Ultrahard bulk amorphous carbon from collapsed fullerene.

Amorphous materials inherit short- and medium-range order from the corresponding crystal and thus preserve some of its properties while still exhibiting novel properties1,2. Due to its important applications in technology, amorphous carbon with sp2 or mixed sp2-sp3 hybridization has been explored and prepared3,4, but synthesis of bulk amorphous carbon with sp3 concentration close to 100% remains a challenge. Such materials inherit the short-/medium-range order of diamond and should also inherit its superior properties5. Here, we successfully synthesized millimetre-sized samples-with volumes 103-104 times as large as produced in earlier studies-of transparent, nearly pure sp3 amorphous carbon by heating fullerenes at pressures close to the cage collapse boundary. The material synthesized consists of many randomly oriented clusters with diamond-like short-/medium-range order and possesses the highest hardness (101.9 ± 2.3 GPa), elastic modulus (1,182 ± 40 GPa) and thermal conductivity (26.0 ± 1.3 W m-1 K-1) observed in any known amorphous material. It also exhibits optical bandgaps tunable from 1.85 eV to 2.79 eV. These discoveries contribute to our knowledge about advanced amorphous materials and the synthesis of bulk amorphous materials by high-pressure and high-temperature techniques and may enable new applications for amorphous solids.

A Sodium Germanosilicide with Unusual Network Topology.

The germanosilicide Na4-xGeySi16-y (0.4 ≤ x ≤ 1.1, 4.7 ≤ y ≤ 9.3) was synthesized under high-pressure, high-temperature conditions. The novel guest-host compound comprises a unique tetrel framework with dual channels housing sodium and smaller, empty (Si,Ge)9 units. The arrangement represents a new structure type with an overall structural topology that is closely related to a hypothetical carbon allotrope. Topological analysis of the structure revealed that the guest environment space cannot be tiled with singular polyhedra as in cage compounds (e.g., clathrates). The analysis of natural tilings provides a convenient method to unambiguously compare related tetrel-rich structures and can help elucidate new possible structural arrangements of intermetallic compounds.

Early episodes of high-pressure core formation preserved in plume mantle.

The decay of short-lived iodine (I) and plutonium (Pu) results in xenon (Xe) isotopic anomalies in the mantle that record Earth's earliest stages of formation. Xe isotopic anomalies have been linked to degassing during accretion, but degassing alone cannot account for the co-occurrence of Xe and tungsten (W) isotopic heterogeneity in plume-derived basalts and their long-term preservation in the mantle. Here we describe measurements of I partitioning between liquid Fe alloys and liquid silicates at high pressure and temperature and propose that Xe isotopic anomalies found in modern plume rocks (that is, rocks with elevated 3He/4He ratios) result from I/Pu fractionations during early, high-pressure episodes of core formation. Our measurements demonstrate that I becomes progressively more siderophile as pressure increases, so that portions of mantle that experienced high-pressure core formation will have large I/Pu depletions not related to volatility. These portions of mantle could be the source of Xe and W anomalies observed in modern plume-derived basalts. Portions of mantle involved in early high-pressure core formation would also be rich in FeO, and hence denser than ambient mantle. This would aid the long-term preservation of these mantle portions, and potentially points to their modern manifestation within seismically slow, deep mantle reservoirs with high 3He/4He ratios.

Reconciliation of Experiments and Theory on Transport Properties of Iron and the Geodynamo.

We measure the electrical resistivity of hcp iron up to ∼170 GPa and ∼3000 K using a four-probe van der Pauw method coupled with homogeneous flattop laser heating in a DAC, and compute its electrical and thermal conductivity by first-principles molecular dynamics including electron-phonon and electron-electron scattering. We find that the measured resistivity of hcp iron increases almost linearly with temperature, and is consistent with our computations. The results constrain the resistivity and thermal conductivity of hcp iron to ∼80±5 µΩ cm and ∼100±10 W m^{-1} K^{-1}, respectively, at conditions near the core-mantle boundary. Our results indicate an adiabatic heat flow of ∼10±1 TW out of the core, supporting a present-day geodynamo driven by thermal and compositional convection.

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.

Evidence for an oxygen-depleted liquid outer core of the Earth.

