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The structural changes along the c axis, of the Ba-exchanged montmorillonite (Swy-2-Ba), under variable relative humidity (% RH), is investigated. In this regard, the arrangement, amount and position of both exchangeable cation and the water molecules in the interlamellar space (IS), are evaluated. This aim is achieved using the X-ray diffraction (XRD) profile modeling approach that consists of comparing experimental and theoretical patterns calculated from structural models. The contributions of the hydration states and the interlayer water amounts, as a function of the % RH, are registered by quantitative XRD investigation. The validated structural models are heterogeneous, suggesting various proportions of layer types at different RH ranges, which means the coexistence of different mixed layer structure MLS packages, exhibiting different proportions of layers with contrasting hydration states. This result is attributed to the orientation of the applied hydration sequence. Indeed, the interlayer water molecule amounts, which led to the appearance of a logic hydration hysteresis, are strongly affected by hydrous perturbation.

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 c ∗ 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.