Gas Admixture Research Articles

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Benzonitrile (BZN) and carbon tetrachloride (CCl4) are versatile solvents used as a precursor for the synthesis of many products. As multi-usage molecules, these compounds may be involved in sustainable chemistry processes such as the cold plasma techniques for which the generated electrons are known to be responsible for reactions. Therefore, it is desirable to explore the interaction of low energy electrons with the co-compounds in the gas phase. The production of chlorine and cyanine anions, initiated by the electron collision with CCl4 and BZN, respectively, undergo nucleophilic substitution SN2 reaction with the precursors molecules for the synthesis of chlorobenzene and tricholoacetonitrile. The mechanism of fragmentation of benzonitrile and the synthesis reactions are rationalized by DFT calculations. The yield of the cyanine anion produced from the ion reaction increases with the temperature of the admixture gas, probed in the 25-100 °C temperature range. The present work may contribute to a potential process for the production of chlorobenzene for instance via (cold) plasma techniques.

Influence of energy transfer processes on the rovibrational characteristics of CO2 in low-temperature conversion plasma with Ar and He admixture.

The influence of argon and helium on the rovibrational kinetics of carbon dioxide (CO2) and CO in low-temperature conversion plasma is investigated. With this objective, a combined experimental and computational study is conducted, applying quantum cascade laser infrared absorption spectroscopy to a pulsed DC CO2 glow discharge with varying noble gas admixture and modeling it with a two-term Boltzmann solver. Time-resolved rovibrational temperatures and dissociation fractions are presented, exhibiting an increase in rotational-vibrational non-equilibrium and an increasing CO2 conversion with argon (Ar) and helium (He) admixtures. Results are discussed in the context of energy transfer processes for collisions involving electrons, corroborated by electron-kinetic modeling, and heavy particle collisions. With noble gas addition, an increase in the electron number density, promoting excitation, and the high-energy tail of the electron energy distribution function are found. Penning ionization processes are proposed as an explanation for the increase in conversion, showing higher conversion for Ar due to the lower excitation thresholds and, therefore, larger state population. In the context of rovibrational kinetics, processes leading to the gain or loss of vibrational energy of CO2 are analyzed, pointing out subtle differences in, for example, relaxation rate coefficients between Ar and He. However, the cooling of the gas through conductive heat transfer is identified as the most important influence of the Ar and He admixture, as it keeps the relaxation rate for vibrational quenching low.

Study of gas hazard pattern in underground workings after blasting

Determining the sources of hazardous and toxic substances released into mine air, their gas composition, as well as providing each such source of pollution with the required amount of fresh air are important issues in terms of ensuring normal healthy and safe working conditions for miners. This paper studies blasting as one of the most dangerous sources of mine air pollution. The study was carried out for a long dead-end exploration working, and a development (preparatory) working of a copper-nickel mine. In accordance with the federal rules and regulations (FNiP), a number of requirements, including monitoring of gas hazard at a face, is applied to blasting operations.The study examined the behavior of gas-air mixture in dead-end mine workings after blasting. The findings are based on the experimental data obtained in the conditions of two dead-end workings at an operating coppernickel mine. A technique for the experimental studies of gas release after blasting in a dead-end working was developed. The main technical characteristics of the instruments involved in the in-situ measurements are given. Time dependences of the concentrations of toxic gases after blasting at the blasted working mouth, at the return ventilation current, and near a booster were established. In order to assess the reliability of the data obtained, the volume of released carbon oxides was calculated based on the data of gas analyzers and chemical reactions of explosives decomposition during detonation, depending on the types and weights of the explosives. A model of gas-air mixture transfer was described, constructed, and calibrated allowing for longitudinal dispersion. The Voronin model was used to simulate the gradual removal of toxic gases from the working face and solving the problem of boundary conditions. Based on experimental data, the coefficients of longitudinal dispersion, ventilation efficiency, and volume concentration of the considered gas admixture in the mixing zone at initial time were determined for a long dead-end mine working.The constructed gas-dynamic model and longitudinal dispersion coefficients obtained as a result of the analysis enabled the time required for long dead-end mine workings ventilation to be analysed and estimated. Based on the model, the algorithm for calculating the velocity of spreading the combustion products in a mine ventilation network in emergency situations is being improved. The value of longitudinal dispersion coefficient for different operating conditions is also being refined.Based on the gas distribution simulation within the interval of 1,500 m from a working face, the time required for the ventilation of a dead-end mine working was determined.

