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.     

难熔金属钽、钼、钨的高温高压状态方程及声速的第一性原理研究

难熔金属的高压熔化曲线在动-静高压实验之间存在巨大争议,而在发生冲击熔化之前是否存在固-固相变是目前的研究热点问题.本文以3种典型难熔金属钽、钼、钨为例,通过第一性原理晶格动力学方法,计算了钽、钼、钨的声子色散曲线.采用准谐近似的方法,获得了Hugoniot状态方程以及Hugoniot声速.对于钽和钨的声速计算表明,其基态体心立方结构在高压下一直保持其稳定性;而钼的晶格动力学计算表明其基态结构的稳定性在高压下消失,而钼的Hugoniot声速在175–275GPa区域内发生了拐折,这一结果证实了冲击波实验中对于钼的声速测量的结果:在210GPa压力附近声速发生间断.     

ZnO岩盐结构熔化特性的分子动力学模拟

利用分子动力学方法和经验势模型对岩盐结构ZnO高压下的熔化特性进行了研究．对ZnO闪锌矿结构常压下的熔化进行模拟，发现存在过热熔化现象，通过与实验比较得到其过热48％的结论，然后利用该结论修正得到了ZnO岩盐结构0-50GPa的高压熔化相图．其中岩盐结构ZnO高压熔化曲线在压力低于7GPa时和由Lindemann熔化方程得到的结果符合很好．     

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.     

用米埃-格临爱森模型计算苯的高压物态方程

采用简化模型，假定高压下冲击产物全部转变成金刚石和原子氢，计算了苯的理论物态方程。理论羽贡纽曲线与实验结果在高压段较为符合。分析了模型的局限性。从结果分析推断在40GPa以上，产物中石墨相全部转变成金刚石。     

流体模型假定下无氧铜等熵卸载线的计算与分析

等熵卸载线的研究对物态方程、冲击波在自由面的卸载等问题有重要的意义.基于流体模型假定下推导等熵线的方法,计算得到了无氧铜分别以线性和二次Hugoniot关系为参考的等熵卸载线.在P-u图中,随着初始卸载压力增大,两条等熵卸载线间偏离逐渐变大,等熵卸载线与镜像的Hugoniot线逐渐出现较大的偏离.通过与无氧铜向空气卸载实验的数据比较,采用二次Hugoniot关系为参考得到的等熵卸载线与实验结果更相符,并且自由面卸载过程近似为等熵过程分析是合理的.压力大于180GPa时,用自由面速度的1/2近似得到粒子速度的误差达5%以上,实验中试图通过测量自由面速度得到粒子速度时必须做相应的计算修正.      

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.     

A quantum fluid of metallic hydrogen suggested by first-principles calculations

It is generally assumed that solid hydrogen will transform into a metallic alkali-like crystal at sufficiently high pressure. However, some theoretical models have also suggested that compressed hydrogen may form an unusual two-component (protons and electrons) metallic fluid at low temperature, or possibly even a zero-temperature liquid ground state. The existence of these new states of matter is conditional on the presence of a maximum in the melting temperature versus pressure curve (the 'melt line'). Previous measurements of the hydrogen melt line up to pressures of 44 GPa have led to controversial conclusions regarding the existence of this maximum. Here we report ab initio calculations that establish the melt line up to 200 GPa. We predict that subtle changes in the intermolecular interactions lead to a decline of the melt line above 90 GPa. The implication is that as solid molecular hydrogen is compressed, it transforms into a low-temperature quantum fluid before becoming a monatomic crystal. The emerging low-temperature phase diagram of hydrogen and its isotopes bears analogies with the familiar phases of 3He and 4He (the only known zero-temperature liquids), but the long-range Coulomb interactions and the large component mass ratio present in hydrogen would result in dramatically different properties.     

