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

Title: Structure of International Simple Glass and properties of passivating layer formed in circumneutral pH conditions

Abstract

Knowing the structure of a material is necessary to understand its evolution under various influences; here, the alteration by water of a reference glass of nuclear interest, called International Simple Glass (ISG), is studied. The ISG atomic structure has not yet been thoroughly characterized. Short- and medium-range order in this six-oxide glass was investigated by molecular dynamics (MD) methods. Combining the simulated data with experimental observations acquired from both pristine and altered ISG provided new insight into the formation of surface layers and passivation of the underlying glass. In the tested conditions of 90 °C, silica-saturated solution, and pH 90°C 7, the passivating layer partly inherits the structure of the pristine glass network despite the release of mobile elements (Na, B, and some Ca), with a reorganization of the silicate network following B release. The layer appears to minimize its internal energy by relaxing strain accumulated during glass quenching. The resulting passivated glass shows a strong resistance to hydrolysis. The nanopores of this hydrated material, displaying a mean pore size of ~1 nm, are filled with various water species. Water speciation determination inside the nanopores is therefore an achievement for future water dynamic study in the passivated glass.

Authors:
 [1]; ORCiD logo [1];  [1]; ORCiD logo [2];  [2];  [3];  [3];  [3];  [1]
  1. Alternative Energies and Atomic Energy Commission (CEA), Bagnols-sur-Ceze (France)
  2. Univ. Paris-Saclay, Gif-sur-Yvette (France)
  3. Univ. of North Texas, Denton, TX (United States)
Publication Date:
Research Org.:
The Ohio State Univ., Columbus, OH (United States). Energy Frontier Research Center (EFRC) Center for Performance and Design of Nuclear Waste Forms and Containers (WastePD)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470161
Grant/Contract Number:  
SC0016584
Resource Type:
Accepted Manuscript
Journal Name:
npj Materials Degradation
Additional Journal Information:
Journal Volume: 2; Journal Issue: 1; Journal ID: ISSN 2397-2106
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Collin, Marie, Fournier, Maxime, Frugier, Pierre, Charpentier, Thibault, Moskura, Mélanie, Deng, Lu, Ren, Mengguo, Du, Jincheng, and Gin, Stéphane. Structure of International Simple Glass and properties of passivating layer formed in circumneutral pH conditions. United States: N. p., 2018. Web. doi:10.1038/s41529-017-0025-y.
Collin, Marie, Fournier, Maxime, Frugier, Pierre, Charpentier, Thibault, Moskura, Mélanie, Deng, Lu, Ren, Mengguo, Du, Jincheng, & Gin, Stéphane. Structure of International Simple Glass and properties of passivating layer formed in circumneutral pH conditions. United States. doi:10.1038/s41529-017-0025-y.
Collin, Marie, Fournier, Maxime, Frugier, Pierre, Charpentier, Thibault, Moskura, Mélanie, Deng, Lu, Ren, Mengguo, Du, Jincheng, and Gin, Stéphane. Mon . "Structure of International Simple Glass and properties of passivating layer formed in circumneutral pH conditions". United States. doi:10.1038/s41529-017-0025-y. https://www.osti.gov/servlets/purl/1470161.
@article{osti_1470161,
title = {Structure of International Simple Glass and properties of passivating layer formed in circumneutral pH conditions},
author = {Collin, Marie and Fournier, Maxime and Frugier, Pierre and Charpentier, Thibault and Moskura, Mélanie and Deng, Lu and Ren, Mengguo and Du, Jincheng and Gin, Stéphane},
abstractNote = {Knowing the structure of a material is necessary to understand its evolution under various influences; here, the alteration by water of a reference glass of nuclear interest, called International Simple Glass (ISG), is studied. The ISG atomic structure has not yet been thoroughly characterized. Short- and medium-range order in this six-oxide glass was investigated by molecular dynamics (MD) methods. Combining the simulated data with experimental observations acquired from both pristine and altered ISG provided new insight into the formation of surface layers and passivation of the underlying glass. In the tested conditions of 90 °C, silica-saturated solution, and pH90°C 7, the passivating layer partly inherits the structure of the pristine glass network despite the release of mobile elements (Na, B, and some Ca), with a reorganization of the silicate network following B release. The layer appears to minimize its internal energy by relaxing strain accumulated during glass quenching. The resulting passivated glass shows a strong resistance to hydrolysis. The nanopores of this hydrated material, displaying a mean pore size of ~1 nm, are filled with various water species. Water speciation determination inside the nanopores is therefore an achievement for future water dynamic study in the passivated glass.},
doi = {10.1038/s41529-017-0025-y},
journal = {npj Materials Degradation},
number = 1,
volume = 2,
place = {United States},
year = {2018},
month = {2}
}

