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  

Effect of Phosphomolybdic Heteropolyacid Salt Content on Structure and Leaching Resistance of Borosilicate Glass Solidified Body

作　　者：杨静泊 罗欣 陈远扬 安红娜 徐立国 吴浪[1,3] YANG Jingbo;LUO Xin;CHEN Yuanyang;AN Hongna;XU Liguo;WU Lang(School of Materials and Chemistry,Southwest University of Science and Technology,Mianyang 621010,China;Sichuan Environmental Protection and Engineering Co.,Ltd,Guangyuan 610006,China;State Key Laboratory of Environment-Friendly Energy Materials,Southwest University of Science and Technology,Mianyang 621010,China)

机构地区：[1]西南科技大学材料与化学学院,绵阳621010 [2]中核四川环保工程有限责任公司,广元610006 [3]西南科技大学环境友好能源材料国家重点实验室,绵阳621010

出　　处：《硅酸盐通报》2023年第4期1448-1457,共10页Bulletin of the Chinese Ceramic Society

基　　金：国家自然科学基金(11775182)。

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[SiO_(4)]结构逐渐解聚,[MoO_(4)]^(2-)结构逐渐增加,且[BO_(4)]、Q^(3)和Q^(4)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。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[SiO_(4)]structure in glass network structure gradually depolymerizes,the[MoO_(4)]^(2-)structure gradually increases,the content of[BO_(4)],Q^(3) and Q^(4) 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.

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 

分 类 号：TQ171.9[化学工程—玻璃工业]