Particle Injection in Direct Current Air Plasma Spray: Salient Observations and Optimization Strategies

External injection of high-melting point low thermal conductivity ceramics orthogonal to a typical direct current thermal plasma jet plays a vital role in determining the in-flight state of the particles and the process downstream. The interactions between low density ceramic particles and high temperature plasma jet is quite complex, which influences the spray process and associated deposition. Detailed in-flight particle diagnostics as well as spray stream visualization have significantly enhanced our capability to diagnose and control the process. In this paper we present some salient observations on the role of key variables on particle injection. A number of experiments were conducted using a 7MB torch (Sulzer Metco, Westbury, NY) with both Ar–H₂ and N₂–H₂ plasma gases, where the carrier gas flow to inject Yttria Stabilized Zirconia (YSZ) was varied systematically and the resulting in-flight particle state was captured using an array of particle and spray stream sensors arranged in a 3D set-up. A notable observation is the existence of a “sweet-spot” in the plasma jet where the particle temperatures and velocities achieved a maximum. This sweet-spot can be characterized by the plume position (location of centroid of the spray stream) rather than carrier gas flow rate and is independent of primary gas flows and other process/material conditions. This result suggests a possible approach to optimize particle injection independent of plasma-forming-torch-parameters. Controlling particle injection at this sweet-spot has shown to benefit the overall process efficiency (in terms of melting) and process reliability (both in-flight measurement and coating build-up) with concomitant application benefits.     

Characteristics of Multi-Phase Alternating Current Arc for Glass In-Flight Melting

An innovative in-flight melting technology with multi-phase AC arc was developed for glass industry. The enthalpy probe and high speed video camera were used to characterize the temperature, velocity, and discharge behavior of multi-phase AC arc. The effects of input power and sheath gas flow rate on arc and melting behavior were investigated. Results show that the temperature and velocity on arc center are increased with input power or sheath gas flow increase. The fluctuation of luminance area ratio and coefficient of variation reflects the change of arc discharge behavior. High temperature of plasma enhances the melting of granulated raw particles during in-flight heating treatment. The shrinkage of particle and the volatilization degree of Na₂O increase under a larger flow rate of sheath gas. The characterized arc behavior agrees with the melting behavior of glass raw materials, which can provide valuable guidelines for the process control of glass melting.     

In-flight Melting Behavior of Granulated Alkali-Free Raw Material in Induction Thermal Plasmas

A new in-flight glass melting technology with induction thermal plasmas was developed to reduce the energy consumption and the emissions of greenhouse gases for glass production. The effects of carrier gas on the in-flight melting behavior of granulated alkali-free raw material were investigated by various modern analyses. Results show that the particles have smooth spherical surface and compact structure after heat treatment. As the carrier gas flow rate increases, the vitrification degree decreases and the average diameter increases. Higher vitrification results in more shrinkage of particle. The carbonates in raw material decompose completely during in-flight melting. The highest volatilization of B₂O₃ is attributed to more heat transferred from plasmas to particles at the lowest carrier gas flow rate.     

The Particle In-Flight Characteristics in Plasma Spraying Process Measured by Phase Doppler Anemometry (PDA)

Detailed measurements of particle in-flight characteristics have been carried out using a PDA system for benchmarking as well as to provide further information to aid the development of simulation models. The parameters studied included four conditions of primary gas flow rate and carrier gas flow rate. The particle velocities, diameters, and the corresponding volume flux at different locations were obtained. Due to the one port particle injection arrangement, it was noted that particles in general sprayed with an angle deviated from the nozzle axis Z_n, to the opposite side of the powder feeder port. The particles would also deviate from the spraying cone axis with a divergence angle (). The deviation and divergence angles were examined under different plasma spraying conditions. The measurement data rates at different cross-sectional planes were also obtained so as to compare the results derived from the volume flux measurement and the actual coating on a substrate at the equivalent standoff distance. It was found that the spraying area obtained from the measurement-data-rate increased with downstream distance and a linear relationship between spraying area and distance was also established. Comparing the integrated results, it was noted that the spraying areas derived from the measurement data rate were close to the actual spraying areas obtained from the coordinate measurement machine (CMM) results.     

