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  • 1
    Electronic Resource
    Electronic Resource
    [s.l.] : Nature Publishing Group
    Nature 381 (1996), S. 407-409 
    ISSN: 1476-4687
    Source: Nature Archives 1869 - 2009
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
    Notes: [Auszug] It has been recognized for some time that non-equilibrium cation ordering in minerals might provide a means to measure rock cooling rates, from early work on Mg/Fe ordering in amphi-boles6 and extensive studies of pyroxenes7'8 to more recent analysis of Al/Si ordering in alkali feldspars9. ...
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  • 2
    ISSN: 1600-5740
    Source: Crystallography Journals Online : IUCR Backfile Archive 1948-2001
    Topics: Chemistry and Pharmacology , Geosciences , Physics
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  • 3
    Electronic Resource
    Electronic Resource
    Copenhagen : International Union of Crystallography (IUCr)
    Applied crystallography online 30 (1997), S. 84-84 
    ISSN: 1600-5767
    Source: Crystallography Journals Online : IUCR Backfile Archive 1948-2001
    Topics: Geosciences , Physics
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  • 4
    Electronic Resource
    Electronic Resource
    Copenhagen : International Union of Crystallography (IUCr)
    Acta crystallographica 53 (1997), S. 102-112 
    ISSN: 1600-5740
    Source: Crystallography Journals Online : IUCR Backfile Archive 1948-2001
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Rietveld analysis of neutron powder diffraction data on the sanmartinite (ZnWO4)-cuproscheelite (CuWO4) solid solution has enabled the comparison of microscopic and macroscopic order parameters associated with the P2/c–P\overline 1 structural phase transition. The macroscopic spontaneous strain, calculated from the lattice parameters, conforms well with a second-order Landau model. Furthermore, this is also true of the symmetry-related atomistic M—O order parameter and the quadratic elongation of the MO6 octahedra. It is clear that the Jahn–Teller effect, associated with the divalent Cu cation, is the driving force for the phase transition and the excess elongation evident in the M—O(2) bond giving rise to the non-symmetry predicted strain element e22. The existence of a large region of order parameter saturation at the copper-rich end of the solid solution is also associated with the MO6 elongation and the breakdown of the homogeneous strain field of the zinc solute atoms.
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  • 5
    ISSN: 1600-5740
    Source: Crystallography Journals Online : IUCR Backfile Archive 1948-2001
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 1432-0967
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract The enthalpy of calcite has been measured directly between 973 K and 1325 K by transposed-temperature- drop calorimetry. The excess enthalpy has been analysed in terms of Landau theory for this tricritical phase transition. The zero-point enthalpy and entropy allow estimates of the parameters a and C in the Landau expansion for free energy which expresses excess free energy ΔG as a function of the order parameter Q and temperature T: ΔG 1/2a(T 2c−T)Q 2+1/6CQ 6 with a=24 J·Kℒ·mol-1, C = 30 kJ·mol− T c = 1260 ±5 K. The entropy of disorder below the transition has been formulated as a function of temperature allowing the calculation of the calcite/aragonite phase boundary when taking this extra entropy into account. There is remarkable agreement between the calculated equilibrium curve and previous experimental observations. The Landau theory predicts behaviour which fully accounts for the change in slope of the calcite/aragonite phase boundary, which is thus wholly due to the R¯3c –R¯3m transition in calcite.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 16 (1989), S. 539-544 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract The phase transition between the $$P\bar 1$$ and $$I\bar 1$$ phases of anorthite has been studied at elevated pressure by single-crystal X-ray diffraction in a diamond-anvil cell. The phase transition is shown to be first-order in character for both end-member anorthite (CaAl2Si2O8) and for an anorthite with a small amount of albite component (NaAlSi3O8) in solid solution. Reversals of the transition across the phase boundary at three other compositions show that the transition pressure (P Tr) increases with increasing albite content. This behaviour is compared with that observed at elevated temperatures, and is analysed in terms of Landau theory.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 26 (1999), S. 591-600 
    ISSN: 1432-2021
    Keywords: Key words Montmorillonite ; Fuller's earth ; Dehydration ; Kinetics ; Thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract Isothermal thermogravimetric experiments have been carried out to determine the reaction kinetics of the dehydration processes in fuller's earth, a natural Ca-montmorillonite. Dehydration in swelling clays is a complex reaction, and analysis of the thermogravimetric data using empirical rate equations and time-transformation analysis reveals that the nature of the rate controlling mechanism is dependent upon both the temperature regime of the sample as well as the extent of reaction. For fuller's earth, we find that the dehydration kinetics are dominated by a nucleation and growth mechanism at low temperatures and fractions transformed (stage I), but above 90 °C the last stages of the reaction are diffusion controlled (stage II). The activation energy for dehydration during stage I is around 35 kJ · mol−1, whereas the removal of water during stage II requires an activation energy of around 50 kJ · mol−1. These two stages of dehydration are associated with primary collapse of the interlayer (stage I) and movement of water that is hydrated to cations within the interlayer (stage II).
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  • 9
    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.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 20 (1993), S. 375-381 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract The solid solution sanmartinite (ZnWO4)—cuproscheelite (CuWO4) has been studied using Cu 2p X-ray absorption spectroscopy. While a single L3 absorption peak is observed for CuWO4, two distinct L3 absorption peaks with a separation of ∼0.8 eV are observed for the intermediate samples in the solid solution. The two peaks represent distinct Cu sites: one with all CuO6 next nearest neighbours in the (Cu,Zn)O6 chains, another having at least one ZnO6 next nearest neighbour. Both sites show a linear increase in covalency as a function of increasing Cu-content. The relative intensities of the two absorption peaks is dependent upon the Cu-content and has been used to model the site occupancies. The results reveal that the local structural effects can be associated with a composition-dependent structural phase transition from P2/c (ZnWO4) to P $$\bar 1$$ (CuWO4). Deviations from a single-site model are explained in terms of the local environments, and evidence for site preferences and local clustering are explored.
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