An overall mechanism for the deposition of plasma polymers from methane in a low-pressure argon plasma jet

An overall mechanism for plasma polymer deposition from a methane-seeded argon plasma jet was established from experimental measurements and a simplified model of reaction kinetics within the plasma jet. Total mass deposition rates were obtained at various substrate positions and methane flow rates. Methane consumption was estimated from residual gas analysis. The influence of substrate coolant temperature on deposition rate was evaluated. The model was based on particle densities, jet temperature, and jet velocity data published previously, and reaction rate constants from the literature were used. No adjustable parameters were employed in this model. Experimental results for total deposition rate and methane consumption were in good agreement with model predictions. The overall deposition mechanism consists of three steps: Penning ionization of methane by excited argon neutrals, followed by dissociative recombination of CN _x ⁺ to yield CH, followed by incorporation of CH into the growing film upon impact. Contributions of species other than CH to the total deposition rate are minor, and adsorption is not a prerequisite for incorporation into the growing film.     

Hydrogen/argon plasma jet with methane addition

Spatial distributions of plasma parameters are presented for a H₂/Ar plasma jet with addition of methane. The plasma has been generated at atmospheric pressure by a 200 A (20 kW) nontransferred do arc. Optical emission spectroscopy has been used for the measurements assuming the plasma jet to be optically thin and to have an axial symmetry. Local spectral ernissivity values have been evaluated using a routine Abel inversion procedure. Half- width and emissivity of H spectral line have been measured to determine the electron density and temperature of the plasma. The densities of excited C, CH radicals have been evaluated from the absolute emissivities of relevant molecular emission bands measured in limited spectral intervals in the visible spectrum. The emissivity ratios have been used to fund rotational and vibrational temperatures. The results supply information on methane decomposition and the behavior of molecular radicals in close-to-thermal plasma jets.     

A comparison of experimental measurements and theoretical predictions regarding the behavior of a turbulent argon plasma jet discharging into air

Computed results are presented describing the temperature and concentration fields obtained when an argon plasma jet is being discharged into ambient air. A previously published mathematical model for turbulent plasma plumes is used for the calculations. These predictions are compared with recent), published experimental measurements by Brossa and Pfender, performed with an enthalpy probe. The theoretical predictions appear to agree reasonably well with the measurements of both the temperature and concentration profiles, with a maximum deviation in the 10–20% range.Notation A _max maximum temperature or velocity in the torch exit profile - C ₁ C ₂ C _D constants inK- model - h enthalpy - I torch current - K turbulent kinetic energy per unit mass - m mass concentration of plasma p pressure - Q How rate of argon through the torch - r radial coordinate - r _n nozzle radius (inside) - S source term for dependent variable      

Heat Generation and Particle Injection in a Thermal Plasma Torch

The operation of plasma guns used for plasma spraying involves a continuous movement of the anode arc root. The resulting fluctuations of voltage and thermal energy input introduce an undesirable element in the spray process. This paper deals with the effects of these arc instabilities on the plasma jet, and the behavior of particles injected in the flow. The first part refers to the formation of the plasma jet. Measurements show that the static behavior of the arc depends strongly upon the plasma-forming gas mixture, especially the mass flow rate, of the heavy gas, injection mode, nozzle diameter, and arc current. These parameters control the electric field in the arc column, the arc length, its stability, and the gas velocity and temperature. The dynamic behavior of the arc is examined to determine how the tempeature and velocity of the plasma gas vary with voltage variations. Relationships between the gas velocity at the nozzle exit and the lifetime of the arc roots, and the independent operating parameters of the gun can be established from a dimensional analysis. The second part discusses the interaction between the plasma jet and the particles injected into the flow. The parameters controlling particle injection and trajectory are examined to determine how injection velocity must vary with particle size and density to achieve a given trajectory. The effect of the transverse injection of the powder carrier gas is investigated using a 3-D computational fluid dynamics code. Finally, the effect of the jet fluctuations on particle trajectory is studied under the assumption that the jet velocity follows the voltage variation. The result is a continuous variation of the particle spray jet position in the flow. Experimental observations confirm the model predictions.     

