Local-field approximation of homonuclear dipolar interactions in 7Li-NMR: density-matrix calculations and random-walk simulations tested by echo experiments on borate glasses.

NMR echo techniques have proven to be important to study dynamics in ion conductors and other solid materials. Using the spin-3/2 nucleus (7)Li as a probe, both the quadrupolar and the often neglected homonuclear dipolar interactions modulate the NMR frequency as the ion performs jump processes. Retaining only the local-field term of the many-body Hamiltonian, the impact of the dipolar interaction on various echo experiments was studied using spin dynamics calculations yielding products of dipolar and quadrupolar correlation functions. Using a simple stochastic model these functions were simulated with particular emphasis on the impact of ionic motions and on the conditions under which the dipolar and quadrupolar contributions factorize. The results of the computations and of the random-walk simulations are compared with experimental data obtained for various lithium borate and lithium borophosphate glasses. It is concluded that the local-field approximation is a useful means of treating the Li-Li dipole interactions and that the simple model that we introduce is capable of describing many experimentally observed features. Furthermore, because the dipolar and quadrupolar contributions essentially factorize, a selective determination of the corresponding correlation functions becomes possible.

Rheo-NMR of the secondary flow of non-Newtonian fluids in square ducts.

We report the first real-time observations of the entire fully developed laminar secondary flow field of aqueous 2% Viscarin GP-209NF (a λ-carrageenan polysaccharide) in a square duct as made using a modest rheological NMR imaging (rheo-NMR) apparatus. Simulations using the Reiner-Rivlin constitutive equation verify the results. An included rheo-NMR flow rate quantification study assesses the measurement precision. Rheo-NMR resolves slow flows superimposed on primary flows about 300 times greater, making it a universally accessible technique by which full secondary flow field data may be systematically gathered.

(6)Li NMR in lithium borate glasses.

In anticipation of using fluctuations in the nuclear dipolar and quadrupolar interaction as a probe of lithium ion motion in lithium borate glasses, the static values of these interactions were measured using a variety of echo techniques. The static quadrupolar echo spectrum of (7)Li and a calculation of the dipolar interaction in crystalline Li(2)B(4)O(7) (same chemical composition as the glass under study) were used to estimate the strength of the two interactions. These indicate that the dipolar and quadrupolar interactions for (6)Li will be of similar size and the dipolar interaction will be dominated by the unlike spin interaction between the (6)Li and the (10)B, (11)B spins. An appropriate theoretical model is proposed and explicit expressions for the echo amplitude are calculated in terms of the dipolar and quadrupolar second moments. This single spin model takes into account the quadrupolar interaction but treats the dipolar interaction as an effective magnetic field. Experimental results are presented which show the essential validity of the model and measurements lead to reasonable values for the dipolar and quadrupolar second moments. The relative merits of the various echo techniques are discussed.

Analysis of charge transport in gels containing polyoxometallates using methods of different sensitivity to migration.

Two methods have been used for examination of transport of charge in gels soaked with DMF and containing dissolved polyoxometallates. The first method is based on the analysis of both Cottrellian and steady-state currents and therefore is capable of giving the concentration of the electroactive redox centres and their transport (diffusion-type) coefficient. The second method provides the real diffusion coefficients, i.e. transport coefficients free of migrational influence, for both the substrate and the product of the electrode reaction. Several gels based on poly(methyl methacrylate), with charged (addition of 1-acrylamido-2-methyl-2-propanesulphonic acid to the polymerization mixture) and uncharged chains, have been used in the investigation. The ratio obtained for the diffusion coefficient (second method) and transport coefficient (first method) was smaller for the gels containing charged polymer chains than for the gels with uncharged chains. In part these changes could be explained by the contribution of migration to the transport of polyoxomatallates in the gels. However, the impact of the changes in the polymer-channel capacity at the electrode surface while the electrode process proceeds was also considered. These structural changes should affect differently the methods based on different time domains.