Breakdowns and the formation of microdischarge channels in surface barrier discharges

The dynamics of the space-time evolution of a creeping (surface) barrier discharge in pure oxygen at atmospheric pressure was studied by numerical simulation. The breakdown through a gas gap was found to end by the formation of a cathode layer. The distribution of parameters in this layer was close to that in the “normal” cathode layer. The cathode layer, which was a source of electrons, sustained the formation of a microdischarge channel above a dielectric. Microdischarge channel elongation over a dielectric was shown to be effected by a streamer formed in the head of the channel and to be accompanied by charge fall-out onto the surface of the dielectric barrier. This noticeably decreased the mean electric field strength in the channel and the intensity of discharge processes and eventually caused their cessation.     

Development of an Atmospheric Pressure Glow Discharge Detector for Capillary Column Gas Chromatography

 The use of the change in the oscillation frequency of the current of a new atmospheric helium glow discharge for sensitive signal detection for gas chromatography is studied. The effluent of a capillary column is directed into the glow discharge cell perpendicular to the axis of the glow discharge that existed between a platinum anode and cathode. A stable discharge is obtained when several hundred volts are applied between the 0.2-mm gap between the anode and cathode. The effects of the electrode gap, discharge voltage and gas flow rate on the baseline frequency and discharge current were investigated. The chromatogram shows that the discharge current and discharge gap have a strong influence on the detector response. The discharge current shows positive peaks; however, frequency peaks are positive or negative depending on the discharge conditions. The response of the detector is in the femto-mole and pico-mole range for nonane and decane. Received August 5, 1997. Revision September 2, 1999     

丙烯和氧等离子体直接气相合成环氧丙烷

在室温和大气压下,在针板式反应器中,通过脉冲电晕放电等离子体对分子氧和丙烯直接合成环氧丙烷的活化作用,考察了放电电极间距、电晕放电脉冲电压以及电晕放电重复频率参数对丙烯转化率、环氧丙烷产率和其选择性的影响,反应物及各产物通过在线色谱法进行分析.实验结果表明,在室温和大气压下,用脉冲电晕等离子体法可转化丙烯和氧气直接生成环氧丙烷,适当调节上述各参数可提高环氧丙烷的收率.当反应气总流速为200mL/min,极间距为4mm,脉冲放电电压为18kV,放电频率为120Hz时,环氧丙烷的收率、丙烯的转化率及环氧丙烷的选择性分别为5.15%,19.15%和26.89%.     

Analytical Potentials and Features of Atomic Emission Analysis Using Electron-Impact Excitation of Atoms in Helium under Atmospheric Pressure

A device is described for the atomic emission analysis of vaporous samples using electron-impact excitation in helium under atmospheric pressure. The device consists of a cathode atomizer with a test sample applied onto it and the anode located at 1–3 mm from the cathode. The electrons emitted by the cathode upon heating are accelerated by applying a constant voltage to the electrodes. The mechanism for the formation of a non-self-sustained gas discharge between the cathode and anode is considered and the properties of the discharge are compared to those of the known discharges used in atomic emission spectrometry. The influence of atomization temperature and helium pressure on the analytical and background signals was studied. It is shown that, under certain conditions, the analytical signal increases with helium pressure. The relative detection limits attained for a number of elements are from tenths to dozens of nanogram per liter; this is two or three orders of magnitude lower than those in inductively coupled plasma atomic emission spectrometry and of the same order of magnitude as detection limits in inductively coupled plasma mass spectrometry.     

Cathode of a fuel cell with a solid polymer electrolyte: Calculating overall currents in the presence of a gas-diffusion layer

Mathematical apparatus, which makes it possible to perform calculations of the current-voltage characteristics of cathodes of fuel cells with a solid polymer electrolyte in conditions where there are present extraneous diffusion restrictions is proposed. In so doing, the partial pressure of oxygen and the absolute pressure of gas in the gas chamber may assume any values. First of all presented are the results of calculations of the current-voltage characteristics intrinsic to active layers of the air and oxygen cathodes, which are performed under the assumption that the extraneous diffusion restrictions are absent altogether. Thereafter, in the same conditions (at the same parameters that characterize the active layer of a cathode), obtained are results of a calculation of the current-voltage characteristics inherent in the air and oxygen cathodes in the presence of extraneous diffusion restrictions. Afterward there is performed an analysis of the way a gas-diffusion layer restricts the process of generation of current in a cathode and of what measures should be taken in order for the extraneous diffusion restrictions to become less significant.     

