On phenomena in ionized gases
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- 5. References
- Atmospheric pressure plasma assisted preparation of ceramic submicron fibers
- 2. Results and discussion
- 4. References
- Plasma vs combustion in analytical chemistry: comparing the kinetics of DBD plasma and flame-based atomizers
- Effect of the magnetic field on formation of Cu nanoparticles during the magnetron sputtering in a gas aggregation source
- Acknowledgements
- Study of chemical modifications induced by an APPJ on an ultra-pure water target
- Numerical modelling of high-pressure arc discharges: computing anode heating voltage
- 1. Anode heating voltage
3. Results EFs in several situations have been investigated. In each one, EF measured by the spectroscopy in the plasma was compared with the one obtained thanks to the probe placed next to the capillary or the plume. If the plasma is powered with positive polarity voltage, both methods give results with a good agreement. For example, the transient EF was measured in the plume with a metallic grounded target 1cm away from the end of the capillary. The value given by the spectroscopy in the plasma was compared with the one obtained with the probe, placed 5mm away from the axis of the tube. Both methods gave a value around 10kV.cm -1
is not as easy to evaluate. Spectroscopy shows that the EF is weaker than with positive polarity voltage: 5kV.cm -1
same other conditions at the end of the capillary. Yet, electro-optic sensor finds comparable values of EF, around 10kV.cm -1 for both polarities near the end of the capillary. 4. Acknowledgments This work was supported by the bilateral project PHD Pavle Savic 2016 (no 36216UA). X.D. acknowledges his grant funding Thermofisher Scientific INEL/Région Centre Val de Loire.
[1] E. Robert et al., Phys. Plasmas, 22 (2015) 122007. [2] G. Gaborit et al., IEEE Trans. Plasma Sci., 42 (2014) 1265. [3] G. Sretenović et al.. Phys. D. Appl. Phys., 47 (2014) 102001. 6 276
XXXIII ICPIG, July 9-14, 2017, Estoril/Lisbon, Portugal
Atmospheric pressure plasma assisted preparation of ceramic submicron fibers
V. Medvecká P 1 P , U A. Zahoranová UP 1 P , D. Kováčik 1, P 2 P , M. Černák P 1,2
P
P 1 P
Mlynská dolina F2, 842 48 Bratislava, Slovakia P
P
Atmospheric pressure plasma generated in ambient air by Diffuse Coplanar Surface Barrier Discharge was used as an alternative to the conventional thermal sintering for the oxidation and removal of polymer matrix by the preparation of zinc oxide submicron fibers from polymer/precursor fibers. Morphology of fibers was observed by Scanning Electron Microscopy (SEM). Efficiency of removal of organics was studied by Energy-Dispersive X-Ray Spectroscopy (EDX). Changes in chemical bonds were investigated using Fourier Transform Infrared Spectroscopy (FTIR).
Significant decrease of organics was detected and high porosity of fibers was observed after plasma exposure time in the order of minutes.
Zinc oxide (ZnO) nanofibers, due to the unique electrical and optical properties, have attracted attention for applications in solar cells, gas and biosensors, transparent conductors, etc. [1]. Most common technique for preparation of ZnO fibers in submicron scale is
thermal calcination of polymer/precursor fibers [2]. Due to the high temperature approach and long treatment times, conventional thermal calcination is economically and energetically demanding process. Plasma assisted calcination (PAC) is a novel low temperature process of oxidation and removal of base polymer by non-thermal plasma [3,4]. In this work, special type of dielectric barrier discharge, so called Diffuse Coplanar Surface Barrier Discharge (DCSBD) [5,6], was used for PAC of polyvinyl
2 CCH 3 ) 2 ) submicron fibers in ambient air.
ATR-FTIR was used for characterization of specific chemical groups in the composite material before and after plasma treatment. Reduction of all major peaks related to PVA and zinc acetate indicate decomposition of the organic part of composite fibers. The surface of fibers observed by SEM became after plasma calcination rough due to the removal of organics. Higher porosity of fibers can be advantageous in the application requiring high specific surface. However, DCSBD plasma does not cause breaking of fibers. EDX measurements show decrease of carbon and increase of oxygen and zinc content. After 60 minutes of plasma treatment the atomic ratio of C/Zn decreased from 32.7 to 4.3 and O/Zn decreased from 18.0 to 6.1. Decrease of C/Zn atomic ratio indicates a very strong decline already in the first minutes.