Experimental research on flammability characteristics and ignition conditions of hybrid mixture emissions venting from a large format thermal failure lithium-ion battery

When the concentration of gas is below its lower flammable limit and the content of the particles is below its minimum explosible concentration, it can be explosible. Thermal abuse tests for 50 Ah lithium-ion batteries were conducted under an inert atmosphere. The battery failure venting emissions were collected and their composition was identified previously. It still needs further research for the flammability characteristics and ignition conditions for hybrid mixture emissions venting from a large format lithium-ion battery thermal failure. In this study, the likelihood, severity, and kinetics of the batteries' hybrid mixture emissions flammability have been researched. To analyze battery emission flammability characteristics, five indexes have been investigated; they are ignition temperature (Tig), ignition time (τig), maximum explosion pressure (Pmax), pressure rise maximum rate ((dP/dτ)max), and size-normalized maximum rate pressure rise (KSt). Based on quantitative analysis for the hybrid mixture flammability characteristics, it indicates that particle size and gas content can impact hybrid mixture emission flammability characteristics. As for the mixture with finer particles, the optimum combustion condition of the particle and gas concentration pairs were 0.3 and 0.7. The ignition temperature for the optimum combustion conditions was 495 °C. The pressure rising velocity was 23 Mpa/s during ignition. High solvent content and low particle concentration are the conditions for optimum combustion. This indicates that the gas admixture solvent plays a major role in the combustion kinetics of the mixture emission. This research offers a fundamental perspective and provides preventive and protective thermal safety designs that are more suitable for large format commercial battery thermal systems.

Experimental Studies of Aerosol and Gas Admixtures in the Near-Water Layer of the Atmosphere of Lake Baikal (Ship-Based Expedition, September 2021)

Experimental Studies of Aerosol and Gas Admixtures in the Near-Water Layer of the Atmosphere of Lake Baikal (Ship-Based Expedition, September 2021)

Experimental investigations of plasma dynamics in the hysteresis regime of reactive RF sputter processes

Reactive radio frequency (RF) sputter processes are highly relevant for thin film deposition, but there is no complete understanding of the fundamentals of their operation. While the Berg model describes the hysteresis regime considering the oxygen coverage of the boundary surfaces, a complete fundamental understanding of the plasma–surface interactions and their effects on the discharge is still missing. In this work, we provide such fundamental insights based on an extensive experimental analysis of the physics in the hysteresis regime of magnetized reactive sputter processes, where the same reactive gas admixture can lead to different discharge characteristics depending on the previous state of the plasma. A variety of plasma and surface diagnostics is used to reveal these insights. A low pressure capacitively coupled RF discharge (CCP, 13.56 MHz) with a magnetron-like magnetic field topology adjacent to the target is operated in argon gas with a variable admixture of O2. The applied RF power, the gas flows/pumping speed, as well as the neutral gas pressure are changed systematically to understand the effects of these external control parameters on the hysteresis regime. The magnetic asymmetry effect is found to play an important role, since an axially non-uniform magnetic field is used to realize a local electron confinement at the target. Similar to process control in applications, the DC self-bias is measured to stabilize the surface composition using a feedback controller with the oxygen gas flow as the manipulated variable.

Modelling of dcMS and HiPIMS process with hydrocarbon gas admixture

Magnetron sputtering in an argon and hydrocarbon gas mixture is a complex deposition process exhibiting features of both physical vapour deposition and plasma enhanced chemical vapour deposition. The hydrocarbon gas decomposes within the plasma and then it is able to form a carbide phase with the target metal atoms or to be deposited as amorphous carbon. In this paper, a simple model for both the direct current (dcMS) and the high power impulse magnetron sputtering (HiPIMS) processes with hydrocarbon gas admixture is presented. The sputtered target racetrack is divided into metallic, compound, and carbon fractions to take into account both the carbide formation and the carbon deposition. To simulate the HiPIMS process, the back-attraction of ionised sputtered metal particles is incorporated into the model. The model is cross-validated with the previously published experiments which were conducted using the same deposition apparatus allowing for the direct comparison of the dcMS and HiPIMS processes. The simulated results correlate with the measured dependencies of the deposition rate, the carbon content in deposited films, and the racetrack fractions on the acetylene supply rate. The presented model is further successfully validated with the evolution of the racetrack composition calculated by SDTrimSP.

