Characterization of argon metastable species as function of time, space, and current of a pulsed dc glow discharge

Optical measurements performed through an iCCD camera equipped with an optical bandpass filter have been carried out on a pulsed dc glow discharge (GD) in order to study the spatial, temporal, and current dependency of the 1s₅ (³P₂) Ar metastable (Ar*) species. For the spatial and temporal study the pressure was held constant at 1 hPa. The combination of the iCCD camera with the bandpass filter has allowed to acquire time-resolved images of the Ar* in a spatial region between the cathode and the anode. Those measurements have been performed through optical emission and absorption spectroscopy and have shown that the Ar* during the powering phase of the pulsed GD maximize in a spatial region close to the cathode (ca. 1 mm) and that at the end of the pulsed GD, in the so-called afterglow region, the Ar* maximize in a spatial region far from the cathode (between 6–8 mm). Then they reach their maximum intensity within the first 100 μs and decay within 200–250 μs, both after the end of the GD. It has also been observed that the Ar* species increase by increasing current.     

Thermoluminescence of thin polymeric films obtained in a glow discharge plasma

The thermoluminescence and radiothermoluminescence were studied of thin polymeric films produced in a glow discharge plasma. It was shown that during the formation of polymeric films in the plasma, not only radical states but also ionic states are stabilized in them. Four luminescence maxima were detected on the radiothermoluminescence curves of the films. The possible assignment of the position of these maxima on a temperature scale to the relaxational transitions in the films is discussed.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 24, No. 6, pp. 743–747, November–December, 1988.     

Reduction of supported noble-metal ions using glow discharge plasma

A novel plasma reduction method has been developed to reduce supported noble-metal ions without the use of any reducing chemicals. H2PtCl6, PdCl2, AgNO3, and HAuCl4 supported on nonporous TiO2 and porous gamma-Al2O3 and HZSM-5 were reduced using an Ar glow discharge plasma. Optical absorption spectra and X-ray photoelectron spectroscopy show that the supported metal ions are completely reduced to metallic species. Transmission electron microscopy shows that the prepared metals are amorphous clusters and homogeneously distributed with nanoscale sizes. X-ray diffraction also confirms that the plasma-reduced metals exist as small crystallites or amorphous clusters. Thermal annealing of plasma-reduced samples at elevated temperature transforms the clusters into crystals with a slight increase in particle sizes, but the sizes are still smaller than those of H2-reduced metals. O2 glow discharge plasma can also reduce noble-metal ions, accompanied by production of a small amount of oxides. Plasma reduction is very promising for the preparation of metal nanoparticles and supported metal catalysts.     

Thermoluminescence of a polyethylene surface after plasma treatment with a high-frequency glow discharge

The plasma treatment of polyethylene (PE) gives a specific pattern of thermoluminescence (TL). The qualitative difference between the TL curves of PE after plasma treatment and the curves for radioluminescence appears to be due both to specific features of the plasma treatment (attack on the surface of the sample and the unavoidable effect of photobleaching) and to the particular structure of the surface of the polymer (the existence or formation in the surface layer of special low-molecular structures). TL after plasma treatment can therefore be used to investigate the surface structure of polymers.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1742–1744, August, 1990.     

Aqueous p-nitrotoluene oxidation induced with direct glow discharge plasma

A plasma induced degradation process has been studied to treat 4-nitrotoluene (4-NT) present as an aqueous pollutant. The plasma was locally generated from a glow discharge around a tip of a platinum anode in an electrolytic solution. The influence of initial pH and Fe²⁺ on the degradation was examined. Major intermediates resulting from the degradation process were identified. Amongst the aromatic intermediates, p-hydroxybenzoic acid was the predominant degradation product. The formation of oxalic acid, malic acid was also observed. The final products of degradation were NH ₄ ⁺ , NO ₃ ⁻ and CO₂. Based on the analysis of intermediates and the kinetic considerations, the degradation was shown to follow a pseudo-first order reaction hence, a possible reaction pathway was proposed.     

Investigation of glow discharge plasma for surface modification of polypropylene

Material surface properties of polymers, plastics, ceramics and textiles can be modified by atmospheric or low‐pressure glow discharge plasma. The aim of the present work is to study the surface modification of biaxially oriented polypropylene (BOPP) film in order to improve its hydrophilic and wetting properties. In this article we used low‐pressure, low‐temperature oxygen plasma for the surface treatment of BOPP. Scanning electron microscopy indicates that plasma treatment causes mainly physical changes by creating microcraters and roughness on the surface and increasing surface friction. Attenuated total reflectance infrared spectra show oxygen‐containing groups such as ? OH at 3513 cm^?1 and C?O at 1695 cm^?1. Microscopic investigations of water droplets on BOPP (treated, untreated) show that the interfacial adhesion of treated surfaces is increased. Copyright © 2003 John Wiley & Sons, Ltd.     