Formation and Role of a Hollow-Cathode Plasma Plug in Mass-Spectrometric Analysis

The use of plasma electron and ion sources based on a glow discharge is often restricted by a too high plasma-forming gas pressure in the process volume. Experiments with a new design of a hollow cathode, a type of glow discharge, are described in this paper. It was found that, if a cap with an orifice is arranged at the vertex of a cylindrical hollow cathode (the orifice diameter is 10 to 90% of the inner diameter of the hollow cathode), a plasma plug, which offers resistance to a plasma-forming gas flow from the cathode hole to the vacuum chamber, is formed in the cathode hole near the orifice. As a result, a pressure drop is formed between the cathode hole and the vacuum chamber. This pressure drop depends on the orifice diameter, and it can be as high as three orders of magnitude with the use of a hollow cathode with an internal diameter of 20 mm and an orifice diameter of 4 mm in the cap at the cathode vertex.     

Study of some excitation characteristics of the discharge in a hot hollow cathode

Some excitation characteristics of the discharge in a hot hollow cathode were investigated. A graphite cathode coated with evaporated films of copper, iron, manganese or titanium, and argon or helium fill gas were applied. The dependence of spectral-line intensities on fill gas pressure and discharge current were studied. At 0.4 A discharge current and various fill gas pressures, the excitation temperatures for iron, manganese and titanium were determined.     

Unveiling the High-valence Oxygen Degradation Across the Delithiated Cathode Surface

Charge compensation on anionic redox reaction (ARR) has been promising to realize extra capacity beyond transition metal redox in battery cathodes. The practical development of ARR capacity has been hindered by high-valence oxygen instability, particularly at cathode surfaces. However, the direct probe of surface oxygen behavior has been challenging. Here, the electronic states of surface oxygen are investigated by combining mapping of resonant Auger electronic spectroscopy (mRAS) and ambient pressure X-ray photoelectron spectroscopy (APXPS) on a model LiCoO₂ cathode. The mRAS verified that no high-valence oxygen can sustain at cathode surfaces, while APXPS proves that cathode electrolyte interphase (CEI) layer evolves and oxidizes upon oxygen gas contact. This work provides valuable insights into the high-valence oxygen degradation mode across the interface. Oxygen stabilization from surface architecture is proven a prerequisite to the practical development of ARR active cathodes.     

Improvement of Atmospheric Water Surface Discharge with Water Resistive Barrier

Atmospheric water surface discharge is a promising method for water treatment. The selection of discharge gap distance must take a pair of conflicting aspects into account: the chemical efficiency grows as the discharge gap distance decreases, while the spark breakdown voltage decreases as the gap distance decreases. To raise the spark breakdown voltage and the chemical efficiency of atmospheric pressure water surface discharge, resistive barrier discharge is introduced in this paper. Both the high voltage electrode and the ground electrode are suspended above water surface to form an electrode-water-electrode discharge system. The water layer plays the role of a resistive barrier which inhibits the growth rate of discharge current as voltage increases. Experiments conducted at different discharge gap distances and water conductivities indicate that both the spark breakdown voltage and the chemical efficiency are remarkably raised in comparison with traditional water surface discharge. After parameter optimization, the discharge reactor is scaled up with activated carbon fiber electrodes and advantages of water resistive barrier discharge are kept.     

Modeling the effect of the cathode geometry in a DC glow discharge ion source for mass spectrometry

A self-consistent, two-dimensional hybrid fluid-particle model is used to study the effect of cathode geometry on the plasma produced in an argon glow discharge for conditions typically of the commercially available glow discharge mass spectrometer system (VG9000 spectrometer and Megacell source). For a given power supply voltage and gas pressure, we show that the spatial distribution of the plasma in the discharge volume is strongly dependent on the cathode geometry. The plasma created in a discharge with a pin cathode tends to form a ring around the cathode, while the plasma in a discharge with a larger diameter, disk cathode is centered on-axis between the cathode face and the anode. The ion current arriving at the entry plane of the mass spectrometer thus depends strongly on the cathode geometry. This suggests that analytical performance can be enhanced by optimization of the cathode (sample) geometry.     

Reducing the Background Level of a Mass-Spectrometric Hollow Cathode Glow Discharge Ion Source

Glow discharge mass spectrometry was used for the direct elemental analysis of solids with gas inclusions. The background signal of a glow discharge, which converts the analyte into ions, is higher than the background signals of other plasma sources by several orders of magnitude. The structure and sources of background contamination were analyzed in this work. It was found that hydrocarbon and water impurities, which are adsorbed on the inner surfaces of the discharge chamber, make the major contribution to the background signal of a glow discharge source. A glow discharge plasma licked the walls of the discharge chamber to desorb contaminants. We proposed using a hollow cathode with a holed cap arranged at the vertex. On the appearance of a discharge, a plasma plug is formed in the cathode hole in front of the orifice. This plasma plug prevents a gas flow from the hole to the source chamber. As a result, a gas pressure drop is formed whose magnitude depends on the orifice diameter in the cap.     

