RESUMO
The structure of aqueous dispersion of charged anisotropic nano-composites (synthetic Laponite clays) have been studied by NMR and numerical simulations based on a multi-scale statistical analysis have been used to interpret the mobility of the confined water molecule diffusing within dense Laponite aqueous dispersions (29-52% w/w) prepared by uniaxial compression. Firstly, the lineshape detected by NMR quadrupolar spectroscopy of the counterions ((23)Na or (7)Li) exhibits a large residual splitting Delta nu which is the fingerprint of the macroscopic nematic ordering of the anisotropic particles. Secondly, these results are also confirmed by the anisotropy of the self-diffusion tensor of the water molecule measured by (1)H Pulsed Gradient Spin Echo NMR. This self-diffusion anisotropy increases with the suspension density. Thirdly, the multi-scale statistical analysis of the water mobility bridges the gap between the time-scale (ps) accessible by Molecular Dynamics simulations and the time-scale (micros) accessible by Brownian Dynamics, leading to macroscopic behaviour comparable with PGSE-NMR data measurements.
RESUMO
The anisotropy of the solvent self-diffusion coefficient within suspensions of nanoparticles is measured by (1)H nuclear magnetic resonance with pulsed field gradient and used as a new procedure to detect nematic ordering. The potentiality of this method is illustrated using aqueous clay dispersions whose nematic ordering was already detected by (23)Na quadrupolar splitting.
RESUMO
The purpose of this study is to investigate possible differences in geometry and connectivity of the liquid phase in a partially water-satured porous medium between the adsorption and the desorption branches, using a series of silica gels. This was done by comparing the T1 and T2 relaxation times (in 1H and 2H nuclear magnetic resonance (NMR) relaxation) as well as the water self-diffusion coefficient D (in 1H) along the two branches of the adsorption/desorption isotherms. The results show that the two relaxation times and the diffusion coefficient are strongly dependent on the water content (saturation level). When plotted in normalized coordinates, the T1 and T2 vs. P/Po curves fit closely the adsorption/desorption isotherms, which validates the two-population, fast-exchange model. Furthermore, because at equivalent saturation levels, there is no difference between the relaxation times and diffusion coefficients obtained along the adsorption branch and those obtained along the desorption branch, one is led to the conclusion that despite different equilibrium conditions, the geometry and connectivity of the liquid phase are statistically the same along the two branches.