R. Boehler

Synthesis of cubic silicon nitride

Silicon nitride (Si3N4) is used in a variety of important technological applications. The high fracture toughness, hardness and wear resistance of Si3N4-based ceramics are exploited in cutting tools and anti-friction bearings; in electronic applications, Si3N4 is used as an insulating, masking and passivating material. Two polymorphs of silicon nitride are known, both of hexagonal structure: α- and β-Si3N4. Here we report the synthesis of a third polymorph of silicon nitride, which has a cubic spinel structure. This new phase, c-Si3N4, is formed at pressures above 15 GPa and temperatures exceeding 2,000 K, yet persists metastably in air at ambient pressure to at least 700 K. First-principles calculations of the properties of this phase suggest that the hardness of c-Si3N4 should be comparable to that of the hardest known oxide (stishovite, a high-pressure phase of SiO2), and significantly greater than the hardness of the two hexagonal polymorphs.

Melting of the FeFeO and the FeFeS systems at high pressure: Constraints on core temperatures

Melting temperatures of FeO, FeS and FeS2 have been accurately determined in a hydrostatic, inert pressure environment up to about 0.5 Mbar using a new yttrium-lithium-fluoride (YLF) heating laser. The melting curve for FeO is in perfect agreement with data obtained from multi-anvil experiments at 160 kbar [1], but is in stark disagreement with previous laser heating experiments [2]. Preliminary measurements show strong melting depression on mixtures of Fe and FeS, whereas mixtures of Fe and FeO were observed to melt close to the melting curve of iron. The Kraut-Kennedy melting relationship [3], in which the melting temperature is a linear function of volume, is successfully tested in this study for Li, Na, K, Fe, FeS, FeS2 and FeO, to compressions up to > 30%. At 1.36 Mbar (core-mantle boundary, CMB) FeO, Fe, and FeS are estimated to melt at 3670, 3260 and 3060 (± 100) K respectively. Assuming outer core compositions with about 60% Fe and about 40% FeO or FeS, and a solid solution system, the melting temperature at the CMB, on the core side, would be 3300 K (± 200 K), compared to a temperature at the bottom of the mantle of 2650 ± 100 K. If these systems exhibit eutectic behaviour, the melting gradient through the outer core would have to be substantially higher than the adiabatic gradient in order to maintain a thermal boundary at the CMB. The present melting data, and experimental constraints on the adiabatic gradient in the outer core suggest a temperature at the inner core-outer core boundary of nearly 4200 K.

New anvil designs in diamond-cells

New diamond anvils with conical support are introduced. Compared to conventional anvils the new design offers superior alignment stability, larger aperture, and reduced cost owing to significantly smaller anvil diameters. Except for table and culet, all surfaces are precision ground on a lathe, which lowers cost compared to faceted anvils. The conical design allows for steel supports, which are significantly easier and cheaper to manufacture than tungsten carbide supports. Conical support also prevents seat damage upon diamond failure. An additional new feature of the anvils is the roughened outer portion of the culet, which increases friction between the anvils and the gasket. This increases the height to diameter ratio of the pressure cell and prevents bonding between gasket and diamond, which causes ring cracks during pressure release. This technique replaces complicated diamond coating procedures. The anvils have been extensively tested for culets ranging from 0.1 to 1 mm diameter up to megabar pressures. A new anvil shape with cup-shaped culets to further increase the cell volume and gasket stability is also introduced.

New diamond cell for single-crystal x-ray diffraction

A new design for a high-precision diamond cell is described. Two kinematically mounted steel disks are elastically deflected to generate pressure. This principle provides higher precision in the diamond anvil alignment than most sliding piston-cylinder or guide-pin devices at significantly lower cost. With this new diamond cell conical diamond anvils with an x-ray aperture of 85° were successfully tested to over 50GPa using helium as a pressure medium. Anvil thickness of less than 1.4mm provides high x-ray transmission and low background, a significant improvement compared to beryllium or diamond-disk backing plates. Because the diamond anvils are supported by tungsten carbide seats, samples and pressure media can be annealed by external or laser heating to provide hydrostatic pressure conditions.

Thermodynamics and behavior of ?-Mg2SiO4 at high pressure: Implications for Mg2SiO4 phase equilibrium

Raman spectra of γ-Mg2SiO4 taken to 200 kbar were used to calculate entropy and heat capacity at various P-T conditions. These new thermodynamic data on γ-MgSiO4, similar data on MgSiO3 perovskite (pv), previous data on β-MgSiO4 and MgO (mw), and previous volumetric data of all phases were used to calculate the phase boundaries in the Mg2SiO4 phase diagram. Our resulting slope for the β→γ transition (50±4 bar K-1) is in excellent agreement with recent multi-anvil studies. The slopes for the β→pv+MgO and γ→pv+MgO are-7±3 and -25±4 bar K-1, respectively, and are consistent with our CO2 laser heated diamond anvil studies. These slopes result in a β-γ-MgO+pv triple point at approximately 229 kbar and 2260 K for the iron free system.

