skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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

Abstract

Here, we report and discuss results of atom probe tomography (APT) and energy-filtered transmission electron microscopy (EFTEM) applied to a borosilicate glass sample of nuclear interest altered for nearly 26 years at 90°C in a confined granitic medium in order to better understand the rate-limiting mechanisms under conditions representative of a deep geological repository for vitrified radioactive waste. The APT technique allows the 3D reconstruction of the elemental distribution at the reactive interphase with sub-nanometer precision. Profiles of the B distribution at pristine glass/hydrated glass interface obtained by different techniques are compared to show the challenge of accurate measurements of diffusion profiles at this buried interface on the nanometer length scale. Our results show that 1) Alkali from the glass and hydrogen from the solution exhibit anti-correlated 15 ± 3 nm wide gradients located between the pristine glass and the hydrated glass layer, 2) boron exhibits an unexpectedly sharp profile located just at the outside of the alkali/H interdiffusion layer; this sharp profile is more consistent with a dissolution front than a diffusion-controlled release of boron. The resulting apparent diffusion coefficients derived from the Li and H profiles are DLi = 1.5 × 10-22 m2.s-1 and DH = 6.8 ×more » 10-23 m2.s-1. These values are around two orders of magnitude lower than those observed at the very beginning of the alteration process, which suggests that interdiffusion is slowed at high reaction progress by local conditions that could be related to the porous structure of the interphase. As a result, the accessibility of water to the pristine glass could be the rate-limiting step in these conditions. More generally, these findings strongly support the importance of interdiffusion coupled with hydrolysis reactions of the silicate network on the long-term dissolution rate, contrary to what has been suggested by recent interfacial dissolution-precipitation models for silicate minerals.« less

Authors:
 [1];  [2];  [2];  [2];  [3]
  1. CEA Marcoule DTCD SECM LCLT, Bagnols-sur-Ceze (France)
  2. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
  3. Aix-Marseille Universite, CP2M, Marseille (France)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1097327
Report Number(s):
PNNL-SA-92809
Journal ID: ISSN 0009-2541; 47580; 46403; 42495; AF5805000; TRN: US1400334
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Geology
Additional Journal Information:
Journal Volume: 349-350; Journal ID: ISSN 0009-2541
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Environmental Molecular Sciences Laboratory; nuclear glass; atom probe tomography; interdiffusion; alteration layers; long-term rate

Citation Formats

Gin, Stephane, Ryan, Joseph V., Schreiber, Daniel K., Neeway, James J., and Cabie, 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. United States: N. p., 2013. Web. https://doi.org/10.1016/j.chemgeo.2013.04.001.
Gin, Stephane, Ryan, Joseph V., Schreiber, Daniel K., Neeway, James J., & Cabie, 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. United States. https://doi.org/10.1016/j.chemgeo.2013.04.001
Gin, Stephane, Ryan, Joseph V., Schreiber, Daniel K., Neeway, James J., and Cabie, M. Mon . "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". United States. https://doi.org/10.1016/j.chemgeo.2013.04.001. https://www.osti.gov/servlets/purl/1097327.
@article{osti_1097327,
title = {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},
author = {Gin, Stephane and Ryan, Joseph V. and Schreiber, Daniel K. and Neeway, James J. and Cabie, M.},
abstractNote = {Here, we report and discuss results of atom probe tomography (APT) and energy-filtered transmission electron microscopy (EFTEM) applied to a borosilicate glass sample of nuclear interest altered for nearly 26 years at 90°C in a confined granitic medium in order to better understand the rate-limiting mechanisms under conditions representative of a deep geological repository for vitrified radioactive waste. The APT technique allows the 3D reconstruction of the elemental distribution at the reactive interphase with sub-nanometer precision. Profiles of the B distribution at pristine glass/hydrated glass interface obtained by different techniques are compared to show the challenge of accurate measurements of diffusion profiles at this buried interface on the nanometer length scale. Our results show that 1) Alkali from the glass and hydrogen from the solution exhibit anti-correlated 15 ± 3 nm wide gradients located between the pristine glass and the hydrated glass layer, 2) boron exhibits an unexpectedly sharp profile located just at the outside of the alkali/H interdiffusion layer; this sharp profile is more consistent with a dissolution front than a diffusion-controlled release of boron. The resulting apparent diffusion coefficients derived from the Li and H profiles are DLi = 1.5 × 10-22 m2.s-1 and DH = 6.8 × 10-23 m2.s-1. These values are around two orders of magnitude lower than those observed at the very beginning of the alteration process, which suggests that interdiffusion is slowed at high reaction progress by local conditions that could be related to the porous structure of the interphase. As a result, the accessibility of water to the pristine glass could be the rate-limiting step in these conditions. More generally, these findings strongly support the importance of interdiffusion coupled with hydrolysis reactions of the silicate network on the long-term dissolution rate, contrary to what has been suggested by recent interfacial dissolution-precipitation models for silicate minerals.},
doi = {10.1016/j.chemgeo.2013.04.001},
journal = {Chemical Geology},
number = ,
volume = 349-350,
place = {United States},
year = {2013},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 55 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Thermodynamic and kinetic constraints on reaction rates among minerals and aqueous solutions; I, Theoretical considerations
journal, March 1982


