p-CH3C6H4SR型硫醚与钯(II)配合物热分解反应动力学

热重分析(TG)和微商热重法(DTG)广泛应用于各个研究领域,用非等温热重法测定固体化合物的热分解动力学参数已有报导.许多作者提出各种不同的数据处理方法.本文用的ρ-CH_3C_6H_4SR 型硫醚对钯的萃取具有选择性好、分配比高、气味较小、易溶于脂肪烃类溶剂、易于合成、是很有发展前途的一类萃取剂.我们合成五种ρ-CH_3C_6H_4SR(R:n-C_4H_9,n-C_6H_(13),n-C_8H_(17),n-C_(10)H_(21),n-C_(12)H_(25))型硫醚与钯(Ⅱ)的配合物,用TG-DTG 法研究它们的热分解过程,用微商法(Freeman-Carroll 方程)及积分法(Coats-Redfern 方程)获得了这些配合物的热分解动力学参数.     

Effects of C3-aromatic heterocycles on 1,3,5-triaryl-2-pyrazoline sulfonium salt photoacid generators as light-emitting diode-sensitive cationic photoinitiators

Four 1,5-diphenyl-3-aromatic heterocyclyl-2-pyrazoline-based sulfonium salt photoacid generators (PAGs) with different aromatic heterocycles substituted on C3 atom and dimethyl sulfonium group on C5 atom were synthesized. These PAGs were highly photosensitive in the 365–425 nm light-emitting diode region, and the intramolecular charge transfer from the pyrazoline ring to sulfonium salts induced efficient photolysis and high Φ_H⁺. The heterocycles as well as their substituted positions significantly influenced the energy of the S₂ orbital, which was determined by the electrochemical and absorption properties of the PAGs. The raising of the S₂ orbital energy enlarged the energy gap of S₀–S₂ and S₁–S₂, resulting in blue shift of the absorption spectra and increase in the quantum yield of photoacid generation (Φ_H⁺), respectively. When the energy of excited electrons was higher than that of the S₂ orbital, the transition from S₀ to S₂ (π–π*) occurred before the C-S cleavage on S₁ and the PAGs showed high Φ_H⁺ values (0.52–0.72). The transition from S₀ to S₁ (π–σ*) occurred when the energy of electrons is lower than that of the S₂ orbital, and the PAGs showed low Φ_H⁺ value. The photopolymerization kinetics demonstrated that these PAGs were highly efficient cationic photoinitiators.     

水热法制备富锂型Li_(2+4x)Mn_(0.6+2x)Ni_(0.6-6x)Cr_(0.8)O_4及其结构与电化学特性

采用水热法制备了系列富锂尖晶石型正极材料Li2+4xMn0.6+2xNi0.6-6xCr0.8O4(x=1/30,1/20,1/15,1/12),通过X射线衍射(XRD)、电感耦合等离子体-原子发射光谱(ICP-AES)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、傅里叶变换红外光谱(FTIR)、拉曼光谱、循环伏安(CV)和充放电测试等手段对其结构及电化学性能进行表征.结果表明,所制备的系列材料为富锂型高电压尖晶石结构正极材料,该系列样品在4.7 V左右有放电平台.x=1/15和x=1/12时,样品中的Cr为+3价,没有观测到Cr6+.随着x值的增大,样品中Li离子与过渡金属离子的混排减小,样品的充放电比容量逐渐增大,且2.7 V处的放电平台容量也增加.当x=1/12时,样品具有较好的充放电比容量和倍率特性,首次放电比容量为107.3 mA·h/g,20次循环后容量保持率为84.9%.     

复杂大气入流下海上风机力学特性研究

随着风能技术的不断进步, 风机叶片逐渐向大型化发展, 这使得真实复杂大气入流对风机运行性能的影响愈发显著. 为研究真实复杂大气入流下海上风机的力学特性响应, 利用基于大涡模拟的域前模拟方法生成复杂大气入流, 并结合致动线模型模拟风机叶片, 对中性复杂大气入流下海上固定式风机进行数值模拟, 重点分析风机的气动性能及转子和叶片根部的力学特性, 并与均匀入流计算工况进行对比. 计算结果表明, 中性复杂大气入流中的大尺度低速气流团使得风机气动功率输出值在较长一段时间处于较低水平, 此外, 中性复杂大气入流的高湍流强度特征使得风机气动功率的变化幅值和标准差较均匀入流工况大幅增加; 风机轴向推力的标准差值增加到均匀入流的53倍, 中性复杂大气入流的来流流场扰动引起偏航力矩的最大值、均方根和标准差分别增加到均匀入流的10、4.4和4.3倍; 速度垂向分布的不均匀性以及轮毂高度附近的大尺度低速羽流结构导致摆振剪力和弯矩的标准差响应值分别为均匀入流的2倍和4.6倍.      

