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The time evolution of the dissociation fraction in a pulsed radio frequency (rf) CO2 discharge is studied by infrared absorption. A large parametric study performed in a closed reactor brings valua...

Numerous applications have required the study of $$\hbox {CO}_2$$ plasmas since the 1960s, from $$\hbox {CO}_2$$ lasers to spacecraft heat shields. However, in recent years, intense research activities on the subject have restarted because of environmental problems associated with $$\hbox {CO}_2$$ emissions. The present review provides a synthesis of the current state of knowledge on the physical chemistry of cold $$\hbox {CO}_2$$ plasmas. In particular, the different modeling approaches implemented to address specific aspects of $$\hbox {CO}_2$$ plasmas are presented. Throughout the paper, the importance of conducting joint experimental, theoretical and modeling studies to elucidate the complex couplings at play in $$\hbox {CO}_2$$ plasmas is emphasized. Therefore, the experimental data that are likely to bring relevant constraints to the different modeling approaches are first reviewed. Second, the calculation of some key elementary processes obtained with semi-empirical, classical and quantum methods is presented. In order to describe the electron kinetics, the latest coherent sets of cross section satisfying the constraints of “electron swarm” analyses are introduced, and the need for self-consistent calculations for determining accurate electron energy distribution function (EEDF) is evidenced. The main findings of the latest zero-dimensional (0D) global models about the complex chemistry of $$\hbox {CO}_2$$ and its dissociation products in different plasma discharges are then given, and full state-to-state (STS) models of only the vibrational-dissociation kinetics developed for studies of spacecraft shields are described. Finally, two important points for all applications using $$\hbox {CO}_2$$ containing plasma are discussed: the role of surfaces in contact with the plasma, and the need for 2D/3D models to capture the main features of complex reactor geometries including effects induced by fluid dynamics on the plasma properties. In addition to bringing together the latest advances in the description of $$\hbox {CO}_2$$ non-equilibrium plasmas, the results presented here also highlight the fundamental data that are still missing and the possible routes that still need to be investigated.

Mueller polarimetry measurements are increasingly being used to image highly dynamic and short-lived phenomena such as plasma discharges. For phenomena such as these, exposure times below 1 µs must be used. Unfortunately, these low exposure times significantly reduce the signal-to-noise ratio, making accurate and consistent measurements difficult. To overcome this limitation, we investigated increasing the number of Stokes vectors produced from a polarization state analyzer and polarization state generator, a process known as over-determination. To conduct our analysis, we used results from physical experiments using Stokes vectors generated by liquid crystal variable retarders. These results were then verified using data from simulations. First, we conclude that increasing the degree of over-determination is a simple and effective way of dealing with this noise; however, we also convey that choosing the best scheme is not an entirely trivial process. Second, we demonstrate that over-determination gives rise to hitherto inaccessible information that allows for the quantification of statistical noise and, crucially, the pinpointing of the origin of systematic error, a highly beneficial process that has been lacking until now.

The ionosphere of Titan hosts a complex ion chemistry leading to the formation of organic dust below 1200 km. Current models cannot fully explain the observed electron temperature in this dusty environment. To achieve new insight, we have re-analyzed the data taken in the ionosphere of Titan by the Cassini Langmuir probe (LP), part of the Radio and Plasma Wave Science package. A first paper (Chatain et al., 2021) introduces the new analysis method and discusses the identification of 4 electron populations produced by different ionization mechanisms. In this second paper, we present a statistical study of the whole LP dataset below 1200 km which gives clues on the origin of the 4 populations. One small population is attributed to photo- or secondary electrons emitted from the surface of the probe boom. A second population is systematically observed, at a constant density (~500 cm-3), and is attributed to background thermalized electrons from the ionization process of precipitating particles fom the surrounding magnetosphere. The two last populations increase in density with pressure, solar illumination and EUV flux. The third population is observed with varying densities at all altitudes and solar zenith angles except on the far nightside (SZA > ~140{\deg}), with a maximum density of 2700 cm-3. It is therefore certainly related to the photo-ionization of the atmospheric molecules. Finally, a fourth population detected only on the dayside and below 1200 km reaching up to 2000 cm-3 could be photo- or thermo-emitted from dust grains., Comment: 25 pages, version accepted for publication in JGR

