Understanding the flowing atmospheric-pressure afterglow (FAPA) ambient ionization source through optical means

The advent of ambient desorption/ionization mass spectrometry (ADI-MS) has led to the development of a large number of atmospheric-pressure ionization sources. The largest group of such sources is based on electrical discharges; yet, the desorption and ionization processes that they employ remain largely uncharacterized. Here, the atmospheric-pressure glow discharge (APGD) and afterglow of a helium flowing atmospheric-pressure afterglow (FAPA) ionization source were examined by optical emission spectroscopy. Spatial emission profiles of species created in the APGD and afterglow were recorded under a variety of operating conditions, including discharge current, electrode polarity, and plasma-gas flow rate. From these studies, it was found that an appreciable amount of atmospheric H₂O vapor, N₂, and O₂ diffuses through the hole in the plate electrode into the discharge to become a major source of reagent ions in ADI-MS analyses. Spatially resolved plasma parameters, such as OH rotational temperature (T_rot) and electron number density (n_e), were also measured in the APGD. Maximum values for T_rot and n_e were found to be ~1100 K and ~4 × 10¹⁹ m^–3, respectively, and were both located at the pin cathode. In the afterglow, rotational temperatures from OH and N₂⁺ yielded drastically different values, with OH temperatures matching those obtained from infrared thermography measurements. The higher N₂⁺ temperature is believed to be caused by charge-transfer ionization of N₂ by He₂⁺. These findings are discussed in the context of previously reported ADI-MS analyses with the FAPA source.     

Low Cost Compact Nanosecond Pulsed Plasma System for Environmental and Biomedical Applications

Nanosecond pulsed non-thermal atmospheric-pressure plasmas are promising for numerous applications including air and water purification, ozone synthesis, surface sterilization, material processing, and biomedical care. However, the high cost of the nanosecond pulsed power sources has hindered adaptation of the plasma-based technologies for clinical and industrial use. This paper presents a low cost (<100US$) nanosecond pulsed plasma system that consists of a Cockcroft–Walton high voltage charging circuit, a compact nanosecond pulse generator using a spark gap as switch, and a plasma reactor. The nanosecond pulse power source requires only a 12 V DC input, hence is battery operable. Through the optimization of the experimental parameters, pulses with a peak voltage >10 kV, a 3 ns rise time (10 to 90 %), and a 10 ns pulse duration (full width at half maximum) at a pulse repetition rate of up to 500 Hz were achieved in the present study. It has been successfully tested to power three different plasma reactors to form pulsed corona discharges, dielectric barrier discharges, and sliding discharges. The energy efficiency of such a nanosecond pulsed sliding discharge system was assessed in the context of ozone synthesis using air or oxygen as the feed gas, and was found comparable to a previously reported non-thermal plasma system that used commercial high voltage pulsed power sources. This study demonstrated that this low-cost nanosecond pulsed power source can prove to be an energy efficient and simple supply to drive various non-thermal atmospheric-pressure plasma reactors for environmental, medical and other applications.     

Overview of Atmospheric Pressure Discharges Producing Nonthermal Plasma

Recently, much attention has been paid to gas discharges producing nonthermal plasma because of many potential benefits in industrial applications. Historically, past work focused on Dielectric Barrier (silent) Discharges (DBD) and pulse-periodical corona discharges. Recently, a number of new different discharge techniques succeeded in producing stable gas discharge at atmospheric pressure. Among these are repetitively pulsed glow discharge; continuous glow discharge in a gas flow; hollow-cathode atmospheric pressure discharge; RF and microwave (MW) discharges. Several new variants of the DBD have been demonstrated over a rather wide range of frequencies. All these forms of gas discharge are characterized by a strong nonequilibrium plasma state. We attempt to classify these discharges with respect to their properties, and an overview of possible applications is made. Conditions for the existence of homogenous and filamentary forms of each of the discharge types are discussed.     

Investigation of the Atmospheric Helium Dielectric Barrier Discharge Driven by a Realistic Distorted-Sinusoidal Voltage Power Source

The non-equilibrium atmospheric-pressure parallel-plate helium dielectric barrier discharge (DBD) driven by a realistic 20 kHz distorted-sinusoidal voltage waveform has been investigated by means of simulations and experiments. A self-consistent one-dimensional fluid modeling code considering the non-local electron energy balance was applied to simulate the helium DBD. The effect of selecting plasma chemistry was investigated by comparing simulations with experiments. The results show that the simulations, which include more excited helium, metastable helium and electron–ion-related reaction channels, can faithfully reproduce the measured discharged temporal current quantitatively. Based on the simulated discharge properties, we have found that there is complicated mode transition of discharges from the long Townsend-like to the “dark current”-like, then to the short primary Townsend-like and the short secondary Townsend-like for the helium DBD that is driven by a realistic distorted-sinusoidal voltage power source. Discharge properties in different periods of discharge are discussed in detail in the paper.     

