Chrystele Sanloup

Density measurements of liquid Fe‐S alloys at high‐pressure

We present the first static measurements of the density of metallic liquids in the Fe-S system in the pressure and temperature range 1.5 GPa-6.2 GPa and 1500 K - 1780 K. Density is inferred from X-ray absorption experiments carried out with a large volume press at the European Synchrotron Radiation Facility. It is shown that increasing the amount of sulfur in liquid iron decreases the bulk incompressibility by -2.5 GPa per 1 weight% of S. These data are important for constraining the presence and amount of sulfur in the cores of small planetary bodies.

Structural change in molten basalt at deep mantle conditions

Silicate liquids play a key part at all stages of deep Earth evolution, ranging from core and crust formation billions of years ago to present-day volcanic activity. Quantitative models of these processes require knowledge of the structural changes and compression mechanisms that take place in liquid silicates at the high pressures and temperatures in the Earth’s interior. However, obtaining such knowledge has long been impeded by the challenging nature of the experiments. In recent years, structural and density information for silica glass was obtained at record pressures of up to 100 GPa (ref. 1), a major step towards obtaining data on the molten state. Here we report the structure of molten basalt up to 60 GPa by means of in situ X-ray diffraction. The coordination of silicon increases from four under ambient conditions to six at 35 GPa, similar to what has been reported in silica glass. The compressibility of the melt after the completion of the coordination change is lower than at lower pressure, implying that only a high-order equation of state can accurately describe the density evolution of silicate melts over the pressure range of the whole mantle. The transition pressure coincides with a marked change in the pressure-evolution of nickel partitioning between molten iron and molten silicates, indicating that melt compressibility controls siderophile-element partitioning.

OsN2: Crystal structure and electronic properties

Osmium nitride belongs to a family of nitrides synthesized recently at high pressures from their parent elements. Here we show, based on first-principles calculations, that the crystal structure of osmium nitride is isostructural to marcasite. Excellent agreement is obtained between the authors’ results and x-ray, Raman, and compressibility measurements. In the OsN2 marcasite structure single-bonded N2 units occupy the interstitial sites of the Os close-packed lattice, giving rise to a metallic compound. A comparison between the formation energies of OsN2 and PtN2 explains the similar thermodynamic conditions of formation reported experimentally for the two compounds.

Retention of xenon in quartz and Earth's missing xenon

The reactivity of xenon with terrestrial oxides was investigated by in situ synchrotron x-ray diffraction. At high temperature (T > 500 kelvin), some silicon was reduced, and the pressure stability of quartz was expanded, attesting to the substitution of some xenon for silicon. When the quartz was quenched, xenon diffused out and only a few weight percent remained trapped in samples. These results show that xenon can be covalently bonded to oxygen in quartz in the lower continental crust, providing an answer to the missing xenon problem; synthesis paths of rare gas compounds are also opened.

High P-T transformations of nitrogen to 170 GPa.

X-ray diffraction and optical spectroscopy techniques are used to characterize stable and metastable transformations of nitrogen compressed up to 170 GPa and heated above 2500 K. X-ray diffraction data show that varepsilon-N2 undergoes two successive structural changes to complex molecular phases zeta at 62 GPa and a newly discovered kappa at 110 GPa. The latter becomes an amorphous narrow gap semiconductor on further compression and if subjected to very high temperatures (approximately 2000 K) crystallizes to the crystalline cubic-gauche-N structure (cg-N) above 150 GPa. The diffraction data show that the transition to cg-N is accompanied by 15% volume reduction.

HIGH-PRESSURE TRANSFORMATIONS IN XENON HYDRATES

A high-pressure investigation of the Xe⋅H2O chemical system was conducted by using diamond-anvil cell techniques combined with in situ Raman spectroscopy, synchrotron x-ray diffraction, and laser heating. Structure I xenon clathrate was observed to be stable up to 1.8 GPa, at which pressure it transforms to a new Xe clathrate phase stable up to 2.5 GPa before breaking down to ice VII plus solid xenon. The bulk modulus and structure of both phases were determined: 9 ± 1 GPa for Xe clathrate A with structure I (cubic, a = 11.595 ± 0.003 Å, V = 1,558.9 ± 1.2 Å3 at 1.1 GPa) and 45 ± 5 GPa for Xe clathrate B (tetragonal, a = 8.320 ± 0.004 Å, c = 10.287 ± 0.007 Å, V = 712.1 ± 1.2 Å3 at 2.2 GPa). The extended pressure stability field of Xe clathrate structure I (A) and the discovery of a second Xe clathrate (B) above 1.8 GPa have implications for xenon in terrestrial and planetary interiors.

Dissociative melting of ice VII at high pressure.

We have used x-ray diffraction to determine the structure factor of water along its melting line to a static pressure of 57 GPa (570 kbar) and a temperature of more than 1500 K, conditions which correspond to the lower mantle of the Earth, and the interiors of Neptune and Uranus up to a depth of 7000 km. We have also performed corresponding first principles and classical molecular dynamics simulations. Above a pressure of 4 GPa the O-O structure factor is found to be very close to that of a simple soft sphere liquid, thus permitting us to determine the density of liquid water near the melting line. By comparing these results with the density of ice, also determined in this study, we find that the enthalpy of fusion (DeltaH(f)) increases enormously along the melting line, reaching approximately 120 kJ/mole at 40 GPa (compared to 6 kJ/mole at 0 GPa), thus revealing significant molecular dissociation of water upon melting. We speculate that an extended two-phase region could occur in planetary processes involving the adiabatic compression of water.

Development of chemical and topological structure in aluminosilicate liquids and glasses at high pressure.

The high pressure structure of liquid and glassy anorthite (CaAl(2)Si(2)O(8)) and calcium aluminate (CaAl(2)O(4)) glass was measured by using in situ synchrotron x-ray diffraction in a diamond anvil cell up to 32.4(2) GPa. The results, combined with ab initio molecular dynamics and classical molecular dynamics simulations using a polarizable ion model, reveal a continuous increase in Al coordination by oxygen, with 5-fold coordinated Al dominating at 15 GPa and a preponderance of 6-fold coordinated Al at higher pressures. The development of a peak in the measured total structure factors at 3.1 Å(-1) is interpreted as a signature of changes in topological order. During compression, cation-centred polyhedra develop edge- and face- sharing networks. Above 10 GPa, following the pressure-induced breakdown of the network structure, the anions adopt a structure similar to a random close packing of hard spheres.

On the ϵ-ζ transition of nitrogen

Group theory analysis and synchrotron x-ray diffraction measurements show that the recently proposed crystal structure of ζ-nitrogen is inconsistent with the available experimental data for that phase.

Viscosity of mafic magmas at high pressures: VISCOSITY OF MAGMAS AT HIGH PRESSURES

While it is accepted that silica-rich melts behave anomalously with a decrease of their viscosity at increased pressures (P), the viscosity of silica-poor melts is much less constrained. However, modeling of mantle melts dynamics throughout Earths history, including the magma ocean era, requires precise knowledge of the viscous properties of silica-poor magmas. We extend here our previous measurements on fayalite melt to natural end-members pyroxenite melts (MgSiO 3 and CaSiO 3) using in situ X-ray radiography up to 8 GPa. For all compositions, viscosity decreases with P, rapidly below 5 GPa and slowly above. The magnitude of the viscosity decrease is larger for pyroxene melts than for fayalite melt and larger for the Ca end-member within pyroxene melts. The anomalous viscosity decrease appears to be a universal behavior for magmas up to 13 GPa, while the P dependence of viscosity beyond this remains to be measured. These results imply that mantle melts are very pervasive at depth.