Role of Surface Layers in the Leaching Behavior of Glass

1988 ◽  
Vol 125 ◽  
Author(s):  
B.K. Zoitos ◽  
D.E. Clark
Keyword(s):  
Surface Layer ◽  
Nuclear Waste ◽  
Surface Composition ◽  
Analytical Techniques ◽  
Surface Layers ◽  
Leaching Behavior ◽  
Leach Rate ◽  
Layer Analysis ◽  
Nuclear Waste Glass

ABSTRACTResults are presented from a two-year dynamic leach test of nuclear waste glass under conditions designed to simulate those of the Stripa granite repository. Solution and surface analytical techniques were used to assess the glass leach rate as well as surface composition and morphology. Glass leach rates were observed to decrease by a factor of two during the first six months. This effect is attributed to the formation of a protective surface layer. Analysis of this layer shows it to be rich in silicon and iron and depleted in lithium, sodium and boron. It was also found that the layer is subject to dissolution.

Secondary Phase Formation and the Microstructural Evolution of Surface Layers During Vapor Phase Alteration of the French Son68 Nuclear Waste Glass at 200 °C

1995 ◽  
Vol 412 ◽  
Author(s):  
W. L. Gong ◽  
R. C. Ewing ◽  
L. M. Wang ◽  
E. Vernaz ◽  
J. K. Bates ◽  
...  
Keyword(s):  
Surface Layer ◽  
Nuclear Waste ◽  
Vapor Phase ◽  
Rare Earths ◽  
Waste Glass ◽  
Transition Elements ◽  
Surface Layers ◽  
Crystalline Phases ◽  
Developed Surface ◽  
Nuclear Waste Glass

AbstractThe SON68 inactive “R7T7” composition is the French reference glass for the LWR nuclear waste glass. Vapor phase alteration was used to accelerate the reaction progress of glass corrosion and to develop the characteristic suite of secondary, alteration phases. Extensive solid-state characterization (AEM/SEM/HRTEM) was completed on six inactive R7T7 waste glasses which were altered in the presence of saturated water vapor (200 °C) for 91, 241, 908, 1000, 1013, and 1021 days. The AEM samples were examined in cross-section (lattice-fringe imaging, microdiffraction, and quantitative thin-film EDS analysis). The glass monoliths were invariably covered with a thin altered rind. The layer became thicker with time: 0.5μm for 22 days; 4 μm for 91 days; 6 μm for 241 days; 10 μm for 908 days; 26 μm for 1013 days; and <35μm for 1021 days. The composite alteration layer of the SON68 samples is at least four time less thick than that of the SRL 131 glass composition.Six distinctive zones, based on phase chemistry and microstructure, were distinguished within the well-developed surface layers. Numerous crystalline phases such as analcime, tobermorite, apatite, and weeksite were identified on the surfaces of the reacted glasses as precipitates. Two crystalline phases, Ag2TeO3 and (Ca,Sr)Mo3O9(OH)2, were found within the inner zones of surface layers, and they must have nucleated in situ, indicating that Ag, Te, Sr, and Mo can be retained within the surface layer. The majority of the surface layer volume is composed of two morphologically and chemically different structures: one consists of well-crystallized fibrous smectite aggregates occurring along with cavities, the A-domain; and the other consists of poorlycrystallized regions containing needle-like smectite (montmorillonite) crystallites, a silica-rich amorphous matrix, and possibly ZrO2 particles, the B-domain. The retention of rare-earths and Zr mostly occurred within B-domains and that of transition elements, such as Zn, Cr, Ni, and Mn, in A-domains. The recrystallization of poorly-crystallized B-domains into well-crystallized Adomains may influence the long-term behavior of rare-earths, Zr, and transition elements. The mechanism of surface layer formation during vapor phase alteration is discussed based on the cross-sectional AEM studies of surface layers of the SON68 waste glasses.