It has been recently advocated that Mars has excellent conditions for oxygen and fuel production directly from atmospheric CO2 using non-equilibrium plasmas. The Martian conditions would be favorable for vibrational excitation and/or enhanced dissociation by electron impact, two important pathways for CO2 plasma dissociation. Herein we confirm these theoretical predictions by measuring, for the first time, the vibrational temperatures of CO2 and the CO and CO2 concentrations in realistic Martian conditions. In situ Fourier transform infrared spectroscopy (FTIR) measurements are performed in experiments conducted in DC glow discharges operating at pressures p=1-5 Torr, discharge currents I=10-50 mA, initial gas temperatures of 220 K and 300 K, both in pure CO2 and in the synthetic Martian atmosphere 96% CO2-2% Ar-2% N2. To analyse and interpret the experimental results, we develop a detailed self-consistent kinetic model for pure CO2 plasmas, describing the coupled electron and heavy-particle kinetics. The simulation results are in very good agreement with the experimental data. It is shown that the low-temperature conditions may enhance the degree of vibrational non-equilibrium and that the Martian atmospheric composition has a positive effect on CO2 decomposition. Accordingly, the present investigation confirms the potential of plasma technologies for in-situ resource utilization (ISRU) on Mars.

Plasma catalysis is gaining increasing interest for various gas conversion applications, such as CO2 conversion into value-added chemicals and fuels, CH4 activation into hydrogen, higher hydrocarbons or oxygenates, and NH3 synthesis. Other applications are already more established, such as for air pollution control, e.g. volatile organic compound remediation, particulate matter and NOx removal. In addition, plasma is also very promising for catalyst synthesis and treatment. Plasma catalysis clearly has benefits over ‘conventional’ catalysis, as outlined in the Introduction. However, a better insight into the underlying physical and chemical processes is crucial. This can be obtained by experiments applying diagnostics, studying both the chemical processes at the catalyst surface and the physicochemical mechanisms of plasma-catalyst interactions, as well as by computer modeling. The key challenge is to design cost-effective, highly active and stable catalysts tailored to the plasma environment. Therefore, insight from thermal catalysis as well as electro- and photocatalysis is crucial. All these aspects are covered in this Roadmap paper, written by specialists in their field, presenting the state-of-the-art, the current and future challenges, as well as the advances in science and technology needed to meet these challenges.

The interaction of kHz μs-pulsed atmospheric pressure He jets with metallic targets is studied through simulations and experiments, focusing on the differences between floating and grounded targets. It is shown that the electric potential of the floating target is close to grounded in the instants after the impact of the discharge, but rises to a high voltage, potentially more than half of the applied voltage, at the end of the 1 μs pulse. As a result, a return stroke takes place after the discharge impact with both grounded and floating targets, as a redistribution between the high voltage electrode and the low voltage target. Electric field, electron temperature and electron density in the plasma plume are higher during the pulse with grounded target than with floating target, as gradients of electric potential progressively dissipate in the latter case. Finally, at the fall of the pulse, another electrical redistribution takes place, with higher intensity with the highly-charged floating target than with the grounded target. It is shown that this phenomenon can lead to an increase in electric field, electron temperature and electron density in the plume with floating target.

Over the past few decades many diagnostics have been developed to study the non-equilibrium nature of plasma. These developments have given experimentalists the possibility to measure in situ molecular and atomic densities, electron and ion densities, temperatures and velocities of species in the plasma, to just name a few. Many of the diagnostic techniques are based on the ‘photon-in, photon-out’ principle and were at first developed to perform spectroscopy on atoms and molecules. Much later they were introduced in the research of plasmas. In this foundation paper we will focus on optical-based diagnostics that are now for quite some time common use in the field of low-temperature plasma physics research. The basic principles of the diagnostics will be outlined and references will be given to papers where these techniques were successfully applied. For a more comprehensive understanding of the techniques the reader will be referred to textbooks.

