Cathode erosion on copper electrodes in steam,hydrogen, and oxygen plasmas

Experimental data are presented for cathode erosion rates on copper cathodes (or magnetically rotated arcs in steam, and mixtures of steam, hydrogen, and oxygen with argon. Measurements were also made of the arc voltage and velocity. The erosion rates for steam and oxygen plasmas were significantly lower than those .16r argon and hydrogen. Pure steam and 10% oxygen in argon gave erosion rates of 2.3 and 6.1 g/ C respectively while pure argon and 70% hydrogen in argon gave rates of 14.8 and 13.0 g/C respectively. Erosion rates decreased with increasing are velocities. The variation of arc velocity with operating conditions is described in terms of both aerodynamic and surface drag on the arc and arc root respectively.     

The effect of low concentrations of a polyatomic gas in argon on erosion on copper cathodes in a magnetically rotated arc

Experimental results are presented for electrode erosion on copper cathodes in magnetically rotated arcs in argon, dry air, nitrogen, ammonia, and carbon monoxide as well mixtures of the above with argon. Water-saturated argon was also used. Erosion rates were determined by weight loss after chemical cleaning, and the runs were sufficiently long (between 5 to 60 min) to represent steady-state operation. Arc currents of 100 A and gas pressures of 1.1 atm. were used. Pure argon gave the highest erosion rates and the lowest arc velocities. Small concentrations of any of the diatomic gases in argon greatly increased the arc velocity and decreased the erosion rates. The results suggest that erosion is primarily a thermal phenomenon but that the surface chemistry can greatly influence erosion rates by modifying arc behavior.     

The behavior of titanium,stainless steel,and copper-nickel alloys as plasma torch cathodes

Cathode erosion continues to be a problem hindering the widespread application of plasma technology. In this work, cathode erosion was studied on titanium, stainless steel 314, copper-nickel 10% and 30%, and copper 122 for magnetically rotated arcs operating in argon, nitrogen, and argon/hydrogen mixtures at a constant magnetic flux density of 0.1 T Titanium and stainless steel gave very low erosion rates in argon (0.2 and 0.3, g/C respectively). Cupronickels were shown to be suitable for nitrogen and hydrogen plasmas. The slope of hydrogen solubility versus temperature in the cathode material was found to be important in determining hydrogen plasma erosion characteristics. When the plasma gas has a high solubility in the cathode material, or can react with the cathode, a negative erosion rate may result. When gas solubility in the cathode is low, oxide stability and mode of electron emission may govern the erosion rate. A high gas solubility in the cathode material, as with hydrogen, can result in mechanical erosion due to micro-explosions near the cathode surface.     

Basic investigations for laser microanalysis: III. Application of different buffer gases for laser-produced sample plumes

We have measured the diameters and depths of craters in a copper sample and the amount of material ablated by the 1.06-m radiation of a pulsed Nd: YAG laser in the buffer gases argon, neon, helium, air and nitrogen as well as the emission intensities of analyte atoms in dependence on laser power and buffer gas pressure. The results are correlated with corresponding data of the plasma temperatures and the relative electron densities in the plasma. Criteria for the choice of the buffer gas, the buffer gas pressure and the laser power for optical emission spectrometry of microplasmas are given.     

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     

Temperature Distribution in a Pilot Plasma Tundish: Comparison Between Plasma Torch and Graphite Electrode Systems

Arc, bath, and refractory wall temperatures are measured in a pilot transferred-arc plasma furnace by atomic emission spectroscopy (AES) and multiwavelength pyrometry. Argon plasma torch and graphite electrode with nitrogen as plasma gas are both examined and compared using the steel bath as anode. With argon, a two-slope characteristic curve is measured for arc temperature, which ranges from 9000 to 25,000 K. Another trend is observed with nitrogen for temperatures in the range 8000–12,000 K. In this latter case, the bath temperature is very sensitive to arc length: more than 100 K increase results in arc length rise from 50 to 150 mm. Experimental data shows the variation of heat transfer efficiency between the two configurations, which is supported by results about surface emissivity in the spectral domain 1–15 m.     

Spectroscopic study of a magnetically rotating arc between opper electrodes in contaminated argon

The effects of N₂ and CO contaminants in atmospheric-pressure argon on an arc rotating between two concentric copper electrodes has been studied using optical spectroscopy of copper lines. The axial temperature of the magnetically driven arc in Ar + %N₂ was determined to be around 10,000 K for arc currents of SO to 200 A. The diffusion process of the copper vapor from the cathode was also studied. A copper density maximum 1 mm from the cathode along the arc column was found in Ar + %N₂. Removal of the contaminated cathode surface layers by the arc when contaminant injection in the plasma gas was stopped was found to be a slow process with a time scale depending on the type of the gas contaminant. The presence of gas contaminant in the electrode material controls the cathode erosion mechanism and the overall arc behavior in the transition between a contaminated to a pure argon arc.     