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.     

Powder Loading Effects of Yttria-Stabilized Zirconia in Atmospheric dc Plasma Spraying

Powder loading effects have been reexamined for various yttria-stabilized zirconia powders under atmospheric dc plasma spraying. A laser illumination method was utilized to observe powder injection into the plasma jet, while single particle and ensemble methods to measure particle state parameters. Statistical temperature distributions of in-flight particles suggested a rapid increase in the number of semi-molten particles above a certain powder loading rate. Despite drops in the particle temperature and velocity due to the powder loading effect, the deposition efficiency tends to have increased in some cases. Reliability of the single particle and ensemble methods has also been examined at various powder feed rates. Particle temperature measurement by the ensemble method at low powder feed rates could cause a significant error, which may affect powder injection optimization. Particle plume trajectory was not affected as much by the powder loading, which hence had only a limited effect on the particle diagnostics.     

A new configuration for coupling purge-and-trap/cryogenic focusing/capillary column gas chromatography with splitless injection mode

A new configuration for coupling a purge-and-trap unit to a capillary column gas chromatograph via a cryogenic focusing interface has been developed. In this configuration, the precolumn of the cryogenic focusing interface was inserted through the septum of a split/splitless injection port where it served as both sample transfer and carrier gas supply lines. The injection port of the gas chromatograph was modified by plugging the carrier gas and the septum purge lines. This configuration allowed for the desorption of analytes at high flow rates while maintaining low, analytical-column flow rates which are necessary for optimum capillary column operation. The capillary column flow rate is still controlled by the column backpressure regulator. Chromatograms of purgeable aromatics exhibited improved resolution, especially for early eluting components compared to those obtained by direct liquid injection using the normal splitless injection mode. Quantitative sample transfer to the analytical column afforded excellent linearity and reproducibility of compounds studied.     

Plasma Spray Process Operating Parameters Optimization Based on Artificial Intelligence

During plasma spray process, many intrinsic operating parameters allow tailoring in-flight particle characteristics (temperature and velocity) by controlling the plasma jet properties, thus affecting the final coating characteristics. Among them, plasma flow mass enthalpy, flow thermal conductivity, momentum density, etc. result from the selection of extrinsic operating parameters such as the plasma torch nozzle geometry, the composition and flow rate of plasma forming gases, the arc current intensity, beside the coupled relationships between those operating parameters make difficult in a full prediction of their effects on coating properties. Moreover, temporal fluctuations (anode wear for example) require “real time” corrections to maintain particle characteristic to targeted values. An expert system is built to optimize and control some of the main extrinsic operating parameters. This expert system includes two parts: (1) an artificial neural network (ANN) which predicts an extrinsic operating window and (2) a fuzzy logic controller (FLC) to control it. The paper details the general architecture of the system, discusses its limits and the typical characteristic times. The result shows that ANN can predict the characteristics of particles in-flight from coating porosity within maximal error 3 and 2 % in temperature and velocity respectively. And ANN also can predict the operating parameters from in-flight particle characteristics with maximal error 2.34, 4.80 and 8.66 % in current intensity, argon flow rate, and hydrogen flow rate respectively.     

Numerical Modeling in Radio Frequency Suspension Plasma Spray of Zirconia Powders

A comprehensive model was developed to investigate the suspension spraying for a radio frequency (RF) inductively coupled plasma torch. Firstly, the electromagnetic field is solved with the Maxwell equations and validated by the analytical solutions. Secondly, the plasma field with different power inputs is simulated by solving the governing equations of the fluid flow coupled with the RF heating. Then, the suspension droplets embedded with nano particles are modeled in a Lagrangian manner, considering feeding, collision, heating and evaporation of the suspension droplets, as well as tracking, acceleration, melting and evaporation of the nano or agglomerate particles. The non-continuum effects and the influence of the evaporation on the heat transfer are considered. This particle model predicts the trajectory, velocity, temperature and size of the in-flight nano- or agglomerate particles. The effects of operating conditions and intial inputs on the particle characteristics are investigated. The statistical distributions of multiple particles’ size, velocity, temperature are also discussed for the cases with and without consideration of suspension droplets collision.     

