Stability of the body-centred-cubic phase of iron in the Earth's inner core

Iron is thought to be the main constituent of the Earth's core, and considerable efforts have therefore been made to understand its properties at high pressure and temperature. While these efforts have expanded our knowledge of the iron phase diagram, there remain some significant inconsistencies, the most notable being the difference between the 'low' and 'high' melting curves. Here we report the results of molecular dynamics simulations of iron based on embedded atom models fitted to the results of two implementations of density functional theory. We tested two model approximations and found that both point to the stability of the body-centred-cubic (b.c.c.) iron phase at high temperature and pressure. Our calculated melting curve is in agreement with the 'high' melting curve, but our calculated phase boundary between the hexagonal close packed (h.c.p.) and b.c.c. iron phases is in good agreement with the 'low' melting curve. We suggest that the h.c.p.-b.c.c. transition was previously misinterpreted as a melting transition, similar to the case of xenon, and that the b.c.c. phase of iron is the stable phase in the Earth's inner core.     

Elasticity of iron at the temperature of the Earth's inner core.

Seismological body-wave and free-oscillation studies of the Earth's solid inner core have revealed that compressional waves traverse the inner core faster along near-polar paths than in the equatorial plane. Studies have also documented local deviations from this first-order pattern of anisotropy on length scales ranging from 1 to 1,000 km (refs 3, 4). These observations, together with reports of the differential rotation of the inner core, have generated considerable interest in the physical state and dynamics of the inner core, and in the structure and elasticity of its main constituent, iron, at appropriate conditions of pressure and temperature. Here we report first-principles calculations of the structure and elasticity of dense hexagonal close-packed (h.c.p.) iron at high temperatures. We find that the axial ratio c/a of h.c.p. iron increases substantially with increasing temperature, reaching a value of nearly 1.7 at a temperature of 5,700 K, where aggregate bulk and shear moduli match those of the inner core. As a consequence of the increasing c/a ratio, we have found that the single-crystal longitudinal anisotropy of h.c.p. iron at high temperature has the opposite sense from that at low temperature. By combining our results with a simple model of polycrystalline texture in the inner core, in which basal planes are partially aligned with the rotation axis, we can account for seismological observations of inner-core anisotropy.     

Melting of iron at the physical conditions of the Earth's core

Seismological data can yield physical properties of the Earth's core, such as its size and seismic anisotropy. A well-constrained iron phase diagram, however, is essential to determine the temperatures at core boundaries and the crystal structure of the solid inner core. To date, the iron phase diagram at high pressure has been investigated experimentally through both laser-heated diamond-anvil cell and shock-compression techniques, as well as through theoretical calculations. Despite these contributions, a consensus on the melt line or the high-pressure, high-temperature phase of iron is lacking. Here we report new and re-analysed sound velocity measurements of shock-compressed iron at Earth-core conditions. We show that melting starts at 225 +/- 3 GPa (5,100 +/- 500 K) and is complete at 260 +/- 3 GPa (6,100 +/- 500 K), both on the Hugoniot curve-the locus of shock-compressed states. This new melting pressure is lower than previously reported, and we find no evidence for a previously reported solid-solid phase transition on the Hugoniot curve near 200 GPa (ref. 16).     

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

The boundary between the Earth's 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 Earth's 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.     

Constraints on the composition of the Earth's core from ab initio calculations

Knowledge of the composition of the Earth's core is important for understanding its melting point and therefore the temperature at the inner-core boundary and the temperature profile of the core and mantle. In addition, the partitioning of light elements between solid and liquid, as the outer core freezes at the inner-core boundary, is believed to drive compositional convection, which in turn generates the Earth's magnetic field. It is generally accepted that the liquid outer core and the solid inner core consist mainly of iron. The outer core, however, is also thought to contain a significant fraction of light elements, because its density--as deduced from seismological data and other measurements--is 6-10 per cent less than that estimated for pure liquid iron. Similar evidence indicates a smaller but still appreciable fraction of light elements in the inner core. The leading candidates for the light elements present in the core are sulphur, oxygen and silicon. Here we obtain a constraint on core composition derived from ab initio calculation of the chemical potentials of light elements dissolved in solid and liquid iron. We present results for the case of sulphur, which provide strong evidence against the proposal that the outer core is close to being a binary iron-sulphur mixture.     

