German Science Foundation (DFG)

Determining Chemical Reaction Systems in Plasma-Assisted Conversion of Methane Using Genetic Algorithms

Even for processes with only a few gas species involved the detailed description of plasma-assisted conversion processes in gas mixtures requires a large amount of processes to be taken into account and a large number of neutral and charged particles must be considered. In addition, setting up the corresponding reaction kinetics model needs the knowledge of the rate coefficients and their temperature dependence for all possible reactions between those species. Reduced reaction networks offer a simplified and pragmatic way to obtain an overall reaction kinetics model, already useful for the analysis of experimental data even if not all details of chemistry can be covered. In this paper we present a derivation of a data driven reduced model for plasma-assisted conversion of methane in an helium environment. By consideration of a small number of elementary reactions, a simple model is set up. Experimental data are analyzed by a genetic algorithm that provides best-fit approximations for the open parameters of the model. In a further step non-relevant parameters of the model are identified and a further model reduction is achieved. The data driven analysis of methane conversion serves as an illustrative example of the proposed method. The parameters and reaction channels found are compared with known results from the literature. The method is described in detail. The main goal of this work is to present the potential of this data driven method for a simplified and pragmatic modeling in the increasingly important field of plasma-assisted catalytic processes.

Publisher: 
EP2
IEK-4
Project: 
SFB 1316
Authors: 
D. Reiser
A. von Keudell
T. Urbanietz

Computational study of simultaneous positive and negative streamer propagation in a twin surface dielectric barrier discharge via 2D PIC simulations

The propagation mechanisms of plasma streamers have been observed and investigated in a surface dielectric barrier discharge (SDBD) using 2D particle in cell simulations. The investigations are carried out under a simulated air mixture, 80% N2 and 20% O2, at atmospheric pressure, 100 kPa, under both DC conditions and a pulsed DC waveform that represent AC conditions. The simulated geometry is a simplification of the symmetric and fully exposed SDBD resulting in the simultaneous ignition of both positive and negative streamers on either side of the Al2O3 dielectric barrier. In order to determine the interactivity of the two streamers, the propagation behavior for the positive and negative streamers are investigated both independently and simultaneously under identical constant voltage conditions. An additional focus is implored under a fast sub nanosecond rise time square voltage pulse alternating between positive and negative voltage conditions, thus providing insight into the dynamics of the streamers under alternating polarity switches. It is shown that the simultaneous ignition of both streamers, as well as using the pulsed DC conditions, provides both an enhanced discharge and an increased surface coverage. It is also shown that additional streamer branching may occur in a cross section that is difficult to experimentally observe. The enhanced discharge and surface coverage may be beneficial to many applications such as, but are not limited to: air purification, volatile organic compound removal, and plasma enhanced catalysis.

Publisher: 
AEPT
Project: 
SFB 1316
Authors: 
Quan-Zhi Zhang
R.T. Nguyen-Smith
F. Beckfeld
Y. Liu
T. Mussenbrock
P. Awakowicz
J. Schulze

Electric field measurements in a He:N2 nanosecond pulsed discharge with sub-ns time resolution

The electric field in the He:N_2 nanosecond Atmospheric Pressure Plasma Jet (ns-APPJ) is studied using Electric-Field Induced Second Harmonic generation (E-FISH) technique. It is shown that the calibration obtained with a DC voltage applied to the discharge cell may lead to incorrect results of the electric field measurements. It is proposed to use nanosecond high voltage pulses at low repetition rates for the calibration instead of a DC voltage. The temporal development of the electric field in the discharge at different distances from the cathode is measured with high temporal (100~ps) and spatial (50~µm) resolution. An electric field profile structure similar to the one in streamers or ionization fronts is observed. The velocity of the propagation of the falling edge of the ionization front is determined as 0.85x10^6 m/s. The validity of the local field approximation, important for modeling of these kind of discharges, is confirmed for the present conditions based on time and space derivatives of the measured electric field. The temporal evolution of the electron density is obtained by the measured electrical current and the time resolved electric field measurement combined with the electron mobility calculated with BOLSIG+.

Publisher: 
EP5
Project: 
SFB 1316
Authors: 
N. D. Lepikhin
D. Luggenhölscher
U. Czarnetzki

Determination of NO densities in a surface dielectric barrier discharge using optical emission spectroscopy

A new computationally assisted diagnostic to measure NO densities in atmospheric-pressure microplasmas by Optical Emission Spectroscopy (OES) is developed and validated against absorption spectroscopy in a volume Dielectric Barrier Discharge (DBD). The OES method is then applied to a twin surface DBD operated in N2 to measure the NO density as a function of the O2 admixture (0:1%–1%). The underlying rate equation model reveals that NO(A2Σ+) is primarily excited by reactions of the ground state NO(X2Π) with metastables N2(A3Σ+u).

