Ultrafast x-ray detection of low-spin iron in molten silicate under deep planetary interior conditions.

The spin state of Fe can alter the key physical properties of silicate melts, affecting the early differentiation and the dynamic stability of the melts in the deep rocky planets. The low-spin state of Fe can increase the affinity of Fe for the melt over the solid phases and the electrical conductivity of melt at high pressures. However, the spin state of Fe has never been measured in dense silicate melts due to experimental challenges. We report detection of dominantly low-spin Fe in dynamically compressed olivine melt at 150 to 256 gigapascals and 3000 to 6000 kelvin using laser-driven shock wave compression combined with femtosecond x-ray diffraction and x-ray emission spectroscopy using an x-ray free electron laser. The observation of dominantly low-spin Fe supports gravitationally stable melt in the deep mantle and generation of a dynamo from the silicate melt portion of rocky planets.

A MHz X-ray diffraction set-up for dynamic compression experiments in the diamond anvil cell.

An experimental platform for dynamic diamond anvil cell (dDAC) research has been developed at the High Energy Density (HED) Instrument at the European X-ray Free Electron Laser (European XFEL). Advantage was taken of the high repetition rate of the European XFEL (up to 4.5 MHz) to collect pulse-resolved MHz X-ray diffraction data from samples as they are dynamically compressed at intermediate strain rates (≤103 s-1), where up to 352 diffraction images can be collected from a single pulse train. The set-up employs piezo-driven dDACs capable of compressing samples in ≥340 µs, compatible with the maximum length of the pulse train (550 µs). Results from rapid compression experiments on a wide range of sample systems with different X-ray scattering powers are presented. A maximum compression rate of 87 TPa s-1 was observed during the fast compression of Au, while a strain rate of ∼1100 s-1 was achieved during the rapid compression of N2 at 23 TPa s-1.

Stratification in planetary cores by liquid immiscibility in Fe-S-H.

Liquid-liquid immiscibility has been widely observed in iron alloy systems at ambient pressure and is important for the structure and dynamics in iron cores of rocky planets. While such previously known liquid immiscibility has been demonstrated to disappear at relatively low pressures, here we report immiscible S(±Si,O)-rich liquid and H(±C)-rich liquid above ~20 GPa, corresponding to conditions of the Martian core. Mars' cosmochemically estimated core composition is likely in the miscibility gap, and the separation of two immiscible liquids could have driven core convection and stable stratification, which explains the formation and termination of the Martian planetary magnetic field. In addition, we observed liquid immiscibility in Fe-S-H(±Si,O,C) at least to 118 GPa, suggesting that it can occur in the Earth's topmost outer core and form a low-velocity layer below the core-mantle boundary.

Structural and Electronic Transitions in Liquid FeO Under High Pressure.

FeO represents an important end-member for planetary interiors mineralogy. However, its properties in the liquid state under high pressure are poorly constrained. Here, in situ high-pressure and high-temperature X-ray diffraction experiments, ab initio simulations, and thermodynamic calculations are combined to study the local structure and density evolution of liquid FeO under extreme conditions. Our results highlight a strong shortening of the Fe-Fe distance, particularly pronounced between ambient pressure and ∼40 GPa, possibly related with the insulator to metal transition occurring in solid FeO over a similar pressure range. Liquid density is smoothly evolving between 60 and 150 GPa from values calculated for magnetic liquid to those calculated for non-magnetic liquid, compatibly with a continuous spin crossover in liquid FeO. The present findings support the potential decorrelation between insulator/metal transition and the high-spin to low-spin continuous transition, and relate the changes in the microscopic structure with macroscopic properties, such as the closure of the Fe-FeO miscibility gap. Finally, these results are used to construct a parameterized thermal equation of state for liquid FeO providing densities up to pressure and temperature conditions expected at the Earth's core-mantle boundary.

X-ray Free Electron Laser-Induced Synthesis of ε-Iron Nitride at High Pressures.

The ultrafast synthesis of ε-Fe3N1+x in a diamond-anvil cell (DAC) from Fe and N2 under pressure was observed using serial exposures of an X-ray free electron laser (XFEL). When the sample at 5 GPa was irradiated by a pulse train separated by 443 ns, the estimated sample temperature at the delay time was above 1400 K, confirmed by in situ transformation of α- to γ-iron. Ultimately, the Fe and N2 reacted uniformly throughout the beam path to form Fe3N1.33, as deduced from its established equation of state (EOS). We thus demonstrate that the activation energy provided by intense X-ray exposures in an XFEL can be coupled with the source time structure to enable exploration of the time-dependence of reactions under high-pressure conditions.