This paper quantitatively characterizes a kHz atmospheric pressure He plasma jet without target powered by a pulse of positive applied voltage. It focuses on a quantitative comparison between experimental measurements and numerical results of a two-dimensional fluid model using the same configuration, for different values of magnitude and width of pulsed applied voltage. Excellent agreement is obtained between experiments and simulations on the gas mixture distribution, the length and velocity of discharge propagation and the electric field in the discharge front. For the first time in the same jet, the experimentally measured increase of the electric field in the plume is confirmed by the simulations. The electron density and temperature, measured behind the high field front, are found to agree qualitatively. Moreover, the comparison with simulations shows that discharge propagation stops when the potential in the discharge head is lower than a critical value. Hence, pulse width and magnitude allow to control propagation length. For long pulses, the potential in the discharge front reaches this critical value during the pulse. For shorter pulses, propagation is determined by the pulse shape, as the critical value is reached around 90-130 ns after the fall of the pulse. The results suggest that the magnitude of this critical value is defined by the gas mixture at the position of the front.

The plasma-surface interaction is studied for a low temperature helium plasma jet generated at atmospheric pressure using Mueller polarimetry on an electro-optic target. The influence of the AC kHz operating frequency is examined by simultaneously obtaining images of the induced electric field and temperature of the target. The technique offers high sensitivity in the determination of the temperature variation on the level of single degrees. Simultaneously, the evolution of the electric field in the target caused by plasma-driven charge accumulation can be measured with the threshold of the order of 105 V/m. Even though a specific electro-optic crystal is used to obtain the results, they are generally applicable to dielectric targets under exposure of a plasma jet when they are of 0.5 mm thickness, have a dielectric constant greater than 4 and are at floating potential. Other techniques to examine the induced electric field in a target do not exist to the best of our knowledge, making this technique unique and necessary. The influence of the AC kHz operating frequency is important because many plasma jet designs used throughout the world operate at different frequency which changes the time between the ionization waves and hence the leftover species densities and stability of the plasma. Results for our jet show a linear operating regime between 20 and 50 kHz where the ionization waves are stable and the temperature increases linearly by 25 K. The charge deposition and induced electric fields do not increase significantly but the surface area does increase due to an extended surface propagation. Additionally, temperature mapping using a 100 μm GaAs probe of the plasma plume area has revealed a mild heat exchange causing a heating of several degrees of the helium core while the surrounding air slightly cools. This peculiarity is also observed without plasma in the gas plume.

23 pags., 16 figs., 4 tabs., In this work, we present the results of simulations carried out for N2 –H2 capacitively coupled radio-frequency discharges, running at low pressure (0.3–0.9 mbar), low power (5–20 W), and for amounts of H2 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 in the discharge, 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 vibrationally and electronic excited states, and contains a detailed surface chemistry that includes recombination processes and the production of NHx molecules. The results obtained highlight the relevance of the interactions between plasma and surface, given the role of the secondary electron emission in the electrical parameters of the discharge and the critical importance of the surface production of ammonia to the neutral and ionic chemistry of the discharge., L Marques and M Jiménez-Redondo acknowledge the financial support of the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UIDB/04650/2019 and project UTAPEXPL/NTec/0107/2017. L L Alves acknowledges the financial support of the Portuguese Foundation for Science and Technology (FCT) through project UID/FIS/50010/2019 and grant SFRH/BSAB/150267/2019. N Carrasco acknowledges the financial support of the European Research Council (ERC Starting Grant PRIMCHEM, Grant agreement no. 636829). A Chatain acknowledges ENS Paris-Saclay Doctoral Program