The presented results show availability of DCSBD-based atmospheric pressure plasma assisted calcination for preparation of inorganic submicron fibers. The low temperature approach and short treatment time of process are very attractive as pre- treatment method or alternative to conventional thermal calcination.
from the European Union's Horizon 2020 research and innovation programme under grant agreement No 692335.
[1] Z. L. Wang, J. Phys. Condens. Matter 16, (2004), R829.
[2] J.-A. Park, J. Moon, S.-J. Lee, S.-C. Lim, and T. Zyung, Curr. Appl. Phys. 9, (2009), S210. [3] P. Baroch, J. Hieda, N. Saito, and O. Takai, Thin Solid Films 515, (2007), 4905. [4] H. Wang, H. Tang, J. He, and Q. Wang, Mater. Res. Bull. 44, (2009), 1676. [5] M. Černák, L. Černáková, I. Hudec, D. Kováčik, and A. Zahoranová, Eur. Phys. J. Appl. Phys. 47, (2009). [6] V. Medvecká, D. Kováčik, A. Zahoranová, M. Stupavská, and M. Černák, Mater. Lett. 162, (2016), 79.
277 XXXIII ICPIG, July 9-14, 2017, Estoril/Lisbon, Portugal
Plasma vs combustion in analytical chemistry: comparing the kinetics of DBD plasma and flame-based atomizers
A. Obrusnik P 1 , M. Mrkvičková UP 1 P , M. Talába P 1 P , J. Kratzer 2 , P. Dvořák 1 , J. Dědina P 2
P 1 P
P
P
In this contribution, we discuss the reaction kinetics in so-called atomizers, i.e. devices which are used in analytical chemistry to convert molecules of hydride forming elements to free atoms being subsequently detected by atomic absorption or fluorescence spectroscopy. It is known that the atomic hydrogen plays a key role during this process of volatile metal hydrides atomization, and it is produced in conventional atomizers by oxyhydrogen combustion. A logical alternative to the combustion-based atomizers is the DBD plasma, in which the energetic electrons can dissociate the hydrogen molecules directly. We compare the atomic hydrogen production and loss channels in the two respective devices with the help of validated numerical models. We also illustrate the role of advection on the chemistry and atomic hydrogen retaining.
We have previously developed a numerical model which combined a model of the background gas dynamics in full 3D coupled to a 0D kinetics model [1] and was implemented in COMSOL Multiphysics finite-element method package.
Figure 1: Benchmarking the model with TALIF measurements of atomic hydrogen density for different oxygen admixtures to the plasma.
The gas flow model solves the incompressible Navier-Stokes equation for the mixture of argon, hydrogen and oxygen, and includes diffusion of ambient air into the atomizer (which was, however, previously found to be negligible compared to the impurity of the laboratory gases). By integrating the velocity obtained from the gas dynamics model, we obtain information about spatially resolved gas residence time inside the atomizer which allows us to map the 0D kinetic model onto the 3D gas flow model, on the assumption of neglecting cross- streamline diffusion. When the model is correlated with TALIF measurements (see figure 1), reasonable agreement is obtained, though it becomes apparent at some conditions [1], that the assumption of negligible cross-streamline diffusion is limiting and the transport of reactive species in this atmospheric- pressure plasma is both advection-driven and diffusion-driven. For this reason, we have begun developing a model which solves the gas flow and kinetics in full 3D geometry and is implemented in the OpenFOAM finite-volume method library which will also be presented and compared to the simpler model.
[1] P. Dvořák et al. Concentration of atomic
Sources Sci. Technol. under review
This work was supported by Czech Science Foundation (P206/17-04329S), Institute of Analytical Chemistry of the CAS, v. v. i. (project no. RVO: 68081715) and by project LO1411 (NPU I) funded by Ministry of Education, Youth and Sports of Czech Republic. AO is a Brno PhD Talent scholarship holder – funded by Brno municipality. Topic number 5 278
XXXIII ICPIG, July 9-14, 2017, Estoril/Lisbon, Portugal
Effect of the magnetic field on formation of Cu nanoparticles during the magnetron sputtering in a gas aggregation source
M. Vaidulych 1 , J J. Hanuš 1 , S. Kadlec 2 , A. Marek 2 , I. Khalakhan 1 , O. Kylián 1 , A. Choukourov 1 , H. Biederman 1 .