Chemical interaction of Fe and Al(2)O3 as a source of heterogeneity at the Earth's core-mantle boundary

Seismological studies have revealed that a complex texture or heterogeneity exists in the Earth's inner core and at the boundary between core and mantle. These studies highlight the importance of understanding the properties of iron when modelling the composition and dynamics of the core and the interaction of the core with the lowermost mantle. One of the main problems in inferring the composition of the lowermost mantle is our lack of knowledge of the high-pressure and high-temperature chemical reactions that occur between iron and the complex Mg-Fe-Si-Al-oxides which are thought to form the bulk of the Earth's lower mantle. A number of studies have demonstrated that iron can react with MgSiO3-perovskite at high pressures and high temperatures, and it was proposed that the chemical nature of this process involves the reduction of silicon by the more electropositive iron. Here we present a study of the interaction between iron and corundum (Al(2)O3) in electrically- and laser-heated diamond anvil cells at 2,000-2,200 K and pressures up to 70 GPa, simulating conditions in the Earth's deep interior. We found that at pressures above 60 GPa and temperatures of 2,200 K, iron and corundum react to form iron oxide and an iron-aluminium alloy. Our results demonstrate that iron is able to reduce aluminium out of oxides at core-mantle boundary conditions, which could provide an additional source of light elements in the Earth's core and produce significant heterogeneity at the core-mantle boundary.     

Inner-core shear-wave anisotropy and texture from an observation of PKJKP waves

Since the discovery of the Earth's core a century ago, and the subsequent discovery of a solid inner core (postulated to have formed by the freezing of iron) seismologists have striven to understand this most remote part of the deep Earth. The most direct evidence for a solid inner core would be the observation of shear-mode body waves that traverse it, but these phases are extremely difficult to observe. Two reported observations in short-period data have proved controversial. Arguably more successful have been studies of longer-period data, but such averaging limits the usefulness of the observations to reported sightings. We present two observations of an inner-core shear-wave phase at higher frequencies in stacked data from the Japanese High-Sensitivity Array, Hi-Net. From an analysis of timing, amplitude and waveform of the 'PKJKP' phase we derive constraints on inner-core compressional-wave velocity and shear attenuation at about 0.3 Hz which differ from standard isotropic core models. We can explain waveform features and can partially reconcile the otherwise large differences between core wavespeed and attenuation models that our observations apparently suggest if we invoke shear-wave anisotropy in the inner core. A simple model of an inner core composed of hexagonal close-packed iron with its c axis aligned perpendicular to the rotation axis yields anisotropy that is compatible with both the shear-wave anisotropy that we observe and the well-established 3 per cent compressional-wave anisotropy.     

Superconductivity in compressed lithium at 20 K

Superconductivity at high temperatures is expected in elements with low atomic numbers, based in part on conventional BCS (Bardeen-Cooper-Schrieffer) theory. For example, it has been predicted that when hydrogen is compressed to its dense metallic phase (at pressures exceeding 400 GPa), it will become superconducting with a transition temperature above room temperature. Such pressures are difficult to produce in a laboratory setting, so the predictions are not easily confirmed. Under normal conditions lithium is the lightest metal of all the elements, and may become superconducting at lower pressures; a tentative observation of a superconducting transition in Li has been previously reported. Here we show that Li becomes superconducting at pressures greater than 30 GPa, with a pressure-dependent transition temperature (T(c)) of 20 K at 48 GPa. This is the highest observed T(c) of any element; it confirms the expectation that elements with low atomic numbers will have high transition temperatures, and suggests that metallic hydrogen will have a very high T(c). Our results confirm that the earlier tentative claim of superconductivity in Li was correct.     

