In this work, we investigated borophosphate glasses with additions of 0.5 to 1.5 mol. % of rare-earth fluorides LnF3 (Ln = La, Ce, Nd), considered as simulants of radioactive waste from the now developing molten salt nuclear reactors. During the synthesis of the samples, it was found that even the small additions of LnF3 (?1.25 mol. % of LaF3 or NdF3, ?1.5 mol. % of CeF3) leads to formation of LnPO4 crystalline phase, which precipitated to the bottom of the crucible with the melt. This affects the ratios of the nominal and actual compositions of the glasses. Glass samples obtained from the upper, homogeneous, region of the melt exhibit an amorphous structure and a uniform distribution of the components throughout the volume. Their glass transition temperature Tg is 430 °C and remains constant over the entire range of the considered compositions; however, the introduction of LnF3 increases thermal stability and significantly changes the nature of crystallization processes. Moreover, for the samples with CeF3, the crystallization processes from that for the samples with LaF3 or NdF3, which is apparently due to the partial transition Ce3+ ? Ce4+. Analysis of the local structure indicates the presence of the ordering in the glass at the level of 2–3-coordination spheres and the invariance of phosphate groupings upon the introduction of LnF3. At the same time, with an increase in the LnF3 content, an increase in the proportion of 6-coordinated aluminum ions is detected, which is associated with the incorporation of fluoride ions into its environment. Consequently, in the environment of Ln ions, fluorine anions are replaced by oxygen, which causes the appearance of Ce4+. Based on the results of chemical and mechanical stability tests, it is shown that the glasses meet the regulatory requirements for the matrices for immobilization of radioactive wastes and can be considered as promising matrices for the incorporation of rare-earth fluorides.
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
Nikolai A. Zhuravlev – PhD (Physical and Mathematical Sciences), senior researcher at the A. L. Ivanovsky Laboratory of Quantum Chemistry and Spectroscopy, Institute of Solid State Chemistry of the Ural Branch of the Russian Academy of Sciences, Yekaterinburg, Russia
Tatiana A. Denisova – Doctor of Chemical Sciences, chief researcher at the A. L. Ivanovsky Laboratory of Quantum Chemistry and Spectroscopy, Institute of Solid State Chemistry of the Ural Branch of the Russian Academy of Sciences, Yekaterinburg, Russia
Dmitry M. Tsymbarenko – PhD (Chemical Sciences), senior researcher, Department of Inorganic Chemistry, Faculty of Chemistry, Lomonosov Moscow State University, Moscow, Russia
Dmitry Yu. Suntsov – head of department, Joint-Stock Company "Bochvar High-Technology Research Institute for Inorganic Materials", Moscow, Russia
Aleksandra I. Tuchkova – major specialist, Joint-Stock Company "Bochvar High-Technology Research Institute for Inorganic Materials", Moscow, Russia
Alina A. Trefilova – industrial engineer of 2nd category, Joint-Stock Company "Bochvar High-Technology Research Institute for Inorganic Materials", Moscow, Russia
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