Bestimmung von Argon neben Stickstoff und Sauerstoff in pulvermetallurgisch hergestellten Werkstoffen mit einem modifizierten Tr?gergas-Hei?extraktionsger?t

Summary The modification of a commercial carrier-gas fusion instrument for the simultaneous determination of argon is described. In order to separate argon from nitrogen, a gas-chromatographic column with molecular sieve was incorporated between the absorption traps for H₂O and CO₂ and the thermal conductivity detector. A computing integrator was used for the evaluation of the detector signals. The calibration was done by introduction of defined volumes of dry air into the carrier-gas line. The conditions for the liberation of argon from samples of ODS-alloys and the separation from the other extracted gases were optimized. Results of analysis of powders and compact samples were compared with the results obtained by means of a vacuum-fusion instrument. In the concentration range 25 to 50 g/g argon the relative standard deviations were 1.5 to 3% (six determinations). With powders of 3 to 5 g/g relative standard deviations of about 8% were achieved. The limit of detection for 1 g samples was found to be ca. 0.5 g/g.     

Characteristics and electrode erosion rates of a D.C. plasma torch operating with TiCl4 plasma gas

A stable TiCl₄ plasma was produced using a simplified d.c. torch. The arc was struck between two concentric ring electrodes, d mm apart, and rotated using a magnetic coil. The electrode material was a new TaC composite. The arc was operated at 100 A for up to I h using plasma gas containing 0–30% TiCl₄. The voltage was 24–60 V, depending on the TiCl₄ concentration. The electrode erosion rate was of the order of 20g/C. It is shown that the erosion rate is a function of the aerodynamic drag of the are column.     

Determination of tetraethyllead and tetramethyllead using high performance liquid chromatography and electrochemical detection

Summary A new method for the separation of tetramethyllead (TML) and tetraethyllead (TEL) was developed using high-performance liquid chromatography. The electrochemical detection was examined with different electrodes. Amperometric and pulse-amperometric techniques were investigated and the optimal working potential for each electrode was determined. Linearity for the glassy carbon electrode was observed between 350 ng and 30 g; the detection limit is 310 ng (TML) resp. 340 ng (TEL). In case of the mercury gold electrode the linearity range was 300 g–3 g and the detection limit 1.5 m (TML) resp. 1.7 g (TEL).     

Electrogenerated chemiluminescence using solution phase and immobilized tris(4,7-diphenyl-1,10-phenanthrolinedisulfonic acid)ruthenium(II)

Electrogenerated chemiluminescence (ECL) with tris(4,7-diphenyl-1,10-phenanthrolinedisulfonic acid)rathenium(II) (RuBPS) in solution and immobilized on an electrode surface is investigated. Flow injection analysis with a thin layer electrochemical cell modified for ECL detection is used to determine the analytical utility of solution phase RuBPS and RuBPS immobilized in a cationic polypyrrole derivative. The solution phase reaction of RuBPS with oxalate is investigated with regard to the dependence of ECL emission on RuBPS concentration, carrier stream flow rate, and pH. In the parameter range studied, ECL intensity is not linear with the concentration of RuBPS in the sample. A maximum ECL intensity is observed with a RuBPS concentration of approximately 250 M. Slower linear velocities give greater ECL intensities which is the opposite of what is observed for Ru(bpy) ₃ ³⁺ and oxalate. Greater ECL intensity is observed at lower pHs for oxalate and at higher pHs for proline. RuBPS ECL with oxalate yields a working curve with a linear range from 0.1–100 M oxalate. Solution phase ECL is observed for RuBPS and other amines such as NADH, proline, tripropylamine, and antibiotics including streptomycin and gentamicin. RuBPS is also immobilized by electrochemical polymerization of 1-methyl-3-(pyrrol-1-ylmethyl)pyridinium chloride (MPP) in the presence of RuBPS. This polymer-modified electrode yields ECL for oxalate and for amines.Deceased     

Influence of nonishothermicity on drag coefficient of a spherical Al particle in a plasma

Experimental results of drag coefficient measurements of spherical Al particles with diameter 100–300 m in an electric-arc argon plasma for Re ynolds numbers 0.4-10, Mach numbers 0.05 in a plasmatron channel with an intersection cavity for an arc current of 75–190A, gas flow rate 0.2–2.75g/.sec, and channel radius 0.75–1.5cm are reported. Plasma flow characteristics obtained using MHD equations are used for treatment of experimental data.     

