Fluid-cell Raman spectroscopy is a space and time-resolving application allowing in operando studies of dynamic processes during solution–solid interactions. A currently heavily debated example is the corrosion mechanism of borosilicate glasses, which are the favoured material for the immobilization of high-level nuclear waste. With an upgraded fluid-cell lid design made entirely from the glass sample itself, we present the polymerization of the surface alteration layer over time in an initially acidic environment, including the differentiation between pore and surface-adsorbed water within it. Our results support an interface-coupled dissolution-precipitation model, which opposes traditional ion-exchange models for the corrosion mechanism. A sound description of the corrosion mechanism is essential for reliable numerical models to predict the corrosion rate of nuclear waste glasses during long-term storage in a geological repository.

流体单元拉曼光谱是一种空间和时间分辨应用，允许在溶液-固体相互作用期间对动态过程进行操作研究。目前一个备受争议的例子是硼硅酸盐玻璃的腐蚀机制，它是固定高放核废料的首选材料。通过完全由玻璃样品本身制成的升级后的流体池盖设计，我们展示了表面变化层在初始酸性环境中随时间的聚合，包括孔隙和表面吸附水之间的差异。我们的结果支持界面耦合溶解-沉淀模型，该模型与腐蚀机制的传统离子交换模型相反。