Discharge characteristics and reactive species production of unipolar and bipolar nanosecond pulsed gas-liquid discharge generated in atmospheric

In this paper,unipolar pulse (including positive pulse and negative pulse) and bipolar pulse voltage are employed to generate diffuse gas-liquid discharge in atmospheric N2 with a trumpet-shaped quartz tube.The current-voltage waveforms,optical emission spectra of excited state active species,FTIR spectra of exhaust gas components,plasma gas temperature,and aqueous H2O2,NO2-,and NO3-production are compared in three pulse modes,meanwhile,the effects of pulse peak voltage and gas flow rate on the production of reactive species are studied.The results show that two obvious discharges occur in each voltage pulse in unipolar pulse driven discharge,differently,in bipolar pulse driven discharge,only one main discharge appears in a single voltage pulse time.The intensities of active species (OH(A),and O(3p)) in all three pulsed discharge increase with the rise of pulse peak voltage and have the highest value at 200 ml min-1 of gas flow rate.The absorbance intensities of NO2 and N2O increase with the increase of pulse peak voltage and decrease with the increase of gas flow rate.Under the same discharge conditions,the bipolar pulse driven discharge shows lower breakdown voltage,and higher intensities of excited species (N2(C),OH(A),and O(3p)),nitrogen oxides (NO2,NO,and N2O),and higher production of aqueous H2O2,NO2-,and NO3-compared with both unipolar positive and negative discharges.     

Spectroscopic study of bipolar nanosecond pulse gas-liquid discharge in atmospheric argon

Atmospheric gas-liquid discharge with argon as a working gas is presented by employed nanosecond pulse power. The discharge is presented in a glow-like mode. The discharge powers are determined to be less than 1 W, and remains almost constant when the discharge duration time increases. Bountiful active species are determined by capturing optical emission spectra,and their main generation processes are also discussed. The plasma gas temperature is calculated as 350 K by comparing the experimental spectra and the simulated ones of N_2(C~3Ⅱ_g→B~3Ⅱ_g, Δv =-2). The time resolved vibrational and rotational temperature is researched to present the stability of discharge when pulse voltage and discharge duration vary.The electron density is determined to be 10~(16) cm~(-3) according to the Stark broadening effect of the H_α line.     

Evaluation on a double-chamber gas-liquid phase discharge reactor for benzene degradation

A double-chamber gas-liquid phase DBD reactor (GLDR), consisting of a gas-phase discharge chamber and a gas-liquid discharge chamber in series, was designed to enhance the degradation of benzene and the emission of NOx. The performance of the GLDR on discharge characteristics, reactive species production and benzene degradation was compared to that of the single-chamber gas phase DBD reactor (GPDR). The effects of discharge gap, applied voltage, initial benzene concentration, gas flow rate and solution conductivity on the degradation and energy yield of benzene in the GLDR were investigated. The GLDR presents a higher discharge power, higher benzene degradation and higher energy yield than that of the GPDR. NO₂ emission was remarkably inhibited in the GLDR, possibly due to the dissolution of NO₂ in water. The benzene degradation efficiency increased with the applied voltage, but decreased with the initial concentration, gas flow rate, and gas discharge gap, while the solution conductivity presented less influence on benzene degradation. The benzene degradation efficiency and the energy yield reached 61.11% and 1.45 g kWh^–1 at 4 mm total gas discharge gap, 15 kV applied voltage, 200 ppm benzene concentration, 0.2 L min⁻¹ gas flow rate and 721 μS cm⁻¹ water conductivity. The intermediates and byproducts during benzene degradation were detected by FT-IR, GC-MS and LC-MS primarily, and phenols, CO_x, and other aromatic substitutes, O₃, NO_x, etc, were determined as the main intermediates. According to these detected byproducts, a possible benzene degradation mechanism was proposed.     

