Borosilicate glass is an important material used in various industries due to its chemical durability, such as for the immobilization of high-level nuclear waste. However, it is susceptible to aqueous corrosion, recognizable by the formation of surface alteration layers (SALs). Here, we report in situ fluid-cell Raman spectroscopic experiments providing real-time insights into reaction and transport processes during the aqueous corrosion of a borosilicate glass. The formation of a several-micrometre-thick water-rich zone between the SAL and the glass, interpreted as an interface solution, is detected, as well as pH gradients at the glass surface and within the SAL. By replacing the solution with a deuterated solution, it is observed that water transport through the SAL is not rate-limiting. The data support an interface-coupled dissolution–reprecipitation process for SAL formation. Fluid-cell Raman spectroscopic experiments open up new avenues for studying solid–water reactions, with the ability to in situ trace specific sub-processes in real time by using stable isotopes.
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The datasets collected and analysed in the current study are available from the corresponding author upon request.
Newton, R. G. The durability of glass - a review. Glass Technol. 26, 21–38 (1985).
Bunker, B. Molecular mechanisms for corrosion of silica and silicate glasses. J. Non-Cryst. Solids 179, 300–308 (1994).
Stroncik, N. A. & Schmincke, H.-U. Palagonite – a review. Int. J. Earth Sci. 91, 680–697 (2002).
Grambow, B. Nuclear waste glasses - How durable? Elements 2, 357–364 (2006).
Gin, S. et al. An international initiative on long-term behavior of high-level nuclear waste glass. Mater. Today 16, 243–248 (2013).
Cailleteau, C. et al. Insight into silicate-glass corrosion mechanisms. Nat. Mater. 7, 978–983 (2008).
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).
Gin, S. et al. The controversial role of inter-diffusion in glass alteration. Chem. Geol. 440, 115–123 (2016).
Geisler, T. et al. Aqueous corrosion of borosilicate glass under acidic conditions: A new corrosion mechanism. J. Non-Cryst. Solids 356, 1458–1465 (2010).
Geisler, T. et al. The mechanism of borosilicate glass corrosion revisited. Geochim. Cosmochim. Acta 158, 112–129 (2015).
Hellmann, R. et al. Nanometre-scale evidence for interfacial dissolution–reprecipitation control of silicate glass corrosion. Nat. Mater. 14, 307–311 (2015).
Lenting, C. et al. Towards a unifying mechanistic model for silicate glass corrosion. npj Mater. Degrad. 2, 28 (2018).
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).
Gin, S., Beaudoux, X., Angéli, F., Jégou, C. & Godon, N. Effect of composition on the short-term and long-term dissolution rates of ten borosilicate glasses of increasing complexity from 3 to 30 oxides. J. Non-Cryst. Solids 358, 2559–2570 (2012).
Vernaz, E., Gin, S., Jégou, C. & Ribet, I. Present understanding of R7T7 glass alteration kinetics and their impact on long-term behavior modeling. J. Nucl. Mater. 298, 27–36 (2001).
Xing, S.-B., Buechele, A. C. & Pegg, I. L. Effect of surface layers on the dissolution of nuclear waste glasses. Mater. Res. Soc. Proc. 333, 541 (1993).
Rebiscoul, D. et al. Morphological evolution of alteration layers formed during nuclear glass alteration: new evidence of a gel as a diffusive barrier. J. Nucl. Mater. 326, 9–18 (2004).
Rebiscoul, D., Frugier, P., Gin, S. & Ayral, A. Protective properties and dissolution ability of the gel formed during nuclear glass alteration. J. Nucl. Mater. 342, 26–34 (2005).
Gin, S., Ribet, I. & Couillard, M. Role and properties of the gel formed during nuclear glass alteration: importance of gel formation conditions. J. Nucl. Mater. 298, 1–10 (2001).
Gin, S. et al. Dynamics of self-reorganization explains passivation of silicate glasses. Nat. Commun. 9, 2169 (2018).
Gin, S. et al. Origin and consequences of silicate glass passivation by surface layers. Nat. Commun. 6, 6360 (2015).
Collin, M. et al. Structure of International Simple Glass and properties of passivating layer formed in circumneutral pH conditions. npj Mater. Degrad. 2, 4 (2018).
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).
Grambow, B. A general rate equation for nuclear waste glass corrosion. MRS Online Proc. Libr. Arch. 44, 15 (1984).
Ma, T. et al. A mechanistic model for long-term nuclear waste glass dissolution integrating chemical affinity and interfacial diffusion barrier. J. Nucl. Mater. 486, 70–85 (2017).
Putnis, A. Why mineral interfaces matter. Science 343, 1441–1442 (2014).
Putnis, A. Mineral replacement reactions: from macroscopic observations to microscopic mechanisms. Mineral. Mag. 66, 689–708 (2002).
Putnis, C. V. & Ruiz-Agudo, E. The mineral‒water interface: where minerals react with the environment. Elements 9, 177–182 (2013).
