Title: Toward an Understanding of Surface Layer Formation, Growth, and Transformation at the Glass–Fluid Interface

Abstract

Silicate glass is a metastable and durable solid that has application to a number of energy and environmental challenges (e.g., microelectronics, fiber optics, and nuclear waste storage). If allowed to react with water over time silicate glass develops an altered layer at the solid-fluid interface. In this study, we used borosilicate glass (LAWB45) as model material to develop a robust understanding of altered layer formation (i.e., amorphous hydrated surface layer and crystalline reaction products). Experiments were conducted at high surface area-to-volume ratio (~200,000 m-1) and 90 °C in the pressurized unsaturated flow (PUF) apparatus for 1.5-years to facilitate the formation of thick altered layers and allow for the effluent solution chemistry to be monitored continuously. A variety of microscopy techniques were used to characterized reacted grains and suggest the average altered layer thickness is 13.2 ± 8.3 μm with the hydrated and clay layer representing 74.8% and 25.2% of the total altered layer, respectively. This estimate is within the experimental error of the value estimated from the B release rate data (~10 ±1 μm/yr) over the 1.5-year duration. PeakForce® quantitative nanomechanical mapping results suggest the hydrated layer has a modulus that ranges between ~20 to 40 GPa, which is inmore » the range of porous silica that contains from ~20 to ~50% porosity, yet significantly lower than dense silica (~70 to 80 GPa). Scanning transmission electron microscopy (STEM) images confirm the presence of pores and an analysis of a higher resolution image of a region provides a qualitative estimate of ≥ 22% porosity in this layer with variations in the hydrated layer in void volume with increasing distance from the unaltered glass. Chemical composition analyses, based on a combination of time-of-flight secondary-ion mass spectrometry (ToF-SIMS) and scanning electron microscopy with X-ray energy dispersive spectroscopy (EDS) and STEM-EDS, clearly show that the altered layer is mainly composed of Al, H, Si, and O with the clay layer being enriched in Li, Zn, Fe, and Mg. The amorphous hydrated layer is enriched in Ca, H, and Zr with a minor amount of K. Furthermore, ToF-SIMS results also suggest the B profile is anti-correlated with the H profile in the hydrated layer. Our selected-area electron diffraction results suggest the structure of the hydrated layer closely resembles opal-AG (amorphous gel-like) with an average crystallite size of ~0.7 nm which is smaller than the critical nucleus for silica nanoparticles (i.e., 1.4 to 3 nm). These results suggest the hydrated layer is more consistent with a polymeric gel rather than a colloidal gel and is comprised of molecular units (<1 nm in size) that result from the difficult to hydrolyze bonds, such as Si—O—Zr units, during the glass corrosion process. The size of individual particles or molecular units is a function of formation conditions (e.g., pH, ionic strength, nano-confinement, solute composition) in the hydrated layer.« less

Authors:

Hopf, Juliane ^[1]; Eskelsen, Jeremy R.  ^[1];

• Search DOE PAGES for author "Eskelsen, Jeremy R."
• Search DOE PAGES for ORCID "0000-0003-2828-9099"

Chiu, Michelle Y.  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-7924-1645"

Ievlev, Anton  ^[2];

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• Search DOE PAGES for ORCID "0000-0003-3645-0508"

Ovchinnikova, Olga S.  ^[2];

• Search DOE PAGES for author "Ovchinnikova, Olga S."
• Search DOE PAGES for ORCID "0000-0001-8935-2309"

Leonard, Donovan N.  ^[3];

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• Search DOE PAGES for ORCID "0000-0002-1806-4526"

Pierce, Eric M.  ^[1]

• Search DOE PAGES for author "Pierce, Eric M."
• Search DOE PAGES for ORCID "0000-0002-4951-1931"

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+ Show Author Affiliations

1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Environmental Sciences Division
2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division

Publication Date:

Thu Feb 01 00:00:00 EST 2018

Research Org.:

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:

USDOE

OSTI Identifier:

1423113

Grant/Contract Number:  

AC05-00OR22725

Resource Type:

Accepted Manuscript

Journal Name:

Geochimica et Cosmochimica Acta

Additional Journal Information:

Journal Name: Geochimica et Cosmochimica Acta; Journal ID: ISSN 0016-7037

Publisher:

The Geochemical Society; The Meteoritical Society

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; Quantitative Nanomechanical Peak Force® TappingModeTM; atomic force microscopy; borosilicate glass corrosion; leaching mechanism; interfacial dissolution reprecipitation; silica diagenesis; altered layer; scanning transmission electron microscopy electron energy loss spectroscopy spectrum imaging