Activated persulfate by DBD plasma and activated carbon for the degradation of acid orange Ⅱ

In this study, the effect of activated peroxydisulfate(PDS) by dielectric barrier discharge(DBD) plasma and activated carbon(HGAC) on the removal of acid orange Ⅱ(AOⅡ) was investigated. The effects of applied voltage, PDS dosage, HGAC dosage, initial pH value, and inorganic anions on the removal rate of AOⅡ were discussed. The main free radicals degrading azo dyes during the experiment were also studied. Experimental results show that the removal rate of AOⅡ in DBD/HGAC/PDS synergistic system is much higher than that in the single system. With the applied voltage of 16 kV, HGAC dosage of 1 g l-1, PDS and AOⅡ molar ratio of 200:1, initial pH value of 5.4 and concentration of AOⅡ solution of 20 mg l-1, the removal rate of AOⅡ reached 97.6% in DBD/HGAC/PDS process after 28 min of reaction.Acidic and neutral conditions are beneficial for AOⅡ removal. Sulfate and hydroxyl radicals play an important role in the removal of AOⅡ. Inorganic anions are not conducive to the removal of AOⅡ.     

Dynamics of plasma bullets by nanosecond pulsed micro-hollow cathode discharge within air

In this paper, the air plasma jet produced by micro-hollow cathode discharge(MHCD) is investigated. The discharge is powered by a positive nanosecond pulse high voltage supply. The waveforms of the discharge, the images of the jet, the evolution of the plasma bullet and the reactive species are obtained to analyze the characteristics of the MHCD plasma jet. It is found that the length of the plasma jet is almost proportional to the air flow rate of 2–6 slm. Two plasma bullets appear one after another during a single period of the voltage waveform, and both of the two plasma bullets are formed during the positive pulse voltage off. The propagation velocity of the two plasma bullets is on the order of several hundred m/s, which is approximate to that of the air flow. These results indicate that the gas flow has an important influence on the formation of this MHCD plasma jet.     

Spectroscopic diagnosis of plasma in atmospheric pressure negative pulsed gasliquid discharge with nozzle-cylinder electrode

The plasma characteristics of a gas-liquid phase discharge reactor were investigated by optical and electrical methods.The nozzle-cylinder electrode in the discharge reactor was supplied witha negative nanosecond pulsed generator.The optical emission spectrum diagnosis revealed that OH(A~2∑~+?→?X~2Π,306–309 nm),N~3_2(CΠ→B~3Π_g,337 nm),O(3p~5p→3s~5s~0,777.2 nm)and O(3p~3p→3s~3s~0,844.6 nm)were produced in the discharge plasma channels.The electron temperature(T_e)was calculated from the emission relative intensity ratio between the atomic O 777.2 nm and 844.6 nm,and it increased with the applied voltage and the pulsed frequency and fell within the range of 0.5–0.8 e V.The gas temperature(T_g)that was measured by Lifbase was in a range from 400 K to 600 K.     

Research on quinoline degradation in drinking water by a large volume strong ionization dielectric barrier discharge reaction system

Quinoline is widely used in the production of drugs as a highly effective insecticide, and its derivatives can also be used to produce dyes. It has a teratogenic carcinogen to wildlife and humans once entering into the aquatic environment. In this study, the degradation mechanism of quinoline in drinking water by a strong ionization dielectric barrier discharge(DBD) lowtemperature plasma with large volume was explored. High concentration of hydroxyl radical(·OH)(0.74 mmol l-1) and ozone(O3)(58.2 mg l-1) produced by strongly ionized discharge DBD system were quantitatively analyzed based on the results of electron spin resonance and O3 measurements. The influencing reaction conditions of input voltages, initial p H value, ·OH inhibitors, initial concentration and inorganic ions on the removal efficiency of quinoline were systematically studied. The obtained results showed that the removal efficiency and TOC removal of quinoline achieved 94.8% and 32.2%, degradation kinetic constant was 0.050 min-1 at 3.8 k V and in a neutral p H(7.2). The proposed pathways of quinoline were suggested based on identified intermediates as hydroxy pyridine, fumaric acid, oxalic acid, and other small molecular acids by high-performance liquid chromatography/tandem mass spectrometry analysis. Moreover, the toxicity analysis on the intermediates demonstrated that its acute toxicity, bioaccumulation factor and mutagenicity were reduced. The overall findings provided theoretical and experimental basis for the application of a high capacity strong ionization DBD water treatment system in the removal of quinoline from drinking water.     

