Model of microsecond pulsed glow discharge in hollow cathode for mass spectrometry

A new model for microsecond pulsed glow discharge in a hollow cathode and its afterglow is described. The model is based on the Monte-Carlo method together with a new method for electrical field calculation, which is based on some phenomenological laws of plasma behavior. The afterglow model uses continuity and Poisson equations. A qualitative agreement between the model results and results published in experimental and theoretical works is demonstrated. Some processes in the microsecond pulsed discharge in the hollow cathode, such as sputtering, ionization and transfer of sample, are investigated. The model is successfully used for the optimization of the operational parameters of the time-of-flight mass spectrometer with ionization by microsecond pulsed glow discharge in a hollow cathode.     

Gas and liquid phases interaction at the FeO·Cr2O3 cathode of a direct-current arc discharge

The study of an arc discharge in argon has been made with the cathode of the discharge system in the form of molten chromite, FeO·Cr₂O₃. The partial pressure distributions of the elements Fe and Cr, as well as the temperature distributions, have been determined in the arc by spectroscopic methods. The data obtained were used, in conjunction with a mathematical model, for the determination of the oxygen species distribution in the same medium. The cathode bath surface was measured by means of the two-wavelength method. From a consideration of free energy of reaction values, it is concluded that the presence of elemental Fe and Cr in the cathode bath is mainly related to the migration of Fe⁺ and Cr⁺, present in the arc, toward the liquid cathode. The formation of these elements in the molten cathode is very unlikely.     

The design and characteristics of direct current glow discharge atomic emission source operated with plain and hollow cathodes

A compact direct current glow discharge atomic emission source has been designed and constructed for analytical applications. This atomic emission source works very efficiently at a low-input electrical power. The design has some features that make it distinct from that of the conventional Grimm glow discharge source. The peculiar cathode design offered greater flexibility on size and shape of the sample. As a result the source can be easily adopted to operate in Plain or Hollow Cathode configuration. I-V and spectroscopic characteristics of the source were compared while operating it with plain and hollow copper cathodes. It was observed that with hollow cathode, the source can be operated at a less input power and generates greater Cu I and Cu II line intensities. Also, the intensity of Cu II line rise faster than Cu I line with argon pressure for both cathodes. But the influence of pressure on Cu II lines was more significant when the source is operated with hollow cathode.     

Amplification of noble gas ion lines in the afterglow of a pulsed hollow cathode discharge and possible benefit for analytical glow discharge mass spectrometry

A high-current pulsed hollow cathode discharge was used to study the role of atomic and ionic metastables involved in ionization plasma processes. We observed the enhancement of the spectral emission lines of noble gas ions in the afterglow. A study of the processes that involve atomic and ionic metastables is of great interest since it should lead to a better understanding of and enhanced control over the ionization mechanisms crucial to analytical glow discharge mass spectrometry (GDMS) analysis. Figure Time profile of Ti, Ti⁺, and Ne⁺ spectral lines     

氢气辅助的水中埋弧法制备小直径碳纳米管

用改进的石墨电弧放电方法制备了小直径、高质量的碳纳米管,以水为打弧介质,氢气为保护气体.该方法具有装置简单,电流小,无催化剂,制备出的多壁碳纳米管直径小于10 nm等优点.     

Study of a transferred-arc plasma reactor with a converging wall and flow through a hollow cathode

In this paper the behavior of an arc in a transferred-arc plasma reactor with a converging wall geornetrr and flow through a hollow cathode is investigated numerically with emphasis on the fluid dynamics. The general conservation equations and auxiliary relations for the calculation domain are established based on reasonable assumptions Then, the coupled nonlinear differential equations are solved with suitable boundary conditions and temperature-dependent argon plasma properties at atmospheric pressure, by employing an efficient finite-difference method. The results, for a hollow cathode geornetrr with low injection flow rates, clear/y demonstrate the existence of the Maecker elect which is responsible Joy the formation of two recirculation zones. As the plasma gas flow rate is increased, the downstream recirculation zoner is swept away leaving only an upstream recirculation zone.     

