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Title: Sol–Gel Synthesis and Characterization of Gels with Compositions Relevant to Hydrated Glass Alteration Layers

Journal Article · · ACS Omega
ORCiD logo [1]; ORCiD logo [2];  [2]
  1. Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States, Chemistry Department, Washington State University, Pullman, Washington 99164, United States
  2. Chemistry Department, Washington State University, Pullman, Washington 99164, United States

During the processes associated with glass corrosion, porous hydrated glass alteration layers typically form upon exposure to aqueous conditions for extended time periods. The impacts of the alteration layer on glass durability have not been agreed upon in the glass science community. In particular, the formation mechanisms of hydrated glass alteration layers are still largely unknown and require further investigation, but these layers often require months to years to develop and are often too thin to adequately characterize. Meanwhile, sol–gel-derived silicate gels are relatively easy to synthesize in bulk with custom compositions relevant to hydrated glass alteration layers. If alteration layers and synthetic silicate gels demonstrate physical and chemical properties that are sufficiently similar, synthetic silicate gels could be used as analogues for hydrated glass alteration layers in future studies. However, synthetic gels must first be prepared and evaluated before comparisons between glass alteration layers and synthetic silicate gels can be made. This work focuses entirely on the synthesis and observed physical properties of synthetic silicate gels. A future work will compare the characteristics of synthetic gels described in this work with altered waste glass formed in similar pH environments. In this study, synthetic gels were made with custom compositions at various pH values to evaluate the effect of pH on gel structure and morphology. Several other variables were examined also, such as composition, drying, and aging. Gels were produced by sequential additions of organometallic precursors in a single container. Gels were analyzed with several techniques including small-angle X-ray scattering, gas adsorption, and He pycnometry to determine the effects of the variables on physical properties. Results show that gels prepared at pH 3 consistently contained fewer primary particles with diameters larger than 7.2 nm and fewer pores with diameters larger than 30 nm compared to gels synthesized at pH 7 and 9. In conclusion, composition was shown to have no discernable effect on primary particle and pore sizes at any pH.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Environmental Management (EM); USDOE Office of Nuclear Energy (NE)
Grant/Contract Number:
AC02-06CH11357; AC06-76RL01830
OSTI ID:
1566905
Journal Information:
ACS Omega, Journal Name: ACS Omega Journal Issue: 15 Vol. 4; ISSN 2470-1343
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (62)