Publisher: 
AEPT
Project: 
SFB 1316
Authors: 
B. Offerhaus
F. Kogelheide
D. Jalat
N. Bibinov
J. Schulze
K. Stapelmann
P. Awakowicz

The role of humidity and UV-C emission in the inactivation of B. subtilis spores during atmospheric-pressure dielectric barrier discharge treatment

Experiments are performed to assess the inactivation of Bacillus subtilis spores using a non-thermal atmospheric-pressure dielectric barrier discharge. The plasma source used in this study is mounted inside a vacuum vessel and operated in controlled gas mixtures. In this context, spore inactivation is measured under varying nitrogen/oxygen and humidity content and compared to spore inactivation using ambient air. Operating the dielectric barrier discharge in a sealed vessel offers the ability to distinguish between possible spore inactivation mechanisms since different process gas mixtures lead to the formation of distinct reactive species. The UV irradiance and the ozone density within the plasma volume are determined applying spectroscopic diagnostics with neither found to fully correlate with spore inactivation. It is found that spore inactivation is most strongly correlated with the humidity content in the feed gas, implying that reactive species formed, either directly or indirectly, from water molecules are strong mediators of spore inactivation.

Publisher: 
AEPT
Project: 
SFB 1316
Authors: 
F. Kogelheide
F. Voigt
B. Hillebrand
R. Möller
F. Fuchs
A. Gibson
P. Awakowicz
K. Stapelmann
M. Fiebrandt

Intra-cavity dynamics in a microplasma channel by side-on imaging

Here, a microplasma channel was investigated. The setup consists of three stacked layers: a magnet, a dielectric foil and two nickel foils that are separated by a 120 μm wide gap. The magnet is grounded while the two nickel foils are powered. The setup was operated with a triangular voltage with a frequency of 10 kHz and an amplitude of up to 700 V in Helium at atmospheric pressure. Phase resolved emission images were used to investigate the microplasma channel dynamics with line of sight from the top and from the side to the inside of the cavity. The top view images revealed that the discharge in the microplasma channel and the microplasma arrays behave similar. The already known asymmetric discharge behavior, the self-pulsing and the wavelike ignition was also observed in the microplasma channel. For the wavelike ignition in the channel a simple one dimensional model was proposed. With the additional side view images the asymmetric discharge behavior was examined more thoroughly. Unlike in the microplasma arrays, the discharge expands here in both half periods of the applied voltage above the upper edge of the powered electrodes. The discharge extends over a larger width in the half period, in which the potential of the upper electrodes is increasing, while it extends over a larger height in the other half period. Phase resolved images were also used to investigate the ignition phase of the discharge. The discharge ignites in the two half periods on a different height. This was explained by modeling the drift and diffusion of the charged particles between two discharge pulses.

Publisher: 
EP2
Project: 
SFB 1316
Authors: 
S. Kreuznacht
M. Böke
V. Schulz-von der Gathen

Characterisation of volume and surface dielectric barrier discharges in N2–O2 mixtures using optical emission spectroscopy

A volume and a twin surface dielectric barrier discharge (VDBD and SDBD) are generated in different nitrogen–oxygen mixtures at atmospheric pressure by applying damped sinusoidal voltage waveforms with oscillation periods in the microsecond time scale. Both electrode configurations are located inside vacuum vessels and operated in a controlled atmosphere to exclude the influence of surrounding air. The discharges are characterised with different spatial and temporal resolution by applying absolutely calibrated optical emission spectroscopy in conjunction with numerical simulations and current–voltage measurements. Plasma parameters, namely the electron density and the reduced electric field, and the dissipated power are found to depend strongly on the oxygen content in the working gas mixture. Different spatial and temporal distributions of plasma parameters and dissipated power are explained by surface and residual volume charges for different O2 admixtures due to their effects on the electron recombination rate. Thus, the oxygen admixture is found to strongly influence the breakdown process and plasma conditions of a VDBD and a SDBD.

