磷钼杂多酸盐含量对硼硅酸盐玻璃固化体结构和抗浸出性能的影响

摘要/Abstract

摘要： 我国现存高放泥浆主要成分为磷钼杂多酸盐(PM),磷和钼在硼硅酸盐玻璃中溶解度较低,超过一定溶解度后会在玻璃表面产生分相从而影响玻璃化的效率和安全。本文主要研究了PM含量对硼硅酸盐玻璃固化体物相组成、微观结构和抗浸出性能的影响。结果表明,当PM掺量为0%~4%(质量分数,下同)时,样品为透明玻璃,而PM掺量高于5%时,样品为含钼酸钙和钼酸钡晶相的玻璃陶瓷。随着PM掺量从0%增加至6%,玻璃网络结构中的[SiO₄]结构逐渐解聚,[MoO₄]^2-结构逐渐增加,且[BO₄]、Q³和Q⁴结构单元含量逐渐降低,玻璃网络结构的致密程度也逐渐降低。随着PM掺量增加,Si、B和Na元素28 d归一化浸出率先降低后升高,Mo元素28 d归一化浸出率先升高后降低。

关键词: 高放泥浆, 磷钼杂多酸盐, 硼硅酸盐玻璃, 玻璃化, 固体核磁, 抗浸出性能

Abstract: The main component of existing high-level radioactive sludge in China is phosphomolybdic heteropolyacid salt. Due to the low solubility of phosphorus and molybdenum in borosilicate glass, beyond certain solubility limit, phosphomolybdic heteropolyacid salt causes phase separation on the surface of glass and affects the efficiency and safety of vitrification. In this paper, the effect of PM content on the phase composition, microstructure and leaching resistance of borosilicate glass was mainly investigated. The results show that when PM content is 0%~4% (mass fraction, the same below), the sample is transparent glass. When PM content is higher than 5%, the sample is glass ceramic containing calcium molybdate and barium molybdate phases. With the increase of PM content from 0% to 6%, the [SiO₄] structure in glass network structure gradually depolymerizes, the [MoO₄]^2-structure gradually increases, the content of [BO₄], Q³ and Q⁴ units in glass network decreases, and the compactness of glass network structure decreases. With the increase of PM content, the normalized leaching rates of Si, B and Na decrease first and then increase after 28 d, while the normalized leaching rate of Mo increases first and then decreases after 28 d.

Key words: high-level radioactive sludge, phosphomolybdic heteropolyacid salt, borosilicate glass, vitrification, solid-state NMR, leaching resistance

中图分类号:

TQ171.9

杨静泊, 罗欣, 陈远扬, 安红娜, 徐立国, 吴浪. 磷钼杂多酸盐含量对硼硅酸盐玻璃固化体结构和抗浸出性能的影响[J]. 硅酸盐通报, 2023, 42(4): 1448-1457.

YANG Jingbo, LUO Xin, CHEN Yuanyang, AN Hongna, XU Liguo, WU Lang. Effect of Phosphomolybdic Heteropolyacid Salt Content on Structure and Leaching Resistance of Borosilicate Glass Solidified Body[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(4): 1448-1457.

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