Nonequilibrium modeling of low-pressure argon plasma jets; Part I: Laminar flow

This paper presents a modeling attempt related to low-pressure plasma spraying processes which find increasing applications for materials processing. After a review of the various models for ionization and recombination processes, a two-temperature model for argon plasmas in chemical (ionization) nonequilibrium is established using finite rate chemistry. Results of sample calculations manifest departures from kinetic as well as chemical equilibrium, demonstrating that the conventional models based on the LTE (local thermodynamic equilibrium) assumption cannot provide proper prediction for low-pressure plasma jets.     

Electron temperature and radiative attachment continua in enclosed inductively coupled plasma in argon and chlorine

Inductively coupled plasma (ICP) discharges in chlorine, argon, and their mixtures sustained inside a spherical quartz container at atmospheric pressure have been investigated. Continua of radiative attachment of a free electron to a chlorine atom in ICP are elucidated and are utilized to derive a spatial profile of electron temperature. A qualitative picture of elementary processes in enclosed ICP is given. Differences between electron and gas temperatures are discussed. Electron temperature is maximum in a periphery layer near the induction coil that is chosen for impurity determination. Concentrations of carbon and metal impurities are estimated.     

Probe measurements in argon plasma jets operated in ambient argon

Measurements of local enthalpies and velocities have been performed in plasma jets generated by a DC plasma spray torch, using an enthalpy probe. The torch has been operated in an argon confined atmosphere at different currents and argon flow rates.⁽¹⁾ The validity of the measured enthalpy and velocity profiles has been checked by performing energy flux and mass flux balances, which show reasonable agreement between the input quantities, measured independently, and those obtained by integrating over the experimental profiles. The data are compared with those obtained by operating the same torch in ambient air. The results show that temperatures and velocities measured in pure argon are substantially higher than those in air, and consequently, the jets in argon appear wider and substantially longer.     

Numerical simulation of a nonequilibrium plasma jet in an applied magnetic field using three-fluid model

A three fluid model is applied for the numerical simulation of the axisymmetric flow and temperature fields in a nonequilibrium argon plasma jet which can be controlled by applying art electromagnetic field. The effects of the magnetic field on the characteristics of each plasma species, i.e., electrons, positive ions, and neutral particles, should be accurately clamed. The three-fluid model applied here can clarify the behavior of each plasma species. Equations of conservation for each plasma species coupled witli the generalized Ohm's law, Maxwell's equations, and the equation of state are simultaneously solved taking variable transport properties into account. It is shown that the electron temperature is the highest and the electron velocity is strongly influenced by the magnetic field. Furthermore, the momentum and energy exchanges through electrons can be varied even by a small magnetic flux.Nomenclature B magnetic flux density (T) - c mathematical mean thermal velocity (m/s) - C _p specific heat at constant pressure (J/(kg · K)) d ₀ nozzle diameter (m) - e electron charge (C) - E electric field (V/m) - E effective electric field (V/m) - Ex ^* energy transfer by collision - g relative velocity (m/s) - G partition function - h enthalpy (J/kg) - h _Planck Planck's constant (J · s) - H diffusion enthalpy (J/kg) - j ^* current density (j/en ₀ u ₀ - k Boltzmann constant (J/K) - l mean free path length (m) - L ₀ length of calculation domain along stream (m) - m mass (kg) - M ^* momentum transfer by collision - n number density (m^–3) - production rate of species [/(m³ · 3)] - p pressure (Pa) - collision cross section (m²) - q heat flux (W/m²) - r radial coordinate (m) - r _in inner radius of round tube (m) - R gas constant (J/(kg · K)) - R _in magnetic Reynolds number (=u ₀ d ₀₀µ₀) - s ion slip coefficient [=( _n /gr ₂)² _{e i} ] - S ₁ cross section parameter (m²/J) - T temperature (K) - u axial component of velocity (m/s) - U axial component of diffusion velocity (m/s) - radial component of velocity (m/s) - V radial component of diffusion velocity (m/s) - w peripheral component of velocity (m/s) - W peripheral component of diffusion velocity (m/s) - z axial coordinate (m) - degree of ionization [=n _e /)n _e +n _i +n _n )] - Hall parameter (= ) - ₀ permittivity in vacuum (F/m) - ge ₁ first excitation energy (J) - _ion ionization energy (J) - viscosity (Pa · s) - peripheral coordinate - thermal conductivity [W/(m · K)] - µ₀ permeability in vacuum (H/m) - density (kg/m³) - electrical conductivity (S/m) - mean collision time (s) - cyclotron frequency (Hz) Suffix 0 nozzle exit - e electron - i ion - n neutral particle - r radial component - s plasma species ofs kinds - z axial component - gq peripheral component Originally published inTrans. of the Japan Society of Mechanical Engineers, Ser.B,60, No. 577, 3072–3079 (1994) (in Japanese).     

