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  • 1
    Publication Date: 2022-10-04
    Description: Elastic properties of B2‐Fe0.67Ni0.06Si0.27 (15 wt.% Si) alloy have been investigated by combined high‐resolution inelastic X‐ray scattering and powder X‐ray diffraction in diamond anvil cells up to 100 GPa at room temperature. Densities (ρ), compressional (VP) and shear (VS) wave velocities were extrapolated to inner core conditions to enable comparison with the preliminary reference Earth model. The modeled aggregate compressional and shear wave velocities and densities of the two‐phase mixture of B2‐Fe0.67Ni0.06Si0.27 and hcp‐Fe‐Ni are consistent with inner core PREM values of VP, VS, and ρ based on a linear mixing model with 30(5) vol % B2‐Fe0.67Ni0.06Si0.27 and 70(5) vol % hcp Fe‐Ni, which corresponds to ∼3–5 wt.% Si and ∼5–12 wt.% Ni.
    Description: Plain Language Summary: The composition of the inner core holds key information about how Earth evolved and how current processes such as the geomagnetic field work. Because the core cannot be directly sampled, our best estimates of its composition are based on the comparison of geophysical data with laboratory measurements of candidate materials. Decades of study have shown the inner core to be composed mainly of iron (with a minor amount of nickel) alloyed with one or more light elements, such as silicon. However, the effect of Si on the geophysical properties of Fe‐Ni alloys is not well established. In this study, we performed laboratory experiments to determine the density and sound velocity of Fe‐Ni‐Si alloy under extreme pressure conditions. We compared our results with seismological determinations and found that Earth's inner core can be accounted for by a mechanical mixture of cubic Fe‐Ni‐Si and hexagonal Fe‐Ni alloys. This mixture has a bulk composition of ∼3–5 weight % Si and ∼5–12 weight % Ni and is consistent with geophysical constraints.
    Description: Key Points: Sound velocities and densities of B2‐Fe‐Ni‐Si alloy are determined at high pressure, up to 100 GPa, using inelastic X‐ray scattering and X‐ray diffraction. Seismologically observed compressional and shear wave velocities and density of Earth's inner core can be accounted for by a two‐phase mixture of 30 vol % B2‐Fe‐Ni‐Si and 70 vol % hcp Fe‐Ni alloys. Extrapolated results at inner core boundary conditions are consistent with an inner core composition containing ∼3–5 wt.% Si and ∼5–12 wt.% Ni.
    Description: Japan Society for the Promotion of Science http://dx.doi.org/10.13039/501100001691
    Description: Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659
    Description: JSPS Japanese‐German graduate externship
    Description: https://doi.org/10.6084/m9.figshare.13370795.v1
    Description: https://doi.org/10.6084/m9.figshare.13370792.v1
    Keywords: ddc:551.112
    Language: English
    Type: doc-type:article
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 24 (1997), S. 569-573 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract  57Fe Mössbauer studies at room temperature and temperature-dependent resistance studies have been performed on a natural specimen of cubanite (CuFe2S3) in a diamond-anvil cell at pressures up to ∼10 GPa. An insulator-metal phase transition occurs in the range 3.4–5.8 GPa coinciding with a previously observed structural transition from an orthorhombic to a hexagonal NiAs (B8) structure. The room temperature data shows that the metallization process concurs with a gradual transition from a magnetically ordered phase at low pressure to a nonmagnetic or paramagnetic phase at high-pressure. The change in magnetic behaviour at the structural transition may be attributed to a reduction of the Fe-S-Fe superexchange angle formed by edge-sharing octahedra occurring in the high-pressure phase. The non-magnetic or paramagnetic metallic phase at high pressure is retained upon decompression to ambient pressure-temperature conditions, indicative of substantial hysteresis associated with the pressure driven orthorhombic→hexagonal structural transition. The pressure evolution of both the 57Fe Mössbauer hyperfine interaction parameters and resistance behaviour is consistent with the transition from mixed-valence character in the low pressure orthorhombic structure to that of extended-electron delocalization in the hexagonal phase at high-pressure.