Optimizing the relationship between chromatographic efficiency and retention times in temperature‐programmed gas chromatography

A methodology that can maximise the chromatographic efficiency that can be achieved within a defined time frame in temperature‐programmed gas chromatography is described. The efficiency can be defined as the inverse of peak widths measured in retention index units. This parameter can be described by a model similar to the van Deemter equation, which is expanded to account for the effect of the temperature rate in addition to the effect of carrier gas velocity. The model of efficiency is found by response surface methodology, where the temperature rates and the carrier gas velocities are systematically varied in the experiments. A second model that accurately explains the retention time of the last eluting compound can be found from the same experiments, and optimal conditions are found by combining the two models. The methodology has been evaluated with four capillary columns and three carrier gases, using fatty acid methyl esters as analytes. All experiments showed that there is a fairly linear decrease in efficiency with increasing temperature rates. At any temperature rate, optimal velocity is only marginally higher than the velocity that maximises chromatographic efficiency, since the carrier gas velocity has a limited effect on the retention times.     

Alignment of retention time obtained from multicapillary column gas chromatography used for VOC analysis with ion mobility spectrometry

Multicapillary column (MCC) ion mobility spectrometers (IMS) are increasingly in demand for medical diagnosis, biological applications and process control. In a MCC-IMS, volatile compounds are differentiated by specific retention time and ion mobility when rapid preseparation techniques are applied, e.g. for the analysis of complex and humid samples. Therefore, high accuracy in the determination of both parameters is required for reliable identification of the signals. The retention time in the MCC is the subject of the present investigation because, for such columns, small deviations in temperature and flow velocity may cause significant changes in retention time. Therefore, a universal correction procedure would be a helpful tool to increase the accuracy of the data obtained from a gas-chromatographic preseparation. Although the effect of the carrier gas flow velocity and temperature on retention time is not linear, it could be demonstrated that a linear alignment can compensate for the changes in retention time due to common minor deviations of both the carrier gas flow velocity and the column temperature around the MCC-IMS standard operation conditions. Therefore, an effective linear alignment procedure for the correction of those deviations has been developed from the analyses of defined gas mixtures under various experimental conditions. This procedure was then applied to data sets generated from real breath analyses obtained in clinical studies using different instruments at different measuring sites for validation. The variation in the retention time of known signals, especially for compounds with higher retention times, was significantly improved. The alignment of the retention time—an indispensable procedure to achieve a more precise identification of analytes—using the proposed method reduces the random error caused by small accidental deviations in column temperature and flow velocity significantly.     

Stability of the FID sensitivity during an analysis in capillary GC

The sensitivity of an FID may change when the carrier gas flow rate changes during a chromatographic run. Sample parts which are eluted at reduced FID sensitivity produce a reduced peak area, hence are discriminated as compared to other components. Sensitivity changes were studied for hydrogen as carrier gas. For the detector tested, differences in the carrier gas flow rates of 1 ml/min shifted the FID sensitivity by 1 to 5% (depending on the fuel gas supply). Thus the stability of the sensitivity is no longer ensured as soon as the carrier gas flow rate is changed manually or by an automatic programmer during an analysis. Sensitivity drifts may also occur during temperature programmed runs with a pressure regulated carrier gas supply since the gas flow through the capillary drops with increasing temperature. Such shifts in the response became noticeable as soon as relatively high carrier gas flow rates combined with long range temperature programmes were used. The typical patterns of such discriminations are shown, closing with a discussion on the possibilities for minimizing such undesired effects.     

