强短脉冲供电时空心阴极灯的放电特性研究

空心阴极灯是原子光谱分析中常用的线光源。对它的光谱和放电特性的研究已有报道,但多为针对直流供电或一般脉冲供电状态时的空心阴极灯。黄本立等报道了市售空心阴极灯在强短脉冲供电时的时间分辩光谱特性及其作为高强度离子线或原子线光源的可行性。本文通过对Eu空心阴极灯在强短脉冲供电时的伏安特性,以及对直流和强短脉冲供电时空心阴极灯发射光谱差异的研究,探讨了强短脉冲供电时空心阴极灯的放电机制,讨论了离子线和原子线强度增强的过程。 1 实验部分 1.1 仪器 1.0m平面光栅光谱仪(中国科学院长春应用化学研究所),光栅刻线1200条/mm,入射和出射狭缝宽度分别为10和35μm,一级光谱倒色散率0.8nm/mm;MF-1A型脉冲发生器(南通电子仪器厂);自制HCL供电电源和Boxcar积分器;BS-5504型双踪示波器(40 MHz,韩国安罗);瞬态记录仪频率为20 MHz(中国科技大学快电子学实验室),1P28A和EMI 6265型PMT;LM-15型X-Y记录仪;所用HCL为市售商品灯。 1.2 实验装置 研究空心阴极灯(HCL)光谱特性的装置见图1.由脉冲发生器产生的脉冲信号通过灯电源控制HCL,由HCL发射的光经单色仪后由光电倍增管(PMT)将光信号转化为电信号,经前置放大器以及Boxcar积分器或瞬态记录仪后采集并记录脉冲信号。图1中PG为脉冲发生器,HCL Dr     

空心阴极灯在强短脉冲供电时元素离子线的时间分辨光谱

本文报道了普通空心阴极灯在强短脉冲供电时离子线发射的时间分辨光谱。实验表明,在微秒级脉宽、数十安培电流的脉冲作用下,阴极的发射能量由直流供电时集中在原子共振级的状态转变到集中在离子共振级的状态。以钙灯为例,其离子线的发射强度约增加了10~5倍。     

强短脉冲供电空心阴极灯激发的ICP原子荧光光谱研究

强短脉冲供电空心阴极灯激发的ＩＣＰ原子荧光光谱研究弓振斌，杨原，王小如，黄本立（厦门大学化学系，厦门，３６１００５）关键词空心阴极灯，强短脉冲供电，ＩＣＰ原子荧光光谱，离子荧光光谱Ｗｉｎｅｆｏｒｄｎｅｒ等［１］报道了大电流短脉冲供电的空心阴极灯（ＨＣ...     

强短脉冲辉光放电阴极溅射逐层分析研究

利用强短脉冲供电电源和一种新型的辉光放电灯联用进行阴极表面溅射，发现它与在直流供电下有不同的结果，扫描电镜进行观察，得到样品溅射表面的扫描图，结果表明，该技术的金属或合金样品表面的逐层分析提供了一种新方法。     

辉光放电质谱法测定纯锡中24种杂质元素和锡记忆效应的消除

采用辉光放电质谱法(GDMS)测定了纯锡中24种杂质元素,分析方法为无标定量分析。分析前纯锡样品须依次用乙醇、水及乙醇冲洗以除去表面的灰尘颗粒,凉干后用于分析。本工作对辉光放电过程中的三项关键因素,即辉光放电电压、放电电流及放电气流三者在辉光放电溅射/电离时的相互关系及其对总离子流强度的影响进行了试验和讨论,并确定了仪器在最佳状态时辉光放电的优化条件为:放电电压590V,放电电流30mA,放电气流450mL·min~(-1)。为排除各元素测定中质谱(MS)干扰的影响,选择了在不同的分辨模式(中/高)下用相对丰度较高、干扰较少的质量数进行分析。所测定元素测定结果的相对标准偏差(n=5)均小于15%。各元素的检出限(3s)为0.003～0.174μg·g~(-1)之间。本方法所得测定结果与电感耦合等离子体原子发射光谱法(ICP-AES)或电感耦合等离子体质谱法(ICP-MS)的测定结果基本一致。经试验,通过更换GDMS的阳极帽、导流管、采样锥和透镜等4种耗材,可完全消除锡的记忆效应。     

