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XAFS Study of Iron and Nickel Speciation in Complex Sodium Aluminophosphate Based Glasses

Published online by Cambridge University Press:  20 February 2017

S.V. Stefanovsky*
Affiliation:
A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences, Moscow, Russia
V.Y. Murzin
Affiliation:
National Research Center “Kurchatov Institute”, Moscow, Russia
M.B. Remizov
Affiliation:
Production Association “Mayak”, Ozersk, Chelyabinsk reg., Russia
B.F. Myasoedov
Affiliation:
A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences, Moscow, Russia Vernadsky Institute of Geochemistry and Analytical Chemistry of the Russian Academy of Sciences, Moscow, Russia
*
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Abstract

Iron and nickel oxidation state and coordination in complex sodium aluminophosphate based glasses suggested as potential matrices for immobilization of legacy high level waste currently stored in stainless steel tanks at PA «Mayak» (Ural reg., Russia) were determined by X-ray absorption fine structure spectroscopy (XAFS: XANES/EXAFS). The glasses containing (wt.%) 20-30 Na2O, 6-12 Al2O3, 40-52 P2O5, 2-5 Fe2O3, 1-3 NiO, 0-6 B2O3, 10-15 other waste oxides produced by quenching of their melts were fully amorphous or contained minor Fe and Ni free phases. Fe in the glasses was found to be predominantly trivalent with an average Fe-O distance and a coordination number (CN) in the first shell of 1.94 to 1.97 Å and 5.2 to 5.8, respectively, mostly in octahedral oxygen environment. Ni is divalent in all the glasses and has in the first shell an average Ni-O distance and CN of 1.97 to 2.03 Å and 4.9 to 5.6, respectively. The first shell of both Fe and Ni is somewhat distorted. The second and further coordination shells are weakly appeared exhibiting no clustering and homogeneous distribution of Fe and Ni ions in the glass network. The data on Fe obtained are in good agreement with those from Mössbauer study of same glasses. After annealing glasses were partly devitrified and interpretation of XAFS data is strongly complicated due to Fe and Ni partitioning among crystalline and vitreous phases.

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Articles
Copyright
Copyright © Materials Research Society 2017 

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References

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