Parametric study of the decomposition of NH3 for an induction plasma reactor design

The present paper reports a study of the gas mixing and chemical transformation in an induction plasma reactor under atmospheric pressure, and its dependence on the plasma operating conditions. For this purpose, the thermal dissociation of ammonia into nitrogen and hydrogen was chosen because of the relative simplicity of the reactions involved and its use in a number of studies on plasma synthesis of ultrafine nitride ceramic powders using ammonia as nitriding agent. A hot-wall reactor configuration is investigated in which ammonia is injected radially through multiple orifices into the gases at the exit nozzle of an induction plasma torch. Concentration mapping in the mixing zone was carried out, using a VG-Micromass-PC 300 D quadrupole mass spectrometer, for different plasma power levels, in the range 13–24 kW. A 3-point injection mode is used with the injection ports oriented upstream at 45° to the torch axis. This allows uniform mixing of the injected gas in the plasma jet. A systematic study of the effects of plate power and ammonia and plasma gas flow rates on the mixing and dissociation of NH₃ in the reactor is reported. The results are analyzed and discussed from the viewpoint of their use for optimizing the design of induction plasma reactors, to he applied to the vapor-phase synthesis of ultrafine silicon nitride powders.     

Mixing study of the induction plasma reactor: Part II. Radial injection mode

A study was undertaken on the mixing pattern in am induction plasma torch and reactor system. The results presented in this part of the paper relate to the radial injection mode, in which an auxiliary gas is injected into the main plasma stream through a set of 2, 4, or 8 injection ports located in the torch nozzle at the level of the torch exit flange. A much faster mixing of the gases occurred in this mode compared to the axial injection mode investigated in Part I of this paper. As in the case of axial injection, the present study demonstrates that gas mixing, in the presence of the discharge, is considerably more difficult than under ambient temperature conditions. Lower turbulence levels exist in the plasma reactor. due to the considerably higher viscosity of the gases under plasma conditions. Results obtained with a three-point injection flange, in which the injection ports were oriented at 45° to the torch and reactor axes toward the upstream .side, mere most interesting since they achieved essentially the same degree of mixing as was obtained with the radial injection ports without the need to locate the injection ports at the exit nozzle of the plasma torch. This arrangement provides for added flexibility in reactor design.     

In-Flight Spheroidization of Alumina Powders in Ar–H<Subscript>2</Subscript> and Ar–N<Subscript>2</Subscript> Induction Plasmas

In-flight spheroidization of alumina powders in Ar–H₂ (H₂–7.6%, vol/vol) and Ar–N₂ (N₂–13.0%, vol/vol) RF induction plasmas was investigated numerically and experimentally. The mathematical model for the plasma flows incorporates the k– turbulence model, and that for particles is the Particle-Source-in-Cell (PSI-Cell) model. Experimental results demonstrate that spheroidized alumina particles are produced in both Ar–H₂ and Ar–N₂ RF plasmas, with different particle size distributions and crystal phases. Agreement between the predicted and measured particle size distributions is satisfactory under high particle feed rate conditions, while the results obtained for the Ar–H₂ plasma are better than those for the Ar–N₂ plasma. The discrepancy occurring in low feed rate conditions suggests that particle evaporation is an important factor affecting the plasma–particle heat transfer.     

The Treatment of Water-Based Toxic Waste Using Induction Plasma Technology

A study of the treatment of liquid wastes in a radio frequency (rf) induction plasma reactor is reported. Ethylene glycol was used as a surrogate for the waste because of safety considerations. Thermodynamic analyses demonstrated complete and safe decomposition at the conditions studied. The solution was injected axially into the center of an argon–oxygen plasma operated at a plate power of 50 kW to study blast atomization and operating conditions. A factorial analysis revealed, at a confidence level of 0.99, that both reduction of pressure and liquid flow rate increase the destruction and removal efficiency (DRE) and that a higher plate power increased DRE. The study also revealed that poor atomization was responsible for the reduction of the DRE by 10–15% (to 80–85%) and that 94% of the exothermic energy of the reaction was available for further use. The specific energy requirement (SER) of the process was estimated at 8.33 kWh/kg of solute. This value can be expected to drop significantly with scale-up of the process.     

