Determination of N and O‐atoms and N2 (A) Metastable Molecule Densities in the Afterglows of N2‐H2, Ar‐N2‐H2 and Ar‐N2‐O2 Microwave Discharges

Early afterglows of N₂‐H₂, Ar‐N₂‐H₂ and Ar‐N₂‐O₂ flowing microwave discharges are characterized by optical emission spectroscopy. The N and O atoms and the N₂ (A) metastable molecule densities are determined by optical emission spectroscopy after calibration by NO titration for N and O‐atoms and measurements of NO and N₂ band intensities. If an uncertainty of 30% is estimated on N‐atomic density, an inaccuracy of one order of magnitude is obtained on the O and N₂ (A) densities. In N₂‐(0.05‐2.5%)H₂ and Ar‐(1‐50%)N₂‐(0.05‐2.5%) H₂ gas mixtures, the O‐atoms are coming from O₂ impurities in the discharge. Concentrations of N and O‐atoms and of N₂ (A) densities are compared to the ones obtained in Ar‐(5‐50%)N₂‐(0.2‐2.5%) O₂ gas mixtures in which a controlled amount of O₂ is added. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nitrocarburizing treatments using flowing afterglow processes

Nitrocarburizing of pure iron samples is achieved at 853 K and is easily controlled by introducing C₃H₈ in the afterglow of a flowing microwave Ar-N₂-H₂ plasma. The carbon uptake in the solid is actually possible with methane but strongly limited. The use of propane enhances the carbon flux and the ?/α configuration is synthesized for the first time by this kind of process. For this stack, diffusion paths in the ternary system determined from chemical analyses by secondary neutral mass spectrometry reproduce satisfactorily X-ray diffraction results which only reveal, as optical micrographs, ? and α phases. Propane offers an accurate control of the nitrocarburizing conditions. As an example, a modulation of N and C contents in iron could be achieved to create new carbonitride multilayers.     

Recombination in nitrogen afterglow at low temperatures

A flowing post-discharge of N₂ and N₂-CH₄ gas mixtures has been used to produce nitrogen and carbon atoms. New technique for qualitative and quantitative measurement of various gas phase hydrocarbon species in a flow and the apparatus for its implementation are described. The method is based on C+N chemiluminiscent reactions in flowing post-discharge of N₂+hydrocarbon gas mixtures at low temperature (77 K). Detection of hydrocarbon species has been demonstrated from concentrations greater than 10¹⁰ molecules.cm^–3.Dedicated to the memory of Professor Jozef Kvasnica.     

Determination of N and O – Atom and N2(A) Metastable Molecule Densities in the Afterglows of N2 and N2‐O2 Microwave Discharges

Early afterglows of N₂ and N₂‐O₂ flowing microwave discharges are characterized by optical emission spectroscopy. The N and O atom and N₂(A) metastable molecule densities are determined by optical emission spectroscopy after calibration by NO titration for N‐atoms and measurements of NO and N₂ band intensities for O‐atoms and N₂(A) metastable molecules. By using N₂ tanks with 50 and 10 ppm impurity, it is determined in the afterglow an O‐ atom impurity of 150‐200 ppm. Variations of the N and O‐atom and N₂(A) metastable molecule densities are obtained in the early afterglow of N₂–(9·10^–5–3·10^–3)O₂ gas mixtures. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of parameters of inductively coupled plasma and its use in steel nitriding

Parameters of inductively coupled plasma (ICP) discharges in a mixture of gases N₂, H₂, and Ar at a total pressure of 1.5 × 10^–3 mbar and a partial pressure ratio N₂: H₂: Ar = 2: 12: 1 are discussed. The plasma properties are analyzed using Langmuir probes and optical emission spectroscopy. The ICP discharge is used for the nitriding of specimens made of Russian grade 30ChGSA structural steel. The nitriding experiments are performed at different bias voltages V_b in the range of–200 V to +100 V with respect to the walls of the discharge chamber. The surface hardness of the treated specimens depends substantially on the bias voltage, being much higher than the initial value in all cases. The obtained results demonstrate the possibility of increasing the surface hardness up to 1000 HV (4–5 times the initial values) at the bias voltage equal to the floating potential.     

