碱铝磷酸盐玻璃的近程结构及化学稳定性  

Short-Range Structure and Chemical Stability of Alkaline Aluminum Phosphate Glass

作　　者：王任乐 任进军[1,2] WANG Ren;REN Jinjun(Advanced Laser and Optoelectronic Functional Materials Department,Shanghai Institute of Optics and Fine Mechanics,Chinese Academy of Sciences,Shanghai 201800,China;Center of Materials Science and Optoelectronics Engineering,University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院上海光学精密机械研究所,先进激光与光电功能材料部,上海201800 [2]中国科学院大学材料科学与光电工程中心,北京100049

出　　处：《硅酸盐学报》2024年第12期3685-3694,共10页Journal of The Chinese Ceramic Society

基　　金：国防科工局乏燃料后处理科研专项(FKY1683ZHG001SSJSB01-001)。

摘　　要：为了揭示碱金属、玻璃结构及化学稳定性之间的内在联系,以及对未来核废料基质玻璃的发展及化学稳定性的评估,本工作通过熔融淬冷法制备了一系列不同碱金属组成的铝磷酸盐玻璃,其组成为[x Na_(2)O–y K_(2)O–(41.6–x–y)Cs_(2)O]–16.7Al_(2)O_(3)–41.7P_(2)O_(5)。采用产品一致性测试B方法研究了这些玻璃的化学稳定性,并使用先进的固体核磁共振技术对玻璃的原子尺度结构进行了精确解析。结果表明,碱金属种类的改变不仅通过调节对非桥氧的电场吸引力影响了玻璃网络的致密性,而且明显改变了玻璃的网络结构。在这些玻璃中,不同配位数的铝都只被磷氧四面体(PO_(4))所包围。随着碱金属离子场强的增大,高配位铝的含量增加,导致铝与磷氧四面体的化学键连接增多。这种结构变化进一步增强了玻璃网络的致密性,最终提高了其化学稳定性。Introduction The chemical stability of phosphate glass is vital for its applications in various fields,i.e.,biomedicine,laser gain media,sealing,and high-level nuclear waste solidification.Alkali metals affect the chemical stability of phosphate glass.Some studies indicate that alkali metals with a higher ionic field strength can enhance the chemical stability of glass via reinforcing the ionic crosslinking between alkali ions and non-bridging oxygen atoms.However,a few studies indicate that certain phosphate glasses containing low-field strength alkali metals exhibit a better chemical stability,compared to the glasses containing high-field strength alkali metals.These results cannot be explained based on the simple field strength.It is thus necessary to further investigate the influence of alkali metals on the chemical stability of phosphate glass.In this study,we utilized various advanced solid-state nuclear magnetic resonance(SSNMR)techniques to analyze the network structure of the aluminum phosphate glasses containing different alkali metals in an atomic scale.The intrinsic correlation among alkali metals,glass structure,and chemical stability was discussed.Methods The glasses with molar compositions of[x Na_(2)O–y K_(2)O–(41.6–x–y)Cs_2O]–16.7Al_(2)O_(3)–41.7P_(2)O_(5)were synthesized by melt quenching methods.The values of(x,y)used were(41.6,0),(0,41.6),(20.8,0),and(0,20.8),respectively.The raw materials required for glass preparation were Al(OH)_(3)(purity>99%),Al(PO_3)_(3)(purity>99%),NaPO_(3)(purity>95.0%),KPO_(3)(purity>99%,),Cs_2CO_(3)(purity>99%),and NH_(4)H_(2)PO_(4)(purity>99%).Each batch,consisting of 20 g of mixed raw materials,was loaded into a platinum crucible and subjected to a high-temperature furnace at 1250–1300℃for 30 min to melt raw materials.Thereafter,the melt was poured onto a steel plate and quickly pressed to obtain a bulk glass.The chemical stability of these glasses was assessed by the Product Consistency Test B(PCT-B)method.1 g of dried glass powder with particle si

关 键 词：碱金属 铝磷酸盐玻璃 结构 化学稳定性 固体核磁共振 

分 类 号：TQ171.1[化学工程—玻璃工业]