Numerical simulation of atmospheric pulse-modulated radio-frequency glow discharge ignition characteristics assisted by a pulsed discharge

A one-dimensional self-consistent fluid numerical model was developed to study the ignition characteristics of a pulse-modulated(PM) radio-frequency(RF) glow discharge in atmospheric helium assisted by a sub-microsecond voltage excited pulsed discharge. The temporal evolution of discharge current density and electron density during PM RF discharge burst was investigated to demonstrate the discharge ignition characteristics with or without the pulsed discharge. Under the assistance of pulsed discharge, the electron density in RF discharge burst reaches the magnitude of 1.87 × 10~(17) m~(-3) within 10 RF cycles, accompanied by the formation of sheath structure. It proposes that the pulsed discharge plays an important role in the ignition of PM RF discharge burst. Furthermore, the dynamics of PM RF glow discharge are demonstrated by the spatiotemporal evolution of the electron density with and without pulsed discharge. The spatial profiles of electron density, electron energy and electric field at specific time instants are given to explain the assistive role of the pulsed discharge on PM RF discharge ignition.     

Spatio-temporal evolution characteristics and pattern formation of a gas–liquid interfacial AC current argon discharge plasma with a deionized water electrode

A discharge ignited by an AC power source in contact with deionized water as one of the electrodes is investigated. Immediately after initiation, the discharge exhibits a unique phenomenon: the gasphase discharge is extended into the liquid. Later, a cone-like structure is observed at the liquid surface. Synchronous monitoring of current–voltage characteristics and liquid properties versus time suggests that the discharge shapes are functions of the liquid properties. The spatio-temporal profiles indicate the potential effects of water, ambient air impurities, and metastable argon on the discharge chemistry. This becomes more obvious near the liquid surface due to increasing production of various transient reactive species such as ·OH and NO·. Moreover, it is revealed that thermalization of the rotational population distributions of the rotational states(N' ≤ 6,J'≤13/2) in the Q_1 branch of the OH(A~2∑~+,v'S=0→X~2∏_(3/2),v'=0 ) band ro-vibrational system is influenced by the humid environment near the liquid surface. In addition, the transient behaviors of instantaneous concentrations of long-lived reactive species(LRS) such as H_2O_2,NO_2~-, and-NO_3~- are observed with lengthening the discharge time. The production of multiple transient and LRS proposes AC excited gas–liquid argon discharge as a potential applicant in industrial wastewater cleaning, clinical medicine, and agriculture.     

Characteristics of gas-liquid diaphragm discharge and its application on decolorization of brilliant red B in aqueous solution

A simple gas-liquid diaphragm discharge reactor was designed and characteristics of the discharge and its application on decolorization of brilliant red B in an aqueous solution were investigated. The results showed that strong oxidizing agents such as ·OH and ·O radicals were generated. Average electron temperature of the discharge was 0.72 eV, 1.15 eV and 0.83 eV with air, oxygen and argon as the discharge gas, respectively. Solution p H and conductivity changed little when oxygen or argon was used as the discharge gas; however, these two parameters changed significantly when the discharge was performed in air. During the discharge treatment,the characteristic absorption peaks of brilliant red B gradually decreased where the decolorization followed the first-order kinetics. With 10 min of discharge, the decolorization of brilliant red B(30 mg L~(-1)) can reach 96%, 81% and 62% in the cases of oxygen, argon and air,respectively. The analysis of by-products showed that the brilliant red B molecule can be effectively destroyed in this discharge mode.     