On the basis of geophysical observations, cosmochemical constraints, and high-pressure experimental data, the Earth's liquid outer core consists of mainly liquid iron alloyed with about ten per cent (by weight) of light elements. Although the concentrations of the light elements are small, they nevertheless affect the Earth's core: its rate of cooling, the growth of the inner core, the dynamics of core convection, and the evolution of the geodynamo. Several light elements-including sulphur, oxygen, silicon, carbon and hydrogen-have been suggested, but the precise identity of the light elements in the Earth's core is still unclear. Oxygen has been proposed as a major light element in the core on the basis of cosmochemical arguments and chemical reactions during accretion. Its presence in the core has direct implications for Earth accretion conditions of oxidation state, pressure and temperature. Here we report new shockwave data in the Fe-S-O system that are directly applicable to the outer core. The data include both density and sound velocity measurements, which we compare with the observed density and velocity profiles of the liquid outer core. The results show that we can rule out oxygen as a major light element in the liquid outer core because adding oxygen into liquid iron would not reproduce simultaneously the observed density and sound velocity profiles of the outer core. An oxygen-depleted core would imply a more reduced environment during early Earth accretion.

Slab melting versus slab dehydration in subduction-zone magmatism.

The second critical endpoint in the basalt-H(2)O system was directly determined by a high-pressure and high-temperature X-ray radiography technique. We found that the second critical endpoint occurs at around 3.4 GPa and 770 °C (corresponding to a depth of approximately 100 km in a subducting slab), which is much shallower than the previously estimated conditions. Our results indicate that the melting temperature of the subducting oceanic crust can no longer be defined beyond this critical condition and that the fluid released from subducting oceanic crust at depths greater than 100 km under volcanic arcs is supercritical fluid rather than aqueous fluid and/or hydrous melts. The position of the second critical endpoint explains why there is a limitation to the slab depth at which adakitic magmas are produced, as well as the origin of across-arc geochemical variations of trace elements in volcanic rocks in subduction zones.

Exploring toroidal anvil profiles for larger sample volumes above 4 Mbar.

With the advent of toroidal and double-stage diamond anvil cells (DACs), pressures between 4 and 10 Mbar can be achieved under static compression, however, the ability to explore diverse sample assemblies is limited on these micron-scale anvils. Adapting the toroidal DAC to support larger sample volumes offers expanded capabilities in physics, chemistry, and planetary science: including, characterizing materials in soft pressure media to multi-megabar pressures, synthesizing novel phases, and probing planetary assemblages at the interior pressures and temperatures of super-Earths and sub-Neptunes. Here we have continued the exploration of larger toroidal DAC profiles by iteratively testing various torus and shoulder depths with central culet diameters in the 30-50 µm range. We present a 30 µm culet profile that reached a maximum pressure of 414(1) GPa based on a Pt scale. The 300 K equations of state fit to our P-V data collected on gold and rhenium are compatible with extrapolated hydrostatic equations of state within 1% up to 4 Mbar. This work validates the performance of these large-culet toroidal anvils to > 4 Mbar and provides a promising foundation to develop toroidal DACs for diverse sample loading and laser heating.

Three-dimensional coherent x-ray diffraction imaging of molten iron in mantle olivine at nanoscale resolution.

We report quantitative 3D coherent x-ray diffraction imaging of a molten Fe-rich alloy and crystalline olivine sample, synthesized at 6 GPa and 1800 °C, with nanoscale resolution. The 3D mass density map is determined and the 3D distribution of the Fe-rich and Fe-S phases in the olivine-Fe-S sample is observed. Our results indicate that the Fe-rich melt exhibits varied 3D shapes and sizes in the olivine matrix. This work has potential for not only improving our understanding of the complex interactions between Fe-rich core-forming melts and mantle silicate phases but also paves the way for quantitative 3D imaging of materials at nanoscale resolution under extreme pressures and temperatures.

Catalyst-free synthesis of transparent, mesoporous diamond monoliths from periodic mesoporous carbon CMK-8.

