Effect of Ar/H2 and Kr/H2 mixtures as discharge gas on the ion intensity in dc glow discharge mass spectrometry

 In dc glow discharge mass spectrometry, the addition of small amounts of H₂ to pure Ar as discharge gas has greatly increased the ion intensities of elements compared with the conventional method using pure Ar. This phenomenon was also observed for the addition of H₂ to pure Kr. The reason for the increase of the ion intensities of elements was studied by using a Kr gas mixture containing 0.2% (v/v) H₂. The ion intensities of the elements P, Se and As (whose first ionization potentials are higher than the energy levels of the excited state of Kr) did not increase even if the Kr/H₂ gas mixture was used. The results show that the addition of H₂ significantly contributed to increasing the number of metastable argon or krypton atoms (Penning ionization). Received: 4 November 1995/Revised: 5 January 1996/Accepted: 10 January 1996     

Effect of Ar/H2 and Kr/H2 mixtures as discharge gas on the ion intensity in dc glow discharge mass spectrometry

 In dc glow discharge mass spectrometry, the addition of small amounts of H₂ to pure Ar as discharge gas has greatly increased the ion intensities of elements compared with the conventional method using pure Ar. This phenomenon was also observed for the addition of H₂ to pure Kr. The reason for the increase of the ion intensities of elements was studied by using a Kr gas mixture containing 0.2% (v/v) H₂. The ion intensities of the elements P, Se and As (whose first ionization potentials are higher than the energy levels of the excited state of Kr) did not increase even if the Kr/H₂ gas mixture was used. The results show that the addition of H₂ significantly contributed to increasing the number of metastable argon or krypton atoms (Penning ionization). Received: 4 November 1995/Revised: 5 January 1996/Accepted: 10 January 1996     

H2/Ar direct current glow discharge mass spectrometry at constant voltage and pressure

The addition of hydrogen to a direct current (dc) - argon glow discharge (GD) coupled to a time of flight mass spectrometer has been studied using a fixed voltage between the electrodes and a fixed discharge pressure. Hydrogen contents investigated were 0.5%, 1% and 10% v/v in the argon discharge and the samples under study consisted of a copper-base, a nickel-base and an iron-base homogeneous materials. Also, the in-depth profile analysis of a tin plate was investigated. Results have shown that hydrogen addition gives rise to significant changes in the slope of the linear relationship between the electrical current and the discharge voltage. Clearly, the electrical resistance of the discharge at the typical operation voltages in the interval 600–1000 V increases with hydrogen added to pure argon.A decrease of the sputtering rates was observed the higher the hydrogen concentrations. Besides, the “reduced sputtering rates”, i.e. the sputtering rates divided by the corresponding electrical current, were also lower for the H₂/Ar discharges than for pure argon. However, the analytical ion signals observed using discharge voltages higher than 900 V turned out to be higher in a 0.5% H₂/Ar discharge than in pure argon for the copper and nickel materials. Besides, for the three samples investigated the ion yields were from 1.5 up to 3 times higher in 0.5% H₂/Ar discharges as compared to the pure argon.Finally, the effect of 0.5% H₂ addition to the Ar discharge on the in-depth profile of a tin plate has also been investigated. As compared to the use of a pure Ar GD, higher sensitivity for major and minor components of the coating were observed without loss of the relative depth resolution achieved.     

Application of RF GDMS for trace element analysis of nonconducting La0.65Sr0.3MnO3 ceramic layers

Radio-frequency glow discharge mass spectrometry (RF GDMS) has been applied to the determination of trace elements in ceramic perovskite layers (La_0.65Sr_0.3MnO₃) using synthetic standards. For the preparation of these standards high-purity powder of the basic material (La_0.65Sr_0.3MnO₃) was doped with trace elements in concentrations from 20 to 500 μg/g and the mixture was pressed to compact samples. The resulting calibration curves and the calculated relative sensitivity factors (RSF) differed only from 0.4 to 2 for different elements. For nearly all elements the standard deviations in the determination of trace elements in La_0.65Sr_0.3MnO₃ were better than 15% and detection limits (using the 3σ-criterion) were below 10 μg/g. Changes of the discharge parameters (RF power, pressure of the discharge gas (Ar) in the RF glow discharge) have no significant influence on the sensitivity to elements.     