1 Department of Macromolecular Physics, Faculty of Mathematics and Physics, Charles University, Prague, Czech Republic 2 HVM Plasma Ltd., Prague, Czech Republic
In this study, the impact of the adjustable magnetic field on the formation of Cu nanoparticles (NPs) in the Gas Aggregation Source (GAS) of nanoparticles was investigated. It was found that the deposition rate of NPs passed through a maximum when decreasing the magnetic field from 83 mT down to 30 mT. The change in the deposition rate was furthermore accompanied by alteration of the size distribution and the shape of produced NPs. Spherical NPs with the size of 26±1 nm as well as cubic NPs with the size of up to 150 nm were successfully prepared.
Over the last few decades, there was an increasing interest in efficient and wet chemical-free preparation of metal NPs by means of gas aggregation sources. Gas pressure and flow as well as magnetron current were recognized to be crucial parameters for tuning the structure, size distribution and yield of produced NPs. An impressive number of metallic nanoparticles (Ag, Cu, Ti etc.) were studied in terms of the influence of these parameters. Nevertheless, energetic conditions of the plasma can be also affected by the intensity of the magnetic field above the magnetron target, a parameter which has been given much less attention. Vernieres and co- authors studied the impact of the magnetic field (adjusted by thickness of the magnetron target) on the efficiency of the deposition of Fe NPs [1]. In their research, the intensity changed together with the shape of the magnetic field. In our work, we demonstrate an approach that conserves the shape of the magnetic field and thus allows studying the formation of Cu NPs solely by changing the field intensity.
Cu NPs were deposited by means of a Haberland type GAS. The GAS was equipped with a specially constructed 81 mm planar magnetron that enabled the adjustment of the magnetic induction above the target from 30 mT to 83 mT. Variation of the field was performed manualy by changing the distance between the magnetic circuit and the target surface. A special circuit of permanent magnets was designed to provide the invariable shape of the magnetic field with different intesity.
3. Results It was found that the deposition rate of Cu NPs, their size and shape can be indeed tailored by the intensity of the magnetic field. This is demonstrated for two selected values of magnetic field in Fig. 1, where are presented 3D maps of the deposition rate in dependence on pressure and magnetron power for a given magnetic field together with SEM images of produced NPs. As can be seen either spherical or bigger cubic NPs may be produced depending on the magnetic field.
Fig. 1. Dependence of the deposition rate of Cu NPs on pressure and power with magnetic field of: a) 83 mT; b) 53 mT and examples of SEM images of produced NPs.
The work was supported by the grant SVV– 2017–260444
[1] J. Vernieres, S. Steinhauer, J. Zhao and A. Chapelle et al., Adv. Funct. Mater. (2017) 1605328 18
279 XXXIII ICPIG, July 9-14, 2017, Estoril/Lisbon, Portugal
Study of chemical modifications induced by an APPJ on an ultra-pure water target C. Muja
1 , L. Invernizzi 1 , F. P. Sainct 1 and Ph. Guillot 1
1 Laboratoire Diagnostics des Plasmas Hors Equilibre (DPHE), Université Toulouse, INU Champollion,
Due to the increased oxidizing capacities of non-thermal plasmas, they are good candidates for wastewater chemical decontamination. The aim of this work was to assess the chemical changes produced by the exposure of a liquid to a plasma jet and to evaluate its capacity to decompose complex molecules such as pharmaceuticals. An asymmetric atmospheric pressure plasma jet was used to treat liquid samples and several colorimetric methods were used to assess the concentrations of nitrite, nitrate, ozone and hydrogen peroxide. Finally, samples containing acetaminophen (paracetamol) were exposed to the plasma jet and the concentrations following exposure were measured.
In the
last decades, the behaviour of pharmaceuticals in water cycle, raised concerns in both scientific and public media [1]. These molecules generally enter environment though wastewater, where can have negative effects on the ecosystem. Due to the increased oxidation capacity, non-thermal plasmas can potentially be used as oxidation agent for the treatment of polluted wastewater. The aim of this work was to characterize the chemical changes taking place inside the liquid exposed to plasma, with a special interest on reactive species generation. Finally, the capacity of the plasma jet to degrade pharmaceutical products was estimated using as model molecule the acetaminophen.
