Investigation of the role of Mg and Ca in the structure and durability of aluminoborosilicate glass
Investigation of the role of Mg and Ca in the structure and durability of aluminoborosilicate glass
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DOI：
10.1016/j.jnoncrysol.2019.03.003
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发表时间：
2019-05
影响因子：
3.5
通讯作者：
D. Backhouse;C. Corkhill;N. Hyatt;R. Hand
中科院分区：
文献类型：
--
作者：
D. Backhouse;C. Corkhill;N. Hyatt;R. Hand
采用核磁共振谱和静态溶解实验研究了与英国核废料玻璃组成相关的Na 2 O·CaO·（15-x）Al 2 O3·xB 2 O3·SiO2和Na 2 O·MgO·（15-x）Al 2 O3·xB 2 O3·SiO2玻璃的结构和溶解行为。11 B、27 Al和29 Si NMR分析结果表明，随着[B2 O3]/（[Al 2 O3] + [B2 O3]）比值的增加，碱-碱土铝硼硅酸盐玻璃中非硅酸盐四面体物种（IVAl +IVB）的比例总体下降，Sisingle键O单键X键（Xdouble bond dB，Al）减少。含镁玻璃的IVB分数低于含钙玻璃，这可能是由于IVMg四面体在网络中的存在。测得的腐蚀速率是类似的钙和镁的玻璃，虽然出乎意料地一些含钙的玻璃表现出更高的腐蚀损失比含镁的时间段高达112天。然而，有证据表明，含Mg的比含Ca的更倾向于速率恢复。发现含Ca玻璃的蚀变产物含有Ca、Si和Al，含Mg玻璃的蚀变产物含有Ca、Mg、Si和Al;在蚀变产物中未检测到Na，尽管根据获得的数据不能排除其存在。
The structure and dissolution behaviour of Na2O·CaO·(15–x)Al2O3·xB2O3·SiO2and Na2O·MgO·(15–x)Al2O3·xB2O3·SiO2glasses, relevant to compositions of UK nuclear waste glass, have been investigated using nuclear magnetic resonance (NMR) spectroscopy and static dissolution experiments using the PCT protocol. Structural data from11B,27Al and29Si NMR analyses show that increasing the [B2O3]/([Al2O3] + [B2O3]) ratio of the alkali-alkaline-earth aluminoborosilicate glasses led to an overall decrease in the proportion of non-silicate tetrahedral species (IVAl +IVB) and a decrease in Sisingle bondOsingle bondX bonds (Xdouble bondB, Al). The Mg-containing glasses exhibited lowerIVB fractions than their Ca-containing counterparts, which is thought to be due to the presence ofIVMg tetrahedra in the network. The measured corrosion rates were similar for both Ca and Mg-containing glasses although unexpectedly some Ca-containing glasses exhibited higher corrosion losses than the Mg-containing ones for time periods up to 112 d. However, there was evidence of a greater tendency to rate resumption in the Mg containing than the Ca containing ones. Alteration products were found to contain Ca, Si and Al with the Ca containing glasses and Ca, Mg, Si and Al with the Mg containing glasses; Na was not detected in the alteration products although its presence cannot be ruled out based on the data obtained.