We report on the synthesis of optically transparent, mesoporous, monolithic diamond from periodic mesoporous carbon CMK-8 at a pressure of 21 GPa. The phase transformation is already complete at a mild synthesis temperature of 1,300 degrees C without the need of a catalyst. Surprisingly, the diamond is obtained as a mesoporous material despite the extreme pressure. X-ray diffraction, SEM, transmission electron microscopy, selected area electron diffraction, high-resolution transmission electron microscopy, and Z-contrast experiments suggest that the mesoporous diamond is composed of interconnected diamond nanocrystals having diameters around 5-10 nm. The Brunauer Emmett Teller surface area was determined to be 33 m2 g(-1) according Kr sorption data. The mesostructure is diminished yet still detectable when the diamond is produced from CMK-8 at 1,600 degrees C and 21 GPa. The temperature dependence of the porosity indicates that the mesoporous diamond exists metastable and withstands transformation into a dense form at a significant rate due to its high kinetic inertness at the mild synthesis temperature. The findings point toward ultrahard porous materials with potential as mechanically highly stable membranes.

A partially equilibrated initial mantle and core indicated by stress-induced percolative core formation through a bridgmanite matrix.

The Earth's core formation mechanism determines the siderophile and light elements abundance in the Earth's mantle and core. Previous studies suggest that the sink of massive liquid metal through a solid silicate mantle resulted in an unequilibrated core and the lower mantle. Here, we show that percolation can be an effective core formation mechanism in a convective mantle and modify the compositions of the lower mantle and the core through partial equilibration between them. This grain-scale metal flow has a high velocity to meet the time constraint of core formation. The Earth's core could have been enriched with light elements, and the abundance of the moderately siderophile elements in the mantle could have been elevated to the current value during this process. The trapped core-forming melt in the mantle during the stress-induced percolation can also explain the highly siderophile element abundance in the Earth's mantle.

In situ measurements of electrical resistivity of metals in a cubic multi-anvil apparatus by van der Pauw method.

On the basis of the van der Pauw method, we developed a new technique for measuring the electrical resistivity of metals in a cubic multi-anvil high-pressure apparatus. Four electrode wires were introduced into the sample chamber and in contact with the pre-pressed metal disk on the periphery. The sample temperature was measured with a NiCr-NiSi (K-type) thermocouple, which was separated from the sample by a thin hexagonal boron nitride layer. The electrodes and thermocouple were electrically insulated from each other and from the heater by an alumina tube as well. Their leads were in connection with cables through the gap between the tungsten carbide anvils. We performed experiments to determine the temperature dependence of electrical resistivity of pure iron at 3 and 5 GPa. The experiments produce reproducible measurements and the results provide an independent check on electrical resistivity data produced by other methods. The new technique provides reliable electrical resistivity measurements of metallic alloys and compounds at high pressure and temperature.

Nitrogen isotope evidence for Earth's heterogeneous accretion of volatiles.

The origin of major volatiles nitrogen, carbon, hydrogen, and sulfur in planets is critical for understanding planetary accretion, differentiation, and habitability. However, the detailed process for the origin of Earth's major volatiles remains unresolved. Nitrogen shows large isotopic fractionations among geochemical and cosmochemical reservoirs, which could be used to place tight constraints on Earth's volatile accretion process. Here we experimentally determine N-partitioning and -isotopic fractionation between planetary cores and silicate mantles. We show that the core/mantle N-isotopic fractionation factors, ranging from -4‰ to +10‰, are strongly controlled by oxygen fugacity, and the core/mantle N-partitioning is a multi-function of oxygen fugacity, temperature, pressure, and compositions of the core and mantle. After applying N-partitioning and -isotopic fractionation in a planetary accretion and core-mantle differentiation model, we find that the N-budget and -isotopic composition of Earth's crust plus atmosphere, silicate mantle, and the mantle source of oceanic island basalts are best explained by Earth's early accretion of enstatite chondrite-like impactors, followed by accretion of increasingly oxidized impactors and minimal CI chondrite-like materials before and during the Moon-forming giant impact. Such a heterogeneous accretion process can also explain the carbon-hydrogen-sulfur budget in the bulk silicate Earth. The Earth may thus have acquired its major volatile inventory heterogeneously during the main accretion phase.

Inner core composition paradox revealed by sound velocities of Fe and Fe-Si alloy.

