Glow Discharge Research Articles

Analysis of Blackening Reaction of Zn–Mg–Al Alloy Coated Steel Prepared by Anodizing Process

The rising demand for black-treated steel faces challenges with conventional black painting due to issues like scratching and peeling, impacting corrosion resistance and aesthetics. This study explores an alternative method, anodic oxidation, to blacken the surfaces of galvanized or coated steel plates. Parameters like temperature, duration, current density, and gas type were varied during the blackening process. The investigation aimed to identify key factors influencing the blackening. Scanning electron microscopy observed the morphology, while energy-dispersive X-ray spectroscopy and glow discharge mass spectrometry analyzed the chemical composition distribution. X-ray diffraction and X-ray photoelectron spectroscopy conducted compound crystal structure analysis. Results indicate higher temperatures, longer durations, and higher current densities improve blackening through anodic oxidation. Increased magnesium proportion on the surface leads to roughness and porous magnesium oxide formation, enhancing light absorption and explaining the observed blackening effect.

Evolution of hydrogen isotopes retention behavior of in-situ boronization films in EAST

Effective management of hydrogen isotopes retention in plasma-facing materials (PFMs) is crucial, particularly when utilizing tritium (T) as fuel, for the success of burning plasma operations. Boronization, a widely employed technique for controlling fuel recycling and mitigating impurity influx from plasma-surface interactions into the core of burning plasma, significantly influences hydrogen isotopes retention in PFMs. In this study, boronization films were generated by ion cyclotron range of frequency (ICRF) discharge assisted boronization with C2B10H12 as boron source on tungsten substrates at Experimental Advanced Superconducting Tokamak (EAST) which employing ITER-like water-cooled W monoblock PFMs and components (PFCs), followed by in-situ glow discharge (GD) cleaning for 2 h and 20 shots (180 s) edge-plasma exposure. Employing the Material and Plasma Evaluation System (MAPES), representative samples were analyzed after each process. The resultant carbon–boron films, dense and continuous, exhibited thickness up to 120 nm and were identified as amorphous in structure. It was observed that the D2-GD cleaning resulted in a significant isotopic exchange effect, effectively reducing the hydrogen (H) retention in the carbon–boron films. This hydrogen isotope replacement efficiency was found to be influenced by the thickness of the films. Notably, after boundary plasma exposure, samples with thicker films demonstrated an enhanced capacity to capture deuterium (D), adsorbing 10 times more D than bare tungsten (W). Our findings offer transformative insights for T recycling analysis and the plasma operation of devices like International Thermonuclear Experimental Reactor (ITER), highlighting the impact of boronization and subsequent treatments on hydrogen isotope retention behavior in PFMs.

Angle-resolved X-ray photoelectron spectroscopy intensity modeling of SiNx ultrathin layer grown on Si (100) and Si (111) substrates by N2 plasma treatment

In this work, we investigate the silicon nitridation process using a N2 plasma Glow Discharge Source (GDS) in an ultra-high vacuum chamber. In situ Angle Resolved X-ray Photoelectron Spectroscopy (ARXPS) measurements were performed to determine various chemical environments of the surface species. The main goals of this study are determination of the film chemical composition, to estimate its thickness and identify various phenomena taking place during the nitridation process under different experimental conditions. To achieve these objectives, we developed an ARXPS intensity model for an ultrathin SiNx overlayer. Based on the ARXPS results, which indicate that the silicon nitride film is not homogenous, we adopted a bi-layer model composed of two SixNyOz layers with varying thickness and chemical composition. The model is built from analysis of photoelectron intensities, considering a comparison between experimental and theoretical data. This bi-layer model revealed that the silicon nitride layer consists of a surface layer composed of approximately equal amounts of silicon and nitrogen (50% each), and an interfacial layer containing varying amounts of oxygen depending on experimental parameters. The presence of oxygen is due to residual air contamination in the vacuum chamber and/or to Si native oxide. The estimated thickness of silicon nitride film is less than 9 nm, depending on the nitridation time and temperature.The model developed in this work enabled us to study the effects of initial surface state (as received or chemically cleaned), Si substrate crystallographic orientation (such as (100) and (111)), and the nitridation temperature (room temperature and 500°C). The diffusing species (N+, N2+, O+), which play a crucial role during nitridation, were found to be influenced by temperature, treatment time, and substrate orientation. The diffusion phenomenon competed with other processes such as NO desorption, leading to a significant impact on formation of the SiNx film. Furthermore, we compared the thickness obtained from the ARXPS model using cross-sectional High-Resolution Transmission Electron Microscopy (HR-TEM) images. Additional Low-Energy Electron Diffraction (LEED) measurements indicated that the SiNx film was amorphous.

