第ⅣB族非茂金属烯烃聚合催化剂

烯烃聚合催化剂技术的发展关系着聚烯烃工业的命脉,而第ⅣB族非茂金属烯烃聚合催化剂作为目前催化剂研究的热点之一,不仅具有催化活性高、共聚单体范围广以及聚合物结构可控等优点,并且相比于茂金属催化剂而言,合成简单、成本低廉,有利于丰富烯烃聚合催化剂的种类和开发新型聚烯烃产品。本文按照配体的价齿类型综述了近十年来第ⅣB族非茂金属烯烃聚合催化剂的结构特点,及其在烯烃均聚和共聚反应中的催化性能,讨论了配体的电子效应和位阻效应对于配合物催化活性以及所得聚合物的结构、分子量等性质的影响,并对相关领域的未来发展提出了建议。     

On the Josephson effect between superconductors in singlet and triplet spin-pairing states

An expression is derived for the Josephson current between two weakly coupled superconductors of which one or both have pairs in a spin-triplet state. It is shown that there can be no Josephson effect up to second order in the transition matrix elements between a superconductor with spin-triplet pairs and one with spin-singlet pairs if the coupling between the two superconductors can be described with a spin-conserving tunnel hamiltonian. This is shown to offer a possibility to investigate experimentally whether a particular superconductor has spin-triplet pairs by coupling it weakly to a well-known spin-singlet pairing superconductor.     

毛竹化学成分光谱分析的快速建模方法研究

研究了毛竹综纤维素和木质素含量近红外光谱定量分析方法的建立。选用不同竹龄、纵向和横向部位的54个竹材粉末样品,用湿化学方法测定其综纤维素和木质素含量。在综纤维素和木质素含量的分布范围内,从低值、中间值和高值中挑选11个代表性样品,11个样品按预定比例混合得到21个混合样品,混合样品的综纤维素和木质素含量计算得到,再挑选22个目标成分含量不同的样品组成54个样品的校正集。用偏最小二乘法分别建立样品综纤维素含量、木质素含量和近红外漫发射光谱之间的相关模型。结果表明,综纤维素含量的预测模型的相关系数(R_p)为0.92,标准偏差(SEP)为1.04％;木质素含量的预测模型的R_p为0.93,SEP为0.91％,与常规方法建立的模型预测精度相似。说明利用样品混合的方式可快速增加校正集样品的数量、改善校正集样品的分布状况,继而建立稳定可靠的近红外定量分析模型。     

Expanding new chemistry of aza-boracyclophanes with unique dipolar structures,AIE and redox-active open-shell characteristics

π-Conjugated macrocycles involving electron-deficient boron species have received increasing attention due to their intriguing tunable optoelectronic properties. However, most of the reported B(sp²)-doped macrocycles are difficult to modify due to the synthetic challenge, which limits their further applications. Motivated by the research of non-strained hexameric bora- and aza-cyclophanes, we describe a new class of analogues MC-BN5 and MC-ABN5 that contain charge-reversed triarylborane (Ar₃B) units and oligomeric triarylamines (Ar₃N) in the cyclics. As predicted by DFT computations, the unique orientation of the donor–acceptor systems leads to an increased dipole moment compared with highly symmetric macrocycles (M1, M2 and M3), which was experimentally represented by a significant solvatochromic effect with large Stokes shifts up to 12 318 cm⁻¹. Such a ring-structured design also allows the easy peripheral modification of aza-boracyclophanes with tetraphenylethenyl (TPE) groups, giving rise to a change in the luminescence mechanism from aggregation-caused quenching (ACQ) in MC-BN5 to aggregation-induced emission (AIE) in MC-ABN5. The open-shell characteristics have been chemically enabled and were characterized by UV-Vis-NIR spectroscopy and electron paramagnetic resonance (EPR) for MC-BN5. The present study not only showed new electronic properties, but also could expand the research of B/N doped macrocycles into the future scope of supramolecular chemistry, as demonstrated in the accessible functionalization of ring systems.

We have achieved the synthesis of new B/N doped macrocycles by stitching oligoarylamine pentamers using arylborane acceptor segments. They exhibit open-shell radical species and AIE under ambient conditions.     

Development of hydrides for motor vehicles

The storage of hydrogen in metal hydrides is suitable for motor vehicles as well as for stationary applications. Since the metal hydrides are used both for fuel and for heat storage some interesting technical developments are possible. The development and applications of low and high temperature hydrides are reported and the solutions of some technical problems (e.g. improvement of heat transfer and hydride manufacture) are presented.     

基于Simulink大功率电子管放大器仿真

选用4616V4型四极电子管,单管输出350 kW,采用两路并行放大链路,设计了一套输出功率350 kW2的大功率电子管功率源系统。基于四极电子管的恒流特性曲线及实验数据,拟合输出功率与阳极电压、输入功率的关系曲线,利用Origin软件拟合函数,建立数学模型,并利用闭环比例-积分(PI)反馈控制,稳定输出电压,通过Simulink仿真探寻最佳工作点,较低的阳极电压以及近饱和的输入功率既能有效增大工作频率,又能满足高功率输出的要求,仿真结果与实际联机调试数据对比,误差低于5%,根据仿真数据得到的结论与13点分析法一致,可以有效指导探寻最佳工作点。     

基于Visco-SCRAM模型的侵彻装药点火研究

针对弹体侵彻过程中装药的安全性,基于黏弹性统计裂纹力学(visco-statistical crack mechanics, Visco-SCRAM)模型计算装药整体温升、装药裂纹摩擦生热以及弹体装药与壳体摩擦生热,考察这3种机制对装药温升的贡献以及侵彻装药的点火机制,得到了装药点火对应的弹体侵彻临界初始速度。结果表明：(1)装药与弹体内壁摩擦生热对装药温升有一定贡献,随着弹体初始撞击速度的提高,摩擦生热对温升的贡献逐渐增大;(2)黏性、损伤和绝热体积变化导致的装药整体温升对装药点火的作用有限; (3)裂纹摩擦形成热点是侵彻装药点火的物理机制;(4)采用Visco-SCRAM模型可预测低强度、长脉冲载荷作用下的装药点火响应。

     

Thermodynamics of solvent extraction processes: Effect of diluent on the enthalpy of formation of tri-n-octylammonium chloride

Four thermodynamic functions, pK, ΔH, ΔS and ΔG, of neutralization of tri-n-octylamine by hydrogen chloride, R₃N + HCl ⇌ R₃NHCl, in benzene, cyclohexane and chloroform have been determined calorimetrically at 303.15K. The free energy changes of the neutralization reaction indicate that the stability of the triocylammonium chloride formed increases from cyclohexane to benzene to chloroform. This is the order of decreasing tendency of the salt toward aggregation. It is suggested that the phenomenon is due to the difference in solvation between the amine base and the ammonium salt in any one solvent, rather than to the effect of solvation of the salt alone.