The paper presents the results of the studies of a matrix based on borophosphate glass (BFS) with the addition of lithium chloride as a simulator of spent electrolyte, a type of radioactive waste formed during the pyrochemical processing of spent nuclear fuel. Based on the results of X-ray phase analysis and scanning electron microscopy, the phase composition and microstructure of the glasses were evaluated – the amorphous structure and homogeneity of the obtained material were confirmed. Using differential scanning calorimetry and thermal conductivity measurements, the thermophysical properties of the material are described, and it is shown that the inclusion of LiCl does not affect the glass transition temperature for the obtained glasses which equals ~410 ?C. However, the addition of lithium chloride affects the electrical conductivity properties studied by electrochemical impedance spectroscopy. Tests of mechanical strength and hydrolytic stability were carried out in accordance with the established requirements for the matrices for immobilization of radioactive waste. When studying the morphology of the glass surface in contact with water, the formation of a diffusion layer is observed as a result of the transition of sodium ions into a solution.
The performed studies confirm the possibility of using glasses of the selected composition as a matrix for immobilization of the spent electrolyte based on lithium chloride.
Maxim I. Vlasov – PhD (Physical and Mathematical Sciences), Head of the Laboratory for High-Temperature Electrochemistry of Actinides and Rare-Earth Metals, Institute of High-Temperature Electrochemistry of the Ural Branch of the Russian Academy of Sciences, Yekaterinburg, Russia
Elizaveta D. Vedernikova – engineer of the Laboratory of High-Temperature Electrochemistry of Actinides and Rare Earth Metals, Institute of High-Temperature Electrochemistry of the Ural Branch of the Russian Academy of Sciences, Yekaterinburg, Russia
Svetlana V. Pershina – PhD (Chemical Sciences), senior scientist, Laboratory for Chemical Power Sources, Institute of High-Temperature Electrochemistry of the Ural Branch of the Russian Academy of Sciences, Yekaterinburg, Russia
Victor A. Bykov – PhD (Physical and Mathematical Sciences), senior scientist, Laboratory for Disordered Systems, Institute of Metallurgy of the Ural Branch of the Russian Academy of Sciences, Yekaterinburg, Russia
Matvey D. Kisel – laboratory assistant at the Laboratory of High-Temperature Electrochemistry of Actinides and Rare Earth Metals, Institute of High-Temperature Electrochemistry of the Ural Branch of the Russian Academy of Sciences, Yekaterinburg, Russia
Dmitry Yu. Suntsov – Head of Department, Joint-Stock Company “A. A. Bochvar Advanced Research Institute of Inorganic Materials”, Moscow, Russia
Aleksandra I. Tuchkova – leading industrial engineer, Joint-Stock Company “A. A. Bochvar Advanced Research Institute of Inorganic Materials”, Moscow, Russia
Roman D. Demin-Geyner – first category industrial engineer, Joint-Stock Company “A. A. Bochvar Advanced Research Institute of Inorganic Materials”, Moscow, Russia
Diana S. Shtivel – industrial engineer, Joint-Stock Company “A. A. Bochvar Advanced Research Institute of Inorganic Materials”, Moscow, Russia
Alina A. Lavrentyeva – second category industrial engineer, Joint-Stock Company “A. A. Bochvar Advanced Research Institute of Inorganic Materials”, Moscow, Russia
1. Ojovan M. I. Vitrification as a key solution for immobilisation within nuclear waste management // Arabian Journal for Science and Engineering. 2024. URL: https://doi.org/10.1007/s13369-024-09292-z
2. Corkhill C., Hyatt N. Nuclear waste management. Bristol, IOP Publishing Ltd, 2018. 18 p. URL: https://doi.org/10.1088/978-0-7503-1638-5
3. Lee W. E., Ojovan M. I., Jantzen C. M. Radioactive waste management and contaminated site clean-up. Woodhead Publishing, 2013. 879 p.
