Brownian dynamics of water confined in AOT reverse micelles: A field-cycling deuteron NMR relaxometry study

Reversed micelles and water in oil micro-emulsions can be used to solubilize biopolymers and genetic materials allowing analyzing their properties in a confined geometry. Nuclear Magnetic Resonance Dispersion (NMRD) provides a powerful and a noninvasive experimental technique to probe the long-term dynamics of these confined systems. However, the first step is to analyze and understand the slow dynamics of water inside these micro-reactors without any guest molecule. This is the aim of this presentation. Experimental results have been obtained for deuteron ²H NMRD of water confined in reverse micelles of bis (2-ethylhexyl) sodium sulfosuccinate (AOT) dispersed in isooctane C₈H₁₈. The water content is expressed as the molar ratio W₀ = [Water]/[AOT]. The radius of the spherical reversed micelles, R_m, increases almost linearly with W₀. In our case, W₀ is chosen in the range 20 ≤ W₀ ≤ 50 (35 ≤ R_m ≤ 80 Å). The frequency dependence for the spin-lattice relaxation rate R₁(ω) exhibits two regimes, for all W₀ values: a plateau at low frequency, proportional to 1/R_m, followed by the beginning of an algebraic decay. These experimental observations are discussed and compared to a numerical simulation of the intermittent Brownian diffusion of a water molecule inside a rotating reverse micelle. The possibility to probe some properties of the confinement, such as the localisation time on the sulfonated palisade and/or the water self-diffusion inside the water pool is emphasised.     

Aqueous suspensions of natural swelling clay minerals. 1. Structure and electrostatic interactions

In this article, we present a general overview of the organization of colloidal charged clay particles in aqueous suspension by studying different natural samples with different structural charges and charge locations. Small-angle X-ray scattering experiments (SAXS) are first used to derive swelling laws that demonstrate the almost perfect exfoliation of clay sheets in suspension. Using a simple approach based on geometrical constraints, we show that these swelling laws can be fully modeled on the basis of morphological parameters only. The validity of this approach was further extended to other clay data from the literature, in particular, synthetic Laponite. For all of the investigated samples, experimental osmotic pressures can be properly described by a Poisson-Boltzmann approach for ionic strength up to 10(-3) M, which reveals that these systems are dominated by repulsive electrostatic interactions. However, a detailed analysis of the Poisson-Boltzmann treatment shows differences in the repulsive potential strength that are not directly linked to the structural charge of the minerals but rather to the charge location in the structure for tetrahedrally charged clays (beidellite and nontronites) undergoing stronger electrostatic repulsions than octahedrally charged samples (montmorillonites, laponite). Only minerals subjected to the strongest electrostatic repulsions present a true isotropic to nematic phase transition in their phase diagrams. The influence of ionic repulsions on the local order of clay platelets was then analyzed through a detailed investigation of the structure factors of the various clay samples. It appears that stronger electrostatic repulsions improve the liquidlike positional local order.     

Insertion of small anisotropic clay particles in swollen lamellar or sponge phases of nonionic surfactant

we have established experimentally the region of existence of smectic and sponge lyotropic microstructures in the presence of synthetic hydrophilic clay particles. Taking into account the adsorption isotherm, we determined the extension of the single-phase regions by visual inspection and looking at low-q behaviour of the small-angle neutron scattering. Conditions of stability such as geometric constraints associated with fluctuation quenching are discussed. Received 11 December 2000 and Received in final form 11 April 2001     

Über die FINSLERschen höheren arithmetischen Operationen

Ohne Zusammenfassung Diese Arbeit wurde von demOffice of Scientific Research of the United States Air Force unterstützt.     

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.