“能干而低调”的钨元素

较为详细地介绍了钨元素的发现历程，钨金属与合金、含钨杂多配合物、氧化钨、碳化钨、钨硫族化合物和含有W-W四重键的化合物的应用。     

Lewis Pair Polymerization of Epoxides via Zwitterionic Species as a Route to High‐Molar‐Mass Polyethers

A dual catalytic setup based on N‐heterocyclic olefins (NHOs) and magnesium bis(hexamethyldisilazide) (Mg(HMDS)₂) was used to prepare poly(propylene oxide) with a molar mass (M_n) >500 000 g mol^?1, in some cases even >10⁶ g mol^?1, as determined by GPC/light scattering. This is achieved by combining the rapid polymerization characteristics of a zwitterionic, Lewis pair type mechanism with the efficient epoxide activation by the Mg^II species. Transfer‐to‐monomer, traditionally frustrating attempts at synthesizing polyethers with a high degree of polymerization, is practically removed as a limiting factor by this approach. NMR and MALDI‐ToF MS experiments reveal key aspects of the proposed mechanism, whereby the polymerization is initiated via nucleophilic attack by the NHO on the activated monomer, generating a zwitterionic species. This strategy can also be extended to other epoxides, including functionalized monomers.     

Experimental determination of interfacial energy for solid Al in the Al-Sn-Mg eutectic system with Bridgman-type apparatus

The equilibrated grain boundary groove shape of solid Al in equilibrium with Al-Sn-Mg eutectic liquid was observed by using a Bridgman type directional solidification apparatus. The ratio of the thermal conductivity of the equilibrated liquid to the thermal conductivity of solid Al has been obtained as 0.91. In addition, the average Gibbs-Thomson coefficient, $\bar{\mathrm{\Gamma }}=(4.20\pm 0.35)\times {10}^{-8}\mathrm{Km}$, the solid-liquid interfacial energy, ${\sigma }_{SL}=180.68\pm 23.48\text{mJ}/{\text{m}}^2$ and the grain boundary energy, ${\sigma }_{GB}=309.30\pm 29.47\text{mJ}/{\text{m}}^2$, in the Al/Al-Sn-Mg system have been calculated from the measured grain boundary shapes.     

电阻率与强度性能的关联及铜合金性能分区

铜合金以低电阻率为特征,由于电阻率与强度存在着共同的微观结构机理,两者往往协同变化,而导致难以对合金进行性能的全面评估和选材.本文以Cu-Ni-Mo合金作为研究对象,以团簇结构[Mo_1-Ni_(12)]构建固溶体的近程序结构模型,解析了电阻率和强度依赖于成分的定量变化规律,并定义了拉伸强度/电阻率的值为代表合金本质特性的"强阻比",得到了完全固溶态Cu-Ni-Mo合金的强阻比为7×10~8MPa/?·m,完全析出态的强阻比为(310—490)×10~8MPa/?·m.进而应用强阻比对常用铜合金进行了性能分区,给出铜合金材料选材的依据,得出了基于Cu-(Cr, Zr, Mg, Ag, Cd)等二元基础体系的铜合金适用于高强高导应用,而基于Cu-(Be, Ni, Sn, Fe, Zn, Ti, Al)等为基础二元体系的铜合金不能实现高强高导.该强阻比为310的特征性能分界线的发现为合金性能的全面评估提供了量化依据,可指导高强高导铜合金的选材和研发.     

Chemoselective Chromium(II)‐Catalyzed Cross‐Coupling Reactions of Dichlorinated Heteroaromatics with Functionalized Aryl Grignard Reagents

Chromium(II) chloride catalyzes the chemoselective cross‐coupling reaction of dichloropyridines with a range of functionalized (hetero)aromatic Grignard reagents at room temperature. Functional groups, such as esters and acetals, are well tolerated in this transformation. Previously challenging substrates, quinolines and isoquinolines, participate in the selective Cr‐catalyzed cross‐coupling in cyclopentyl methyl ether (CPME) as the solvent. The effective purging of Cr salts is demonstrated by using various solid supports.     

