Self-Diffusion of Sodium Ions in Compacted Sodium Montmorillonite

Abstract

Diffusion of sodium ions through compacted sodium montmorillonite in a water-saturated state was studied to obtain fundamental information for performance assessments of geological disposal of high-level radioactive waste.Basal spacings obtained from X-ray diffraction measurements indicated a decrease in the interlamellar spacing with increasing dry density of the montmorillonite; the three-water-layer hydrate was observed at low dry density (≤1.3 Mg/m3), and the two-water-layer hydrate was observed at high dry density (≥1.6 Mg/m3), whereas both were observed at dry densities between 1.4 and 1.5 Mg/m3.Activation energies from 14.1 to 24.7 kJ/mol were obtained from the temperature dependence of the self-diffusion coefficients of sodium ions. Activation energies lower than that for the diffusion of sodium ions in free water were found for montmorillonite specimens with dry densities of ≤1.2 Mg/m3, while higher activation energies were observed at dry densities ≥1.4 Mg/m3.The pore water diffusion model, the general model used for migration of nuclides, is based on geometric parameters; however, findings cannot be explained by only the changes in the geometric parameters. Possible explanations for the dry density dependence of the activation energy are changes in the temperature dependence of the distribution coefficients of sodium ions on the montmorillonite, changes in the diffusion process with an increase in dry density, or both.