Pulsed glow discharges for analytical applications

Non equilibrium plasmas such as glow discharges have become a commonly used tool in direct surface and interface analysis of solid materials. The application of pulsed glow discharges to material analysis has been studied by several research groups over the last 20 years. Two European projects, EMDPA and GLADNET currently work on the analytical applications of glow discharges, giving a particular attention to pulsed discharges. This review demonstrates the advantages of pulsed discharge operation by showing how the specific excitation and ionisation processes observed during the plasma ignition phase and the afterglow can be used for analytical applications.     

Spectroscopic Characterization of Miniaturized Atmospheric-Pressure dc Glow Discharge Generated in Contact with Flowing Small Size Liquid Cathode

The miniaturized atmospheric pressure glow discharge (APGD) generated between a solid electrode and a flowing small size liquid cathode (dimension 2 mm) was investigated here using optical emission spectroscopy. The discharge was studied in an open air atmosphere, and the spectral characteristics of the plasma source was examined. Analysed APGD was operated at a discharge voltage of 1,100–1,700 V, a discharge current of 20 mA and gaps between a solid anode and a liquid cathode in the range from 0.5 to 3.5 mm. The emission intensities of the main species were measured as a function of various experimental conditions, including the solution flow rate, the gap between the electrodes, and the concentration of hydrochloric acid. The excitation temperature, the vibrational temperatures calculated from N₂, OH, and NO bands, and the rotational temperatures determined from band of OH, N₂ and NO, were found to be dependent on these experimental parameters. The electron number density was determined from the Stark broadening of H_β line. Additionally, the ionization temperature and degree were calculated using the Saha–Boltzmann equation, with the ion to atom ratio for magnesium (MgII/MgI). The results demonstrated that T _exc(H), T _vib(N₂), T _vib(OH), T _vib(NO) and T _rot(OH) were well comparable (~3,800–4,200 K) for selected plasma generation conditions (gap ≥2.5 mm, HCl concentration ≥0.1 mol L⁻¹), while the rotational temperatures determined from band of N₂ (~1,700–2,100 K) and band of NO (~3,000 K) were considerably lower. The electron number density was evaluated to be (3.4–6.8) × 10²⁰ m⁻³ and the ionization temperature varied, throughout in the 4,900–5,200 K range.     

One-Dimensional Modeling on the Asymmetric Features of a Radio-Frequency Atmospheric Helium Glow Discharge Produced Using a Co-Axial-Type Plasma Generator

In this paper, a one-dimensional transient fluid model is used to investigate the asymmetric characteristics of the radio-frequency atmospheric-pressure helium glow discharges produced using a co-axial-type plasma generator. Based on the analysis of the particle and energy balance processes in the discharge region, the modeling results show that the asymmetric features of the time-averaged plasma parameters, e.g., the species number densities, electron energy and the electric field, become significant resulting from the increase in the discrepancy between the surface areas of the inner and outer electrodes. And the influence of the inner electrode radius on the asymmetric features of the discharges becomes more significant compared with the electrode gap spacing for the cases with smaller inner electrode radius. The calculated asymmetric features of the discharges are also validated by the experimental analysis on the discharge images using the visible image processing technique qualitatively.     

Comparison of Aluminium Nanostructures Created by Discharges in Various Dielectric Liquids

Synthesis of aluminium-containing nanoparticles (NPs) by electrical discharges was performed in three dielectric liquids (heptane, liquid nitrogen and water) with aluminium electrodes. The nature of the liquid plays an essential role in the synthesis yield and in the structural properties of NPs. Time-resolved optical emission spectroscopy of selected emission lines emitted during the discharge and its time afterglow was used to observe the chemical changes occurring in the gas phase. It turns out that in heptane and liquid nitrogen, crystalline metallic NPs (from 5 to 10 nm in diameter) are synthesized and oxidized next into amorphous alumina when they are in contact with air, once the liquid is evaporated. In heptane, the transformation of the liquid itself into hydrogenated amorphous carbon creates a kind a matrix in which the aluminium NPs are embedded. Sometimes, a protective graphite shell grows around the NPs and protects them from any further oxidation. In water, these crystalline metallic NPs are synthesized during the first 800 ns of the discharge process, when oxidation is limited by the outward flux of the metallic vapour. They are oxidized next in water. A second type of alumina NPs (several 10 s of nm in diameter) are produced from 800 ns on. They are likely formed from AlO molecules and no longer from aluminium atoms. In every liquid, sub-micrometric particles are also found due to droplet emission from the liquid well created during impacts of spark discharges on electrodes.     

