Corrosion of Borosilicate Glasses Subjected to Aggressive Test Conditions: Structural Investigations

Sodium borosilicate (NBS) and barium sodium borosilicate (BBS) glasses, used for immobilization of high‐level nuclear waste with compositions (SiO₂)_0.477(B₂O₃)_0.239(Na₂O)_0.170(TiO₂)_0.023(CaO)_0.068(Al₂O₃)_0.023 and (SiO₂)_0.482(B₂O₃)_0.244(Na₂O)_0.220(BaO)_0.054 were subjected leaching experiments under hydrothermal conditions in an autoclave at 200°C for different time durations. Morphological and structural transformations associated with leaching, have been monitored with techniques like XRD, SEM, solid‐state nuclear magnetic resonance. XRD and SEM along with NMR studies have confirmed that, upon leaching, formation of an aluminosilicate phase, Zeolite‐P (Na₆Al₆Si₁₀O₃₂·12H₂O), occurs with NBS glass. BBS glass upon subjecting to the same conditions leads to formation of multiple amorphous phases having Q⁴ (silica rich phase) and Q³ structural units of Silicon along with structurally modified residual glass. Upon leaching BO₃ structural units preferentially get released from BBS glass. Comparison of results with international simple glass confirmed that, for the latter, mass loss rates are one order of magnitude lower.     

Durability of High-level Waste Glass in Groundwater

This paper reviews the leaching behavior of simulated high-level-waste glass in Japanese groundwater both on an in situ burial site and in our laboratory. During in situ burial leach tests, the glass is immersed in groundwater for up to 1 year and 7 months, retrieved, and analyzed. A leach rate obtained from the in situ burial tests is compared with other leach data under different conditions. Two factors, i.e., flow rate and composition of the groundwater, are extensively studied in the laboratory to supplement the in situ burial data. Effects of γ irradiation on the groundwater chemistry are also examined. Based on the results, mechanisms observed with the leaching of the glass in groundwater are discussed.     

X‐ray tomography of feed‐to‐glass transition of simulated borosilicate waste glasses

High‐level waste feed composition affects the overall melting rate by influencing the chemical, thermophysical, and morphological properties of a cold cap layer that floats on the molten glass where most feed‐to‐glass reactions occur. Data from X‐ray computed tomography imaging of melting pellets comprised of a simulated high‐aluminum feed reveal the morphology of bubbles, known as the primary foam, for various feed compositions at temperatures between 600°C and 1040°C. These feeds were formulated to make glasses with viscosities ranging from 0.5 to 9.5 Pa s at 1150°C, which was accomplished by changing the SiO₂/(B₂O₃+Na₂O+Li₂O) ratio in the final glass. Pellet dimensions and profile area, average and maximum bubble areas, bubble diameter, and void fraction were evaluated. The feed viscosity strongly affects the onset of the primary foaming and the foam collapse temperature. Despite the decreasing amount of gas‐evolving components (Li₂CO₃, H₃BO₃, and Na₂CO₃), as the feed viscosity increases, the measured foam expansion rate does not decrease. This suggests that the primary foaming is not only affected by changes in the primary melt viscosity but also by the compositional reaction kinetic effects. The temperature‐dependent foam morphological data will be used to inform cold cap model development for a high‐level radioactive waste glass melter.     