High-pressure polymorphs of olivine and the 660-km seismic discontinuity

It had long been accepted that the 400-km seismic discontinuity in the Earths mantle results from the phase transition of (Mg,Fe)2-SiO4-olivine to its high-pressure polymorph β-spinel (wadsleyite), and that the 660-km discontinuity results from the breakdown of the higher-pressure polymorph γ-spinel (ringwoodite) to MgSiO3-perovskite and (Mg,Fe)O-magnesiowüstite. An in situ multi-anvil-press X-ray study indicated, however, that the phase boundary of the latter transition occurs at pressures 2 GPa lower than had been found in earlier studies using multi-anvil recovery experiments and laser-heated diamond-anvil cells. Such a lower-pressure phase boundary would be irreconcilable with the accuracy of seismic measurements of the 660-km discontinuity, and would thus require a mineral composition of the mantle that is significantly different from what is currently thought. Here, however, we present measurements made with a laser-heated diamond-anvil cell which indicate that γ-Mg2SiO4 is stable up to pressure and temperature conditions equivalent to 660-km depth in the Earths mantle (24 GPa and 1,900 K) and then breaks down into MgSiO3-perovskite and MgO (periclase). We paid special attention to pressure accuracy and thermal pressure in our experiments, and to ensuring that our experiments were performed under nearly hydrostatic, inert pressure conditions using a variety of heating methods. We infer that these factors are responsible for the different results obtained in our experiments compared to the in situ multi-anvil-press study.

Synthesis of a cubic Ge3N4 phase at high pressures and temperatures

The two known phases of germanium nitride (Ge3N4) have hexagonal and trigonal symmetries and consist of three-dimensional networks of corner-connected Ge–N tetrahedra. A new cubic spinel phase (space-group Fd3m, a0=8.3 A, Z=8, ρ=6.36 g/cm3) containing Ge–N octahedra and tetrahedra in a 2:1 ratio was synthesized from elemental germanium and molecular nitrogen starting materials in a laser-heated diamond-anvil cell above 14 GPa. This phase is isostructural to the recently discovered cubic spinel phase of Si3N4.

Melting curve of aluminum in a diamond cell to 0.8 Mbar: implications for iron

Abstract The melting curve of aluminum was measured in a laser-heated diamond cell up to a pressure of 0.8 Mbar in order to test the agreement between this technique and shock wave measurements, which has been lacking in the case for iron. At this pressure, which is over an order of magnitude higher than in previous experiments [1, 2], the melting temperature is 3800 K, comparable to that measured for iron at 2 Mbar [3]. The present results for aluminum extrapolate smoothly to the previous melting measurements in a multi-anvil apparatus to 60 kbar and to the calculated shock melting point of 4750 K at 1.25 Mbar. They are also in excellent agreement with theoretical calculations. A review of the shock data reported for Al, Ta and Mo, close-packed metals, in which a break in the sound velocity-pressure curve is used to determine the melting pressure, shows that the change in velocity at melting is about 10% for all three metals. In the case of iron, the sound velocity data have been used to infer two transitions: a solid-solid transition at 2.0 Mbar and melting at 2.4 Mbar, each of these transitions having about a 5% change in sound velocity. It is unlikely that a phase transition between close-packed cubic structures will have a 5% velocity change, the same as is found in the melting transition. We therefore suggest that for iron there exists only a single transition, starting at 2.0 Mbar, a region of incomplete shock melting between 2 and 2.4 Mbar, and a total change in sound velocity of about 10%, which is closer to the value of the other metals studied. This interpretation introduces a very good agreement between the shock melting results of Brown and McQueen [4] and diamond cell measurements for iron [3] which has up to now been lacking.

Structural transformation of molecular nitrogen to a single-bonded atomic state at high pressures.

The transformation of molecular nitrogen to a single-bonded atomic nitrogen is of significant interest from a fundamental stand point and because it is the most energetic non-nuclear material predicted. We performed an x-ray diffraction of nitrogen at pressures up to 170 GPa. At 60 GPa, we found a transition from the rhombohedral (R3c) epsilon-N(2) phase to the zeta-N(2) phase, which we identified as orthorhombic with space group P222(1) and with four molecules per unit cell. This transition is accompanied by increasing intramolecular and decreasing intermolecular distances. The major transformation of this diatomic phase into the single-bonded (polymeric) phase, recently determined to have the cubic gauche structure (cg-N), proceeds as a first-order transition with a volume change of 22%.

Double-sided laser heating system for in situ high pressure–high temperature monochromatic x-ray diffraction at the esrf

A new double-sided laser heating system optimized for monochromatic X-ray diffraction at high pressure and high temperature has been developed at beamline ID27 of the European Synchrotron Radiation Facility (ESRF). The main components of this system including optimized focusing optics to produce a large and homogenous heated area, optimized mirror optics for temperature measurements and a state-of-the-art diffraction setup are described in details. Preliminary data collected at high pressure and high temperature on tungsten and iron are presented.