Optical emission spectroscopy diagnostics of an atmospheric pressure direct current microplasma jet

This paper is about the use of optical emission spectroscopy as a diagnostic tool to determine the gas discharge parameters of a direct current (98% Ar–2% H₂) non-thermal microplasma jet, operated at atmospheric pressure. The electrical and optical behaviors were studied to characterize this glow discharge. The microplasma jet was investigated in the normal and abnormal glow regimes, for current ranging from 10 to 130 mA, at ~ 220 V of applied voltage for copper cathode. OH (A ²∑⁺, ν = 0 → X ²Π, ν′ = 0) rotational bands at 306.357 nm and also the 603.213 nm Ar I line, which is sensitive to van der Waals broadening, were used to determine the gas temperature, which ranges from 550 to 800 K. The electron number densities, ranging from 6.0 × 10¹⁴ to 1.4 × 10¹⁵ cm^? 3, were determined through a careful analysis of the main broadening mechanisms of the H_β line. From both 603.213 nm and 565.070 nm Ar I line broadenings, it was possible to obtain simultaneously electron number density and temperature (~ 8000 K). Excitation temperatures were also measured from two methods: from two Cu I lines and from Boltzmann-plot of 4p–4s and 5p–4s Ar I transitions. By employing H_α line, the hydrogen atoms' H temperature was estimated (~ 18,000 K) and found to be surprisingly hotter than the excitation temperature.     

Multisignal calibration in optical emission spectroscopy

Summary The possibility of using more than one line for calibration in optical emission spectroscopy has been investigated. By means of principal component regression, sensitivity can be increased and part of noise can be removed. Thus, lower limits of detection can be obtained. The extent of improvement of sensitivity is considered theoretically and investigated by simulation. In the ideal case the sensitivity of the principal component regression for more than one line is calculated from the square root of the sum of squares of the sensitivities of the single lines. Practical applications in arcoptical emission spectroscopy and ICP-OES show that the theoretically expected improvements can almost be reached. The reduction in noise depends on the nature and source of noise.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

The DC arc as radiation source for optical emission spectroscopy

Summary During recent years the number of scientific papers treating arc excitation sources has rapidly decreased. But there is still a continuing interest in the research of the fundamental properties and application of arc sources. Different scientific contributions treating arc discharge and novel variations of d. c. arc sources used as radiation sources for optical emission spectroscopy are reviewed: theoretical investigations of the arc and its fundamental properties, improvement and development of arc radiation sources, influence of added substances, controlled atmosphere, matrix effects, as well as the analytical applications of the arc.

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Gleichstrombogen-Strahlungsquelle für die optische Emissionsspektroskopie

Zusammenfassung Die Anzahl wissenschaftlicher Arbeiten, die sich mit Bogenanregungsquellen befassen, hat in letzter Zeit stark abgenommen. Dennoch besteht aber ein ständiges Interesse für Untersuchungen der Grundeigenschaften und der Anwendung dieser Anregungsquellen. Verschiedene wissenschaftliche Beiträge, die sich mit Bogenentladung befassen und neue Typen von Gleichstrombogenquellen, die als Strahlungsquellen für die optische Emissionsspektroskopie angewandt werden, sind zusammenfassend dargestellt: theoretische Untersuchungen des Lichtbogens und seiner Grundeigenschaften, Verbesserung und Entwicklung von Bogenstrahlungsquellen, Einfluß von Zusätzen, kontrollierte Atmosphäre, Matrixeffekte sowie auch die analytische Anwendung des Bogens.

     

Elemental analysis of horse hair by optical emission spectroscopy

A spectrographic method is developed for the simultaneous determination of trace elements in horse hair. The quantitative estimates of elements Ag, Al, B, Ca, Cu, Fe, Mg, Mn, Na, P, Pb, Si, Ti, v, and Zn are reported and the precision of determination for some elements is given.     

Resonance fluorescence spectroscopy in laser-induced cavitation bubbles

Laser-induced breakdown spectroscopy (LIBS) in liquids using a double-pulse Q-switched Nd:YAG laser system has provided reliable results that give trace detection limits in water. Resonant laser excitation has been added to enhance detection sensitivity. A primary laser pulse (at 532 nm), transmitted via an optical fiber, induces a cavitation bubble and shockwave at a target immersed in a 10 mg l⁻¹–100 mg l⁻¹ indium (In) water suspension. The low-pressure rear of the shockwave induces bubble expansion and a resulting reduction in cavity pressure as it extends away from the target. Shortly before the maximum diameter is expected, a secondary laser pulse (also at 532 nm) is fed into the bubble in order to reduce quenching processes. The plasma field generated is then resonantly excited by a fiber-guided dye laser beam to increase detection selectivity. The resulting resonance fluorescence emission is optically detected and processed by an intensified optical multichannel analyzer system.      

