Effect of different interlayer counter-ions on montmorillonite swelling:

Key controlling factors evaluated by molecular dynamic simulations

Abstract

  The understanding of the swelling phenomenon of montmorillonite is essential to predict the physical and chemical behavior of clay-based barriers in radioactive waste disposal systems. This study investigated the key factors controlling crystalline swelling behavior of montmorillonite with different interlayer counter-ions by molecular dynamics (MD) simulations. On the basis of the comparisons between MD simulated and experimental results, the water content in the interlayer in five homoionic (Na-, K-, Cs-, Ca- and Sr-) montmorillonite was strongly correlated to the hydration number of each counter-ion. The analyses for these results offer insights that the hydration number is controlled by the hydration free energy, the volume and the distribution of each interlayer counter-ion. The systematic MD simulations with virtually variable parameters clarified that the hydration free energy and the charge of interlayer counter-ions compete as influencing factors, and the control the formation rate of an outer-sphere complex of each counter-ion. The empirical relationships between these key factors will allow essential insights into predicting the swelling behavior of montmorillonite with different interlayer counter-ions.