Modeling of the cathode jet of a high-power transferred arc

A physical model of two zones (constricted arc and cathode jet) of a 1-MW transferred arc in air is presented. It is based on the solution al conservation equations by a finite-differenee method. Turbulence is treated with Prandtl's approximation, whereas radiative transfer is solved considering a nonhontogeneous medium, with the hypothesis of gray spectral bands. The in of radiative transfer on the temperature field is illustrated using two-band and four-band radiation models. We also show the influence of several parameters on plasma jet properties: current intensity between 500 and 1500 A; gas mass /low rate between 10 and 90g/s, vortex injection. The arc characteristics are analyzed in accordance with physical mechanisms such as heat conduction, radiation, turbulence, convection, and miring of cold gas.     

Methane activation by chromium oxide cations in the gas phase: a theoretical study

Density Functional Theory, in its B3LYP formulation, was used to explore quantitative details of the potential energy hypersurfaces for the C-H bond activation reaction of methane by chromium dioxide cation. Both doublet ground and quartet excited states of the cation were considered, and all the minima and transition states localized along the paths leading to the formation of the experimentally observed products were characterized. All the calculated paths involve spin inversions that decrease the barrier heights of the involved transition states but do not play a significant role. Reaction pathways were also studied employing the nonhybrid BP86 functional, the reparametrized B3LYP* functional, and the CCSD(T) approach. Because other examples in the literature indicate that sequential ligation enhances the reactivity of bare transition metals cations, the state-selective reactivity of the chromium monoxide cation with respect to methane was also investigated and compared with that of the bare cation.     

Nitrogen incorporation in saturated aliphatic C6–C8 hydrocarbons and ethanol in low‐pressure nitrogen plasma generated by a hollow cathode discharge ion source

Ion/molecule reactions of saturated hydrocarbons (n‐hexane, cyclohexane, n‐heptane, n‐octane and isooctane) in 28‐Torr N₂ plasma generated by a hollow cathode discharge ion source were investigated using an Orbitrap mass spectrometer. It was found that the ions with [M+14]⁺ were observed as the major ions (M: sample molecule). The exact mass analysis revealed that the ions are nitrogenated molecules, [M+N]⁺ formed by the reactions of N₃⁺ with M. The reaction, N₃⁺ + M → [M+N]⁺ + N₂, were examined by the density functional theory calculations. It was found that N₃⁺ abstracts the H atom from hydrocarbon molecules leading to the formation of protonated imines in the forms of R′R″C?NH₂⁺ (i.e. C–H bond nitrogenation). This result is in accord with the fact that elimination of NH₃ is the major channel for MS/MS of [M+N]⁺. That is, nitrogen is incorporated in the C–H bonds of saturated hydrocarbons. No nitrogenation was observed for benzene and acetone, which was ascribed to the formation of stable charge‐transfer complexes benzene????N₃⁺ and acetone????N₃⁺ revealed by density functional theory calculations. Copyright © 2016 John Wiley & Sons, Ltd.     

Evaluation of a magnetically coupled microcavity hollow cathode discharge for atomic emission spectroscopy

A magnetically coupled microcavity hollow cathode discharge device was evaluated for its analytical potential as a boosted atomic emission source. A magnetic field using an electromagnet was applied perpendicular to the axis of the microcavity hollow cathode. The intensity of the atomic emission of copper, aluminum and the ionic emission of magnesium increased with increasing magnetic field until it reached a maximum. A further increase in the field strength did not lead to an enhancement of these emissions. The attainment of the maxima was attributed to the increase in the electron temperature and radial diffusion of the electrons from the center of the microcavity axis. Electron temperatures in the presence of the magnetic field calculated based on the semicorona model were shown to be proportional to the square of the reduced field strength. Further, these maxima were correlated to the energies of the upper levels of the transition studied.     

