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  • 1995-1999  (19)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Mineralogy and petrology 53 (1995), S. i 
    ISSN: 1438-1168
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract  Two natural clinopyroxene single crystals were investigated, an aegirine-augite (AEG) and a magnesian hedenbergite (HED). Both samples were carefully characterized by electron microprobe, X-ray diffraction, and Mössbauer spectroscopy. Magnetic susceptibility measurements of powdered samples reveal low temperature antiferromagnetic coupling and Curie-Weiss behaviour with T N =7.5(5) K, Θ P =−19(1) K for AEG, and T N =31(1) K, Θ P =+21(1) K for HED, respectively. Low temperature Mössbauer spectra exhibit relaxation phenomena. Magnetic susceptibility measurements of the single crystals show the direction of the magnetic moments to be lying within the a/c plane for both samples: 50(±2)° from a and 57(±2)° from c in AEG, and 45(±2)° from a and 60(±2)° from c in HED, respectively. The antiferromagnetic interchain interaction competes with the ferromagnetic intrachain interaction in both pyroxenes. In the magnesian hedenbergite a field induced magnetic transition is found. Its dependence on temperature, magnetic field and crystallographic direction is investigated and described.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 25 (1998), S. 522-533 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract  The electrical conduction in the mineral ilvaite was studied between ≈170 and 450 K. A natural ilvaite from Elba (Italy) was found to be semiconducting with a DC conductivity 1.8×10–3 (Ωcm)–1 at 300 K, measured parallel (∥) to the [001] direction; perpendicular (⊥) to [001] it was 1.4×10–5 (Ωcm)–1, i.e. the conductivity is highly anisotropic. The conduction is effected by a hopping charge transport between localized levels in the energy gap associated with activation energies E A =0.3–0.5 eV. It is concluded that impurities (Mg,Al,Mn) may play a decisive role in the charge hopping transport ∥ [001] that is basically governed by Fe2+-Fe3+ pairs on A-sites of the lattice as the source of electrons. Although the EA-values were similar for both measured directions, the sign of thermopower is different which points to different charge transfer mechanisms. The bulk DC conductivity σDC AC for measurements ∥ [001], obtained by extrapolation of AC data using impedance spectroscopy, could only be determined at T〈300 K owing to sample–electrode interfacial effects. In contrast, the bulk σDC AC⊥ [001] showed a slight break at ≈380 K that may reflect the structural phase transition monoclinic→orthorhombic at ≈345 K. From AC conductivity measurements in the frequency range 20 Hz–1 MHz at T〈300 K, a dispersive character of electronic relaxation was found, resembling that of amorphous semiconductors and of impurity conduction in crystalline semiconductors where it was ascribed to charge hopping processes of electrons between localized levels of cation pairs or clusters of limited lengths.
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  • 4
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract Micas of the composition K(Fe3−x Mg x )AlSi3 O10(OH)2 (x=0.6, 1.2, 1.8, 2.4 and 3.0, corresponding to ann80phl20, ann60phl40, ann40phl60, ann20phl80 and ann0phl100) were synthesized hydrothermally under controlled oxygen fugacity conditions. Lattice parameters a 0 and b 0 show a distinct linear decrease with increasing Mg content. With increasing ferric iron content a deviation from this linear trend is observed especially within iron rich samples. The tetrahedral rotation angle α increases smoothly from 0° in annite to 9.1° in phlogopite. Mössbauer spectra show Fe2+ and Fe3+ on the octahedral M1 and M2 sites and partially also Fe3+ on the tetrahedral site. There is a smooth increase of the quadrupole splitting on both the M1 and the M2 site going from annite to phlogopite, probably due to changes in the lattice contribution to the electric field gradient, assuming a positive correlation between quadrupole splitting and distortion. Fe3+ contents, as determined by Mössbauer spectroscopy, versus oxygen fugacity shows that, depending on the composition of the micas, minimum amounts of Fe3+ are present. For ann80phl20 this minimum amount of Fe3+ is about 8% decreasing to about 1–2% Fe3+ for ann20phl80. The molar volume of each solid solution member has been estimated from the determined relations of the molar volume versus % Fe3+ contents, extrapolated back to 0% Fe3+. Plotting these volumes as a function of Xphl shows that negative excess volume occur in the annitephlogopite join, with the maximum deviation from ideality around X phl=0.3. Margules volume parameters have been constrained as: Wv, AnnPhl=0.018±0.016 J/(bar.mol) and Wv, PhlAnn=-0.391±0.025 J(bar.mol) (three site basis).
