Free volume characteristics of 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole-co-tetrafluoroethylene copolymers: Effect of composition and molecular weight

2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole-co-tetrafluoroethylene (PDD-TFE) copolymer is a good candidate to prepare gas separation membranes with excellent permeability due to its free volume characteristics. However, the influence of PDD-TFE copolymer structure on its free volume characteristics is less studied. In this paper, PDD-TFE copolymers with different compositions and molecular weights were synthesized, and their free volume characteristics were analyzed by positron annihilation lifetime spectroscopy and a molecular dynamics simulation. It indicated that the molar fraction of PDD in copolymers had a significant effect on free volume characteristics, while the molecular weight of copolymers exerted a slight influence on free volume when the molecular weight exceeded a critical region (intrinsic viscosity [η] > 68 ml g⁻¹). PDD-TFE copolymers with greater PDD molar fractions (i.e., 72% and 84%) showed bimodal distributions in positron lifetime and free volume size distributions, while PDD-TFE copolymers with lower PDD molar fractions (i.e., 27% and 35%) exhibited a single peak. The long-lifetime parameter τ₃ was assigned to micro-cavities formed by [-(TFE)_y-PDD-] segments and τ₄ was attributed to micro-cavities formed by [-(PDD)_x-TFE-] segments. The cis and trans transitions of PDD led to a local multilayer spiral structure with a 2.6–4.3 Å layer spacing, which would also increase the free volume of copolymers.     

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.     

基于TPG2000的三路输出线理论设计与仿真

基于单台脉冲功率源产生多路电子束驱动多路微波器件的构想,提出了一种三路螺旋线输出方案,三路脉冲是由同一主脉冲产生,具有时间同步精度高的特点。以Tesla型脉冲功率源TPG2000为基础,经过理论计算,给出了三路输出线理论设计结果,对脉冲传输过程进行了建模仿真和结构优化,得到了三路参数相同的脉冲,其中两路脉冲比另一路延迟20 ns。     

高速电枢的尾翼结构设计及实验研究

设计了T2LXD1系列电枢,分析了6061-T6铝合金材料的弹塑性特点,利用线性强化理论和接触理论并结合ANSYS软件,建立了T2LXD1系列电枢弹塑性接触模型,研究了电枢尾翼结构对电枢/导轨滑动界面接触状态的影响规律,得到了界面接触力、接触面积和接触压力分布等状态参数的数值模拟结果。利用短导轨电磁驱动系统,进行了T2LXD1系列电枢滑行实验,分析了电枢/导轨界面滑磨状态,比较了滑行性能曲线。实验结果表明:长尾翼电枢并不能带来实际接触面积的增     

大口径非球面元件可控气囊抛光系统

根据大口径非球面光学元件的实际加工需要,设计并制造可控气囊抛光系统,并对机构进行运动学仿真,仿真结果表明,气囊自转轴的运动空间可以满足大口径非球面光学元件的连续进动加工要求。为了证明所设计系统的可加工性,以直径320 mm的圆形平面光学元件进行加工实验。经过该气囊抛光工具24 h的抛光后,工件达到较好的面型精度,光学元件的表面粗糙度由0.272减小到0.068(＝632.8 nm), PV值从1.671降低到0.905。对光学元件的实际加工实验结果表明：可控气囊抛光系统在加工过程中结构稳定性好,符合设计要求,可有效提高加工工件面型精度。     

脉冲离子束作用下靶面次级电子的抑制

论述了离子束作用下固体表面次级电子产生的机制,介绍了特种真空器件中次级电子抑制的各种方法及其优缺点,提出了脉冲离子束作用下靶面次级电子抑制的自偏势法和曲面靶法等设计思路,并在实验上进行了初步验证。实验结果表明,自偏势电压大于80 V后,次级电子得到很好的抑制。在相同束流情况下,曲面靶较平面靶的次级电子产额少。利用实验结果进行估算得到了近似的次级电子产额约为0.67,比文献中的结果(0.58)偏大。对实验中自偏势法抑制反峰电子电流的效果进行了分析和讨论,结果表明：自偏势法不但能够有效抑制离子打靶产生的次级电子,还能抑制由功率源不稳定带来的入射反峰电子流。     

Comprehensive Mechanism for CO Electroreduction on Dual-Atom-Catalyst-Anchored N-Doped Graphene

Carbon neutrality has drawn increasing attention for realizing the carbon cyclization and reducing the greenhouse effect. Although the C1 products, such as CO, can be achieved with a high Faraday efficiency, the targeted production of C2 fuels as well as the mechanism have not been systematically investigated. In this work, we carry out a first-principles study to screen dual-atom catalysts (DACs) for producing C2 fuels through the electrocatalytic carbon monoxide reduction reaction (e-CORR). We find that methanol, ethanol and ethylene can be produced on both DAC−Co and DAC−Cu, while acetate can be achieved on DAC−Cu only. Importantly, methanol and ethylene are preferred on DAC−Co, while acetate and ethylene on DAC−Cu. Furthermore, we show that the explicit solvent can enhance the adsorption and influence the protonation steps, which subsequently affects the protonation and dimerization behavior as well as the performance and selectivity of e-CORR on DACs. We further demonstrate that the C−C coupling is easy to be formed and stabilized if the Integrated Crystal Orbital Hamilton Population (ICOHP) is low because of the low energy barrier. Our findings provide not only guidance on the design of novel catalysts for e-CORR, but an insightful understanding on the reduction mechanism.     

Cobalt and nitrogen atoms co-doped porous carbon for advanced electrical double-layer capacitors

Electrical double-laye r capacitors are widely concerned fo r their high power density,long cycling life and high cycling efficiency.However,their wide application is limited by their low energy density.In this study,we propose a simple yet environmental friendly method to synthesize cobalt and nitrogen atoms co-doped porous carbon(CoAT-NC) material.Cobalt atoms connected with primarily pyridinic nitrogen atoms can be uniformly dispersed in the amorphous carbon matrix,which is benefit for improving electrical conductivity and density of states of the carbon material.Therefore,an enhanced perfo rmance is expected when CoAT-NC is served as electrode in a supercapacitor device.CoAT-NC displays a good gravimetric capacitance of 160 F/g at 0.5 A/g combing with outstanding capacitance retention of 90% at an extremely high current density of 100 A/g in acid electrolyte.Furthermore,a good energy density of30 Wh/kg can be obtained in the organic electrolyte.     

内噪声作用下的随机共振算法对弱信号的检测

基于随机共振理论提出了一种简便、有效地检测弱信号的方法。在内噪声协同作用下，通过调节输入噪声信号的大小能较好地提高系统输出信号的信噪比，从而实现检测背景噪声很强的弱信号的目的。应用于模拟信号和实验信号的结果证明了方法是可行的。