Boron Speciation in Soda-Lime Borosilicate Glasses Containing Zirconium: Boron Speciation in Soda-Lime Borosilicate Glasses
journal, April 2010

  • Angeli, Frédéric; Charpentier, Thibault; De Ligny, Dominique
  • Journal of the American Ceramic Society, Vol. 93, Issue 9
  • DOI: 10.1111/j.1551-2916.2010.03771.x

A general protocol for the reconstruction of 3D atom probe data
journal, March 1995


Molecular Dynamics Simulations of Water Structure and Diffusion in Silica Nanopores
journal, May 2012

  • Bourg, Ian C.; Steefel, Carl I.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 21
  • DOI: 10.1021/jp301299a

Water solubility in calcium aluminosilicate glasses investigated by first principles techniques
journal, December 2010

  • Bouyer, Frédéric; Geneste, Grégory; Ispas, Simona
  • Journal of Solid State Chemistry, Vol. 183, Issue 12
  • DOI: 10.1016/j.jssc.2010.08.031

Impact of Pore Size and Pore Surface Composition on the Dynamics of Confined Water in Highly Ordered Porous Silica
journal, March 2012

  • Briman, Ibrahim Matar; Rébiscoul, Diane; Diat, Olivier
  • The Journal of Physical Chemistry C, Vol. 116, Issue 12
  • DOI: 10.1021/jp3001898

Molecular mechanisms for corrosion of silica and silicate glasses
journal, November 1994


Insight into silicate-glass corrosion mechanisms
journal, October 2008

  • Cailleteau, Céline; Angeli, Frédéric; Devreux, François
  • Nature Materials, Vol. 7, Issue 12
  • DOI: 10.1038/nmat2301

Why Do Certain Glasses with a High Dissolution Rate Undergo a Low Degree of Corrosion?
journal, March 2011

  • Cailleteau, Céline; Devreux, François; Spalla, Olivier
  • The Journal of Physical Chemistry C, Vol. 115, Issue 13
  • DOI: 10.1021/jp111458f

Helium diffusion coefficient measurements in R7T7 nuclear glass by 3He(d,α)1H nuclear reaction analysis
journal, May 2010


Solid state diffusion during nuclear glass residual alteration in solution
journal, May 2007


Glass–water interphase reactivity with calcium rich solutions
journal, August 2011


Effects of annealing on local composition and electrical transport correlations in MgO-based magnetic tunnel junctions
journal, September 2008

  • Chiaramonti, A. N.; Schreiber, D. K.; Egelhoff, W. F.
  • Applied Physics Letters, Vol. 93, Issue 10
  • DOI: 10.1063/1.2970964

On-site Raman identification and dating of ancient glasses: A review of procedures and tools
journal, December 2008


Nature and role of natural alteration gels formed on the surface of ancient volcanic glasses (Natural analogs of waste containment glasses)
journal, September 2003

  • Crovisier, Jean-Louis; Advocat, Thierry; Dussossoy, Jean-Luc
  • Journal of Nuclear Materials, Vol. 321, Issue 1
  • DOI: 10.1016/S0022-3115(03)00206-X

Kinetic aspects of basaltic glass dissolution at 90°C: role of aqueous silicon and aluminium
journal, October 1997


Investigations of Omega Precipitation in Titanium Molybdenum Alloys by Coupling 3D Atom Probe Tomography and High Resolution (S)TEM
journal, July 2009


Interdiffusion of hydrogen and alkali ions in a glass surface
journal, December 1975


Modification of a transmission electron microscope to give energy-filtered images and diffraction patterns, and electron energy loss spectra
journal, December 1975

  • Egerton, R. F.; Philip, J. G.; Turner, P. S.
  • Journal of Physics E: Scientific Instruments, Vol. 8, Issue 12
  • DOI: 10.1088/0022-3735/8/12/017