Rotational temperature of nitrogen glow discharge obtained by optical emission spectroscopy

Measurements of rotational temperature as low as several hundred Kelvin have been measured using optical emission spectroscopy (OES) in nitrogen direct current (DC) glow discharge. The strongest band of the first negative system of nitrogen was chosen to deduce the rotational temperature at four different positions in nitrogen DC glow discharge, the back of cathode; cathode sheath; positive column; and anode glow. In positive column the rotational temperature increased apparently with the increasing discharge voltage from 500 to 1000 V when the pressure was 10 Pa. But with pressure of 20 Pa the rotational temperature in positive column increased slightly with the increase of discharge voltage. On the contrary, the rotational temperature in cathode sheath took reverse tendencies when the discharge voltage varies from 500 to 1000 V. As regard the anode glow, the rotational temperature at 10 Pa decreased with the increase of discharge voltage, but that at pressure of 20 Pa increased. We attribute the different tendencies of the rotational temperature to the different discharge statues at different pressures. When the discharge voltage varies from 500 to 1100 V, the discharge with pressure of 10 Pa is normal glow and that with 20 Pa is abnormal glow.     

Battery-operated, argon-hydrogen microplasma on hybrid, postage stamp-sized plastic-quartz chips for elemental analysis of liquid microsamples using a portable optical emission spectrometer

A battery-operated, atmospheric pressure, self-igniting, planar geometry Ar–H₂ microplasma for elemental analysis of liquid microsamples is described. The inexpensive microplasma device (MPD) fabricated for this work was a hybrid plastic–quartz structure that was formed on chips with an area (roughly) equal to that of a small-sized postage stamp (MPD footprint, 12.5-mm width by 38-mm length). Plastic substrates were chosen due to their low cost, for rapid prototyping purposes, and for a speedy microplasma device evaluation. To enhance portability, the microplasma was operated from an 18-V rechargeable battery. To facilitate portability even further, it was demonstrated that the battery can be recharged by a portable solar panel. The battery-supplied dc voltage was converted to a high-voltage ac. The ∼750-μm (diameter) and 12-mm (long) Ar–H₂ (3% H₂) microplasma was formed by applying the high-voltage ac between two needle electrodes. Spectral interference from the electrode materials or from the plastic substrate was not observed. Operating conditions were found to be key to igniting and sustaining a microplasma that was simply “warm” to the touch (thus alleviating the need for cooling or other thermal management) and that had a stable background emission. A small-sized (900 μL internal volume) electrothermal vaporization system (40-W max power) was used for microsample introduction. Microplasma background emission in the spectral region between 200 and 850 nm obtained using a portable fiber-optic spectrometer is reported and the effect of the operating conditions is described. Analyte emission from microliter volumes of dilute single-element standard solutions of Cd, Cu, K, Li, Mg, Mn, Na, Pb, and Zn is documented. The majority of spectral lines observed for the elements tested were from neutral atoms. The relative lack of emission from ion lines simplified the spectra, thus facilitating the use of a portable spectrometer. Despite the relative spectral simplicity, some spectral interference effects were noted when running a multi-element solution. An example of how interference in the spectral domain can be resolved in the time domain using selective thermal vaporization is provided. Analytical utility and performance characteristics are reported; for example, K concentrations in diluted (∼30 times) bottled water were determined to be 4.1 ± 1.0 μg/mL (4 μg/mL was the stated concentration), precision was about 25%, and the estimated detection limits were in the picogram range (or in nanograms per milliliter in relative units).     

Procedure for correcting interferences in emission spectroscopy

Summary A procedure for correcting interferences in emission spectroscopy is suggested. It is based on the use of error curves, which are a measure of the extent of the enhancing (or suppressing) effect of the interfering element upon the sought-for one. The flame-photometric determination of potassium in the presence of large amounts of sodium is described as an example.

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Verfahren zur Korrektur von Störeinflüssen in der Emissionsspektrographie

Zusammenfassung Das beschriebene Verfahren zur Korrektur des Einflusses störender Begleitionen beruht auf dem Gebrauch von Fehlerkurven, die das Ausmaß der verstärkenden oder schwächenden Wirkung von Fremdionen angeben. Die flammenphotometrische Kaliumbestimmung in Gegenwart großer Mengen Natrium dient als Beispiel.