Effects of process parameters on ultrafine SiC synthesis using induction plasmas

A study is reported of the formation of ultrafine SiC powder through the reaction of elemental silicon and CH₄ in an induction plasma. The reaction route used involved in the first place the vaporization of a fine elemental silicon powder axially injected into the center of the discharge followed by the carburization reaction through the coinjection of CH₄. The powder obtained was composed of a mixture of α- and β-SiC with varying amounts of free carbon and free silicon. The particle size distribution was typically in the range of 40–60 nm with a corresponding specific surface area of 30–50 m²/g. A parametric study showed that the quality of the powder obtained varied with the plasma plate power and the position of the injection probe. The plasma gas composition employed was found to influence the proportions of α- and β-SiC in the synthesized SiC powder. With an Ar/N₂ mixture as the plasma gas, the ratio of the α to β phases was less than 1.0, whereas the ratio was greater than 1.5 when using a mixture of Ar/H₂ as plasma gas. The Si powder feed rate and the input C/Si molar ratio in the injected reactants significantly affected both the formation of the SiC and the free Si and free C content in the synthesized powder. Lining the cylindrical reactor wall with graphite resulted in improved conversion of Si to SiC. The weight fraction of the powder collected at different sections of the reactor system varied with the reactor operating conditions. The experimental results support the view that the formation mechanism for ultrafine SiC is dominated by the reaction of Si vapor with the thermal decomposition products of CH₄.     

Langmuir probe measurements of axial variation of plasma parameters in 27.1 MHz rf oxygen planar discharges

Langmuir probe studies have been performed on rf (27.1 MHz) discharges in O₂ under planar reactor conditions to determine the axial variation of the plasma parameters (positive ion density, electron temperature, and dc space potential) as a function of pressure (20–220 Pa) and power (10–150 W) or current (0.1–2 A). By monitoring the second derivative of the I–V probe characteristics, the suppression of the rf component in the probe circuit can be optimized. Referring to this problem, numerical studies provide relations for the determination of the residual rf component as well as of the dc component of the plasma potential at incomplete rf compensation. The positive ion density is obtained from the ion saturation currents. Here the effect of collisions between ions and neutral particles within the probe sheath (for p> 100 Pa) is considered. The electron energy distribution function is found to be of the Maxwellian type for all discharge conditions investigated here. If the pressure and the power exceed critical values, the axial charge carrier distribution is characterized by a valley formation in the bulk plasma center. This fact demonstrates that secondary electron emission due to ion impact on the electrode surfaces and following ionization by these electrons near the sheaths in front of the electrodes are significant processes for sustaining the discharge. At low pressures (p60 Pa) the dc plasma potential was found to be identical with the half-peak maintaining voltage of the discharge, in agreement with the model idea of a symmetric rf planar discharge where the rf voltage drop across the bulk plasma can be neglected. For growing pressure, however, the plasma system moves gradually toward a situation where the V-I characteristics of the discharge are significantly controlled by processes in the bulk plasma. This transition depends on the current density.     

