Synchrotron infrared reflectivity measurements of iron at high pressures.

The infrared reflectance of iron was studied using high-pressure synchrotron radiation methods up to 50 GPa at room temperature in a diamond anvil cell of 1000-8000 cm(-1) (1.25-10 microm). The magnitude of the reflectivity shows a weak pressure dependence up to the transition from the body centered cubic (alpha) to hexagonal close packed (epsilon) phase transition, where a discontinuous change in both the slope and magnitude of the reflectivity was observed. Reflectance spectra were corrected for diamond absorption and treated with a Kramers-Kronig analysis to extract the optical constants; the emissivity of iron was derived from Kirchoff's law. The pressure and wavelength dependence of the emissivity is characterized by an empirical function for 1.5-1.9 microm; this wavelength range is useful for spectroradiometric temperature measurements from 1000 K up to approximately 2500 K. Alpha-Fe is a nonideal emitter; however, epsilon-Fe behaves as an almost perfect greybody in the infrared up to the highest pressures of the measurements. Temperature measurements based on the spectroradiometry of iron samples should take into account the wavelength dependent emissivity below the alpha-epsilon phase transition at approximately 13 GPa.

Iron-rich silicates in the Earth's D'' layer.

High-pressure experiments and theoretical calculations demonstrate that an iron-rich ferromagnesian silicate phase can be synthesized at the pressure-temperature conditions near the core-mantle boundary. The iron-rich phase is up to 20% denser than any known silicate at the core-mantle boundary. The high mean atomic number of the silicate greatly reduces the seismic velocity and provides an explanation to the low-velocity and ultra-low-velocity zones. Formation of this previously undescribed phase from reaction between the silicate mantle and the iron core may be responsible for the unusual geophysical and geochemical signatures observed at the base of the lower mantle.

Ferromagnesian postperovskite silicates in the D'' layer of the Earth.

Natural olivine with 12 mol % Fe(2)SiO(4) and synthetic orthopyroxenes with 20% and 40% FeSiO(3) were studied beyond the pressure-temperature conditions of the core-mantle boundary. All samples were found to convert entirely or partially into the CaIrO(3) postperovskite structure, which was recently reported for pure MgSiO(3). The incorporation of Fe greatly reduces the pressure needed for the transition and establishes the new phase as the major component of the D'' layer. With the liquid core as an unlimited reservoir of iron, core-mantle reactions could further enrich the iron content in this phase and explain the intriguing seismic signatures observed in the D'' layer.

Bonding changes in compressed superhard graphite.

Compressed under ambient temperature, graphite undergoes a transition at approximately 17 gigapascals. The near K-edge spectroscopy of carbon using synchrotron x-ray inelastic scattering reveals that half of the pi-bonds between graphite layers convert to sigma-bonds, whereas the other half remain as pi-bonds in the high-pressure form. The x-ray diffraction pattern of the high-pressure form is consistent with a distorted graphite structure in which bridging carbon atoms between graphite layers pair and form sigma-bonds, whereas the nonbridging carbon atoms remain unpaired with pi-bonds. The high-pressure form is superhard, capable of indenting cubic-diamond single crystals.

Stability of magnesiowustite in Earth's lower mantle.

Magnesiowüstite [(Mg,Fe)O] is the second most abundant mineral of Earth's lower mantle. Understanding its stability under lower mantle conditions is crucial for interpreting the physical and chemical properties of the whole Earth. Previous studies in an externally heated diamond anvil cell suggested that magnesiowüstites decompose into two components, Fe-rich and Mg-rich magnesiowüstites at 86 GPa and 1,000 K. Here we report an in situ study of two magnesiowüstites [(Mg(0.39),Fe(0.61))O and (Mg(0.25),Fe(0.75))O] at pressures and temperatures that overlap with mantle conditions, using a laser-heated diamond anvil cell combined with synchrotron x-ray diffraction. Our results show that addition of Mg in wüstite (FeO) can stabilize the rock-salt structure to much higher pressures and temperatures. In contrast to the previous studies, our results indicate that Mg-rich magnesiowüstite is stable in the rock-salt structure in the lower mantle. The physical and chemical properties of magnesiowüstite should change gradually and continuously in the lower mantle, suggesting that it does not make a significant contribution to seismic-wave heterogeneity of the lower mantle. Stable Mg-rich magnesiowüstite in lowermost mantle can destabilize FeO in the core-mantle boundary region and remove FeO from the outer core.

Iron-silicon alloy in Earth's core?

We have investigated the phase relations in the iron-rich portion of the iron-silicon (Fe-Si) alloys at high pressures and temperatures. Our study indicates that Si alloyed with Fe can stabilize the body-centered cubic (bcc) phase up to at least 84 gigapascals (compared to approximately 10 gigapascals for pure Fe) and 2400 kelvin. Earth's inner core may be composed of hexagonal close-packed (hcp) Fe with up to 4 weight percent Si, but it is also conceivable that the inner core could be a mixture of a Si-rich bcc phase and a Si-poor hcp phase.

Experimental and Theoretical Studies of ScS under Pressure.

The compressibilities of ScS and a series of Sc(1)(-)(x)()S metal defect structures (x > 0) were studied using a diamond anvil cell and synchrotron radiation at pressures up to 73 GPa. The results show that the bulk modulus increases with x, in contrast to the usual view that a less dense material is more easily compressed. The results are in qualitative agreement with existing band structure calculations designed to probe the mechanism of the ready metal atom loss from ScS at high temperatures. They are also in agreement with new calculations, both of the tight-binding and the first-principles FLAPW type. Numerically the latter show an increase in the bulk modulus of 30% between ScS and Sc(0.875)S and are in exact numerical agreement with the experimental results.