HGZ－Ⅱ型自动辉光放电光源的研制

在仔细研辉光放电光源工作过程的基础上，在国内首先设计、制成了ＨＧＺ－Ⅱ型自动辉光放电光源。该光源除换样品外，实现了抽空、进气、对光、预燃、曝光、充气、复位等摄谱全过程的自动控制。有水压、真空度、短路保护措施和醒铃线路。设计合理，性能良好，操作简便，工作安全，可靠。程控部分的编排包括顺序控制。时序控制和条件控制。由于使用了通用执行元、器件，降低了成本，提高了耐用性。为满足表层，逐层分析的需要，还专门设计了计数电路。供电源实现了高压直流供电和脉冲供电。该光源可应用于合金中主成分和少量杂质分析及金属、合金表层，逐层成分分析。     

辉光放电质谱研究与应用新进展

简要介绍了辉光放电的基本原理,主要概述了过去４年有关辉光放电质谱研究的新进展,包括辉光放电质谱的基础研究,新装置和新方法的发展,以及辉光放电质谱的分析应用。文中最后展望了辉光放电质谱法的发展前景。     

辉光放电原子发射光谱法快速分析生铸铁

通过对辉光光源参数-放电电流、放电电压、预溅射时间和分析时间对生铸铁标样放电强度和稳定性影响的研究,优化光源参数,建立了辉光放电原子发射光谱法同时测定生铸铁中碳、硅、锰、磷、硫等12个元素的快速分析方法。分析生铸铁试样时发现了不同灰口铸铁在碳分析结果方面存在偏差,对碳的偏差进行了讨论并通过制样条件和光源参数的调整可以有效地减小偏差。通过对不同生铸铁样品进行准确度和精密度试验,结果表明:分析结果与标准值或化学法结果一致。分析一件试样的时间仅需2~5 min。     

微波等离子体增强辉光放电光源激发温度的研究

研究了一种改进型的微波等离子体增强辉光放电光源在光谱分析中的应用，对其重要的参数指标－激发温度进行了较为较细的考察。结果表明引入微波等离子体后辉光放电的激发温度明显高于单纯辉光放电时的激发温度。     

辉光放电低温等离子体分解乙醇水溶液制氢

在辉光放电分解乙醇制氢过程中, 高能电子在反应中起到了最为关键的作用, 非法拉第效应使得电流效率获得大幅度提升, 产物产量远远高于理论产量. 本文研究了乙醇水溶液辉光放电等离子体电解制氢的过程. 实验研究发现, 辉光放电分解乙醇水溶液的产物主要以H₂和CO为主, 还有少量的C₂H₄、CH₄、O₂和C₂H₆. H₂体积分数能达到59%以上, CO为20%左右. 通过对影响辉光放电的因素进行实验后发现: 乙醇体积分数的大小不会影响辉光放电的伏安特性参数; 电导率的提高会使‘Kellogg 区’收窄, 同时使放电尽快进入辉光放电. 此外, 乙醇体积分数越高H₂体积分数越低, 产气速率在乙醇体积分数为30%和80%附近时达到极大值; 提高放电电压和电导率对辉光放电的影响规律是相类似的, 其实质都是增大了辉光放电加载在等离子鞘层两端的电压,H₂体积分数基本不随二者的变化而变化, 但提高溶液的电导率更有利于减少辉光放电引起的焦耳热.     