The use of plasmas for CO2 utilization has been under investigation in recent years following a wave of environmental awareness. In this work, previously published experimental results on vibrationally cold CO2 plasmas are modelled to define a reaction mechanism, i.e. a set of reactions and rate coefficients validated against benchmark experiments. The model couples self-consistently the electron and heavy particle kinetics. In turn, the simulated results are validated against measurements taken in CO2 DC glow discharges in a relatively large range of experimental conditions: at pressures from 0.4 to 5 Torr, reduced electric fields ranging from 50 to 100 Td and gas flowing from 2 to 8 sccm. The model predicts the measured values of product formation (CO and O) as well as discharge power and electric field. After validation, a thorough analysis of the model’s results is presented, including: electron properties, species densities, power distribution into different excitation channels and main creation and destruction mechanisms of the main species. It is shown that, although vibrational populations are low, they have a significant effect on the electron properties and thus on the electric field and conversion. Moreover, the shape of the EEDF is significantly dependent on the dissociation degree. The role of electronically excited states on CO2 dissociation is also analyzed, showing that the first electronic excited state of CO can have a beneficial or detrimental effect in further producing CO and O in the discharge.

Organic aerosols accumulated in Titan's orange haze start forming in its ionosphere. This upper part of the atmosphere is highly reactive and complex ion chemistry takes place at altitudes from 1200 to 900 km. The ionosphere is a nitrogen plasma with a few percent of methane and hydrogen. Carbon from methane enables the formation of macromolecules with long organic chains, finally leading to the organic aerosols. On the other hand, we suspect that hydrogen and the protonated ions have a different erosive effect on the aerosols. Here we experimentally studied the effect of hydrogen and protonated species on organic aerosols. Analogues of Titan's aerosols were formed in a CCP RF plasma discharge in 95% N2 and 5% CH4. Thereafter, the aerosols were exposed to a DC plasma in 99% N2 and 1% H2. Samples were analysed by scanning electron microscopy and in situ infrared transmission spectroscopy. Two pellet techniques - KBr pressed pellets and thin metallic grids - were compared to confirm that modifications seen are not due to the material used to make the pellet. We observed that the spherical aerosols of ~500 nm in diameter were eroded under N2-H2 plasma exposure, with the formation of holes of ~10 nm at their surface. Aerosols were globally removed from the pellet by the plasma. IR spectra showed a faster disappearance of isonitriles and/or carbo-diimides compared to the global band of nitriles. The opposite effect was seen with beta-unsaturated nitriles and/or cyanamides. Double bonds as C=C and C=N were more affected than amines and C-H bonds. N-H and C-H absorption bands kept a similar ratio in intensity and their shape did not vary. Therefore, it seems that carbon and hydrogen play opposite roles in Titan's ionosphere: the carbon from methane lead to organic growth while hydrogen and protonated species erode the aerosols and react preferentially with unsaturated chemical functions., Comment: 30 pages, 16 figures

International audience; Sending a manned mission to Mars is one of the next major steps in space exploration. Creating a breathable environment, however, is a substantial challenge. A sustainable oxygen supply on the red planet can be achieved by converting carbon dioxide directly from the Martian atmosphere. A new solution to do so is on the way: plasma technology.

International audience; A kHz-operated atmospheric pressure plasma jet is investigated by measuring charge transferred to a dielectric electro-optic surface (BSO crystal) allowing for the measurement of electric field by exploiting the Pockels effect. The electric field values, distribution of the surface discharge and amount of deposited charge are obtained for various parameters, including gas flow, applied voltage, target distance and the length of the capillary from ground to the end. A newly formed surface discharge emerges at the target when enough charge is deposited at the impact point and electric fields are high enough, i.e. 200 pC and 9 ± 2 kV cm−1. The maximum amount of charge transferred by a single ionization wave ('plasma bullet') is 350 ± 40 pC. Due to the emerging new surface discharge behind the impact point, the total charge deposited on the surface of the dielectric target can increase up to 950 pC. The shape of the secondary discharge on the target is found to be mainly driven by gas flow, while the applied voltage allows us to utilize longer distances within the boundaries set by this gas mixing. Finally the ionization wave is found to lose charge along its propagation on the inner walls of the capillary. The loss is estimated to be approximately 7.5 pC mm−1 of travel distance inside the capillary.

