Use of orthophosphate complexing agents to investigate mechanisms limiting the alteration kinetics of French SON 68 nuclear glass

Abstract

This investigation was carried out to assess the protective properties of the alteration film that develops during aqueous alteration of the French SON 68 (R7T7-type) nuclear glass, notably by examining the behavior of some network-forming cations in the presence of complexing anions. Glass alteration was studied here in the presence of orthophosphate ions. Comparisons were established between two series of tests performed with a solution containing orthophosphate ions and control tests performed under the same conditions but without phosphates. The first series of experiments was performed under initial rate conditions (i.e. in dilute media) to assess the effect of pH and phosphate concentration on the initial glass dissolution rate. Under these conditions, which ensure maximum chemical affinity of the glass dissolution reaction, phosphate adsorption occurs at the reaction interface only with acid pH values, at which the glass dissolution reaction is strongly inhibited. The elements that form complexes with the phosphates (Al, Fe, etc.) partially control glass dissolution in acidic media. Additional experiments carried out under saturated conditions — notably with respect to Si — in a solution enriched with phosphates showed that rare earth and Ca phosphates precipitated in the outer region of the alteration film, maintaining a glass dissolution rate significantly higher than in the control experiment. These observations have several implications. (1) Comparing the results obtained in the presence of phosphates and in the reference medium, the authors demonstrate deductively that glass dissolution is limited by the inner portion of the alteration film, i.e. the amorphous gel. (2) A kinetic law of SON 68 glass dissolution cannot be based on silica alone; the results of these experiments contradict Grambow’s model. (3) With regard to control of the glass dissolution kinetics by the protective properties of the gel, this type of experiment shows that the relation between the chemical composition and the microstructure of the gel is an important aspect in modeling the glass alteration kinetics, but that it is still poorly understood.