Thermal equation of state and stability of (Mg_(0.06)Fe_(0.94))O

We present the pressure-volume-temperature (P-V-T) equation of state of polycrystalline (Mg_(0.06)Fe_(0.94))O (Mw94) determined from laser-heated x-ray diffraction experiments up to 122 GPa and 2100 K, conditions approaching those of the deep mantle. We conducted two sets of experiments, one with an in situ Fe metal oxygen fugacity buffer and one without such a buffer. The internal pressure markers used in these experiments were B2-NaCl and hcp-Fe in the buffered experiment and B2-NaCl in the unbuffered experiment. In the sampled P-T range of the high temperature part of this study, only the B1 structure of Mw94 was observed, indicating that the addition of Mg to FeO stabilizes the B1 phase with respect to the B8 phase at these conditions. Both datasets were fit to a Birch-Murnaghan and Mie-Grüneisen-Debye thermal equation of state using a new open-source fitting routine, also presented here. Analysis of these data sets using the same internal pressure marker shows that the P–V–T data of Mw94 obtained in the unbuffered experiment are well explained by the equation of state parameters determined from the buffered data set. We have also compared the thermal equation of state of Mw94 with that of wüstite and conclude that Mw94 has measurably distinct thermoelastic properties compared with those of wüstite. We use the results obtained in the buffered experiment to determine the density and bulk sound velocity of Mw94 at the base of the mantle and compare these values to geophysical observations of ultralow-velocity zones

Isothermal compression behavior of (Mg,Fe)O using neon as a pressure medium

We present isothermal volume compression behavior of two polycrystalline (Mg,Fe)O samples with FeO = 39 and 78 mol% up to ~90 GPa at 300 K using synchrotron X-ray diffraction and neon as a pressure-transmitting medium. For the iron-rich (Mg_(0.22)Fe_(0.78))O sample, a structural transition from the B1 structure to a rhombohedral structure was observed at 41.6 GPa, with no further indication of changes in structural or compression behavior changes up to 93 GPa. In contrast, a change in the compression behavior of (Mg_(0.61)Fe_(0.39))O was observed during compression at P ≥ 71 GPa and is indicative of a spin crossover occurring in the Fe^(2+) component of (Mg_(0.61)Fe_(0.39))O. The low-spin state exhibited a volume collapse of ~3.5%, which is a larger value than what was observed for a similar composition in a laser-heated NaCl medium. Upon decompression, the volume of the high-spin state was recovered at approximately 65 GPa. We therefore bracket the spin crossover at 65 ≤ P (GPa) ≤ 77 at 300 K (Mg_(0.61)Fe_(0.39))O. We observed no deviation from the B1 structure in (Mg_(0.61)Fe_(0.39))O throughout the pressure range investigated

How “Hollow” Are Hollow Nanoparticles?

Diamond anvil cell (DAC), synchrotron X-ray diffraction (XRD), and small-angle X-ray scattering (SAXS) techniques are used to probe the composition inside hollow γ-Fe₃O₄ nanoparticles (NPs). SAXS experiments on 5.2, 13.3, and 13.8 nm hollow-shell γ-Fe₃O₄ NPs, and 6 nm core/14.8 nm hollow-shell Au/Fe₃O₄ NPs, reveal the significantly high (higher than solvent) electron density of the void inside the hollow shell. In high-pressure DAC experiments using Ne as pressure-transmitting medium, formation of nanocrystalline Ne inside hollow NPs is not detected by XRD, indicating that the oxide shell is impenetrable. Also, FTIR analysis on solutions of hollow-shell γ-Fe₃O₄ NPs fragmented upon refluxing shows no evidence of organic molecules from the void inside, excluding the possibility that organic molecules get through the iron oxide shell during synthesis. High-pressure DAC experiments on Au/Fe₃O₄ core/hollow-shell NPs show good transmittance of the external pressure to the gold core, indicating the presence of the pressure-transmitting medium in the gap between the core and the hollow shell. Overall, our data reveal the presence of most likely small fragments of iron and/or iron oxide in the void of the hollow NPs. The iron oxide shell seems to be non-porous and impenetrable by gases and liquids