Synthesis of ultra-incompressible superhard rhenium diboride at ambient pressure

The quest to create superhard materials rarely strays from the use of high-pressure synthetic methods, which typically require gigapascals of applied pressure. We report that rhenium diboride (ReB2), synthesized in bulk quantities via arc-melting under ambient pressure, rivals materials produced with high-pressure methods. Microindentation measurements on ReB2 indicated an average hardness of 48 gigapascals under an applied load of 0.49 newton, and scratch marks left on a diamond surface confirmed its superhard nature. Its incompressibility along the c axis was equal in magnitude to the linear incompressibility of diamond. In situ high-pressure x-ray diffraction measurements yielded a bulk modulus of 360 gigapascals, and radial diffraction indicated that ReB2 is able to support a remarkably high differential stress. This combination of properties suggests that this material may find applications in cutting when the formation of carbides prevents the use of traditional materials such as diamond.     

"Debye-Scherrer Ellipses" from 3D fullerene polymers: An anisotropic pressure memory signature

High-pressure studies on fullerenes have previously shown the existence of one- and two-dimensional (2D) polymerized C60 structures. Synchrotron radiation measurements, performed on C60 samples quenched from 13 gigapascals and 820 kelvin, yield unambiguous proof for the existence of a three-dimensional (3D) polymerized C60 derivative. Moreover, unusual ellipsoidal Debye-Scherrer diffraction patterns are observed, which shows that the giant anisotropic deformation induced by the nonhydrostatic compression is retained in the quenched samples. The multiple bonding possibilities of the highly symmetrical C60 allow the retention (down to ambient pressure) of the deformation, a phenomenon reported previously only under high pressure.     

Bonding changes in compressed superhard graphite

Compressed under ambient temperature, graphite undergoes a transition at approximately 17 gigapascals. The near K-edge spectroscopy of carbon using synchrotron x-ray inelastic scattering reveals that half of the pi-bonds between graphite layers convert to sigma-bonds, whereas the other half remain as pi-bonds in the high-pressure form. The x-ray diffraction pattern of the high-pressure form is consistent with a distorted graphite structure in which bridging carbon atoms between graphite layers pair and form sigma-bonds, whereas the nonbridging carbon atoms remain unpaired with pi-bonds. The high-pressure form is superhard, capable of indenting cubic-diamond single crystals.     

Phase Composition of Commercial "Ammonium Carbonate"

A unique crystalline phase was the sole constituent in newly opened containers of commercial reagent-grade "ammonium carbonate." The chemical composition, optical constants, x-ray powder diffraction pattern, infrared absorption spectrum, and density indicate a double salt, ammonium bicarbonate-carbamate (NH(4)HCO(3).NH(4) CO(2)NH(2)), which is unstable in air at ambient temperature and decomposes rapidly to ammonium bicarbonate.     

Nickel orthouronate: high-pressure synthesis

The compound NiUO(4) has been synthesized at high pressure and temperature. No material of this composition is known to be synthesized at ambient pressure. The NiUO(4) structure is of the orthorhombic body centered MgUO(4) type; cell dimensions: a(1), 6.415 A; a(2) 6.435 A; and a(3), 6.835 A.     

Nitric oxide reduction coupled with carbon monoxide oxidation in the presence of soluble metal catalysts

Solutions of RhCl(3).xH(2)O in ethanol and Ru(NO)(2)[P(C(6)H(5))(3)](2) in benzene catalyze the reduction of nitric oxide to nitrous oxide concomitant with the oxidation of carbon monoxide to carbon dioxide at ambient temperature and atmospheric pressure. The reaction, which is followed by gas chromatography and by the decrease in pressure of the system, proceeds to 47 percent conversion of the reactants after 63 hours.     

Elasticity of single-crystal MgO to 8 gigapascals and 1600 kelvin

The cross pressure (P) and temperature (T) dependence of the elastic moduli (Cij) of single-crystal samples of periclase (MgO) from acoustic wave travel times was measured with ultrasonic interferometry: partial differential2C11/ partial differentialP partial differentialT = (-1.3 +/- 0.4) x 10(-3) per kelvin; partial differential2C110/ partial differentialP partial differentialT = (1. 7 +/- 0.7) x 10(-3) per kelvin; and partial differential2C44/ partial differentialP partial differentialT = (-0.2 +/- 0.3) x 10(-3) per kelvin. The elastic anisotropy of MgO decreases with increasing pressure at ambient temperature, but then increases as temperature is increased at high pressure. An assumption of zero cross pressure and temperature derivatives for the elastic moduli underestimates the elastic anisotropy and overestimates the acoustic velocities of MgO at the extrapolated high-pressure and high-temperature conditions of Earth's mantle.     