Re-emerging superconductivity at 48 kelvin in iron chalcogenides

Pressure has an essential role in the production and control of superconductivity in iron-based superconductors. Substitution of a large cation by a smaller rare-earth ion to simulate the pressure effect has raised the superconducting transition temperature T(c) to a record high of 55?K in these materials. In the same way as T(c) exhibits a bell-shaped curve of dependence on chemical doping, pressure-tuned T(c) typically drops monotonically after passing the optimal pressure. Here we report that in the superconducting iron chalcogenides, a second superconducting phase suddenly re-emerges above 11.5?GPa, after the T(c) drops from the first maximum of 32?K at 1?GPa. The T(c) of the re-emerging superconducting phase is considerably higher than the first maximum, reaching 48.0-48.7?K for Tl(0.6)Rb(0.4)Fe(1.67)Se(2), K(0.8)Fe(1.7)Se(2) and K(0.8)Fe(1.78)Se(2).     

铁硒基超导体的高压研究进展

FeSe及其衍生化合物因表现出奇特的正常态和超导态性质,成为近年来铁基超导领域的研究热点,其中高压技术在揭示FeSe中的竞争电子序和调控高温超导方面发挥了重要作用.本文概述了利用六面砧装置对FeSe基超导体的高压研究进展,主要内容包括:(1)通过建立FeSe的完整温度-压力相图,观察到圆拱形的反铁磁相界并详细揭示了电子向列序、长程反铁磁序和超导相之间的竞争关系,结合高压下的霍尔效应测试进一步表明反铁磁临界涨落对实现高温超导具有重要作用;(2)在多个插层FeSe高温超导体中,普遍发现高压会首先抑制超导I相,然后在临界压力之上诱导出高温超导Ⅱ相,呈现出双拱形超导相图,而且最高临界温度突破50 K;(3)结合高压X射线衍射和霍尔效应测试,指出超导Ⅱ相的出现和伴随的载流子浓度提高很可能源于压力诱导的费米面重构.     

Superconductivity at 43 K in an iron-based layered compound LaO(1-x)F(x)FeAs

The iron- and nickel-based layered compounds LaOFeP (refs 1, 2) and LaONiP (ref. 3) have recently been reported to exhibit low-temperature superconducting phases with transition temperatures T(c) of 3 and 5 K, respectively. Furthermore, a large increase in the midpoint T(c) of up to approximately 26 K has been realized in the isocrystalline compound LaOFeAs on doping of fluoride ions at the O2- sites (LaO(1-x)F(x)FeAs). Experimental observations and theoretical studies suggest that these transitions are related to a magnetic instability, as is the case for most superconductors based on transition metals. In the copper-based high-temperature superconductors, as well as in LaOFeAs, an increase in T(c) is often observed as a result of carrier doping in the two-dimensional electronic structure through ion substitution in the surrounding insulating layers, suggesting that the application of external pressure should further increase T(c) by enhancing charge transfer between the insulating and conducting layers. The effects of pressure on these iron oxypnictide superconductors may be more prominent than those in the copper-based systems, because the As ion has a greater electronic polarizability, owing to the covalency of the Fe-As chemical bond, and, thus, is more compressible than the divalent O2- ion. Here we report that increasing the pressure causes a steep increase in the onset T(c) of F-doped LaOFeAs, to a maximum of approximately 43 K at approximately 4 GPa. With the exception of the copper-based high-T(c) superconductors, this is the highest T(c) reported to date. The present result, together with the great freedom available in selecting the constituents of isocrystalline materials with the general formula LnOTMPn (Ln, Y or rare-earth metal; TM, transition metal; Pn, group-V, 'pnicogen', element), indicates that the layered iron oxypnictides are promising as a new material platform for further exploration of high-temperature superconductivity.     

