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Nagelschmidtite as a candidate host phase for actinides, rare earth and different waste elements

Published online by Cambridge University Press:  17 December 2017

Sergey V. Stefanovsky ,
Olga I. Stefanovsky  and
Ivan L. Prusakov
Sergey V. Stefanovsky*
Affiliation:
Laboratory of Radioecology and Radiation Problems, Frumkin Institute of Physical Chemistry and Electrochemistry RAS, 31-4 Leninskii av., Moscow, 119071Russia
Olga I. Stefanovsky
Affiliation:
Laboratory of Radioecology and Radiation Problems, Frumkin Institute of Physical Chemistry and Electrochemistry RAS, 31-4 Leninskii av., Moscow, 119071Russia
Ivan L. Prusakov
Affiliation:
Department of Glass and Glass Ceramics, D. Mendeleev University of Chemical Technology, Miusskaya sq. 1, 125047, Russia
*
*(Email: [email protected])
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Abstract

Nagelschmidtite, Ca7P2Si2O16, is an end-member of continuous solid solution Ca2SiO4 – Ca3(PO4)2⋅2Ca2SiO4 within the pseudo-binary system Ca3(PO4)2 – Ca2SiO4 (whitlockite – larnite). This phase is capable to wide isomorphic exchanges in Ca, P and Si sites: Ca2+ = Sr2+; Ca2+ = Eu2+; Ca2+ + P5+ = (RE,An)3+ + Si4+, 2Ca2+ = Na+ + (RE,An)3+; 2Ca2+ = An4+ + ☐; Ca2+ + Si4+ = (RE,An)3+ + (Al,Fe)3+; Ca2+ + Si4+ = Na+ + P5+; 2Ca2+ = Na+ + (Al,Fe)3+; Ca2+ + P5+ = Na+ + S6+. It was found in metallurgical slags and geological formations. We revealed nagelschmidtite-type phase in vitrified phosphorus-bearing radioactive incinerator slags. The materials were glass-crystalline and contained nano-sized nagelschmidtite crystals distributed in vitreous matrix phase. Average chemical composition of the largest (few microns) crystals was recalculated to formula Na1.21K1.05Ca2.22Al2.02Fe0.46Si2.69P1.26U0.08O15.76. Significant oxygen misbalance suggests higher than U(IV) oxidation state for uranium – U(V) or U(VI). Capability of nagelschmidtite to be crystallized from melt makes it promising phase for actinides, rare earths and some other fission and corrosion products at using a melting route to nuclear waste forms including cold crucible induction melting and self-propagating high-temperature synthesis.

Keywords

actinideglassnuclear materialsceramicwaste management
Type
Articles
Information
MRS Advances , Volume 3 , Issue 20: Scientific Basis for Nuclear Waste Management XLI , 2018 , pp. 1073 - 1083
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Copyright © Materials Research Society 2017 

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