NMR has long been used to obtain structural information about glasses. Fairly recent reviews of standard wide line NMR have been given by MullerWarmuth and Eckert (1982), Bray et at. (1983) and Bray and Gravina (1985). The information given by these studies has, in the main, been concentrated on quadrupolar nuclei, for example the use of llB to determine the relative amounts of 3 and 4 fold co-ordinated boron in glasses. Other main themes have been concerned with using dipolar broadened lineshapes to test for the probability of particular local configurations.Much of the structural information potentially available from NMR experiments is masked in solids by various static anisotropic nuclear interactions which broaden the line and make the small differences in position undetectable. These include the magnetic dipolar interaction, the anisotropic chemical shift interaction and, for nuclei with spin I> 112, the quadrupolar interaction. The dipolar interaction arises from the magnetic field at one nucleus produced by neighbouring nuclei and varies as the inverse cube of the distance between nuclei. The chemical shift is caused by bonding of the atom to its surroundings so that each crystallographic site will have a particular shift with three components corresponding to the three principal axes. For a site of cubic point group the chemical shift will be isotropic, for sites of lower symmetry the shift will be anisotropic and in microcrystalline and glassy (it is the local symmetry that is important) samples lineshapes such as those shown in Fig is defined as (all + a22 + a33)/3, thus a,!:la = a33 -alb 17 are sufficient to describe the chemical shift parameters.For nuclei with spin I> 112 the interaction of the nuclear quadrupole moment (eQ) with the electric field gradient (a 2 VlaZ 2 = eq) at the nucleus will alter the nuclear energy levels depending upon the relative orientation of the electric field gradient and the applied magnetic field and to first order in the quadrupolar interaction will give the powder pattern shown in
MAS NMR: a new technique for structure determinationobservable in powders, and it will be broadened and can have a complex shape dependent on the quadrupolar asymmetry parameter; examples are shown in Fig. 1.2(b) and (c).In a liquid the NMR lines are usually very narrow because all of these broadening mechanisms have, in first order, a 3 cos 2 0-1 angular dependence and this averages to zero under the rapid motion present. Recently various line narrowing techniques, such as magic angle spinning (MAS) where the sample is orientated at 54° 44' (cos 0 = 1/y3) to the magnetic field and spun rapidly (Andrew, 1981), have been developed such that in favourable crystalline materials a reduction in linewidth of more than two orders of magnitude can be achieved and the underlying structural information present in the spectrum obtained. The improvement is less marked in glasses because of the disorder but the resolution is often sufficient to give much unique structural information. corresponds to ...