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1.
Angew Chem Int Ed Engl ; 54(50): 15109-12, 2015 Dec 07.
Article in English | MEDLINE | ID: mdl-26509919

ABSTRACT

Alloy and nitride solid solutions are prominent for structural, energy and information processing applications. There are frequently however barriers to making them. We remove barriers to reactivity here using pressure with a new synthetic approach. We target pressures where the reasons for cubic endmember nitride instability can become the driving force for cubic nitride solid solution stability. Using this approach we form a novel rocksalt Mg0.4 Fe0.6 N solid solution at between 15 and 23 GPa and up to 2500 K. This is a system where, neither an alloy nor a nitride solid solution form at ambient conditions and bulk MgN and FeN endmembers do not form, either at ambient or at high pressure. The new nitride is formed, by removing endmember lattice mismatch with pressure, allowing a stabilizing redistribution of valence electrons upon heating. This approach can be employed for a range of normally unreactive systems. Mg, Fe and enhanced nitrogen presence, may also indicate a richer reaction chemistry in our planets interior.

2.
Inorg Chem ; 53(11): 5656-62, 2014 Jun 02.
Article in English | MEDLINE | ID: mdl-24824209

ABSTRACT

High-pressure and -temperature experiments on Ge and Si mixtures to 17 GPa and 1500 K allow us to obtain extended Ge-Si solid solutions with cubic (Ia3) and tetragonal (P4(3)2(1)2) crystal symmetries at ambient pressure. The cubic modification can be obtained with up to 77 atom % Ge and the tetragonal modification for Ge concentrations above that. Together with Hume-Rothery criteria, melting point convergence is employed here as a favored attribute for solid solution formation. These compositionally tunable alloys are of growing interest for advanced transport and optoelectronic applications. Furthermore, the work illustrates the significance of employing precession electron diffraction for mapping new materials landscapes resulting from tailored high-pressure and -temperature syntheses.

3.
Science ; 324(5924): 224-6, 2009 Apr 10.
Article in English | MEDLINE | ID: mdl-19359580

ABSTRACT

Seismic shear anisotropy in the lowermost mantle most likely results from elastic shear anisotropy and lattice preferred orientation of its constituent minerals, including perovskite, post-perovskite, and ferropericlase. Measurements of the elastic shear anisotropy of single-crystal (Mg0.9Fe0.1)O up to 69 gigapascals (GPa) show that it increased considerably across the pressure-induced spin transition of iron between 40 and 60 GPa. Increasing iron content further enhances the anisotropy. This leads to at least 50% stronger elastic shear anisotropy of (Mg,Fe)O in the lowermost mantle compared to MgO, which is typically used in geodynamic modeling. Our results imply that ferropericlase is the dominant cause of seismic shear anisotropy in the lower mantle.

4.
Phys Rev Lett ; 93(21): 215502, 2004 Nov 19.
Article in English | MEDLINE | ID: mdl-15601026

ABSTRACT

The complete elastic tensor of Fe0.94O (wüstite) has been determined to 10 GPa using acoustic interferometry at GHz frequencies inside a diamond-anvil cell. The soft mode (C44) elastic constant of FeO is reduced by 20% over the experimental pressure range. An unusual discontinuity in the pressure derivatives of C11 and C12 at 4.7+/-0.2 GPa corresponds to the pressure at which the onset of a magnetic ordering transition is observed by high-pressure Mössbauer spectroscopy and neutron powder diffraction. Our new results combined with literature structural high P-T data suggest that there is a magnetic, although still cubic, phase of FeO between approximately 5 and approximately 17 GPa.

5.
Proc Natl Acad Sci U S A ; 101(16): 5867-71, 2004 Apr 20.
Article in English | MEDLINE | ID: mdl-15079080

ABSTRACT

The emerging picture of Earth's deep interior from seismic tomography indicates more complexity than previously thought. The presence of lateral anisotropy and heterogeneity in Earth's mantle highlights the need for fully anisotropic elasticity data from mineral physics. A breakthrough in high-frequency (gigahertz) ultrasound has resulted in transmission of pure-mode elastic shear waves into a high-pressure diamond-anvil cell using a P-to-S elastic-wave conversion. The full elastic tensor (c(ij)) of high-pressure minerals or metals can be measured at extreme conditions without optical constraints. Here we report the effects of pressure and composition on shear-wave velocities in the major lower-mantle oxide, magnesiowüstite-(Mg,Fe)O. Magnesiowüstite containing more than approximately 50% iron exhibits pressure-induced c(44) shear-mode softening, indicating an instability in the rocksalt structure. The oxide closer to expected lower-mantle compositions ( approximately 20% iron) shows increasing shear velocities more similar to MgO, indicating that it also should have a wide pressure-stability field. A complete sign reversal in the c(44) pressure derivative points to a change in the topology of the (Mg,Fe)O phase diagram at approximately 50-60% iron. The relative stability of Mg-rich (Mg,Fe)O and the strong compositional dependence of shear-wave velocities (and partial differential c(44)/ partial differential P) in (Mg,Fe)O implies that seismic heterogeneity in Earth's lower mantle may result from compositional variations rather than phase changes in (Mg,Fe)O.

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