Chemical structure and surface morphology evolution of glow discharge polymer films by Ar‐ions intermittent etching

The Ar‐ions intermittent‐etching technique was successfully incorporated during the deposition of glow discharge polymer (GDP) films. The ionic components and ion energy distributions (IEDs) of C₄H₈/H₂ and C₄H₈/H₂/Ar plasma were diagnosed by an energy‐resolved mass spectrometer, respectively. The Fourier transform infrared spectroscopy, scanning electron microscope, and white‐light interferometer were used to studying the chemical structure, surface morphology, and roughness of the GDP films, which are deposited with the various time of Ar‐ions intermittent etching. With the introduction of Ar into the chamber, the intensity of the C H absorption peaks becomes weak and the large‐mass C H species were ionized and dissociated from the mass spectrometer results. The surface roughness of GDP films are decreased with Ar‐ions intermittent etching, the lowest surface roughness (Rq) is only 33.6 nm when the intermittent cycle is 60 minutes/15 minutes. The highest sp³CH₃ (sym) absorption peaks are attributed to samples also with 60‐minute/15‐minute intermittent cycle, which shortens the length of the carbon chain and reduces the probability of the cluster formations.     

Simple and quick rotational temperature determination in N2-containing discharge plasma

A quick spectroscopic method of rotational temperature determination based on the low-resolution emission spectrum of the N₂ (v=2v=()) vibronic band profile of the second positive system iras developed. The new method of molecular gas temperature determination was used in an rf glow discharge excited in N₂ and N₂ + Ar + B₂ H₆ gas mixture at u pressure range 500–13011 Pa. This method of molecular gas temperature measurement is applicable to nonisothermic plasmas used in plasma-chemical reactors.     

Determinations of Intermediate Neutral Species in Hydrocarbon Discharge Plasma

This work reports laser ionization combined with Time-Of-Flight (TOF) mass spectrometry investigation on intermediate species in the hydrocarbon plasma of atmospheric-pressure fast-flow pulsed dc-discharge. All neutral intermediate species including transient radicals from benzene/Ar discharge have been characterized by a molecular beam sampling combined with TOF mass spectrometry. This shows that with a hydrocarbon gas mixture of 0.3% C₆H₆ in Ar discharge the intermediate species consist of simple radicals (such as C₂, C₅H₅, C₇H₇) and polycyclic organic molecules (C₁₀H₈, C₁₃H₁₀, C₁₄H₁₀). Theoretical studies on total energies and ionization potentials of the intermediate species have been carried out using the hybrid density functional theory. Effect of the ionization potential on mass spectral intensity has been discussed. Based on the observed data, the possible major neutral reaction channels of the plasma chemistry have been discussed. The developed experimental method has implications in volatile organic compounds removing and impurities diagnosis in Tokamak edge-plasma.     

The dehydrogenation of cyclohexane on an AP-64 industrial platinum catalyst subjected to plasma chemical treatments

The influence of glow discharge plasma in oxygen and argon and high-frequency discharge plasma in hydrogen on the activity of the AP-64 (Pt/γ-Al₂O₃) catalyst in the dehydrogenation of cyclohexane was studied. The catalytic experiments were performed in a flow unit and under static conditions in a vacuum. Under flow conditions, catalyst treatment with plasmas in O₂ and Ar decreased the yield of benzene by ～50% but strengthened temperature hysteresis because of the formation of active carbon on the surface of the catalyst. Under static conditions, argon plasma and high-frequency discharge H₂ plasma multiply increased the rate of the reaction because of an increase in the number of active centers, whereas an oxygen plasma decreased the rate of the reaction by two times because of an increase in activation energy. The determination of the order of the reaction led us to suggest that the stage scheme of the reaction did not change after plasma chemical catalyst treatments.     

Some aspects of plasma copolymerization of acetylene with N2 and/or water

Plasma polymerizations of mixture of acetylene-N₂, acetylene-H₂O, were investigated by using an electrodeless glow discharge from a 13.5-MHz radiofrequency source. Properties of plasma polymers were examined as functions of mole ratios of N₂ and/or H₂O to acetylene. The concentration of trapped free radicals and the internal stress in a plasma polymer decreased as the mole ratio of N₂ or H₂O increased. Water showed the most pronounced effects in those properties at the mole ratio of 0.3. Gas permeabilities increased by the copolymerization of N₂ and/or H₂O. Surface energies were also investigated by analysis of contact angles of liquids. Copolymerization of N₂ caused a remarkable increase in polar contribution of surface energy. Some fundamental aspects of flow-rate pressure relationship of mixed gases are presented.     

The vibrational relaxation of H2. I. Experimental measurements of the rate of relaxation by H2, He,Ne, Ar,and Kr

The vibrational relaxation of gaseous H₂ in mixtures with He, Ne, Ar, and Kr was studied by the laser Schlieren technique in incidents shock waves at 1350–3000 K. From the results of 155 experiments the following standard relaxation times for self-relaxation of H₂ and relaxation of H₂ by He, Ne, Ar and Kr were obtained:

pτ is in atm s, and the qouted uncertainties are standard deviations. The results for H₂/H₂ and H₂/Ar are in very good agreement with previous results of Kiefer and Lutz, and the extrapolated for H₂/H₂, H₂/He and H₂/Ar agree very well with low temperature data Ducuing.The linear mixture rule for a additivity of relaxation rates was found to hold, to within experimental accuracy, for the mixtures studied in the present work.     