International audience; Oxygen atom densities were measured in situ in a CO2 glow discharge, at pressures between 0.2 and 5 Torr (26.7?666.6 Pa). Two measurement techniques were compared, namely optical emission actinometry (using Ar as the actinometer) and high-resolution two-photon absorption laser induced fluorescence normalised to Xe, and were found to give consistent results. The variation of the atomic oxygen density with gas pressure shows two different regimes with a transition around 1 Torr. Measurements of the O atom loss frequency under plasma exposure showed that this behaviour is caused by a change in the O atom loss mechanisms, which are dominated by surface processes in our experimental conditions. The corresponding recombination probabilities on Pyrex ? O are found to vary with the gas temperature near the wall for a constant surface temperature, similarly to what has recently been obtained in pure O2. However, the measured values are more than two times lower than ? O obtained in a O2 plasma in similar conditions. The O atom densities are also compared to the dissociation fraction of CO2 determined by infra-red absorption. The obtained CO and O densities show different behaviour as a function of the energy input. The simultaneous measurement of gas temperature, electric field, O, CO and CO2 densities and O atoms loss frequency in the same conditions provides an ideal set of constraints for validating CO2 plasma kinetic models.

International audience; This work employs in situ rotational Raman spectroscopy to study the effect of N2 and O2 addition to CO2 in pulsed glow discharges in the mbar range. The spatiotemporally resolved measurements are performed in CO2 and 25%, 50% and 75% of N2 or O2 admixture, in a 5–10 ms on-off cycle, 50 mA plasma current and 6.7 mbar total pressure. The rotational temperature profile is not affected by adding N2, ranging from 400 to 850 K from start to end of the discharge pulse, while the addition of O2 decreases the temperature at corresponding time points. Molecular number densities of CO2, CO, O2 and N2 are determined, showing the spatial homogeneity along the axis of the reactor and uniformity during the cycle. The measurements in the N2 containing mixtures show that CO2 conversion factor α increases from 0.15 to 0.33 when the content of N2 is increased from 0% to 75%, demonstrating the potential of N2 addition to enhance the vibrational pumping of CO2 and its beneficial effect on CO2 dissociation. Furthermore, the influence of admixtures on CO2 vibrations is examined by analysing the vibrationally averaged nuclear spin degeneracy. The difference between the fitted odd averaged degeneracy and the calculated odd degeneracy assuming thermal conditions increases with the addition of N2, demonstrating the growth of vibrational temperatures in CO2. On the other hand, the addition of O2 leads to a decrease of α, which might be attributed to quenched vibrations of CO2, and/or to the influence of the back reaction in the presence of O2.

International audience; The recombination of O (3P) atoms on the surface of a Pyrex tube containing a DC glow discharge in pure O2 was studied over a wide range of pressure (0.2–10 Torr) and discharge current (10–40 mA) for two fixed surface temperatures ( 50 °C and 5 °C). The recombination probability, γ, was deduced from the observed atom loss rate (dominated by surface recombination) determined by time-resolved optical emission actinometry in partially-modulated (amplitude ~15%–17%) discharges. The value of γ increased with discharge current at all pressures studied. As a function of pressure it passes through a minimum at ~0.75 Torr. At pressures above this minimum γ is well-correlated with the gas temperature, T g, (determined from the rotational structure of the O2 (b1Σg , v = 0) → O2(X3Σg −, v = 0) emission spectrum) which increases with pressure and current. The temperature of the atoms incident at the surface was deduced from a model, calibrated by measurements of the spatially-averaged gas temperature and validated by radial temperature profile measurements. The value of γ follows an Arrhenius law depending on the incident atom temperature, with an activation energy in the range 0.13–0.16 eV. At the higher surface temperature the activation energy is the same, but the pre-exponential factor is smaller. Under conditions where the O flux to the surface is low γ falls below this Arrhenius law. These results are well explained by an Eley–Rideal (ER) mechanism with incident O atoms recombining with both chemisorbed and more weakly bonded physisorbed atoms on the surface, with the kinetic energy of the incident atoms providing the energy to overcome the activation energy barrier. A phenomenological ER model is proposed that explains both the decrease in recombination probability with surface temperature as well as the deviations from the Arrhenius law when the O flux is low. At pressures below 0.75 Torr γ increases significantly, and also increases strongly with the discharge current. We attribute this effect to incident ions and fast neutrals arriving with sufficient energy to clean or chemically modify the surface, generating new adsorption sites. Discharge modeling confirms that at pressures below ~0.3 Torr a noticeable fraction of the ions arriving at the surface have adequate kinetic energy to break surface chemical bonds (>3–5 eV).

