Spectroscopic characterization of a neon surface-wave sustained (2.45 GHz) discharge at atmospheric pressure

In this paper a spectroscopic study of a microwave (2.45 GHz) neon surface-wave sustained discharge (SWD) at atmospheric pressure in a quartz tube has been carried out in order to determine the plasma characteristic parameters (e.g. electron temperature and density, gas temperature, absorbed power per electron) and also to identify possible deviations from the thermodynamic equilibrium for this kind of microwave discharge. The results have been compared to experiments in the literature for other noble gas (helium and argon) SWDs generated under similar experimental conditions. Intermediate values between those of argon and helium plasmas were obtained for characteristic neon plasma parameters (temperatures and electron density). An important departure from the Saha equilibrium was exhibited by neon SWDs.     

An improved microwave plasma torch for atomic spectrometry

The analytical performance of a microwave plasma torch was improved through mechanical alterations. Several problems reported in earlier designs were addressed: the ignition and stabilization of a helium plasma in the MPT was difficult; high powers were required to both ignite and operate the plasma; otherwise, the plasma would erratically change from an annular to a filament type discharge. In the new torch, the helium discharge was stabilized by replacing the copper central tube with one made of quartz. In addition, air entrainment was alleviated through use of a sheathing gas. This modification simplified the background mass spectrum and raised the effective ionization temperature of the discharge. A detailed schematic diagram of the new microwave plasma torch is presented.     

Non-thermal features of atmospheric-pressure argon and helium microwave-induced plasmas observed by laser-light Thomson scattering and Rayleigh scattering

Laser-light Thomson scattering and Rayleigh scattering have been measured from a microwave-induced plasma sustained at atmospheric pressure, using both argon and helium as a support gas. The measurements were performed at several spatial positions in each plasma, and at forward microwave power levels of 350 W for argon, and at 350 W and 100 W for helium. It was found from these measurements that both argon and helium plasmas deviate substantially from local thermodynamic equilibrium (LTE), Measured electron temperatures range from 13 000–21 500 K, whereas gas temperatures are generally lower by a factor of 2 to 10, depending on the support gas and the spatial position in the discharge. At the same forward microwave power, the electron temperature of the helium plasma is about 3500–7000 K higher than that of the argon plasma. Yet, the argon plasma has a higher electron number density than the helium plasma. Electron number densities in both argon and helium plasmas are roughly two to three orders of magnitude lower than what LTE would predict, based on the measured electron temperatures and the Saha Equation. Even more interestingly, signals in the far-wing portion of the Thomson-scattering spectrum were found to be significantly higher than are predicted by a fitted Maxwellian curve, indicating that there exists an over-population of high-energy electrons. It is concluded that, compared to the inductively coupled plasma, the microwave-induced plasma is highly non-thermal and remains in an ionizing mode in the analytical zone.     

Modified helium pulse-operated microwave induced plasma for spectrochemical analysis of liquid samples

To minimize problems caused by sample introduction into helium pulse operated microwave-induced plasma (He-pulsed-MIP), a simple plasma torch was developed. This torch is constructed from commonly available components with an absolute minimum of machining. In this torch, plasma is kept operating by partially isolating it from the rest of the plasma (within the plasma chamber). This auxiliary plasma is by-passed during sample or solvent injection and is therefore not affected. The design of this discharge chamber was thoroughly examined and each parameter affecting its analytical performance was evaluated. Measurements reported include effect of helium flow rate, discharge tube position and microwave power on analytical performance. Analytical calibration curves and detection limits data are shown for Ca, Cd, Cr, Cu, Fe, Mg, Ni and Zn. Plasma excitation temperature was determined using iron and copper as thermometric species. Finally, the present technique was applied to the analysis of real biological samples (liver, brain, heart, bone, kidney, tests, serum, spleen and muscles of white albino rats). The results were compared with those obtained using flame atomic absorption spectroscopy.     

Spectroscopic characterization of atmospheric pressure argon plasmas sustained with the Torche à Injection Axiale sur Guide d'Ondes

An argon microwave (2.45 GHz) plasma produced by a microwave plasma torch known as “Torche à Injection Axiale sur Guide d'Ondes” (TIAGO) in air ambience at atmospheric pressure was experimentally characterized. The conditions for appropriate TIAGO torch operation in argon and flame morphology were researched under several experimental conditions of gas flow (0.15–5.00 L · min^–1) rates and microwave input powers (100–1000 W). Gas temperature and electron density values were studied by means of optical emission spectroscopy. Besides, the processes inside the discharge and their interaction with the surrounding atmosphere were described according to the recorded spectra.     

