On the cation dependence of interlamellar and interparticular water and swelling in smectite clays.

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.

Thermodynamic analysis of the immersion of a smectite substituted with Na or Ca: heat effect due to the cation.

The enthalpy produced during immersion in water of a smectite, identified as a montmorillonite, substituted by Ca or Na is analyzed using three different approaches. The heat of immersion is measured using the classical calorimetric method. It is compared to an estimate using adsorption techniques. And it is calculated from a theoretical estimate of the surface energy of a crystal model of montmorillonite. The comparison of the different values allows the enthalpy linked to the swelling phenomenon to be estimated. The Ca form appears in every case to interact more strongly with water molecules than the Na form.

Study of the surface energy of montmorillonite using PACHA formalism.

The surface energy of exchanged forms of montmorillonite has been computed using a partial charge model introduced in the calculation of the lattice energy. The results are in correct agreement with data on heats of adsorption. However, the difference between theoretical and experimental data increases from light cations to heavy cations associated with the clay network. This indicates that the heat of adsorption depends highly on the step hydration of the cations. This type of behavior was expected and thus the quantification seems realistic.

Hydration of a Na(+)-montmorillonite studied by thermally stimulated depolarization current.

Thermally stimulated depolarization current (TSDC) technique is a powerful tool for probing dipole re-orientational motions in condensed matter. In the case of cation-exchangeable aluminosilicates, it allows the assessment of the potential barrier related to the hopping mechanism of cations and, consequently, the measurement of its evolution when molecules, i.e. water, are adsorbed and interact with the cations embedded in the solid framework. Then, using suitable models based on thermodynamics, the analysis of TSDC signals obtained at various hydration states provides insights about the surface properties of the studied solid and the mechanism of adsorption at the cationic site. In this work, TSDC is used to study the first stage, i.e. when the number of adsorbed molecules is below the occurrence of the water monolayer, of water adsorption in a Na(+)-montmorillonite from Mostaganem (Algeria). It is shown that the hydration process follows two stages. Using the "chemical force" concept it can then be concluded that when the number of adsorbed water molecules per cation is lower than 2, cation-water interaction dominates the energetics of adsorption, whereas at higher water loading the water "chemical force" is also involved into water-water and/or water-clay framework interactions. The number of water molecules for the monohydrated state is found to be about 7.

Use of dielectric relaxation for measurements of surface energy variations during adsorption of water on mordenite.

This paper tries to assess simply and quantitatively the link between classical adsorption theories and dielectric spectroscopy, in order to demonstrate that dielectric spectroscopy can be used as a tool of determination of surface energy variations due to movements of charge carriers at the surface of solids. A simple theory is developed to analyze hops of cations at the surface of mordenite, which are detected by complex impedance spectroscopy during adsorption of water. An energy of extraction of the cation can be determined from measurements and its dependence on the quantity of water molecules adsorbed is shown and qualitatively and quantitatively explained, using relationships developed in order to interpret adsorption phenomena generally. The agreement with other determinations of the adsorption energies and solid surface energy is correct.

Thermodynamic assessment of the variation of the surface areas of two synthetic swelling clays during adsorption of water.

Two synthetic smectites (montmorillonite and beidellite) are studied by a water adsorption technique in order to assess their specific surface areas under atmospheric conditions. A route recently proposed for extracting the thermodynamic data from experimental adsorption isotherms is used. The variation of the specific surface area during water adsorption is obtained, which can be linked to the enlargement of the interlayer space determined using X-ray diffraction. This variation is compared to an idealized specific surface area obtained from TEM and X-ray measurements in agreement with crystallographic models. All these results are also compared with those obtained previously for a natural montmorillonite. A simple view of swelling is proposed.

Calculation of surface enthalpy of solids from an ab initio electronegativity based model: case of ice.

A very simple route to calculation of the surface energy of solids is proposed because this value is very difficult to determine experimentally. The first step is the calculation of the attractive part of the electrostatic energy of crystals. The partial charges used in this calculation are obtained by using electronegativity equalization and scales of electronegativity and hardness deduced from physical characteristics of the atom. The lattice energies of the infinite crystal and of semi-infinite layers are then compared. The difference is related to the energy of cohesion and then to the surface energy. Very good results are obtained with ice, if one compares with the surface energy of liquid water, which is generally considered a good approximation of the surface energy of ice.

Contact angle and film pressure: study of a talc surface.

Talc samples in both sheet and powder form are studied by adsorption calorimetry and adsorption isotherm techniques. A model is used to determine the solid surface energy, the solid surface tension and the dispersive, acidic, and basic components of these terms. These results are introduced in an approximate equation relating adsorption to contact angle data. Experimental contact angles are in correct agreement with this approach. The Neumann equation of state is used to fit the data and discussed. It appears as a numerical form of the general equation taking into account gas adsorption and film pressure. Behaviors of talc in contact with liquids do not appear very different whether the solid is in sheet or powder form.

Surface heterogeneity of passively oxidized silicon carbide particles: vapor adsorption isotherms.

The surfaces of silicon carbide particles subjected to two different passive oxidation treatments have been characterized by immersion calorimetry and vapor adsorption techniques. Surface enthalpies and surface free energies have been computed using semiempirical models and are compared to theoretical estimations. The surface entropy term appears higher than in the case of other solids studied with the same analysis. The definition of the surface entropy term is discussed in order to explain the discrepancy between calculation and experiment. An explanation of results is proposed, which is related to the constitution of silicon oxide layers at the surface of silicon carbide, a fact demonstrated by previous XPS measurements.

Study of the influence of location of substitutions on the surface energy of dioctahedral smectites.

The surface energy of some clays belonging to the smectite group has been calculated starting from crystal structures and combining a partial charge model with the computation of the lattice energy. The dioctahedral smectites studied here include montmorillonite; beidellites; and nontronite. One of the differences between these clays is the location of the substitution in the octahedral sheet or in the tetrahedral one. Another is the possibility of vacancies in cis- or trans-octahedral positions. These locations and vacancies have an effect on the distortion of the crystal framework and therefore on the surface energy. Calculated surface energies of the solid samples increase in the order beidellites > montmorillonite > nontronite. The bond energy between the interlayer cation and the layer appears to follow the same order and to depend both on the nature of the most electropositive elements of the layer and on their location. The trends obtained provide elements for an analysis of data related to interlayer enlargement.