4. Сорокин В. Т., Павлов Д. И., Кащеев В. А. и др. Научные и проектные аспекты остекловывания жидких радиоактивных отходов АЭС с ВВЭР-1200 // Радиоактивные отходы. 2020. № 2(11). С. 56 – 65. DOI: 10.25283/2587-9707-2020-2-56-65
5. Ojovan M. I., Batyukhnova O. G. Glasses for nuclear waste immobilization. WM’07 Conference, February 25 – March 1, 2007, Tucson, AZ.
6. Ojovan M. I., Lee W. E. Glassy wasteforms for nuclear waste immobilization // Metallurgical and Materials Transactions A. 2011. No. 42A. Р. 837 – 851. DOI: 10.1007/s11661-010-0525-7
7. Стефановский С. В., Стефановская О. И., Семенова Д. В. Фазовый состав и структура стекломатериалов на натрий-алюмофосфатной основе, содержащих оксиды редкоземельных элементов // Радиоактивные отходы. 2018. № 1(2). С. 97 – 101.
8. Vavilov S., Kobayashi T., Myochin M. Principle and test experience of the RIAR’s oxide pyro-process // Journal of Nuclear Science and Technology. 2004. V. 41, No. 10. Р. 1018 – 1025.
9. Choi E.-Y., Jeong S. M. Electrochemical processing of spent nuclear fuels // An overview of oxide reduction in pyroprocessing technology. Progress in Natural Science: Materials International. 2015. No. 25. Р. 572 – 582. URL: http://dx.doi.org/10.1016/j.pnsc.2015.11.001
10. Park H.-S., Cho I.-H., Eun H. C., Kim I.-T., et al. Characteristics of wasteform composing of phosphate and silicate to immobilize radioactive waste salts // Environmental Science & Technology. 2011. No. 45(5). Р. 1932 – 1939. DOI: 10.1021/es1029975
11. Frolova A. V., Belova K. Y., Vinokurov S. E. Medium-temperature glass-composite phosphate materials for the immobilization of chloride radioactive waste // Journal of Composites Science. 2023. No. 7(9). Р. 363. URL: https://doi.org/10.3390/jcs7090363
12. Riley B. J., Peterson J. A., Kroll J. O., Frank S. M. Immobilization of LiCl–Li2O pyroprocessing salt wastes in chlorosodalite using glass-bonded hydrothermal and salt-occlusion methods // Journal of Nuclear Materials. 2018. No. 502. P. 236 – 246. DOI: 10.1016/j.jnucmat.2018.02.005
13. Белова К. Ю., Куликова С. А., Винокуров С. Е. и др. Иммобилизация хлоридных отходов от пирохимической переработки ОЯТ с использованием магний-калий-фосфатной матрицы // Успехи в химии и химической технологии. 2019. Т. 33, № 1. C. 36–37.
14. Riley B. J., Kroll J. O., Peterson J. A., et al. Assessment of lead tellurite glass for immobilizing electrochemical salt wastes from used nuclear fuel reprocessing // Journal of Nuclear Materials. 2017. No. 495. P. 405 – 420. URL: https://doi.org/10.1016/j.jnucmat.2017.08.037
15. Lavrinovich Yu. G., Kuzin M. A., Kormilitsyn M. V., et al. Combined vitrification of chloride and phosphate wastes by pyroelectrochemical reprocessing of nuclear fuel // Atomic Energy. 2006. V. 101, No. 6. P. 894 – 896.
16. Riley B. J., Peterson J. A., Vienna J. D., et al. Dehalogenation of electrochemical processing salt simulants with ammonium phosphates and immobilization of salt cations in an iron phosphate glass waste form // Journal of Nuclear Materials. 2020. No. 529. P. 151949.
17. Donald I. W., Metcalfe B. L., Fong S. K., et al. A glass-encapsulated calcium phosphate wasteform for the immobilization of actinide-, fluoride-, and chloride-containing radioactive wastes from the pyrochemical reprocessing of plutonium metal // Journal of Nuclear Materials. 2007. No. 361(1). P. 78 – 93. URL: https://doi.org/10.1016/j.jnucmat.2006.11.011
18. Мусатов Н. Д., Кащеев В. А., Тучкова А. И., Смелова Т. В. Анализ возможных методов увеличения степени включения хлорсодержащих РАО в матричный материал // Вопросы атомной науки и техники. Сер. Материаловедение и новые материалы. 2020. № 1(102). C. 66 – 75.