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract To study the crystal chemistry of bernalite, Fe(OH)3, and the nature of the octahedral Fe3+ environment, Mössbauer spectra were recorded from 80 to 350 K, optical spectra were recorded at room temperature and a sample was studied using transmission electron microscopy. The Mössbauer spectrum of bernalite consists of a single six-line magnetic spectrum at 80 K. A broadened six-line magnetic spectrum with significantly less intensity is observed at higher temperatures, and is attributed to a small fraction of bernalite occurring as small particles. The variation of hyperfine magnetic field data for bulk bernalite with temperature is well described by the Weiss molecular field model with parameters of H 0 = 55.7±0.3 T and T N = 427±5K. The centre shift data were fitted to the Debye model with parameters δ0=0.482±0.005 mm/s (relative to α-Fe) and ΘM=492±30 K. The quadrupole shift is near zero at 300 K, and does not vary significantly with temperature. Absorption spectra in the visible and near infrared range show three crystal field bands of Fe3+ at 11 300, 16000 and 23 200 cm-1, giving a crystal field splitting of 14 570 cm-1 and Racah parameters of B=629 cm-1 and C=3381 cm-1. Infrared reflection spectra show two distinct OH-stretching frequencies, which could correspond to two structurally different types of OH groups. A band was also observed at 2250 cm-1, suggesting the presence of molecular CO2 in the large cation site. Analytical transmission electron microscopy indicates that Si occurs within the bernalite structure as well as along domain boundaries. Electron diffraction and imaging show that bernalite is polysynthetically twinned along {100} planes with twin domains ranging from 3 to 20 nm in thickness. Results are discussed with respect to the nature of the octahedral Fe3+ site, and compared with values for other iron oxides and hydroxides.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1432-2021
    Keywords: Key words Single crystal ; Mössbauer milliprobe ; Hedenbergite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract We report Mössbauer milliprobe measurements on small single-crystals of a magnesium-rich hedenbergite, approximate composition CaFe0.54Mg0.46 (SiO3)2, in which each of the electric-field gradient and mean-squared displacement tensors for Fe2+ in the M1 site of the crystal are precisely determined. Each tensor has in common, as required of crystal symmetry, the twofold axis of the monoclinic unit cell, but the principal directions of the two tensors in the perpendicular plane are non-coincident. The mean-squared displacements determined in the Mössbauer experiment exceed those determined from the X-ray vibration ellipsoids for Fe2+/M1 by a factor of 1.6; the anisotropy in the mean-squared displacement tensor from the Mössbauer measurements exceeds that from X-ray by a factor of around 5. The ramifications of these differences are discussed.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 10 (1984), S. 106-113 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract An experimental study using piston-cylinder, Bridgman anvil and diamond anvil cell techniques was undertaken to study the effect of pressure on the composition of Fe x O in equilibrium with Fe. At constant temperature the value of x first increases and then decreases with increasing pressure. The rate of change of x is a function of temperature. We have theoretically calculated the variation of the composition of wüstite with pressure and temperature. The initial increase of x with pressure for P〈10 GPa occurs because the partial molar volume of FeO in Fe x O is smaller than the molar volume of Fe, favouring an increase in stoichiometry of Fe x O. To reproduce the experimentally observed decrease in x above 10GPA, the bulk modulus of Fe x O must vary strongly with x for x≳0.96, causing a rapid increase in the partial molar volume of Fe in Fe x O. Continuation of a strong sensitivity of K to x in Fe x O for x≲0.96, however, leads to absurdly low molar volumes of Fe x O at high pressure and no equilibrium between Fe and Fe x O exists. Observations therefore require a reduced sensitivity of K with x for x〈0.96, achieved by a negligible variation of K 0 with x for x〈0.96, or a strong variation of dK/dP with x, or perhaps both.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 11 (1985), S. 250-254 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract The Mössbauer spectra of five samples of Fe x O with compositions in the range 1.00〉x〉0.95 have been recorded at 298 K and 4.2 K. The spectrum of Fe x O at 298 K consists of an asymmetric doublet which was fitted to one Fe2+ singlet, two Fe2+ doublets and 1 Fe3+ singlet. The Mössbauer parameters vary consistently with the increasing density of defects as x decreases. The Mössbauer spectrum of Fe x O at 4.2 K consists of a large number of unresolved lines. The data were fitted to a series of singlets to enable the rough calculation of quantities relating to the mean Fe2+ and Fe3+ environments. The results of the fits to the 298 K spectra are briefly discussed in terms of a physical model for the defect structure of Fe x O.