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

Save / Share:

Works referenced in this record:

Nature of Incorporated Water in Hydrated Silicate Glasses
journal, July 1980


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

The controversial role of inter-diffusion in glass alteration
journal, November 2016


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

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


Contribution of first-principles calculations to multinuclear NMR analysis of borosilicate glasses
journal, September 2010

  • Soleilhavoup, Anne; Delaye, Jean-Marc; Angeli, Frédéric
  • Magnetic Resonance in Chemistry, Vol. 48, Issue S1
  • DOI: 10.1002/mrc.2673

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

Modelling one- and two-dimensional solid-state NMR spectra: Modelling 1D and 2D solid-state NMR spectra
journal, December 2001

  • Massiot, Dominique; Fayon, Franck; Capron, Mickael
  • Magnetic Resonance in Chemistry, Vol. 40, Issue 1
  • DOI: 10.1002/mrc.984

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

Contribution of 43Ca MAS NMR for probing the structural configuration of calcium in glass
journal, June 2007


Oxide glass structure evolution under swift heavy ion irradiation
journal, April 2014

  • Mendoza, C.; Peuget, S.; Charpentier, T.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 325
  • DOI: 10.1016/j.nimb.2014.02.002

Local structure of silicate glasses
journal, October 1981

  • Greaves, G. N.; Fontaine, A.; Lagarde, P.
  • Nature, Vol. 293, Issue 5834
  • DOI: 10.1038/293611a0

Effects of fictive temperature on the leaching of soda lime silica glass surfaces
journal, February 2017

  • Amma, Shin-ichi; Luo, Jiawei; Kim, Seong H.
  • Journal of the American Ceramic Society, Vol. 100, Issue 4
  • DOI: 10.1111/jace.14754

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


An international initiative on long-term behavior of high-level nuclear waste glass
journal, June 2013


Glass dissolution rate measurement and calculation revisited
journal, August 2016


An infrared spectroscopic study of water-related species in silica glasses
journal, June 1996


Modeling of multicomponent glasses: a review
journal, October 2001


Solid-state NMR characterization of a controlled-pore glass and of the effects of electron irradiation
journal, January 2008

  • Brunet, F.; Charpentier, T.; Le Caër, S.
  • Solid State Nuclear Magnetic Resonance, Vol. 33, Issue 1-2
  • DOI: 10.1016/j.ssnmr.2007.12.001

Analytical molecular surface calculation
journal, October 1983


Multinuclear NMR study of silica fiberglass modified with zirconia
journal, May 2011

  • Lapina, O. B.; Khabibulin, D. F.; Terskikh, V. V.
  • Solid State Nuclear Magnetic Resonance, Vol. 39, Issue 3-4
  • DOI: 10.1016/j.ssnmr.2010.12.002

Molecular Water in Glass
journal, January 1977


Quantitative determination of water speciation in aluminosilicate glasses: a comparative NMR and IR spectroscopic study
journal, April 2001


Probing silicon and aluminium chemical environments in silicate and aluminosilicate glasses by solid state NMR spectroscopy and accurate first-principles calculations
journal, January 2014

  • Gambuzzi, Elisa; Pedone, Alfonso; Menziani, Maria Cristina
  • Geochimica et Cosmochimica Acta, Vol. 125
  • DOI: 10.1016/j.gca.2013.10.025

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


Global Model for Calculating Room-Temperature Glass Density from the Composition
journal, August 2007


Water speciation in rhyolitic melt determined by in-situ infrared spectroscopy
journal, December 1999


Development of empirical potentials for sodium borosilicate glass systems
journal, September 2011


