Iron oxidation state and coordination, and hydrolytic durability of sodium-aluminum iron phosphate glasses

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• 作者：I.S. Glazkova^a ; S.N. Kalmykov^a ; ^c ; I.A. Presniakov^a ; A.V. Sobolev^a ; O.I. Stefanovsky^b ; S.V. Stefanovsky^b ; ^{serge.stefanovsky@yandex.ru} ; S.E. Vinokurov^c ; B.F. Myasoedov^b ; ^c
• 关键词：Iron ; Fourier Transform Infrared spectroscopy ; Hydrolytic durability ; Mö ; ssbauer spectroscopy ; Sodium-aluminum iron phosphate glass ; Raman spectroscopy
• 刊名：Progress in Nuclear Energy
• 出版年：2017
• 出版时间：January 2017
• 年：2017
• 卷：94
• 期：Complete
• 页码：235-239
• 全文大小：1064 K
• 卷排序：94

文摘

The structure of anionic motif, oxidation state and coordination of iron in the series of glasses (mol.%): 40 Na2O, (20-x) Al2O3, x Fe2O3, 40 P2O5 considered as matrices for immobilization of high Fe/Al legacy high level waste were determined by FTIR, Raman and Mössbauer study. The glass network is built from ortho- and pyrophosphate units linked by aluminum-oxygen and iron-oxygen polyhedra. Iron in all the glasses was present as primarily octahedrally coordinated Fe(III) and Fe(II). Fe(III) content in the glasses increased with the increase of the x value and reached ∼74% of total Fe in the glass with x = 15 while reduced to ∼67% of total Fe at x = 20. At the same time the lowest values of cumulative release from glasses into a deionized water for all the elements were found at x = 5. Thus no correlation between the Fe(III)/Fe(II) ratio and cumulative elemental release values was found and iron speciation seems to be not a key factor determining their chemical durability.