properties of melts in binary borate systems. Teplofizika i aeromekhanika = Thermophysics and Aeromechanics. 2005;12(4):669–684. (In Russian)Воронько Ю.К., Соболь А.А., Шукшин В.Е. Исследование фазовых превращений в LiB3O5 и Li2B4O7 при нагревании и плавлении методом спектроскопии комбинационного рассеяния света // Неорганические материалы. 2013. Т. 49. N 9. С. 991–997. https://doi.org/10.7868/S0002337X13090200Voron'ko YuK, Sobol' AA, Shukshin VE. Investigation of phase transformations in LiB3O5 and Li2B4O7 during heating and melting by Raman spectroscopy. Neorganicheskie materialy = Inorganic Materials. 2013;49(9):991–997. (In Russian) https://doi.org/10.7868/S0002337X13090200Bazarova Zh.G., Nepomnyashchikh A.I., Kozlov A.A., Bogdan-Kurilo V.D., Bazarov B.G., Subanakov A.K., et al. Phase Equilibria in the Sys-tem Li2O–MgO–B2O3 // Russian Journal of Inorganic Chemistry. 2007. Vol. 52. Issue 12. P. 1971–1973. https://doi.org/10.1134/S003602360712025XBazarova ZhG, Nepomnyashchikh AI, Ko-zlov AA, Bogdan-Kurilo VD, Bazarov BG, Subanakov AK, et al. Phase Equilibria in the System Li2O– MgO–B2O3. Russian Journal of Inorganic Chemistry. 2007;52(12):1971–1973. https://doi.org/10.1134/S003602360712025XDepci T., Özbayoğlu G., Yilmaz A. The effect of different starting materials on the synthesis of lithium triborate // Physicochemical Problems of Mineral Processing. 2007. Vol. 41. P. 101–105.Depci T, Özbayoğlu G, Yilmaz A. The effect of different starting materials on the synthesis of lithium triborate. Physicochemical Problems of Mineral Processing. 2007;41:101–105.Mikhailov M.A., Mamontova S.G., Zelentcov S.Z., Demina T.V., Belozerova O.Yu., Bogdanova L.A. On the Coexistence of Chemically Similar Stable and Metastable Phases in the BeO–MgO–Al2O3– SiO2 System // Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques. 2018. Vol. 12. Issue 4. P. 756–760. https://doi.org/10.1134/S1027451018040328Mikhailov MA, Mamontova SG, Zelentcov SZ, Demina TV, Belozerova OYu, Bogdanova LA. On the Coexistence of Chemically Similar Stable and Metastable Phases in the BeO–MgO–Al2O3– SiO2 System. Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques. 2018;12(4): 756–760. https://doi.org/10.1134/S1027451018040328Gorelik V.S., Vdovin A.V., Moiseenko V.N. Raman and hyperrayleigh scattering in lithium tetraborate crystals // Journal of Russian Laser Research. 2003. Vol. 24. Number 6. P. 553–605. https://doi.org/10.1023/B:JORR.0000004168.99752.0eGorelik VS, Vdovin AV, Moiseenko VN. Raman and hyperrayleigh scattering in lithium tetraborate crystals. Journal of Russian Laser Research. 2003;24(6):553–605. https://doi.org/10.1023/B:JORR.0000004168.99752.0e

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