Hydrogen bonding and vibrational properties of hydroxy groups in the crystal lattice of dioctahedral clay minerals by means of first principles calculations

The hydroxy groups of the crystal lattice of dioctahedral 2:1 phyllosilicates were investigated by means of quantum-mechanical calculation. The standard Kohn-Sham self-consistent density functional theory (DFT) method was applied using the generalized gradient approximation (GGA) with numerical atomic orbitals and double-zeta polarized functions as basis set. Isomorphous cation substitution of different cations in the octahedral and tetrahedral sheet was included along with several interlayer cations reproducing experimental crystal lattice parameters. The effect of these substitutions and the interlayer charge on the hydroxyl group properties was also studied. These structures represent different cation pairs among Al³⁺, Fe³⁺ and Mg²⁺ in the octahedral sheet of clays joined to OH groups. The geometrical disposition of the OH bond in the crystal lattice and the hydrogen bonds and other electrostatic interactions of this group were analyzed. The frequencies of different vibrational modes of the OH group [(OH), (OH) and (OH)] were calculated and compared with experimental data, finding a good agreement. These frequencies depend significantly on the nature of cations which are joined with, and the electrostatic interactions with, the interlayer cations. Besides, hydrogen-bonding interactions with tetrahedral oxygens are important for the vibrational properties of the OH groups; however, also the electrostatic interactions of these OH groups with the rest of tetrahedral oxygens within the tetrahedral cavity should be taken into account. The cation substitution effect on the vibration modes of the OH groups was analyzed reproducing the experimental behaviour.Dr. V. Botella passed away last February     

The effect of mineralogical and cationic heterogeneities on rheological properties of suspensions with Li-smectites, extracted from Volclay MX-80

The rheological study of colloidal suspensions contributes to the understanding of the aggregation phenomena of colloidal particles within a suspended fluid. The infra-2-μm (equivalent diameter) fraction of a bulk material, Volclay MX-80 bentonite was intensively analysed in order to understand the relative rheological data scattering observed with Li-smectite suspensions, prepared with the usual saturation procedure. A good mineralogical characterisation, especially for secondary minerals, coupled to a verification of cation exchanges on clayey fraction allowed us to propose a new way for investigating the observed differences of the bentonites rheological behaviour. Indeed, for a well Li-saturated smectite obtained from the purified infra-2-μm fraction, rheological data proved to be very accurate and perfectly reproducible. This emphasises the role of other minerals as well as the commonly observed discrepancy between the rheological behaviours of natural and industrial bentonites.