Application of a modulated Grimm-type glow discharge plasma as primary light source for simultaneous reading atomic absorption spectrometry

Summary The Grimm-type glow discharge lamp (GDL) working in a modulated way can be used as primary light source for atomic absorption measurements. The number of element radiations is given by the composition of the target (sample on GDL) which becomes sputtered. Its composition can be adopted to the analytical problem to be solved. It is easy to change the target.The glow discharge source generated at relatively low power (10–24 W) is burning stable for >20 min on the same spot. This is time enough to operate atomic absorption measurements of 10 samples simultaneously, for example, by using the normal flame technique or the graphite tube furnace or the atomsource sputter method to generate atoms of the sample material. The monochromator device of an AA spectrometer has to be replaced by a polychromator one.The spectral behaviour of the glow discharge source compared to that of the hollow cathode lamps of the elements studied is described here by using a double beam two channel AA spectrometer for simultaneous reading of both the signals. In most cases the glow discharge source is the better one. Home-made targets are used to measure first analytical results.

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Einsatz einer modulierten Glimmentladungslampe als Primärlichtquelle zur simultan messenden Atomabsorptionsspektrometrie

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We have to thank the Spectruma company and Bernhard Bogdain especially for supporting this work.     

Chemical ionization mass spectrometry using a glow discharge ion source combined with a nebulizer sampling system

A glow discharge chemical ionization (CI) source equipped with a pneumatic nebulizer for sample introduction has been constructed. A comparative study of the discharge CI and conventional CI by electron impact from a hot filament is made for various polar compounds using oxygen-containing reagents such as water and methanol. The potential utility of the discharge ion source to liquid chromatography/mass spectrometry is also discussed.     

Spatially-resolved observation of glow discharge plasma for atomic emission spectrometry.

An imaging spectrograph equipped with a CCD detector was employed to measure two-dimensional emission images from a glow discharge plasma in atomic emission spectrometry. The emission images at Zn I 334.50 nm for a zinc sample and at Cu I 324.75 nm for a copper sample could be obtained. Their emission intensities were not uniform in the radial direction of the plasma region but became weaker at larger distance from the central zone. The two-dimensional distribution would result from a spatial variation in the excitation efficiency of the plasma and thus provide useful information for understanding the excitation processes occurring in the plasma.     

Factors influencing the analytical performance of an atmospheric sampling glow discharge ionization source as revealed via ionization dynamics modeling

A kinetic model is developed for the dynamic events occurring within an atmospheric sampling glow discharge that affect its performance as an ion source for analytical mass spectrometry. The differential equations incorporate secondary electron generation and thermalization, reagent and analyte ion formation via electron capture and ion-molecule reactions, ion loss via recombination processes, diffusion, and ion-molecule reactions with matrix components, and the sampling and pumping parameters of the source. Because the ion source has a flow-through configuration, the number densities of selected species can be estimated by applying the steady-state assumption. However, understanding of its operation is aided by knowledge of the dynamic behavior, so numerical methods are applied to examine the time dependence of those species as well. As in other plasma ionization sources, the ionization efficiency is essentially determined by the ratio of the relevant ion formation and recombination rates. Although thermal electron and positive reagent ion number densities are comparable, the electron capture/ion-molecule reaction rate coefficient ratio is normally quite large and the ion-electron recombination rate coefficient is about an order of magnitude greater than that for ion-ion recombination. Consequently, the efficiency for negative analyte ion formation via electron capture is generally superior to that for positive analyte ion generation via ion-molecule reaction. However, the efficiency for positive analyte ion formation should be equal to or better than that for negative analyte ions when both ionization processes occur via ion-molecule reaction processes (with comparable rate coefficients), since the negative reagent ion density is considerably less than that for positive reagent ions. Furthermore, the particularly high number densities of thermal electrons and reagent ions leads to a large dynamic range of linear response for the source. Simulation results also suggest that analyte ion number densities might be enhanced by modification of the standard physical and operating parameters of the source.     

The pulsed glow discharge as an elemental ion source

A pulsed glow discharge, rather than a conventional constant dc voltage discharge, is used as an ion source for a quadrupole mass spectrometer. Both sputter yield and ion signal are enhanced by using the pulsed system because of an increase in the voltage necessary to maintain a constant average current at the cathode over the pulse period. Irregularities are seen in the pulse spectrum that appear as rapid surges in the ion signal for both sputtered and contaminant gas species. These peaks appear at the beginning of the pulse for gaseous species but are limited to the postpulse period for sputtered species. Differences in the signal forms allow for the discrimination against selected types of ion signals by using narrow data collection gates placed over different portions of the pulse period.     

Determination of arsenic by hydride generation coupled to time-of-flight mass spectrometry with a gas sampling glow discharge

Hydride generation has been used with a gas-sampling glow discharge (GSGD) and time-of-flight mass spectrometry (TOFMS) for the determination of arsenic in solution. Helium, neon, hydrogen, and argon glow discharges have been successfully generated and characterized. Current–pressure–voltage curves were generated for each discharge in the presence and absence of hydride generation. The arsenic detection limit for each of the discharges was found to be 0.60 (HeGSGD), 3.8 (NeGSGD) and 6.4 ppb (H₂GSGD). The HeGSGD was found to be the most attractive source for arsenic determination due to the lower detection limit, higher sensitivity and greater stability. The figures of merit for these discharges were also compared to those obtained with hydride generation-inductively coupled plasma TOFMS. Noise power spectra obtained for the neon GSGD indicated that no discernible discrete-frequency (whistle-noise) components were present in the analyte signal.     