Electrokinetics, Adsorption and Colloid Study of Simulated Nuclear Waste Glasses Leached in Aqueous Solutions

1984 ◽  
Vol 44 ◽  
Author(s):  
Cheng T. Lee ◽  
D. E. Clark
Keyword(s):  
Surface Layer ◽  
Nuclear Waste ◽  
Glass Surface ◽  
Charged Particles ◽  
Electrostatic Repulsion ◽  
Surface Layers ◽  
Short Term ◽  
Chloride Solutions ◽  
Zeta Potentials ◽  
Glass Surfaces

AbstractZeta potentials of SRL-131-29.8% TOS simulated nuclear waste glasses leached in D.I. water, Al, Ca, Mg, and Zn chloride solutions at 90°C were measured as a function of leaching time. For short term leaching, the adsorption of Ca, Mg, Zn and Al reverses the glass surface potential from negative to positive. Colloids were found to be stable in D.I. water and AICl3 solutions after leaching, presumably due to the electrostatic repulsion between the glass surface and similarly charged particles. Colloids were not found in Mg, Zn or Ca chloride solutions after leaching; instead, a relatively thick metasilicate surface layer was formed on glass surfaces leached in these solutions. The concentration of Si in solution is reduced by the formation of these surface layers.

scholarly journals Does Fully Radioactive Glass Behave Differently than Simulated Waste Glass?

1992 ◽  
Vol 294 ◽  
Author(s):  
X. Feng ◽  
J. K. Bates ◽  
C. R. Bradley ◽  
E. C. Buck
Keyword(s):  
Radiation Field ◽  
Nuclear Waste ◽  
Potassium Feldspar ◽  
Waste Glass ◽  
Solution Ph ◽  
Static Tests ◽  
Leach Rate ◽  
Nuclear Waste Glass ◽  
Surface Alteration ◽  
Leach Behavior

ABSTRACTStatic tests at SA/V (ratio of surface area of glass to solution volume) 20,000 m−1 on SRL 200 glass compositions show that, at long test periods, the simulated nuclear waste glass (nonradioactive) leaches faster than the corresponding radioactive glass by a factor of about 40, although comparative tests, done through 560 days, at lower SA/V, 2000 m−1, indicate little difference in the leach behavior of the two types of glasses. The similarity in leach behavior between radioactive and simulated glasses at SAN of 2000 m−1 or lower is also observed for SRL 165/42 and 131/11 compositions. The accelerated glass reaction with the simulated glass 200S is associated with the formation of crystalline phases such as clinoptilolite (or potassium feldspar), and a pH excursion. The radiation field generated by the fully radioactive glass reduces the solution pH. This lower pH, in turn, may retard the onset of increased reaction rate. The radiation field generated by the radioactive glasses does not directly affect the stability of the glass surface alteration layer under those conditions where the radioactive and simulated glasses react at the same rate. These results suggest that the fully radioactive nuclear waste glass 200R may maintain a much lower leach rate than the simulated 200S, if the lower pH in the 200R leachate can be sustained. Meaningful comparison tests between radioactive and simulated nuclear waste glasses should include long-term and high SA/V tests.

Leaching behavior of nuclear waste glass heterogeneities

1986 ◽  
Vol 80 (1-3) ◽  
pp. 324-334 ◽  
Author(s):  
Zhu Bing-Fu ◽  
D.E. Clark ◽  
L.L. Hench ◽  
G.G. Wicks
Keyword(s):  
Nuclear Waste ◽  
Waste Glass ◽  
Leaching Behavior ◽  
Nuclear Waste Glass

Borosilicate Nuclear Waste Glass Alteration Kinetics: Chemical Inhibition and Affinity Control

1997 ◽  
Vol 506 ◽  
Author(s):  
T. Advocat ◽  
J. L. Chouchan ◽  
J. L. Crovisier ◽  
C. Guy ◽  
V. Daux ◽  
...  
Keyword(s):  
Nuclear Waste ◽  
Mathematical Formulation ◽  
Order Kinetic ◽  
Exact Role ◽  
Dissolved Silica ◽  
First Order ◽  
Nuclear Waste Glass ◽  
Chemical Inhibition ◽  
Kinetics Of

ABSTRACTThe objective of this work was to develop a more representative mathematical formulation of the alteration kinetics of the borosilicate SON68 glass by combining three approaches: (1) Compare extensive prior experimental static leaching results for SON68 glass with the first-order kinetic law in which silica is the predominant element, (2) Assess the exact role of dissolved silica on the alteration rate under conditions near and far from saturation, by means of dynamic leach tests and, (3) Compare the new data with the general kinetic law for silicates in which the reaction affinity, catalysis and inhibition are the three influencing factors.