Impact of nitrogen doping on homoepitaxial diamond (111) growth

The impacts of nitrogen (N) doping on the lateral growth mode during two-dimensional (2D) nucleation, on the growth rate, and the incorporation of nitrogen (concentration [N]) of (111)-oriented diamond films were investigated by modulating the [N2]/[CH4] gas admixture ratio. The 2D nucleation density first increased with increasing [N2]/[CH4] ratio between 0.02 and 20%. Further increase of the [N2]/[CH4] ratio to up 200% caused a decrease of the nucleation density. The growth rates showed the similar N-doping dependence as the nucleation density variation. This is attributed to an initial increase of CN radicals in the regime 0.02 to 20%, followed by a reduction of CHx radicals in the regime 20 to 200%. The nitrogen incorporation concentration increases with increasing the [N2]/[CH4] ratio. The highest nitrogen concentration with 2 × 1020 atoms/cm3 is detected with [N2]/[CH4] = 200% and a relatively low nucleation density is achieved. These results are beneficial for the optimized formation of nitrogen-vacancy centers used in a quantum metrology and for device application such as inversion-channel diamond MOSFETs.

Study of the Influence of Oxygen on the Hydrodynamic Behavior of Helium Atmospheric Pressure Plasma Jet by Shadowgraphy System

This work investigates the effect of oxygen (O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> ) as gas admixture on hydrodynamic characteristics of a coaxial double-ring electrode helium plasma jet by a “Z-type” shadowgraphy system. The shadowgraphy images and visual optical photographs show that the addition of O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> will slow down the transition of gas flow from the laminar region to the turbulent region regardless of the plasma is ignited or not. The hydrodynamic behaviors of the plasma jet at the impact region for epoxy resin (EP) and aluminum substrates are also researched. The addition of oxygen reduces the vortex on the surface of both EP and aluminum surface. As a result, with the increase of O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> , the decrease of gas temperature caused by reduction of electrons and the reduction of the density difference between the mixed gas and the ambient air weaken the gas velocity and results in a weaker collision between the gas and the substrate, which is the main factor for less vortex on the substrate surface.

The Impact of Hydrogen Admixture into Natural Gas on Residential and Commercial Gas Appliances

Hydrogen as a carbon-free fuel is commonly expected to play a major role in future energy supply, e.g., as an admixture gas in natural gas grids. Which impacts on residential and commercial gas appliances can be expected due to the significantly different physical and chemical properties of hydrogen-enriched natural gas? This paper analyses and discusses blends of hydrogen and natural gas from the perspective of combustion science. The admixture of hydrogen into natural gas changes the properties of the fuel gas. Depending on the combustion system, burner design and other boundary conditions, these changes may cause higher combustion temperatures and laminar combustion velocities, while changing flame positions and shapes are also to be expected. For appliances that are designed for natural gas, these effects may cause risk of flashback, reduced operational safety, material deterioration, higher nitrogen oxides emissions (NOx), and efficiency losses. Theoretical considerations and first measurements indicate that the effects of hydrogen admixture on combustion temperatures and the laminar combustion velocities are often largely mitigated by a shift towards higher air excess ratios in the absence of combustion control systems, but also that common combustion control technologies may be unable to react properly to the presence of hydrogen in the fuel.

