On phenomena in ionized gases
Decomposition of Acetic Acid Solution by Dielectric Barrier Discharge
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- 3. References
- Effects of the Driving Frequency on Generation of O 3 , NOx in DBD plasma
- 3. Results and Conclusions
- Continual radiation of H 2 and D 2 (a 3 Σ g
- 4. References
- Radiation trapping in non-equilibrium plasmas: matrix methods and its application to arcs and glow discharges
Decomposition of Acetic Acid Solution by Dielectric Barrier Discharge
K. Teranishi 1 P , U K. Murata UP 1
, M. Yonezawa P 1 P , N. Shimomura P 1
P 1 P
P
This study deals with the decomposition of an acetic acid solution by a water treatment reactor based on a dielectric barrier discharge (DBD) with a parallel plate electrode configuration. The treat water is supplied onto an electrode surface as a water film and exposed to the DBD. The total organic carbon of the solution is estimated to evaluate the decomposition of acetic acid by the DBD.
Water treatment by discharge plasma is promising technology to
decompose persistent organic pollutants by chemically active species produced in the plasma. Although a great deal of the water treatment reactor using discharge plasma has been actively developed with various configurations [1], [2], the authors have developed the water treatment reactor based on a dielectric barrier discharge (DBD) produced on a treat water surface [3]. In this work, an acetic acid solution, commonly used as an indicator of persistent organic pollutants, is treated by our reactor and the total organic carbon (TOC) concentration of the solution is measured. 2. Experimental setup The water treatment reactor used in this study was previously presented in [3], of which the several parts were modified. The reactor has a parallel plate electrode configuration, consisting of a dielectric barrier, a ring-shaped metallic back electrode and a lower metal electrode. The dielectric barrier is a borosilicate glass plate with 75 mm in diameter and 1.1 mm in thickness. It has a hole at its centre for supplying the treat water. The ring-shaped metal electrode applying a high voltage is made of a copper tape with the inner and outer diameters of 28 and 51 mm, respectively. It is adhered on one side of dielectric barrier. The lower electrode is made of stainless steel whose diameter of the planer surface is 52 mm. It is movable in the vertical direction using a micrometer gauge and a stepper motor, which is capable of adjusting the gap distance automatically and precisely. With forming the water film on the lower electrode surface, the DBD is generated between the dielectric barrier and the treat water surface. An acetic acid solution of 20 mg/L in concentration is prepared as the treat water by dissolving a guaranteed reagent of acetic acid with pure water. Total amount of the treat water is 0.5 L, which is circulated by a water pump with a flow rate of 1.5 L/min. The TOC concentration is measured by a TOC analyser (TOC-L CSN , Shimadzu Corp.) to evaluate the decomposition of acetic acid. Although the TOC concentration of the 20-mg/L acetic acid solution should be 8 mg TOC
/L, the TOC concentration before the plasma treatment become around 7.04
TOC /L.
3. Experimental results and discussions The acetic acid solution is treated for 2 hours with different gap distances of 1 2.5 mm. The results are shown in Fig. 1. Argon gas is fed into the reactor with a flow rate of 1.0 L/min. The initial discharge powers adjusted in an effort to be 1.7 W for all gap distances were within the range of 1.57 1.75 W. By 2 hours’ treatment, the TOC concentration decreases for all gap distances. The consumption energy for 2 hours estimated from discharge power and treatment time is also indicated in Fig. 1. The consumption energy slightly becomes large with longer gap distance. However, the higher TOC reduction is observed with the shorter gap distance. These results indicate that the shorter gap distance is expected to effectively decompose the persistent organic pollutants.
[1]
N. Takeuchi et al., Jpn. J. Appl. Phys., 54 (2015) 116201. [2]
M. S. Jović et al., Chem. Eng. J., 248 (2014) 63–70 [3]
K. Teranishi et al., 32nd ICPIG (2015). Topic number 0 1 2 3 4 5 6 7 8 9 10 1.0 mm 1.5 mm
2.0 mm 2.5 mm
(3.18 Wh) (3.37 Wh) (3.42 Wh) (3.56 Wh) T O
co n ce n tra
ti o n [mg
T O C /L ] Gap distance (Consumption energy for 2 hrs.) Before DBD treatment 2 hours Ar-DBD treatment Decomposiotn rate: D D=26.4% D=19.4% D=17.2% D=12.9%
Fig. 1 TOC concentration of acetic acid before and after Ar-DBD plasma treatment for 2 hrs. 240
XXXIII ICPIG, July 9-14, 2017, Estoril/Lisbon, Portugal
Effects of the Driving Frequency on Generation of O 3 , NOx in DBD plasma
Hyeongwon Jeon 1 P , Sangheum Eom 1 P , Hyewon Mun 2 P UPP
, Seong Bong Kim 1 P , Suk Jae Yoo 1 P and Seungmin Ryu 1 P
1 Plasma Technology Research Center, National Fusion Research Institute, Gunsan-city, Korea 2 Department of Plasma Convergence Engineering, Kunsan National University, Korea
The effects of driving frequency on generation of plasma reactive species were investigated in air plasma. The conventional dielectric barrier discharge(DBD) type plasma source and frequency tunable power were selected as a plasma generator. The frequency was considered as the main factor affecting the generation of plasma reactive species at air DBD plasma. The plasma reactive species, such as O 3 , NO, NOx were measured with different frequency condition (operating range is from 100Hz to 8000Hz). Electrical and optical characteristics were additional measured. Experimental results show that the plasma reactive species are changed according to the frequency. It is considered that the plasma reactive species can be selectively generated through the frequency control.
