Water radiolysis in exchanged-montmorillonites: the H2 production mechanisms.

The radiolysis of water confined in montmorillonites is studied as a function of the composition of the montmorillonite, the nature of the exchangeable cation, and the relative humidity by following the H2 production under electron irradiation. It is shown that the main factor influencing this H2 production is the water amount in the interlayer space. The effect of the exchangeable cation is linked to its hydration enthalpy. When the water amount is high enough to get a basal distance higher than 1.3 nm, then a total energy transfer from the montmorillonite sheets to the interlayer space occurs, and the H2 production measured is very similar to the one obtained in bulk water. For a basal distance smaller than 1.3 nm, the H2 production increases with the relative humidity and thus with the water amount. Lastly, electron paramagnetic resonance measurements evidence the formation of a new defect induced by ionizing radiation. It consists of a hydrogen radical (H2 precursor) trapped in the structure. This implies that structural hydroxyl bonds can be broken under irradiation, potentially accounting for the observed H2 production.

Effect of pH on Rheological Properties of Purified Sodium Bentonite Suspensions.

The effect of pH on the rheological behavior of three purified sodium bentonite (HP, GP, and WP) suspensions is studied. Each clay is studied as a function of pH, at a chosen constant concentration. These concentrations correspond to the lower concentrations at which the yield stress can be detected. They are 12.5, 8.5, and 5.5% w/w, respectively, for the three clay suspensions. The natural pH of these samples measured by a pH meter or by a colorimetric test paper are usually neutral or weakly basic. To obtain a large range of pH values, HCl or NaOH solutions are used in the preparation of the suspensions. From the natural pH and when pH values become more basic, the yield stress measured, using the vane method, decreases. It reaches a minimum before it increases sharply, at very high basic medium. When the pH decreases, the yield stress increases and reaches a maximum for pH in weakly acidic media before decreasing again, in a very highly acidic medium where the structure of the clay is probably attacked. The pH where the maximum appears depends on the nature of the clay. At the same time, the conductivity and the electrophoretic mobility are measured, at the different pH values, on the supernatants obtained after centrifugation of the previous suspensions. The isoelectric points of the edges of the three studied purified sodium bentonites, which are of a great importance for the understanding of the interactions between the clay particles, have been determined. In summary, a correlation between rheological and electrokinetic results, is shown. And moreover, different types of interactions between clay particles are deduced, depending on the pH value of the medium. At acidic medium, there is a dominance of the attractive forces between particles. At high basic medium, interparticle interactions lead to a card-house-like structure based on edge to edge, edge to face, and face to face repulsion, instead of attraction. Copyright 1999 Academic Press.

Adsorption of a Cationic Surfactant on Na-Montmorillonite: Inspection of Adsorption Layer by X-Ray and Fluorescence Spectroscopies.

The adsorption of the cationic surfactant BDDAC on a hydrophilic smectite (montmorillonite) surface has been investigated, especially in the range of low coverage ratios where surfactant ions are adsorbed through cation-exchange with the counterions of the clay. The surfactant coions (Cl(-)) were found to be adsorbed simultaneously with the cationic part after a complete alkyl ammonium ion-exchange of montmorillonite (CEC). We observe that organoclay particles remain flocculated in aqueous medium in almost all the range of adsorption isotherms up to 1.38 CEC and afterward redisperse incompletely. The intercalation of surfactant in the interlamellar space was followed by X-ray measurements. Fluorescence spectroscopy was used to obtain information about the adsorption layer at the interface. A calculation from geometrical considerations and from adsorption isotherms shows that below 1.38 CEC, there is a flat double layer in the interlamellar space and after this amount of adsorbed surfactant, an interstratified clay-surfactant mixed system is formed. Copyright 1999 Academic Press.

Interactions of Monovalent Organic Cations with Pillared Clays.

Interactions between an acid-activated pillared clay and several organic cations including dyes (methylene blue, MB; crystal violet, CV; acriflavin, AF) and benzyl derivatives (benzyltrimethylammonium, BTMA; benzyltriethylammonium, BTEA) were studied by adsorption measurements and X-ray diffraction. When the dyes were adsorbed from low ionic strength solutions, adsorption was irreversible but saturated at levels below the cation exchange capacity (CEC) of the clay (0.6 meq/g). The difference with CEC value was largest for CV. This mode of adsorption was interpreted in terms of interlayer adsorption with steric hindrance in the pillared galleries. On the other hand, when the dyes were adsorbed from high ionic strength solutions, adsorption levels well beyond the CEC of the clay could be reached, in particular for MB and CV. This was interpreted in terms of a second adsorption mode, involving formation of molecular aggregates on the outer surface of the clay, as evidenced by X-ray diffraction. The behavior of the cationic benzyl derivatives was markedly different, with an adsorption level always below the CEC and a decrease of adsorption as the ionic strength was increased, as expected for non-complex-forming cations. Copyright 1999 Academic Press.