Oxidation states and structural role of iron in sodium iron aluminophosphate glass: A combined study of XAFS experiments and MD simulations

IF 3.2 3区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Journal of Non-crystalline Solids Pub Date : 2024-11-04 DOI:10.1016/j.jnoncrysol.2024.123303

Hailong Dong , Fangling Jiang , Min Qian , Tianfeng Xue , Sijun Fan , Minzhi Ruan , Zhongdi Li , Shubin Chen , Lu Deng

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Abstract

Vitrification has gained global recognition as one of the most mature techniques for solidification of high-level nuclear waste, and borosilicate glass has been widely used in various countries as the base material. However, iron aluminophosphate glass also found advantages in solidify waste forms containing high concentrations of Zr, Mo and rare earth elements. In this work, oxidation states of Fe and its structural role of sodium iron aluminophosphate glass have been investigated using X-ray absorption fine structure spectroscopy experiments and molecular dynamic simulations. Results show that both the Fe²⁺ concentration and the average phosphorus number around Fe increase with the replacement of Na by Fe; whereas, the average oxygen number around Fe decreases. Fe²⁺ ions are mainly four-coordinated, and Fe³⁺ ions are mainly five-coordinated. Moreover, additional Fe content leads to the gradual replacement of Al/P–O–P linkages by Fe²⁺–O–P linkages, resulting in the enhancement of the chemical durability of the glass.

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铁铝磷酸钠玻璃中铁的氧化态和结构作用：XAFS 实验和 MD 模拟的综合研究

作为最成熟的高水平核废料固化技术之一，玻璃固化技术已得到全球认可，各国已广泛采用硼硅酸盐玻璃作为基础材料。然而，磷酸铁铝玻璃在固化含有高浓度锆、钼和稀土元素的废物形式方面也具有优势。在这项工作中，利用 X 射线吸收精细结构光谱实验和分子动力学模拟研究了铁铝酸钠玻璃中铁的氧化态及其结构作用。结果表明，随着 Na 被 Fe 取代，Fe2+ 浓度和 Fe 周围的平均磷数都会增加；而 Fe 周围的平均氧数则会减少。Fe2+ 离子主要是四配位离子，而 Fe3+ 离子主要是五配位离子。此外，Fe 含量的增加会导致 Al/P-O-P 链接逐渐被 Fe2+-O-P 链接取代，从而提高玻璃的化学耐久性。

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来源期刊

Journal of Non-crystalline Solids 工程技术-材料科学：硅酸盐

CiteScore

6.50

自引率

11.40%

发文量

576

审稿时长

35 days

期刊介绍： The Journal of Non-Crystalline Solids publishes review articles, research papers, and Letters to the Editor on amorphous and glassy materials, including inorganic, organic, polymeric, hybrid and metallic systems. Papers on partially glassy materials, such as glass-ceramics and glass-matrix composites, and papers involving the liquid state are also included in so far as the properties of the liquid are relevant for the formation of the solid. In all cases the papers must demonstrate both novelty and importance to the field, by way of significant advances in understanding or application of non-crystalline solids; in the case of Letters, a compelling case must also be made for expedited handling.