Aluminium control of argon solubility in silicate melts under pressure

Understanding of the crystal chemistry of the Earth's deep mantle has evolved rapidly recently with the gradual acceptance of the importance of the effect of minor elements such as aluminium on the properties of major phases such as perovskite. In the early Earth, during its formation and segregation into rocky mantle and iron-rich core, it is likely that silicate liquids played a large part in the transport of volatiles to or from the deep interior. The importance of aluminium on solubility mechanisms at high pressure has so far received little attention, even though aluminium has long been recognized as exerting strong control on liquid structures at ambient conditions. Here we present constraints on the solubility of argon in aluminosilicate melt compositions up to 25 GPa and 3,000 K, using a laser-heated diamond-anvil cell. The argon contents reach a maximum that persists to pressures as high as 17 GPa (up to 500 km deep in an early magma ocean), well above that expected on the basis of Al-free melt experiments. A distinct drop in argon solubility observed over a narrow pressure range correlates well with the expected void loss in the melt structure predicted by recent molecular dynamics simulations. These results provide a process for noble gas sequestration in the mantle at various depths in a cooling magma ocean. The concept of shallow partial melting as a unique process for extracting noble gases from the early Earth, thereby defining the initial atmospheric abundance, may therefore be oversimplified.     

方解石晶体的低压冲击压缩特性

在57mm气炮上采用与电磁粒子速度计相结合的正向冲击和反向冲击两种 实验构形及其相应分析技术,研究了方解石晶体（初始密度为2．714g/cm^3）的冲击压缩特性,获得了0．35－1．41GPa下方解石晶体的雨贡纽数据,确定了冲击波速度D与粒子速度u的关系。     

Partial melting of the dry mafic continental crust: Implications for petrogenesis of C-type adakites

C-type adakites have been commonly considered as a result of partial melting of the mafic lower continental crust (LCC) at high pressure, as supported by high P-T experiments on hydrous basalts. However, because the mafic eclogitic LCC is generally dry, experiments on water-bearing materials cannot be used to constrain the melting processes of the dry mafic LCC. Due to the lack of systematic melting experimental studies on dry mafic rocks at crustal pressures, MELTs software was applied to simulating melting of the dry mafic LCC at 1–2 GPa. Comparison of model results with experimental data indicates that, when melting degree is greater than 20%, melts from the dry mafic LCC at 1–3 GPa cannot produce the C-type adakitic melt with high SiO₂ content (~70%). Although the limited experimental results about dry mafic rock melting at 1–2 GPa in the literature suggest that low degree melting (<10%) cannot produce silicic melt either, MELTs software simulation shows that, at pressure >1.8 GPa, low-degree melting can produce dacitic melt with high K₂O/Na₂O (~1) if SiO₂ content of the melt is controlled by residual garnet. Furthermore, the simulation also suggests that, if pressure is <1.8 GPa, abundant plagioclase (plg) in the residual phase may decrease SiO₂ content in the melt to below 62%, much lower than that of the C-type adakites observed in eastern China. Given the high P-T conditions required to produce melts with high SiO₂ and extremely low HREE contents, such melts could easily be contaminated by other crustal-derived melts, implying that the C-type adakites from eclogite melting could be less commonly observed in the outcrops than previously believed. Besides the interpretation that garnet fractionates Sr, Y, and REE, high Sr/Y and La/Yb could be also produced by multiple ways such as inheriting the source features and fractional crystallizing clinopyroxene (cpx). Therefore, it may be problematic using high Sr/Y and La/Yb as criteria to identify adakites. Instead, REE patterns with strong depletion of HREE relative to MREE (e.g. high Gd/Yb) could be a better parameter to identify the role of garnet and thus adakites. Finally, geochemical models based on MELTs simulation indicate that Eu anomaly cannot be simply used to constrain the role of plg in magmatism because Eu anomaly in the melt is a function of source characteristics, oxygen fugacity (fO₂) of magmatic systems, and plg/mafic minerals mode ratio.     

FeO熔化曲线的分子动力学模拟

利用壳层模型分子动力学方法,研究了高温高压条件下FeO的熔化温度,同时还计算了温度在300K及压强上升到140 GPa时FeO的状态方程.作者在研究中,考虑了分子动力学模拟熔化存在的过热现象,通过晶体的现代熔化理论,对FeO的分子动力学模拟熔化温度进行了修正,获得了高温高压下FeO正确的熔化温度.因此,为常压下利用壳层模型分子动力学研究物质熔化提供了一种较好的方法,该方法亦可进一步推广应用到其它物质的高压熔化研究工作.     