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 22 (1995), S. 259-267 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract Mössbauer measurements on synthetic iron orthosilicate Fe2SiO4 (fayalite) were carried out in the antiferromagnetic spin state below T N ≃65 K. The Mössbauer parameters isomer shift δ, inner magnetic field H(0), angle Θ between H(0) and the z-component of the electric field gradient (efg), quadrupole splitting QS and asymmetry parameter η were determined as a function of temperature. These parameters could be attributed to the two crystallographic sites M1 and M2. The smaller isomer shift on M1 with respect to M2 displays the more covalent character of the Fe-O bond on M1, which is supported by previous neutron diffraction experiments. H(0) shows a Brillouin-type behaviour with different fields on the two crystallographic sites (stronger on M1) and a small discontinuity at T = 23 K which corresponds with previous magnetic measurements. The quadrupole splitting is equal on both sites within error bars, in agreement with previous theoretical results and in contradiction to previous Mössbauer refinements published elsewhere. Single crystal Mössbauer spectroscopy revealed the orientation of the crystallographic c-axis (Pnma) with respect to the axes of the efg. A second parameter set which also holds true for the powder refinement yields the angle between c and H(0) on M1 to be temperature-dependent in quantitative agreement with previous neutron diffraction results and solves an old discrepancy discussed elsewhere. On M2, the angle between c and H(0) is found to be much smaller than 90° in contradiction to symmetry requirements.
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  • 6
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract The present work reports Mössbauer investigations for several temperatures below T N on fayalite single crystal sections cut perpendicularly to the crystallographic a and b-axis (Pnma). The previously detected correspondence between the c-component of the magnetic moment on M1 from neutron diffraction and our own Mössbauer measurements published elsewhere are confirmed for the other principal sections to a large extent. Small humps in the angular dependence of two components of the internal magnetic field H(0) on T below T=23 K are in good agreement with magnetometric and calorimetric data published elsewhere; a reinterpretation of single reflection neutron data has been possible by our results. Moreover, the axes of the electric field gradient (efg) are oriented within the crystallographic axes for the M1-site at low temperatures. The violation of symmetry on the M2 position as a result of our previous investigations could be confirmed for the section ⊥ a, but not with respect to b. A possible explanation in terms of saturation effects of large line intensities at the expense of the small ones is given in the context.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 23 (1996), S. 276-283 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract Many independent investigations have shown, that the ligand field stabilization energy LFSE has, in addition to other factors such as ionic size, site distortion, covalency, respectively, an important influence on the distribution of transition elements between different coexisting minerals as well as between different, crystallographic sites within the same mineral. A transition element prefers or is enriched in that mineral or that lattice position within a mineral, in which its LFSE has its maximum value. Principally, the LFSE of transition metal ions can be evaluated from the absorption spectra in the visible and near infrared parts of the electromagnetic spectrum. In the present paper, the influence of the LFSE on the polyhedral distortion, the phase stability, the intra-as well as the intercrystalline cation distribution of transition metal ions in some well established examples is presented and discussed. The Gibbs free energies of the exchange reactions can be evaluated from the site occupancies and used as a measure for the site preference. Deviations from a pure ionic model are explained on the basis of MO-theory and covalent bonding and other crystal chemical effects.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Hyperfine interactions 113 (1998), S. 219-248 
    ISSN: 1572-9540
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Mössbauer spectra of fayalite-, 7#x03B1;-Fe2SiO4, powder and single crystals were taken in the antiferromagnetic temperature region below T N≅65 K. The orientation of the efg and H(0) with respect to the crystallographic axes was determined as function of the temperature and compared to neutron diffraction and magnetic susceptibility data. A similar study was performed with Li‐acmite LiFeSi2O6, whose magnetic structure can be regarded as a model compound for quasi one‐dimensional systems. Synthetic annite KFe3[AlSi3O10(OH)2] has to contain at least about 10% Fe3+ in order to be stable. A comparison of the evaluation of the spectra assuming either Lorentzian line shape of the doublets or quadrupole splitting distributions QSDs shows that Fe3+/Fe2+‐ratios can be determined precisely by both methods. However, M2/M1-site distributions cannot be evaluated with great accuracy. In ilvaite CaFe3[Si2O7/O/(OH)], there is a thermally activated intersite electron hopping between Fe2+ and Fe3+ at temperatures around 300 K in a double octahedron chain. At temperatures above 395 K there is extended electron delocalization in a narrow d‐ or polaron‐band. The substitution of Fe by Mn favours both effects and lowers the temperature of the crystallographic phase transition monoclinic to orthorhombic distinctly. In the solid solution series member acmite(50%)‐hedenbergite(50%) Na0.5Ca0.5Fe2[Si2O6] just intersite electron hopping between Fe2+ and Fe3+ in the M1 octahedron chain and no formation of polaron bands is observed. This is explained by the larger Fe–Fe‐intrachain distances compared to those in ilvaite or magnetite.
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  • 9
    Publication Date: 1998-01-01
    Description: Mössbauer experiments on a Li-acmite single crystal section with the crystallographic
    Print ISSN: 2194-4946
    Electronic ISSN: 2196-7105
    Topics: Geosciences , Physics
    Published by De Gruyter
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  • 10
    Publication Date: 1996-08-08
    Print ISSN: 0108-7673
    Electronic ISSN: 2053-2733
    Topics: Chemistry and Pharmacology , Geosciences , Physics
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