Alkali influence on the water speciation and the environment of protons in silicate glasses revealed by 1H MAS NMR spectroscopy
journal, February 2015

  • Le Losq, C.; Cody, G. D.; Mysen, B. O.
  • American Mineralogist, Vol. 100, Issue 2-3
  • DOI: 10.2138/am-2015-5004

Influence of lanthanum on borosilicate glass structure: A multinuclear MAS and MQMAS NMR investigation
journal, September 2013


Structure and properties of sodium aluminosilicate glasses from molecular dynamics simulations
journal, July 2013

  • Xiang, Ye; Du, Jincheng; Smedskjaer, Morten M.
  • The Journal of Chemical Physics, Vol. 139, Issue 4
  • DOI: 10.1063/1.4816378

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

Effects of boron oxide substitution on the structure and bioactivity of SrO-containing bioactive glasses
journal, February 2017


Hydration of rhyolitic glass during weathering as characterized by IR microspectroscopy
journal, January 2008

  • Yokoyama, Tadashi; Okumura, Satoshi; Nakashima, Satoru
  • Geochimica et Cosmochimica Acta, Vol. 72, Issue 1
  • DOI: 10.1016/j.gca.2007.10.018

Resumption of Alteration at High Temperature and pH: Rates Measurements and Comparison with Initial Rates
journal, January 2014


An enhanced resolution of the structural environment of zirconium in borosilicate glasses
journal, December 2013


pH-dependent control of feldspar dissolution rate by altered surface layers
journal, November 2016


Exafs and xanes study of the local coordination environment of sodium in a series of silica-rich glasses and selected minerals within the Na2OAl2O3SiO2 system
journal, November 1985


Structural study of sol–gel silicate glasses by IR and Raman spectroscopies
journal, April 2009


Qn distribution in stoichiometric silicate glasses: thermodynamic calculations and 29Si high resolution NMR measurements
journal, September 2003


DL_POLY_2.0: A general-purpose parallel molecular dynamics simulation package
journal, June 1996


Effect of clayey groundwater on the dissolution rate of the simulated nuclear waste glass SON68
journal, January 2012


Various effects of magnetite on international simple glass (ISG) dissolution: implications for the long-term durability of nuclear glasses
journal, July 2017


Initial Dissolution Rate of the International Simple Glass as a Function of pH and Temperature Measured Using Microchannel Flow-Through Test Method
journal, October 2013

  • Inagaki, Yaohiro; Kikunaga, Taiki; Idemitsu, Kazuya
  • International Journal of Applied Glass Science, Vol. 4, Issue 4
  • DOI: 10.1111/ijag.12043

Nuclear Waste Glasses - How Durable?
journal, December 2006


The fate of silicon during glass corrosion under alkaline conditions: A mechanistic and kinetic study with the International Simple Glass
journal, February 2015

  • Gin, Stéphane; Jollivet, Patrick; Fournier, Maxime
  • Geochimica et Cosmochimica Acta, Vol. 151
  • DOI: 10.1016/j.gca.2014.12.009

Influence of glass composition and alteration solution on leached silicate glass structure: A solid-state NMR investigation
journal, May 2006

  • Angeli, Frédéric; Gaillard, Marina; Jollivet, Patrick
  • Geochimica et Cosmochimica Acta, Vol. 70, Issue 10
  • DOI: 10.1016/j.gca.2006.02.023

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


Self-healing capacity of nuclear glass observed by NMR spectroscopy
journal, May 2016

  • Charpentier, Thibault; Martel, Laura; Mir, Anamul H.
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep25499

NMR Study of a Rare-Earth Aluminoborosilicate Glass with Varying CaO-to-Na2O Ratio
journal, December 2007


Durable Glass for Thousands of Years
journal, March 2010


SiO2–Na2O–B2O3 density: A comparison of experiments, simulations, and theory
journal, December 2013


    Works referencing / citing this record:

    Application of GRAAL model to the resumption of International Simple Glass alteration
    journal, July 2018

    • Fournier, Maxime; Frugier, Pierre; Gin, Stéphane
    • npj Materials Degradation, Vol. 2, Issue 1
    • DOI: 10.1038/s41529-018-0043-4