DC plasma polymerization of hexamethyldisiloxane

Hexamethyldisiloxane (HMDS) was polymerized onto metallic and insulating substrates in a parallel-plate DC reactor. The limits of the DC reactor with respect to pressure and power were determined for deposition of PP-HMDS films. In all conditions ranging from 5 Pa/0.3 W to 100 Pa/50 W, solid films were deposited. No powders or oily films were obtained under any condition in this operating range. The films were polymeric in nature,i.e., they were neither carbon-like nor SiO _x -like films. The structures and crosslink densities of the plasma films dependend strongly on the deposition conditions. The highest deposition rates, up to 2 μm per minute (or0.3 mg/cm² min), were obtained at high power, pressure, and flow rate conditions. An efficiency ɛ is introduced, defined as the fraction of the monomer that is retained in the form of a polymer deposited on the substrate. Efficiencies as high as 25% could be obtained in certain conditions. Pulsing the discharge power increased the conversion efficiency markedly, but the effect depended strongly on the monomer used. In addition to HMDS, plasma polymers were also deposited from pyrrole in pulsed conditions for comparison. A method is described for depositing films on insulators from a DC glow discharge using two wire meshes held at a negative potential.     

Parametric Study on Nitridation and Carburization of MoSi2 Powders in an Induction Plasma

An investigation of in-flight nitridation and carburization of MoSi ₂ powders has been carried out using the induction plasma process. Response surface methodology (RSM) with the Box–Behnken experimental design was utilized in this investigation, in order to study the influence of some induction plasma processing parameters on the efficiency of nitridation and carburization reactions performed on inflight treated MoSi ₂ powders. The parameters examined included the level of inductive power, reactor pressure, and the quantity of reaction gases supplied. Under the optimal process conditions achieved during this investigation, about 2.8 wt.% of nitrogen (in the case of nitridation) and about 8.0 wt.% of carbon (in the case of carburization) were able to be incorporated into the MoSi ₂ powder particles.     

Formation of gaseous intermediates in titanium(IV) chloride plasma oxidation

A number of experiments were made to study tire gas phase reactions that precede TiO₂ aerosol formation from TiCl₄ in an O₂/Ar plasma. The gaseous .species from the plasma-aerosol reactor were detected by a high-resolution QP mass spectrometer. The feed ratio of Ar: O₂: TiCl₄ was typically 4. l: 0.1. Under such conditions both titanium oxychlorides and oxides of chlorine could be recognized. In the reactor the decay of oxychlorides from the reactions it-as fast, compared to the decay of chlorine. A rough estimate of the quantities of both ClO(g) and Ti0Cl_x(g) metastable species present is given. TiCl₄ oxidation reaction mechanisms with mentioned oxychlorides as intermediates are discussed The theoretical calculations were conducted in tire temperature range from 800 to 3500°C.     

Static pressure and heat flux measurements of a thermal argon plasma flow in a water-cooled tube

The momentum and energy transfer phenomena with large temperature difference were investigated experimentally and theoretically, using an argon atmospheric thermal plasma. The plasma was generated by an arc discharge, 4–6 kW, and flowed into a water-cooled copper tube for static pressure measurements and into a copper block with the same size hole (8 mm i.d.) for measuring heat fluxes using a transient method. The argon flow rate was 2.77–8.31×10^–4 kg/s. The static pressure of the plasma flow shows a different variation from that of an ordinary flow and does not decrease monotonically. The axial distributions of the numerical calculations are in fair agreement with those of the experiments, and it is concluded that the contributions of recombination and of physical properties play important roles in the behavior of the confined thermal plasma flow.     

Experimental and Theoretical Studies of a Pulsed Microwave Excited Ar/CF4 Plasma

The present work deals with a pulsed microwave discharge in an Ar/CF ₄ gas mixture under a low pressure (1–10 mbar). The discharge chamber developed has a cylindrical geometry with a coupling window alternatively made of quartz or alumina. The setup allows one to investigate the plasma–wall interactions (here etching of the quartz window) and the ignition process of the pulsed microwave plasma. Microwave pulses with a duration of 50–200 s and repetition rate between 1 and 10 kHz are typical for the experiments. The space-time behavior of the fluorine number density in the discharge has been investigated experimentally by optical actinometry. The discharge kinetics is modeled using electron-transport parameters and rate coefficients derived from solutions of the Boltzmann equation. Together with the solution of the continuity and electron balance equations and the rate equations describing the production of CF _x (x=2, 3, 4) radicals and F atoms, a good agreement between experimental and theoretical data can be achieved.     

