Sol/gel and isotropic/nematic transitions in aqueous suspensions of natural nontronite clay. Influence of particle anisotropy. 1. Features of the i/n transition

The phase behavior of a natural nontronite clay was studied for size-selected particles by combining osmotic pressure measurements, visual observations under polarized light, and rheological experiments. In parallel, the positional and orientational correlations of the particles were analyzed by small-angle X-ray scattering. Aqueous suspensions of nontronite exhibit a true isotropic/nematic (I/N) transition that occurs before the sol/gel transition, for ionic strengths below 10(-3) M/L. In this region of the phase diagrams, the system appears to be purely repulsive. The I/N transition shifts toward lower volume fractions for increasing particle anisotropy, and its position in the phase diagram agrees well with the theoretical predictions for platelets. SAXS measurements reveal the presence of characteristic interparticular distances in the isotropic, nematic, and gel phases. The swelling law (separation distance vs swelling law) exhibits two regimes. For high volume fractions, the swelling law is one-dimensional as in layered systems and reveals the presence of isolated platelets. At lower volume fraction, distances scale as phi(-1/3), indicating isotropic volumic swelling. Finally, the experimental osmotic pressure curves can be satisfactorily reproduced by considering the interparticle distances between two charged planes whose effective charge is around 10% of the structural charge.