Knowledge of the sound velocity of core materials is essential to explain the observed anomalously low shear wave velocity (VS) and high Poisson's ratio (σ) in the solid inner core. To date, neither VS nor σ of Fe and Fe-Si alloy have been measured under core conditions. Here, we present VS and σ derived from direct measurements of the compressional wave velocity, bulk sound velocity, and density of Fe and Fe-8.6 wt%Si up to ~230 GPa and ~5400 K. The new data show that neither the effect of temperature nor incorporation of Si would be sufficient to explain the observed low VS and high σ of the inner core. A possible solution would add carbon (C) into the solid inner core that could further decrease VS and increase σ. However, the physical property-based Fe-Si-C core models seemingly conflict with the partitioning behavior of Si and C between liquid and solid Fe.

Perovskite retrieved from the lower mantle.

The calcium silicate compound was characterized and named as "davemaoite".

Melting and density of MgSiO3 determined by shock compression of bridgmanite to 1254GPa.

The essential data for interior and thermal evolution models of the Earth and super-Earths are the density and melting of mantle silicate under extreme conditions. Here, we report an unprecedently high melting temperature of MgSiO3 at 500 GPa by direct shockwave loading of pre-synthesized dense MgSiO3 (bridgmanite) using the Z Pulsed Power Facility. We also present the first high-precision density data of crystalline MgSiO3 to 422 GPa and 7200 K and of silicate melt to 1254 GPa. The experimental density measurements support our density functional theory based molecular dynamics calculations, providing benchmarks for theoretical calculations under extreme conditions. The excellent agreement between experiment and theory provides a reliable reference density profile for super-Earth mantles. Furthermore, the observed upper bound of melting temperature, 9430 K at 500 GPa, provides a critical constraint on the accretion energy required to melt the mantle and the prospect of driving a dynamo in massive rocky planets.

Synthesis of periodic mesoporous coesite.

Periodic mesoporous coesite was obtained by a modified nanocasting process from a periodic mesoporous silica SBA-16/C composite at a pressure of 12 GPa and 350 degrees C.

Synthesis of stishovite nanocrystals from periodic mesoporous silica.

Faceted stishovite nanocrystals with sizes of 200-400 nm were synthesized at a pressure of 12 GPa and a temperature of 400 degrees C in a multianvil apparatus using mesoporous silica SBA-16 as the precursor.

Temperature-induced amorphization in CaCO3 at high pressure and implications for recycled CaCO3 in subduction zones.

Calcium carbonate (CaCO3) significantly affects the properties of upper mantle and plays a key role in deep carbon recycling. However, its phase relations above 3 GPa and 1000 K are controversial. Here we report a reversible temperature-induced aragonite-amorphization transition in CaCO3 at 3.9-7.5 GPa and temperature above 1000 K. Amorphous CaCO3 shares a similar structure as liquid CaCO3 but with much larger C-O and Ca-Ca bond lengths, indicating a lower density and a mechanism of lattice collapse for the temperature-induced amorphous phase. The less dense amorphous phase compared with the liquid provides an explanation for the observed CaCO3 melting curve overturn at about 6 GPa. Amorphous CaCO3 is stable at subduction zone conditions and could aid the recycling of carbon to the surface.

Oxygen-17 nuclear magnetic resonance study of the structure of mixed cation calcium-sodium silicate glasses at high pressure: implications for molecular link to element partitioning between silicate liquids and crystals.

The structure of silicate glasses and the corresponding liquids at high pressure and their structure-property relations remain difficult questions in modern physical chemistry, geochemistry, and condensed matter physics. Here we report high- resolution solid-state O-17 3QMAS NMR spectra for mixed cation Ca-Na silicate glasses quenched from melts at high pressure up to 8 GPa. The spectra provide the experimental evidence for the varying pressure-dependence in two different types of nonbridging oxygen (NBO) environments (i.e., Na-O-Si and mixed (Ca,Na)-O-Si) in the single glass composition. The percentage of NBO drops significantly with increasing pressure and is a complex function of melt composition, including cation field strength of network modifying cations. A decrease in NBO fraction with pressure is negatively correlated with the element partitioning coefficient between crystals and liquids at high pressure.