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Title: Durability of Silicate Glasses: An Historical Approach

Abstract

We present a short review of current theories of glass weathering, including glass dissolution, and hydrolysis of nuclear waste glasses, and leaching of historical glasses from an XAFS perspective. The results of various laboratory leaching experiments at different timescales (30 days to 12 years) are compared with results for historical glasses that were weathered by atmospheric gases and soil waters over 500 to 3000 years. Good agreement is found between laboratory experiments and slowly leached historical glasses, with a strong enrichment of metals at the water/gel interface. Depending on the nature of the transition elements originally dissolved in the melt, increasing elemental distributions are expected to increase with time for a given glass durability context.

Authors:
 [1];  [2];  [3];  [4];  [3];  [5];  [6];  [7];  [2]
  1. USM 201 'Mineralogie-Petrologie', Museum National d'Histoire Naturelle, CNRS UMR 7160, Paris (France)
  2. (United States)
  3. Laboratoire des Geomateriaux, Universite de Marne la Vallee (France)
  4. (France)
  5. Service de Recherches de Metallurgie Physique, Commissariat a l' Energie Atomique (CEA), Saclay (France)
  6. Laboratory of Waste Management, Paul Scherrer Institut (PSI), Villigen (Switzerland)
  7. Department of Geological and Environmental Sciences, Stanford University, Stanford, CA (United States)
Publication Date:
OSTI Identifier:
21054652
Resource Type:
Journal Article
Resource Relation:
Journal Name: AIP Conference Proceedings; Journal Volume: 882; Journal Issue: 1; Conference: XAFS13: 13. international conference on X-ray absorption fine structure, Stanford, CA (United States), 9-14 Jul 2006; Other Information: DOI: 10.1063/1.2644427; (c) 2007 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ABSORPTION SPECTROSCOPY; DISTRIBUTION; FINE STRUCTURE; GELS; GLASS; HYDROLYSIS; INTERFACES; LEACHING; RADIOACTIVE WASTES; SILICATES; SOILS; TRANSITION ELEMENTS; WEATHERING; X-RAY SPECTRA; X-RAY SPECTROSCOPY

