Characteristics of transferred-arc plasmas at high TiCl4 concentrations

The possibility of reducing low-boiling metal halides to the metal in thermal plasmas is attracting increasing attention. However, instability of the arcs in the presence of even low halide concentrations has so far thwarted all research efforts. An experimental study of the effects of adding TiCl₄ to an argon transferred arc has shown that instabilities and eventual extinction of the arc are due to severe chemical corrosion of the thoriated tungsten cathode in the presence of chloride. The corrosion results in both the loss of cathode material and the deposition of a blanket of titanium metal on the cathode's surface which supresses electron emission. A systematic search has shown that tantalum carbide cathodes will provide stable operation. Additions of TiCI₄ cause a sharp increase in total arc voltage, largely due to an increased cathode /all potential.     

Cathode erosion phenomena in a transferred-arc plasma reactor

Phenomena occurring on file surface of a thoriated tungsten cathode operating in a transferred-arc reactor were investigated. The effects of cathode geometry (pointed-tip vs. flat-tip) and plasma gas composition (argon vs. helium) on the rate and mechanisms of cathode erosion were studied experimentally by examining the morphology of the surface before and after runs of prespecified duration, up to one hour in length. For flat-tip cathodes in argon, the major characteristic was the migration of thoria and its concentration at segregated sites. Both geometries in helium operated at much higher temperatures, around the boiling point of tungsten, giving rise to extensive vaporization of cathode material, followed by apparent redeposition of the ionized species carried by file ionic current, in characteristic ringlike sites on the surface. Erosion rates were low and similar in magnitude, except for pointed-tip cathodes operated in argon, where the formation of a large molten sphere of tungsten and its subsequent release gave rise to a higher rate of erosion.     

Effect of Anode Arc Root Position on the Behavior of the DC Non-transferred Plasma Jet at Field Free Region

A special bi-anode plasma torch that can change the anode arc root position without changing working gas flow rate has been developed to investigate the effect of anode arc root position on the behavior of the plasma jet. It has two nozzle-shaped anodes at different axial distances from the cathode tip. The arc root can be formed at anodes either close to the cathode tip (anode I) or far away from it (anode II) to obtain different attachment positions and arc voltages. The characteristics of pure argon plasma jets operated in different anode modes were measured in the field free region by using an emalpy probe, and the thermal efficiency of the torch was determined by measuring the temperature differences between cooling water flowing in and out of the torch. The results show that compared with the normal arc operated in anode I mode, the elongated arc operated in anode II mode significantly reduced the plasma energy loss inside the torch, resulting in a higher temperature and a higher velocity of the plasma jet in the field free region.     

Negative surface ionisation of hyperthermal halogen atoms

Negative surface ionisation of hyperthermal halogen atoms was studied as a function of their kinetic energy on thoriated tungsten and on niobium wires. The transition from a thermal equilibrium process to direct reflection causes the ionisation to increase drastically above thermal energies: efficiencies up to 40% were found for 30 eV Cl atoms impinging on thoriated tungsten.     

Methane polymerization with a hollow cathode: Influence of the cathode metal

Methane, mixed with argon, has been polymerized by means of a hollow-cathode discharge system. Two types of cathodes were studied; one was made of a solid solution of 81% tungsten and 19% platinum, while the other was of pure tungsten. Under identical operating conditions, a higher polymer yield was found in the case of the platinum cathode (90% against 70% for tungsten). The work function of the solid solution was estimated to be 6.3 eV, compared with 4.4 eV for tungsten. In terms of the data available, the thermionic current, which is the main source of energetic electrons, is about one order of magnitude lower for the solid solution cathode when compared with the tungsten cathode thermionic current. However, the polymer yield observed is higher in the former case. The concentration of the CH species in the hollow cathode was found to differ greatly for the cathodes tested and was about 5 times higher in the case of tungsten-platinum cathodes. Since no excited platinum vapor could be detected in the gas phase, the increase in CH concentration was attributed to a catalytic effect of the cathode inside surface. An evaluation of the plasma polymer deposition rate yields 70 nm·s^–1 for the platinum-tungsten type hollow cathode and 42 nm·s^–1 for the tungsten one. In both cases, the deposition rate is much higher than those obtained from the most widely used methods for plasma polymer deposition (0.10–1.0 nm·s^–1) implying methane-argon mixtures, and is comparable to the results obtained with a new type of plasma polymer deposition reactor described in the literature.     

