CEA, DEN, DE2D, SEVT, 30207, Bagnols sur Cèze, France.
Tescan Analytics, ZAC St Charles, 13710, Fuveau, France.
Nat Commun. 2018 Jun 4;9(1):2169. doi: 10.1038/s41467-018-04511-2.
Understanding the dissolution of silicate glasses and minerals from atomic to macroscopic levels is a challenge with major implications in geoscience and industry. One of the main uncertainties limiting the development of predictive models lies in the formation of an amorphous surface layer--called gel--that can in some circumstances control the reactivity of the buried interface. Here, we report experimental and simulation results deciphering the mechanisms by which the gel becomes passivating. The study conducted on a six-oxide borosilicate glass shows that gel reorganization involving high exchange rate of oxygen and low exchange rate of silicon is the key mechanism accounting for extremely low apparent water diffusivity (∼10 m s), which could be rate-limiting for the overall reaction. These findings could be used to improve kinetic models, and inspire the development of new molecular sieve materials with tailored properties as well as highly durable glass for application in extreme environments.
从原子到宏观尺度理解硅酸盐玻璃和矿物的溶解是地球科学和工业领域面临的一个挑战。限制预测模型发展的主要不确定性之一在于非晶态表面层(称为凝胶)的形成,在某些情况下,凝胶可以控制埋藏界面的反应性。在这里,我们报告了实验和模拟结果,这些结果揭示了凝胶钝化的机制。对六种氧化物硼硅酸盐玻璃的研究表明,涉及高氧交换率和低硅交换率的凝胶重组是导致表观水扩散率极低(约 10 m/s)的关键机制,这可能是整个反应的限速步骤。这些发现可用于改进动力学模型,并为具有定制特性的新型分子筛材料以及用于极端环境的高耐用性玻璃的开发提供启示。