Heating and quenching of metastable superconducting compounds with a plasma jet

Superconducting compounds, such as cubic -MoC_1–x, cubic -WC_1–x, hexagonal MoB₂, and cubic -TaN, which are metastable at room temperature, have been formed by heating and quenching of their respective equilibrium phases, such as hexagonal -MoC_1–x, hexagonal WC, rhombohedral Mo₂B₅, and hexagonal -TaN in a plasma jet. From calculations based on a simple model, the quenching rate of particles has been estimated to be 10⁵ deg s^–1.     

Diagnostics of a thermal plasma jet by optical emission spectroscopy and enthalpy probe measurements

An accurate determination of electron density, temperature, and velocity distributions is of primary interest for the characterization of steady-state thermal plasma spray jets. Our diagnostic capabilities based on optical emission spectroscopy include measurements of absolute emission coefficients and Stark broadening. In addition, enthalpy probe diagnostics has also been used for temperature and velocity measurements. Observation of large discrepancies between temperatures derived from absolute emission coefficients, Stark broadening, and from enthalpy probe measurements indicate that severe deviations from LTE (local thermal equilibrium) exist in various regimes of plasma spray jets. Nonequilibrum characterization of such turbulent thermal plasma jets suggests that diffusion of high-energy electrons into the fringes of plasma jets and deviations from chemical equilibrium due to high velocities in the core of plasma jets and entrainment of cold gas, are the main reasons for these discrepancies. The establishment of a reliable data base, taking these nonequilibrium effects into account, is a prerequisite for meaningful modeling of real plasma jets.     

Use of solvents in the low-pressure plasma oxidation of olefins

The oxidation ofn-octene has been studied in mixtures with dimethylbutane, 1,4-dimethylcyclohexane, ethylcyclohexane, and dibutyl ether. Except for dimethylbutane, total yields increase on addition of a solvent, and the fraction of epoxide among the products is higher than in reactions with neat octene.     

Reactions of hydrocarbons in a supersonic vacuum plasma jet

The plasma plume of a hydrogen plasma jet used for diamond synthesis is analyzed by a Pitot tube and by mass spectrometry. In the investigated pressure range of 2–10 mbar, supersonic gas velocities with Mach numbers of up to 2 were observed, which decreased with increasing pressure and increasing distance from the nozzle. The injection of the carbon-containing species either at the exit of the jet nozzle or simply into the background gas of the reaction chamber confirmed the importance of recirculation of background gas into the plasma plume. In the case of background injection the rise of the total carbon content in the plume with increasing distance from the nozzle is much slower than in the case of nozzle injection. The results of a numerical model of the hydrocarbon gas-phase reactions in the jet are presented. The model considers the entrainment of background gas into the plasma plume. Two domains along the jet axis can be distinguished. The first one in the vicinity of the nozzle is dominated by methyl radicals, the second one by atomic carbon. Increase of the hydrogen dissociation level results in the broadening of the atomic carbon domain and the rise of C₂ far from the nozzle. Background injection of CH₄ leads to lower total carbon content in the plume but has little effect on the species distribution along the jet axis.     

Particle velocity measurements in induction plasma spraying

Laser Dopple anemometry (LDA) measurements of the particle velocity are carried out during an induction plasma spraying operation. The velocity of nickel alloy particles, or molten droplets, at the exit of an induction plasma torch prior to impact on the substrate is shown to vary with the plasma and powder injection conditions. Plasma spraying under soft vacuum (150–450 Torr) gives rise to substantially higher particle velocities (40–60 m/sec) compared to those attained at atmospheric pressure (10–20 m/sec).     

