In water-rich smectite gels, bound or less mobile H2O layers exist near negatively-charged clay platelets. These bound H2O layers are obstacles to the diffusion of unbound H2O molecules in the pore-space, and therefore reduce the H2O self-diffusion coefficient, D, in the gel system as a whole. In this study, the self-diffusion coefficients of H2O molecules in water-rich gels of Na-rich smectites (montmorillonite, stevensite and hectorite) were measured by pulsed-gradient spin-echo proton nuclear magnetic resonance (NMR) to evaluate the effects of obstruction on D. The NMR results were interpreted using random-walk computer simulations which show that unbound H2O diffuses in the gels while avoiding randomly-placed obstacles (clay platelets sandwiched in immobilized bound H2O layers). A ratio (volume of the clay platelets and immobilized H2O layers)/(volume of clay platelets) was estimated for each water-rich gel. The results showed that the ratio was 8.92, 16.9, 3.32, 3.73 and 3.92 for Wyoming montmorillonite (⩽5.74 wt.% clay), Tsukinuno montmorillonite (⩽3.73 wt.% clay), synthetic stevensite (⩽8.97 wt.% clay), and two synthetic hectorite samples (⩽11.0 wt.% clay), respectively. The ratios suggest that the thickness of the immobilized H2O layers in the gels is 4.0, 8.0, 1.2, 1.4 and 1.5 nm, respectively, assuming that each clay particle in the gels consists of a single 1 nm-thick platelet. The present study confirmed that the obstruction effects of immobilized H2O layers near the clay surfaces are important in restricting the self-diffusion of unbound H2O in water-rich smectite gels.

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