AEM study of reacted surface layer of borosilicate nuclear waste glasses

1992 ◽  
Vol 50 (1) ◽  
pp. 352-353
Author(s):  
L.M. Wang ◽  
S.A. Kaser ◽  
R.C. Ewing ◽  
J.K. Bates
Keyword(s):  
Electron Microscopy ◽  
Surface Layer ◽  
Nuclear Waste ◽  
Reaction Pathway ◽  
Sample Surface ◽  
Carbon Films ◽  
Waste Glass ◽  
Thin Sections ◽  
Nuclear Waste Glass

Analysis of the reacted surface layer of borosilicate glass is important to the understanding of the long term nuclear waste glass reaction process. The objective is to assess the simulated nuclear waste glass/water reaction pathway by identifying new crystalline phases that appear on the glass surfaces during the reaction. The results can be used to validate models generated to predict long-term performance of the nuclear waste glass under a range of conditions.In this study, extensive scanning electron microscopy (SEM) with qualitative energy dispersive x-ray spectroscopy (EDS) analysis, quantitative analytical and high resolution transmission electron microscopy (AEM and HRTEM) have been performed on two 202U glasses which were reacted in saturated water vapor for 14 and 23 days, respectively. In order to study the microchemical and microstructural changes with increasing depth from the reaction surface, TEM specimens were prepared in cross-section using the ultramicrotomy slicing technique similar to that described by Bates et al. In this process, small chunks containing the reacted surface layer and a thin layer of glass were first broken off from the sample surface and each of these chunks was then embedded in resin to form a block. Finally, thin sections, approximately 90 nm thick, were microtomed from these blocks and were transfered to copper mesh grids covered by holey carbon films for observation. AEM and HRTEM analyses were accomplished using a JEOL JEM-2000FX microscope attached with a Noran/TN-5500 EDS system at the University of New Mexico.

Nature and Effect of the Alteration Layer During Nuclear Waste Glass Dissolution

2002 ◽  
Vol 713 ◽  
Author(s):  
A. Gauthier ◽  
P. Le Coustumer ◽  
J-H. Thomassin
Keyword(s):  
Nuclear Waste ◽  
Pure Water ◽  
Aqueous Media ◽  
Glass Dissolution ◽  
Icp Ms ◽  
Nuclear Waste Glass ◽  
Texture Structure ◽  
The Stability ◽  
Short Time

ABSTRACTThe goal of this study is to understand the role of the interface developed during R7T7 glass alteration. This glass has been leached in two different aqueous media (pure water, silica rich water and phosphorous rich water). The lixiviation tests have been optimized to assess the role of the alteration layer developed on the surface of the glass. The solution and the solid have been characterized by ICP-MS and TEM/X-EDS respectively. The results put in evidence that a complex alteration layer is formed. Its texture, structure and chemistry are discussed with respect to the evolution of the solution during the tests. The alteration layer is always present on the surface of the glass and is considered to control (at short time) diffusion of the different species through the layer. Further study must be undertaken to assess the evolution and the stability of the interface for longer time periods.

Effects of Flow Parameters on the Leaching of Nuclear Waste Glass

1984 ◽  
Vol 44 ◽  
Author(s):  
R. B. Adiga ◽  
E. P. Akomer ◽  
D. E. Clark
Keyword(s):  
Nuclear Waste ◽  
Flow Rate ◽  
Volume Ratio ◽  
Water Volume ◽  
Leaching Rate ◽  
Leaching Behavior ◽  
Waste Package ◽  
Flow Parameters ◽  
Nuclear Waste Glass ◽  
Independent Effects

Environmental conditions in a repository are expected to be significantly different from those encountered by a glass tested under MCC-1 specifications. In addition to variations in flow rate and glass surface area to water volume ratio (SA/V), the water chemistry and presence of waste package components in the repository will most certainly affect the leaching behavior of the glass. The independent effects of each of these variables have been studied by numerous investigators. For example, it is well known that the leaching rate increases as the flow rate increases (1). Also, the rate of approach to saturation is increased as SA/V is increased under MCC-1 type testing (2). The use of silicate water generally decreases the rate of leaching while waste package components such as iron enhances the leaching rate of glass under MCC-1 type testing (3–4).

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