Plasma spraying of alumina: Plasma and particle flow fields

A comprehensive experimental examination of the interaction between a subsonic thermal plasma jet and injected alumine, particles is presented. Measurements of plasma velocity, temperature, and entrained air were obtained from an enthalpy probe and mass spectrometer combination. A diffusive separation, or demixing, of the Ar and He plasma gas was observed. Centerline plasma velocities and temperatures ranged from 1501500 m/s and 2000 to 14,000 K, respectively, in the region between the torch and a typical substrate location of 90 mm. Measurements of particle size, velocity, tempearture and local number density were obtained from a combination laser particle sizing system, Laser doppler velocimeter (LDV), and two-color pyrometer. Centerline temperatures and velocities for the nominally 30 m particles used were 2400–2800 K and 150–200 m/s, respectively.     

Effects of UV light irradiation on propane in an argon plasma

It has been shown that propane conversion into acetylene, by propane cracking in an argon plasma, is increased when the reaction site is irradiated with UV light in the range 220–400 nm. The reactions were carried out between 4500 and 6400 K. A model is outlined following which the propane conversion increase at 6400 K (40%) is tied up to energy absorption by acetylene in the lower wavelengths range (220–250 nm). Also, a combined adsorption-photochemical process, related to precursors and submicron carbon particles, could be responsible for the yield increase observed at 5400 K (45%), around 365.0 nm.     

Thermal decomposition of carbon dioxide in an argon plasma jet

The decomposition of carbon dioxide to carbon monoxide and oxygen in an argon plasma is studied. The overall kinetic and energy-related parameters of the process, as well as the quenching rates of the products, are evaluated on the basis of measured radial and longitudinal profiles of both temperature and degree of decomposition in the high-temperature reaction zone.     

Noninvasive plasma diagnostics in a parallel-plate reactor for RF discharges

Extensive studies on the discharge current of a 50-kHz argon glow discharge in a parallel-plate reactor has led to a model that is able to describe the discharge in a wide range of pressures and powers for the evaluation of plasma parameters. The network simulation program PSPICE can be used to simulate the model in a way easily adopted to other plusma reactors as well. This may lead to a new plasma diagnostic method that does not require a complicated setup. The behavior of the discharge current can also he used for numerical simulations of the sell bias voltage in capacitively coupled plasma reactors. The influence of power and pressure can be integrated and allows an estimation of the self-bias for given reactor geometries and process parameters.     

Nonequilibrium modeling of low-pressure argon plasma jets; Part II: Turbulent flow

The nonequilibrium behavior of low-pressure, turbulent plasma jets has been tested using the k- turbulence model and the model described in the previous paper. It also has been shown that nonequilibrium effects cannot be excluded in the case of turbulent jets.     

Analysis of glass and glass melts during the vitrification process of fly and bottom ashes by laser-induced plasma spectroscopy. Part I: Normalization and plasma diagnostics

For laser-induced plasma spectroscopy (LIPS) analysis of the main components (Si, Al, and Ca) in glasses utilized for vitrification of ashes from waste incineration, a normalization procedure for line ratios is presented. Even in homogeneous glass samples, considerable pulse-to-pulse variations of the plasma electronic excitation temperature and electron density were observed because of changes in the material–laser interaction. A normalization procedure is outlined using Saha–Boltzmann equilibrium relationships to include the electronic excitation temperature and density in the calibration model. As a result of the normalization, the variation of the line ratios is reduced and linear calibrations for LIPS intensity ratios versus concentration ratios are achieved. For samples with high aluminum concentrations, the analysis was hampered by self-reversal effects.     

Nanoparticle formation using a plasma expansion process

We describe a process in which nanosize particles with u narrow size distribution are generated by expanding a thermal plasma carrying vapor-phase precursors through a nozzle. The plasma temperature and velocity profiles are characterized by enthalpy probe measurements. by calorimetric energy balances. and by a model of the nozzle flow. Aerosol samples are extracted from the flow downstream of the nozzle by means of a capillary probe interfaced to a two-stage ejection diluter. The diluted aerosol is directed to a scanning electrical mobility spectrometer (SEMS) which provides on-line size distributions down to particle diameters of 4 nmt. We have generated silicon, carbon, and silicon carbide particles with number mean diameters of about 10 not or less, and we have obtained some correlations between the product and the operating conditions. Inspection of the size distributions obtained in the experiments, together with the modeling results, suggests that under our conditions silicon carbide formation is initiated by nucleation of extremely small silicon particles from supersaturated silicon vapor, followed by chemical reactions at the particle surfaces involving carbon-containing species from the gas phase.