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Nanometre-scale evidence for interfacial dissolution–reprecipitation control of silicate glass corrosion

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Abstract

Silicate glasses are durable solids, and yet they are chemically unstable in contact with aqueous fluids—this has important implications for numerous industrial applications related to the corrosion resistance of glasses1, or the biogeochemical weathering of volcanic glasses in seawater2. The aqueous dissolution of synthetic and natural glasses results in the formation of a hydrated, cation-depleted near-surface alteration zone1,3,4,5,6,7,8 and, depending on alteration conditions, secondary crystalline phases on the surface1,2,4,5,6,7. The long-standing accepted model of glass corrosion is based on diffusion-coupled hydration and selective cation release, producing a surface-altered zone2,5,6,7,8. However, using a combination of advanced atomic-resolution analytical techniques, our data for the first time reveal that the structural and chemical interface between the pristine glass and altered zone is always extremely sharp, with gradients in the nanometre to sub-nanometre range. These findings support a new corrosion mechanism, interfacial dissolution–reprecipitation. Moreover, they also highlight the importance of using analytical methods with very high spatial and mass resolution for deciphering the nanometre-scale processes controlling corrosion. Our findings provide evidence that interfacial dissolution–reprecipitation may be a universal reaction mechanism that controls both silicate glass corrosion and mineral weathering9,10,11,12,13.

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Figure 1: STEM-HAADF images and EFTEM elemental maps of boron and silicon showing surface alteration in cross-section as a function of time.
Figure 2: Three-dimensional reconstruction of one-month glass by atom probe tomography.
Figure 3: Chemical profiles of one-month glass as a function of depth (expressed in terms of sputtering time) measured by ToF-SIMS.

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Acknowledgements

R.H. thanks ANDRA for the postdoctoral position awarded to S.C. and providing travel funding. The glass samples were altered and the aqueous solutions were analysed at Subatech, Nantes, France—we in particular thank J. Neeway and A. Abdelouas. The TEM samples prepared by Ar ion milling were made by V. Svechnikov (Delft); further TEM-FIB sections were made by G. Hughes (Oxford). The instrumental analyses were funded from the European Union Seventh Framework Programme under Grant Agreement 312483—ESTEEM2 (Integrated Infrastructure Initiative–I3). The authors acknowledge financial support from the French CNRS (FR3507) and CEA METSA network. The views expressed herein are those of the authors, and do not necessarily correspond to those of the funding agencies.

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R.H. conceived and designed the research project, assisted with all measurements, interpreted the data and wrote the manuscript. S.C. assisted with the development of the research, prepared some of the samples and assisted with the majority of the measurements and analyses. E.C. carried out the APT measurements and analysed the data. S.M. and L.S.K. conducted the TEM work and analysed the data; S.L-P. assisted with the TEM analyses and wrote the codes to calculate the EEL spectrum images. M.C. prepared nearly all of the FIB ultrathin sections. A.S. performed the ToF-SIMS measurements and analysed the data. All authors commented on the final version of the manuscript.

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Correspondence to Roland Hellmann.

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Hellmann, R., Cotte, S., Cadel, E. et al. Nanometre-scale evidence for interfacial dissolution–reprecipitation control of silicate glass corrosion. Nature Mater 14, 307–311 (2015). https://doi.org/10.1038/nmat4172

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