The plastic deformation of iron at pressures of the Earth's inner core

Soon after the discovery of seismic anisotropy in the Earth's inner core, it was suggested that crystal alignment attained during deformation might be responsible. Since then, several other mechanisms have been proposed to account for the observed anisotropy, but the lack of deformation experiments performed at the extreme pressure conditions corresponding to the solid inner core has limited our ability to determine which deformation mechanism applies to this region of the Earth. Here we determine directly the elastic and plastic deformation mechanism of iron at pressures of the Earth's core, from synchrotron X-ray diffraction measurements of iron, under imposed axial stress, in diamond-anvil cells. The epsilon-iron (hexagonally close packed) crystals display strong preferred orientation, with c-axes parallel to the axis of the diamond-anvil cell. Polycrystal plasticity theory predicts an alignment of c-axes parallel to the compression direction as a result of basal slip, if basal slip is either the primary or a secondary slip system. The experiments provide direct observations of deformation mechanisms that occur in the Earth's inner core, and introduce a method for investigating, within the laboratory, the rheology of materials at extreme pressures.     

Outer-core compositional stratification from observed core wave speed profiles

Light elements must be present in the nearly pure iron core of the Earth to match the remotely observed properties of the outer and inner cores. Crystallization of the inner core excludes light elements from the solid, concentrating them in liquid near the inner-core boundary that potentially rises and collects at the top of the core, and this may have a seismically observable signal. Here we present array-based observations of seismic waves sensitive to this part of the core whose wave speeds require there to be radial compositional variation in the topmost 300?km of the outer core. The velocity profile significantly departs from that of compression of a homogeneous liquid. Total light-element enrichment is up to five weight per cent at the top of the core if modelled in the Fe-O-S system. The stratification suggests the existence of a subadiabatic temperature gradient at the top of the outer core.     

延拓法在油气相平衡计算中的应用

用延拓法、经典的Newton算法和Broyden算法分别计算了四个实际油气体系的露点(用PR方程),对同一体系的重馏分使用同样的临界参数,对比不同压力初值下这三种方法的迭代收敛情况。对同一体系同样的压力初值对比了改变重馏分的临界参数拟合实验露点时这三种算法的适应性。结果表明延拓法对初值要求低,是油藏流体相平衡计算的一种有效算法。     

唐钢二炼铁厂使用巴西MBR块矿的生产应用

分析了巴西MBR块矿的矿相结构、矿物组成及冶金性能.MBR块矿的各项冶金性能较好,与烧结矿组成的综合炉料在高炉内的同化过程开始温度和结束温度均较高,但同化速度相对减慢.唐钢二炼铁厂的炼铁生产实践结果表明,适当配用MBR块矿,高炉入炉品位上升,矿耗降低,综合焦比下降,铁成本降低,高炉顺行状态良好.MBR块矿在改善高炉综合技术经济指标的过程中起着重要作用.     

Southern Ocean dust-climate coupling over the past four million years

Dust has the potential to modify global climate by influencing the radiative balance of the atmosphere and by supplying iron and other essential limiting micronutrients to the ocean. Indeed, dust supply to the Southern Ocean increases during ice ages, and 'iron fertilization' of the subantarctic zone may have contributed up to 40?parts per million by volume (p.p.m.v.) of the decrease (80-100 p.p.m.v.) in atmospheric carbon dioxide observed during late Pleistocene glacial cycles. So far, however, the magnitude of Southern Ocean dust deposition in earlier times and its role in the development and evolution of Pleistocene glacial cycles have remained unclear. Here we report a high-resolution record of dust and iron supply to the Southern Ocean over the past four million years, derived from the analysis of marine sediments from ODP Site 1090, located in the Atlantic sector of the subantarctic zone. The close correspondence of our dust and iron deposition records with Antarctic ice core reconstructions of dust flux covering the past 800,000 years (refs 8, 9) indicates that both of these archives record large-scale deposition changes that should apply to most of the Southern Ocean, validating previous interpretations of the ice core data. The extension of the record beyond the interval covered by the Antarctic ice cores reveals that, in contrast to the relatively gradual intensification of glacial cycles over the past three million years, Southern Ocean dust and iron flux rose sharply at the Mid-Pleistocene climatic transition around 1.25 million years ago. This finding complements previous observations over late Pleistocene glacial cycles, providing new evidence of a tight connection between high dust input to the Southern Ocean and the emergence of the deep glaciations that characterize the past one million years of Earth history.     