Optical study of radicals (OH,O, H,N) in a needle-plate bi-directional pulsed corona discharge

In this study, analysis of optical emission spectra are used for the detection of OH (A²Σ) radicals and O (3p⁵P), H_α (3P) and N (3p⁴P) active atoms produced by the high-voltage bi-directional pulsed corona discharge of N₂ and H₂O mixture gas in a needle-plate reactor at one atmosphere. The relative vibrational populations and the vibrational temperature of N₂ (C, v') are determined. The effects of pulse peak voltage, pulse repetition rate and the added O₂ flow rate on the relative populations of OH (A²Σ) radicals and O (3p⁵P), H_α (3P) and N (3p⁴P) active atoms are investigated. It is found that when pulse peak voltage and pulse repetition rate are increased, the relative populations of those excited states radicals rise correspondingly. The relative population of OH (A²Σ) radicals decreases with increasing the flow rate of oxygen. The relative populations of O (3p⁵P), H_α (3P) and N (3p⁴P) active atoms increase with the flow rate of oxygen at first and exhibit a maximum value at about 30 ml/min. When the flow rate of oxygen is increased further, the relative populations of those excited states active atoms decrease correspondingly. The main involved physicochemical processes also have been discussed.     

Excitation of iron atoms in a plasma of excimer emitters under transverse-discharge pumping

The optical characteristics of a transverse-discharge plasma initiated in He/Xe(Kr)/HCl(CF₂Cl₂) mixtures were studied. The mixtures contained a small amount of iron vapor due to metal cathode erosion. The iron atoms were shown to be excited by the spontaneous emission of KrCl (λ=22 nm) and XeCl (λ=308 nm) molecules in a nanosecond transverse discharge.     

Mechanism of ignition by non-equilibrium plasma

The kinetics of ignition in stoichiometric C_nH_2n+2:O₂:Ar mixtures with 90% dilution for n = 1-5 has been studied experimentally and numerically under the action of a high-voltage nanosecond discharge. It was shown that the initiation of the discharge by a high-voltage pulse 115 kV in amplitude with a specific deposited energy of 10-30 mJ/cm³ leads to more than an order of magnitude decrease in the ignition delay time. The generation of atoms, radicals and excited and charged particles by the discharge was numerically described. The role of different atoms and radicals (O, H and C_nH_2n+1) was analyzed. The temporal evolution of the densities of intermediate components in the plasma assisted ignition was discussed.     

Crystal structure and magnetic properties of hard magnetic Sm2Fe17Nδ thin films with Co substitution

The crystal structure and magnetic properties of the hard magnetic Sm₂(Fe_1−xCo_x)₁₇N_δ thin films prepared by dc magnetron sputtering and subsequent nitrogenation process were investigated. It is found that the N content and crystal structure determine the non-monotonic dependence of the coercivity H_C on nitriding temperature for the films with x=0. With nitriding temperature exceeding 300 °C, N atoms can enter the Sm₂Fe₁₇ phase and the N content increases with increasing nitriding temperature, which leads to an increased coercivity. However, the maximum value of the H_C is observed at 400 °C. The α-Fe soft phase appears with nitriding temperature further increasing to 500 °C, which is responsible for the decreased H_C. When x is between 0 and 0.36, the films exhibit single Th₂Zn₁₇-type structure. Co atoms are found to go into the lattice of the 2:17 phase, generating an enhanced exchange coupling interaction between the nano-grains, which is responsible for the improved hard magnetic properties of the films with Co substitution at a certain range. Especially, the optimal value of the coercivity H_C and remanence ratio M_R/M_S reaches 4.0 kOe and 0.70 for the films with x=0.17 and 0.36, respectively.     

大气压等离子体辅助多晶硅薄膜化学气相沉积参数诊断

本文采用发射光谱法诊断了大气压下Ar气、SiCl₄及H₂气混合气体（Ar/SiCl₄/H₂）射频放电等离子体射流特性.利用Si原子谱线强度计算了电子激发温度并以此估算了Si原子数密度,研究了射频功率及气体流量对电子激发温度和Si原子数密度以及SiCl₄解离率的作用.     