A temperature nonequilibrium phase transition of the chaotic state in the belousov-zhabotinskii reaction in a closed ideal mixing reactor

The influence of the temperature close to the threshold of generation of a chaotic state in an oscillatory ferroin-catalyzed Belousov-Zhabotinskii chemical reaction was studied in a closed ideal mixing reactor. On the basis of the data obtained it was shown that when the temperature is varied in this chemical system, a nonequilibrium phase transition is observed, in which there is an abrupt change in the reciprocal of the induction period. Under these conditions, close to the temperature of the phase transition the origin of the oscillations is probabilistic.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 30, No. 3, pp. 147–151, May–June, 1994.     

H2 plasma development of X-ray imaged patterns on plasma-polymerized resists

An X-ray imaged pattern on a plasma-polymerized film was successfully developed by H₂ plasma etching. Plasma-polymerized MMA and 6FBMA were formed by using an inductively coupled argon flow type reactor. An X-ray imaged pattern on the film was attained through a knife-cut window of a gold plate. The X-ray was generated from a Cu target at 20 kV and main wavelength 1.54 Å. The pattern development was performed using a tubular type reactor with parallel plate electrodes. The quality of plasma-polymerized resists in an X-ray lithography was evaluated by comparing it with the conventional polymer in the dry and wet process, and the minimum dose rate for a visible pattern fabrication was measured to be 4.1 J/cm² for both resists in H₂ plasma etching development.     

Cleaning of Air Streams from Organic Pollutants by Plasma–Catalytic Oxidation

Oxidative removal of a mixture of chlorinated ethylenes and aromaticcompounds in air in a pulse corona discharge reactor combined with metaloxide catalyst downstream was investigated in a field experiment. Dischargewas initiated by high-voltage pulses of 70–75 kV peak voltage and200 ns risetime. A flow of 60 m³/h was treated at11–12 Wh/m³ with catalyst held at 110°C at a spacevelocity of 6000 h^–1. Removal rates of 70–90% havebeen found with input concentrations in the parts per million and thesubparts per million range. No partially oxidized hydrocarbons could bedetected in cleaned air. A closed carbon balance was confirmed underlaboratory test conditions.     

Surface Functionalization at Atmospheric Pressure by DBD-Based Pulsed Plasma Polymerization

Dielectric barrier discharge (DBD)-based plasma deposition at atmospheric pressure, using glycidyl methacrylate (GMA, methacrylic acid-[2,3-epoxy-propyl ester]) as a prototype precursor was investigated in order to evaluate the applicability of dielectric barrier discharges to obtain plasma polymers with a high degree of structural retention of the starting precursor. Using pulsed excitation of the discharge, up to about 90% of the epoxy groups of GMA can be retained in plasma polymers obtainableat deposition rates in the order of 3–5nm/s. Preliminary investigations of the mechanism of film formation under pulsed plasma conditions indicate that the reaction of intact monomer molecules withsurface radicals generated during the pulses play a prominent role.     

Synthesis of ammonia in high-frequency discharges

The synthesis of ammonia from nitrogen-hydrogen plasma prepared using radiofrequency discharge and microwave discharge was studied under the same experimental conditions except the driving frequency. Twice larger amounts of ammonia were adsorbed on zeolite used as adsorbent in the microwave discharge than in the radiofrequency discharge. Relative intensities of NH band head (A³–X^3–,0–0) as well as hydrogen atomic line (H\) observed in the plasma prepared using microwave discharge were one order of magnitude larger than those in the plasma prepared using radiofrequency discharge. Since NH_x radicals and H atoms are considered ammonia precursors, the advantage of microwave discharge over radiofrequency discharge on ammonia synthesis is discussed from the results obtained above and from the plasma parameters,kT _e andn _e , obtained by the electric double probe technique.Partly presented at the 8th International Symposium on Plasma Chemistry, August 31 to September 4, 1987, Tokyo, Japan.     