Enhancing Si3N4 Selectivity over SiO2 in Low-RF Power NF3-O2 Reactive Ion Etching: The Effect of NO Surface Reaction.

Highly selective etching of silicon nitride (Si3N4) and silicon dioxide (SiO2) has received considerable attention from the semiconductor community owing to its precise patterning and cost efficiency. We investigated the etching selectivity of Si3N4 and SiO2 in an NF3/O2 radio-frequency glow discharge. The etch rate linearly depended on the source and bias powers, whereas the etch selectivity was affected by the power and ratio of the gas mixture. We found that the selectivity can be controlled by lowering the power with a suitable gas ratio, which affects the surface reaction during the etching process. X-ray photoelectron spectroscopy of the Si3N4 and QMS measurements support the effect of surface reaction on the selectivity change by surface oxidation and nitrogen reduction with the increasing flow of O2. We suggest that the creation of SiOxNy bonds on the surface by NO oxidation is the key mechanism to change the etch selectivity of Si3N4 over SiO2.

Coated boron layers by boronization and a real-time boron coating using impurity powder dropper in LHD

Abstract In Large Helical Device (LHD), diborane (B2H6) is used as a standard boron source for boronization, which is assisted by helium glow discharges. In 2019, a new Impurity Powder Dropper (IPD) system has been installed and is under evaluation as a real-time wall conditioning technique. In LHD), which is a large size heliotron device, an additional helium (He) glow discharge cleaning (GDC) after boronization has been operated for a reduction of hydrogen recycling from coated boron layers, and this operational time of 3 h was determined by spectroscopic data during glow discharges. A flat hydrogen profile is obtained on the top surface of coated boron on the specimen exposed to boronization, the result suggests a reduction of hydrogen at the top surface by He-GDC. Trapped oxygen in coated boron was obtained by boronization, and the coated boron, which has boron-oxide, on the first wall by B-IPD was also shown. 
Considering the difference in coating areas between B2H6 boronization and B-IPD operation, it would be most effective to use the IPD and B2H6 boronization coating together for optimized wall conditioning.



Experimental study of the influence of O2 content on electrical and optical characteristics of He/CF4 APPJ

CF4 is an important source of reactive F-containing species (RFS) so that it is used to mix with inert gas as the working gas of atmospheric pressure plasma jet (APPJ) for material surface fluoridation modification. The addition of a small amount of O2 can increase the density of RFS in He/CF4 APPJ. Therefore, the hydrodynamic, electrical and optical properties of He/CF4/O2 APPJ interacting with the dielectric are experimentally investigated in this paper. Meanwhile, the influence of the excitation source on plasma discharge is discussed in detail and the internal mechanism of the experimental phenomenon in this paper is analyzed using the simulation results based on the model established in the previous paper. It is found that the addition of a small amount of O2 can increase the intensity and accelerate the axial propagation speed of He/CF4 APPJ due to the low ionization energy of O2 and the increase of the Penning ionization between metastable He and O2. With the increase of O2 content, the stability of the discharge is gradually enhanced due to the electron attachment reaction of O2 and the position of the primary current pulse in each half voltage cycle gradually approaches the position of the peak voltage because the increase in O2 content raises the breakdown threshold in dielectric barrier discharge region. In the presence of downstream dielectric, the addition of 0.1%O2 does not significantly change the radial development radius of APPJ due to the higher electron attachment rate and electron collision excitation loss power. The discharge pulse intensity is generally reduced compared to the absence of dielectric and the glow discharge in the strict sense no longer exists. The continuous spectrum intensity of RFS increases with the addition of a small amount of O2 while decreases significantly when O2 content is too high.

Characterization of arsenic species by liquid sampling-atmospheric pressure glow discharge ionization mass spectrometry.

