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Insight into silicate-glass corrosion mechanisms

Nature Materials volume 7, pages 978–983 (2008)Cite this article

Abstract

The remarkable chemical durability of silicate glass makes it suitable for a wide range of applications. The slowdown of the aqueous glass corrosion kinetics that is frequently observed at long time is generally attributed to chemical affinity effects (saturation of the solution with respect to silica). Here, we demonstrate a new mechanism and highlight the impact of morphological transformations in the alteration layer on the leaching kinetics. A direct correlation between structure and reactivity is revealed by coupling the results of several structure-sensitive experiments with numerical simulations at mesoscopic scale. The sharp drop in the corrosion rate is shown to arise from densification of the outer layers of the alteration film, leading to pore closure. The presence of insoluble elements in the glass can inhibit the film restructuring responsible for this effect. This mechanism may be more broadly applicable to silicate minerals.

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Figure 1: Glass alteration kinetics.
Figure 2: Dye penetration into the gel in sample 0Zr.
Figure 3: Small-angle X-ray scattering.
Figure 4: Neutron scattering with contrast variation.
Figure 5: Scanning transmission electron microscopy of sample 0Zr at the end of alteration.
Figure 6: Monte Carlo simulation of the gel layer.

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Acknowledgements

We acknowledge the help of Wahib Saikaly at CP2M (Marseille, France) for the scanning transmission electron microscopy experiments and the assistance of Laurent Dupuy at BiophyResearch (Marseille, France) for the ToF-SIMS experiments.

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Authors and Affiliations

  1. CEA, DEN, Laboratoire d’étude du Comportement à Long Terme, 30207 Bagnols-sur-Cèze, France

    Céline Cailleteau, Frédéric Angeli, Stéphane Gin & Patrick Jollivet

  2. Laboratoire de Physique de la Matière Condensée, Ecole Polytechnique-CNRS, 91128 Palaiseau, France

    François Devreux

  3. Laboratoire Léon Brillouin, CNRS-CEA, 91191 Gif-sur-Yvette, France

    Jacques Jestin

  4. CEA, DSM, Laboratoire Interdisciplinaire sur l’Organisation Nanométrique et Supramoléculaire, 91191 Gif-sur-Yvette, France

    Olivier Spalla

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  1. Céline Cailleteau
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Correspondence to François Devreux.

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Cailleteau, C., Angeli, F., Devreux, F. et al. Insight into silicate-glass corrosion mechanisms. Nature Mater 7, 978–983 (2008). https://doi.org/10.1038/nmat2301

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