How the Solid/Liquid Ratio Affects the Cation Exchange Process and Porosity in the Case of Dioctahedral Smectite: Structural Analysis?

The performance of a clay mineral geomembrane used in the context of a geological barrier for industrial and radioactive waste confinement must pass through the understanding of its hydrous response as well as the limits of the cation exchange process which are closely related to the solid/liquid ratio constraint. The Na-rich montmorillonite is used, as starting material, to evaluate the link between the applied external constraint (variable solid/liquid ratio) and the structural response of the material. The geochemical constraint is realized at the laboratory scale, and the possible effects are investigated in the cases of Ba2+ and Ni2+ heavy metal cations. The structural analysis is achieved using the XRD profile modeling approach to quantify the interlayer space (IS) deformation. The quantitative XRD analysis, which consists of the comparison of experimental 001 reflections with the calculated ones deduced from structural models, allowed us to determine the optimal structural parameters describing IS configuration along the axis. The obtained result showed an interstratified hydration character, for both studied exchangeable cations, regardless of the solid/liquid ratio being described probably by a partial cation exchange process. The theoretical mixed layer structure (MLS) suggests the coexistence of more one cristallite species saturated by more than one exchangeable cations, indicating a partial saturation of all exchangeable sites. The optimum structural parameter values, from the theoretical model, allowed us to follow the evolution of several intrinsic properties versus the applied constraint strength. The variable solid/liquid ratio effect on the material porosity is examined by the BET-specific surface area and BJH pore size distribution (PSD) analyses. The adsorption measurement outcomes confirm XRD results concerning mainly the link between several intrinsic clay properties and the constraint strength.