Modified helium pulse-operated microwave induced plasma for spectrochemical analysis of liquid samples

To minimize problems caused by sample introduction into helium pulse operated microwave-induced plasma (He-pulsed-MIP), a simple plasma torch was developed. This torch is constructed from commonly available components with an absolute minimum of machining. In this torch, plasma is kept operating by partially isolating it from the rest of the plasma (within the plasma chamber). This auxiliary plasma is by-passed during sample or solvent injection and is therefore not affected. The design of this discharge chamber was thoroughly examined and each parameter affecting its analytical performance was evaluated. Measurements reported include effect of helium flow rate, discharge tube position and microwave power on analytical performance. Analytical calibration curves and detection limits data are shown for Ca, Cd, Cr, Cu, Fe, Mg, Ni and Zn. Plasma excitation temperature was determined using iron and copper as thermometric species. Finally, the present technique was applied to the analysis of real biological samples (liver, brain, heart, bone, kidney, tests, serum, spleen and muscles of white albino rats). The results were compared with those obtained using flame atomic absorption spectroscopy. Received: 3 February 2000 / Revised: 16 May 2000 / Accepted: 22 May 2000     

微波等离子体炬光源基本特性的研究

用计算机化断层扫描成象技术研究了微波等离子体炬(MPT)放电的发射轮廓,证明该光源具有良好的对称性,并有一个有利于样品引入的中央通道,最佳分析区在炬管上方5～10 mm,用激光Thomson散射和Rayleigh散射技术测定了ArMPT和HeMPT放电的电子温度、电子密度和气体温度,证明MPT放电的电子温度很高而气体温度较低,是一种非热光源。其中的高能电子处于过布居状态,具有很高的激发能力。     

The electromagnetic performance of a surfatron-based coaxial microwave plasma torch

Low power microwave plasma torches are of particular interest to analytical chemists. The torch design investigated herein, called TPS, is based on the known surfatron structure to which a coaxial section is added consisting of an impedance transformer followed by the metallic nozzle at the tip of which the discharge occurs. A series of experiments illustrate the main electromagnetic features and performance of this novel coaxial microwave plasma torch operating at 2.45 GHz and with input power in the range 10–180 W. A specially devised slotted coaxial line with a movable probe arrangement can be inserted into the torch in place of the transformer section to provide in situ measurements of the plasma impedance. Analyzing these results, we show that the shape of the torch tuning characteristics can be controlled to improve the power transfer to the plasma and stability of operation with respect to changes in discharge conditions; under these conditions, the design of the device can be simplified. The procedures presented have a general character and can be applied to various torch configurations.     

Performance of a microwave induced plasma (MIP) operated in a liquid-cooled discharge tube for atomic emission spectrometry

Different types of microwave induced plasma (MIP) discharge operated in liquid-cooled tubes, namely a glass tube of Duran^®, a quartz tube of Herasil^®, and a very simple demountable discharge tube made of glass and quartz have been investigated. The last tube leads to the best analytical properties and the longest lifetime. The intensities of silicon lines and of the continuum spectral background, together with the signal-to-background ratios for B, Ca, Cd, Co and Zn in the case of the pneumatic nebulization of solutions have been measured and used as an indicator for the cooling efficiency. The MIP torch was cooled with a thermostated silicon oil. The decrease of the temperature of the cooling medium causes a measurable decrease of the spectral background intensity. Diagnostic measurements of the plasma include radial profiles of spectral line intensities and excitation temperatures with the lines of Fe I; values of 5000–6000 K are found. The influence of different plasma parameters, e.g. microwave power and helium flow rate, is investigated. The preliminary analytical characterization of a helium MIP maintained with the liquid-cooled demountable discharge tube is presented. Limits of detection for Al, B, Ca, Co, Fe, P, Sb and Zn (between 0.002 and 1.2 μg ml⁻¹) are comparable with or better than those reported for low power helium MIPs with sample introduction in the form of a wet aerosol.     

Some fundamental measurements of the atmospheric-pressure,microwave-induced discharge

Measurements of several fundamental parameters in a microwave-induced atmospheric-pressure flowing plasma are presented. Optical and electrical measurements were performed on argon and argon/nitrogen plasmas in the region 1–7 cm outside the cavity, as the applied microwave power, and plasma composition were varied.The stability of the plasma, atomic emission from the argon support gas, and emission from the analyte species, are proportional to the electron density. The observed electron density was varied when the power was changed,-when an electrophilic species was added, and as the observation zone was moved relative to the microwave field. In all cases, the change in the emission signal followed the change in electron density.The electron temperature, as measured by the double-probe method, is related to the kinetic energy of the fastest-moving electrons in the plasma. It is unchanged by variations in power, plasma gas composition, flow rate, and is independent of the location of the probes relative to the cavity. The spectroscopic and electrical data are consistent with excitation by ion—electron radiative recombination.     

