Temperature-dependent ion chemistry in nanosecond discharge plasma-assisted CH4 oxidation

Ion chemistry with temperature evolution in weakly ionized plasma is important in plasma-assisted combustion and plasma-assisted catalysis, fuel reforming, and material synthesis due to its contribution to plasma generation and state transition. In this study, the kinetic roles of ionic reactions in nanosecond discharge (NSD) plasma-assisted temperature-dependent decomposition and oxidation of methane are investigated by integrated studies of experimental measurements and mathematical simulations. A detailed plasma chemistry mechanism governing the decomposition and oxidation processes in a He/CH4/O2 combustible mixture is proposed and studied by including a set of electron impact reactions, reactions involving excited species, and ionic reactions. A zero-dimensional model incorporating the plasma kinetics solver ZDPlasKin and the combustion chemical kinetics solver CHEMKIN is used to calculate the time evolution of the ion density. Uncertainty analysis of ionic reactions on key species generation is conducted by using different referenced data, and insignificant sensitivity is found. The numerical model is consistent with experimental data for methane consumption and generation of major species including CO, CO2, and H2. By modeling the temporal evolution of key ions, it is observed that O2+ presents the largest concentration in the discharge stage, followed by CH4+, CH3+, and CH2+, which is in accordance with the traditional ion chemistry in hydrocarbon flames and agrees well with molecular-beam mass spectrometer investigations. The path flux shows that the concentrations of key species, including electrons, O, OH, H, O(1D), O2(a1Δg), O2+, CH3+, and CH4+, change within 1–2 orders of magnitude and that the transition from a homogeneous state to a contracted/constricted state does not occur. The path flux and sensitivity analysis reveal the significant roles of cations in the stimulation of active radical generation, including CH, O, OH, and O(1D), thus accelerating methane oxidation. This work provides a deep insight into the ion chemistry of temperature-dependent plasma-assisted CH4 oxidation.

High-Voltage Nanosecond Discharge as a Means of Fast Energy Switching

The formation of a nanosecond discharge with the use of a Hamamatsu streak-camera and with simultaneously wideband (10 GHz) measurement of voltage and displacement current caused by a streamer in one pulse has been studied. Nanosecond voltage pulses of various amplitudes (16, 20, and 27 kV) were applied across a point-to-plane gap (8.5 mm) filled with air at various pressures (13, 25, 50, 100, and 200 kPa). It was found that the voltage across the gap drops as soon as a streamer appears in the vicinity of the pointed electrode. At the same time, a pre-breakdown current begins to flow. The magnitude of the pre-breakdown current, as well as the voltage drop, is determined by the rate of formation of dense plasma and, accordingly, by the rate of redistribution of the electric field in the gap. The streamer velocity determines the rise time and amplitude of the current. The higher the streamer velocity, the shorter the rise time and the higher the amplitude of the pre-breakdown current. The propagation of a backward and third ionization waves was observed both with the streak camera and by measuring the displacement current. As they propagate, the discharge current increases to its amplitude value.

Dynamics of macro- and micro-bubbles induced by nanosecond discharge in liquid water

Gaseous micro-bubbles dispersed in liquid water represent perturbations of the homogeneity of the liquid and influence the onset of electrical discharge in the bulk liquid. In this study, we systematically examined shadowgraph images to analyse the gaseous structures occurring in response to nanosecond micro-discharges produced in deionised water. The images revealed the dynamics of resolved bubbles and unresolved sub-micrometric structures starting from nanoseconds after the onset of discharge. We provide absolute counts and the radii distributions of micro-bubbles that occur near the anode needle and show how this depends on the amplitude and repetition frequency of the applied high-voltage pulses, when the latter varies between 0.1 and 100 Hz. A systematic statistical analysis showed that the probability of producing bubble-assisted nanosecond discharge in the liquid phase rapidly increases with the discharge repetition rate (>0.5 Hz). Although the cavitation bubble formed around the anode disintegrates and disappears from the anode region within the first millisecond, the sub-micrometric structures remain for tens of milliseconds, and fragmented micro-bubbles survive even for hundreds of milliseconds. Our findings impose strict limitations on the experimental setups used to investigate the mechanisms of direct discharge in liquid water.

The dynamics of the formation of initial stages of a transverse nanosecond discharge with an extended slot cathode in argon

The dynamics of the main characteristics of a limited nanosecond discharge in an extended slot cathode in argon at the values of the applied voltage to the electrodes close to the values of the voltages of the formation of a volume discharge are studied by numerical simulation. It is shown that this type of discharge can be used to create an extended dense plasma column with a high density of charged and excited particles. The analysis of the spatiotemporal dynamics of development of the electron density and the electron energy distribution function was carried out. It is shown that the high-energy electrons are formed at the front of the ionization wave due to the hollow-cathode effect.

Measurement of the duration of runaway current pulses using measuring equipment with bandwidths up to 50 GHz

The duration of current pulses of runaway electrons generated during the formation of a nanosecond discharge in air in a sharply inhomogeneous electric field was measured using measuring equipment with a bandwidth of 50 GHz. The influence of the gas pressure and the shape of a cathode on the duration of the RE current pulses is investigated. Current pulses with full width at half maximum of 16–28 ps were recorded, depending on the conditions.

Characteristics and Parameters of Overstressed Nanosecond Discharge Plasma in Air between an Electrode from Aluminum and Electrode from Chalcopyrite (CuInSe2)

The characteristics and parameters of an overstressed high-current discharge with a duration of 100–150 ns in air, which was ignited between an aluminum electrode and a chalcopyrite electrode (CuInSe2), are presented. The air pressure was 13.3 and 101.3 kPa. In the process of microexplosions of inhomogeneities on the working surfaces of electrodes in a strong electric field, aluminum vapors and chalcopyrite vapors were introduced into the interelectrode gap, which creates the prerequisites for the synthesis of thin films based on quaternary chalcopyrite – CuAlInSe2. The films synthesized from the products of electrode destruction were deposited on a quartz plate at a distance of 2–3 cm from the center of the discharge gap. The current and voltage pulses across the discharge gap of d = 1 mm, as well as the pulse energy input into the discharge, were investigated. The plasma emission spectra were studied, which made it possible to establish the main decay products of the chalcopyrite molecule and the energy states of atoms and singly charged ions of aluminum, copper and indium, which are formed in the discharge. The reference spectral lines of atoms and ions of aluminum, copper, and indium were established, which can be used to control the process of deposition of thin films of quaternary chalcopyrite. Thin films were synthesized from the degradation products of chalcopyrite molecules and aluminum vapors, which may have the composition of the quaternary chalcopyrite CuAlInSe2; the transmission spectra of the synthesized films in the spectral range of 200–800 nm were studied. By the method of numerical simulation of the plasma parameters of an overstressed nanosecond discharge based on aluminum and chalcopyrite vapors in air by solving the Boltzmann kinetic equation for the electron energy distribution function, the temperature and density of electrons, the specific power losses of the discharge for the main electronic processes and their rate constants depending on the value parameter E/N for plasma of vapor-gas mixtures based on air, aluminum vapor and ternary chalcopyrite were modulated.