Abstract
29Si MAS-NMR spectra were obtained for vermiculite with tetrahedral composition x=Al/(Al+Si)=0.28, a synthetic mica with x=0.43, and margarite with x=0.5. Comparison between the observed and Monte-Carlo simulated spectra was used to test different Al-Si distribution schemes in the tetrahedral sheet. The results of this analysis are interpreted including earlier data corresponding to lower Al for Si substitutions (0.12≤x≤0.28), and it is shown that for all samples (8 compositions in the range 0.1≤x≤0.5) the Al-Si distribution complies with the principle of homogeneous dispersion of charges (HDC). Thus, Al-Si distribution models for any particular x can be predicted on the basis of a simple crystallochemical criterion. HDC is a short range order concept and implies that, within the restrictions imposed by the principle, charges be distributed at random. For increasing values of x, however, the observance of HDC implies a coupling between adjacent hexamer rings which restricts the degrees of freedom for random distribution and is equivalent to a progressive extension of order. This is reflected by the frequencies of meta and para substitutions in the hexamer rings, which vary in a characteristical, continuous way with x, until the fully ordered distribution scheme of margarite (x=0.5) is reached. Partial long-range order for x<0.5, with alternating Si and (Al+Si) tetrahedra and all substitutions in meta disposition, could not be confirmed.
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Herrero, C.P., Gregorkiewitz, M., Sanz, J. et al. 29Si MAS-NMR spectroscopy of mica-type silicates: Observed and predicted distribution of tetrahedral Al-Si. Phys Chem Minerals 15, 84–90 (1987). https://doi.org/10.1007/BF00307613
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DOI: https://doi.org/10.1007/BF00307613