模拟高放废液硼硅酸盐玻璃固化体钼分相与化学稳定性的结构基因模拟  

Structural Gene Modeling for Mo-Phase and Chemical Stability of Simulated High Level Waste Borosilicate Glass

作　　者：戴晨 李洪 张丽艳[2] 胡丽丽[2] 朱小莉 潘安练 DAI Chen;LI Hong;ZHANG Liyan;HU Lili;ZHU Xiaoli;PAN Anlian(College of Materials Science and Engineering,Hunan University,Changsha 410082,China;Key Laboratory of Materials for High Power Laser,Shanghai Institute of Optics and Fine Mechanics,Chinese Academy of Sciences,Shanghai 201800,China;Nippon Electric Glass,North Carolina 28150,The United States)

机构地区：[1]湖南大学,材料科学与工程学院,长沙410082,中国 [2]中国科学院上海光学精密机械研究所,高功率激光单元技术实验室,上海201800,中国 [3]日本电气硝子株式会社(NEG)美国分公司,北卡罗来纳28150,美国

出　　处：《硅酸盐学报》2024年第6期2068-2080,共13页Journal of The Chinese Ceramic Society

基　　金：两步法冷坩埚玻璃固化工程样机研制及验证(FKY1683ZH G001SSJS-B01-001)。

摘　　要：碱金属钼酸盐黄相在高放废液玻璃固化过程中难以处理,严重影响玻璃的化学稳定性。为了对高钼废液固化玻璃的化学稳定性进行较为准确的预判,从而加速配方研发进程,利用玻璃结构基因模拟法(GSg M)研究了高Mo (2.6%~3.3%,质量分数)模拟高放废液硼硅酸盐玻璃的化稳性和钼分相累积情况,建立了B、Li、Na、Mo浸出率、玻璃转变温度和钼分相累积程度的结构预测模型,并进行了模型验证。研究显示,在本工作的成分研究范围内,钼分相成分主要为CsLiMoO_(4)(水溶性黄相)及CaMoO_(4)(耐水性晶相)。成分–结构–性质关系表明,提高Li_(2)O和CaO会显著促进钼分相的形成。518~528 cm^(-1)Si—O—Si振动增强,则钼分相加剧,但[BO_(3)]基团中B—O—B振动增强,可有效减少钼分相的析出。模型验证结果表明,各性质的结构预测模型可对设计玻璃的化稳性及钼分相累积程度进行快速预测,以筛选设计玻璃配方是否有进一步研究的必要。Introduction The solubility of Mo in borosilicate glasses is relatively low.Therefore,molybdate is easy to separate from glass,forming Mo-yellow phase(alkali molybdates,such as Na_(2)MoO_(4),CsLiMoO_(4),and Li_(2)MoO_(4))or CaMoO_(4) crystals.The crystal CaMoO_(4) performs a superior water resistance ability,which can effectively reduce the Mo leaching rate of a high Mo content and high level waste(HLW)solidification glass.On the contrary,alkali-Mo-yellow phase is highly water-soluble,leading to a serious Mo-leaching,and thus decreases the chemical durability of the products.The duration of the chemical durability test of solidification glass is 7 or 28 days,thus retarding the whole cycle for the investigation of HLW solidification glass.Effective predicting Mo-yellow phase and the Mo leaching rate can accelerate the research via saving time on glass preparation and chemical durability test.Based on the glass structural gene modeling(GSgM),this paper proposed the Structure-Property(S−P)prediction models of chemical durability and the possibility of Mo-phase separation(PS,its value is xPS)for a simulated high Mo content(MoO_(3)2.6−3.3%)HLW borosilicate solidification glass.The key elements(i.e.,Na,Li,B,and Mo)leaching rate r_(Na),r_(Li),r_(B),r_(Mo) as well as the Mo-phase separation xPS were predicted by the models.The reliability and practicability of the models were proved.In addition,combined with the Structure-Composition(S−C)modeling,the C−S−P analysis was also carried out for xPS and r_(Mo).Methods Fifteen borosilicate glasses were designed by an one-component-at-a-time(OCAT)method.Glasses with different weights(130 g and 800 g)were prepared for each composition.Small samples with the mass of 130 g were melted and quenched.Large glass samples with the mass of 800 g were melted,and annealed.The properties of the samples were determined by X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR)with KBr,differential scanning calorimetry(DSC)and PCT-7 day chemical durability test,respecti

关 键 词：高放废液 硼硅酸盐玻璃固化 钼分相 浸出率 结构基因模拟 

分 类 号：TQ171.1[化学工程—玻璃工业]