Numerical Study of a Free-Burning Argon Arc with Copper Contamination from the Anode

The present modeling of a free-burning argon arc accounts for copper vapor contamination from the anode. Simulations are made for an atmospheric arc that has a length of 10 mm and an electric current of 200 amps. Predicted results for two different anode evaporation rates are compared to those from a pure argon arc with no copper vapor contamination. Copper vapor concentration, temperature, electric potential, and current density profiles are presented. Included in this analysis are radiation losses from both the argon and copper by using recently calculated net emission coefficients. It was found that evaporation of copper from the anode results in a cooling of the arc in a region close to the anode, but has an insignificant influence on the arc close to the cathode. Due to the arc flow characteristics most of the copper vapor tends to be confined to the anode region.     

Study of a d.c. arc in an alternating magnetic field

The distributions of the electron pressure, the temperature, the degree of ionization and the concentration of several elements in the cathode and the anode regions of a d.c. arc to which an external magnetic field is applied are studied. The magnetic field causes oscillations of the arc column which lead to an expansion of the optically integrated image of the discharge on the plane of oscillations. It is shown that the electron pressure and the temperature remain constant over a broad region of the discharge. In the cathode region an intensification of the spectral line-intensities is observed, which is discussed in the paper.     

Characterization of a twin-torch transferred dc arc

The results of a twin-torch transferred de arc .study are presented. The arc system consists of two torches of opposite polarity, and a coupling zone of plasma jets located between them. The torch configuration increases the system reliability and efficiency during material plasma processing. The results of the study present data for the voltage-current characteristics, general behavior of the twin-torch arc, and spatial distribution of the plasma parameters. The plasma parameters have been measured using optical emission spectroscopy for a 200 A (20 k W) do arc, at atmospheric pressure, with argon and nitrogen introduced as plasma forming gases into the anode and the cathode units, respectively. The measurement technique used has allowed the determination of local electron density and temperature values in an inhomogeneous plasma volume having no axial sysmmetry. The data obtained illustrate the novel features of the twin-torch transfrred do arc for its applications in plasma processing.     

Äquidensitometrie-eine Methode zur Beurteilung von Plasmen—XI: Untersuchung des Einflusses von NaCl und Ba(NO3)2 auf die Intensität von Linien und die Verteilung von Teilchen im Gleichstrombogenplasma der Silberstein-Methode

The influence of NaCl and Ba(NO₃)₂ on the intensities of atomic lines of Al, Sn and Be and on the axial particle distribution of these elements in the d.c. arc plasma was investigated. As the analytical method we used the procedure of Silberstein in which micro-amounts of solutions were added to the cathode and also to the anode. The time of evaporation, the temperature, the electron pressure, and the intensities of lines were investigated. We used the combination of spectral photography and photographic equidensitometry to derive particle distribution. The results of these investigations were: (1) NaCl and Ba(NO₃)₂ reduced the temperature of the plasma. The electron pressure was constant both in the presence of fairly large amounts of NaCl or Ba(NO₃)₂ and in the hotter arc without additive. (2) The enhancement of the intensities was best in presence of rather large amounts of Ba(NO₃)₂. (3) The maximum of the particle concentration was shifted, by additives from the cathode, towards the middle of the arc. We found a correlation between intensity and this shifting. In the arc with Ba(NO₃)₂ the most homogeneous plasma was obtained.     

纳米碳纤维-硫正极电化学性能

应用恒流充放电、循环伏安、交流阻抗等测试方法,研究了不同比例的纳米碳纤维(NCF)对硫正极电化学性能的影响.结果表明,NCF-硫正极的倍率放电性能和循环伏安性能都有了一定的提高,添加量为3%和5%时效果较好.3%NCF-硫正极电流密度0.4 mA.cm-2时,比容量达880 mAh.g-1,20次循环后,比容量仍保持630 mAh.g-1.     

Operating characteristics and energy distribution in transferred plasma arc systems

A specially designed plasma chamber was constructed to study the operating characteristics of a dc plasma-transferred arc of argon, struck between a fluid convective cathode and a water-cooled anode. The arc voltage increased markedly with arc length and with an increase in the inlet velocity of the argon flow past the cathode tip, and much less with an increase in current. Radiation from the plasma column to the chamber walls and transfer of energy to the anode were the two principal modes of transfer of the arc energy. The former was dominant in the case of long arcs and at high inlet argon velocities. At the anode, the major contribution was from electron transfer, which occurred on a very small area of the anode (～5 mm in diameter). Convective heat transfer from the plasma was somewhat less. In all cases, the arc energy contributions to cathode cooling and to the exit gas enthalpy were small. From total heat flux and radiative heat transfer measurements, it was estimated that the plasma temperature just above the anode was in the range 10,000–12,000 K. Preliminary experiments with an anode consisting of molten copper showed that the arc root was no longer fixed but moved around continuously. The arc was othwewise quite stable, and its operating characteristics differed little from those reported for solid anodes, in spite of the greater extent of metal vaporization.     