Experimental studies of aerosol and gas admixtures in the near layer of the atmosphere of Lake Baikal (ship expedition, September, 2021)

Experimental studies of aerosol and gas admixtures in the near layer of the atmosphere of Lake Baikal (ship expedition, September, 2021)

Optimized convolutional neural network-based multigas detection using fiber optic sensor

We developed a convolutional neural network-based high-sensitivity gas optical sensor (CNN-HGS) using photonic crystals for detecting different gases (N2, He, and CO2). Square-shaped dielectric rods with a cubic lattice index were used for the maintenance of the exact distance and area between the rods. The flower pollination optimization algorithm was used for the improvement of the hyperparameters of the CNN. The proposed CNN-HGS consists of three resonance nanocavities: one nanocavity with a refractive index of 2.6 located at the center and the other two subnanocavities with a refractive index of 2.1 placed in the path of the input and output waveguides, respectively. The experiment for the proposed CNN-HGS was conducted with three certified sample gas cylinders and a precise mass flow controller. A clean air generator was linked to the same pipeline for the dilution of the flow of hydrocarbon. During the experiment, a typical gas admixture with concentrations of 60 to 900 ppm was used. Training and testing were conducted using a dataset with 80% and 20% of the total, respectively. The result shows that the proposed optimized CNN delivers a 7.5% improvement in the training accuracy. The CNN-HGS was tested and compared with three other optimization techniques, and the result shows the superiority of the proposed method.

Plasma-droplet interaction study to assess transport limitations and the role of ⋅OH, O⋅,H⋅,O2(a 1Δg),O3, He(23 S) and Ar(1s 5) in formate decomposition

Plasmas interacting with liquid microdroplets are gaining momentum due to their ability to significantly enhance the reactivity transfer from the gas phase plasma to the liquid. This is, for example, critically important for efficiently decomposing organic pollutants in water. In this contribution, the role of ⋅OH as well as non-⋅OH-driven chemistry initiated by the activation of small water microdroplets in a controlled environment by diffuse RF glow discharge in He with different gas admixtures (Ar, O2 and humidified He) at atmospheric pressure is quantified. The effect of short-lived radicals such as O⋅ and H⋅ atoms, singlet delta oxygen (O2(a 1Δg)), O3 and metastable atoms of He and Ar, besides ⋅OH radicals, on the decomposition of formate dissolved in droplets was analyzed using detailed plasma diagnostics, droplet characterization and ex situ chemical analysis of the treated droplets. The formate decomposition increased with increasing droplet residence time in the plasma, with ∼70% decomposition occurring within ∼15 ms of the plasma treatment time. The formate oxidation in the droplets is shown to be limited by the gas phase ⋅OH flux at lower H2O concentrations with a significant enhancement in the formate decomposition at the lowest water concentration, attributed to e−/ion-induced reactions. However, the oxidation is diffusion limited in the liquid phase at higher gaseous ⋅OH concentrations. The formate decomposition in He/O2 plasma was similar, although with an order of magnitude higher O⋅ radical density than the ⋅OH density in the corresponding He/H2O plasma. Using a one-dimensional reaction–diffusion model, we showed that O2(a 1Δg) and O3 did not play a significant role and the decomposition was due to O⋅, and possibly ⋅OH generated in the vapor containing droplet-plasma boundary layer.

Tailored Power of an RF Plasma Jet With Admixture of Nitrogen or Oxygen and Its Effects on Human Immune Cells

Parameter studies of plasma treatment are informative about the optimal use of this technology in biomedical applications such as the argon radio-frequency plasma jet kINPen. However, the interdependence of the plasma-dissipated power in relation to input current and feed gas modulation on the resulting biological consequences has not been studied so far. To this end, a parameter study is presented, and the effect on human immune cell viability was investigated across different input current power and argon with oxygen/nitrogen feed gas admixture settings. It was found that with both nitrogen and oxygen admixtures, a concentration-dependent change in plasma-dissipated power emerged, which converged at 27.5 and 26.5 mA, respectively. The extent of cytotoxicity in immune cells confirmed the relevance of these findings, which were in congruency with the plasma-dissipated powers identified. These findings underline the critical role and input parameter-dependent action of plasma sources for biomedical application.

