Real-time in situ observations of reaction and transport phenomena during silicate glass corrosion by fluid-cell Raman spectroscopy

Abstract

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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Fig. 1: Experimental set-up for in situ fluid-cell Raman spectroscopy measurements and representative Raman spectra from the borosilicate glass, the SAL and the deuterated bicarbonate solution at 85 °C.
Fig. 2: Distribution and chemical properties of the solution and the silica product phase as a function of time and space at 85 °C.
Fig. 3: Time dependence of the glass retreat and retreat rate as well as chemical and textural characteristics of the dried SAL.
Fig. 4: Solution pH as a function of the distance from the glass surface at a given time as well as representative Raman spectra of the aqueous carbonate bands from which the pH was determined.
Fig. 5: In situ deuterium concentration profiles across the SAL for different times after partial solution exchange with a deuterated bicarbonate solution.

Data availability

The datasets collected and analysed in the current study are available from the corresponding author upon request.

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Acknowledgements

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.

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T.G. initiated and planned the study and wrote the first draft of the manuscript. L.D. and C.L. performed the experiments. M.B.K.F. performed Raman measurements to evaluate the detection limit of B solution species as well as the temperature calibration measurements. All authors contributed to the data analysis and interpretation as well as to the final manuscript.

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Correspondence to Thorsten Geisler.

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Supplementary Figures 1–5, Supplementary Table 1, Supplementary References 1–7

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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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