Applications of DQ-DRENAR for the structural analysis of phosphate glasses

Abstract

A new solid state NMR technique entitled DQ-DRENAR (Double-Quantum based Dipolar Recoupling Effects Nuclear Alignment Reduction) has been recently described for measuring homonuclear dipole–dipole interactions in multi-spin-1/2 systems under magic-angle spinning conditions. As in rotational echo double resonance (REDOR), the homonuclear dipole–dipole coupling constant can be extracted from a plot of a normalized difference signal (S0−S′)/S0 versus dipolar mixing time, where S is the signal amplitude with the DQ-Hamiltonian present, and S0 is the signal amplitude in the absence of the DQ-Hamiltonian, which is used for normalization. Within the range of (S0−S)/S0≤0.3–0.5 such “homonuclear REDOR curves” can be approximated by simple parabolae, yielding effective squared dipole–dipole coupling constants ∑bjk2 summed over all the pairwise interactions present. The effect of glassy disorder has been studied by simulations, replacing singular-valued internuclear distances by Gaussian distance distributions with the same central value. This situation results in a systematic over-estimation effect, which tends to compensate the implicit under-estimation effect caused by the parabolic fitting approach. The present contribution describes applications to a number of phosphate-based glasses and glass ceramics. The method turns out to be well suited for the differentiation of the various Q(n) phosphate species, for characterizing the spatial distribution of isolated orthophosphate ions and for the detection of incipient nano-segregation and/or phase separation effects in glass ceramics.