Electrical and aerodynamic characteristics of sliding discharge based on a microsecond pulsed plasma supply

Plasma flow control technology has broad prospects for application. Compared with conventional dielectric barrier discharge plasma actuators (DBD-PA), the sliding discharge plasma actuator (SD-PA) has the advantages of a large discharge area and a deflectable induced jet. To achieve the basic performance requirements of light weight, low cost, and high reliability required for UAV (Unmanned Aerial Vehicle) plasma flight experiments, this work designed a microsecond pulse plasma supply that can be used for sliding discharge plasma actuators. In this study, the topology of the primary circuit of the microsecond pulse supply is determined, the waveform of the output terminal of the microsecond pulse plasma supply is detected using the Simulink simulation platform, and the design of the actuation voltage, the pulse frequency modulation function and the construction of the hardware circuit are achieved. Using electrical diagnosis and flow field analysis, the actuation characteristics and flow characteristics of sliding discharge plasma under microsecond pulse actuation are studied, the optimal electrical actuation parameters and flow field characteristics are described.     

Kinetic simulation of the transition from a pulse-modulation microwave discharge to a continuous plasma

The generation of a very strong peak current in the first period(PCFP) in a pulse-modulated microwave discharge has been discussed in previous studies. In this paper we focus on the transition process from a pulsed discharge to a fully continuous one driven by the pulsed microwave power source by means of a kinetic model. The computational results show that by increasing the duty cycle or voltage modulation rate(VMR), the discharge eventually becomes fully continuous and PCFP can no longer be observed. In the transition process, the distributions of the electric field, electron energy probability function(EEPF) and plasma density are discussed according to the simulation data, showing different discharge structures. The simulations indicate that many high-energy electrons with electron energy larger than 20 eV and low-energy electrons with electron energy less than 3 eV could be generated in a pulsed microwave discharge, together with a reversal electric field formed in the anode sheath when PCFP occurs. However, only medium-energy electrons could be observed in a fully continuous discharge. Therefore, by investigating the transition process the pulse-modulated microwave discharges can be further optimized for plasma applications at atmospheric pressure.     

Kinetic analysis of soil contained pyrene oxidation by a pulsed discharge plasma process

A pulsed discharge plasma (PDP) reactor with net anode and net cathode was established for investigating the pyrene degradation in soil under different pulse peak voltage, air flow rate, pyrene content in soil, initial pH value and initial water content of the soil. Pyrene oxidation within the 60 min discharge time was fitting according to the pseudo-first order equation and the corresponding reaction kinetics constants (k values) were calculated. The obtained results show that pyrene oxidation under all the different reaction conditions obeyed the pseudo-first order equation well. Higher pulsed peak voltage and appropriate air flow rate were in favor of the increase of reaction rate of pyrene oxidation. A higher k value could be achieved in the lower initial pyrene content (the value was 100 mg kg⁻¹). The k value of pyrene oxidation in the case of pH=4 was 11.2 times higher than the value obtained under the condition of pH=9, while the initial water content of the soil also has a large effect on the oxidation rate of pyrene due to the effect of PDP.     

Exploration of a MgO cathode for improving the intensity of pulsed discharge plasma at atmosphere

With regard to the lower density and energy of electrons in pulsed discharge plasma (PDP) at atmosphere, leading to the lower energy utilization of plasma, we propose a MgO cathode to enhance the plasma intensity according to field emission principle. The MgO cathode is prepared by an electro-depositing MgO film on a stainless steel plate. This way, the positive charges come to the cathode and accumulate on the surface of the MgO film, leading to the enhancement of the electric field intensity between the cathode and MgO film, and result in the strong emission of secondary electrons from the MgO cathode. As a result, the intensity of plasma can be enhanced. Herein, the effect of the MgO cathode on the intensity of PDP is investigated. It was shown that the discharge peak current was improved by 20% compared with that of without the MgO cathode. With increasing the MgO film thickness, discharge intensity, including the peak current, transforming charge and spectrum intensity first increased and then decreased. Higher enhancement of peak current, transforming charge and spectrum intensity were acquired with a higher peak voltage. Compared to a cathode without MgO film, the ozone production is higher with MgO cathode employed. The research proposes a novel approach for improving the intensity of discharge plasma, and also provides a reference for further application of PDP.     