Following O and OH in He/O2 and He/H2O gas mixtures—from the gas phase through the liquid phase to modifications on a biological sample

Applied cold atmospheric plasma allows for the controlled delivery of reactive oxygen and nitrogen species tailored for specific applications. Through the manipulation of the plasma parameters, feed gases, and careful consideration of the environment surrounding the treatment target, selective chemistries that preferentially influence the target can be produced and delivered. To demonstrate this, the COST reference microscale atmospheric pressure plasma jet is used to study the generation and transport of O and OH from the gas phase through the liquid to the biological model target cysteine. Relative and absolute species densities of OH and O are measured in the gas phase through laser induced fluorescence (LIF) and two-photon absorption LIF respectively. The transport of these species is followed into the liquid phase by hydrogen peroxide quantification and visualized by a fluorescence assay. Modifications to the model biological sample cysteine exposed to OH and H2O2 dominated chemistry (He/H2O (0.25%)) and O dominated chemistry (He/O2 (0.6%)) is measured by FTIR spectroscopy. The origin of these species that modify cysteine is considered through the use of heavy water (HO) and mass spectrometry. It is found that the reaction pathways differ significantly for He/O2 and He/H2O. Hydrogen peroxide is formed mainly in the liquid phase in the presence of a substrate for He/O2 whereas for He/H2O it forms in the gas phase. The liquid chemistry resulting from the He/O2 admixture mainly targets the sulfur moiety of cysteine for oxidation up to irreversible oxidation states, while He/H2O treatment leads preferentially to reversible oxidation products. The more O or OH/H2O2 dominated chemistry produced by the two gas admixtures studied offers the possibility to select species for target modification.

Effects of O2 Addition on the Discharge Parameters and Production of Reactive Species of a Transferred Atmospheric Pressure Plasma Jet

The therapeutic effects of atmospheric pressure plasma jets (APPJs) have been associated with the presence of reactive species, mainly the reactive oxygen and nitrogen ones, generated in this kind of plasmas. Due to that, many studies attempting to enhance the production of reactive species in APPJs have been performed. The employment of gas admixtures, usually mixing a noble gas with oxygen (O2) or water vapor, is one of the most common methods to achieve such goal. This work presents a study of how the addition of small amounts of O2 affects the electrical parameters and the production of reactive species in a transferred APPJ produced at the tip of a long and flexible plastic tube. The study was carried out employing helium (He) as the working gas and applying a high voltage (HV) in the form of amplitude-modulated sine waveform (burst mode). With this configuration it was possible to verify that the O2 addition reduces the discharge power and effective current, as a result of late ignition and shorter discharge duration. It was also found that the addition of O2 to a certain content in the gas admixture makes the light emission from oxygen atoms increase, indicating an increment in oxygen related reactive species in the plasma jet. However, at the same time the light emitted from hydroxyl (OH) and nitric oxide (NO) exhibits the opposite behavior, i.e., decrease, indicating a reduction of such species in the APPJ. For these reasons, the addition of O2 to the working gas seems to be useful for increasing the effectiveness of the plasma treatment only when the target modification effect is directly dependent on the content of atomic oxygen.

Nitrogen fixation in pulsed microwave discharge studied by infrared absorption combined with modelling

A pulsed microwave surfaguide discharge operating at 2.45 GHz was used for the conversion of molecular nitrogen into valuable compounds in several gas mixtures: N2:O2, N2:O2:CO2 and N2:CO2. The ro-vibrational absorption bands of the molecular species were monitored by a Fourier transform infrared apparatus in the post-discharge region in order to evaluate the relative number density of species, specifically NO production. The effects of specific energy input, pulse frequency, gas flow fraction, gas admixture and gas flow rate were studied for better understanding and optimization of the NO production yield and the corresponding energy cost (EC). By both the experiment and modelling, a highest NO yield is obtained at N2:O2 (1:1) gas ratio in N2:O2 mixture. The NO yield reveals a small growth followed by saturation when pulse repetition frequency increases. The energy efficiency start decreasing after the energy input reaches about 5 eV/molec, whereas the NO yield rises steadily at the same time. The lowest EC of about 8 MJ mol−1 corresponding to the yield and the energy efficiency of about 7% and 1% are found, respectively, in an optimum discharge condition in our case.

