An Optical Emission Study on Expanding Low-Temperature Cascade Arc Plasmas

The optical emission spectra from expanding low-temperature cascade arc plasmas were studied. The objective of this study was to examine the distinctive features of low-temperature cascade arc plasmas in comparison with a radio frequency (RF) plasma source. The principal results obtained in this study were: (1) in an expanding cascade arc plasma jet, active heavy particles (mainly excited argon or helium neutral species under our operating conditions), rather than electrons, are responsible for the excitation of reactive species when a reactive gas is injected into the plasma jet, (2) the excitation of reactive species was found to be controlled by the electronic energy levels of these excited argon or helium neutrals, (3) changing the operating parameters affected only the emission intensities of excited species, and no effect on the emission nature of plasmas was observed.     

Penetration of plasma surface modification into porous media. III. Multiple samples exposed to CF4 and C2F4 low temperature cascade arc torch

The depth and possible mechanisms of the penetration of surface modification into porous media by a low temperature cascade are torch are investigated. Two different modes of such penetration (“flow controlled” and “diffusion controlled”) are evaluated. Three porous samples [stacks of 10 sheets of nonwoven fabrics of poly(ethylene terephthalate)each], placed at an axial distance of 24, 28, and 32 cm from the cascade are anode, are exposed to a low temperature cascade arc torch containing argon and CF₄ or C₂F₄, and surface properties of each of the sheets within treated porous samples are examined by ESCA. It is shown that interaction of chemically reactive species, created in the low temperature cascade arc torch, with the surface is not limited to the surface directly contacted by the torch. The flow controlled penetration is more pronounced for the outer layers, while diffusion controlled penetration is within the inner layers of the porous structure. Substantial differences in the fluorination effect of CF₄ (nonpolymer forming gas) and C₂F₄ (polymer forming gas) discharges for the second and third stacks are observed, that can be explained by the fact that the major effect of the CF₄ cascade arc torch treatment is based on the reaction of reactive species with the surface polymer molecules. The effect of C₂F₄ cascade arc torch treatment is based on the reactions of reactive species with polymers as well as reactions of reactive species themselves at the surface (plasma polymerization). Reactivity of the species created in C₂F₄ discharge is much higher compared to that created in CF₄ discharge, which is one of the major factors influencing penetration trends of low temperature cascade arc treatment into porous media. © 1995 John Wiley & Sons, Inc.     

Deposition behavior in a low‐temperature cascade arc torch (CAT) polymerization process

Two kinds of hydrocarbon type monomers and three kinds of organosilicons were polymerized by a low‐temperature cascade arc argon plasma torch. Their deposition behaviors were studied as a function of experimental parameters and monomer elemental compositions. It was found that the normalized deposition rate (DR), expressed as deposition yield of DR/(FM)_m, was determined by a composite operational parameter, W*(FM)_c/(FM)_m, where W is the power input, and (FM)_c and (FM)_m are the mass flow rates of carrier gases and monomers, respectively. Experimental results indicated that the deposition yield is highly dependent on the elementary compositions of monomers. Optical emission spectroscopy study on the argon plasma torch showed that the emission intensity of excited argon neutrals was proportional to the value of the parameter W*(FM)_c. These results further certified that excited argon neutrals are the main energy carriers from the cascade arc column to activate monomers in the argon plasma torch. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 967–982, 1999     

Penetration of plasma surface modification. II. CF4 and C2F4 low-temperature cascade arc torch

The depth of surface modification by low-temperature cascade arc torch is investigated. A stack of 10 sheets of nonwoven fabrics of polyester fibers is exposed to a low-temperature cascade arc torch containing CF₄ or C₂F₄, and the fluorination effect is examined by ESCA. It is shown that interaction of chemically reactive species, created in a low-temperature cascade arc torch, with the surface is not limited to the surface contacted by the torch (flame). The results indicate that the fluorination effect is observed on surfaces which are shadowed from the torch by overlying fibers. The highest degree of fluorination is found on the second layer, rather than on the first layer which the torch contacts directly. No significant differences in the trends of penetration of CF₄ and C₂F₄ treatment through porous samples are observed. However, ESCA data show principal differences in chemical structures of the surfaces treated with CF₄ (nonpolymer-forming gas) and C₂F₄ (polymer-forming gas). These results indicate that chemically reactive species induced by the excited species of argon rather than primary species created by the ionization process seem to play predominant roles in the surface treatment as well as the low-temperature cascade arc torch polymerization of perfluorinated compounds. © 1994 John Wiley & Sons, Inc.     