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 17 (1991), S. 622-628 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract The success of molecular orbital theory in calculating crystal properties such as bond lengths and atomic force constants has been well documented in the literature. Calculations can be extended to crystals under simulated compression and strain to determine elastic moduli and their pressure derivatives. Comparison of the molecular orbital results with both experimental values and results obtained by calculations such as the potential induced breathing model provides insight into the nature of chemical bonding in MgO. In this study, several molecular clusters were investigated as possible models for MgO; the cluster Mg4O4H24 was chosen as the best model. Molecular energies were calculated with respect to bond length for both compression and expansion based on clusters that had been optimized for minimum energy. The resulting energy-volume curve was fitted to a recently derived equation of state (Brown, in preparation) to derive the values of K 0 and dK0/dP and the individual elastic moduli and their pressure derivatives were calculated by applying strain to the molecular cluster at both zero and elevated pressures. Agreement between theory and experiment varies between parameters, but the overall trend is encouraging. Since the molecular orbital model includes only short range interactions, its ability to approximating model the elastic moduli of MgO suggests a strong contribution to the elastic energy from short range interactions.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1432-0967
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract (Mg,Fe)(Si,Al)O3 perovskite samples with varying Fe and Al concentration were synthesised at high pressure and temperature at varying conditions of oxygen fugacity using a multianvil press, and were characterised using ex situ X-ray diffraction, electron microprobe, Mössbauer spectroscopy and analytical transmission electron microscopy. The Fe3+/ΣFe ratio was determined from Mössbauer spectra recorded at 293 and 80 K, and shows a nearly linear dependence of Fe3+/ΣFe with Al composition of (Mg,Fe)(Si,Al)O3 perovskite. The Fe3+/ΣFe values were obtained for selected samples of (Mg,Fe)(Si,Al)O3 perovskite using electron energy-loss near-edge structure (ELNES) spectroscopy, and are in excellent agreement with Mössbauer data, demonstrating that Fe3+/ΣFe can be determined with a spatial resolution on the order of nm. Oxygen concentrations were determined by combining bulk chemical data with Fe3+/ΣFe data determined by Mössbauer spectroscopy, and show a significant concentration of oxygen vacancies in (Mg,Fe)(Si,Al)O3 perovskite.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 1432-0967
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract The Mössbauer milliprobe allows the determination of Fe3+/ΣFe in samples as small as 50 μm. For the first time this technique is applied to a suite of diamonds of eclogitic paragenesis, where three garnet and five clinopyroxene inclusions in diamonds from George Creek, Colorado have been analysed. For garnet Fe3+/ΣFe ranges from 0–7%, while values for clinopyroxene range from 8–14%. These results are consistent with the low oxygen fugacity conditions implied by the presence of the inclusions in diamond.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract (Fe, Mn)S and (Fe, Mg)S solid solutions are examined to study and compare the properties of Fe2+ in two different B1-structured hosts, and also to study the relative stability of the B1 (NaCl) and B8 (NiAs) structures at high pressure. The Mössbauer spectra of (Fe, Mn)S and (Fe, Mg)S B1 solid solutions are quadrupole doublets at 298 K with parameters which vary smoothly with Fe2+ concentration. At 4.2 K the Mössbauer spectra of (Fe, Mn)S and Fe-rich (Fe, Mg)S B1 solid solutions are magnetically split into eight lines, but the spectra of Mg-rich (Fe, Mg)S solid solutions are quadrupole doublets. The line widths of the magnetic spectra are broad, consistent with a multiaxial spin arrangement. Some properties of the hypothetical phase FeS(B1) are calculated from the solid solution data; the phase is inferred to be relatively ionic compared to FeS(B8) and has a molar volume that is 7.2 percent larger than the B8 phase at 298 K. The large inferred volume difference between FeS(B1) and FeS(B8) should cause exsolution of a B8-structured phase from (Fe, Mn)S and (Fe, Mg)S B1 solid solutions at high pressure. This behaviour is confirmed experimentally at high pressure using X-ray diffraction and Mössbauer spectroscopy, and the results are correlated with thermodynamic calculations of the phase boundaries based on estimates of the volume and free energy differences between the B1 and B8 phases of FeS derived from atmospheric pressure data. The absence of an increase in solubility of Mg and Mn in the B8 phase with pressure suggests that any polymorphism in MnS and MgS at high pressure is unlikely to involve the B8 phase. Shock wave data for MgO and Fe0.94O reported in the literature suggest similar behaviour in the system FeO-MgO at high pressure, namely exsolution of essentially pure FeO(hpp) from (Fe, Mg)O B1 solid solutions.
    Type of Medium: Electronic Resource
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