     

Time-resolved measurement of emission profiles in pulsed radiofrequency glow discharge optical emission spectroscopy: Investigation of the pre-peak

Radiofrequency glow discharge coupled to optical emission spectroscopy has been used in pulsed mode in order to perform a detailed study of the measured temporal emission profiles for a wide range of copper transitions. Special attention has been paid to the early emission peak (or so-called pre-peak), observed at the beginning of the emission pulse profile. The effects of the important pulse parameters such as frequency, duty cycle, pulse width and power-off time, have been studied upon the Cu pulse emission profiles. The influence of discharge parameters, such as pressure and power, was studied as well.     

The analysis of archaeological glass by inductively coupled plasma optical emission spectroscopy

Summary An analytical procedure is described for the analysis of archaeological glass by inductively coupled plasma optical emission spectroscopy (ICP-OES). Glass samples were analysed in solution after fusion with lithium metaborate at 1100°C. The analyses were performed in the sequential multielemental mode of operation, with the determination of 15 elements in four analytical runs; only elements with not too large concentration difference were analysed in a single run. The following elements were accounted for: Si, Na, Ca, Al, Fe, Mg, Mn, Ti, Sr, Ba, Cr, Ni, Cu, Co, Pb.     

Monitoring the deposition process of metal-doped polymer films using optical emission spectroscopy

Simultaneous plasma polymerization of halocarbons (CF₄ and C₂F₃Cl) and sputtering of metals (Au and Al) or cosputtering [Au + polytetrafluoroethylene (PTFE, Teflon)] have been performed by means of an RF (20 MHz) glow discharge excited by a planar magnetron. The optical emission spectroscopy (OES) has been used for monitoring the deposition process of metal-doped polymer films. The light emission intensity ratios of the relevant species in the plasma volume are given in connection with the characteristics of the films prepared.     

Use of optical emission spectroscopy for determining the number concentration of chlorine atoms in a chlorine-oxygen plasma

Applicability of the emission spectroscopy technique in calculating the concentration of chlorine atoms in a chlorine-oxygen plasma was shown by comparing experimental and calculated relative intensities of the 452.62-nm chlorine line ( transition, excitation potentialE = 11.94 eV). The number concentration of chlorine atoms found by calibration with pure gases using this emission line was compared with the one measured by absorption spectroscopy. Some discrepancy between the results at an oxygen content greater than 50% in the mixture is due to the presence of oxygen compounds of chlorine which are detected as chlorine atoms by the absorption spectroscopy.     

Field emission spectroscopy

The first experimental evidence of the existence of electron states localised on a clean metal surface was available to us since 1967 in the form of the well known Swanson-Crouser hump in the energy distribution of electrons field-emitted from the W(100) plane, although it took some time before its interpretation as such, in 1976, was established beyond any doubt. Subsequently, angle-resolved photoemission proved to be a more competitive method for the investigation of surface states of metals and semiconductors. However, field emission remains a useful tool in surface physics research.

After a brief introduction to field emission spectroscopy, we review recent work which shows the potentiality of this technique in the investigation of the surface properties of semiconductors, ferromagnetic metals, thermal superconductors, and of the electronic structure of supported clusters.     

Photofield emission spectroscopy

A brief review of the investigations of optical excitations in the bulk and on the surfaces of metals by the photofield emission method is presented. The selected results show that the method is very useful for detailed penetration of band structure near the Fermi level. Examples for bulk band structures and surface density of states of tungsten, tantalum and titanium are presented and compared with theoretical results. The residual gas effect on surface states is described and discussed. Taking into consideration the thermocurrent produced by light radiation, a new and more detailed presentation of surface states observed for titanium (0001) face is shown as the density of states. The method of energy distribution of photofield emitted electrons is briefly mentioned. The inverse and two-photon photoemission methods are mentioned.     

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.     

A modified glow-discharge source for emission spectroscopy

A glow-discharge emission source of the type described by Grimm for spectrochemical analysis has been modified to incorporate a secondary discharge of     

Diagnostics of a thermal plasma jet by optical emission spectroscopy and enthalpy probe measurements

An accurate determination of electron density, temperature, and velocity distributions is of primary interest for the characterization of steady-state thermal plasma spray jets. Our diagnostic capabilities based on optical emission spectroscopy include measurements of absolute emission coefficients and Stark broadening. In addition, enthalpy probe diagnostics has also been used for temperature and velocity measurements. Observation of large discrepancies between temperatures derived from absolute emission coefficients, Stark broadening, and from enthalpy probe measurements indicate that severe deviations from LTE (local thermal equilibrium) exist in various regimes of plasma spray jets. Nonequilibrum characterization of such turbulent thermal plasma jets suggests that diffusion of high-energy electrons into the fringes of plasma jets and deviations from chemical equilibrium due to high velocities in the core of plasma jets and entrainment of cold gas, are the main reasons for these discrepancies. The establishment of a reliable data base, taking these nonequilibrium effects into account, is a prerequisite for meaningful modeling of real plasma jets.