CaO对硼硅酸盐玻璃钼溶解度提升机理的研究

doi:10.16552/j.cnki.issn1001-1625.2025.1037

摘要/Abstract

摘要：

高放废液中钼在玻璃中的溶解度较低，在玻璃固化过程中容易析出黄相，这不利于玻璃固化工程的安全处理处置。本文研究了不同CaO引入量对硼硅酸盐玻璃中钼的溶解能力及玻璃结构的影响，通过SEM-EDS、XRD、Raman等分析技术揭示了样品的物相组成和结构演变规律，结果表明：随着CaO质量分数增加，玻璃的宏观形貌由乳白色不透明（0%~4%）逐步过渡为趋于透明的蓝色（6%），CaO质量分数为8%时乳白色消退，10%时完全透明。微观分析表明，乳白色源于Na₂MoO₄晶体的析出，而CaO的引入显著抑制了Na₂MoO₄晶体析出，并使玻璃基体中钼的溶解度持续提升，最高可达2.8%（质量分数）。拉曼光谱进一步表明，CaO可通过解聚硅酸盐网络、促进Q³结构单元生成，为［MoO₄］^2-的容纳提供了更优化学环境。

关键词: CaO, 硼硅酸盐玻璃, 钼, 溶解度, 玻璃结构

Abstract:

The low solubility of molybdenum in borosilicate glass matrices presents a significant challenge in the vitrification of high-level liquid waste （HLLW）， as it often leads to the precipitation of the undesirable “yellow phase”， thereby compromising the safety and long-term stability of the vitrified waste form. In this study， the effect of CaO content on the molybdenum solubility and the structural evolution of borosilicate glass was investigated. A combination of analytical techniques， including SEM-EDS， XRD， and Raman spectroscopy， was employed to characterize the phase composition and microstructure of the samples. The results indicate that as the mass fraction of CaO increases， the macroscopic appearance of the glass transitions progressively from milky white and opaque （0%~4%） to transparent blue （6%）， when the mass fraction of CaO is 8%， the milky color disappears， and when the mass fraction of CaO is 10%， it is completely transparent. Microscopic analysis reveals that the milky white opacity originates from the crystallization of Na₂MoO₄， which is effectively suppressed by the addition of CaO. Correspondingly， the molybdenum solubility in the glass matrix increases consistently， reaching a maximum of 2.8% （mass fraction）. Raman spectroscopy further demonstrates that CaO modifies the glass structure by depolymerizing the silicate network and promoting the formation of Q³ units， thereby creating a more favorable chemical environment for accommodating ［MoO₄］^2- groups.

Key words: CaO, borosilicate glass, molybdenum, solubility, glass structure

中图分类号:

TQ171

焦云杰, 朱永昌, 杨德博, 崔竹, 董炫疆, 王东宇, 杜瞻远, 杨雅楠. CaO对硼硅酸盐玻璃钼溶解度提升机理的研究[J]. 硅酸盐通报, 2026, 45(3): 806-812.

JIAO Yunjie, ZHU Yongchang, YANG Debo, CUI Zhu, DONG Xuanjiang, WANG Dongyu, DU Zhanyuan, YANG Yanan. Research on Mechanism of CaO Enhancing Molybdenum Solubility in Borosilicate Glass[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(3): 806-812.

图/表 6

表1 玻璃样品组成

Table 1 Composition of glass samples

Sample No.	Mass fraction/%
Sample No.	SiO₂	B₂O₃	Al₂O₃	Na₂O	CaO	MoO₃
C0	61.1	8.9	3.3	26.7	0.0	4
C2	59.9	8.7	3.3	26.1	2.0	4
C4	58.7	8.5	3.2	25.6	4.0	4
C6	57.4	8.4	3.1	25.1	6.0	4
C8	56.2	8.2	3.1	24.5	8.0	4
C10	55.0	8.0	3.0	24.0	10.0	4

图1 不同含量CaO引入后样品的宏观照片

Fig.1 Macrograph images of samples with different CaO content

图 2 不同含量CaO引入后样品的SEM照片

Fig.2 SEM images of samples with different CaO content

图 3 不同含量CaO引入后样品中钼的溶解度

Fig.3 Molybdenum solubility in samples with different CaO content

图4 不同含量CaO引入样品的XRD谱

Fig.4 XRD patterns of samples with different CaO content

图5 不同含量CaO引入样品的归一化拉曼光谱

Fig.5 Normalized Raman spectra of samples with different CaO content

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