A liquid sampling-atmospheric pressure glow discharge (LS-APGD) ionization source operating at a nominal power of 30 W and solution flow rate of 30 µL min-1 and supported in a He sheath gas flow rate of 500 mL min-1 was interfaced to an Orbitrap mass spectrometer and assessed for use in rapid identification of inorganic and organic arsenic species, including As(III), As(V), monomethylarsonic acid, dimethylarsinic acid, and arsenobetaine in a 2% (v/v) nitric acid medium. Mass spectral acquisition in low-resolution mode, using only the ion trap analyzer, provided detection of protonated molecular ions for AsBet (m/z 179), DMA (m/z 139), MMA (m/z 141), and As(V) (m/z 143). As(III) is oxidized to As(V), likely due to in-source processes. Typical fragmentation of these compounds resulted in the loss of either water or methyl groups, as appropriate, i.e., introducing DMA also generated ions corresponding to MMA and As(V) as dissociation products. Structure assignments were also confirmed by high-resolution Orbitrap measurements. Spectral fingerprint assignments were based on the introduction of solutions containing 5 µg mL-1 of each arsenic compound.

Self-pulsing of dielectric barrier discharges at low driving frequencies

This paper investigates the self-pulsing of dielectric barrier discharges (DBDs) at low driving frequencies. In particular, (a) the dependence of current on the product pd of gas pressure p and the gas gap length d, (b) the effects of lossy dielectrics (in resistive discharges) and large dielectric permittivity (in ferroelectrics) on current dynamics, (c) the transition from Townsend to a dynamic capacitively coupled plasma (CCP) discharge with changing pd values, and (d) the transition from Townsend to a high-frequency CCP regime with increasing the driving frequency. A one-dimensional fluid model of argon plasma is coupled to an equivalent RC circuit for lossy dielectrics. Our results show multiple current pulses per AC period in Townsend and CCP discharge modes which are explained by uncoupled electron–ion transport in the absence of quasineutrality and surface charge deposition at dielectric interfaces. The number of current pulses decreases with an increasing applied frequency when the Townsend discharge transforms into the CCP discharge. The resistive barrier discharge with lossy dielectrics exhibits Townsend and glow modes for the same pd value (7.6 Torr cm) for higher and lower resistances, respectively. Finally, we show that ferroelectric materials can amplify discharge current in DBDs. Similarities between current pulsing in DBD, Trichel pulses in corona discharges, and subnormal oscillations in DC discharges are discussed.

Surface recombination in Pyrex in oxygen DC glow discharges: mesoscopic modelling and comparison with experiments

Surface recombination in an oxygen DC glow discharge in a Pyrex (borosilicate glass) tube is studied via mesoscopic modelling and comparison with measurements of recombination probability. A total of 106 experimental conditions are assessed, with discharge current varying between 10 and 40 mA, pressure values ranging between 0.75 and 10 Torr, and fixed outer wall temperatures ( Tw ) of −20, 5, 25 and 50∘C . The model includes O+O and O+O2 surface recombination reactions and a Tw dependent desorption frequency. The model is validated for all the 106 studied conditions and intends to have predictive capabilities. The analysis of the simulation results highlights that for Tw=−20∘C and Tw=5∘C the dominant recombination mechanisms involve physisorbed oxygen atoms ( OF ) in Langmuir–Hinshelwood (L-H) recombination OF+OF and in Eley–Rideal (E-R) recombination O2+OF , while for Tw=25∘C and Tw=50∘C processes involving chemisorbed oxygen atoms ( OS ) in E-R O+OS and L-H OF+OS also play a relevant role. A discussion is taken on the relevant recombination mechanisms and on ozone wall production, with relevance for higher pressure regimes.