Melting properties by X-ray absorption spectroscopy: common signatures in binary Fe-C, Fe-O, Fe-S and Fe-Si systems.

X-ray absorption spectroscopy (XAS) is a widely used technique to probe the local environment around specific atomic species. Applied to samples under extreme pressure and temperature conditions, XAS is sensitive to phase transitions, including melting, and allows gathering insights on compositional variations and electronic changes occurring during such transitions. These characteristics can be exploited for studies of prime interest in geophysics and fundamental high-pressure physics. Here, we investigated the melting curve and the eutectic composition of four geophysically relevant iron binary systems: Fe-C, Fe-O, Fe-S and Fe-Si. Our results show that all these systems present the same spectroscopic signatures upon melting, common to those observed for other pure late 3d transition metals. The presented melting criterion seems to be general for late 3d metals bearing systems. Additionally, we demonstrate the suitability of XAS to extract melt compositional information in situ, such as the evolution of the concentration of light elements with increasing temperature. Diagnostics presented in this work can be applied to studies over an even larger pressure range exploiting the upgraded synchrotron machines, and directly transferred to time-resolved extreme condition studies using dynamic compression (ns) or fast laser heating (ms).

In situ X-ray diffraction of silicate liquids and glasses under dynamic and static compression to megabar pressures.

Properties of liquid silicates under high-pressure and high-temperature conditions are critical for modeling the dynamics and solidification mechanisms of the magma ocean in the early Earth, as well as for constraining entrainment of melts in the mantle and in the present-day core-mantle boundary. Here we present in situ structural measurements by X-ray diffraction of selected amorphous silicates compressed statically in diamond anvil cells (up to 157 GPa at room temperature) or dynamically by laser-generated shock compression (up to 130 GPa and 6,000 K along the MgSiO3 glass Hugoniot). The X-ray diffraction patterns of silicate glasses and liquids reveal similar characteristics over a wide pressure and temperature range. Beyond the increase in Si coordination observed at 20 GPa, we find no evidence for major structural changes occurring in the silicate melts studied up to pressures and temperatures exceeding Earth's core mantle boundary conditions. This result is supported by molecular dynamics calculations. Our findings reinforce the widely used assumption that the silicate glasses studies are appropriate structural analogs for understanding the atomic arrangement of silicate liquids at these high pressures.

Equation of State of Liquid Iron under Extreme Conditions.

The density of liquid iron has been determined up to 116 GPa and 4350 K via static compression experiments following an innovative analysis of diffuse scattering from liquid. The longitudinal sound velocity was also obtained to 45 GPa and 2700 K based on inelastic x-ray scattering measurements. Combining these results with previous shock-wave data, we determine a thermal equation of state for liquid iron. It indicates that Earth's outer core exhibits 7.5%-7.6% density deficit, 3.7%-4.4% velocity excess, and an almost identical adiabatic bulk modulus, with respect to liquid iron.

Dynamic fracture of tantalum under extreme tensile stress.

The understanding of fracture phenomena of a material at extremely high strain rates is a key issue for a wide variety of scientific research ranging from applied science and technological developments to fundamental science such as laser-matter interaction and geology. Despite its interest, its study relies on a fine multiscale description, in between the atomic scale and macroscopic processes, so far only achievable by large-scale atomic simulations. Direct ultrafast real-time monitoring of dynamic fracture (spallation) at the atomic lattice scale with picosecond time resolution was beyond the reach of experimental techniques. We show that the coupling between a high-power optical laser pump pulse and a femtosecond x-ray probe pulse generated by an x-ray free electron laser allows detection of the lattice dynamics in a tantalum foil at an ultrahigh strain rate of [Formula: see text] ~2 × 108 to 3.5 × 108 s-1. A maximal density drop of 8 to 10%, associated with the onset of spallation at a spall strength of ~17 GPa, was directly measured using x-ray diffraction. The experimental results of density evolution agree well with large-scale atomistic simulations of shock wave propagation and fracture of the sample. Our experimental technique opens a new pathway to the investigation of ultrahigh strain-rate phenomena in materials at the atomic scale, including high-speed crack dynamics and stress-induced solid-solid phase transitions.

Crystallization of silicon dioxide and compositional evolution of the Earth's core.