Some properties of a microwave boosted glow discharge source using neon as the operating gas

The use of neon as the operating gas for the analysis of aluminium samples with the microwave boosted glow discharge source has been studied. A new type of anode tube allowed the gas to enter the source near the sample surface so that more material was transported into the discharge. Erosion rates have been measured under conditions optimised for high line-to-background ratios and found to be lower than with argon (9 and 21 n/s, respectively). Despite the lower erosion rate the detection limits measured for a number of elements in aluminium are in the range 0.02–1 g/g and comparable to those obtained with argon as the operating gas.     

Schnelle Bestimmung von Stickstoff in organischen Verbindungen mit Hilfe der W?rmeleitf?higkeitsme?zelle

Zusammenfassung Eine Methode zur Schnellbestimmung von Stickstoff in organischen Substanzen wird beschrieben. Die Substanz wird im Sauerstoffstrom verbrannt. Die Verbrennungsgase werden mit Helium als Trägergas über Kupferoxid, Kupfer und durch Kalilauge geleitet. Der verbleibende elementare Stickstoff wird mit einer Wärmeleitfähigkeitsmeßzelle im strömenden Stickstoff-Helium-Gemisch gemessen. Die der Stickstoffmenge proportionale Gleichspannung am Ausgang der Wärmeleitfähigkeitsmeßzelle wird durch einen Integrator ausgewertet. Die für die Messung erforderliche konstante Gasströmung wird durch ein neu entwickeltes Druckausgleichssystem gewährleistet. Es lassen sich Stickstoffmengen bis hinab zu 1g erfassen. Eine Analyse dauert 4 min.

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Rapid determination of nitrogen in organic compounds by means of a thermal conductivity cell

The substance is combusted in a stream of oxygen. The combustion gases are conducted, with helium as carrier gas, over copper oxide, copper and through potassium hydroxide solution. The remaining elementary nitrogen is measured by a thermal conductivity cell in a flowing mixture of nitrogen and helium. The direct current voltage, proportional to the quantity of nitrogen, at the outlet of the thermal conductivity cell is analyzed by an integrator. The constant gas flow necessary for the measurement is secured by a novel pressure equalizing system. Nitrogen quantities down to 1g can be detected. One determination requires 4 min.

     

Flame atomic absorption spectrometric determination of cadmium and copper in biological reference materials using on-line sorbent extraction preconcentration

Summary Cadmium and copper at the g/g to ng/g level in plant and animal tissue reference materials, and at the g/l level in urine were determined by flame atomic absorption spectrometry using on-line sorbent extraction preconcentration based on flow injection techniques. Bonded silica reversed phase sorbent with octadecyl functional groups (RP-C 18), packed in a 100 l column, was used to collect the diethylammonium-N,N-diethyldithiocarbamate (DDTC) complex formed on-line in the sample digests at low pH. Methanol was used to elute the analyte chelates directly into the nebulizer-burner system of the spectrometer. Small air segments introduced before and after elution prevented the eluent from mixing with the sample solution and increased the sensitivity. A sampling frequency of 85/h could be obtained with a sample loading time of 30 s at a flow rate of 4.0 ml/min. The enrichment factor for both elements was 20 and the enhancement factors, including the effect of the organic solvent and with the flow spoiler removed, were 126 and 114 for cadmium and copper, respectively. The detection limits (3) were 0.15 g/l for cadmium and 0.2 g/l for copper. The precision was 2.3% and 1.4% r.s.d. for 10 g/l Cd and 45 g/l Cu, respectively (n=11). Results for the determination of cadmium and copper in various biological reference materials were typically in good agreement with certified values. Low recoveries were observed, however, for cadmium in samples containing high levels of copper and/or iron, such as bovine liver.On leave from Flow Injection Analysis Research Center, Institute of Applied Ecology, Academia Sinica, Shenyang, China     

Titrimetric determination of thiourea and silver with a picrate ion selective electrode

Summary A method has been developed for the semiautomatic potentiometric titration of thiourea with silver nitrate and of silver with thiourea, in the presence of picrate ions, using a picrate ion selective electrode. Thiourea in the range 15–1500g and silver in the range 200–1800g were determined with relative errors and relative standard deviation of about 1%.