Molecular dynamic study of temperature dependence of mechanical properties and plastic inception of CoCrCuFeNi high-entropy alloy

Molecular dynamics simulations are performed to study mechanical characteristics and homogeneous plastic inception of CoCrCuFeNi high-entropy alloy at various temperatures under uniaxial tension. It is found that the elastic modulus and ultimate tensile strength increase with temperature decreasing. A notable softening effect is observed at the elastic deformation stage caused by the decrease of the interatomic force gradient. Extrinsic stacking faults and deformation twins are extensively observed, which are formed via intrinsic stacking faults overlap.     

Instantaneous work hardening behaviour of two-phase tungsten heavy alloys: a phenomenological approach

ABSTRACT

The present work describes a phenomenological approach to explain the instantaneous behaviour of tungsten heavy alloys (WHAs) in heat-treated and swaged conditions. The strengths and elongation values of heat-treated materials are lower and higher than those of the swaged samples respectively. The heat-treated materials exhibit two slopes in true stress–true plastic strain curves and follow the Ludwigson constitutive equation. On the other hand, swaged materials display a single slope and adhere to typical Swift constitutive equation. The latter reflect the presence of pre-strain in the materials due to swaging deformation. The fracture surfaces in heat-treated materials consist of W-W decohesion along with matrix rupture and W-cleavage, while swaged samples consist of mainly W-cleavage. Both the materials display three typical stages (I, II and III) of work hardening. The second derivatives of true stress–true plastic strain curves of these alloys exhibit a perfect parabola although the nature of true stress–true strain as well as true stress–true plastic strain curves is quite different in heat-treated and swaged materials. This has been observed for the first time in WHAs consisting of matrix and W-grains. The shape of the parabola is simple and easy to fit. The fitting parameters of parabolas have been successfully employed to explain the flow behaviour of a large number of tungsten heavy alloys having two-phase microstructure in different processing conditions.     

Pyrolytic Carbon‐coated Cu‐Fe Alloy Nanoparticles with High Catalytic Performance for Oxygen Electroreduction

Well‐dispersed carbon‐coated or nitrogen‐doped carbon‐coated copper‐iron alloy nanoparticles (FeCu@C or FeCu@C?N) in carbon‐based supports are obtained using a bimetallic metal‐organic framework (Cu/Fe‐MOF‐74) or a mixture of Cu/Fe‐MOF‐74 and melamine as sacrificial templates and an active‐component precursor by using a pyrolysis method. The investigation results attest formation of Cu?Fe alloy nanoparticles. The obtained FeCu@C catalyst exhibits a catalytic activity with a half‐wave potential of 0.83 V for oxygen reduction reaction (ORR) in alkaline medium, comparable to that on commercial Pt/C catalyst (0.84 V). The catalytic activity of FeCu@C?N for ORR (E_half‐wave=0.87 V) outshines all reported analogues. The excellent performance of FeCu@C?N should be attributed to a change in the energy of the d‐band center of Cu resulting from the formation of the copper–iron alloy, the interaction between alloy nanoparticles and supports and N‐doping in the carbon matrix. Moreover, FeCu@C and FeCu@C?N show better electrochemical stability and methanol tolerance than commercial Pt/C and are expected to be widely used in practical applications.     

Structures,binding energies,temperature effects,infrared spectroscopy of [Mg(NH3)n = 1−10]+ clusters from DFT and MP2 investigations

The possible isomers of [Mg(NH₃)_{n = 1 − 10}]⁺ clusters have been investigated using both M06-2X/6-31++G(d,p) and MP2/6-31++G(d,p) levels of theory. The isomeric distribution for each n size has been studied as a function of temperatures ranging from 25 to 400 K. To the best of our knowledge, for clusters size n > 6, this is the first theoretical study available in the literature. From the calculated values in the considered clusters and using a fitting procedure, we have evaluated the binding energies (−14.0 kcal/mol), clustering energies (−10.1 kcal/mol), clustering free energies (−2.8 kcal/mol), and clustering enthalpies (−10.3 kcal/mol). On the basis of our structural and infrared (IR) spectroscopy outcomes, we find that the first solvation shell can hold up to six ammonia molecules. © 2019 Wiley Periodicals, Inc.