Dissolution of R7T7 Glass in Static and Flowing Conditions: Influence of Si Diffusion Mechanism in the Leached Layer

1992 ◽  
Vol 294 ◽  
Author(s):  
F. Delage ◽  
F. Larche ◽  
E. Vernaz

ABSTRACTLeach tests with R7T7 nuclear waste glass in distilled water were conducted at 50 and 90°C under static and slow flowing conditions, with an SA/V ratio of 50 m−1. A computer model for glass dissolution (LIXIVER) Was used to interpret the experimental data. This mechanistic model is based on a combination of the first-order law governing surface reactions, the silicon mass transport equation for the interstitial solution in the alteration film, and an empirical law for partial silicon retention in the alteration layer. The LIXIVER model satisfactorily accounts for most of the experimental results. The importance of the silicon diffusion mechanism in the diffusion layer is stressed. Values are indicated for the apparent silicon diffusion coefficient, Dsi, which ranged from 10−16 to 10−14 m2·s−1 at 50°C, and from 10−15 to 10−13 m2·s−1 at 90°C.

1992 ◽  
Vol 190 ◽  
pp. 191-197 ◽  
Author(s):  
F. Delage ◽  
D. Ghaleb ◽  
J.L. Dussossoy ◽  
O. Chevallier ◽  
E. Vernaz

1997 ◽  
Vol 506 ◽  
Author(s):  
T. Advocat ◽  
J. L. Chouchan ◽  
J. L. Crovisier ◽  
C. Guy ◽  
V. Daux ◽  
...  

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.


1984 ◽  
Vol 44 ◽  
Author(s):  
Aaron Barkatt ◽  
Barbara C. Gibson ◽  
Marek Brandys

AbstractA simple kinetic model for the description of the interaction of nuclear waste borosilicate glass with water has been developed. In the case of SRL TDS-131 glass leached in water at 70°C over a broad range of flow rates this model was found useful both in describing the evolution of leachate composition as a function of exposure time at a particular flow rate and in describing the dependence of the steady-state concentrations of the leached elements in solution on flow rate in a series of flow experiments.


2002 ◽  
Vol 713 ◽  
Author(s):  
A. Gauthier ◽  
P. Le Coustumer ◽  
J-H. Thomassin

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.


1990 ◽  
Vol 212 ◽  
Author(s):  
T. Advocat ◽  
J. L. Crovisier ◽  
E. Vernaz ◽  
G. Ehret ◽  
H. Charpentier

ABSTRACTR7T7 nuclear waste glass dissolution in highly dilute aqueous media under static conditions at 90°C occurs according to two different mechanisms depending on the solution acidity. In acid media (pH 4.8 and 5.5), preferential extraction of glass network modifiers results in the formation of an alkali metal-depleted surface region on which amorphous and crystallized (phosphate) compounds rich in transition elements precipitate. Steady-state dissolution conditions are not reached, as attested by variable normalized SI, B and Na mass losses. Glass dissolution is stoichiometric in basic media (pH 7 to 10): the strong bonds of the silicated network are broken at a rate that increases with the pH: the glass dissolution rate increases by a factor of 15 between pH 7 and 10. Under these conditions, alteration products at the glass/solution interface do not constitute a short-term kinetic barrier against the release of the major glass components.


1992 ◽  
Vol 294 ◽  
Author(s):  
Y. Inagaki ◽  
H. Furuya ◽  
Y. Ono ◽  
K. Idemitsu ◽  
T. Banba ◽  
...  

ABSTRACTA simulated nuclear waste glass was self-irradiated by doping with short-lived actinides of 238Pu and 244Cm. Changes in the hardness, the Young's modulus and the fracture toughness, as a function of irradiation dose, were measured by use of indentation techniques. The irradiated glass was annealed at temperatures from 573K to 723K for periods of up to 48hours, and the recovery of these changes were measured as a function of annealing temperature and time.It was observed that the hardness and the Young's modulus decreased, while the fracture toughness increased exponentially with the cumulative dose. The maximum values of the relative changes in the hardness, the Young's modulus and the fracture toughness were about −25%, −30% and +45%, respectively. The results of the annealing show that the hardness and the Young's modulus were almost recovered to the original values at temperatures above 673K within 10 hours, while the recovery of the fracture toughness was minimal in this region of temperature and time. The changes in the hardness and the Young's modulus can be well explained by the model, in which the changes is proportional to the volume fraction of damaged zones, F, and the recovery of F is first order. On the other hand, the changes in the fracture toughness cannot be explained by the model, which suggests that the mechanism of the change in the fracture toughness is different from that in the hardness and the Young's modulus.


1991 ◽  
Vol 257 ◽  
Author(s):  
Anette Rother ◽  
Werner Lutze ◽  
Peter Schubert-Bischoff

ABSTRACTThis communication gives a detailed characterization of some molybdate solid solutions and cerianite-type material which formed on the French borosilicate nuclear waste glass R7T7 upon corrosion in various saturated salt solutions at 110°C, 150 °C and 190 °C. The glass contained lanthanoid elements, such as neodymium, lanthanum, praseodymium, cerium and yttrium, but did not contain actinoid elements, except uranium and thorium. Various solid solutions containing lanthanoids (Ln) were found on the glass surface after corrosion, including powellite solid solutions and cerianite-type material. The secondary solid phases are characterized based on quantitative microchemical and structural analyses. These phases are expected to incorporate actinoids such as americium and curium in acid magnesiumcontaining salt solutions. The phases then constitute an additional barrier against migration of these radionuclides, which would otherwise be in the aqueous phase.


1989 ◽  
Vol 176 ◽  
Author(s):  
R. Shah ◽  
E.C. Behrman ◽  
D. Oksoy

ABSTRACTViscosity is one of the most important processing parameters and one of the most difficult to calculate theoretically, particularly for multicomponent systems like nuclear waste glasses. Here, we propose a semi-empirical approach based on the Fulcher equation, involving identification of key variables, for which coefficients are then determined by regression analysis. Results are presented for two glass systems, and compared to results of previous workers and to experiment. We also sketch a first-order statistical mechanical perturbation theory calculation for the effects on viscosity of a change in composition of the melt.


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