International audience; This work investigates the dynamical charging of a surface under exposure of a non-equilibrium plasma jet at atmospheric pressure through a quantitative comparison between modeling and experiments. We show using mono-polar pulses with variable pulse duration and amplitude that the charging time (i.e. the time from impact of the ionization wave till the fall of the high voltage pulse) is a crucial element determining the plasma-surface interaction. This is done through direct measurements of the electric field induced inside the target using the optical diagnostic technique called Mueller polarimetry and comparison with the electric field calculated using a 2D fluid model of the plasma jet interaction with the target in the same conditions as in the experiments. When the charging time is kept relatively short (less than 100 ns), the surface spreading of the discharge and consequent surface charge deposition are limited. When it is relatively long (up to microseconds), the increased surface spreading and charge deposition significantly change the electric field to which the target is exposed during the charging time and when the applied voltage returns to zero.

International audience; The excitation and relaxation of the vibrations of CO2 as well as the reduction of CO2 to CO are studied in a pulsed glow discharge. Two diagnostics are employed, being (1) time-resolved in situ Fourier transform infrared (FTIR) spectroscopy and (2) spatiotemporally resolved in situ rotational Raman spectroscopy. Experiments are conducted within a pressure range of 1.3-6.7 mbar and a current range of 10-50 mA. In the afterglow, the rate of exponential decay from the asymmetric stretch temperature (T3) to the rotational temperature (Trot) is found to be only dependent on Trot, in the conditions under study. The decay rate ρT3-Trot follows the relation ρT3-Trot = 388 s-1 exp((Trot - 273 K)/(154 K)). Pressure and varying concentrations of CO and (presumably) atomic oxygen did not show to be of significant influence. In the active part of the discharge the excitation of T3 showed to be positively related to current and negatively to pressure. However, the contribution of current to vibrational excitation is ambiguous: the conversion of CO2 and therefore the fraction of CO in the discharge, is found to be strongly dependent on the current, with a conversion factor of 0.05 to 0.18 for 10 mA to 50 mA, while CO can contribute to the excitation through near-resonant collisions. A clear relation between the elevation of T3 and the dissociation of CO2 could not be confirmed, though conversion peaks are observed in the near afterglow, which motivate future experiments on vibrational ladder-climbing directly after termination of the discharge.

International audience; This work presents the investigation of a 30 kHz operated atmospheric pressure plasma jet impinging a dielectric BSO-crystal, allowing time-resolved electric field measurements based on the Pockels effect. Observations indicate that from the time the voltage is applied, the plasma first develops through unstable branching before a stable periodic behavior is established. This initialization of the plasma jet suggests the importance of the build-up of leftover ionization, which creates a preferred pathway for the streamer-like discharges. After initialization the time and spatially resolved electric field of guided ionization waves induced in the crystal is obtained, showing a highly periodic charging and discharging at the surface of the crystal. When the ionization wave arrives at the crystal charge is deposited and constant electric fields are generated for approximately 14 μs. Then a (back) discharge will remove the deposited charge at the surface, related to the moment when the applied voltage changes polarity and it agrees with imaging reported on in other literature.