Assessing the efficacy of an atmospheric air DC glow discharge system for sustainable nitrogen fixation: a vibrational coherent anti-Stokes Raman scattering study

In addressing the substantial greenhouse gas emissions produced by the energy-intensive Haber–Bosch synthesis, this study investigates the viability of sustainable nitrogen fixation (NF) via low-temperature plasma systems energized by renewable sources. Utilizing vibrational coherent anti-Stokes Raman scattering as a diagnostic tool, we probed the nitrogen rovibrational temperature and population dynamics within a DC glow discharge in atmospheric air, a setting with considerable promise for eco-friendly fertilizer production. Besides, density for atomic N , O , and NO was quantified by laser-induced fluorescence (LIF) or two-photon absorbed LIF methods. Our findings reveal a quasi-equilibrium between rotational and vibrational energy states in the DC glow discharge environment, reaching an approximate value of 3500 K at the discharge core. The discharge parameters, discharge current, air flow rate, and discharge gap influence the rovibrational temperature, density distribution of species of interest, and the NF energy cost. However, the influences induced by these parameters are of limitations. Further analysis implies that the high gas temperature and its induced significant vibrational-rotational and vibrational-translational energy exchange are mainly responsible for the non-ideal NF energy cost.

Numerical characterization of capacitively coupled plasma driven by tailored frequency modulated radio frequency source

Capacitively coupled plasma (CCP) is widely used in plasma etching and deposition processes because of its low cost, simple structure, and easy generation of a uniform plasma in large areas. Conventional CCPs are operated under a fixed frequency power source; however, CCPs driven by a variable frequency power source are poorly understood. In this paper, numerical simulations of CCPs driven by frequency modulated (FM) radio frequency (RF) sources within the frequency range of 2 MHz–18 MHz are carried out with a particle-in-cell/Monte Carlo collision model. Our research indicates that the CCP driven by an FM RF source can maintain a stable glow discharge and form a time-dependent plasma. Plasma density, electron and ion current, energy and heating rate, ion flux, and energy on the electrodes fluctuate consistently with the FM period. The electron and ion energy distribution function can also be modulated by the frequency variation of the FM source. A multi-peak structure that varies and shifts with frequency variation is observed in the ion energy distribution function. In addition, by fixing the chirp period while varying the start or end frequency of the chirp signal (start frequency from 0.4 to 6 MHz, or end frequency from 18 to 48 MHz), effective modulations can be produced on the electron density, electron energy, and the shape of the EEPF and IEDF.

Coupled multi-dimensional modelling of warm plasmas: Application and validation for an atmospheric pressure glow discharge in CO2/CH4/O2

To support experimental research into gas conversion by warm plasmas, models should be developed to explain the experimental observations. These models need to describe all physical and chemical plasma properties in a coupled way. In this paper, we present a modelling approach to solve the complete set of assumed relevant equations, including gas flow, heat balance and species transport, coupled with a rather extensive chemistry set, consisting of 21 species, obtained by reduction of a more detailed chemistry set, consisting of 41 species. We apply this model to study the combined CO2 and CH4 conversion in the presence of O2, in a direct current atmospheric pressure glow discharge. Our model can predict the experimental trends, and can explain why higher O2 fractions result in higher CH4 conversion, namely due to the higher gas temperature, rather than just by additional chemical reactions. Indeed, our model predicts that when more O2 is added, the energy required to reach any set temperature (i.e., the enthalpy) drops, allowing the system to reach higher temperatures with similar amounts of energy. This is in turn related to the higher H2O fraction and lower H2 fraction formed in the plasma, as demonstrated by our model. Altogether, our new self-consistent model can capture the main physics and chemistry occurring in this warm plasma, which is an important step towards predictive modelling for plasma-based gas conversion.

Multiparameter optimization of non-thermal plasma-driven synthesis of carbohydrate-stabilized rhenium nanoparticles towards enhancement of their catalytical activity for reduction of nitroaromatic compounds