Air plasma application technology can be applied in various fields such as agri-food, environment, and energy. The O 3 and NOx are important chemical species of air plasma and these are utilized as a sterilizer. There are many ways to control plasma reactive species. The O 3 generation can be controlled through the driving frequency at the oxygen plasma source.[1] It is considered that O 3 and NOx can be controlled through the driving frequency at the air plasma.
2. Experimental Set-up The experimental set-up for this study is shown in Figure 1.
Figure 1. Experimental Set-up A function generator and a high voltage amplifier were used to control the frequency. O 3 and NOx were measured using gas analyzers. Electrical properties were measured using an oscilloscope and optical properties were measured using OES. Figure 2. OES (a) and O 3 generation(b) Figure 3. NO and NOx generation As the frequency changes, the generation of reactive species is also changed. In this experimental condition, the O3 concentration increases with frequency and gradually decreases from 3kHz.(Fig. 2(b)) The NOx concentration steadily increases with frequency and is highest at 8kHz.(Fig. 3) As a result, it is considered that the generation of plasma reactive species can be controlled by frequency. 4. Acknowledgements This work was supported by R&D Program of ‘Plasma Advanced Technology for Agriculture and Food (Plasma Farming)’ through the National Fusion Research Institute of Korea (NFRI) funded by the Government funds.
[1] Seung-Lok Park, Jin-Gyu Kim. J Korean Inst. IIIum. Electr. Install. Eng. Vol. 18, No.5 (2004) 146-150. 17 241
XXXIII ICPIG, July 9-14, 2017, Estoril/Lisbon, Portugal
Continual radiation of H 2 and D 2 (a 3 Σ g + →b 3 Σ u + ) induced by electron impact
J. Országh P , U M. Danko, M. Ďurian P , Š. Matejčík P
P
Electron induced fluorescence apparatus (EIFA) was used for examination of hydrogen and deuterium excitation by electrons at 14 eV impact energy with subsequent emission in spectral region between 200 – 700 nm. Relative excitation cross section for electrons with energy 0 – 100 eV was measured and compared at two separate wavelengths – 650 nm and 230 nm to confirm the radiation originates from the same deexcitation transition. The radiation of the continuum at wavelengths higher than 500 nm is shown for the first time in experimental studies. Deuterium spectral measurement was performed also at electron energy 14 eV in order to compare the results with hydrogen molecule observation.
Motivation for this research is the application of the results in diagnostic of thermonuclear plasmas in tokamaks [1]. Hydrogen and deuterium plasma is produced in tokamak vessels, and the interaction of H 2 and D 2
molecules with low energy electrons (0 – 100 eV) is particularly important at the plasma edge. 2. Experiment Hydrogen molecule has been examined in detail on EIFA. Spectra on several electron impact energies were obtained. In this work we present the spectrum at 14 eV (Figure 1) where only the continual radiation originating from the fluorescence transition H 2 (a 3 Σ g + →b 3 Σ u + ) is observable. The spectrum was obtained with 0.4 nm optical resolution and it is given in relative scale dependent on the pressure inside the vacuum chamber
(~10 -4
mbar for
H 2
measurements). 200
300 400
500 600
700 0 2 4 6 8 10 12 Intens ity (cps
) Wavelength (nm) H 2
e = 14 eV
D 2 , E e = 14 eV
-20 -10
0 10 20 30 40
2 and D
2 at 14 eV electron impact energy originating from H 2 (black) and D 2 (green) (a 3 Σ
+ →b 3 Σ u + ) radiative transitions. The spectra were corrected for spectral response of the apparatus.
Deuterium spectrum at 14 eV was obtained for the comparison. The pressure in the reaction chamber during the D 2 measurements was slightly lower than the H 2 measurement (~5x10 - 5 mbar) which explains the lower signal – to – noise ratio in D 2 spectrum. In D 2 spectrum only the radiation of continuum is present, as well. The second mode of measurement at EIFA is the excitation cross section measurement at fixed wavelength. The cross sections were measured at 230 nm and 650 nm. According to their identical shape and the threshold energies corresponding to 12.3±0.5 eV it is possible to suggest that both correspond to the bound – to – unbound transition, continuum radiation of H 2 (a 3 Σ g + →b 3 Σ u + ). 3. Acknowledgements This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 692335. This work was supported by the Slovak research and development agency project No APVV-15-0580.
[1] U. Fantz et al. Plasma. Phys. Contr. F. 43 (2001) 907.