The Earth's core is about ten per cent less dense than pure iron (Fe), suggesting that it contains light elements as well as iron. Modelling of core formation at high pressure (around 40-60 gigapascals) and high temperature (about 3,500 kelvin) in a deep magma ocean predicts that both silicon (Si) and oxygen (O) are among the impurities in the liquid outer core. However, only the binary systems Fe-Si and Fe-O have been studied in detail at high pressures, and little is known about the compositional evolution of the Fe-Si-O ternary alloy under core conditions. Here we performed melting experiments on liquid Fe-Si-O alloy at core pressures in a laser-heated diamond-anvil cell. Our results demonstrate that the liquidus field of silicon dioxide (SiO2) is unexpectedly wide at the iron-rich portion of the Fe-Si-O ternary, such that an initial Fe-Si-O core crystallizes SiO2 as it cools. If crystallization proceeds on top of the core, the buoyancy released should have been more than sufficient to power core convection and a dynamo, in spite of high thermal conductivity, from as early on as the Hadean eon. SiO2 saturation also sets limits on silicon and oxygen concentrations in the present-day outer core.

Dynamic X-ray diffraction observation of shocked solid iron up to 170 GPa.

Investigation of the iron phase diagram under high pressure and temperature is crucial for the determination of the composition of the cores of rocky planets and for better understanding the generation of planetary magnetic fields. Here we present X-ray diffraction results from laser-driven shock-compressed single-crystal and polycrystalline iron, indicating the presence of solid hexagonal close-packed iron up to pressure of at least 170 GPa along the principal Hugoniot, corresponding to a temperature of 4,150 K. This is confirmed by the agreement between the pressure obtained from the measurement of the iron volume in the sample and the inferred shock strength from velocimetry deductions. Results presented in this study are of the first importance regarding pure Fe phase diagram probed under dynamic compression and can be applied to study conditions that are relevant to Earth and super-Earth cores.

Toward a mineral physics reference model for the Moon's core.

The physical properties of iron (Fe) at high pressure and high temperature are crucial for understanding the chemical composition, evolution, and dynamics of planetary interiors. Indeed, the inner structures of the telluric planets all share a similar layered nature: a central metallic core composed mostly of iron, surrounded by a silicate mantle, and a thin, chemically differentiated crust. To date, most studies of iron have focused on the hexagonal closed packed (hcp, or ε) phase, as ε-Fe is likely stable across the pressure and temperature conditions of Earth's core. However, at the more moderate pressures characteristic of the cores of smaller planetary bodies, such as the Moon, Mercury, or Mars, iron takes on a face-centered cubic (fcc, or γ) structure. Here we present compressional and shear wave sound velocity and density measurements of γ-Fe at high pressures and high temperatures, which are needed to develop accurate seismic models of planetary interiors. Our results indicate that the seismic velocities proposed for the Moon's inner core by a recent reanalysis of Apollo seismic data are well below those of γ-Fe. Our dataset thus provides strong constraints to seismic models of the lunar core and cores of small telluric planets. This allows us to propose a direct compositional and velocity model for the Moon's core.

Portable multi-anvil device for in situ angle-dispersive synchrotron diffraction measurements at high pressure and temperature.

A recently developed portable multi-anvil device for in situ angle-dispersive synchrotron diffraction studies at pressures up to 25 GPa and temperatures up to 2000 K is described. The system consists of a 450 ton V7 Paris-Edinburgh press combined with a Stony Brook ;T-cup' multi-anvil stage. Technical developments of the various modifications that were made to the initial device in order to adapt the latter to angular-dispersive X-ray diffraction experiments are fully described, followed by a presentation of some results obtained for various systems, which demonstrate the power of this technique and its potential for crystallographic studies. Such a compact large-volume set-up has a total mass of only 100 kg and can be readily used on most synchrotron radiation facilities. In particular, several advantages of this new set-up compared with conventional multi-anvil cells are discussed. Possibilities of extension of the (P,T) accessible domain and adaptation of this device to other in situ measurements are given.

Boron-doped diamond heater and its application to large-volume, high-pressure, and high-temperature experiments.

A temperature of 3500 degrees C was generated using a diamond resistance heater in a large-volume Kawai-type high-pressure apparatus. Re and LaCrO(3) have conventionally been used for heaters in high-pressure studies but they cannot generate temperatures higher than 2900 degrees C and make in situ x-ray observations difficult due to their high x-ray absorption. Using a boron-doped diamond heater overcomes these problems and achieves stable temperature generation for pressure over 10 GPa. The heater starting material is a cold-compressed mixture of graphite with boron used to avoid the manufacturing difficulties due to the extreme hardness of diamond. The diamond heater was synthesized in situ from the boron-graphite mixture at temperature of 1600+/-100 degrees C and pressure of 20 GPa. By using the proposed technique, we have employed the diamond heater for high-temperature generation in a large-volume high-pressure apparatus. Achievement of temperatures above 3000 degrees C allows us to measure the melting points of the important constituents in earth's mantle (MgSiO(3), SiO(2), and Al(2)O(3)) and core (Fe and Ni) at extremely high pressures.