The experimental setup consists of an asymmetric plasma jet with the grounded electrode located on upper large area of the tube and the high voltage electrode on the narrow zone of the source. The discharge was initiated in a Helium-Oxygen mixture (0.2% O
2 ) at a flow of 2 l.min -1 . The high voltage power supply connected to the electrode provides a 6 kV voltage pulse at a frequency of 20 kHz. The plasma jet is studied in contact with a liquid surface (Milli-Q water). Colorimetric assays were used to determine the concentrations of nitrate, nitrite, ozone and hydrogen peroxide in the liquid phase. In order to assess the plasma jet capacity to remove complex molecules from water, several acetaminophen solutions were exposed to plasma. Following the
exposure, the
acetaminophen concentration was then measured using the Glynn and Kendal colorimetric method [2,3].
Figure 1 shows the nitrite concentration as a function of the time of exposition to the plasma jet, for various pulse lengths. For treatment durations ranging from 0 to 5 minutes, the nitrite production is linear for all the pulse lengths tested. In the same time, for pulse lengths ranging from 0.5 µs to 1.5 µs the nitrite production increases with the pulse length but remains stable for 1.5 µs - 2,5 µs pulse lengths.
Fig. 1. Nitrite concentration in plasma treated water.
These results as well as the results concerning the other reactive species will be used to discuss the interaction of the plasma jet with the liquid, and the possible mechanisms that leads to the removal of complex molecules from water.
[1] Fent, K., et al. Aquatic toxicology, (2006).76(2) [2] Glynn, J.P., Kendal, S.E. The Lancet (1975). [3] Shihana, F., Dissanayake, D.M., Dargan, P.I., Dawson, A.H. Clin Toxicol (Phila) 2010 48(1) 42- 46. Topic number 17 280 XXXIII ICPIG, July 9-14, 2017, Estoril/Lisbon, Portugal
Numerical modelling of high-pressure arc discharges: computing anode heating voltage N. A. Almeida, M. D. Cunha, and M. S. Benilov
P
P Instituto de Plasmas e Fusão Nuclear, Instituto Superior Técnico, Universidade de Lisboa, Lisboa, Portugal Two simple approaches to simulation of plasma-electrode interaction in high-pressure arc discharges are available in the literature: the so-called model of nonlinear surface heating, which is applicable for cathodes, and an approximate model based on the concept of electrode heating voltage, applicable for anodes. In this work, the anode heating voltage is computed for three plasma-producing gases (Ar, Xe, and Hg) in a wide range of plasma pressures, anode surface temperatures, and current densities. The results can be used for modelling the plasma-anode interaction in a wide range of conditions of high-pressure arc discharges. As an example, modelling is reported of interaction of arc plasmas with rod electrodes in both dc and ac arcs.
It is known from the experiment that the power input Q from the plasma to anodes of high-pressure arc discharges is proportional to the arc current I:
h
I, where the proportionality coefficient U h
(the anode heating voltage) may depend on the plasma-producing gas, its pressure, and the electrode material. For example, results of experiments with tungsten rod electrodes of different dimensions in an arc in argon at pressure of 2.6 bar are well described by this relation with U h = 6.24 V [1]. The anode heating voltage may be theoretically evaluated by means of a suitable 1D numerical model of near-anode layers in thermal plasmas; e.g., [2, 3]. A few results have been calculated for conditions typical of UHP lamps: xenon or mercury plasmas at very high pressures (of the order of 100 bar) [2]. In this work, the anode heating voltage is calculated for a wide range of conditions: the plasma-producing gas is Ar, or Xe, or Hg; the anode material is tungsten (the work function 4.55 eV); the plasma pressure is atmospheric, p = 1 bar, or very high, p = 100 bar; the temperature of the anode T w =
300, 1000, 3000 K for the atmospheric pressure and T w = 1500, 2500, 3500 K for p = 100 bar; the current density varies in the range j = 10 5 -10 7 A m
-2 .
Calculations have been performed by means of the code [2] and another code, in which the original equations are
solved without
preliminary transformations. An example of results is shown in Fig. 1. The density q of energy flux from the plasma to the anode is governed primarily by the local current density j and varies approximately proportionally to j: q = U h
heating voltage U h is virtually independent of the anode temperature and close to 6 V for all the three gases for p = 1 bar. For p = 100 bar, U h is close to 7 V for Ar, 6 V for Xe, and 9 V for Hg.
U h = 6 V
T w = 300 K T w = 1000 K T w = 3000 K 0 2 4 6 0 0.2 0.4 0.6
0.8 1 q (10 7 W/m
2 ) j (10 7 A/m
2 )
Fig. 1. Points: modelling, p = 1 bar, Ar. Line: q = U h j with U h = 6 V.
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