Water diffusion in the simulated French nuclear waste glass SON 68 contacting silica rich solutions: Experimental and modeling
journal, September 2006


SON68 nuclear glass dissolution kinetics: Current state of knowledge and basis of the new GRAAL model
journal, October 2008


Application of the GRAAL model to leaching experiments with SON68 nuclear glass in initially pure water
journal, August 2009


Advances in the reconstruction of atom probe tomography data
journal, May 2011


Hydrogen–sodium interdiffusion in borosilicate glasses investigated from first principles
journal, August 2006


A review of focused ion beam milling techniques for TEM specimen preparation
journal, June 1999


Theoretical consideration on the application of the Aagaard–Helgeson rate law to the dissolution of silicate minerals and glasses
journal, September 2008


Nuclear Glass Durability: New Insight into Alteration Layer Properties
journal, August 2011

  • Gin, Stéphane; Guittonneau, Claire; Godon, Nicole
  • The Journal of Physical Chemistry C, Vol. 115, Issue 38
  • DOI: 10.1021/jp205477q

Effect of composition on the short-term and long-term dissolution rates of ten borosilicate glasses of increasing complexity from 3 to 30 oxides
journal, September 2012


Analytical electron microscopy study of surface layers formed on the French SON68 nuclear waste glass during vapor hydration at 200°C
journal, April 1998


Nuclear Waste Glasses - How Durable?
journal, December 2006


First-order dissolution rate law and the role of surface layers in glass performance assessment
journal, September 2001


A 25-year laboratory experiment on French SON68 nuclear glass leached in a granitic environment – First investigations
journal, January 2011


Analysis of Three-dimensional Atom-probe Data by the Proximity Histogram
journal, September 2000

  • Hellman, Olof C.; Vandenbroucke, Justin A.; Rüsing, Järg
  • Microscopy and Microanalysis, Vol. 6, Issue 05
  • DOI: 10.1007/S100050010051

Three-dimensional analysis of porous BaTiO3 ceramics using FIB nanotomography
journal, October 2004


Durable Glass for Thousands of Years
journal, March 2010


About the use of electron energy-loss spectroscopy for chemical mapping of thin foils with high spatial resolution
journal, January 1978


Investigation of gel porosity clogging during glass leaching
journal, November 2008


Atom Probe Tomography 2012
journal, August 2012


Monte Carlo simulations of the dissolution of borosilicate and aluminoborosilicate glasses in dilute aqueous solutions
journal, September 2011


Monte Carlo simulations of borosilicate glass corrosion: predictions for morphology and kinetics
journal, October 2004


The use of natural and archeological analogues for understanding the long-term behavior of nuclear glasses
journal, February 2011

  • Libourel, Guy; Verney-Carron, Aurelie; Morlok, Andreas
  • Comptes Rendus Geoscience, Vol. 343, Issue 2-3
  • DOI: 10.1016/j.crte.2010.12.004

Probing the improbable: imaging C atoms in alumina
journal, October 2010


The structure of Na2O–Al2O3–SiO2 glass: impact on sodium ion exchange in H2O and D2O
journal, December 2001


Ultraviolet-laser atom-probe tomographic three-dimensional atom-by-atom mapping of isotopically modulated Si nanoscopic layers
journal, January 2011

  • Moutanabbir, Oussama; Isheim, Dieter; Seidman, David N.
  • Applied Physics Letters, Vol. 98, Issue 1
  • DOI: 10.1063/1.3531816

The ion exchange phase in corrosion of nuclear waste glasses
journal, November 2006


Hydrated-layer formation during dissolution of complex silicate glasses and minerals
journal, July 1990


Long-term dissolution rate of nuclear glasses in confined environments: does a residual chemical affinity exist?
journal, July 1990

  • Petit, J. -C.; Magonthier, M. -C.; Dran, J. -C.
  • Journal of Materials Science, Vol. 25, Issue 7
  • DOI: 10.1007/BF00587648

Combined Experimental and Computational Approach to Predict the Glass-Water Reaction
journal, October 2011


X-ray reflectometry characterization of SON 68 glass alteration films
journal, September 2003


Protective properties and dissolution ability of the gel formed during nuclear glass alteration
journal, June 2005


Water penetration mechanisms in nuclear glasses by X-ray and neutron reflectometry
journal, July 2007


Impact of soda-lime borosilicate glass composition on water penetration and water structure at the first time of alteration
journal, November 2012


Role of neoformed phases on the mechanisms controlling the resumption of SON68 glass alteration in alkaline media
journal, January 2004


In situ site-specific specimen preparation for atom probe tomography
journal, February 2007


