Active sites deterioration of MgCl2‐supported catalyst induced by the electron donor extraction by alkylaluminium

To investigate the role of the internal donor in a Ziegler–Natta catalyst, the nature and existing states of the internal donor were intentionally varied by alkylaluminium treatment before polymerization, and the catalytic properties during propene polymerization were accurately evaluated using the stopped‐flow method. A significant decrease in the amount of the remaining internal donor was observed during the initial stage of the extraction. The polymerization results show a gradual decrease in the polymer isotacticity with an increase in the extraction time. These different patterns, as a function of the extraction time, indicate that the amount of the remaining internal donor is not directly related to the isotacticity of the produced polymer. © 2002 Society of Chemical Industry     

Ultra-high-precision time control system over any long time delay for laser pump and synchrotron x-ray probe experiment

An ultra-high-precision clock system for long time delay has been developed for picosecond time-resolved x-ray diffraction measurements using synchrotron radiation (SR) pulses and synchronized femtosecond laser pulses. The time delay control between pump laser pulse and the probe SR pulse was achieved by combining an in-phase quadrature modulator and a synchronous counter. This method allowed us to change the delay time by a nearly infinite amount while maintaining the precision of +/-8.40 ps. Time-resolved diffraction measurements using the delay control system were demonstrated for precise measurement of an acoustic velocity in a single crystal of gallium arsenide.     

Influence of Element Substitution on Corrosion Behavior of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Based Compounds

Atmospheric water may condense on the surface of Bi₂Te₃-based compounds constituting the Peltier module, depending on the operating environment used. In the stage of disposal, Bi₂Te₃-based compounds may come into contact with water in waste disposal sites. There are very few publications about the influence of condensed water on Peltier modules. Bi₂Te₃-Sb₂Te₃ or Bi₂Te₃-Bi₂Se₃ pseudo binary system compounds are used as p-type material or n-type material, respectively. The lattice distortion will be induced in the crystal of Bi₂Te₃-based compounds by element substitution due to the reduction in their thermal conductivity. However, the influence of element substitution on the corrosion behavior of Bi₂Te₃-based compounds remains unclear. In this study, the influence of element substitution on the corrosion behavior of Bi₂Te₃-based compounds with practical compositions has been investigated. Bi_0.5Sb_1.5Te₃ or Bi₂Te_2.85Se_0.15 was prepared by the vertical Bridgman method. The electrochemical properties at room temperature were evaluated by cyclic voltammetry in a standard three-electrode cell. The working electrolyte was a naturally aerated 0.6 or 3.0 mass% NaCl solution. From the tendency for corrosion potential for all the samples, the corrosion sensitivity of ternary compounds was slightly higher than that of binary compounds. From the trend of current density, it was found that Bi_0.5Sb_1.5Te₃ had a corrosion resistance intermediate between Bi₂Te₃ and Sb₂Te₃. On the other hand, corrosion resistance was affected despite a small amount of Se substitution, and the corrosion resistance of Bi₂Te_2.85Se_0.15 was close to or lower than that of Bi₂Se₃. From the observation results of the corrosion products, the trends of morphology and composition of corrosion products for Bi_0.5Sb_1.5Te₃ or Bi₂Te_2.85Se_0.15 were consistent with those of Sb₂Te₃ or Bi₂Se₃, respectively. From the results of x-ray photoelectron spectroscopy for the electrolyte after testing, the possibility that a corrosion product diffuses to the environment including the salt was suggested in Bi_0.5Sb_1.5Te₃. However, the amount of dissolved corrosion product was very low, and the chemical stability of the corrosion product was not changed or improved by element substitution.     

Sodium‐Ion Batteries: Building Effective Layered Cathode Materials with Long‐Term Cycling by Modifying the Surface via Sodium Phosphate

Surface stabilization of cathode materials is urgent for guaranteeing long‐term cyclability, and is important in Na cells where a corrosive Na‐based electrolyte is used. The surface of P2‐type layered Na_2/3[Ni_1/3Mn_2/3]O₂ is modified with ionic, conducting sodium phosphate (NaPO₃) nanolayers, ≈10 nm in thickness, via melt‐impregnation at 300 °C; the nanolayers are autogenously formed from the reaction of NH₄H₂PO₄ with surface sodium residues. Although the material suffers from a large anisotropic change in the c‐axis due to transformation from the P2 to O2 phase above 4 V versus Na⁺/Na, the NaPO₃‐coated Na_2/3[Ni_1/3Mn_2/3]O₂/hard carbon full cell exhibits excellent capacity retention for 300 cycles, with 73% retention. The surface NaPO₃ nanolayers positively impact the cell performance by scavenging HF and H₂O in the electrolyte, leading to less formation of byproducts on the surface of the cathodes, which lowers the cell resistance, as evidenced by X‐ray photoelectron spectroscopy and time‐of‐flight secondary‐ion mass spectroscopy. Time‐resolved in situ high‐temperature X‐ray diffraction study reveals that the NaPO₃ coating layer is delayed for decomposition to Mn₃O₄, thereby suppressing oxygen release in the highly desodiated state, enabling delay of exothermic decomposition. The findings presented herein are applicable to the development of high‐voltage cathode materials for sodium batteries.     