Bulk Al–Al3Zr composite prepared by mechanical alloying and hot extrusion for high-temperature applications

Bulk Al/Al3Zr composite was prepared by a combination of mechanical alloying (MA) and hot extrusion processes. Elemental Al and Zr powders were milled for up to 10 h and heat treated at 600°C for 1 h to form stable Al3Zr. The prepared Al3Zr powder was then mixed with the pure Al powder to produce an Al–Al3Zr composite. The composite powder was finally consolidated by hot extrusion at 550°C. The mechanical properties of consolidated samples were evaluated by hardness and tension tests at room and elevated temperatures. The results show that annealing of the 10-h-milled powder at 600°C for 1 h led to the formation of a stable Al3Zr phase. Differential scanning calorime-try (DSC) results confirmed that the formation of Al3Zr began with the nucleation of a metastable phase, which subsequently transformed to the stable tetragonal Al3Zr structure. The tension yield strength of the Al?10wt%Al3Zr composite was determined to be 103 MPa, which is approximately twice that for pure Al (53 MPa). The yield stress of the Al/Al3Zr composite at 300°C is just 10% lower than that at room tem-perature, which demonstrates the strong potential for the prepared composite to be used in high-temperature structural applications.     

A theoretical investigation on phase transition and dissociation of ammonium bromide under high pressure

Structures of ammonium bromide under high pressure were investigated through ab initio evolutionary algorithm and total-energy calculations based on density functional theory. Static enthalpy calculations indicate that the low-pressure phase V（space group P4/nmm） transforms into a monoclinic P21/m structure at 71 GPa and then an orthorhombic structure Cmma at 130 GPa, which is found to be energetically stable up to 264 GPa. Mechanism of phonon softening at the P4/nmm P21/m transformation is discussed. Ab initio calculations show that the band overlap in the molecular Cmma phase, which causes the pressure-induced insulator-to-metal transition, occurs at about 240 GPa. Enthalpy calculations show that Cmma NH4 Br becomes unstable and dissociates into NH3 and HBr above 264 GPa.     

Superconductivity in doped cubic silicon

Although the local resistivity of semiconducting silicon in its standard crystalline form can be changed by many orders of magnitude by doping with elements, superconductivity has so far never been achieved. Hybrid devices combining silicon's semiconducting properties and superconductivity have therefore remained largely underdeveloped. Here we report that superconductivity can be induced when boron is locally introduced into silicon at concentrations above its equilibrium solubility. For sufficiently high boron doping (typically 100 p.p.m.) silicon becomes metallic. We find that at a higher boron concentration of several per cent, achieved by gas immersion laser doping, silicon becomes superconducting. Electrical resistivity and magnetic susceptibility measurements show that boron-doped silicon (Si:B) made in this way is a superconductor below a transition temperature T(c) approximately 0.35 K, with a critical field of about 0.4 T. Ab initio calculations, corroborated by Raman measurements, strongly suggest that doping is substitutional. The calculated electron-phonon coupling strength is found to be consistent with a conventional phonon-mediated coupling mechanism. Our findings will facilitate the fabrication of new silicon-based superconducting nanostructures and mesoscopic devices with high-quality interfaces.     

Efficacy of the post-perovskite phase as an explanation for lowermost-mantle seismic properties

Constraining the chemical, rheological and electromagnetic properties of the lowermost mantle (D') is important to understand the formation and dynamics of the Earth's mantle and core. To explain the origin of the variety of characteristics of this layer observed with seismology, a number of theories have been proposed, including core-mantle interaction, the presence of remnants of subducted material and that D' is the site of a mineral phase transformation. This final possibility has been rejuvenated by recent evidence for a phase change in MgSiO3 perovskite (thought to be the most prevalent phase in the lower mantle) at near core-mantle boundary temperature and pressure conditions. Here we explore the efficacy of this 'post-perovskite' phase to explain the seismic properties of the lowermost mantle through coupled ab initio and seismic modelling of perovskite and post-perovskite polymorphs of MgSiO3, performed at lowermost-mantle temperatures and pressures. We show that a post-perovskite model can explain the topography and location of the D' discontinuity, apparent differences in compressional- and shear-wave models and the observation of a deeper, weaker discontinuity. Furthermore, our calculations show that the regional variations in lower-mantle shear-wave anisotropy are consistent with the proposed phase change in MgSiO3 perovskite.     