Combination of glow-discharge and arc plasmas for CF4 abatement

Decomposition of CF₄ by glow-discharge and arc plasmas was studied using a tubular quartz reactor, a disk type, and a T-type quartz reactor. The effects of different metal electrodes, input voltage, and reactor type on the efficiency of CF₄ total destruction (DRE) were studied. The T-shape reactor was more efficient in CF₄ destruction than either the disk or tubular type due to a combined effect of glow discharge and arc plasmas. Several hydrogen and oxygen sources, such as H₂O, H₂, O₂, and CH₄, were used to convert CF₄. Using H₂ and O₂ as the hydrogen and oxygen sources presented better DRE than using H₂O. The effect of different hydrogen and oxygen sources on the conversion of CF₄ followed the trend: (H₂ + O₂) > (CH₄ + O₂) > H₂O. The maximum DRE of 95% was observed with 0.5% CF₄ using H₂ and O₂. A mass spectrometer and an emission spectroscope equipped with a charge-coupled detector (CCD) were used to characterize the products and intermediates. Mass spectrometric studies indicated that the reaction products were HF, CO₂, and trace amounts of NO. N₂ first negative and second positive emission lines were observed in the glow discharge plasmas as well as in the arc plasmas of N₂. However, C and F intermediates were observed only in arc plasmas of CF₄. Reactions occurring in the glow discharge plasmas and arcs seem to follow different mechanisms.     

POLYMERIZATION OF OCTAFLUOROCYCLOBUTANE IN GLOW DISCHARGE Ⅱ. ESCA AND IR CHARACTERIZATION OF POLYMER STRUCTURE*

In a capacitively coupled discharge with external electrodes, He, H_2, N_2 or Ar were used as plasmagas, polymerization of octafluorocyclobutane was carried out under different conditions by varyingdischarge power, pressure, plasma gas and plasma-gas/monomer ratio. Structure of polymerizedproducts was characterized by IR spectroscopy and ESCA measurement. It was found that therewere six elements in the products, i.e. C, F, Si, O, N and H. The probably existed groups in poly-mers wer investigated. By analyzing the resolved peaks of C_(1S) region in ESCA spectra, effect of thereaction conditions on degree of branching of the polymerized products and the relationship of thepolymer structure wth the mechanism of the competitive ablation and polymerization process werestudied. In addition, polymer deposition process occurring in glow discharge was discussed.     

Ultrasensitive determination of mercury by ICP-OES coupled with a vapor generation approach based on solution cathode glow discharge

We herein proposed a sample introduction technique based on solution cathode glow discharge（SCGD）of a portable design for inductively coupled plasma-optical emission spectrometry（ICP-OES） and its application in sensitive determination of mercury. The products from SCGD containing mercury vapor, were transported by an Ar flow to ICP spectrometer for detection. A gas liquid separator（GLS） and a dryer were used to condense and remove most of the accompanying moisture, which greatly improved both th...     

A simple reactive gasdynamic model for the computation of gas temperature and species concentrations behind reflected shock waves

A simple gasdynamic model, called CHEMSHOCK, has been developed to predict the temporal evolution of combustion gas temperature and species concentrations behind reflected shock waves with significant energy release. CHEMSHOCK provides a convenient simulation method to study various sized combustion mechanisms over a wide range of conditions. The model consists of two successive suboperations that are performed on a control mass during each infinitesimal time step: (1) first the gas mixture is allowed to combust at constant internal energy and volume; (2) then the gas is isentropically expanded (or compressed) at frozen composition to the measured pressure. The CHEMSHOCK model is first validated against results from a one‐dimensional reacting computational fluid dynamics (CFD) code for a representative case of heptane/O₂/Ar mixture using a reduced mechanism. CHEMSHOCK is found to accurately reproduce the results of the CFD calculation with significantly reduced computational time. The CHEMSHOCK simulation results are then compared to experimental results, for gas temperature and water vapor concentration, obtained using a novel laser sensor based on fixed‐wavelength absorption of two H₂O rovibrational transitions near 1.4 μm. Excellent agreement is found between CHEMSHOCK simulations and measurements in a progression of shock wave tests: (1) in H₂O/Ar, with no energy release; (2) in H₂/O₂/Ar, with relatively small energy release; and (3) in heptane/O₂/Ar, with large energy release. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 189–198, 2008     

Nitrogen effects in multi-matrix calibrations by radiofrequency glow discharge – optical emission spectrometry