Predicting Solid–Liquid Equilibrium of Fatty Acid Methyl Ester and Monoglyceride Mixtures as Biodiesel Model Fuels

Fatty acid methyl esters from plant oils are the main component of biodiesel and used as a substitute for petroleum diesel. Biodiesel generally contains a small amount of monoglycerides as intermediate compounds, which have high melting points and often solidify and clog fuel filters. The prediction of the cold-flow property of biodiesel is of great importance for practical application. In this study, a thermodynamic study was conducted for mixtures of monoglycerides and fatty acid methyl esters. Temperatures of the solid–liquid equilibrium for the mixtures were measured by differential scanning calorimetry and visual observation, while the theoretical values were calculated using the modified Universal Quasi-chemical Functional-group Activity Coefficients (UNIFAC) model (Dortmund). The theoretical and experimental results were in good agreement, especially for binary mixtures of monoglycerides and methyl esters. The importance of monoglycerides on the cold-flow properties of biodiesel was determined, and the effects could be well described by the modified UNIFAC model (Dortmund).     

考虑脉动风影响的斜拉索在支点激励下的非线性振动

应用柔性拉索的非线性振动响应计算理论,提出考虑横向脉动风荷载作用及支点激励的拉索非线性振动计算方法。以力学特性不同的两种斜拉索为对象,通过数值方法分析横风作用和支点激励下的钢索、CFRP拉索非线性振动响应,比较支点激励频率、风速、阻尼器对参数振动响应的影响。结果表明,在拉索基频f1以及两倍基频2f1的支点位移激励下,脉动风虽然导致拉索出现不规则的竖向和横向水平振动轨迹,但不会改变拉索的参数振动特性;横向风荷载对参数振动具有空气阻尼力的效应;总体上CFRP拉索的参数振动振幅小于钢索,特别当拉索跨度比较大时,CFRP拉索的振幅将明显低于同跨度的钢索;黏性阻尼装置的减振效果与拉索的结构条件有关,当拉索的无量纲参数λ(Irvine参数)较大时,阻尼器的减振效果不明显,反之当λ较小时阻尼器有一定的减振效果。     

Selective catalytic reduction of nitrogen oxides with hydrocarbons over Zn–Al–Ga complex oxides

Selective reduction of NO with hydrocarbons was studied using metal oxide catalysts having a spinel structure. A Zn–Al–Ga complex oxide was found to be very active and selective for the catalytic reduction of NO with both C₃H₆ and CH₄. It was revealed that the role of oxygen at the initial stage of the reaction strongly depends on the reductants; oxygen is mainly used for NO oxidation to NO₂ in the reduction with CH₄, whereas it is used both for NO oxidation to NO₂ and oxidation of C₃H₆ to an active intermediate in the reduction with C₃H₆. This revised version was published online in July 2006 with corrections to the Cover Date.     

快速加热和冷却法制备的极细多芯Nb3Al线材的超导特性

介绍了一种快速加热快速冷却制备接近化学计量的Ｎｂ３Ａｌ极细多芯线材的方法。用四控地测定试样的临界温度为１７Ｋ,用Ｓｐｌｉｔ ｐａｉｒ型磁体测试了试样随温度和磁场变化的临界电流。归一化后的单位体积钉轧力与所加磁场符合Ｋｒａｍｅｒ方程,晶界为可能的磁力线钉扎源。由临界电流得到的上临界磁场与温度呈线性关系,外摊得到临界温度的计算值与实测值基本一致。通过临界电流与温度和磁场的关系得到了Ｉｃ－Ｔ－Ｂ三维临界     

Finishing characteristics of brittle materials by ELID-lap grinding using metal-resin bonded wheels

ELID-lap grinding is a method of constant pressure grinding which utilizes an electrically conductive wheel and the electrolytic in-process dressing (ELID) method. This method has the advantage of using micro grain-wheels above #10 000 and also, through simple modification, can be used on existing lap machines. To find the characteristics of metal-resin bonded wheels developed for ELID-lap grinding, experiments on the grinding of brittle materials were performed using wheels with a variety of grain diameters. The wheels used in the experiments were #8000, #120 000 and #3 000 000 metal-resin bonded diamond wheels (#8000 MRB-D, #120 000 MRB-D and #3 000 000 MRB-D wheels). The workpieces were silicon and glass. The results of the experiments showed that stable grinding can be achieved with the #8000 to #3 000 000 MRB-D wheels. With the #3 000 000 MRB-D wheel, very smooth surface finishes were obtained for both silicon (PV 2.8 nm) and glass (PV 2.5 nm). Atomic Force Microscope (AFM) and Scanning Electron Microscope (SEM) observations indicated these surfaces to be very smooth in the order of several nanometers, obtained by mechanical removal using an ultrafine wheel.