Topic number 1 242 XXXIII ICPIG, July 9-14, 2017, Estoril/Lisbon, Portugal
Modelling of N 2 -H 2 capacitively coupled radio-frequency discharges
M. Jiménez-Redondo 1 , L. Marques 1,2 , N. Carrasco 3 , G. Cernogora 3 , L. L. Alves 2
1 Centro de Física das Universidades do Minho e do Porto, Universidade do Minho, 4710-057, Braga, Portugal 2 Instituto de Plasmas e Fusão Nuclear, Instituto Superior Técnico, Univ. Técnica de Lisboa, Lisboa, Portugal 3 Université Versailles St-Quentin, CNRS, LATMOS, 11 blvd d’Alembert, 78280 Guyancourt, France
2 -H 2 low pressure, low power capacitively coupled radio-frequency discharges, for amounts of H 2 up to 5%. Simulations are performed using a hybrid code that couples a two-dimensional time-dependent fluid module, describing the dynamics of the charged particles, to a zero-dimensional kinetic module, that solves the Boltzmann equation and describes the production and destruction of neutral species. The model accounts for the production of several excited states, and contains a detailed surface chemistry that includes recombination processes and the production of NH x molecules. Simulations show that surface production of NH 3 plays a key role in the neutral and ion kinetics of the discharge. 1. Introduction Capacitively coupled radio-frequency (ccrf) discharges in nitrogen-containing mixtures have been used in planetary studies to simulate, in laboratory environment, the
reactivity of
ionospheres. The present work is part of a research strategy, involving both simulations and experiment, to analyse the N 2 -CH 4 ionospheric chemistry of Titan, the biggest satellite of Saturn. The first step was the study of ccrf discharges in pure N 2 [1], and now continues with the analysis of N 2 -H 2
discharges. 2. Modelling The simulations run at low pressures (0.6–1.2 mbar), for 30–100 sccm gas flows and 5–20 W coupled powers, in N 2 -H 2 mixtures with hydrogen concentrations up to 5%. The model consists of a hybrid code that couples a two-dimensional (r,z) time-dependent fluid-type module, which describes the transport of the charged particles, to a very complete zero- dimensional kinetic module for the nitrogen- hydrogen mixture. The fluid module solves the continuity and the momentum transfer equations for electrons, positive ions N 2 + , N 4 + , H + , H 2 + , H 3 + , HN 2 + , NH + , NH 2 + , NH 3 + and NH 4 + , and negative ions H –
and NH 2 – , the electron mean energy transport equations, and Poisson's equation for the rf electric potential. The space-time map of the electron transport and rate coefficients are obtained from the electron mean energy profile, using the local mean energy approximation [1,2]. The kinetic module solves the two-term homogeneous and stationary electron Boltzmann equation (accounting for inelastic collisions from ground-state molecules and atoms, and inelastic and superelastic collisions involving vibrationally excited states) and the rate balance equations of the ground-state vibrational excited states of N 2 and H
2 , the most relevant electronic excited states for N 2 and N, H, and the most important crossed-species NH y (y=1-3) and N 2 H y (y=2-4) resulting from interactions within the N 2
2 systems [2,3]. An extended surface chemistry is considered, taking in account adsorption, surface association and heterogeneous reactions, which are key to the formation of NH 3 . The electron impact chemistry of hydrogen has been updated using the latest set of cross sections available from the IST- Lisbon database of LXCat [4,5].
3. Results Simulations show that significant amounts of NH 3 are produced in the discharge, with a high dependence on the parameters for the surface kinetics. The abundances of positive ions are greatly affected by the neutral composition, with NH 4 +
quickly becoming the major ion when sufficient NH 3 is present.
4. Acknowledgments This work was partially supported by the Portuguese FCT under project UID/FIS/50010/2013.
5. References [1] L.L. Alves et al, Plasma Sources Sci. Technol. 21 (2012) 045008. [2] L. Marques, J. Jolly, L.L. Alves, J. Appl. Phys. 102 (2007) 063305. [3] E. Tatarova et al, Plasma Sources Sci. Technol. 14 (2005) 19. [4] L.L. Alves, J. Phys. Conf. Ser. 565 (2014) 012007.
[5] www.lxcat.net Topic number: 5 243
XXXIII ICPIG, July 9-14, 2017, Estoril/Lisbon, Portugal
Radiation trapping in non-equilibrium plasmas: matrix methods and its application to arcs and glow discharges
Yu. Golubovskii 1 P , U D. Kalanov UP 1
, V. Maiorov P 1 P , M. Baeva 2 , D. Uhrlandt 2 , S. Gortschakow P 2
P
P
P
P
Summary of recent experimental and theoretical studies by authors, related to radiation trapping in non-equilibrium plasmas is presented. A free-burning Ar arc and a constricted positive column of the Ar glow discharge were considered as plasma sources. Role of radiation trapping in formation of spatial distributions of excited species is demonstrated. Excited species densities and its radial distributions are determined by means of emission and absorption spectroscopy. Experimental data is compared with results of simulations. A new universal matrix method of radiation transport description in plasmas of arbitrary geometry, line shape and absorption coefficient is presented. The method is tested against existing matrix methods which are based on source symmetry.
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