This study aims to optimize the synthesis of carbohydrate-stabilized rhenium nanoparticles (ReNPs) utilizing cold atmospheric pressure plasma (CAPP), specifically direct current atmospheric pressure glow discharge (dc-APGD), hypothesizing that controlling synthesis parameters will enhance catalytic efficiency in the reduction of nitroaromatic compounds (NACs). The dc-APGD system operated in flowing liquid cathode (FLC-dc-APGD) and flowing liquid anode (FLA-dc-APGD) modes. Design of experiments (DOE) and response surface methodology (RSM) were employed for the first time to optimize ReNPs synthesis. This included optimizing the concentration of ReO4- in ReNPs precursor solution, solution flow rate as well as discharge current. ReNPs were characterized using high-resolution transmission electron microscopy (HRTEM), dynamic light scattering (DLS), and X-Ray photoelectron spectroscopy (XPS). In turn, optical emission spectroscopy (OES) was employed for the identification of reactive species generated in plasma phase that contributed to the synthesis of ReNPs. The resultant sizes, surface charges, and phase compositions were linked with synthesis parameters and then with catalytic activities revealed by the variety of ReNPs. HRTEM photomicrographs revealed spherical and spherical-like morphologies of obtained ReNPs synthesized using FLC-dc-dc-APGD and FLA-dc-APGD modes with the actual sizes of 7.28 ± 2.90nm and 3.24 ± 0.57nm, respectively. Optimized conditions yielded ReNPs with exceptional catalytic activity, reducing 94.9% (FLC-dc-APGD) and 90.5% (FLA-dc-APGD) of 4-nitrophenol (4-NP) with the apparent rate constants (k1) 0.269 and 0.107min-1, respectively. Further, the conversions of 90% were achieved over FLC-dc-APGD-based ReNPs for nitrobenzene (NB), 2,4,6-trinitrophenol (2,4,6-TNP), 2,4-dinitrophenol (2,4-DNP), and 4-nitroaniline (4-NA). In these cases, the k1 values were 0.235, 0.174, 0.070, 0.001min-1 for, respectively. The results allowed to find a correlation between ReNP size distribution, oxidation state, and catalytic activity that suggested a potential for tailored Re nanocatalysts in environmental remediation.

Development of a-C:H coatings doped with trimethylsilyl acetate prepared using plasma enhanced chemical vapor deposition

The main aim of the present study was to develop hard a-C:H:SiOx coatings prepared from the unique gaseous mixture of trimethylsilyl acetate (TMSAc) with methane using plasma of RF capacitively coupled glow discharge. Studied coatings were prepared using different methane ratios in TMSAc/CH4 gaseous mixtures ranging from 7.1 % to 85.7 %. Simultaneously, the influence of the power supplied to the discharge (25–100 W) on the properties of resulting coatings was investigated. The presented research work discusses in detail the evolution of chemical composition, mechanical characteristics, and optical properties of resulting coatings depending on variable CH4 ratio and discharge power. Within this study, various materials with the smooth surface structure were achieved. Applying low CH4 ratio and 25 W power led to the formation of soft SiOxCyHz coatings with high content of SiO and -CH3 groups exhibiting hardness of approx. 0.95 GPa. Gradually increasing the CH4 ratio and discharge power up to the specified limit values (85 % and 100 W, respectively) induced structural changes, resulting in a-C:H:SiOx coatings with a remarkable hardness of 11 GPa and excellent fracture resistance. These attributes are of utmost importance in numerous industrial applications, including anticorrosive coatings, low-friction wear-resistant coatings to prolong the lifetime of car engines, biocompatible coatings, components for plastic molds, as well as parts for optical disc molds and textile machinery.

Preparation of large diameter/thickness ratio glass shells and “In situ” high temperature infrared spectroscopy study

The millimeter-sized glass (SiO2) shells play key roles in inertial confinement fusion (ICF) experiments, especially for the so-called "direct-drive" configuration. The preparation of large diameter/thickness ratio glass shells and the exploration of transformation mechanisms for silicon-doped glow discharge polymer (Si-GDP) to SiO2 still face challenges. Here, we prepared large diameter/thickness ratio glass shells with the diameter of ∼1200 μm and shell thickness of ∼5 μm by increasing the Si contents in Si-GDP precursors. The influence of Si contents in Si-GDP shells on the compositions, morphologies and geometrical properties of glass shells were carefully investigated. The formability and uniformity of micro morphologies of the glass shells will improve with the increase of Si contents in precursors. The chemical composition of the prepared glass shells is SiO2 with some carbides adsorbed on their surfaces and the compositions present negligible relationship with the Si contents. The sphericity, thickness uniformity and surface quality will increase with the increase of Si contents in precursors. Besides, the oxidation mechanisms for Si-GDP to SiO2 were explored by the combination of an in situ high temperature infrared spectroscopy and a simultaneous thermal analyzer.