19. Szumera M. Structural investigations of silicate–phosphate glasses containing MoO3 by FTIR, Raman and 31P MAS NMR spectroscopies // Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy. 2014. No. 130. P. 1 – 6. URL: https://doi.org/10.1016/j.saa.2014.03.052
20. Вашман А. А., Демин А. В., Крылова Н. В. и др. Фосфатные стекла с радиоактивными отходами / под ред. Вашмана А. А., Полякова А. С. М.: ЦНИИатоминформ, 1997. 172 с.
21. Сунцов Д. Ю., Шестопёров И. Н., Богданов А. И. и др. Разработка макета опытно-промышленной установки для остекловывания ВАО // Вопросы атомной науки и техники. Сер. Материаловедение и новые материалы. 2018. № 4(95). С. 71 – 81.
22. Freitas A. M., Bell M. J. V., Anjos V., et al. Thermal analyzes of phosphate glasses doped with Yb3+ and ZnTe Nanocrystals // Journal of Luminescence. 2016. No. 169A. P. 353 – 358. URL: https://doi.org/10.1016/j.jlumin.2015.08.062
23. Hofmeister A. Whittington. Thermal diffusivity and conductivity of glasses and melts // Encyclopedia of Glass Science, Technology, History, and Culture. V. I, First Edition. John Wiley & Sons, 2021. P. 487 – 500. URL: https://doi.org/10.1002/9781118801017.ch4.5
24. Habasaki J., Ngai K. L. The mixed alkali effect in ionically conducting glasses revisited: A study by molecular dynamics simulation // Physical Chemistry Chemical Physics. 2007. No. 9(33). P. 4673. DOI: 10.1039/b704014h
25. Wilkinson C. J., Potter A. R., Welch R. S. Topological origins of the mixed alkali effect in glass // The Journal of Physical Chemistry B. 2019. No. 123. Р. 7482 – 7489. DOI: 10.1021/acs.jpcb.9b06512
26. Maji B. K., Jena H., Asuvathraman R. Electrical conductivity and glass transition temperature (Tg) measurements on some selected glasses used for nuclear waste immobilization // Journal of Non-Crystalline Solids. 2016. No. 434. P. 102 – 107. DOI: 10.1016/j.jnoncrysol.2015.12
27. Jlassi I., Sdiri N., Elhouichet H., Ferid M. Raman and impedance spectroscopy methods of P2O5–Li2 O–Al2O3 glass system doped with MgO // Journal of Alloys and Compounds. 2015. No. 645. P. 125 – 130. DOI: 10.1016/j.jallcom.2015.05.025
28. Bih L. Electronic and ionic conductivity of glasses inside the Li2O–MoO3–P2O5 system // Solid State Ionics. 2000. No. 132(1–2). Р. 71 – 85. DOI: 10.1016/s0167-2738(00)00697-4
29. Mogu?-Milankovi? A. ?anti?, Li?ina V., Day D. E. Dielectric behavior and impedance spectroscopy of bismuth iron phosphate glasses // Journal of Non-Crystalline Solids. 2005. No. 351(40 – 42). Р. 3235 – 3245. DOI: 10.1016/j.jnoncrysol.2005.08.011
30. Zubekhina B. Y., Burakov B. E., Ojovan M. I. Surface alteration of borosilicate and phosphate nuclear waste glasses by hydration and irradiation // Challenges. 2020. No. 11(2). P. 14. DOI: 10.3390/challe11020014
31. Bing-Fu Z., Clark D. E., Hench L. L., Wicks G. G. Leaching behavior of nuclear waste glass heterogeneities // Journal of Non-Crystalline Solids. 1986. No. 80(1 – 3). Р. 324 – 334. DOI: 10.1016/0022-3093(86)90414-x
32. Feng X., Cunnane J. C., Bates J. K. A literature review of surface alteration layer effects on waste glass behavior // Chemical Technology Division Argonne National Laboratory, IL 60439.
The article can be purchased
electronic!
PDF format
700
DOI: 10.14489/glc.2025.01.pp.003-016
Article type:
Research Article
Make a request