Separation and purification of four compounds from Desmodium styracifolium using off‐line two‐dimensional high‐speed counter‐current chromatography

An off‐line 2D high‐speed counter‐current chromatography technique in preparative scale has been successfully applied to separate and purify the main compounds from the ethyl acetate extract of Desmodium styracifolium. A two‐phase solvent system composed of n‐hexane/ethyl acetate/methanol/water at an optimized volume ratio of 1:2:1:2 v/v/v/v was used. Conventional high‐speed counter‐current chromatography was used as the first dimension, and the upper phase of the solvent system was used as the stationary phase in the head‐to‐tail elution mode at a flow rate of 2.0 mL/min and a rotation speed of 900 rpm. Recycling high‐speed counter‐current chromatography served as the second dimension to separate an impure fraction of the first dimension. A total of four well‐separated substances including vanillic acid ( 1 ), β‐sitosterol ( 2 ), formononetin ( 3 ), and aromadendrin ( 4 ) were obtained, and their purities and structures were identified by HPLC–MS and ¹H NMR spectroscopy. The results illustrated that off‐line 2D high‐speed counter‐current chromatography is an effective way to isolate compounds in complex samples.     

Catechol-Coordinated Framework Film-based Micro-Supercapacitors with AC Line Filtering Performance

Coordination polymer frameworks (CPFs) have broad applications due to their excellent features, including stable structure, intrinsic porosity, and others. However, preparation of thin-film CPFs for energy storage and conversion remains a challenge because of poor compatibility between conductive substrates and CPFs and crucial conditions for thin-film preparation. In this work, a CPF film was prepared by the coordination of the anisotropic four-armed ligand and Cu^II at the liquid–liquid interface. Such film-based micro-supercapacitors (MSCs) are fabricated through high-energy scribing and electrolytes soaking. As-fabricated MSCs displayed high volumetric specific capacitance of 121.45 F cm⁻³. Besides, the volumetric energy density of MSCs reached 52.6 mWh cm⁻³, which exceeds the electrochemical performance of most reported CPF-based MSCs. Especially, the device exhibited alternating current (AC) line filtering performance (−84.2° at 120 Hz) and a short resistance capacitance (RC) constant of 0.08 ms. This work not only provides a new CPF for MSCs with AC line filtering performance but also paves the way for thin-film CPFs preparation with versatile applications.     

Alternating current electrolysis for organic synthesis

Electrochemical organic synthesis has recently attracted much attention because of its unique reactivity and environmentally benign approach. Conventional electrosynthesis uses either constant current or constant potential, known as direct current electrolysis. However, recently, alternating current electrolysis has begun receiving more attention. The purpose of this study is to give a short overview of the history and recent advances in the field of alternating current electrolysis for organic synthesis.     

Phase Sensitive Alternating Current Polarography: A Chemometric Approach for the Selection of Phase Angles

A method based on the combined use of multivariate curve resolution by alternating least squares (MCR‐ALS) with phase sensitive alternating current polarography (ACP) is proposed to evaluate the phase angle where capacitive current is minimized in a much more accurate way than the visual inspection of ACP signals. The method allows, through the analysis of series of AC polarograms measured at different phase angles out the potential, to distinguish between faradaic and capacitive contributions. Then the angle at which the capacitive current is negligible can be shown and, in some cases, the influence of adsorption on measured currents minimized.     

An investigation of aromaticity in hydroxybenzenes based on the study of magnetically induced current density

Hydroxybenzenes are derivatives of benzene in which one or more H atoms are replaced by OH groups. This work considers the effect of such replacement on the aromaticity of the ring, by assessing the aromaticity through the values and patterns of the magnetically induced current density. The results show that aromaticity is quenched and the quenching depends on the number and positions of the substituting OH groups. The isosurfaces of the magnitude of the current density also highlight connections between the donor and acceptor atoms forming an intramolecular hydrogen bond.     

Chemometrics assisted resolving of net faradaic current contribution from total current in potential step and staircase cyclic voltammetry

Total current in the electroanalytical data is assumed to be consisting of three main constituents: faradaic current, step charging current and induced charging current. Both charging currents can cause an interfering effect on precise determination of faradaic currents, and hence insert direct effects on sensitivity and detection limit of the electroanalytical techniques. Despite the widespread techniques introduced until now, the extraction of the net faradaic current from total current still remains a challenge. In this work, by using multivariate curve resolution-alternating least square (MCR-ALS) as a powerful curve resolution-based chemometrics method, a straightforward method has been introduced for resolving faradaic current from the two types of charging currents (step charging current and induced charging current) in single potential step and staircase cyclic voltammetric methods. By simultaneous analyses of the current data matrices for different electrochemical systems, the three sources of current were successfully identified and their contributions in the total signal were easily calculated. Also, in this manner, the cell time constant can be obtained easily. Contrary to the previously reported methods, the present method does not need any pre-determined mathematical method; particularly there is no need to know the cell time constant.     