Some analytical characteristics of an argon—nitrogen d.c. plasma arc for emission spectrometry

A low-power d.c. plasma arc device was used to estimate the analytical characteristics of an Ar—N₂ plasma arc compared to those of an argon plasma arc. When the flow rate of added nitrogen was varied from 0 to 1 l min^-1, the Cd I 228.802-nm line showed a maximum signal-to-background ratio at a nitrogen flow rate of approximately 0.3 1 min^-1 which corresponds to 0.23% of the total argon flow rate. Ratios of the signal intensities with the Ar—0.23%N₂ and argon plasma arcs are given for the spectral lines of seventeen elements. Relatively higher ratios were found for the atom lines of the group VIII through IIIA elements in the periodic table. Better precision and lower detection limits were attained for aluminium and cadmium with the Ar—0.23%N₂ plasma arc than with the argon plasma arc.     

Thin film deposition from plasmas of tetramethylsilane–helium–argon mixtures with oxygen and with nitrogen

Films were produced by plasma enhanced chemical vapor deposition (PECVD) of tetramethylsilane (TMS)–helium–argon mixtures with either oxygen or nitrogen in a vacuum system fed with radiofrequency power. Actinometric optical emission spectroscopy was used to determine trends in the concentrations of plasma species of interest (H, CH, O, CO, and CN) as a function of the ratio of the inorganic reactive gas (oxygen or nitrogen) to the monomer (TMS) in the system feed. As the ratio of oxygen to TMS in the feed is increased, the degree of oxygenation of the deposited material, as revealed by transmission infrared spectroscopy, is also increased. Similarly, the degree of nitrogenation of the films increases with increasing nitrogen to monomer ratio in the feed. Strong correlations exist between the plasma concentrations of the above-mentioned plasma species and film structure and composition. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1873–1879, 1998     

Influence of hydrocarbon gasses on PECVD a-C:H film deposition

Hydrogenated amorphous carbon layers (a-C:H) deposited at near room temperature by CH₄ and C₂H₂-Ar rf discharges have been studied. Discharge processes were investigated using growth kinetics and optical emission spectroscopy (OES). The role of plasma chemistry and of ion bombardment is discussed. Addition of argon, necessary to stabilize the C₂H₂ discharge, is found to enhance susbstantially gas phase processes such as dissociation, formation of atomic hydrogen and of CH, C₂, C₃ species (revealed by OES). It appears that rf plasma is very efficient for dissociation and ionization processes with threshold energies in the ten eV range. The layers' properties have been characterized by means of UV-Visible absorption, Fourier transform IR and Raman spectroscopies.     

The Effects of Gas Composition on Active Species and Byproducts Formation in Gas–Water Gliding Arc Discharge

The effects of gas composition on hybrid gas–water gliding arc discharge plasma reactor have been studied. The voltage cycles are characterized by a moderate increase in the tension which is represented by a peak followed by an abrupt decrease and a current peak in the half period (10 ms). Emission spectrum measurements revealed that ^•OH hydroxyl radicals are present in the discharge with feeding any gas. The H₂O₂ concentrations reach 38.0, 15.0, 10.0, and 8.0 mg/l after 25 min plasma treatment with oxygen, argon, air, and nitrogen, respectively. O₃ was produced when oxygen and air are used, but not when nitrogen and argon. The O₃ concentration reached the highest value 1.0 mg/l after 25 min plasma treatment with oxygen feeding gas, but gradually decreased to 0.2 mg/l after that. With feeding nitrogenous gas, NO₂ ⁻ and NO₃ ⁻ byproducts were formed by the plasma chemical process.     

Diagnostics of a Radio-Frequency Plasma Expanding Through a Nozzle (PETN) at Low Pressure

The diagnostics of the radio-frequency (induction mode) plasma expanded through a nozzle (PETN) at low pressures (100–1000 Pa) was performed by on-line optical emission spectroscopy (OES) and on line quadrupole mass spectrometry (QMS). The OES was used for evaluating the electronic, vibrational, and rotational temperatures (T_e, T_v, and T_r) along the plasma reactor before and after the nozzle. The PETN gas mixtures analyzed were Ar+N₂, Ar+CO, and Ar+O₂with an addition of 1 vol.% N₂to the last two gas mixtures. For the same conditions in the PETN the values of T_e, T_v, and T_r were found to be different for the different gas mixtures and related to the depopulation of excited N ₂ ⁺ by oxygen atoms. Moreover the Ar+O₂PETN aqueous solutions of lanthanum and manganese nitrates were nebulized for the deposition of LaMnO₃perovskite. The QMS, in real time, measuring the mass species formed before and after the nozzle, explained the reasons in the different values of T_e, T_v, and T_r for the three gas mixtures as well as for the formation of oxides in the PETN from the aqueous nitrate solutions.     

