Leonid Dubrovinsky

Materials science - The hardest known oxide

A material as hard as diamond or cubic boron nitride has yet to be identified, but here we report the discovery of a cotunnite-structured titanium oxide which represents the hardest oxide known. This is a new polymorph of titanium dioxide, where titanium is nine-coordinated to oxygen in the cotunnite (PbCl2) structure. The phase is synthesized at pressures above 60 gigapascals (GPa) and temperatures above 1,000 K and is one of the least compressible and hardest polycrystalline materials to be described.

Body-centered cubic iron-nickel alloy in Earth's core.

Cosmochemical, geochemical, and geophysical studies provide evidence that Earths core contains iron with substantial (5 to 15%) amounts of nickel. The iron-nickel alloy Fe0.9Ni0.1 has been studied in situ by means of angle-dispersive x-ray diffraction in internally heated diamond anvil cells (DACs), and its resistance has been measured as a function of pressure and temperature. At pressures above 225 gigapascals and temperatures over 3400 kelvin, Fe0.9Ni0.1 adopts a body-centered cubic structure. Our experimental and theoretical results not only support the interpretation of shockwave data on pure iron as showing a solid-solid phase transition above about 200 gigapascals, but also suggest that iron alloys with geochemically reasonable compositions (that is, with substantial nickel, sulfur, or silicon content) adopt the bcc structure in Earths inner core.

Experimental and theoretical identification of a new high-pressure phase of silica

Following the discovery of stishovite (the highest-pressure polymorph of silica known from natural samples), many attempts have been made to investigate the possible existence of denser phases of silica at higher pressures. Based on the crystal structures observed in chemical analogues of silica, high-pressure experiments on silica and theoretical studies, several possible post-stishovite phases have been suggested. But the likely stable phase of silica at pressures and temperatures representative of Earths lower mantle remains uncertain. Here we report the results of an X-ray diffraction study of silica that has been heated to temperatures above ∼2,000 K and maintained at pressures between 68 and 85 GPa. We observe the occurrence of a new high-pressure phase which we identify with the aid of first-principles total-energy calculations. The structure of this phase (space group Pnc2) is intermediate between the α-PbO2 and ZrO2 structures, and is denser than other known silica phases.

Superhard nanocomposite of dense polymorphs of boron nitride: Noncarbon material has reached diamond hardness

The authors report a synthesis of unique superhard aggregated boron nitride nanocomposites (ABNNCs) showing the enhancement of hardness up to 100% in comparison with single crystal c-BN. Such a great hardness increase is due to the combination of the Hall-Petch and the quantum confinement effects. The decrease of the grain size down to 14nm and the simultaneous formation of the two dense BN phases with hexagonal and cubic structures within the grains at nano- and subnanolevel result in enormous mechanical property enhancement with maximum hardness of 85(5)GPa. Thus, ABNNC is the first non-carbon-based bulk material with the value of hard-ness approaching that of single crystal and polycrystalline diamond and aggregated diamond nanorods. ABNNC also has an unusually high fracture toughness for superhard materials (K1C=15MPam0.5) and wear resistance (WH=11; compare, for industrial polycrystalline diamond, WH=3–4), in combination with high thermal stability (above 1600K in air), making it an exceptional super...

Synchrotron X-ray Study of Iron at High Pressure and Temperature

X-ray synchrotron experiments with in situ laser heating of iron in a diamond-anvil cell show that the high-pressure ε phase, a hexagonal close-packed (hcp) structure, transforms to another phase (possibly a polytype double-layer hcp) at a pressure of about 38 gigapascals and at temperatures between 1200 and 1500 kelvin. This information has implications for the phase relations of iron in Earths core.