大气压等离子体辅助多晶硅薄膜化学气相沉积参数诊断

本文采用发射光谱法诊断了大气压下Ar气、SiCl₄及H₂气混合气体（Ar/SiCl₄/H₂）射频放电等离子体射流特性.利用Si原子谱线强度计算了电子激发温度并以此估算了Si原子数密度,研究了射频功率及气体流量对电子激发温度和Si原子数密度以及SiCl₄解离率的作用. 关键词： 大气压等离子体射流 发射光谱 电子激发温度 多晶硅薄膜沉积     

Unusual nucleation and growth of γ′ iron nitride upon nitriding Fe–4.75 at.% Al alloy

The influence of substitutionally dissolved Al in ferritic Fe–4.75 at.% Al alloy on the nucleation and growth of γ′ iron nitride (Fe₄N_{1? x} ) was investigated upon nitriding in NH₃/H₂ gas mixtures. The nitrided specimens were characterised employing optical microscopy, scanning electron microscopy, transmission electron microscopy, electron probe microanalysis and X-ray diffraction. As compared to the nitriding of pure ferrite (α-Fe), where a layer of γ′ develops at the surface, upon nitriding ferritic Fe–4.75 at.% Al an unusual morphology of γ′ plates develops at the surface, which plates deeply penetrate the substrate. In the diffusion zone, nano-sized precipitates of γ′ and of metastable, cubic (NaCl-type) AlN occur, having, with the ferrite matrix, a Nishiyama–Wassermann orientation relationship and a Bain orientation relationship, respectively. The γ′ plates contain a high density of stacking faults and fine ε iron nitride (Fe₂N_{1? z} ) precipitates, although the formation of ε iron nitride is not expected for the employed nitriding parameters. On the basis of dedicated nitriding experiments it is shown that the unusual microstructural development is a consequence of the negligible solubility of Al in γ′ and the obstructed precipitation of the thermodynamically stable, hexagonal (wurtzite-type) AlN in ferrite.     

Effect of helium/argon gas ratio in a He-Ar-Cu<Superscript>+</Superscript> IR hollow-cathode discharge laser: modeling study and comparison with experiments

The He-Ar-Cu⁺ IR laser operates in a hollow-cathode discharge, typically in a mixture of helium with a few-% Ar. The population inversion of the Cu⁺ ion levels, responsible for laser action, is attributed to asymmetric charge transfer between He⁺ ions and sputtered Cu atoms. The Ar gas is added to promote sputtering of the Cu cathode. In this paper, a hybrid modeling network consisting of several different models for the various plasma species present in a He-Ar-Cu hollow-cathode discharge is applied to investigate the effect of Ar concentration in the gas mixture on the discharge behavior, and to find the optimum He/Ar gas ratio for laser operation. It is found that the densities of electrons, Ar⁺ ions, Ar_m ^* metastable atoms, sputtered Cu atoms and Cu⁺ ions increase upon the addition of more Ar gas, whereas the densities of He⁺ ions, He₂ ⁺ ions and He_m ^* metastable atoms drop considerably. The product of the calculated Cu atom and He⁺ ion densities, which determines the production rate of the upper laser levels, and hence probably also the laser output power, is found to reach a maximum around 1–5 % Ar addition. This calculation result is compared to experimental measurements, and reasonable agreement has been reached. Received: 14 October 2002 / Revised version: 28 November 2002 / Published online: 19 March 2003 RID="*" ID="*"Corresponding author. Fax: +32-3/820-23-76, E-mail: annemie.bogaerts@ua.ac.be     

Modes of a Ne-H2 laser employing a hollow-cathode discharge

An Ne-H₂ laser employing the 2s-2p transition in Ne is examined at current densities up to 300 ma/cm². The H₂ removes metastable Ne atoms and reduces the rate of excitation of the 2p level, so the discharge currents may be raised considerably. The gain at 11 143 Å is measured as a function of discharge current for near-optimal conditions.     