A method is presented for the determination of the absolute densities of O(3P) atoms and O2(a1Δg) molecules in an O2 electrical discharge, which does not depend on any calibration procedure or knowledge of optical transition strengths. It is based on observing the recovery dynamics of the O2(X3Σg -) density in the afterglow of a fully-modulated discharge, and is demonstrated in a dc glow discharge in pure О2 at pressures of 0.2-4 Torr. The time-resolved O2(X3Σg -) density was measured by VUV absorption spectroscopy using the monochromator branch of the VUV DESIRS beamline at Synchrotron SOLEIL, but this methodology could be used with another density measurement technique. During the active discharge, the O2(X3Σg -) density is depleted by a combination of О2 dissociation, excitation into metastable states (principally (a1Δg) ) and gas heating/dilation. After discharge extinction, the O2(X3Σg -) density progressively recovers to its initial (before discharge) value, with three distinct time-constants due to: i) gas cooling (fast), ii) O(3P) atom recombination (intermediate), and iii)O2(a1Δg) quenching (slow). The O(3P) and O2(a1Δg) dynamics can be separated easily, allowing the O(3P) and O2(a1Δg) afterglow loss kinetics to be determined, as well as their mole fractions in the steady-state discharge. Both the O(3P) and (a1Δg) mole-fractions increase with current (up to the highest current studied, 40 mA) and pass through maxima with pressure at 1 Torr, reaching 16.5% and 8%, respectively. O(3P) atoms are principally lost by recombination at the borosilicate tube surface, with a loss probability in the afterglow of ~8x10-4, nearly independent of gas pressure and discharge current (in contrast to previous observations in the active discharge [1] . The (a1Δg) dynamics were also measured by IR emission spectroscopy. In the late afterglow this agrees well with the O2(X3Σg -) recovery dynamics, corresponding to an (a1Δg) surface loss probability of ~2.2x10-4. The initial (a1Δg) loss is faster than in the later afterglow, indicating that it is also quenched by O atoms.

This is the second of two papers presenting the study of vibrational energy exchanges in non-equilibrium CO2 plasmas in low-excitation conditions. The companion paper addresses a theoretical and experimental investigation of the time relaxation of ∼70 individual vibrational levels of ground-state CO molecules during the afterglow of a pulsed DC glow discharge, operating at pressures of a few Torr and discharge currents around 50 mA, where the rate coefficients for vibration-translation (V-T) and vibration-vibration (V-V) energy transfers among these levels are validated (Silva et al 2018 Plasma Sources Sci. Technol. 27 015019). Herein, the investigation is focused on the active discharge, by extending the model with the inclusion of electron impact processes for vibrational excitation and de-excitation (e-V). The time-dependent calculated densities of the different vibrational levels are compared with experimental data obtained from time-resolved in situ Fourier transform infrared spectroscopy. It is shown that the vibrational temperature of the asymmetric stretching mode is always larger than the vibrational temperatures of the bending and symmetric stretching modes along the discharge pulse - the latter two remaining very nearly the same and close to the gas temperature. The general good agreement between the model predictions and the experimental results validates the e-V rate coefficients used and provides assurance that the proposed kinetic scheme provides a solid basis to understand the vibrational energy exchanges occurring in CO2 plasmas.

International audience; Mueller polarimetry is used to investigate the behavior of an electro optic target (BSO crystal) under exposure of guided ionization waves produced by an atmospheric pressure plasma jet. For the first time, this optical technique is time resolved to obtain the complete Mueller matrix of the sample right before and after the impact of the discharges. By analyzing the induced birefringence, the spatial profiles and local values are obtained of both the electric field and temperature in the sample. Electric fields are generated due to deposited surface charges and a temperature profile is present, due to the heat transferred by the plasma jet. The study of electric field dynamics and local temperature increase at the target, due to the plasma jet is important for biomedical applications, as well as surface functionalization. This work shows how Mueller polarimetry can be used as a novel diagnostic to simultaneously acquire the spatial distribution and local values of both the electric field and temperature, by coupling the external source of anisotropy to the measured induced birefringence via the symmetry point group of the examined material.

