Effect of sonication on the particle size of montmorillonite clays.

This paper reports on the effect of sonication on SAz-1 and SWy-1 montmorillonite suspensions. Changes in the size of the particles of these materials and modifications of their properties have been investigated. The variation of the particle size has been analyzed by DLS (dynamic light scattering). In all cases the clay particles show a bimodal distribution. Sonication resulted in a decrease of the larger modal diameter, as well as a reduction of its volume percentage. Simultaneously, the proportion of the smallest particles increases. After 60 min of sonication, SAz-1 presented a very broad particle size distribution with a modal diameter of 283 nm. On the other hand, the SWy-1 sonicated for 60 min presents a bimodal distribution of particles at 140 and 454 nm. Changes in the properties of the clay suspensions due to sonication were evaluated spectroscopically from dye-clay interactions, using Methylene Blue. The acidic sites present in the interlamellar region, which are responsible for dye protonation, disappeared after sonication of the clay. The changes in the size of the scattering particles and the lack of acidic sites after sonication suggest that sonication induces delamination of the clay particles.

Preparation of a clay-modified carbon paste electrode based on 2-thiazoline-2-thiol-hexadecylammonium sorption for the sensitive determination of mercury.

A montmorillonite from Wyoming-USA was used to prepare an organo-clay complex, named 2-thiazoline-2-thiol-hexadecyltrimethylammonium-clay (TZT-HDTA-clay), for the purpose of the selective adsorption of the heavy metals ions and possible use as a chemically modified carbon paste electrode (CMCPE). Adsorption isotherms of Hg2+, Pb2+, Cd2+, Cu2+, and Zn2+ from aqueous solutions as a function of the pH were studied at 298 K. Conditions for quantitative retention and elution were established for each metal by batch and column methods. The organo-clay complex was very selective to Hg(II) in aqueous solution in which other metals and ions were also present. The accumulation voltammetry of Hg(II) was studied at a carbon paste electrode chemically modified with this material. The mercury response was evaluated with respect to the pH, electrode composition, preconcentration time, mercury concentration, "cleaning" solution, possible interferences and other variables. A carbon paste electrode modified by TZT-HDTA-clay showed two peaks: one cathodic peak at about 0.0 V and an anodic peak at 0.25 V, scanning the potential from -0.2 to 0.8 V (0.05 M KNO3 vs. Ag/AgCl). The anodic peak at 0.25 V presents excellent selectivity for Hg(II) ions in the presence of foreign ions. The detection limit was estimated as 0.1 microg L(-1). The precision of determination was satisfactory for the respective concentration level.

Influence of the layer charge and clay particle size on the interactions between the cationic dye methylene blue and clays in an aqueous suspension.

The spectroscopic behavior of the dye MB in suspensions of different clays have been used for evaluating layer charge density influence on the adsorption properties of the particles. The clays with higher charge density, like SAz-1 and SCa-3, promote a higher aggregation and do not show deaggregation at longer times, so that practically only the aggregate peak at approximately 570 nm is observed, without any change with time. This is due to, on one side, the larger particle size that decreases the surface area available for adsorption. Additionally, the clay layers will be held together more tightly, avoiding the migration of the dye to the interlamellar region. On the other hand, SWy-1, having a lower charge density, shows a completely different behavior. The dye molecules, initially adsorbed as aggregates on the outer surface of the clay, deaggregate to form monomers that migrate to the interlamellar spaces, giving rise to absorption bands at 670 and 760 nm. Experiments using Ca-exchanged SWy-1, variation of the ionic strength by addition of salt, and the use of different size fractions of the clays confirm the finding that the main factor ruling the adsorption behavior of the probe is the size of the clay particles.

The Heavy-Atom Effect on the Photophysics of Aromatic Hydrocarbons in the Presence of Solid Clays.

The exchange of the original cation present on a Laponite clay (usually Na(+)) for heavy atoms such as Rb(+), Cs(+), and Tl(+) significantly alters the emission characteristics of some aromatic hydrocarbons (p-terphenyl, naphthalene, pyrene, and biphenyl). The increase of the atomic mass of the cation induces a decrease of the fluorescence emission simultaneous with an increase of the emission in the region of lower energies of the spectra, ascribed to the phosphorescence of those hydrocarbons. Time-resolved experiments for the pyrene-clay system showed a decrease of singlet lifetimes for the heavier atoms. Hydrocarbon aggregates were also detected from both the emission spectra and the time-resolved studies. The "excimer-like" emission showed longer lifetimes (10-25 ns) than the monomolecular hydrocarbons (1-3 ns), as already found for other similar systems. The amount of aggregates increased for the heavier cations due to the smaller surface available on the clay particles. Experiments increasing the amount of Tl(+) in samples containing a constant concentration of naphthalene allowed evaluation of the distance between the heavy atoms and the probe on the clay surface. The Perrin model treatment was used and resulted in approximately R(0)=9.2 Å. Copyright 2001 Academic Press.