BX90: A new diamond anvil cell design for X-ray diffraction and optical measurements

We present a new design of a universal diamond anvil cell, suitable for different kinds of experimental studies under high pressures. Main features of the cell are an ultimate 90-degrees symmetrical axial opening and high stability, making the presented cell design suitable for a whole range of techniques from optical absorption to single-crystal X-ray diffraction studies, also in combination with external resistive or double-side laser heating. Three examples of the cell applications are provided: a Brillouin scattering of neon, single-crystal X-ray diffraction of α-Cr(2)O(3), and resistivity measurements on the (Mg(0.60)Fe(0.40))(Si(0.63)Al(0.37))O(3) silicate perovskite.

Implementation of micro-ball nanodiamond anvils for high-pressure studies above 6 Mbar.

Since invention of the diamond anvil cell technique in the late 1950s for studying materials at extreme conditions, the maximum static pressure generated so far at room temperature was reported to be about 400 GPa. Here we show that use of micro-semi-balls made of nanodiamond as second-stage anvils in conventional diamond anvil cells drastically extends the achievable pressure range in static compression experiments to above 600 GPa. Micro-anvils (10–50 μm in diameter) of superhard nanodiamond (with a grain size below ∼50 nm) were synthesized in a large volume press using a newly developed technique. In our pilot experiments on rhenium and gold we have studied the equation of state of rhenium at pressures up to 640 GPa and demonstrated the feasibility and crucial necessity of the in situ ultra high-pressure measurements for accurate determination of material properties at extreme conditions.

MossA: a program for analyzing energy-domain Mössbauer spectra from conventional and synchrotron sources

The program MossA provides a straightforward approach to the fitting of 57Fe conventional and synchrotron energy-domain Mossbauer spectra. Sites can be defined simply by mouse clicks and hyperfine parameters can be constrained to constant values, within specific ranges, and can be coupled linearly between different subspectra. The program includes a full transmission integral fit with Lorentzian line shape (conventional source) or Lorentzian-squared line shape (synchrotron source). The fitting process is graphically displayed in real time while fitting and can be interrupted at any time. Gaussian-shaped quadrupole splitting distributions for analyzing nonmagnetic amorphous materials are included. MossA is designed especially for the rapid and comprehensive analysis of complex Mossbauer spectra, made possible by its native graphical user input.

Iron–silica interaction at extreme conditions and the electrically conducting layer at the base of Earth's mantle

The boundary between the Earths metallic core and its silicate mantle is characterized by strong lateral heterogeneity and sharp changes in density, seismic wave velocities, electrical conductivity and chemical composition. To investigate the composition and properties of the lowermost mantle, an understanding of the chemical reactions that take place between liquid iron and the complex Mg-Fe-Si-Al-oxides of the Earths lower mantle is first required. Here we present a study of the interaction between iron and silica (SiO2) in electrically and laser-heated diamond anvil cells. In a multianvil apparatus at pressures up to 140 GPa and temperatures over 3,800 K we simulate conditions down to the core–mantle boundary. At high temperature and pressures below 40 GPa, iron and silica react to form iron oxide and an iron–silicon alloy, with up to 5 wt% silicon. At pressures of 85–140 GPa, however, iron and SiO2 do not react and iron–silicon alloys dissociate into almost pure iron and a CsCl-structured (B2) FeSi compound. Our experiments suggest that a metallic silicon-rich B2 phase, produced at the core–mantle boundary (owing to reactions between iron and silicate), could accumulate at the boundary between the mantle and core and explain the anomalously high electrical conductivity of this region.

Stability of Perovskite (MgSiO3) in the Earth's Mantle

Available thermodynamic data and seismic models favor perovskite (MgSiO3) as the stable phase in the mantle. MgSiO3 was heated at temperatures from 1900 to 3200 kelvin with a Nd-YAG laser in diamond-anvil cells to study the phase relations at pressures from 45 to 100 gigapascals. The quenched products were studied with synchrotron x-ray radiation. The results show that MgSiO3 broke down to a mixture of MgO (periclase) and SiO2 (stishovite or an unquenchable polymorph) at pressures from 58 to 85 gigapascals. These results imply that perovskite may not be stable in the lower mantle and that it might be necessary to reconsider the compositional and density models of the mantle.