High-Pressure Synthesis of Molybdates with the Wolframite Structure

A series of small cation molybdates, MgMoO(4), MnMoO(4), FeMoO(4), CoMoO(4), NiMoO(4), and ZnMoO(4) with the wolframite structure characteristic of the corresponding tungstates have been synthesized at high pressure and temperature. The high-pressure compounds revert to the ambient pressure modifications if heated in air at 600 degrees C.     

Pressure Dependence of Superconductivity in Single-Phase K3C60

The superconducting compound K(3)C(60) (with transition temperature T(c) = 19.3 kelvin at ambient pressure), formed as a single phase by reaction of alkali vapor with solids of the icosahedral C(60) molecule (buckminsterfullerene), shows a very large decrease of T(c) with increasing pressure. Susceptibility measurements on sintered pellets showing bulk superconductivity are reported up to 21 kilobars of pressure, where T(c) is already less than 8 kelvin. The results are consistent with a piling up of the density of states at the Fermi level.     

Pressure-induced coordination changes in alkali-germanate melts: an in situ spectroscopic investigation

The structure of liquid Na(2)Ge(2)O(5).H(2)O, a silicate melt analog, has been studied with Raman spectroscopy to pressures of 2.2 gigapascals. Upon compression, a peak near approximately 240 wavenumbers associated with octahedral GeO(6) groups grows relative to a peak near approximately 500 wavenumbers associated with tetrahedral GeO(4) groups. This change corresponds to an increase in octahedral germanium in the liquid from near 0% at ambient pressures to >50% at a pressure of 2.2 gigapascals. Silicate liquids plausibly undergo similar coordination changes at depth in the Earth. Such structural changes may generate decreases in the fusion slopes of silicates at high pressures as well as neutrally buoyant magmas within the transition zone of the Earth's mantle.     

Protonic diffusion in high-pressure ice VII

Near ambient pressures, molecular diffusion dominates protonic diffusion in ice. Theoretical studies have predicted that protonic diffusion will dominate at high pressures in ice. We measured the protonic diffusion coefficient for the highest temperature molecular phase of ice VII at 400 kelvin over its entire stable pressure region. The values ranged from 10(-17) to 10(-15) square meters per second at pressures of 10 to 63 gigapascals. The diffusion coefficients extrapolated to high temperatures close to the ice VII melting curve were less by a factor of 10(2) to 10(3) than a superionic criterion of approximately 10(-8) square meters per second, at which protons would diffuse freely.     

立方尖晶石C3N4硬度的理论研究

基于密度泛函理论的第一性原理,在广义梯度近似和局域密度近似下,计算了立方尖晶石C3N4的体变模量,切变模量和维氏硬度。结果表明：维氏硬度相对于体变模量和切变模量能更好地描述立方尖晶石C3N4的硬度,C3N4的维氏硬度约为72GPa,且有较高的电子密度,较短的键长和较大的共价性。     

肺动脉高压和脂质过氧化作用对肉鸡肺血管重构的影响

【目的】对比观察常温和低温饲养条件下肉鸡肺动脉压、血液脂质过氧化水平和肺阻力血管显微结构的变化，以探讨肺血管重构的机理及其在肉鸡肺动脉高压综合征(PHS)形成中的病理意义。【方法】商品代艾维茵肉鸡180羽，14日龄时随机分为两组, 一组为常温对照组，按常规饲养；一组为低温诱病组。试验过程中连续测定肉鸡平均肺动脉压（mPAP）、右心/全心比（RV/TV）；测定血浆超氧化物歧化酶（SOD）、谷胱甘肽过氧化物酶（GSH-Px）活性和丙二醛（MDA）水平；采集肺组织进行弹力纤维染色,应用计算机图像分析系统测定肺小动脉平均中膜厚度（mMTPA）和相对中膜面积（WA/TA）。【结果】低温组mPAP， RV/TV值和血浆MDA浓度比常温组显著升高；低温组肉鸡肺小动脉mMTPA和WA/TA显著高于常温组；回归分析表明,血浆MDA值与mMTPA，WA/TA显著正相关， mPAP与mMTPA，WA/TA亦呈显著正相关。【结论】低温条件下肉鸡体内脂质过氧化作用增强、肺动脉压升高，导致肺血管重构并进一步升高肺动脉压，这一改变是低温诱导肉鸡PHS形成的重要病理基础之一。     

负压场中木材平衡含水率的探索

为了初步探明负压场中木材平衡含水率如何受相对湿度、温度和绝对压力的影响,以俄罗斯产落叶松(Larix gmelinii Rupr.)小试件为试验对象,采用称重法测量真空罐内相对湿度40%~90%、温度45~70℃、绝对压力30~70kPa范围内木材的平衡含水率。在此基础上分析相对湿度、温度和绝对压力对木材平衡含水率的影响。结果表明：相对湿度从40%升高到90%,平衡含水率从6.13%增大到13.18%(50 kPa, 60℃);温度从45℃升高到70℃,平衡含水率从16.60%降低到8.40%(70%, 50 kPa);绝对压力从30 kPa提高到70 kPa,平衡含水率从6.66%减小到6.02%(50%, 70℃)。因此,负压场中木材平衡含水率随相对湿度升高而增大,随温度、绝对压力的升高而减小。     