铬铁矿中三氧化二铬测定结果不确定度的评定

讨论了影响铬铁矿中三氧化二铬测定结果不确定度的各种因素,并评定了地质样品中三氧化二铬测定结果的不确定度.结果表明,采用硫酸亚铁铵溶液滴定方法,当样品三氧化二铬的含量为43.78％时,其扩展不确定度U=0.32％.     

Study of some excitation characteristics of the discharge in a hot hollow cathode

Some excitation characteristics of the discharge in a hot hollow cathode were investigated. A graphite cathode coated with evaporated films of copper, iron, manganese or titanium, and argon or helium fill gas were applied. The dependence of spectral-line intensities on fill gas pressure and discharge current were studied. At 0.4 A discharge current and various fill gas pressures, the excitation temperatures for iron, manganese and titanium were determined.     

Total protein determinations by particle beam/hollow cathode optical emission spectroscopy (PB/HC-OES) system III: Investigation of carrier salts for enhanced particle transport

Particle beam hollow cathode optical emission spectroscopy (PB/HC-OES) is evaluated as a generic tool for total protein determinations by monitoring the carbon atomic emission (C (I) 193.0 nm) resultant from dissociated analyte species. Previous studies demonstrated the capability of the PB/HC-OES system for total protein determinations with limits of detection for bovine serum albumin (BSA) samples being at the single-nanogram level for 200 l injections. Non-linear behavior across the concentration range in the calibration curve was observed due to the poor transport of small particles (owing to low analyte concentrations) through the PB interface. The potential use of non-volatile salts as carrier agents is investigated in the determination of protein samples by PB/HC-OES. A range of chloride salts (different cations), potassium salts (different anions), and an organic modifier (ammonium acetate) is investigated here for possible use as carriers upon addition as sample injection matrices for protein samples. The analyte response curves of BSA samples with KCl added as the sample injection matrix show higher sensitivity, better linearity (R²) and subsequently lower detection limits in comparison to those obtained with water, HCl, KNO₃ or ammonium acetate as carrier matrices.     

Mass spectrometric diagnosis of the surface nitriding mechanism in a d.c. glow discharge

Reactive constituents have been investigated in a molecular beam generated in the cathode surface glow area and surface boundary layer. Mixtures of nitrogen and hydrogen form NH_x(x=0–4) compounds, which are of relevance in heterogeneous, plasma vs. metal nitriding reactions. Ammonia decomposition leads to NH_x(x=2–4). Strong cataphoretic enrichment of hydrogen has been observed in the cathode glow area. Heterogeneous reactions of NH_x with iron lead to the formation of iron nitrides via intermediates such as FeNH_2–3. In a pulsed d.c. glow discharge, increased sputtering and decreased hydrogen enrichment have been observed.     

A Theoretical study on the charge and discharge states of Na-ion battery cathode material,Na1+xFePO4F

Na₂FePO₄F is a promising cathode material for a Na-ion battery because of its high electronic capacity and good cycle performance. In this work, first principle calculations combined with cluster expansion and the Monte Carlo method have been applied to analyze the charge and discharge processes of Na₂FePO₄F by examining the voltage curve and the phase diagram. As a result of the density functional theory calculation and experimental verification with structural analysis, we found that the most stable structure of Na_1.5FePO₄F has the P2₁/b11 space group, which has not been reported to date. The estimated voltage curve has two clear plateaus caused by the two-phase structure composed of P2₁/b11 Na_1.5FePO₄F and Pbcn Na₂FePO₄F or Na₁FePO₄F and separated along the c-axis direction. The phase diagram shows the stability of the phase-separated structure. Considering that Na₂FePO₄F has diffusion paths in the a- and c-axis directions, Na₂FePO₄F has both innerphase and interphase diffusion paths. We suggest that the stable two-phase structure and the diffusion paths to both the innerphase and interphases are a key for the very clear plateau. We challenge to simulate a nonequilibrium state at high rate discharge with high temperature by introducing a coordinate-dependent chemical potential. The simulation shows agreement with the experimental discharge curve on the disappearance of the two plateaus. © 2018 Wiley Periodicals, Inc.     

