The osmotic character of long-range interlamellar swelling in smectite clays is widely accepted and has been evidenced in the interlayer space by X-ray diffraction. Such a behavior in mesopores was not experimentally confirmed until the determination of the mesopore size distribution in Na-montmorillonite prepared from MX80 bentonite using thermoporometry experiments. This is confirmed here for other montmorillonite samples where the interlayer cations are alkaline and Ca(2+) cations. The nature of the interlayer cation is found as strongly influencing the behavior of the size and the swelling of mesopores. These results are supported by the BJH (Barrett, Joyner and Halenda) pore radius values issued from the nitrogen adsorption-desorption isotherms at the dry state. Thermoporometry results as a function of relative humidity ranging from 11% to 97% have shown an evolution of the mesopore sizes for a purified Na-montmorillonite. New thermoporometry data are presented in this article and confirm that the interparticle spaces in K-, Cs-, or Ca-montmorillonites are not strongly modified for all the range of relative humidity: the swelling is not observed or is strongly limited. It appears in contrast that only Li- and Na-montmorillonites undergo a mesopore swelling, distinct from the interlayer swelling. More generally, our results confirm the possibility to use thermoporometry or differential scanning calorimetry to study the structure and the evolution of swelling materials in wetting conditions such as natural clays or biological cells. In this paper, we describe the different key steps of the hydration of swelling clays such as montmorillonites saturated with alkaline cations. Using thermoporometry results combined with X-ray diffraction data, we distinguish the evolution of the porosity at the two different scales and propose a sequence of hydration dependent on the interlayer cation. From this study, it is shown that the interlayer spaces are not completely filled when the mesopores start to fill up. This implies that the swelling observed in the mesopores for Li and Na samples is due to an osmotic swelling. For the other samples, it is difficult to conclude definitively. Furthermore, we determine the different proportion of water (interlayer water and mesopore water) present in our samples by the original combination of (1) X-ray diffraction data, (2) the pore size distribution obtained by thermoporometry, and (3) recent adsorption isotherm results. It is found that the interlayer space is never completely filled by water at the studied relative humidity values for all samples except for the Cs sample.

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