Synthesis of ammonia in high-frequency discharges. II. Synthesis of ammonia in a microwave discharge under various conditions

The synthesis of ammonia from nitrogen-hydrogen plasma prepared using microwave discharge was studied by changing some experimental conditions, such as pressure (260–2600 Pa), power input (30–280 W), and nitrogen-hydrogen mixing ratio [H₂/(N₂+H₂)=0–1.0]. The ammonia yield increased with decreasing pressure and saturated at lower pressures. When the power input and the nitrogen-hydrogen mixing ratio were changed, the maximum yield of ammonia was obtained at the optimum experimental conditions (power input 150W; H₂/(N₂+H₂)0.75). Amounts of NH, H, and H₂ in the plasma also changed by changing the experimental conditions. From the changes in ammonia yield and amounts of NH, H, and H₂ by changing the experimental conditions, it is suggested that ammonia molecules are formed by the reaction of NH radicals not only with hydrogen atoms but also with hydrogen molecules. Otherwise, the formation and the decomposition of ammonia would occur simultaneously.     

Methane Pyrolysis Stimulated by Admixture of Atomic Hydrogen: 1. An Experimental Study

A method for enhancing the hydrocarbon pyrolysis process by introducing atomic hydrogen into the reaction medium from an arcjet plasma source was considered. It was shown that hydrogen atoms could effectively be introduced by mixing under low pressure. The atomic hydrogen–stimulated methane pyrolysis process was experimentally studied in a continuous stirred reactor with a plasma plume. When hydrogen atoms were present in the plasma jet, the amount of the valuable product increased by a factor of two.     

Optical Emission Spectroscopy of Abnormal Glow Region in Nitrogen Plasma

Optical emission spectroscopy of the active species in N₂ plasma is carried out to investigate their concentration as a function of discharge parameters such as filling pressure (2.0–7.0 mbar), source power (100–200 W) and gas flow rate (50–300 mg/min). The primary motivation of this work is to obtain reliable information about the concentration of the active species of N₂ plasma, which play an important role in plasma surface nitriding processes. Emission intensity from the selected electronic excited states of molecular and atomic species is evaluated as a function of discharge parameters to investigate their concentration. The emission intensity ratio I(N₂⁺)/I(N₂) and I(N⁺)/I(N) of the electronic transitions is also evaluated as a function of discharge parameters to investigate the relative dependence of their concentrations. It is observed that the concentration of the active species of N₂ plasma is strongly affected by the filling pressure and source power whereas flow rate has no significant effect. An increased occurrence of N₂⁺ molecular ions in comparison with N₂ molecules, and N⁺ ions in comparison with N atoms is observed with source power whereas decreased occurrence of N₂⁺ molecular ions in comparison with N₂ molecules, and N⁺ ions in comparison with N atoms is observed with the rise in filling pressure.     

Surface Modification of Textile Fibers and Cords by Plasma Polymerization

In this paper we report on the treatment of industrial fibers and cords by means of plasma polymerization techniques. Coatings of plasma-polymerized pyrrole or acetylene were deposited on aramid fibers, aramid cords and polyester cords. The equipment was a custom-built semi-continuous reactor operated on a pulsed DC glow discharge. The fibers and cords were tested for adhesion to various polymers such as tire cord skim stock rubber compounds and epoxy adhesives. Standard industrial pull-out force adhesion measurement techniques were used. The deposition conditions of the plasma polymer films were varied within wide limits. It was found that, in general, films deposited under low-power and high-pressure conditions performed better than films prepared under high-power and low-pressure conditions. For some systems pulsing of the discharge power improved the performance further. For all systems studied, the optimized plasma polymer surface modification outperformed current industrial standards. The plasma-polymerized coatings were characterized by various techniques and the excellent performance results are explained in a tentative model based on the molecular structure of the films. This structure was found to be strongly dependent on the discharge conditions.