New In-Situ Sampling and Analysis of the Production of CeO<Subscript>2</Subscript> Powders from Liquid Precursors in a rf Thermal Plasma Reactor. Part 2: Analysis of CeO<Subscript>2</Subscript> Powders,Fuel Addition,and Image Analysis

A novel reactor design, sampling probe and wet collection system were used to investigate the combined effects of plasma operating parameters and particle collection mechanisms on the synthesis of CeO₂ particles from liquid precursors. The sampling of particles in-flight and the collection of particles at several reactor regions were used to provide experimental evidence of particle size at different reactor locations at various plasma operating conditions, i.e., power and plasma gas flow rates. This information provided a picture of how CeO₂ particles were formed and how these particles were collected in various locations. The effect of adding water-soluble fuels (alanine and glycine) to the original cerium nitrate solutions was also investigated. Fuel addition decreased the temperature of CeO₂ formation by acting as a local heat source as a result of fuel auto-ignition. Photographs of the particles in-flight were taken using a fast speed CCD camera.     

Effects of GC temperature and carrier gas flow rate on on‐line oxygen isotope measurement as studied by on‐column CO injection

Although deemed important to δ¹⁸O measurement by on‐line high‐temperature conversion techniques, how the GC conditions affect δ¹⁸O measurement is rarely examined adequately. We therefore directly injected different volumes of CO or CO–N₂ mix onto the GC column by a six‐port valve and examined the CO yield, CO peak shape, CO–N₂ separation, and δ¹⁸O value under different GC temperatures and carrier gas flow rates. The results show the CO peak area decreases when the carrier gas flow rate increases. The GC temperature has no effect on peak area. The peak width increases with the increase of CO injection volume but decreases with the increase of GC temperature and carrier gas flow rate. The peak intensity increases with the increase of GC temperature and CO injection volume but decreases with the increase of carrier gas flow rate. The peak separation time between N₂ and CO decreases with an increase of GC temperature and carrier gas flow rate. δ¹⁸O value decreases with the increase of CO injection volume (when half m/z 28 intensity is <3 V) and GC temperature but is insensitive to carrier gas flow rate. On average, the δ¹⁸O value of the injected CO is about 1‰ higher than that of identical reference CO. The δ¹⁸O distribution pattern of the injected CO is probably a combined result of ion source nonlinearity and preferential loss of C¹⁶O or oxygen isotopic exchange between zeolite and CO. For practical application, a lower carrier gas flow rate is therefore recommended as it has the combined advantages of higher CO yield, better N₂–CO separation, lower He consumption, and insignificant effect on δ¹⁸O value, while a higher‐than‐60 °C GC temperature and a larger‐than‐100 µl CO volume is also recommended. When no N₂ peak is expected, a higher GC temperature is recommended, and vice versa. Copyright © 2015 John Wiley & Sons, Ltd.     

Influence of velocity and surface temperature of alumina particles on the properties of plasma sprayed coatings

In this paper are described the main characteristics of the plasma spraying process of alumina deposits, i.e., the temperature and flow field of the plasma jets obtained with the classical spraying torches, the injection of the particles into the plasma jet, the particle surface temperature and velocities in the plasma (measured for calibrated alumina particles), and the coating generation. The measurements on the alumina particles are compared with the predictions of a mathematical model. The experimental and computed particle velocities are in rather good agreement. However, this is not the case for the particle surface temperature. Possible reasons for the discrepancy are proposed (influence of the carrier gas, thermophoretic forces, and poor penetration of the particles into the plasma core even for an injection velocity twice that of the optimal calculated one, as shown by recent measurements). Finally the correlations between the particle velocities and surface temperature, and the properties of the alumina coating (porosity, crystal structure, mechanical properties) are studied.     

Flow Rate and Velocity of Ideal Gas in a Capillary Column with Uniform Permeability

When the column pressure drop is high, the average velocity of a carrier gas is proportional to the square root of the outlet velocity and the flow rate. Characteristic velocity, flow rate and pressure – the boundary conditions between low and high pressure drop regions – are introduced. Previously derived equations for average velocity vs. outlet velocity were modified to include the flow rate and to become more suitable for the separate studies of the low and high pressure drop regions.     