Carbon Dioxide Reforming of Methane Using a Dielectric Barrier Discharge Reactor: Effect of Helium Dilution and Kinetic Model

The carbon dioxide reforming of methane to synthesis gas was investigated in a dielectric barrier discharge reactor at room temperature. The influence of dilution of reactants by helium was studied. We showed that, at a fixed contact time, the conversions of CH₄ and CO₂ increase when the amount of helium in the gas mixture increases. This result is attributed to the “penning ionization” phenomenon, which corresponds to an energy transfer from excited He to molecules in ground state (CH₄, CO₂). The selectivity to products is affected by the dilution factor. As soon as helium is present in a large amount the formation of products resulting from recombination of methyl radicals (such as C₂, C₃ and C₄) is less favourable due to the lowest probability of collisions to proceed. A kinetic model is proposed based on the assumption that the reactant molecules CH₄ or CO₂ are attacked by active species produced by the plasma discharges, and the production of this active species are function of the plasma power. This model which takes into account the dilution by helium fits particularly well the experimental data we obtained.     

The chemical reduction of small inorganic gases in an electrothermal plasma reactor

Chemical reduction of small inorganic gases is accomplished using an electro-thermal plasma reactor. This benchscale reactor maintains a highly reactive plasma zone in a fluidized bed of carbon particles through which an electrical current is discharged. The carbon particles function as current-controlling media, heat sinks and reaction sites. Chemicals introduced into this medium are subjected to a variety of energy sources and chemically reactive species, which result in chemical reduction. It is shown that the inorganic gases, H₂O, CO₂, NO, NO₂ and SO₂, are chemically reduced in the plasma zone of the reactor. The end products consist of hydrogen, carbon monoxide and nitrogen gases. Additionally, elemental sulfur is deposited onto the carbon particles.     

Polymerization and degradation of polyacrylonitrile in gas discharge

The plasma polymerization of acrylonitrile and the plasma degradation of polyacrylonitrile have been studied mass-spectrometrically in high-frequency gas discharge at low pressure. The polymerization was found to proceed without decay to gaseous products. During the polymerization, the monomer partial pressure in the closed plasma-chemical reactor decreased exponentially. When treating polyacrylonitrile in argon plasma, the polymer decayed to C, H₂ and N₂; in oxygen plasma, the species were C, H₂, N₂, H₂O, CO and CO₂. Unlike the thermal decomposition, no traces of monomer and oligomers were detected among the products of plasma degradation.     

A Mathematical Model of the Carbon Arc Reactor for Fullerene Synthesis

A mathematical model of the carbon arc process for the synthesis of fullerenes (C ₆₀ , C ₇₀ ) is developed. The two-dimensional model solves for the velocities, temperature, and total concentration of carbon species. The net emission coefficient method is used for the radiation term. The carbon species conservation equations consider the evaporation of carbon from the anode, cathode surface deposition, and carbon condensation. The thermodynamic and transport properties are calculated as a function of temperature and carbon mass fraction, using the method of Chapman–Enskog. Erosion rates used by the model are determined experimentally. Calculated fields of the velocities, temperatures, carbon mass fraction and current intensity are presented. Comparison is made of the behavior of the arc at 1 and 4 mm interelectrode gaps, and between operation in argon and in helium. The results of simulations provide a justification for the higher yields observed in helium compared to the argon case.     

Excitation of Species in an Expanded Argon Microwave Plasma at Atmospheric Pressure

The excitation capability of an argon microwave plasma flame expanded at atmospheric pressure has been studied. For this purpose, argon with different proportions of nitrogen was introduced at the end of the expanded flame, where the population densities of the atomic argon levels were still high enough. Optical emission spectra allowed the identification of different excited species in the plasma. When argon containing nitrogen was added at the end of the plasma flame, all argon lines emitted in this region were highly quenched, emission due to species containing nitrogen (NH, CN) was enhanced and a noticeable increase in the emission of N₂ (C ³Π_u ? B ³Π_g) was observed. On the contrary, the weak emission of $ {\text{N}}_{2}^{ + } \left( {B^{ 2} \sum_{u}^{ + } - X^{ 2} \sum_{g}^{ + } } \right) $ was scarcely affected. According to these results it is possible to conclude that metastable argon atoms from the expanded flame are the main energy carriers when generating N₂ reactive species in this plasma zone.     

A microwave induced plasma system for the maintenance of moderate power plasmas of helium,argon, nitrogen and air

A microwave induced plasma system capable of maintaining stable plasmas of each of the gases helium, argon, nitrogen and air is presented. The system is capable of operation at powers of up to 500 W. The TM₀₁₀ cavity design is similar to that previously described in the literature with some modifications. A demountable torch facilitates centering of diffuse plasmas of helium, nitrogen and air by providing 6 flows directed tangentially within the quartz tube. This torch was not useful for argon plasmas. Toroidal argon plasmas were maintained with a threaded quartz tube arrangement. The heat generated by these plasmas was dissipated by an outer sheath of coolant air. Details of the design and preliminary characterization of each plasma system is presented.     