Steefel, C. I., Beckingham, L. E. & Landrot, G. Micro-continuum approaches for modeling pore-scale geochemical processes. Rev. Mineral. Geochem. 80, 217–246 (2015).
Schalm, O. & Anaf, W. Laminated altered layers in historical glass: density variations of silica nanoparticle random packings as explanation for the observed lamellae. J. Non-Cryst. Solids 442, 1–16 (2016).
Dohmen, L. et al. Pattern formation in silicate glass corrosion zones. Int. J. Appl. Glass Sci. 4, 357–370 (2013).
Wang, Y., Jove-Colon, C. F. & Kuhlman, K. L. Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals. Sci. Rep. 6, 30256 (2016).
Brinker, C. J. & Scherer, G. W. Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing (Academic, San Diego, 1990).
Iler, R. K. The Chemistry of Silica: Solubility, Polymerization, Colloid and Surface Properties and Biochemistry of Silica (Wiley, New York, 1979).
Brooker, M. H., Hancock, G., Rice, B. C. & Shapter, J. Raman frequency and intensity studies of liquid H2O, H2 18O and D2O. J. Raman Spectrosc. 20, 683–694 (1989).
Parkhurst, D. L. & Appelo, C. Description of Input and Examples for PHREEQC Version 3: A Computer Program for Speciation, Batch-Reaction, One-Dimensional Transport, and Inverse Geochemical Calculations (US Geological Survey, 2013).
Rudolph, W. W., Irmer, G. & Konigsberger, E. Speciation studies in aqueous HCO3 ‒–CO3 2‒ solutions. A combined Raman spectroscopic and thermodynamic study. Dalton Trans. 900–908 (2008).
Putnis, C. V., Tsukamoto, K. & Nishimura, Y. Direct observations of pseudomorphism: compositional and textural evolution at a fluid–solid interface. Am. Mineral. 90, 1909–1912 (2005).
Ruiz-Agudo, E. et al. Control of silicate weathering by interface-coupled dissolution–precipitation processes at the mineral–solution interface. Geology 44, 567–570 (2016).
Icenhower, J. P. & Steefel, C. I. Experimentally determined dissolution kinetics of SON68 glass at 90 °C over a silica saturation interval: Evidence against a linear rate law. J. Nucl. Mater. 439, 137–147 (2013).
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).
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).
Pöml, P. et al. Mechanism of hydrothermal alteration of natural self-irradiated and synthetic crystalline titanate-based pyrochlore. Geochim. Cosmochim. Acta 71, 3311–3322 (2007).
Kasioptas, A., Geisler, T., Putnis, C. V., Perdikouri, C. & Putnis, A. Crystal growth of apatite by replacement of an aragonite precursor. J. Cryst. Growth 312, 2431–2440 (2010).
Sterpenich, J. & Libourel, G. Water diffusion in silicate glasses under natural weathering conditions: evidence from buried medieval stained glasses. J. Non-Cryst. Solids 352, 5446–5451 (2006).
Mills, R. Self-diffusion in normal and heavy water in the range 1–45 deg. J. Phys. Chem. 77, 685–688 (1973).
Bourg, I. C. & Steefel, C. I. Molecular dynamics simulations of water structure and diffusion in silica nanopores. J. Phys. Chem. C 116, 11556–11564 (2012).
Gin, S. et al. The fate of silicon during glass corrosion under alkaline conditions: a mechanistic and kinetic study with the International Simple Glass. Geochim. Cosmochim. Acta 151, 68–85 (2015).
Liesegang, M., Milke, R., Kranz, C. & Neusser, G. Silica nanoparticle aggregation in calcite replacement reactions. Sci. Rep. 7, 14550 (2017).
Saloman, E. B. & Sansonetti, C. J. Wavelengths, energy level classifications, and energy levels for the spectrum of neutral neon. J. Phys. Chem. Ref. Data 33, 1113–1158 (2004).
Everall, N. J. Modeling and measuring the effect of refraction on the depth resolution of confocal Raman microscopy. Appl. Spectrosc. 54, 773–782 (2000).
Applegarth, L. M. S. G. A., Pye, C. C., Cox, J. S. & Tremaine, P. R. Raman spectroscopic and ab initio investigation of aqueous boric acid, borate, and polyborate speciation from 25 to 80 °C. Ind. Eng. Chem. Res. 56, 13983–13996 (2017).
We thank G. Paulus (Schott AG) for synthesizing and characterizing the borosilicate glass, and D. Lülsdorf and H. Blanchard (University of Bonn) as well as W. Bauer (Schott AG) for helping with the design and construction of the fluid cell. We acknowledge Schott AG Mainz, Germany, and the German Research Foundation (grant no. GE1094/21-1) for financial support. T.G. and M.B.K.F. are also grateful for financial support provided by the Otto-Schott-Fond.
The authors declare no competing interests.
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Geisler, T., Dohmen, L., Lenting, C. et al. Real-time in situ observations of reaction and transport phenomena during silicate glass corrosion by fluid-cell Raman spectroscopy. Nat. Mater. 18, 342–348 (2019). https://doi.org/10.1038/s41563-019-0293-8
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