Spin crossover and iron-rich silicate melt in the Earth's deep mantle

A melt has greater volume than a silicate solid of the same composition. But this difference diminishes at high pressure, and the possibility that a melt sufficiently enriched in the heavy element iron might then become more dense than solids at the pressures in the interior of the Earth (and other terrestrial bodies) has long been a source of considerable speculation. The occurrence of such dense silicate melts in the Earth's lowermost mantle would carry important consequences for its physical and chemical evolution and could provide a unifying model for explaining a variety of observed features in the core-mantle boundary region. Recent theoretical calculations combined with estimates of iron partitioning between (Mg,Fe)SiO(3) perovskite and melt at shallower mantle conditions suggest that melt is more dense than solids at pressures in the Earth's deepest mantle, consistent with analysis of shockwave experiments. Here we extend measurements of iron partitioning over the entire mantle pressure range, and find a precipitous change at pressures greater than ～76?GPa, resulting in strong iron enrichment in melts. Additional X-ray emission spectroscopy measurements on (Mg(0.95)Fe(0.05))SiO(3) glass indicate a spin collapse around 70?GPa, suggesting that the observed change in iron partitioning could be explained by a spin crossover of iron (from high-spin to low-spin) in silicate melt. These results imply that (Mg,Fe)SiO(3) liquid becomes more dense than coexisting solid at ～1,800?km depth in the lower mantle. Soon after the Earth's formation, the heat dissipated by accretion and internal differentiation could have produced a dense melt layer up to ～1,000?km in thickness underneath the solid mantle. We also infer that (Mg,Fe)SiO(3) perovskite is on the liquidus at deep mantle conditions, and predict that fractional crystallization of dense magma would have evolved towards an iron-rich and silicon-poor composition, consistent with seismic inferences of structures in the core-mantle boundary region.     

A regular period for Saturn's magnetic field that may track its internal rotation

The rotation rate of a planet is one of its fundamental properties. Saturn's rotation, however, is difficult to determine because there is no solid surface from which to time it, and the alternative 'clock'--the magnetic field--is nearly symmetrically aligned with the rotation axis. Radio emissions, thought to provide a proxy measure of the rotation of the magnetic field, have yielded estimates of the rotation period between 10 h 39 min 22 s and 10 h 45 min 45 s (refs 8-10). Because the period determined from radio measurements exhibits large time variations, even on timescales of months, it has been uncertain whether the radio-emission periodicity coincides with the inner rotation rate of the planet. Here we report magnetic field measurements that revealed a time-stationary magnetic signal with a period of 10 h 47 min 6 s +/- 40 s. The signal appears to be stable in period, amplitude and phase over 14 months of observations, pointing to a close connection with the conductive region inside the planet, although its interpretation as the 'true' inner rotation period is still uncertain.     

半金属元素掺杂TiN的第一性原理研究

基于密度泛函数理论，采用广义梯度近似方法，对半金属元素原子X（X=B、Si、Ge、As、Sb和Te）掺杂TiN体系的平衡晶格常数和电子结构等进行第一性原理计算，并对掺杂前后的电子态分布变化和形成能进行分析计算．结果表明：掺杂体系中主要的电子贡献仍是N2p态和Ti3d态，随着半金属元素B、Si、Ge、As、Sb和Te的掺入，TiN掺杂体系的导电性能有所提高，但并未超过纯净TiN体系；同时由形成能的计算证明Si掺杂体系最容易达到稳定结构，而Te掺杂是最不稳定的体系．