The thermoelectric power of charge-density-wave conductors Rb0.3MoO3 and Rb0.15K0.15MoO3

The thermoelectric power (TEP) of the quasi-one-dimensional charge-density-wave (CDW) conductors rubidium blue bronze Rb_0.3MoO₃ and its alloy Rb_0.15K_0.15MoO₃ were measured in the temperature range 80-280 K. The result showed a sign change from a small positive value to a great negative value where the Peierls transition temperatures (T_p) are 183 and 180 K for Rb_0.3MoO₃ and Rb_0.15K_0.15MoO₃, respectively. Above T_p, the TEP for both samples can be described with the empirical relation S=AT+B; while below T_p, the TEP fits well the relation S=AT+B/T based on the experimental data. The Fermi energies ε_F for Rb_0.3MoO₃ and Rb_0.15K_0.15MoO₃ are estimated to be 1.55 and 0.53 eV, respectively.     

Synthesis and properties of amphoteric copolymer of 5‐vinyltetrazole and vinylbenzyl phosphonic acid

Amphoteric polymers have been studied for various applications such as separation of low molecular weight organic molecules from inorganic salt mixtures, selective ion transport, drug delivery through membranes of biological interest, separation of ionic drugs and proteins, and separation of alcohol and water. Typical amphoteric polymers consist of weak base and weak acid groups. In present study, the copolymerization of 5‐vinyltetrazole (VT) and diisopropyl‐p‐vinylbenzyl phosphate (DIPVBP) via free radical polymerization is studied. The reactivity ratio of VT and DIPVBP, which is calculated from Kelen‐Tudos plot, is 0.251 and 0.345, respectively. The amphoteric copolymer of VT and diisopropyl‐p‐vinylbenzyl phosphonic acid (poly(VT‐co‐VBPA)) is obtained from hydrolysis of the copolymer of VT and DIPVBP (poly(VT‐co‐DIPVBP)). Poly(VT‐co‐VBPA) is thermally stable under 190 °C. The anhydrous proton conductivity of amphoteric poly(VT‐co‐VBPA) can reach 1.54 × 10^‐4 S cm^?1 at 170 °C with an activation energy of 114.7 kJ mol^?1. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3486–3493     

纳米SiC蓝光发射的研究

在４．６８ｅＶ的激光激发下，室温ＣＶＤ合成的纳米ＳｉＣ粉体，可发射４７５ｎｍ的蓝光，经６００～１１００℃在Ｎ２气氛下进行快速退火（ＲＴＡ）处理，其荧光强度随退火温度升高而增强，当Ｔ≥９００℃时，荧光强度下降，但发光峰位与退火温度无关．通过ＸＲＤ、ＩＲ、ＴＥＭ、ＸＰＳ等研究，认为纳米ＳｉＣ中与氧有关的缺陷可能是引起４７５ｎｍ蓝光发射的主要原因     

On the definable ideal generated by the plus cupping c.e. degrees

In this paper, we will prove that the plus cupping degrees generate a definable ideal on c.e. degrees different from other ones known so far, thus answering a question asked by Li and Yang (Proceedings of the 7th and the 8th Asian Logic Conferences. World Scientific Press, Singapore, 2003).     

对动力修正方法SDM3.0的探讨与改进

本文运用理论分析、实验与计算的结果对引进的美国SMS公司的结构动力修正软件SDM3.0作了比较详细的探讨,指出了SDM3.0的优点、局限性与使用范围.提出了改进这一软件的方法,研制了相应的软件.结果表明:改进后的方法及相应的软件是有效和成功的.     

Computability of measurable sets via effective metrics

We consider how to represent the measurable sets in an infinite measure space. We use sequences of simple measurable sets converging under metrics to represent general measurable sets. Then we study the computability of the measure and the set operators of measurable sets with respect to such representations. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)