Publisher: 
AEPT
Project: 
SFB 1316
Authors: 
F. Kogelheide
B. Offerhaus
N. Bibinov
P. Krajinski
L. Schücke
J. Schulze
K. Stapelmann
P. Awakowicz

In-situ control of microdischarge characteristics in unipolar pulsed plasma electrolytic oxidation of aluminum

Microdischarges occurring during plasma electrolytic oxidation are the main mechanism promoting oxide growth compared to classical anodization. When the dissipated energy by microdischarges during the coating process gets too large, high-intensity discharges might occur, which are detrimental to the oxide layer. In bipolar pulsed plasma electrolytic oxidation a so called 'soft-sparking' mode limits microdischarge growth. This method is not available for unipolar pulsing and for all material combinations. In this work, the authors provide a method to control the size- and intensity distributions of microdischarges by utilizing a multivariable closed-loop control. In-situ detection of microdischarge properties by CCD-camera measurements and fast image processing algorithms are deployed. The visible size of microdischarges is controlled by adjusting the duty cycle in a closed-loop feedback scheme, utilizing a PI-controller. Uncontrolled measurements are compared to controlled cases. The microdischarge sizes are controlled to a mean value of A = 510^-3 mm^2 and A = 710^-3 mm^2, respectively. Results for controlled cases show, that size and intensity distributions remain constant over the processing time of 35 minutes. Larger, high-intensity discharges can be effectively prevented. Optical emission spectra reveal, that certain spectral lines can be influenced or controlled with this method. Calculated black body radiation fits with very good agreement to measured continuum emission spectra (T = 3200 K). Variance of microdischarge size, emission intensity and continuum radiation between consecutive measurements is reduced to a large extent, promoting uniform microdischarge and oxide layer properties. A reduced variance in surface defects can be seen in SEM measurements, after coating for 35 minutes, for controlled cases. Surface defect study shows increased number density of microdischarge impact regions, while at the same time reducing pancake diameters, implying reduced microdischarge energies compared to uncontrolled cases.

Publisher: 
AEPT
Project: 
SFB 1316
Authors: 
P. Hermanns
S. Böddeker
V. Bracht
N. Bibinov
P. Awakowicz

Electron density, temperature and the potential structure of spokes in HiPIMS

In high power impulse magnetron sputtering (HiPIMS) bright plasma spots are observed during the discharge pulses that rotate with velocities in the order of 10 km s −1 in front of the target surface. It has proven very difficult to perform any quantitative measurements on these so-called spokes, which emerge stochastically during the build-up of each plasma pulse. In this paper, we propose a new time shift averaging method to perform measurements integrating over many discharge pulses, but without phase averaging of the spoke location, thus preserving the information of the spoke structure. This method is then applied to perform Langmuir probe measurements, employing magnetized probe theory to determine the plasma parameters inside the magnetic trap region of the discharge. Spokes are found to have a higher plasma density, electron temperature and plasma potential than the surrounding plasma. The electron density slowly rises at the leading edge of the spoke to a maximum value of about 1e20 m −3 and then drops sharply at the trailing edge to 4e19 m −3 . The electron temperature rises from 2.1 eV outside the spoke to 3.4 eV at the trailing end of the spoke. A reversal of the plasma potential from about −7 V outside the spoke to values just above 0 V in a spoke is observed, as has been proposed in the literature.

Publisher: 
EP2
Project: 
SFB TR 87
Authors: 
J. Held
P. A. Maaß
A. von Keudell

Atomic oxygen generation in atmospheric pressure RF plasma jets driven by tailored voltage waveforms in mixtures of He and O<sub>2</sub>

Absolute atomic oxygen densities measured space resolved in the active plasma volume of a COST microplasma reference jet operated in He/O2 and driven by tailored voltage waveforms are presented. The measurements are performed for different shapes of the driving voltage waveform, oxygen admixture concentrations, and peak-to-peak voltages. Peaks- and valleys-waveforms constructed based on different numbers of consecutive harmonics, N, of the fundamental frequency f0 = 13.56 MHz their relative phases and amplitudes are used. The results show that the density of atomic oxygen can be controlled and optimized by voltage waveform tailoring (VWT). It is significantly enhanced by increasing the number of consecutive driving harmonics at fixed peak-to-peak voltage. The shape of the measured density profiles in the direction perpendicular to the electrodes can be controlled by VWT as well. For N > 1 and peaks-/valleys-waveforms, it exhibits a strong spatial asymmetry with a maximum at one of the electrodes due to the spatially asymmetric electron power absorption dynamics. Thus, the atomic oxygen flux can be directed primarily towards one of the electrodes. The generation of atomic oxygen can be further optimized by changing the reactive gas admixture and by tuning the peak-to-peak voltage amplitude. The obtained results are understood based on a detailed analysis of the spatio-temporal dynamics of energetic electrons revealed by phase resolved optical emission spectroscopy (PROES).

Publisher: 
AEPT
Project: 
SFB 1316
Authors: 
I. Korolov
D. Steuer
L. Bischoff
G. Hübner
Y. Liu
M. Böke
T. Mussenbrock
J. Schulze