A study about the effect of nitrogen in the calibration curves of a series of analytical emission lines has been carried out in this work. Fifteen reference materials with different matrices (Fe, Al, Zn, Cu and Ni) were used (three of these reference materials contain nitrogen in their composition) and plots of intensity versus the product “sputtering rate times element concentration” were constructed for emission lines of the analytes considered in this work (Al, Fe, Cu, Cr, C, Mo, Zn, Si, Ti and Ni). Two different fits were performed in each plot, first considering only the points corresponding to samples without nitrogen in their composition and secondly including all the points. The results show almost negligible differences in the emission yields calculated. On the other hand, a mixture of Ar containing 0.5% N₂ was employed to check if the nitrogen effect was present at higher concentrations than those expected in analysis when samples with high nitrogen concentrations are used. Differences between the slopes of the calibration curves with the Ar/N₂ and pure Ar discharges were obtained (up to 30%). A study of the molecular bands recorded in the spectra when nitrogen is present in the discharge and determination of the resulting interferences on the analytes have been performed. Figure Glow discharge powered with radiofrequency energy     

Chemical vapor deposition of metal borides: 6. The formation of neodymium boride thin film materials from polyhedral boron clusters and metal halides by chemical vapor deposition

The chemical vapor deposition (CVD) of crystalline thin films of neodymium hexaboride (NdB₆) was achieved using either nido ‐pentaborane(9) or nido ‐decaborane(14) with neodymium(III) chloride on different substrates. The highly crystalline NdB₆ films were formed at relatively moderate temperatures (835 °C, ca. 1 µm/h) and were characterized by scanning electron microscopy, X‐ray emission spectroscopy, X‐ray diffraction and glow discharge mass spectrometry. The NdB₆ polycrystalline films were found to be pure and uniform in composition in the bulk material. Depositions using CoCl₂, NdCl₃ and B₅H₉ as the CVD precursors resulted in the formation of a mixture of NdB₆ and CoB phases, rather than the ternary phase. Copyright © 2008 John Wiley & Sons, Ltd.     

PAHs Formation in the Depositions in a Methyl tert-Butyl Ether/Ar,a Methyl tert-Butyl Ether/O2/Ar and a Methyl tert-Butyl Ether/H2/Ar RF Plasma Environment

Contents and distributions of polycyclic aromatic hydrocarbons (PAHs) in the depositions were investigated and discussed in a MTBE/Ar, a MTBE/O₂/Ar and a MTBE/H₂/Ar plasma systems. A radio-frequency (RF) plasma system was used to produce the depositions under the designed operational condition. The identification and quantification of PAHs was accomplished by using a GC with a mass selectivity detector (GC/MS). Results indicated that when the input power controlled at high wattage (70 W) in the three systems, the contents of total-PAH in the MTBE/Ar system are higher than those of total-PAH in other system with adding O₂ or H₂. The comparison of three systems indicated the formation and accumulation of PAHs in the MTBE/Ar system is easier than other systems. At high input power wattage, when the MTBE/Ar mixture added O₂ or H₂, the domain pattern was shifted from both 3- and 4-ring PAH to 2-ring PAH. As far as the total-PAH content is concerned, the MTBE/Ar system at 70 W was found to have the highest mean total-PAH content (1540 g/g), while the MTBE/O₂/Ar system at 20 W had the lowest mean total-PAH content (44.4 g/g).     

Radiochemical separation methods for the determination of some toxic elements in biological reference materials

The present paper describes radiochemical separation procedures developed for the determination of the elements As, Cr, Hg, Sb and Se in biological reference materials. The methods chosen utilize ion exchange, retention on inorganic exchangers and solvent extraction techniques for the isolation of the elements of interest. These procedures are more rapid than previously used methods, such as distillation and precipitation. As to the sample dissolution, the following procedures were tested using radioactive tracers and reference materials: treatment of the materials in teflon bombs with a mixture of HNO₃+H₂SO₄ or HNO₃ only in a normal oven, and with HNO₃ in a microwave oven using specially designed digestion bombs.     

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.     

Effects of a controlled N2 and O2 addition to Ar on the analytical parameters of the GD-OES

The influence of the controlled addition of N₂ and of O₂ to Ar on the analytical parameters of a dc glow discharge has been investigated for bulk samples of the pure metals Al, Ti, Fe, Ni, Cu, and Ag. The constant voltage discharge mode at 1000 V was applied with a mean power of about 1 W/mm². The N₂ and O₂ concentrations in the discharge gas Ar were varied in the range 0–3 mass-%, corresponding to a partial pressure of about 4 · 10^?3 hPa. The general effect of the gaseous addition is the decrease of the sputtering rate with an increasing concentration of N₂ or O₂. Atomic processes, which might be responsible for the observed effects, are discussed.