Identifying Diffusion Limiting Current to Unravel the Intrinsic Kinetics of Electrode Reactions Affected by Mass Transfer at Rotating Disk Electrode

Rotating disk electrode systems are widely used to study the kinetics of electrocatalytic reactions that may suffer from insufficient mass transfer of the reactants. Kinetic current density at certain overpotential calculated by the Koutecky-Levich equation is commonly used as the metrics to evaluate the activity of electrocatalysts. However, it is frequently found that the diffusion limiting current density is not correctly identified in the literatures. Instead of kinetic current density, the measured current density normalized by diffusion limiting current density (j/j_L) has also been frequently under circumstance where its validity is not justified. By taking oxygen reduction reaction/hydrogen oxidation reaction/hydrogen evolution reaction as examples, we demonstrate that identifying the actual diffusion limiting current density for the same reaction under otherwise identical conditions from the experimental data is essential to accurately deduce kinetic current density. Our analysis reveals that j/j_L is a rough activity metric which can only be used to qualitatively compare the activity trend under conditions that the mass transfer conditions and the roughness factor of the electrode are exactly the same. In addition, if one wants to use j/j_L to compare the intrinsic activity, the concentration overpotential should be eliminated.     

Corrosion resistance of zinc electrodeposited from acidic and alkaline electrolytes using pulse current

Corrosion resistance of zinc coatings was investigated in an accelerated corrosion test in a condensation chamber. Zinc was electrodeposited from alkaline and acidic electrolytes using direct current (DC) or pulse current (PC). The zinc coating was subsequently protected against corrosion with a chrome (III) layer. Morphology and structure of the coatings was investigated using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), and X-ray diffraction analysis (XRD) before and after the corrosion test. Corrosion resistance of alkaline zinc coatings electrodeposited with DC and PC under test conditions was found to be comparable. The corrosion resistance of zinc coatings deposited from acidic electrolytes by PC was lower in comparison with corrosion resistance of zinc coatings deposited using DC. Presented at the 8th Conference on Solid State Chemistry, Bratislava, Slovakia, 6–11 July 2008.     

Ce3+/Ce4+电对在混酸(硫酸和甲磺酸)中的电化学行为

采用循环伏安、线性扫描、交流阻抗等技术研究了Ce³⁺/Ce⁴⁺电对在混酸(硫酸与甲磺酸)中的电化学行为,并对该体系在间接有机电合成中的应用进行了探索.结果表明：当硫酸和甲磺酸(MSA)浓度分别为0.8和1.0 mol·L^-1时,Ce³⁺/Ce⁴⁺电对具有最佳的电化学活性;在上述配比的混酸介质中,铈盐的溶解度得到了大幅提高,同时电解氧化铈(III)离子的电流效率较高（92.1%）,与纯硫酸体系中的电流效率接近（92.8%）,明显高于纯甲磺酸体系（78.5%）;该混酸介质中Ce⁴⁺在氧化茴香醚生成茴香醛这一过程中也表现出很好的氧化能力.     

Different mutual positions of double bonds in open carbon chains and corresponding information from magnetically induced current densities

Magnetically induced current densities have been extensively utilized to investigate aromaticity. However, an applied external magnetic field induces a current in all chemical bonds. The present work investigates the values and patterns of magnetically induced current densities in open hydrocarbon chains containing two or more CC double bonds, considering the three possibilities for the mutual positions of the double bonds (conjugated, isolated, and consecutive) and comparing the corresponding current patterns. The patterns for chains containing three conjugated double bonds are also compared with the patterns in the aromatic benzene ring. The study highlights different current patterns for the three categories of double-bonds arrangements. The differences can be interpreted in terms of presence or absence of electron delocalization (present only in the case of conjugated double bonds) and, for consecutive double bonds, also in terms of the mutual perpendicularity of the π orbitals of adjacent double bonds.