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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References
Grambow, B. Nuclear waste glasses-how durable? Elements 2, 357–364 (2006).
Staudigel, H. et al. 3.5 billion years of glass bioalteration: Volcanic rocks as a basis for microbial life? Earth Sci. Rev. 89, 156–176 (2008).
Trotignon, L., Petit, J-C., Mea, G. D. & Dran, J-C. The compared aqueous corrosion of four simple borosilicate glasses: Influence of Al, Ca and Fe on the formation and nature of secondary phases. J. Nucl. Mater. 190, 228–246 (1992).
Thomassin, J-H., Boutonnat, F., Touray, J-C. & Baillif, P. Geochemical role of the water/rock ratio during the experimental alteration of a synthetic basaltic glass at 50 °C. An XPS and STEM investigation. Eur. J. Mineral. 1, 261–274 (1989).
Frugier, P. et al. SON68 nuclear glass dissolution kinetics: Current state of knowledge and basis of the new GRAAL model. J. Nucl. Mater. 380, 8–21 (2008).
Jégou, C., Gin, S. & Larché, F. Alteration kinetics of a simplified nuclear glass in an aqueous medium: Effects of solution chemistry and of protective gel properties on diminishing the alteration rate. J. Nucl. Mater. 280, 216–229 (2000).
Valle, N. et al. Elemental and isotopic (29Si and 18O) tracing of glass alteration mechanisms. Geochim. Cosmochim. Acta 74, 3412–3431 (2010).
Doremus, R. H. Interdiffusion of hydrogen and alkali ions in a glass surface. J. Non-Cryst. Solids 19, 137–144 (1975).
Geisler, T. et al. Aqueous corrosion of borosilicate glass under acidic conditions: A new corrosion mechanism. J. Non-Cryst. Solids 356, 1458–1465 (2010).
Hellmann, R. et al. Unifying natural and laboratory chemical weathering with interfacial dissolution–reprecipitation: A study based on the nanometer-scale chemistry of fluid–silicate interfaces. Chem. Geol. 294–295, 203–216 (2012).
Hellmann, R., Penisson, J-M., Hervig, R. L., Thomassin, J-H. & Abrioux, M-F. An EFTEM/HRTEM high-resolution study of the near surface of labradorite feldspar altered at acid pH: Evidence for interfacial dissolution–reprecipitation. Phys. Chem. Miner. 30, 192–197 (2003).
Ruiz-Agudo, E., Putnis, C. V., Rodriguez-Navarro, C. & Putnis, A. Mechanism of leached layer formation during chemical weathering of silicate minerals. Geology 40, 947–950 (2012).
Daval, D., Hellmann, R., Saldi, G. D., Wirth, R. & Knauss, K. G. Linking nm-scale measurements of silicate surfaces to macroscopic dissolution rate laws: New insights based on diopside. Geochim. Cosmochim. Acta 107, 121–134 (2013).
Dran, J-C., Petit, J-C. & Brouse, C. Mechanism of aqueous dissolution of silicate glasses yielded by fission tracks. Nature 319, 485–487 (1986).
Crovisier, J. L. et al. Experimental seawater-basaltic glass interaction at 50 °C: Study of early developed phases by electron microscopy and X-ray photoelectron spectrometry. Geochim. Cosmochim. Acta 47, 377–387 (1983).
Grambow, B. & Müller, R. First-order dissolution rate law and the role of surface layers in glass performance assessment. J. Nucl. Mater. 298, 112–124 (2001).
Dran, J-C., Della Mea, G., Paccagnella, A., Petit, J-C. & Trotignon, L. The aqueous dissolution of alkali silicate glasses: Reappraisal of mechanisms by H and Na depth profiling with high energy ion beams. Phys. Chem. Glasses 29, 249–255 (1988).
Petit, J-C. et al. Hydrated layer formation during dissolution of complex silicate glasses and minerals. Geochim. Cosmochim. Acta 54, 1941–1955 (1990).
Bunker, B. C. Molecular mechanisms for corrosion of silica and silicate glasses. J. Non-Cryst. Solids 179, 300–308 (1994).
O’Neil, J. R. & Taylor, H. P. J. The oxygen isotope and cation exchange chemistry of feldspars. Am. Mineral. 52, 1414–1437 (1967).
Cailleteau, C. et al. Insight into silicate-glass corrosion mechanisms. Nature Mater. 7, 978–983 (2008).
Baucke, F. G. K. Investigation of surface layers, formed on glass electrode membranes in aqueous solutions, by means of an ion sputtering method. J. Non-Cryst. Solids 14, 13–31 (1974).
Kelly, T. F. & Miller, M. K. Invited review article: Atom probe tomography. Rev. Sci. Instrum. 78, 031101 (2007).
Gin, S., Ryan, J. V., Schreiber, D. K., Neeway, J. & Cabié, M. Contribution of atom-probe tomography to a better understanding of glass alteration mechanisms: Application to a nuclear glass specimen altered 25 years in a granitic environment. Chem. Geol. 349–350, 99–109 (2013).
Hellmann, R. The albite-water system Part IV. Diffusion modelling of leached and hydrogen-enriched layers. Geochim. Cosmochim. Acta 61, 1595–1611 (1997).
Fenter, P. & Sturchio, N. C. Mineral-water interfacial structures revealed by synchrotron X-ray scattering. Prog. Surf. Sci. 77, 171–258 (2004).
Marry, V., Rotenberg, B. & Turq, P. Structure and dynamics of water at a clay surface from molecular dynamics simulation. Phys. Chem. Chem. Phys. 10, 4802–4813 (2008).
Cailleteau, C. Influence de la morphologie du gel sur la cinétique d’altération des verres borosilicatés: Rôle du calcium et du zirconium. Rapport CEA-R-6217 (CEA, 2009).
King, H. E., Plümper, O., Geisler, T. & Putnis, A. Experimental investigations into the silicification of olivine: Implications for the reaction mechanism and acid neutralization. Am. Mineral. 96, 1503–1511 (2011).
Putnis, A. & Putnis, C. V. The mechanism of reequilibration of solids in the presence of a fluid phase. J. Solid State Chem. 180, 1783–1786 (2007).
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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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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DOI: https://doi.org/10.1038/nmat4172
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