A Critical Assessment of Particle Temperature Distributions During Plasma Spraying: Numerical Studies for YSZ

A three-dimensional computational model is used to simulate the in-flight particle melting behavior during plasma spraying process. The stochastic model is used for the particle size distribution. The particles surface temperature distributions at various spray distances have been presented. The results show that the surface temperature distribution varies with the spray distance. Single peak to double peaks and back to single peak has been observed in the simulations and also in the experiment. The effects of particle size and its distribution and plasma composition on the pattern shift have been investigated. Understanding the pattern shift may enable the design of a good control indicator to determine the particle melting status.     

Three-Dimensional Modeling of the Turbulent Plasma Jet Impinging upon a Flat Plate and with Transverse Particle and Carrier-Gas Injection

Modeling results are presented concerning the turbulent thermal plasma jet impinging normally on a substrate and with transverse injection of feedstock particles and their carrier gas from a single injection tube. The k- two-equation model is employed to model the turbulence, and particle dispersion is studied considering the interaction between the moving particles and turbulent eddies and considering the effect on particle trajectories of the random variation of the turbulent fluctuating velocities in their magnitude and direction. A well-validated three-dimensional (3-D) computer code is used in the modeling. The 3-D effects due to the carrier gas injection on the jet flow field and thus on the particle trajectories and heating histories are shown to be appreciable. The radial location of the injection tube with respect to the plasma jet is shown to be a critical parameter for the study of 3-D effects, besides the carrier-gas/plasma stream mass flux ratio. Particle dispersion considerably widens the distribution of the particle trajectories and heating histories. In addition, although pertinent swirl number is often rather small, swirling may also affect the modeling results.     

Enzyme reactors in unsegmented flow injection analysis

The design of immobilized-enzyme reactors for use in flow injection analysis is discussed. The reactors should be optimized for a short residence time and a very high (> 99.9%) conversion of substrate to products. Selection of carrier and immobilization method is important in order to increase the amount of active enzyme per unit volume. The effeciency of the reactor can be increased by decreasing the particle size in packed-bed reactors and the radius of open tubular reactors. The maximum inherent rate constant that can be obtained under optimal conditions is estimated for a number of enzymes of analytical interest; it is shown that with high rate constants and small particle diamters, residence times less than seconds can be obtained. Some applications of immobilized-enzyme reactors in flow systems are reviewed.     

Evaluation of split/splitless operation and rapid heating of a multi-bed sorption trap used for gas chromatography analysis of large-volume air samples

The effects of split-flow operation and rapid trap heating on injection-plug widths from an electrically heated, microscale, multibed sorption trap were evaluated. The sorption trap has been designed to quantitatively collect volatile organic compounds from large-volume vapor samples and inject them into a gas chromatograph. Previous trap designs resulted in injection-plug widths of typically a second or more, and this significantly degraded chromatographic resolution, particularly for early-eluting sample components and for high-speed separations. Injection-plug widths are determined by the heating rate of the trap during sample desorption and the volumetric flow rate of carrier gas through the trap. The effects of the heating rate of the trap and carrier gas velocity through the trap on the injection-plug widths of pentane, octane, and undecane were studied. Carrier gas velocity through the trap was increased by splitting the flow coming from the trap between the column and a vent. This decreases transport time from the trap to the column, and thus decreases injection-plug widths. The heating rate for the trap was increased by increasing the applied voltage in the range from 4 to 30 V. Increasing the heating rate decreases the time required to desorb the analytes from the sorbent bed, thus decreasing injection-plug width. Injection-plug widths as small as 89, 210, and 520 ms were obtained in the split mode with very fast heating rates for n-pentane, noctane, and n-undecane, respectively. The effect of split ratio on resolving power, peak height, and peak width was also evaluated.