The kinetics of erosion of polyamide films under the action of a glow discharge plasma

Infrared internal reflection and absorption spectroscopy was used to study the kinetics of erosion of AL 60/40 polyamide films under glow discharge treatment. The degree of erosion was estimated quantitatively.     

Characterization of a glow discharge ion source for the mass spectrometric analysis of organic compounds

A glow discharge ion source has been constructed for the mass spectrometric analysis of organic compounds. Characterization of the source has been made by studying the effect of pressure and discharge current on ionic distributions by anodic ion sampling along the discharge axis. Ion and electron densities and electronic temperatures have been calculated by using the single Langmuir probe technique to correlate the extraction efficiency with measured ion distributions and gain some insight into the ionization of organic molecules. The spectra obtained for several classes of organic compounds show that formation of parent-molecular ions by proton transfer, resulting partly from the background water molecules, is a major low energy process while charge transfer, Penning ionization, and electron ionization ace probably responsible for the fragmentation observed. The spectra result from the simultaneous occurrence of high and low energy reactions, and their structural information content is very high, yielding both molecular and extensive fragment ion information. The glow discharge ion source has proved to be essentially maintenance-free, easy to operate, stable, and can be used at reasonable mass resolution (up to 70001. The source also provides picogram range detection limits and has a linear response range of about six orders of magnitude, which makes it an interesting ion source for routine analysis. Preliminary work conducted with chromatographic interfaces indicates that its use can be easily extended to both gas and liquid chromatography.     

Effects of easily ionizable elements on the liquid sampling–atmospheric pressure glow discharge

A series of studies has been undertaken to determine the susceptibility of the liquid sampling–atmospheric pressure glow discharge (LS–APGD) atomic emission source to easily ionizable element (EIE) effects. The initial portions of the study involved monitoring the voltage drop across the plasma as a function of the pH to ascertain whether or not the conductivity of the liquid eluent alters the plasma energetics and subsequently the analyte signal strength. It was found that altering the pH (0.0 to 2.0) in the sample matrix did not significantly change the discharge voltage. The emission signal intensities for Cu(I) 327.4 nm, Mo(I) 344.7 nm, Sc(I) 326.9 nm and Hg(I) 253.6 nm were measured as a function of the easily ionizable element (sodium and calcium) concentration in the injection matrix. A range of 0.0 to 0.1% (w/v) EIE in the sample matrix did not cause a significant change in the Cu, Sc, and Mo signal-to-background ratios, with only a slight change noted for Hg. In addition to this test of analyte response, the plasma energetics as a function of EIE concentration are assessed using the ratio of Mg(II) to Mg(I) (280.2 nm and 285.2 nm, respectively) intensities. The Mg(II)/Mg(I) ratio showed that the plasma energetics did not change significantly over the same range of EIE addition. These results are best explained by the electrolytic nature of the eluent acting as an ionic (and perhaps spectrochemical) buffer.     

Analytical performance of high-voltage neon plasma in glow discharge optical emission spectrometry

In a high-voltage Ne glow discharge plasma (Ne-GDP), calibration factors as well as the limit of determination were compared between atomic resonance lines and singly-ionized lines of copper and aluminium in optical emission spectrometry. These elements have intense ionic lines which are excited by resonance charge-transfer collisions of Ne ions. The ionic lines gave better detection sensitivity in the Ne-GDP, whereas the atomic resonance lines were commonly employed as analytical lines in the other plasma sources such as Ar-GDP and ICP. The limit of determination was 1.3 × 10^–3 mass % for the Cu II 248.58 nm line and 1.0 × 10^–3 mass % Al for the Al II 358.66 nm line at a discharge parameter of 1.60 kV/36 mA.     

射频等离子体对合成低碳醇用CuCoAl催化剂的改性作用

采用共浸渍法制备了CuCo/γ-Al₂O₃催化剂,应用射频等离子体技术对催化剂进行改性处理。以CO加氢合成低碳醇为模型反应对催化剂进行活性评价,通过X射线物相分析(XRD)、氢氧滴定(HOT)、CO程序升温脱附(CO-TPD)和程序升温还原(TPR)等技术对催化剂进行表征,研究了射频等离子体技术强化处理对催化剂结构、吸附性能和还原性能的影响。结果表明,等离子体技术改性处理提高了催化剂活性组分的分散度,细化了铜物种的晶粒尺寸,增加反应活性位并调变了活性位对吸附物种的吸附强度,改进了催化剂的还原性能,等离子体改性处理的催化剂比未处理的样品CO加氢反应活性和低碳醇的时空产率显著提高。     

Kinetic temperatures and electron densities in the plasma of a side view Grimm-type glow discharge

A special source in which the Grimm-type plasma is viewed side-on for spectroscopic measurements was constructed. The kinetic gas temperatures and electron densities were derived from the line profiles of Ar I 415.8 nm and He I 447.1 nm respectively.