Active species in microwave postdischarge for steel-surfacenitriding

Production of nitrogen atoms has been studied in a 2.45-GHz flowing postdischarge in N₂ and N₂-H₂ gas mixtures with Ar as a buffer gas in the high-pressure regime (5×10³ to 6.5×10⁴ Pa). N atom densities have been measured by NO titration in the 10¹⁴-10 ¹⁵ cm³ range and monitored by the first positive emission resulting from the N atom recombination. The rate coefficient of the N+N+N₂ recombination has been found to be _k=6×10^-33 cm⁶ atom^-2 s ^-1 at T₀=300 K, which agrees with previously published data. The N atom production (or degree of N/N₂ dissociation) in front of an Fe-0.1%C substrate correlates well with the thickness of a γ' Fe₄N layer produced by the postdischarge treatment. The H₂ gas was first introduced in the initial phase of treatment to remove surface oxidizing and then was cut off to keep high densities of N atoms. It is deduced that N atoms are more active nitriding species than NH-type radicals     

Temperature Dependence of the Rate of the Reaction N + H + Ar → NH + Ar

The rate constant for the 3 body atom recombination N + H + M with M = Ar has been measured over the temperature range 550 to 750 K in an Ar ? N₂ ? H₂ microwave flowing discharge. A temperature dependence for the rate constant is reported.     

Study of the luminescence of H2O and D2O ices induced by charged-particle bombardment

We measured the optical emission of H₂O and D₂O ices in visible region (300-500 nm) induced by energetic hydrogen ions (H⁺, H₂⁺, and H₃⁺) irradiation. Our analysis of the data of ion-stimulated luminescence (ISL) shows that all spectra of ISL emission are identical, independent of projectile. We show that all lines in the ISL emission spectrum may be assigned to decays from excited particles and/or fragments of H, H₂, OH, and H₂O. From the independence of emission spectrum on projectile we conclude that the final process causing the emissions may be attributed to the interaction between H⁺ (and/or H) and the water molecules.     

Intensity enhancement of the C5+ Balmer radiation excited by capillary discharge pumping

The intensity of the 18.2 nm Balmer α-transition in C⁵⁺ excited in a capillary discharge using alumina and polyacetal tubes was studied. For discharge currents of up to 80 kA in tubes filled with C₂H₂, intense radiation from the excitation of C⁵⁺ ions and from the recombination of C⁶⁺ ions was observed. With increasing length of the discharge, the intensity in the falling edge of the recombination pulse rises faster than proportional. In contrast to previous investigations, gain by stimulated emission is excluded. The enhancement is ascribed to an optical guiding of the XUV radiation in the dense plasma created by ablation from the tube walls. Received: 1 April 1999 / Revised version: 22 July 1999 / Published online: 30 November 1999     

Surface oxides produced during discharge in water ambient iron surface: A conversion electron Mössbauer spectroscopic study

Oxide layers are produced on iron surface, under discharge in water ambient, applying both anodic and cathodic potentials to iron foil. Non-stoichiometric Fe_1−xO containing different ratios of Fe³⁺ and Fe²⁺ has been detected by using CEMS. Corrosion of these samples in 0.5 M H₂SO₄ shows that, cathodically discharge treated iron foil has higher corrosion resistance as compared to the anodically treated sample. This is attributed to the microstructural differences in the Fe_1−xO_x films formed during the discharge.     

Theoretical spin density in nitroxides

The evolution of the hyperfine tensors in the nitroxide series with increasing alkyl substitution on the NO group has been studied theoretically for radicals from H₂NO to C₅H₁₀NO. A projection technique has been applied to the UHF wave-functions in order to correct spin densities for quartet contamination. The magnitude of the isotropic and anisotropic couplings reflects the substitution effect already observed on the spin distribution maps, that is a spin transfer from oxygen to nitrogen when alkyl groups are substituted to hydrogens in H₂NO. The alternation of the signs of the couplings along the chain as well as the cos² γ law for the coupling constants of atoms (C or H) in β position are verified in the series. The orientation of the anisotropic tensors with respect to the chemical bonds depends on the position of the atoms in the molecule (radical site, α, β positions); it is not affected by further substitution, except for strongly asymmetric configurations.