The Lower Cation Exchange Capacity Limit of Montmorillonite

Wyoming montmorillonite (Volclay) with different charges were produced by Li-incorporation and the interlayer cations were replaced by tetramethyl ammonium. Their XRD pattern showed a regular sequence of expanded and collapsed interlayers. The regularly interstratified structure corresponds to a regularity of Reichweite R = 1. The expanded part of the interlayers was calculated by comparing XRD pattern with simulations using NEWMOD software. The calculations of the cation exchange capacity CEC for the expanded interlayer part gives a constant value of 65 ± 2 mmol/100 g fully swellable montmorillonite. This value is denoted as the lower CEC limit of montmorillonite. We propose a model which considers montmorillonite to be a stacked two-dimensional polyelectrolyte. The model propose that interlayers of the stack collapse spontaneously by cation shifting into the neighboring interlayers, if the charge density of a montmorillonite has a value below the lower CEC value. The shifted cations of the collapsed interlayer increase the charge density in the neighboring interlayers and prevent their collapse. A regularly interstratified structure arises with the sequence expanded/collapsed/expanded interlayer, which can be observed by XRD. The behavior of low charged montmorillonite is explained with the properties of a two-dimensional polyelectrolyte. Below the critical layer charge, the Van der Waals forces dominate over electrostatic repulsive forces and the interlayers collapse.