29Si MAS-NMR Study of the Short-Range Order in Lithium Borosilicate Glasses

²⁹Si MAS-NMR measurements have been made on a series of lithium borosilicate glasses of general composition R Li₂O.B₂O₃· K SiO₂. At low alkali contents ( R < 1), the ²⁹Si resonance envelope is broadened and indicates a distribution of Si sites. As R increases above 1, the FWHM of the ²⁹Si resonance narrows considerably to that representative of a single chemical site. Simultaneously, the average chemical shift of the resonance shifts upfield in agreement with the trends found in the binary lithium silicate glass system. Using the chemical shifts for the individual Q species in the binary system it was found that very good agreement between the chemical shifts of the binary glasses and the ternary glasses examined here could be achieved if a model of proportional sharing of the added oxygen (from lithia) between silicate and borate units was used. In contrast to the ¹¹B NMR studies of these same glasses, the ²⁹Si NMR data are quantitatively best-fit if it is assumed that the proportional sharing of the oxygen from the added lithia begins at R = 0. Models of sharing developed from the ¹¹B NMR studies of these glasses, where proportional sharing above a certain fixed (independent of K ) or variable (dependent on K ) minimum R ₀, have been reexamined and were quantitatively shown through residual analysis to give consistently poorer fits to our data. At present the reasons for the discrepancy between the two sets of NMR data are unknown.     

Corrosion of ISG fibers in alkaline solutions

The corrosion behavior of glass fibers synthesized from the International Simple Glass (ISG) reference ingot, an international High‐Level Waste (HLW) borosilicate glass standard, is reported. Bundles of glass fibers were submerged in 120 mL of four different solutions of initial pH values (pH_i) of 9.5, 10.5, 11.5, and 12.5 for static corrosion testing. While all the experiments reached a residual corrosion rate after ~50 days, which remained approximately constant for the duration of the pH_i 9.5‐11.5 experiments, the pH_i 12.5 experiment underwent a Stage II→III dissolution transition after 57 days. This transition was preceded by a decrease in the Al concentration in solution followed by an increase in B and Si concentration in the leachate. Zeolite NaP2 was observed to form on these fibers via scanning electron microscopy and X‐ray diffraction—the crystallinity of the fibers was estimated to be ~40%‐45% (relative to amorphous component) after the Stage II→III transition. Transmission electron microscopy cross‐sectional imaging of sampled fibers revealed several porous layers on the pH_i 9.5‐11.5 samples, and a more aggressive alteration mechanism in the pH_i 12.5 fibers. Potential markers that indicate a transition from Stage II→Stage III corrosion are shown to occur based on experimental observations.     

硝酸钡预处理高放废液玻璃固化体结构和抗浸出性能研究

为提高硼硅酸盐玻璃对硫的包容能力,采用Ba(NO₃)₂将模拟高硫高钠废液中的SO^2-₄转变为BaSO₄,再利用熔融法制备硼硅酸盐玻璃固化体,研究了模拟高放废液掺量对玻璃固化体结构和抗浸出性能的影响。结果表明:采用Ba(NO₃)₂对模拟高硫高钠废液进行预处理后,废物包容量达到23%(质量分数)仍未发生分相;掺入模拟高放废液的玻璃固化体中的Na、B、Si元素归一化质量损失比纯硼硅酸盐玻璃低一个数量级,随着模拟高放废液掺量增加玻璃固化体抗浸出性能无明显变化。¹¹B和²⁹Si核磁共振谱分析表明,模拟高放废液的掺入使部分BO₃结构转变为BO₄结构,玻璃网络结构有所增强。     

硼硅酸盐微晶泡沫玻璃耐酸性研究

以废玻璃粉为主要原料,掺入适量的脱镁硼泥,以C和MnO2为复合发泡剂,以ZrO2、TiO2为晶核剂,引入适量的添加剂,采用粉末烧成法工艺制备硼硅酸盐微晶泡沫玻璃。运用DSC-TG、XRD、SEM等微观测试方法,确定试样的核化和晶化温度、晶相种类以及在酸中浸泡前后的微观形貌,研究试样的耐酸腐蚀性。研究结果表明:当废玻璃粉和脱镁硼泥的质量比为8∶2,添加3%TiO2晶核剂,在1150℃保温30min,制备出硼硅酸盐微晶泡沫玻璃试样。把试样浸泡在0.1mol/L的稀硫酸中,浸泡14d后质量仅增加了0.02%,而浸泡35d-42d试样质量基本不变,说明硼硅酸盐微晶泡沫玻璃具有较强的耐酸性。     

硼硅酸盐玻璃鳞片研制开发概况

叙述了我国玻璃鳞片的研究和开发历程,提出了厚度和表面处理的重要性。