27Al and 29Si NMR study of sol-gel derived aluminosilicates and sodium aluminosilicates journal August 1988
Preparation of glass fibres of the ZrO2-SiO2 and Na2O-ZrO2-SiO2 systems from metal alkoxides and their resistance to alkaline solution journal July 1980
Monolithic glass formation by chemical polymerization journal August 1979
Preparation of glasses and ceramics from metal-organic compounds journal June 1977
Mesoporous Silica Supported Sulfated Zirconia Prepared by a Sol?Gel Process journal January 2005
Ultra-Small-Angle X-ray Scattering Instrument at the Advanced Photon Source: History, Recent Development, and Current Status journal October 2012
Sol-gel transition in simple silicates journal March 1982
Sol-gel transition in simple silicates II journal February 1984
Sol → gel → glass: I. Gelation and gel structure journal April 1985
Structural evolution during the gel to glass conversion journal May 1985
Sol-gel transition in zirconia systems using physical and chemical processes journal June 1986
Study of polymerization processes in acid and base catalyzed silica sol-gels journal May 1986
Effect of formamide additive on the chemistry of silica sol-gels II. Gel structure journal November 1988
Study of structural evolution of silica gel using 1H and 29Si NMR journal November 1989
Structural studies of complex systems using small-angle scattering: a unified Guinier/power-law approach journal September 1994
Polymeric-silica-based sols for membrane modification applications: sol-gel synthesis and characterization with SAXS journal November 1995
Sol-gel chemistry of transition metal oxides journal January 1988
Ambient-temperature supercritical drying of transparent silica aerogels journal July 1985
Sol-gel chemistry journal January 1992
Contribution of atom-probe tomography to a better understanding of glass alteration mechanisms: Application to a nuclear glass specimen altered 25years in a granitic environment journal June 2013
Influence of glass composition and alteration solution on leached silicate glass structure: A solid-state NMR investigation journal May 2006
The fate of silicon during glass corrosion under alkaline conditions: A mechanistic and kinetic study with the International Simple Glass journal February 2015
The mechanism of borosilicate glass corrosion revisited journal June 2015
Sol–gel preparation of 2CaO·SiO2 journal January 2007
Silica aerogel; synthesis, properties and characterization journal April 2008
Structural evolution of aerogels prepared from TEOS sono-hydrolysis upon heat treatment up to 1100 °C journal December 2003
Aqueous alteration of five-oxide silicate glasses: Experimental approach and Monte Carlo modeling journal January 2008
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
Non-destructive characterization of corroded glass surfaces by spectroscopic ellipsometry journal February 2018
Morphological evolution of alteration layers formed during nuclear glass alteration: new evidence of a gel as a diffusive barrier journal March 2004
Long-term Behavior Science: The cornerstone approach for reliably assessing the long-term performance of nuclear waste journal January 2012
An international initiative on long-term behavior of high-level nuclear waste glass journal June 2013
Open Scientific Questions about Nuclear Glass Corrosion journal January 2014
Dynamics of Water Confined in Gel Formed During Glass Alteration at a Picosecond Scale journal January 2013
Silver-Loaded Aluminosilicate Aerogels As Iodine Sorbents journal September 2017
Aerogels and related porous materials journal June 1989
The Sol-Gel Preparation of Silica Gels journal July 1994
Why Do Certain Glasses with a High Dissolution Rate Undergo a Low Degree of Corrosion? journal March 2011
Nuclear Glass Durability: New Insight into Alteration Layer Properties journal August 2011
Mass and Surface Fractal in Supercritical Dried Silica Aerogels Prepared with Additions of Sodium Dodecyl Sulfate journal December 2014
Origin and consequences of silicate glass passivation by surface layers journal February 2015
Dynamics of self-reorganization explains passivation of silicate glasses journal June 2018
Towards a unifying mechanistic model for silicate glass corrosion journal September 2018
Real-time in situ observations of reaction and transport phenomena during silicate glass corrosion by fluid-cell Raman spectroscopy journal February 2019
Sol–gel synthesis of the P2O5–CaO–Na2O–SiO2 system as a novel bioresorbable glass journal January 2005
Irena : tool suite for modeling and analysis of small-angle scattering journal February 2009
Ultra-small-angle X-ray scattering at the Advanced Photon Source journal April 2009
SAXSMorph : a program for generating representative morphologies for two-phase materials from small-angle X-ray and neutron scattering data journal December 2010
Nika : software for two-dimensional data reduction journal March 2012
Approximations Leading to a Unified Exponential/Power-Law Approach to Small-Angle Scattering journal December 1995
Nanoscale Bioactive Glasses in Medical Applications journal April 2013
New Insight into the Residual Rate of Borosilicate Glasses: Effect of S/V and Glass Composition journal October 2013
Current Understanding and Remaining Challenges in Modeling Long-Term Degradation of Borosilicate Nuclear Waste Glasses journal November 2013
Glass-Ceramic Materials for Guided-Wave Optics journal July 2015
Chemical Durability of Oxide Glasses in Aqueous Solutions: A Review journal March 2008
Glass and Medicine journal March 2010
Sol-Gel Processing of Silicates journal August 1985
SON68 Glass Dissolution Kinetics at High Reaction Progress: Experimental Evidence of the Residual Rate journal January 2002
Long-term behavior of R7T7-type nuclear glass: Current state of knowledge and outlook journal January 2004
Nuclear Waste Glasses - How Durable? journal December 2006
Stabilization of Silica Gel against Hydrolysis by Doping with Fˉ or Zr(IV) journal January 2014
Sol-Gel Synthesis of SiO2-CaO-Na2O-P2O5 Bioactive Glass Ceramic from Sodium Metasilicate journal January 2013