Elemental and isotopic (29Si and 18O) tracing of glass alteration mechanisms
journal, June 2010

  • Valle, Nathalie; Verney-Carron, Aurélie; Sterpenich, Jérôme
  • Geochimica et Cosmochimica Acta, Vol. 74, Issue 12
  • DOI: 10.1016/j.gca.2010.03.028

    Works referencing / citing this record:

    Real-time in situ observations of reaction and transport phenomena during silicate glass corrosion by fluid-cell Raman spectroscopy
    journal, February 2019


    A Preliminary Investigation of the ISG Glass Vapor Hydration
    journal, October 2013

    • Abdelouas, Abdesselam; El Mendili, Yassine; Aït Chaou, Abdelouahed
    • International Journal of Applied Glass Science, Vol. 4, Issue 4
    • DOI: 10.1111/ijag.12055

    Pattern Formation in Silicate Glass Corrosion Zones
    journal, October 2013

    • Dohmen, Lars; Lenting, Christoph; Fonseca, Raúl O. C.
    • International Journal of Applied Glass Science, Vol. 4, Issue 4
    • DOI: 10.1111/ijag.12046

    Current Understanding and Remaining Challenges in Modeling Long-Term Degradation of Borosilicate Nuclear Waste Glasses
    journal, November 2013

    • Vienna, John D.; Ryan, Joseph V.; Gin, Stéphane
    • International Journal of Applied Glass Science, Vol. 4, Issue 4
    • DOI: 10.1111/ijag.12050

    Mixed reactions: Glass durability and the mixed‐alkali effect
    journal, June 2019

    • Rodrigues, Alexandra; Fearn, Sarah; Vilarigues, Márcia
    • Journal of the American Ceramic Society, Vol. 102, Issue 12
    • DOI: 10.1111/jace.16665

    A comparative review of the aqueous corrosion of glasses, crystalline ceramics, and metals
    journal, May 2018


    First-Principles Study of Hydrolysis Reaction Barriers in a Sodium Borosilicate Glass
    journal, November 2013

    • Zapol, Peter; He, Haiying; Kwon, Kideok D.
    • International Journal of Applied Glass Science, Vol. 4, Issue 4
    • DOI: 10.1111/ijag.12052

    NanoSIMS imaging alteration layers of a leached SON68 glass via a FIB-made wedged crater: NanoSIMS imaging alternation layers of a leached glass
    journal, June 2014

    • Wang, Yi-Chung; Schreiber, Daniel K.; Neeway, James J.
    • Surface and Interface Analysis, Vol. 46, Issue S1
    • DOI: 10.1002/sia.5585

    Origin and consequences of silicate glass passivation by surface layers
    journal, February 2015

    • Gin, Stéphane; Jollivet, Patrick; Fournier, Maxime
    • Nature Communications, Vol. 6, Issue 1
    • DOI: 10.1038/ncomms7360

    Nanometre-scale evidence for interfacial dissolution–reprecipitation control of silicate glass corrosion
    journal, January 2015

    • Hellmann, Roland; Cotte, Stéphane; Cadel, Emmanuel
    • Nature Materials, Vol. 14, Issue 3
    • DOI: 10.1038/nmat4172

    Nanoscale imaging of hydrogen and sodium in alteration layers of corroded glass using ToF-SIMS: Is an auxiliary sputtering ion beam necessary?
    journal, October 2018

    • Zhang, Jiandong; Zhang, Yanyan; Collin, Marie
    • Surface and Interface Analysis, Vol. 51, Issue 2
    • DOI: 10.1002/sia.6571

    Behavior of molecules and molecular ions near a field emitter
    journal, March 2016


    Diffusive processes in aqueous glass dissolution
    journal, November 2019

    • Goût, Thomas L.; Misra, Sambuddha; Tipper, Edward T.
    • npj Materials Degradation, Vol. 3, Issue 1
    • DOI: 10.1038/s41529-019-0102-5

    New Insight into the Residual Rate of Borosilicate Glasses: Effect of S/V and Glass Composition
    journal, October 2013

    • Gin, Stéphane; Frugier, Pierre; Jollivet, Patrick
    • International Journal of Applied Glass Science, Vol. 4, Issue 4
    • DOI: 10.1111/ijag.12048

    Towards a unifying mechanistic model for silicate glass corrosion
    journal, September 2018

    • Lenting, Christoph; Plümper, Oliver; Kilburn, Matt
    • npj Materials Degradation, Vol. 2, Issue 1
    • DOI: 10.1038/s41529-018-0048-z