Microwave and RF surface wave sustained discharges as plasma sources for plasma chemistry and plasma processing

The surface wave produced plasma belongs to a class of RF and microwave induced plasmas. It results from the propagation of an electromagnetic wave which uses the plasma column it sustains and the plasma tube as its sole propagating media. This type of plasma offers several advantages compared to the positive column plasma of dc discharges or to other RF and microwave produced plasmas. Surface wave plasmas require no internal electrodes, and they can be applied over an extremely broad range of wave frequencies (27 MHz to 10 GHz demonstrated) and gas pressures (about 10^–4 Torr to a few times the atmospheric pressures). Using the surface wave plasma technique, a large variety of plasma column diameters have been created (0.5–150 mm demonstrated) and no limitation on plasma column length (column up to 6 m long demonstrated) has been found. The surface wave produced plasma is used in elemental analysis and to sustain emission in lasing media. This article is intended as a guide for potential users of surface wave plasmas in the field of plasma processing and plasma chemistry.     

Biaxially Oriented Polypropylene (BOPP) Surface Modification by Nitrogen Atmospheric Pressure Glow Discharge (APGD) and by Air Corona

We compare two surface treatments of biaxially-oriented polypropylene (BOPP), which are carried out in the same dielectric barrier discharge (DBD) apparatus, namely air corona, and N₂ atmospheric pressure glow discharge (APGD). Changes in the surface energy and chemistry are investigated by contact angle measurements, by X-ray photoelectron spectroscopy (XPS) and by attenuated total reflectance infrared spectroscopy (ATR-FTIR). It is shown that N₂ APGD treatment leads to a higher surface energy than air corona treatment, and to the formation of mostly amine, amide, and hydroxyl functional groups at the polypropylene surface. Finally, hydrophobic recovery of the treated film is studied; for both treatment types, the increased surface energy is found to decay in a similar manner with increasing storage time after treatment.     

Application of a rotating high-pressure glow discharge for the dissociation of hydrogen sulfide

The dissociation of hydrogen sulfide has been studied in an atmospheric-pressure glow discharge rotating between concentric electrodes in an axial magnetic field. Though the electrodes were heated to remove the sulfur formed in the discharge, stable operation was possible. The characteristics of the discharge and the influence of experimental parameters on the conversion of hydrogen sulfide and the energy efficiency are reported.     

甲醇溶液辉光放电等离子体电解

甲醇溶液辉光放电等离子体电解过程出现明显的非法拉第定律现象, 主要产物是氢气和甲醛, 还有少量一氧化碳、甲烷、乙烷、丙烷、1,3,5-三噁烷和水等, 产物和产量受放电极性和辅助电解质及放电电压等因素的影响. 在甲醇溶液电导率为11.40 mS·cm-1, 放电电压700 V 条件下, 阳极气体产量为55.90 mol/(mol electrons), 阴极气体产量为707.90 mol/(mol electrons), 阴极气体产量是阳极气体产量的12.66 倍, 气相产物中氢气含量在86%(molar fraction)以上. 在等离子体层中甲醇分解过程和其它类型的等离子体分解过程类似, 蒸汽鞘层中的加速电子是引发辉光放电过程非法拉第定律现象的决定因素. 阴极辉光放电过程中等离子体-溶液界面上的主要活性物种是中性粒子和电子,阳极辉光放电过程中等离子体鄄溶液界面上的主要活性物种是中性粒子和正离子. 辅助电解质对产物的影响主要是通过影响界面上发生的后续反应过程来表现.     

