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  • 1
    ISSN: 1432-2021
    Keywords: Key words Olivine ; Order/disorder ; High-temperature cation partitioning ; Neutron diffraction (single crystal)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract  Crystallographic determinations on natural olivine single crystals of mantle composition and origin, carried out by in situ neutron diffraction at high temperature, show that the octahedrally co-ordinated Fe2+ and Mg cations undergo two successive trends of cation ordering with increasing temperature. An initial slight preference of Fe2+ for site M1, up to a temperature of about 850 °C, is followed by a reverse-ordering reaction with a site preference exchange between the two cations. The cross-over between the two regimes of ordering, corresponding to a situation of complete disorder, occurs at about 900 °C. Above this temperature Fe2+ progressively and strongly segregates into site M2 up to 1300 °C, the practical limit of the experimental setup utilized in the experiments. Care was taken to ensure that no chemical changes occurred in the crystals (i.e. oxidation), as testified by Mössbauer spectroscopy determinations carried out before and after the heat treatment. The cation-ordering behaviour is reflected in temperature-dependent changes of geometrical and atomic displacement parameters occurring in the octahedral sites M1 and M2. A thermodynamical explanation of this behaviour is proposed in terms of a prevailing vibrational contribution to entropy.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1432-2021
    Keywords: Key words Olivine ; Order/disorder ; High temperature cation partitioning ; Neutron diffraction (powder)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract  The partitioning of Fe and Mg between the M1 and M2 octahedral sites of olivine has been investigated by in situ time-of-flight neutron powder diffraction. The degree of M-cation order was determined from direct measurements of site occupancies in a synthetic sample of Fo50Fa50 heated to 1250 °C at the Fe-FeO oxygen buffer. Fe shows slight preference for M1 at temperatures below about 600 °C, progressively disordering on heating to this temperature. Above 630 °C, the temperature at which site preferences cross over (T cr), Fe preferentially occupies M2, becoming progressively more ordered into M2 on increasing temperature. The cation-ordering behaviour is discussed in relation to the temperature dependence of the M1 and M2 site geometries, and it is suggested that vibrational entropy, crystal field effects and changes in bond characteristics play a part in the cross-over of partitioning behaviour. The temperature dependence of site ordering is modelled using a Landau expansion of the free energy of ordering of the type ΔG = −hQ + gTQ +   (T − T c)Q 2 +   Q 4, with a/h = 0.00406 K−1, b/h = 2.3, T c = 572 K and g/h = 0.00106 K−1. These results suggest that the high-temperature ordering behaviour across the forsterite-fayalite join will have a bearing on the activity-composition relations of this important rock-forming mineral, and indicate that Fe-Mg olivine solid solutions become less ideal as temperature increases.
    Type of Medium: Electronic Resource
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