Applicability of microwave induced plasma optical emission spectrometry (MIP-OES) for continuous monitoring of mercury in flue gases

The applicability of microwave-induced plasma optical emission spectrometry (MIP-OES) for continuous monitoring of the environmentally hazardous element mercury in flue gases has been studied. Microwave induced plasmas have been sustained using both a TM₀₁₀ cavity (Beenakker resonator) and a so-called Surfatron. The analytical figures of merit for mercury in argon and helium discharges with both types of low-power micro-wave discharges have been examined. To determine mercury in artificial stack gases non-mixed argon/nitrogen discharges have been tested using a tangential flow torch design which allows to introduce a metal-loaded nitrogen gas flow as external gas and argon as internal gas. The addition of main flue gas components such as water vapour (concentration <6 g/m³), oxygen (<4% v/v) and carbon dioxide (<15% v/v) decrease the mercury line intensities to a considerable extent. Trace gases (CO, HCl, SO₂, NO) in concentrations typical to waste incineration processes have been found to have no effect on the mercury and the argon line intensities. The detection limit of mercury in nitrogen is 8 g/m³ using the TM₀₁₀ MIP and 10 g/m³ using the Surfatron. As such low detection limits are below the emission limit values of present-day environmental legislation MIP-OES is useful for on-line monitoring of mercury.Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday     

Study of Mechanism for Hexane Decomposition with Gliding Arc Gas Discharge

The mechanism of hexane decomposition under gliding arc gas discharge conditions is studied from both qualitative and quantitative analyses of its products for various hexane initial concentrations and different background atmospheres : nitrogen, argon, air (O₂ 21% N₂ 79% vol.) and N₂–O₂ mixtures. The decomposition rate, which decreases with increasing hexane initial concentration, can reach 94% when the carrier gas is air. Due to the electron energy consumed by the dissociation of nitrogen, the decomposition rate of hexane in nitrogen is lower than in argon. The radical channel plays a predominant role in the hexane decomposition process. With increasing oxygen concentration in the carrier gas, the hexane decomposition rate increases and promotes the conversion of CO– CO₂, but it also leads to the formation of NO₂.     

Spatially resolved spectroscopic measurements of a dielectric barrier discharge plasma jet applicable for soft ionization

An atmospheric pressure microplasma ionization source based on a dielectric barrier discharge with a helium plasma cone outside the electrode region has been developed for liquid chromatography/mass spectrometry and as ionization source for ion mobility spectrometry. It turned out that dielectric barrier discharge ionization could be regarded as a soft ionization technique characterized by only minor fragmentation similar to atmospheric pressure chemical ionization (APCI). Mainly protonated molecules were detected. In order to characterize the soft ionization mechanism spatially resolved optical emission spectrometry (OES) measurements were performed on plasma jets burning either in He or in Ar. Besides to spatial intensity distributions of noble gas spectral lines, in both cases a special attention was paid to lines of N₂⁺ and N₂. The obtained mapping of the plasma jet shows very different number density distributions of relevant excited species. In the case of helium plasma jet, strong N₂⁺ lines were observed. In contrast to that, the intensities of N₂ lines in Ar were below the present detection limit. The positions of N₂⁺ and N₂ distribution maxima in helium indicate the regions where the highest efficiency of the water ionization and the protonation process is expected.     

Comparison of helium and argon as collision gases in the high energy collision-induced decomposition of MH+ ions of peptides

Collision-induced decompositions (CID) of protonated peptides were studied using a four-sector mass spectrometer. The collision gases employed were helium and argon. The CID spectra of several peptides covering the molecular mass region of 905–2465 u were recorded. These investigations established several previously unrecognized differences between the CID spectra obtained with helium and argon as collision gases. These can be summarized as follows: (1) Structurally significant and specific side chain fragmentations (d_n ^f, w_n ^f and v_n, ion types) are greatly reduced or completely missing in the CID spectra obtained with helium as a collision gas compared to those obtained with argon. (2) As the peptide molecular mass increases, argon, which is heavier than helium, is increasingly more efficient than helium for generating fragment ions.     

Application of Pulsed Traveling Hydrogen Arcs for Metal Oxide Reduction

A plasma reactor that has a transient traveling arc has been used to study hydrogen in relation to in-flight reduction of metal oxide particles. Experiments were done to determine the nature of the arc and its interaction with the reactor gas. The lifetime of the excited atomic hydrogen was measured and it was found to be more than 4 ms after the arc had ceased. Powders and tablets of oxides were exposed to the pulsed-arc treated hydrogen and found to react much more rapidly and intensely than when exposed to hot molecular hydrogen. The results suggest that atomic hydrogen will exist throughout the volume of such a reactor for a period that is sufficient to reduce particles of FeO, Cr₂O₃, and TiO₂.