Study on Glow Discharge in One-Dimensional Transverse Non-uniform Electric Field and Surface Processing of Aramid Fabric

Using a staggered contact electrode structure, the conditions for and mechanism of uniform discharge in one-dimensional transverse non-uniform electric field and with aramid fiber (AF) as a dielectric barrier material were explored for the first time in this study. An atmospheric pressure glow discharge (APGD) plasma was generated, and the large-area and continuous processing of AF was achieved. Through the electric field simulation as well as scanning electron microscope and X-ray photoelectron spectroscopy tests, it was found that the modification method of pressing the electrode closely to the AF could form the extremely strong electric field region of magnitude 1.444 × 10⁷ V/m under the premise of uniform discharge. The highly active plasma generated could not only effectively increase the surface roughness of the treated material, but also introduce nitrogen functional groups which can’t be introduced through traditional air plasma. As found through the contact angle measurement, the contact angle was greatly decreased (by 52.3%) after being treated with 12.05 W/cm³ of plasma for 10 s, indicating that APGD plasma can achieve a good modification effect and high modification efficiency at low discharge power density.     

Two Atmospheric-pressure Plasma Sources for Polymer Surface Modification

Two atmospheric-pressure plasma sources were studied. One was a helium plasma generated by a RF discharge, and the other was an air plasma generated by a dielectric barrier discharge (DBD). The two plasma sources were characterized on electron density, emission spectrum, and ozone density. The modification of polyethyleneterephthalate (PET) surfaces by the two plasmas was investigated. PET strips were exposed to the plasma at the exit of the plasma source. Water contact angles were measured for surfaces modified with different processing parameters. The change in contact angles was monitored as a function of time. Modification mechanisms were also investigated.     

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     

Emission characteristics of mixed gas plasmas in low-pressure glow discharges

Glow discharge optical emission spectrometry (GD-OES) with mixed plasma gases is reviewed. The major topic is the effect of type and content of gases added to an argon plasma on the emission characteristics as well as the excitation processes. Emphasis is placed on argon–helium, argon–oxygen, and argon–nitrogen mixed gas plasmas. Results for non-argon-matrix plasmas, such as neon–helium and nitrogen–helium mixtures, are also presented. Apart from the GD-OES, glow discharge mass spectrometry and furnace atomization plasma emission spectrometry with mixed plasma gases are also discussed.     

Vibrational energy exchanges in nitrogen: application of new rate constants for kinetic modeling

The state-to-state collisional data on vibration-vibration and vibration-translation/rotation energy exchanged in N2(v)-N2(v') collisions recently obtained from accurate ab initio semiclassical calculations have been used to analyze the data measured in nitrogen under two different plasma conditions. In particular, the vibrational distribution function and the time-evolution of the gas temperature measured under post-discharge and glow discharge conditions, respectively, have been calculated and compared with the experimental observations. The theoretical analysis and the related results, generally in very good agreement with the experimental data, provide insight into the various energy-exchange mechanisms that lie behind the macroscopic behaviors of the nitrogen plasmas. In particular, the role played by the vibrationally excited nitrogen molecules in the gas kinetics is pointed out, as well as the importance of nitrogen atom production in the long time scales of the glow discharge.     

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.

     

Analytical inductively coupled nitrogen and air plasmas

The operation of inductively coupled plasmas generated at atmospheric pressure in nitrogen or air in a modified 18 mm i.d. quartz tube assembly is evaluated for the analysis of aqueous solutions and fine powders. The instrumentation and detailed procedure for the generation of molecular-gas discharges are described. Limits of detection for nitrogen and air ICP discharges are compared, and for five elements at the same wavelength the nitrogen ICP produced significantly poorer values than the air plasma. The air ICP provided comparable values to those reported in the literature for argon. The sensitivity, signal-to-background ratio, and limits of detection for calcium were compared for argon, air, and argon with air central gas discharges with pneumatic and ultrasonic nebulization and for airborne calcium carbonate powders.     

Fundamental aspects and applications of glow discharge spectrometric techniques

Glow discharges are kind of plasmas which are used in many fields of application, including analytical spectrometry. This review addresses both the fundamental aspects and analytical applications of glow discharges. In the first part, a systematic overview of the most important plasma processes is presented. To obtain better insight into the complexity of the glow discharge, both mathematical modeling and experimental plasma diagnostics can be carried out. Therefore, the models that were developed for a glow discharge are presented and typical results (e.g. three-dimensional density profiles, fluxes and energy distributions of the various plasma species, the electric field and potential distributions, information about collision processes in the plasma and about sputtering at the cathode, etc.) are summarized. Moreover, the most important plasma diagnostic techniques for glow discharges are discussed. In the second part, an overview is given of the various analytical applications of glow discharges.