Microwave Diagnostics in Diffusive and Constricted Medium-Pressure Discharges

The high-frequency (HF) electron current induced in a dc discharge plasma bysuperimposing a HF electric field presents a useful tool for the diagnosticsof the time-dependent electron behavior of the plasma. This response to theHF field has been recently studied in diffusive discharge plasmas at lowergas pressures and discharge currents. These studies are extended tomedium-pressure plasmas operating in the diffusive as well as in theconstricted mode. In particular, the impact of the electron–electroninteraction on the phase delay between the HF field and electron current inconstricted column plasmas has been experimentally and theoreticallyanalyzed. Furthermore, the problem has been studied if, under the conditionsof pronounced electron–electron interaction, the determination of theelectron density will further on be possible by using the phase delay. Themeasurements of the delay have been performed by means of the microwaveresonator method in a medium-pressure krypton glow discharge operating inthe diffusive as well as the strongly constricted mode. In addition, thedelay has been theoretically determined by treating the appropriatetime-dependent electron kinetic equation at high frequencies of thesuperimposed microwave field.     

A status report on helium inductively coupled plasma mass spectrometry

The current status of helium inductively coupled plasma - mass spectrometry (He ICPMS) is examined, its potentials and limitations are reviewed, and a summary of fundamental properties of atmospheric pressure He ICP discharges is presented. Also included are results of He ICPMS studies with a new helium plasma torch (18 mm i.d.) operated at four sets of operating conditions. Under the "cold plasma" condition (600 W forward power), no secondary discharge is observed and ion kinetic energies ranging from 2.0 eV to 9.5 eV for 6 elements (mass range: 39-208) are measured. At higher power levels, the secondary discharge still is strong. In general, detection limits for certain elements are improved by 1-3 orders of magnitude compared to previous data acquired in 1993 with a 13-mm He ICP torch. Elements such as K, Fe, Cr, Mn, Ni, and Co that suffer from spectral interferences in Ar ICPMS can be detected at pg/mL-levels with an analogue detector and a prototype ICPMS instrument having no photon stops or obstacles present in the ion trajectory path.     

Fundamental properties characterizing low-pressure microwave-induced plasmas as excitation sources for spectroanalytical chemistry

Experimental measurements of the spectroscopic temperature and the electron temperature in low-pressure rare gas plasmas sustained by a microwave generator operating at 2450 MHz have revealed divergent values. These measurements have been interpreted on the basis of a radiative recombination model originally proposed by Schlüter. The importance of Penning ionization by metastable rare gas atoms in the excitation of foreign atoms has been discussed in terms of this model.On the basis of the radiative recombination model for these plasmas, the parameters of analytical importance are the concentration and energy of electrons in a high energy electron group, the concentration and energy of electrons in a low energy electron group, and the concentration of metastable rare gas atoms. Measurements of the spectroscopic temperature of an argon plasma have revealed that the energy of electrons in the low energy electron group is not greatly affected by applied microwave power and pressure over the range from 1–25 torr. The energy of electrons in the high energy electron group is not greatly affected by pressure and applied microwave power over the range studied, but has been shown to depend on the ionization potential of the plasma gas. The total electron concentration is not greatly affected by gas pressure for low applied powers, but varies with applied power, particularly at low pressures. The concentration of metastable argon atoms has been shown to depend on both the applied power and pressure. Studies of the excitation of mercury by these plasmas have led to results which are consistent with the radiative recombination model.     

Preliminary investigation of a tangential flow torch with coupling probe injector for helium microwave induced plasma mass spectrometry

A stable, low gas-flow torch has been developed for use with a helium microwave induced plasma (MIP). A toroidal plasma with central analyte introduction is obtained by the addition of a tantalum coupling probe injector tube. This injector penetrates through 100% of the total cavity depth and aids in the efficiency of power transfer to the cavity, in plasma initiation, and in circumventing the effects of a lack of homogeneity in the microwave field on analyte distribution in the plasma. The tangential helium flow was 41/min and the microwave power was 60 W.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria     

原子发射光谱分析

本文是《分析试验室》期刊定期评述中“原子发射光谱分析”课题的第一篇评述文章。文中对1987～1990年期间我国原子发射光谱分析(AES)领域所取得的进展作了全面评述。内容包括概述、火焰发射光谱法、电弧发射光谱法、火花发射光谱法、电感耦合等离子体原子发射光谱法、直流等离子体原子发射光谱法、微波等离子体原子发射光谱法、亚稳态能量转移发射光谱法、激光显微发射光谱法、空心阴极灯和Grimm灯发射光谱法等方面。     