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Zusammenfassung Eine halbautomatische potentiometrische Titrationsmethode für Thioharnstoff mit Silbernitrat bzw. umgekehrt in Gegenwart von Pikrationen mit Hilfe einer selektiven Pikratelektrode wurde entwickelt. 15–1500g Thioharnstoff bzw. 200–1800g Silber wurden mit einem relativen Fehler und einer relativen Standardabweichung von etwa ±1% bestimmt.

     

Formation of aluminum nitrides in thermal plasmas

Aluminum nitride has been synthesized by evaporation of the aluminum anode of a free-burning atmospheric-pressure nitrogen arc. About 40% of the product was collected in the form of highly oriented polycrystalline aluminum nitride (from the gaseous phase) with a high deposition rate ( 1 m/s) and very low oxygen content (0.34%). The rest was deposited on the reactor walls as an ultrafine powder with an average particle diameter of 300 Å. Destructive and nondestructive tests on the powder and crystals were carried out to determine the morphology and purity of the materials. The impact of other gases on the AlN formation has been studied. The probable mechanism in the AlN crystal growth is discussed.     

Horseradish peroxidase-based organic-phase enzyme electrode

An organic-phase enzyme electrode (OPEE) based on horseradish peroxidase (HRP) immobilized within Nafion on spectroscopic graphite was investigated in acetonitrile. The amperometric electrode response to hydrogen peroxide and cumene hydroperoxide present was found to be the result of the reduction of oxygen, produced upon enzymatic decomposition of both hydroperoxides (i.e., by the catalase-like activity of HRP). The electrode response was found to depend linearly on the hydroperoxide concentration up to 700 M within the range of potentials from –200 to –400 mV (versus Ag|AgCl). Detection limits of approximately 45 M for H₂O₂ and 100 M for cumene hydroperoxide were determined under the selected experimental conditions. Nernstian dependence (the open circuit voltage of HRP-based electrode versus logarithm of H₂O₂ concentration) was obtained between 0.2 and 2.0 mM, with a slope of approximately 23 mV per logarithmic unit, suggesting a catalase-like, two-electron disproportionation of the substrate in acetonitrile.     

Chemical behaviour of helium muonide just after muon catalyzed fusion

Chemical behaviour of a helium muonide atom /He^o/ can be understood on the analogy of its hydrogen homologues, muonium /Mu/, deuterium /D^o/ and tritium /T^o/. In muon catalyzed fusion /CF/, a small fraction of negative muon in the fusion cycle sticks to helium to give proton-like He⁺ which easily picks up one electron forming He^o. The energy of He⁺ at birth is about 3.5 MeV being in a similar situation to the case of a hot tritium atom produced by /n, p/ or /n, / reaction. The reaction cross section and rate of He^o reactions are estimated.     

Komplexometrische Folgetitrationen von Eisen und Nickel sowie Kupfer und Nickel imμg-Bereich

Zusammenfassung Eine quantitative Bestimmungsmethode für Mikromengen Eisen und Nickel sowie Kupfer und Nickel, wie sie in Legierungen, Oxidgemischen und galvanischen Bädern vorkommen, wurde beschrieben. Die Metalle werden komplexometrisch mit ÄDTA und Kupferstandardlösung unter Verwendung einer kupferionensensitiven Elektrode und potentiometrischer Äquivalenzpunktindikation bestimmt. Eisen bzw. Kupfer werden direkt mit ÄDTA titriert, das Nickel dann in der gleichen Lösung durch Rücktitration des überschüssigen ÄDTA mit Kupferstandardlösung bestimmt.Die relativen Standardabweichungen der Bestimmungen liegen für Eisen bei ±(0,6 bis 1,2)%, für Kupfer bei ±(0,4 bis 0,8)% und für Nickel bei ±(0,6 bis 1,2)% jeweils für den Bereich von 800g bis 25g Metall. Unter den gewählten Bedingungen lassen sich mit dem Verfahren noch 25g Eisen, Kupfer bzw. Nickel bestimmen.

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Complexometric sequential titrations of iron and nickel as well as copper and nickel in theg range

Summary A quantitative assay method was described for microamounts of iron and nickel such as occur in alloys, oxide mixtures and galvanic baths. The metals were determined complexometrically with EDTA and standard copper solution using an electrode sensitive to copper ions and potentiometric indication of the equivalence point. Iron and copper were titrated directly with EDTA, and nickel then determined in the same solution by back-titration of the excess EDTA with standard copper solution.The relative standard deviations of the assays are ±(0.6–1.2)% for iron, at ±(0.4–0.8)% for copper, and at ±(0.6–12.2)% for nickel for the range from 800–25g metal respectively. Under the conditions chosen, 25g of iron, copper or nickel can be determined using the procedure.