On the transition of reaction pathway during microwave plasma gas‐phase synthesis of graphene nanosheets: From amorphous to highly crystalline structure

AbstractFourier‐transform infrared spectroscopy and proton‐transfer‐reaction–mass spectrometry are used in a complementary way to study gas‐phase processes during decomposition of ethanol in a microwave plasma torch. Decomposition products (C, C2 and simple hydrocarbons) reassemble into higher hydrocarbons and graphene nuclei and further grow into graphene nanosheets (GNS). Depending on microwave power, ethanol flow rate and molecular gas admixture, the material structure changes from amorphous to crystalline. The presence of C2n + 1H y species was found to be responsible for the formation of defects in the GNS structure. O2 and H2 admixtures change the gas temperature axial profile and consequently modify reaction pathways influencing growth and production rate of GNS. Determination of reaction pathway selectivity enables us to predict whether high‐quality or defective GNS are produced.

Chemical kinetics and density measurements of OH in an atmospheric pressure He + O2 + H2O radiofrequency plasma

This work presents experiments and modelling of OH densities in a radio-frequency driven atmospheric-pressure plasma in a plane-parallel geometry, operated in helium with small admixtures of oxygen and water vapour (He + O2 + H2O). The density of OH is measured under a wide range of conditions by absorption spectroscopy, using an ultra-stable laser-driven broad-band light source. These measurements are compared with 0D plasma chemical kinetics simulations adapted for high levels of O2 (1%). Without O2 admixture, the measured density of OH increases from 1.0 × 1014 to 4.0 × 1014 cm−3 for H2O admixtures from 0.05% to 1%. The density of atomic oxygen is about 1 × 1013 cm−3 and grows with humidity content. With O2 admixture, the OH density stays relatively constant, showing only a small maximum at 0.1% O2. The simulations predict that the atomic oxygen density is strongly increased by O2 addition. It reaches ∼1015 cm−3 without humidity, but is limited to ∼1014 cm−3 beyond 0.05% water content. The addition of O2 has a weak effect on the OH density because, while atomic oxygen becomes a dominant precursor for the formation of OH, it makes a nearly equal contribution to the loss processes of OH. The small increase in the density of OH with the addition of O2 is instead due to reaction pathways involving increased production of HO2 and O3. The simulations show that the densities of OH, O and O3 can be tailored relatively independently over a wide range of conditions. The densities of O and O3 are strongly affected by the presence of small quantities (0.05%) of water vapour, but further water addition has little effect. Therefore, a greater range and control of the reactive species mix from the plasma can be obtained by the use of well-controlled multiple gas admixtures, instead of relying on ambient air mixing.

Clarifications on the Behavior of Alternative Gases to SF6 in Divergent Electric Field Distributions under AC Voltage

Negative and positive partial discharge inception voltages and breakdown measurements are reported in a needle-plane electrode system as a function of pressure under AC voltage for natural gases (N2, CO2, and O2/CO2), pure NovecTM gases (C4F7N and C5F10O) and NovecTM in different natural gas admixtures. For compressed 4% C4F7N–96% CO2 and 6% C5F10O–12% O2–82% CO2 gas mixtures, the positive-streamer mode is identified as the breakdown mechanism. Breakdown and negative partial discharge inception voltages of 6% C5F10O–12% O2–82% CO2 are higher than those of 4% C4F7N–96% CO2. At 8.8 bar abs, the breakdown voltage of 6% C5F10O–12% O2–82% CO2 is equal to that of 12.77% O2–87.23% CO2 (buffer gas). Synergism in negative partial discharge inception voltage/electric field fits with the mean value and the sum of each partial pressure individually component for a 20% C4F7N–80% CO2 and 6% C5F10O–12% O2–82% CO2, respectively. In 9% C4F7N–91% CO2, the comparison of partial discharge inception electric fields is Emax (CO2) = Emax(C4F7N), and Emax (12.77% O2–87.23% CO2) = Emax(C5F10O) in 19% C5F10O–81%(12.77% O2–87.23% CO2). Polarity reversal occurs under AC voltage when the breakdown polarity changes from negative to positive cycle. Polarity reversal electric field EPR was quantified. Fitting results show that EPR (CO2) = EPR(9% C4F7N–91% CO2) and EPR(SF6) = EPR (22% C4F7N–78% CO2). EPR (4% C4F7N–96% CO2) = EPR (12.77% O2–87.23% CO2) and EPR (6% C5F10O–12% O2–82% CO2) &lt; EPR (4% C4F7N–96% CO2) &lt; EPR (CO2).