Katsenovich Yelena, Drozd Vadym, Kandel Shambhu, Lagos Leonel, Asmussen R Matthew
Applied Research Center, Florida International University, 10555 W Flagler St, Miami, FL 33174, USA.
Pacific Northwest National Laboratory, 902 Battelle Blvd, Richland, WA 99354, USA.
Dalton Trans. 2024 Jul 30;53(30):12740-12754. doi: 10.1039/d4dt00855c.
Borosilicate glasses are widely used for radioactive waste disposal due to their ability to incorporate a variety of contaminants and radionuclides while exhibiting high durability in various disposal scenarios. This research evaluated the dissolution of borosilicate glass using both single-pass-flow-through (ASTM C1662-18) and product consistency test (ASTM C1285-21) methods with different solutions, including a cementitious-contacted water (called grout-contacted, GC, from this point) and solutions with varying levels of dissolved cementitious species such as Si, Ca, Al. The results indicated that the presence of Ca plays a crucial role in suppressing glass corrosion, as evidenced by the slower normalized dissolution rates, which were one order of magnitude lower for boron and two orders of magnitude lower for rhenium, observed in both Ca-amended and GC solutions compared to the pH 12 buffer solution. This effect is attributed to the formation of a dense, low-porosity, and strongly bonded calcium silicate hydrate (CSH) layer on the glass surface, which implies that a glass corrosion process is influenced by ion exchange involving alkali ions Na, K, Ca, and hydrogen-containing species. A small number of glass particles treated in the GC solution showed minor corrosion pits in the form of shallow craters with an average diameter of approximately 500 μm. This observation is correlated with a significant reduction, 2000 to 3000 times lower, in the cumulative volume of glass pores, indicating that smaller pore voids were "sealed" in the presence of Ca ions, likely attributed to the formation of CSH precipitation or other corrosion products such as calcium carbonate saturated from the grout solution. These findings suggest that the presence of dissolved Ca in the GC solution can slow down the dissolution of borosilicate glass, contrary to the expected trend of higher dissolution rates resulting from exposure to high alkaline and thus higher pH solutions.
硼硅酸盐玻璃因其能够容纳各种污染物和放射性核素,同时在各种处置场景中表现出高耐久性,而被广泛用于放射性废物处置。本研究使用单通道流通法(ASTM C1662 - 18)和产品一致性测试(ASTM C1285 - 21)方法,在不同溶液中评估硼硅酸盐玻璃的溶解情况,这些溶液包括一种与水泥接触的水(从此时起称为灌浆接触水,GC)以及含有不同水平溶解水泥成分(如硅、钙、铝)的溶液。结果表明,钙的存在对抑制玻璃腐蚀起着关键作用,这一点从归一化溶解速率较慢可以看出,与pH 12缓冲溶液相比,在添加钙的溶液和GC溶液中观察到的硼的归一化溶解速率低一个数量级,铼的归一化溶解速率低两个数量级。这种效应归因于在玻璃表面形成了致密、低孔隙率且结合牢固的硅酸钙水合物(CSH)层,这意味着玻璃腐蚀过程受涉及碱金属离子钠、钾、钙和含氢物种的离子交换影响。在GC溶液中处理的少量玻璃颗粒显示出轻微的腐蚀坑,呈浅坑形式,平均直径约为500μm。这一观察结果与玻璃孔隙累积体积显著减少相关,减少了2000至3000倍,表明在钙离子存在下较小的孔隙被“密封”,这可能归因于CSH沉淀或其他腐蚀产物的形成,如来自灌浆溶液的碳酸钙饱和物。这些发现表明,GC溶液中溶解钙的存在会减缓硼硅酸盐玻璃的溶解,这与暴露于高碱性(即高pH值)溶液会导致更高溶解速率的预期趋势相反。