High-pressure sound velocity of perovskite-enstatite and the possible composition of the Earth's lower mantle

The compressional sound velocity VP for enstatite of polycrystalline specimens were measured at pressures from 40 to 140 GPa using the optical analytical techniques under shock loading. The dependence of VP (in km/s) on Hugoniot pressure (P, in GPa) can be described by lnVP = 3.079-0.691 ln(P ) + 0.094(lnP )2. VP satisfies Birch's law: VP = 4.068 + 1.677r, where ρ is corresponding density, which indicated that enstatite is stable throughout the conditions of the lower mantle. The wave velocity P is 0.5% lower and the wave velocity S is 2% higher than that of PREM respectively. We concluded that the lower mantle is mainly composed of perovskite-(Mg1-x, Fex) SiO3 and only a small amount of (Mg1-x, Fex) O is allowed in it.     

Pressure-induced amorphization and an amorphous-amorphous transition in densified porous silicon.

Crystalline and amorphous forms of silicon are the principal materials used for solid-state electronics and photovoltaics technologies. Silicon is therefore a well-studied material, although new structures and properties are still being discovered. Compression of bulk silicon, which is tetrahedrally coordinated at atmospheric pressure, results in a transition to octahedrally coordinated metallic phases. In compressed nanocrystalline Si particles, the initial diamond structure persists to higher pressure than for bulk material, before transforming to high-density crystals. Here we report compression experiments on films of porous Si, which contains nanometre-sized domains of diamond-structured material. At pressures larger than 10 GPa we observed pressure-induced amorphization. Furthermore, we find from Raman spectroscopy measurements that the high-density amorphous form obtained by this process transforms to low-density amorphous silicon upon decompression. This amorphous-amorphous transition is remarkably similar to that reported previously for water, which suggests an underlying transition between a high-density and a low-density liquid phase in supercooled Si (refs 10, 14, 15). The Si melting temperature decreases with increasing pressure, and the crystalline semiconductor melts to a metallic liquid with average coordination approximately 5 (ref. 16).     

根据铁的熔化热校正铁基二元相图富铁端的固相线

根据铁的熔化热数据，校正了铁与合金元素的二元相图富铁端的固相线，并根据校正后固相线余率与液相线斜率之比值，求出了合金元素在固、液相中分配比的校正值。此值与Ｃｈｉｐｍａｎ得到的数据很接近。     

用水蒸汽吸附法测定毛细管压力

本文叙述了一种测定储集岩毛细管压力的新方法。选用某些无机盐的饱和溶液来控制平衡压力,在真空装置上,通过等温吸附实验,测定了两种天然岩心试样在低饱和度下的毛细管压力,结果与脱附法一致。在双对数坐标图上,毛细管压力与含水饱和度呈线性关系,但平衡时间大大缩短。     

Electronic and structural transitions in dense liquid sodium

At ambient conditions, the light alkali metals are free-electron-like crystals with a highly symmetric structure. However, they were found recently to exhibit unexpected complexity under pressure. It was predicted from theory--and later confirmed by experiment--that lithium and sodium undergo a sequence of symmetry-breaking transitions, driven by a Peierls mechanism, at high pressures. Measurements of the sodium melting curve have subsequently revealed an unprecedented (and still unexplained) pressure-induced drop in melting temperature from 1,000 K at 30 GPa down to room temperature at 120 GPa. Here we report results from ab initio calculations that explain the unusual melting behaviour in dense sodium. We show that molten sodium undergoes a series of pressure-induced structural and electronic transitions, analogous to those observed in solid sodium but commencing at much lower pressure in the presence of liquid disorder. As pressure is increased, liquid sodium initially evolves by assuming a more compact local structure. However, a transition to a lower-coordinated liquid takes place at a pressure of around 65 GPa, accompanied by a threefold drop in electrical conductivity. This transition is driven by the opening of a pseudogap, at the Fermi level, in the electronic density of states--an effect that has not hitherto been observed in a liquid metal. The lower-coordinated liquid emerges at high temperatures and above the stability region of a close-packed free-electron-like metal. We predict that similar exotic behaviour is possible in other materials as well.