Catalytic performance of silica-supported chromium oxide catalysts in ethane dehydrogenation with carbon dioxide

The oxidative dehydrogenation of ethane into ethylene by CO₂ over a series of silica-supported chromium oxide catalysts was investigated. The results showed that the catalysts were effective for the reaction and CO₂ in the feed promoted the catalytic activity. The 5%Cr/SiO₂ catalyst exhibited the excellent performance with 30.7% ethane conversion and 96.5% ethylene selectivity at 700^oC. ESR and UV-DRS were used to probe the active sites and the species with high valent states (Cr⁵⁺ and/or Cr⁶⁺) were found to be important for the reaction.     

Addition of SiO2 to the operation of a polyimide cathode in a sodium battery

The effect of the addition of SiO₂ nanoparticles on the properties of a polyimide cathode was explored by CV, XPS, and galvanostatic cycling methods. The capacity and average cycling potential of the cell increased in the presence of SiO₂. By quantum chemical modeling, it was shown that SiO₂ nanoparticles served as a framework for polyimide, which retained its fixed structure upon metalation with sodium.     

Graphene oxide assisted facile hydrothermal synthesis of LiMn0.6Fe0.4PO4 nanoparticles as cathode material for lithium ion battery

Assisted by graphene oxide（GO）,nano-sized LiMn0.6Fe0.4PO4 with excellent electrochemical performance was prepared by a facile hydrothermal method as cathode material for lithium ion battery.SEM and TEM images indicate that the particle size of LiMn0.6Fe0.4PO4（S2）was about 80 nm in diameter.The discharge capacity of LiMn0.6Fe0.4PO4 nanoparticles was 140.3 mAh-g^1 in the first cycle.It showed that graphene oxide was able to restrict the growth of LiMn0.6Fe0.4PO4 and it in situ reduction of GO could improve the electrical conductivity of LiMn0.6Fe0.4PO4 material.     

Doppler-broadened line shapes of atomic hydrogen in a parallel-plate radio frequency discharge

Doppler-shifted atomic hydrogen emission (Balmer ) is observed from a low-frequency rf discharge through molecular hydrogen by collecting the light through a hole in one of the electrodes. Doppler shifts as large as 0.7 nm, corresponding to an energy of 540 eV or 85% of the peak applied voltage, are observed when ions are accelerated by the sheath electric field. The mechanisms for hot atom production are discussed in terms of both gas-phase and surface ion-impact phenomena. Hot atoms are produced via gas-phase ion-atom and ion-molecule collisions, as a result of simultaneous neutralization and reflection of ions at the electrode surface, and/or by sputtering of adsorbed hydrogen. As much as 30% of the atomic hydrogen emission is substantially Doppler shifted, indicating that most of the atomic emission in the sheaths is actually produced by ion impact and not by electron impact.     

Template synthesis of tin-doped indium oxide (ITO)/polymer and the corresponding carbon composite hollow colloids

SnO₂, In₂O₃, and Sn-doped In₂O₃ (ITO)/polymer and the corresponding carbon composite hollow colloids are template synthesized. It is essential that the sulfonated gel shell of the cross-linked polystyrene hollow colloid can favorably induce adsorption of target precursors. After being calcined in air to remove the template, SnO₂, In₂O₃, and ITO hollow colloids are obtained. Because the cross-linked polymer gel can be transformed into carbon in nitrogen at higher temperature such as 800 °C, metal oxide/carbon hollow colloids are consequently derived, whose shells are mesoporous. The SnO₂-, In₂O₃-, and ITO-containing polymer or carbon composite hollow colloids will be promising in sensors, catalysts, and fuel cells as electrode materials. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.