Numerical Study of a Free-Burning Argon Arc with Anode Melting

Numerical modeling of free burning arcs and their electrodes is useful for clarifying the heat transfer phenomena in the welding process and to elucidate those effects which determine the weld penetration. This paper presents predictions for a stationary welding process by the free-burning argon arc. The whole region of the welding process, namely, tungsten cathode, arc plasma and stainless steel anode is treated in a unified numerical model to take into account the close interaction between the arc plasma and the molten anode. The time dependent development of two-dimensional distributions of temperature and velocity, in the whole region of the welding process, are predicted at a current of 150 A. The weld penetration geometry as a function of time is thus predicted. It is shown also that different surface tension properties can change the direction of re-circulatory flow in the molten anode and dramatically vary the weld penetration geometry.     

Parameters controlling the generation and properties of plasma sprayed zirconia coatings

D.C. plasma jets temperature and velocity distributions as well as the arc root fluctuations at the anode were studied for Ar-H₂ (25 vol%) plasma forming gases. The parameters were the arc current up to 700 A, the total gas flow rate up to 100 slm, and the nozzle diameter which was varied from 6 to 10 mm. The trajectories of partially stabilized zirconia particles into the jet were studied by a 2D laser imaging technique and two fast (100 ns) two color pyrometers. The results have revealed the difficulty to inject small particles into the plasma flow since most were found to by-pass the jet rather than penetrate it. The results also show the broad trajectory distribution within the jet and the influence of the arc root fluctuations on the mean particle trajectory distribution within the jet. Beside the measurements of the particle surface temperature and velocity distributions in flight, the particle flattening and the cooling of the resulting splats were studied statistically for single particles all over the spray cone. Such studies have emphasized the drastic influence of the substrates or previously deposited layers temperature on the contact between them and the splats. At 200–300°C this contact is excellent (cooling rates of the order of 100 K/μs for 1 μm thick splats) and it results in a columnar growth within the splats and the layered splats of a bead (up to 500 layered splats). This growth can be observed through passes provided the bead surface temperature has not cooled too much (a few tens of K) before the next bead covers it. A/C values up to 60 MPa were achieved with PSZ coatings. The effect of impact velocity of the particles, of substrate preheating temperature, of relative movments torch to substrate, of substrate oxidation on A/C values and splat formation were also studied.     

Cathode infiltration with enhanced catalytic activity and durability for intermediate-temperature solid oxide fuel cells

To lower the operation temperature and increase the durability of solid oxide fuel cells(SOFCs), increasing attentions have been paid on developing cathode materials with good oxygen reduction reaction(ORR)activity at intermediate-temperature(IT, 500–750 °C) range. However, most cathode materials exhibit poor catalytic activity, or they thermally mismatch with SOFC electrolytes and undergo severe degeneration. Infiltrating catalysts on existing backbone materials has been proved to be an efficie...     

A novel approach for introducing particulate matter into thermal plasmas: The triple-cathode arc

A coalesced high-intensity dc discharge is maintained between three cathodes and a single anode, stabilized by using resistors on each cathode leg. Jets of plasma gas are produced from either the cathode area or the anode area of the device. Cathode jets are generated by the self-induced pumping at the cathode tips and augmented by central gas injection. Arc voltage-current characteristics show classical convection-stabilized arc behavior. Anode heat transfer rates may be substantially increased by central gas injection toward the anode. Temperature fields in the coalesced, axially symmetric portion of the arc are determined spectrometrically and compared to those of a classical single-cathode free-burning arc.     

Gas and liquid phases interaction at the FeO·Cr2O3 cathode of a direct-current arc discharge

The study of an arc discharge in argon has been made with the cathode of the discharge system in the form of molten chromite, FeO·Cr₂O₃. The partial pressure distributions of the elements Fe and Cr, as well as the temperature distributions, have been determined in the arc by spectroscopic methods. The data obtained were used, in conjunction with a mathematical model, for the determination of the oxygen species distribution in the same medium. The cathode bath surface was measured by means of the two-wavelength method. From a consideration of free energy of reaction values, it is concluded that the presence of elemental Fe and Cr in the cathode bath is mainly related to the migration of Fe⁺ and Cr⁺, present in the arc, toward the liquid cathode. The formation of these elements in the molten cathode is very unlikely.     