A comparative study on the activity of TiO2 in pulsed plasma under different discharge conditions

In the present study,a combination of pulsed discharge plasma and TiO_2(plasma/TiO_2)has been developed in order to study the activity of TiO_2by varying the discharge conditions of pulsed voltage,discharge mode,air flow rate and solution conductivity.Phenol was used as the chemical probe to characterize the activity of TiO_2in a pulsed discharge system.The experimental results showed that the phenol removal efficiency could be improved by about 10%by increasing the applied voltage.The phenol removal efficiency for three discharge modes in the plasma-discharge-alone system was found to be highest in the spark mode,followed by the spark–streamer mode and finally the streamer mode.In the plasma/TiO_2system,the highest catalytic effect of TiO_2was observed in the spark–streamer discharge mode,which may be attributed to the favorable chemical and physical effects from the spark–streamer discharge mode,such as ultraviolet light,O_3,H_2O_2,pyrolysis,shockwaves and high-energy electrons.Meanwhile,the optimal flow rate and conductivity were 0.05 m~3l~(-1)and 10μS cm~(-1),respectively.The main phenolic intermediates were hydroquinone,catechol,and p-benzoquinone during the discharge treatment process.A different phenol degradation pathway was observed in the plasma/TiO_2system as compared to plasma alone.Analysis of the reaction intermediates demonstrated that p-benzoquinone reduction was selectively catalyzed on the TiO_2surface.The effective decomposition of phenol constant(D_e)increased from 74.11%to 79.16%when TiO_2was added,indicating that higher phenol mineralization was achieved in the plasma/TiO_2system.     

Effects of O2 addition on the plasma uniformity and reactivity of Ar DBD excited by ns pulsed and AC power supplies

Dielectric barrier discharges (DBDs) have been widely used in ozone synthesis, materials surface treatment, and plasma medicine for their advantages of uniform discharge and high plasma-chemical reactivity. To improve the reactivity of DBDs, in this work, the O₂ is added into Ar nanosecond (ns) pulsed and AC DBDs. The uniformity and discharge characteristics of Ar ns pulsed and AC DBDs with different O₂ contents are investigated with optical and electrical diagnosis methods. The DBD uniformity is quantitatively analyzed by gray value standard deviation method. The electrical parameters are extracted from voltage and current waveforms separation to characterize the discharge processes and calculate electron density n_e. The optical emission spectroscopy is measured to show the plasma reactivity and calculate the trend of electron temperature T_e with the ratio of two emission lines. It is found that the ns pulsed DBD has a much better uniformity than AC DBD for the fast rising and falling time. With the addition of O₂, the uniformity of ns pulsed DBD gets worse for the space electric field distortion by O₂⁻, which promotes the filamentary formation. While, in AC DBD, the added O₂ can reduce the intensity of filaments, which enhances the discharge uniformity. The ns pulsed DBD has a much higher instantaneous power and energy efficiency than AC DBD. The ratio of Ar emission intensities indicates that the T_e drops quickly with the addition of O₂ both ns pulsed and AC DBDs and the ns pulsed DBD has an obvious higher T_e and n_e than AC DBD. The results are helpful for the realization of the reactive and uniform low temperature plasma sources.     

Study of the influence of discharge loop parameters on anode side on generation characteristics of metal plasma jet in a pulsed vacuum discharge

In a pulsed vacuum discharge, the ejection performance of a metal plasma jet can be effectively improved by preventing charged particles from moving to the anode. In this paper, the effects of resistance and capacitance on the anode side on the discharge characteristics and the generation characteristics of plasma jet are investigated. Results show that the existence of a resistor on the anode side can increase the anode potential, thereby preventing charged particles from entering the anode and promoting the ejection of charged particles along the axis of the insulating sleeve nozzle. The application of a capacitor on the anode side can not only absorb electrons at the initial stage of discharge, increasing the peak value of the cathode hump potential, but also prevent charged particles from moving to the anode, thereby improving the ejection performance of the plasma jet. In addition, the use of a larger resistance and a smaller capacitance can improve the blocking effect on charged particles and further improve the ejection performance of the plasma jet. Results of this study will provide a reference for the improvement of the ejection performance of plasma jets and their applications.     

