Abstract
The ordering of Al and Si in Mg cordierite Mg2Al4Si5O18 is considered using computer simulation. First the enthalpy of interaction J ij between sites is derived by computer modelling 101 different Al/Si configurations and analysing their energies. They are compared with similar results for three other minerals and with ab initio calculations to assess the whole approach. Secondly the ordering process is studied using Monte Carlo simulation applied to the J ij . The ordering phase transition temperature T c is found as 1800°C in reasonable agreement with the experimental estimate of 1450° C. These are much lower than the estimate T c(ABW)≈7600°C obtained from Bragg-Williams theory. Strong short-range order sets in below T c(ABW), and the reasons for much lower temperature T c of long-range ordering are discussed. Strong short-range also sets in very rapidly in a simulated anneal, in agreement with experiment. Thirdly an attempt is made to compare our calculated enthalpies directly with the results of NMR and calorimetry experiments, not completely successfully. A free energy ΔG≈4.6 eV for the activation barrier for ordering is suggested.
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Thayaparam, S., Heine, V., Dove, M.T. et al. A computational study of Al/Si ordering in cordierite. Phys Chem Minerals 23, 127–139 (1996). https://doi.org/10.1007/BF00202308
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DOI: https://doi.org/10.1007/BF00202308