Citation Formats

Farges, Francois, Department of Geological and Environmental Sciences, Stanford University, Stanford, CA, Etcheverry, Marie-Pierre, Laboratoire de Recherche des Monuments Historiques, Champs sur Marne, Haddi, Amine, Trocellier, Patrick, Curti, Enzo, Brown, Gordon E. Jr., and Stanford Synchrotron Radiation Laboratory, SLAC, Menlo Park, CA. Durability of Silicate Glasses: An Historical Approach. United States: N. p., 2007. Web. doi:10.1063/1.2644427.
Farges, Francois, Department of Geological and Environmental Sciences, Stanford University, Stanford, CA, Etcheverry, Marie-Pierre, Laboratoire de Recherche des Monuments Historiques, Champs sur Marne, Haddi, Amine, Trocellier, Patrick, Curti, Enzo, Brown, Gordon E. Jr., & Stanford Synchrotron Radiation Laboratory, SLAC, Menlo Park, CA. Durability of Silicate Glasses: An Historical Approach. United States. doi:10.1063/1.2644427.
Farges, Francois, Department of Geological and Environmental Sciences, Stanford University, Stanford, CA, Etcheverry, Marie-Pierre, Laboratoire de Recherche des Monuments Historiques, Champs sur Marne, Haddi, Amine, Trocellier, Patrick, Curti, Enzo, Brown, Gordon E. Jr., and Stanford Synchrotron Radiation Laboratory, SLAC, Menlo Park, CA. Fri . "Durability of Silicate Glasses: An Historical Approach". United States. doi:10.1063/1.2644427.
@article{osti_21054652,
title = {Durability of Silicate Glasses: An Historical Approach},
author = {Farges, Francois and Department of Geological and Environmental Sciences, Stanford University, Stanford, CA and Etcheverry, Marie-Pierre and Laboratoire de Recherche des Monuments Historiques, Champs sur Marne and Haddi, Amine and Trocellier, Patrick and Curti, Enzo and Brown, Gordon E. Jr. and Stanford Synchrotron Radiation Laboratory, SLAC, Menlo Park, CA},
abstractNote = {We present a short review of current theories of glass weathering, including glass dissolution, and hydrolysis of nuclear waste glasses, and leaching of historical glasses from an XAFS perspective. The results of various laboratory leaching experiments at different timescales (30 days to 12 years) are compared with results for historical glasses that were weathered by atmospheric gases and soil waters over 500 to 3000 years. Good agreement is found between laboratory experiments and slowly leached historical glasses, with a strong enrichment of metals at the water/gel interface. Depending on the nature of the transition elements originally dissolved in the melt, increasing elemental distributions are expected to increase with time for a given glass durability context.},
doi = {10.1063/1.2644427},
journal = {AIP Conference Proceedings},
number = 1,
volume = 882,
place = {United States},
year = {Fri Feb 02 00:00:00 EST 2007},
month = {Fri Feb 02 00:00:00 EST 2007}
}
  • We present a short review of current theories of glass weathering, including glass dissolution, and hydrolysis of nuclear waste glasses, and leaching of historical glasses from an XAFS perspective. The results of various laboratory leaching experiments at different timescales (30 days to 12 years) are compared with results for historical glasses that were weathered by atmospheric gases and soil waters over 500 to 3000 years. Good agreement is found between laboratory experiments and slowly leached historical glasses, with a strong enrichment of metals at the water/gel interface. Depending on the nature of the transition elements originally dissolved in the melt,more » increasing elemental distributions are expected to increase with time for a given glass durability context.« less
  • Pre-edge features in the K absorption edge of X-ray absorption spectra are commonly used to predict Fe 3+ valence state in silicate glasses. However, this study shows that using the entire spectral region from the pre-edge into the extended X-ray absorption fine-structure region provides more accurate results when combined with multivariate analysis techniques. The least absolute shrinkage and selection operator (lasso) regression technique yields %Fe 3+ values that are accurate to ±3.6% absolute when the full spectral region is employed. This method can be used across a broad range of glass compositions, is easily automated, and is demonstrated to yieldmore » accurate results from different synchrotrons. It will enable future studies involving X-ray mapping of redox gradients on standard thin sections at 1 × 1 μm pixel sizes.« less
  • Pre-edge features in the K absorption edge of X-ray absorption spectra are commonly used to predict Fe3+ valence state in silicate glasses. However, this study shows that using the entire spectral region from the pre-edge into the extended X-ray absorption fine-structure region provides more accurate results when combined with multivariate analysis techniques. The least absolute shrinkage and selection operator (lasso) regression technique yields %Fe3+ values that are accurate to ±3.6% absolute when the full spectral region is employed. This method can be used across a broad range of glass compositions, is easily automated, and is demonstrated to yield accurate resultsmore » from different synchrotrons. It will enable future studies involving X-ray mapping of redox gradients on standard thin sections at 1 × 1 μm pixel sizes.« less
  • The Raman scattering intensity of the 1100 cm/sup -1/ polarized band, which appears on the addition of Na/sub 2/O to SiO/sub 2/ glass, reaches a maximum at the disilicate composition. The intensity of the polarized band at 950 cm/sup -1/ increases sharply as the Na/sub 2/O concentration increases above 30 mole %. These data were interpreted by normal mode calculations and by IR and Raman intensity calculations for the silicate anion structural units: SiO/sub 4/ isolated tetrahedra, Si/sub 2/O/sub 7/ dimers, Si/sub 2/O/sub 6/ chain links, Si/sub 2/O/sub 5/ sheet units, and Si/sub 2/O/sub 4/ framework units. According to thesemore » simplified models, the polarized high frequency band is due to symmetric stretching of Si--O/sup -/ nonbridging bonds and the frequency increases with degree of polymerization of the tetrahedra. The previous assignments of the 1100 cm/sup -1/ band to the symmetric stretch of tetrahedra containing one nonbridging oxygen and of the 950 cm/sup -1/ band to the symmetric stretch of tetrahedra containing two nonbridging oxygens were confirmed. The other main feature of the alkali silicate glasses, an intense polarized band in the range of 400--600 cm/sup -1/, was shown to be a mixed stretching bending mode of the Si--O--Si bridging bond. The model also accounts for the loss of intensity of the high frequency band with increasing degree of silica polymerization.« less