PIC simulation of plasma properties in the discharge channel of a pulsed plasma thruster with flared electrodes

Plasma in the discharge channel of a pulsed plasma thruster (PPT) with flared electrodes is simulated by a self-developed two-dimensional code. The fully particle-in-cell method with Monte Carlo collision is employed to model the particle movement and collisions and investigate the plasma properties and acceleration process. Temporal and spatial variations of the electron density distribution and the ion velocity between electrodes are calculated and analyzed in detail. The computational results of the electron number density, which is in the order of 10²³ m⁻³, show good agreements with experimental results of a PPT named ADD SIMP-LEX. The ion velocity distributions along the center line of the channel lead to a comprehensive understanding of ions accelerated by electromagnetic field. The electron distributions of PPT with discharge voltages varying from 1300 to 2000 V are compared. The diffusion of electrons presents strong dependency on discharge voltage and implies higher degree of ionization for higher voltage.     

Degradation of tetracycline in water by gas-liquid plasma in conjunction with rGO-TiO2 nanocomposite

Tetracycline(TC)is an antibiotic mainly used in livestock production and respiratory infection.Traditional methods are not effective in removing TC from solution.In this study,TC was degraded by gas-liquid plasma in the presence of rGO-TiO2 in solution.The rGO-TiO2 was prepared by modified hummers and hydrothermal method.The electrical and optical properties of the gas-liquid discharge plasma were studied and the produced long-lived reactive species were analyzed by spectrophotometer.The degradation efficiency of TC was improved by 41.4％after plasma treatment for 12 min in presence of 30 mg l-1 rGO-TiO2 compared to that with plasma alone.The degradation efficiency increased with increasing discharge power,but as the initial concentration was increased from 20 to 80 mg l-1,the degradation efficiency of TC decreased.The initial pH had no significant effect on the degradation of TC.The intermediate products were determined by UV-vis spectrophotometry and ESI(+)-MS,and the degradation mechanism was analyzed.The reactive species,including O3,OH,and H2O2,etc.,produced in the plasma/catalyst system attracted electron-rich functional groups(amino group,aromatic ring,and double bond).Therefore,the gas-liquid plasma/catalyst system could be an effective and promising method for pharmaceutical wastewater treatment in future.     

Investigation on discharge characteristics of a coaxial dielectric barrier discharge reactor driven by AC and ns power sources

A coaxial dielectric barrier discharge(DBD) reactor with double layer dielectric barriers has been developed for exhaust gas treatment and excited either by AC power or nanosecond(ns)pulse to generate atmospheric pressure plasma. The comparative study on the discharge characteristics of the discharge uniformity, power deposition, energy efficiency, and operation temperature between AC and ns pulsed coaxial DBD is carried out in terms of optical and electrical characteristics and operation temperature for optimizing the coaxial DBD reactor performance. The voltages across the air gap and dielectric layer and the conduction and displacement currents are extracted from the applied voltages and measured currents of AC and ns pulsed coaxial DBDs for the calculation of the power depositions and energy efficiencies through an equivalent electrical model. The discharge uniformity and operating temperature of the coaxial DBD reactor are monitored and analyzed by optical images and infrared camera. A heat conduction model is used to calculate the temperature of the internal quartz tube. It is found that the ns pulsed coaxial DBD has a much higher instantaneous power deposition in plasma, a lower total power consumption, and a higher energy efficiency compared with that excited by AC power and is more homogeneous and stable. The temperature of the outside wall of the AC and ns pulse excited coaxial DBD reaches 158 ℃ and 64.3 ℃ after 900 s operation, respectively.The experimental results on the comparison of the discharge characteristics of coaxial DBDs excited by different powers are significant for understanding of the mechanism of DBDs,reducing energy loss, and optimizing the performance of coaxial DBD in industrial applications.