Abstract
Many solids do not exhibit the long-range order necessary for diffraction studies; in these cases the use of spectroscopic methods is suitable for their structural characterization. In this chapter, the applicacation of solid state NMR spectroscopy is reviewed in relation to the study of geometrical and substitutional disorder in crystalline and amorphous materials. After an introduction to the background theory, we focus on the interpretation of NMR spectra recorded using low and high resolution techniques. In particular, advantages derived from the use of monocrystalline samples in determination of quadrupolar, paramagnetic and dipolar interactions are analyzed. Finally, high-resolution methods (MAS technique, cross-polarization, decoupling…) are briefly rewieved. These methods are used to cancel dipolar interactions, so that, in many cases chemical shift values of NMR lines can be obtained for structural characterization of solids.
In the first group of examples presented, the local structure of amorphous and glassy materials is analyzed. It is shown that the coordination number and polymerization degree depend on the composition and relative distribution of ions. In the second group, the possibilities of NMR for determining tetrahedral framework distortions, site occupation and cation distribution in crystalline solids are discussed. The use of highresolution methods has permitted the study of second cation neighbours of a given atom and from that the determination of some characteristics of cation distribution in aluminosilicates. In particular, the multinuclear NMR study of 2:1 phyllosilicates has shown that, contrary to what might be expected, random distribution of cations does not apply in these minerals and that there are some restrictions on the distribution patterns. In the tetrahedral sheet, the homogeneous dispersion of Si and Al includes the Loewenstein’s rule as a restraint and in the octahedral sheet some clustering of Mg and Fe was detected around F and OH anions. Both types of distribution produce longrange disordered patterns in these minerals. Finally, we show that 29Si MAS-NMR spectroscopy can be used to follow the symmetry changes that accompanies longrange AI,Si ordering in tetrahedral network of certain aluminosilicates (feldspars and cordierite).
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Sanz, J. (1994). NMR Techniques for the Study of Crystalline and Amorphous Solids. In: Catlow, C.R.A. (eds) Defects and Disorder in Crystalline and Amorphous Solids. NATO ASI Series, vol 418. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-1942-9_8
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DOI: https://doi.org/10.1007/978-94-011-1942-9_8
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