Oxygen-Carrying Properties of a Simple Synthetic System

An iridium compound, chloro-carbonyl-bis(triphenylphosphine)-iridium, in solution, takes up molecular oxygen-one molecule per metal atom-which is subsequently recovered by reducing the pressure. The adduct is photosensitive but otherwise stable at ambient temperatures. It is a monomeric molecular complex and probably contains a peroxo group with both oxygens bonded to the same metal atom.     

New phases of c60 synthesized at high pressure

The fullerene C(60) can be converted into two different structures by high pressure and temperature. They are metastable and revert to pristine C(60) on reheating to 300 degrees C at ambient pressure. For synthesis temperatures between 300 degrees and 400 degrees C and pressures of 5 gigapascals, a nominal face-centered-cubic structure is produced with a lattice parameter a(o) = 13.6 angstroms. When treated at 500 degrees to 800 degrees C at the same pressure, C(60) transforms into a rhombohedral structure with hexagonal lattice parameters of a(o) = 9.22 angstroms and c(o) = 24.6 angstroms. The intermolecular distance is small enough that a chemical bond can form, in accord with the reduced solubility of the pressure-induced phases. Infrared, Raman, and nuclear magnetic resonance studies show a drastic reduction of icosahedral symmetry, as might occur if the C(60) molecules are linked.     

立式内浮顶油罐瘪罐现象分析

针对立式内浮顶油罐遭受热带风暴侵袭后瘪罐事故屡有发生的现象,采用ANSYS软件建立有限元模型,对立式油罐进行了几何非线性分析,计算得出风压导致的变形量较小,表明风压对瘪罐事故的影响较小。同时,对呼吸阀的输送能力进行了分析,结果表明,温度骤降时机械呼吸阀换气量不足是导致事故的主要原因。根据分析结果,提出了提高储罐安全性的建议。     

Single-crystal elastic properties of the modified spinel (Beta) phase of magnesium orthosilicate

The single-crystal elastic moduli of the modified spinel structure (beta phase) of magnesium orthosilicate (Mg(2)SiO(4)) have been measured by Brillouin spectroscopy under ambient conditions. Single crystals with dimensions up to 500 micrometers were grown at 22 gigapascals and 2000 degrees C over a period of 1 hour. Growth of crystals larger than 100 micrometers was achieved only when the pressure was within 5 percent of the pressure of the phase boundary separating the beta- and gamma-phase stability fields. A comparison of the elastic properties of the modified spinel phase with those of the olivine phase suggests that the 400-kilometer seismic discontinuity in the earth's mantle can be described by a mantle with 40 percent olivine. These results confirm that the 400-kilometer discontinuity can be due to the transition from olivine to modified spinel. The amount of olivine that must be present is less than that in a pyrolite model, although the results do not exclude pyrolite as a possible mantle model.     

Rising CO2 levels and the fecundity of forest trees

We determined the reproductive response of 19-year-old loblolly pine (Pinus taeda) to 4 years of carbon dioxide (CO2) enrichment (ambient concentration plus 200 microliters per liter) in an intact forest. After 3 years of CO2 fumigation, trees were twice as likely to be reproductively mature and produced three times as many cones and seeds as trees at ambient CO2 concentration. A disproportionate carbon allocation to reproduction under CO2 enrichment results in trees reaching maturity sooner and at a smaller size. This reproductive response to future increases in atmospheric CO2 concentration is expected to change loblolly dispersal and recruitment patterns.     

High-throughput synthesis of zeolitic imidazolate frameworks and application to CO2 capture

A high-throughput protocol was developed for the synthesis of zeolitic imidazolate frameworks (ZIFs). Twenty-five different ZIF crystals were synthesized from only 9600 microreactions of either zinc(II)/cobalt(II) and imidazolate/imidazolate-type linkers. All of the ZIF structures have tetrahedral frameworks: 10 of which have two different links (heterolinks), 16 of which are previously unobserved compositions and structures, and 5 of which have topologies as yet unobserved in zeolites. Members of a selection of these ZIFs (termed ZIF-68, ZIF-69, and ZIF-70) have high thermal stability (up to 390 degrees C) and chemical stability in refluxing organic and aqueous media. Their frameworks have high porosity (with surface areas up to 1970 square meters per gram), and they exhibit unusual selectivity for CO2 capture from CO2/CO mixtures and extraordinary capacity for storing CO2: 1 liter of ZIF-69 can hold approximately 83 liters of CO2 at 273 kelvin under ambient pressure.