氧气常压介质阻挡放电的发射光谱及能量传递机理

为研究氧气常压介质阻挡放电中的物理化学行为, 以纯氧作为放电体系, 用发射光谱(optical emission spectroscopy)诊断技术分析了等离子体中可能存在的化学活性物种. 利用在500-950 nm范围的氧原子发射光谱计算出等离子体中的电子温度为(1.02±0.03) eV; 观测了760 nm处的具有清晰转动结构的氧气A带(atmospheric band)O2(b1∑+g-X3∑-g), 并用其转动结构计算了转动温度(气体温度)为(650±20) K; 在500-700 nm范围观测了氧气的第一负带系(first negative system) O+2(b4∑-g-a4∏u), 在190-240 nm范围观测了微弱但特征清晰的氧气的Hopfield带系O+2(c4∑+u-b4∑-g). 研究发现, 在氧气常压介质阻挡放电等离子体中存在多种激发态氧原子、激发态氧气分子、基态和激发态氧气分子离子等反应活性物种, 这些活性物种的形成涉及氧气分子的激发、解离和电离等多种过程, 每个过程都包含多个能量传递步骤, 氧分子解离产生的氧原子是导致一系列高激发态氧原子生成和氧气电离激发的主要因素.     

Direct optical emission spectroscopy of liquid analytes using an electrolyte as a cathode discharge source (ELCAD) integrated on a micro-fluidic chip

Atomic emission detection of metallic species in aqueous solutions has been performed using a miniaturised plasma created within a planar, glass micro-fluidic chip. Detection was achieved using an Electrolyte as a Cathode Discharge source (ELCAD) in which the sample solution itself is used as the cathode for the discharge. To realise the ELCAD technique within a micro-fluidic device, a parallel liquid-gas flow was set up in a micro-channel and a glow discharge ignited between the flowing liquid sample surface and a metal wire anode. The detection of copper and sodium was achieved, using atmospheric pressure air as a carrier gas, by observation of atomic emission lines of copper at 324 nm, 327 nm, 511 nm, 515 nm and 522 nm and an atomic emission line of sodium at 589 nm using a commercially available miniaturised spectrometer. A total electrical power of less than 70 mW was required to sustain the discharge. A semi-quantitative, absolute detection limit of 17 nmol s(-1) was obtained for sodium with a sample flow rate of 100 microL min(-1) and an integration time of 100 ms in air at atmospheric pressure. The volume required for such detection is approximately 170 nL. Further analysis was performed with an Echelle spectrometer using both argon and air as a carrier gas. The geometry and flow rates used demonstrate the feasibility of integrating such micro-plasmas into other micro-fluidic devices, such as miniaturised CE devices, as a method of detection. The potential for using such micro-plasmas within highly portable miniaturised systems and mu-TAS devices is presented and discussed.     

Depth profile analysis of surface modified SnO2 gas sensors in a hollow cathode discharge

Depth profile analysis of a SnO₂/SiO₂/Si structure, modified with hexamethildisilazane and processed with rapid thermal annealing (RTA) in the temperature range of 800–1200 °C, is investigated in a hollow cathode discharge for the purpose of characterizing gas sensing solid state devices. The depth behavior of the elements tin, nitrogen, carbon and silicon in this structure is deduced from their emission spectra in the hollow cathode plasma. The hollow cathode used is a liquid nitrogen - cooled Al cylinder having 4 mm inner diameter and 12 mm length. Spectrally pure Ne at a pressure of 130 Pa is used as working gas. The hollow cathode discharge is supplied by a pulse generator with 10 μs pulse width, 4 kHz pulse frequency and 0.5 A pulse amplitude. The results are interpreted by possible reconstruction of hexamethyldisilazane molecule.     

Calculation of optimum thickness of active layer of oxygen and air cathodes of fuel cell with Nafion and platinum

It is shown that, for the electrodes of fuel cells with solid polymer electrolyte, the dependence of overall current on the active layer thickness contains an extremum. There is an optimum thickness of active layer, at which the overall current reaches its maximum possible value. The nature of this dependence is explained. The character of the distribution of electrochemical process intensity over the depth of active layer of cathode with solid polymer electrolyte is analyzed. The optimum thicknesses of active layers of oxygen and air cathodes of fuel cells with Nafion and platinum and the corresponding overall currents and contents of catalyst in the active layer are calculated. In the calculations, the temperature of fuel cell, the pressure in the cathode gas chamber, and the cathodic potential were varied. The optimization of active layer thickness of cathode with solid polymer electrolyte can reduce the platinum consumption, i.e. its amount per 1 kW of power produced in a membrane-electrode assembly.     