Multiple Factors Influencing High-Purity Indium Electrolytic Refining

The effects of various contaminants in the electrolytic refinement of indium were investigated using a glow discharge mass spectrometer (GDMS). The effects of several factors such as the indium ion (In3+) concentration, the sodium chloride (NaCl) concentration, the current density, the gelatin concentration, the pH, and the electrode distance, were examined. Significant variations in impurity levels concerning gelatin concentration were observed. Both the gelatin and In3+ concentration were moderately positively correlated with the Pb content. The Sb concentration was associated positively with the NaCl concentration, while the Ti concentration had an adverse correlation with the NaCl concentration. The Bi element content was positively linked to the electrode distance. As the current density increased, Cu, Pb, and Bi impurities initially rose then eventually declined. Notably, a critical current density of 45 A·m–2 was identified in this behavior.

Expulsion of hydrogen negative ions by the anode layer of negative space charge from Penning discharge with metal hydride cathodes

The method of expulsion of hydrogen negative ions in the axial direction by a negative space charge formed in the plasma of Penning discharge with metal hydride cathodes is discussed. The plasma is produced on hydrogen, which is stored in metal hydride cathodes and injected locally into the discharge cell without any external gas supply due to ion current impact from plasma. The process of nonequilibrium desorption resulted in high vibrational excitation of H2 molecules, which greatly increases the efficiency of H− ion production. The method of efficient expulsion of H− ions depends on the external magnetic field. At a high magnetic field, it is performed by the supply of negative electric bias of the opposite cathode, but at a low one, H− ions are pushed out by the negative space charge of the anode layer, which expands toward the axis. The impact of both methods is considered in the case of DC discharge and in pulsating regime implementation.

Simulation of low-current DC discharges in longitudinal flows of atmospheric-pressure air

Characteristics of low-current stationary axially symmetric discharges in longitudinal laminar flows of atmospheric-pressure air calculated in the framework of a two-dimensional model are presented. Non-equilibrium discharge regimes, in the current range from 1 to 100 mA, are considered for gas flow velocities up to 50 m s−1. It is shown that variation of the flow velocity substantially affects the discharge characteristics, such as the width of discharge column, the electric field inside the gap, the current density etc. Validity of the obtained results is confirmed by their comparison with available experimental data.

Diffusion Nitride Surface Layers on Aluminum Substrates Produced by Hybrid Method Using Gas Nitriding

While gas nitriding of steel is currently used in industry, nitriding of aluminum alloys remains an open challenge. The main obstacle is aluminum’s high susceptibility to passivation. The oxide film provides an effective barrier to nitrogen diffusion. Attempts to overcome this problem have mainly focused on glow discharge nitriding using cathode sputtering of an oxide layer. The produced AlN layers exhibit no diffusion zone and show limited performance properties. In this work, the effect of hybrid treatment aimed at producing diffusion layers of nitrides other than AlN on aluminum alloys was investigated on the model system of iron nitride–aluminum substrate. Hybrid treatment combines an electrochemical process involving the removal of the aluminum oxide layer from the substrate, its subsequent iron plating, and a further gas nitriding in high-purity ammonia. The obtained results prove that the hybrid treatment allows the production, at 530 °C/10 h, of diffusion layers of Fe3N iron nitrides on aluminum substrates with a nitrogen diffusion zone range in aluminum of ca. 12 µm. In alloys containing magnesium, its unfavorable effect on the nitrogen diffusion and the functional properties of the layers was observed. An interesting direction for further research is hybrid treatment of precipitation-hardened alloys without magnesium.

Nitrogen plasma treated cotton fabrics coated with SiO2 followed by RGO deposition for water purification process

Experimental investigations have been carried out to modify the surface properties of Cotton fabrics using low temperature DC glow discharge nitrogen plasma. Plasma treatment is an eco-friendly, dry and clean process over wet chemical methods and does not suffer from any environmental and health concerns [1]. The important plasma parameters such as power and working pressure are kept constant with various treatment times (5, 15, 30, and 60 mins). The plasma-treated cotton fabrics are optimized by XRD, FTIR, and SEM. A comparative study has been done for the untreated and different treated fibers. Pure SiO2 is coated on untreated and nitrogen plasma treated cotton fabrics by sputtering method. The samples are coated for different sputtering times (10 and 30 min). Finally, Reduced Graphene Oxide (RGO) is coated on plasma treated SiO2 deposited fabrics. RGO is prepared by modified hummers methods [2]. Our results provide a way to develop a filter for water purification.