Influence of the Shroud Gas Injection Configuration on the Characteristics of a DC Non-transferred Arc Plasma Torch

The characteristics of the plasma jet emanating from a dc non-transferred plasma torch is affected by many factors including arc current, type of gas, gas flow rate, gas injection configuration and torch geometry. The present work focuses on experimental investigation of the influence of shroud gas injection configuration on the I–V characteristics and electro-thermal efficiency of a dc non-transferred plasma torch operated in nitrogen at atmospheric pressure. The plasma gas is injected into the torch axially and shroud gas is injected through three different nozzles such as normal, sheath and twisted nozzles. The effects of flow rates of plasma/axial gas and arc current on I–V characteristics and electro-thermal efficiency of the torch holding different nozzles are investigated. The I–V characteristics and electro-thermal efficiency of the torch are found to be strongly influenced by the shroud gas injection configuration. The effect of arc current on arc voltage decreases with increasing the axial gas flow rate. At higher axial gas flow rate (>?45 lpm), the I–V characteristics of the plasma torch are similar irrespective of the nozzle used. The variation of electro-thermal efficiency with arc current is almost similar to that of arc voltage with arc current. As expected, the electro-thermal efficiency is increased when the axial gas flow rate is increased and at higher axial gas flow rate, it is not influenced by the arc current and shroud gas configuration. The plasma torch with normal nozzle may be better in the range of operating conditions used in this study.     

Optical emission spectroscopy of electron-cyclotron-resonance-heated helium mirror plasmas

In this experiment emission spectroscopy in the 3000–5000 Å range has been utilized to determine the electron temperature (15–60 eV) and ion density (2–5 x 10¹¹ cm^–3) of helium plasmas produced by the Michigan mirror machine⁽¹⁾ (MIMI). The plasma is generated and heated by whistler-mode electron-cyclotron resonance (ECR) waves at 7.43 GHz with 400–900 W power in 80-ms-long pulses. Gas fueling is provided at the midplane region by a leak valve with a range in pressure of 3 x 10 to 2 x 10⁴ Torr. Emission line intensities are interpreted using a model of the important collisional and radiative processes occurring in the plasma. The model examines secondary processes such as radiation trapping, excitation transfer between levels of the carne principle quantum number, and excitation front metastable states for plasmas in the parameter range of MIMI (n _c = 1–6 x 10¹¹ cm^–3). Front the analysis of line intensity ratios for neutral helium, the electron temperature is measured and its dependence upon the gas pressure and microwave power is determined. These temperatures agree with those obtained by Langmuir probe measurements. Art analysis of the line intensity ratio between singly ionized helium and neutral helium yields a measurement of the ion density which is in good agreement with electron density measurements made by a microwave interferometer.     

Parametric study of an atmospheric pressure microwave-induced plasma of the mini MIP torch — II. Two-dimensional spatially resolved excitation temperature measurements

Two-dimensional mapping of the excitation temperatures have been carried out in the microwave-induced plasma torch with tangential argon flow. It is detected that the presence of wet aerosols in a nebulizer gas increases axial excitation temperature while desolvation acts in the opposite direction. The influence of low hydrogen concentration in the support gas and potassium in the nebulizer gas on the temperature distribution is studied in detail. The comparison of excitation temperature and electron number density distributions clearly indicates non-equilibrium plasma conditions.     

MPT-AES测定奶粉中的Ca和Fe

用微波等离子体(MPT)为激发光源,氩气为等离子体工作气体,用气动雾化进样,采用标准曲线法研究了微波等离子体炬原子发射光谱法(MPT-AES)测定奶粉中Ca、Fe的方法。详细考察了溶液中HCl浓度、HNO3浓度、微波前向功率、载气流量、工作气流量等实验参数对测定的影响,同时考察了共存元素钠、镁、锌对钙和铁发射强度的影响。     

On the use of the Hα spectral line to determine the electron density in a microwave (2.45 GHz) plasma torch at atmospheric pressure

The electron density of an argon microwave (2.45 GHz) plasma flame generated at atmospheric pressure has been determined by using the Stark broadening of the experimentally measured H_α line emitted by the discharge. The H_β line was not observable under the experimental conditions of this discharge. Two methods have been employed to obtain the electron density from the Stark broadening of the H_α line. The first used the Gigosos–Cardeñoso computational model that considers the strong broadening of the H_α line by ionic dynamics. Alternatively, a second method based on a calibration of Stark broadenings of H_α and H_β lines offered a simpler way to obtain the electron density.