不同进气方式对热等离子体应用于CH4-CO2重整的影响

采用大功率双阳极热等离子体装置, 对CH4-CO2重整制合成气进行实验研究. 实验采用两种不同的原料气输入方式: 一种是使原料气(CH4和CO2的混合气体)作为等离子体放电气体全部通入第1阳极与第2阳极间的放电区, 直接参与放电; 另一种是保持前述状态, 再附加另一部分原料气通入从等离子体发生器喷出的等离子体射流区. 实验表明: 第1种方式下, CH4和CO2同时具有很高的单程转化率和反应选择性, 但能量转化效率较低; 第2种方式下, 尽管CH4和CO2单程转化率和选择性有所降低, 但由于进料量增加, 所得合成气摩尔量较大, 因此能量转化效率高于第1种进气方式所得结果. 实验还发现, 保持放电电流恒定的情况下, 等离子体放电电压随通入第1阳极与第2阳极间放电区的原料气流量增加而增加, 与通入等离子体射流区的流量无关, 同时实验未发现等离子体发生器阴极和阳极被氧化或出现碳沉积现象.     

Reduction of chromium(VI) in aqueous solution by treatment with direct-current discharge at atmospheric-pressure in air

The kinetics of reduction of Cr(VI) by treating its aqueous solution in atmospheric pressure dc discharge in air has been studied at the discharge current range of 20–80 mA and the concentration range of 1.25–12.5 mg/L. The solution has served as the discharge cathode. It has been shown that the discharge treatment leads to a decrease in the Cr(VI) concentration to its steady-state value, with the latter depending on the discharge current and the initial concentration of the solution. The effective rate constants of the forward and reverse processes have been determined, the energy efficiency of the process has been evaluated, and possible mechanisms of the reactions involved have been discussed.     

Characteristics of the Single-Gap Pseudospark Discharge Under Nanosecond Pulsed Voltages

In this paper, a single-gap pseudospark discharge chamber was built and tested with several electrode gap distances and pressures to explore the characteristics of the pseudospark under nanosecond pulsed voltages. Experimental results show that with the development of the discharge, anode plasma firstly forms near the anode, and then moves towards the cathode. The ionization initial voltage decreases with the increase of the electrode gap distance and pressure in our pseudospark discharge configuration. By analysing the emission spectra, it is concluded that the major emission spectra are composed of the second positive bands, and the electron energy of the plasma is in the level of several tens of electron volts. The mechanism of how the pressure and gap distance influence the characteristics has been discussed with the simulation of the collision ionization process using the Monte Carlo Collision method. Based on the simulation and experimental results, it is inferred that the breakdown voltages is decided by the ionization process of the electron with the neutral gas in the main gap, and a possible reason is put forward to explain the reason that U is a function of p ² d.     

Quantitative Schlieren Diagnostics Applied to a Millisecond Pulsed-DC Hybrid Discharge in Atmospheric Pressure Air

The gas temperature of a hybrid discharge in atmospheric pressure air is investigated by using quantitative schlieren imaging. The discharge is stabilized in a pin-to-plate electrode geometry and operated in a millisecond pulsed-DC regime with current amplitudes up to 75 mA and a duration of 10 ms, applied at a frequency of 100 Hz. An equilibrium composition model is considered to account for the production of N, O, and NO, which influence the Gladstone–Dale coefficient of air at high-gas temperatures. Also, a procedure is described which allows the determination of the errors introduced in the time-average gas refraction index due to gas temperature fluctuations. The results show that the axial values of the gas temperature profiles span a large range from?~?1000 to 5000 K, nearly following the evolution of the discharge current. The temperature values found agree well with those reported in the literature for atmospheric pressure air plasmas, ranging from micro-glow to hybrid discharges.

     

Synthesis of peroxyacetic acid using in situ electrogenerated hydrogen peroxide on gas diffusion electrode

Peroxyacetic acid (PAA) has been first prepared from acetic acid in the presence of solid superacid, Nafion-H, as a catalyst at ambient temperature and atmospheric pressure using gas diffusion electrode (GDE) as an oxygen cathode. Hydrogen peroxide was electrogenerated by the reduction of oxygen on the GDE and PAA could be produced by a redox reaction between electrogenerated hydrogen peroxide and acetic acid. The continuous operation was carried out to examine the electrolysis performance of the present electrolysis system. The results demonstrate that the system can be continuously operated over one month with the production of PAA of ca. 1.9–2.3 mM.