Oxygen reduction kinetics on graphite cathodes in sediment microbial fuel cells

Sediment microbial fuel cells (SMFCs) have been used as renewable power sources for sensors in fresh and ocean waters. Organic compounds at the anode drive anodic reactions, while oxygen drives cathodic reactions. An understanding of oxygen reduction kinetics and the factors that determine graphite cathode performance is needed to predict cathodic current and potential losses, and eventually to estimate the power production of SMFCs. Our goals were to (1) experimentally quantify the dependence of oxygen reduction kinetics on temperature, electrode potential, and dissolved oxygen concentration for the graphite cathodes of SMFCs and (2) develop a mechanistic model. To accomplish this, we monitored current on polarized cathodes in river and ocean SMFCs. We found that (1) after oxygen reduction is initiated, the current density is linearly dependent on polarization potential for both SMFC types; (2) current density magnitude increases linearly with temperature in river SMFCs but remains constant with temperature in ocean SMFCs; (3) the standard heterogeneous rate constant controls the current density temperature dependence; (4) river and ocean SMFC graphite cathodes have large potential losses, estimated by the model to be 470 mV and 614 mV, respectively; and (5) the electrochemical potential available at the cathode is the primary factor controlling reduction kinetic rates. The mechanistic model based on thermodynamic and electrochemical principles successfully fit and predicted the data. The data, experimental system, and model can be used in future studies to guide SMFC design and deployment, assess SMFC current production, test cathode material performance, and predict cathode contamination.     

Impact of anode evaporation on the anode region of a high-intensity argon arc

Experimental studies of a free-burning, high-intensity argon arc operated at 800 Torr with a solid, molten, or resolidified copper anode demonstrate that the cathode region is not affected by Cu vapor from the anode. Also Cu vapor concentrations in the arc core (beyond 1 mm from the anode surface) are negligible. In contrast, there is a strong effect of the Cu vapor on the anode region of the arc. The arc fringes become electrically conducting due to the presence of Cu vapor, resulting in a flattening of the current density distribution and a corresponding drop of the temperature in the arc core. At the same time, the overall arc voltage shows a slight drop (<1 V). In the case of the resolidified anode, the overall arc voltage increases, which seems to be associated with the distribution of the stagnation flow in front of the anode due to a dip in the center of the anode.     

Electrochemical properties of cathodes made of (La,Sr)(Fe,Co)O3 containing admixtures of nanoparticles of cupric oxide and intended for fuel cells with a solid electrolyte based on ceric oxide

The electric and electrochemical characteristics of cathodes made of La_0.6Sr_0.4Fe_0.8Co_0.2O_3?δ (LSFC) and intended for fuel cells with electrolytes based on ceric oxide are studied. Adding cupric oxide into the LSFC cathode is shown to exert a favorable effect of the properties of the LSFC-CuO/SDC electrode system, where SDC stands for the CeO₂-Sm₂O₃ electrolyte. The effect produced by cupric oxide when added in the form of nanopowder is perceptibly greater than in the case of micropowdered CuO. Adding a mere 0.5 wt % of nanopowdered CuO reduces the LSFC cathode resistance nearly tenfold. The cathode’s adhesion to the electrolyte substantially improves as well, which makes it possible to lower the cathode’s firing temperature by 100°C. The maximum of electrochemical activity is intrinsic to cathodes containing 2 wt % CuO, with the caking temperature of 1000°C. According to a 2011-h life test of the LSFC-SDC composite cathodes containing nanopowdered CuO, temporal stability of their electrochemical characteristics improves with the SDC content. The time dependences of the polarization resistance of cathodes containing 40–50 wt % SDC look like decaying exponential curves. The steady-state polarization resistance, calculated on the basis of this, is equal to 0.1–0.2 ohm cm². At an overvoltage of less than 100 mV, the cathodes may provide for a current density of 0.5–1.0 A cm^?2.     

High-performance Fe–Co-based SOFC cathodes

With the aim of reducing the temperature of the solid oxide fuel cell (SOFC), a new high-performance perovskite cathode has been developed. An area-specific resistance (ASR) as low as 0.12 Ωcm² at 600 °C was measured by electrochemical impedance spectroscopy (EIS) on symmetrical cells. The cathode is a composite between (Gd_0.6Sr_0.4)_0.99Fe_0.8Co_0.2O_3-δ (GSFC) and Ce_0.9Gd_0.1O_1.95 (CGO10). Examination of the microstructure of the cathodes by scanning electron microscopy (SEM) revealed a possibility of further optimisation of the microstructure in order to increase the performance of the cathodes. It also seems that an adjustment of the sintering temperature will make a lowering of the ASR value possible. The cathodes were compatible with ceria-based electrolytes but reacted to some extent with zirconia-based electrolytes depending on the sintering temperature.