International audience; Mueller polarimetry is used to investigate the behavior of an electro optic target (BSO crystal) under exposure of guided ionization waves produced by an atmospheric pressure plasma jet. For the first time, this optical technique is time resolved to obtain the complete Mueller matrix of the sample right before and after the impact of the discharges. By analyzing the induced birefringence, the spatial profiles and local values are obtained of both the electric field and temperature in the sample. Electric fields are generated due to deposited surface charges and a temperature profile is present, due to the heat transferred by the plasma jet. The study of electric field dynamics and local temperature increase at the target, due to the plasma jet is important for biomedical applications, as well as surface functionalization. This work shows how Mueller polarimetry can be used as a novel diagnostic to simultaneously acquire the spatial distribution and local values of both the electric field and temperature, by coupling the external source of anisotropy to the measured induced birefringence via the symmetry point group of the examined material.

The implementation of in situ rotational Raman spectroscopy is realized for a pulsed glow discharge in CO2 in the mbar range and is used to study the rotational temperature and molecular number densities of CO2, CO, and O2. The polarizability anisotropy of these molecules is required for extracting number densities from the recorded spectra and is determined for incident photons of 532 nm. The spatiotemporally-resolved measurements are performed in the same reactor and at equal discharge conditions (5-10 ms on-off cycle, 50 mA plasma current, 6.7 mbar pressure) as in recently published work employing in situ Fourier transform infrared (FTIR) spectroscopy. The rotational temperature ranges from 394 to 809 K from start to end of the discharge pulse and is constant over the length of the reactor. The discharge is demonstrated to be spatially uniform in gas composition, with a CO2 conversion factor of 0.15 ± 0.02. Rotational temperatures and molecular composition agree well with the FTIR results, while the spatial uniformity confirms the assumption made for the FTIR analysis of a homogeneous medium over the line-of-sight of absorption. Furthermore, the rotational Raman spectra of CO2 are related to vibrational temperatures through the vibrationally averaged nuclear spin degeneracy, which is expressed in the intensity ratio between even and odd numbered Raman peaks. The elevation of the odd averaged degeneracy above thermal conditions agrees well with the elevation of vibrational temperatures of CO2, acquired in the FTIR study.

A kinetic model describing the time evolution of ∼70 individual CO2(X1Σ+) vibrational levels during the afterglow of a pulsed DC glow discharge is developed in order to contribute to the understanding of vibrational energy transfer in CO2 plasmas. The results of the simulations are compared against in situ Fourier transform infrared spectroscopy data obtained in a pulsed DC glow discharge and its afterglow at pressures of a few Torr and discharge currents of around 50 mA. The very good agreement between the model predictions and the experimental results validates the kinetic scheme considered here and the corresponding vibration-vibration and vibration-translation rate coefficients. In this sense, it establishes a reaction mechanism for the vibrational kinetics of these CO2 energy levels and offers a firm basis to understand the vibrational relaxation in CO2 plasmas. It is shown that first-order perturbation theories, namely, the Schwartz-Slawsky-Herzfeld and Sharma-Brau methods, provide a good description of CO2 vibrations under low excitation regimes.

International audience; The article describes the complex study of the interaction of a helium plasma jet with distilled water and saline. The discharge development, spatial distribution of the excited species, electric field measurement results and the results of the Schlieren imaging are presented. The results of the experiments showed that the plasma–liquid interaction could be prolonged with the proper choice of the gas composition between the jet nozzle and the target. This depends on the gas flow and the target distance. Increased conductivity of the liquid does not affect the discharge properties significantly. An increase of the gas flow enables an extension of the plasma duration on the liquid surface up to 10 µs, but with a moderate electric field strength in the ionization wave. In contrast, there is a significant enhancement of the electric field on the liquid surface, up to 30 kV cm−1 for low flows, but with a shorter time of the overall plasma liquid interaction. Ignition of the plasma jet induces a gas flow modification and may cause turbulences in the gas flow. A significant influence of the plasma jet causing a mixing in the liquid is also recorded and it is found that the plasma jet ignition changes the direction of the liquid circulation.

Vibrational temperatures of CO2 are studied in a pulsed glow discharge by means of time-resolved in situ Fourier transform infrared spectroscopy, with a 10 μs temporal resolution. A method to analyze the infrared transmittance through vibrationally excited CO2 is presented and validated on a previously published CO2 spectrum, showing good agreement between fit and data. The discharge under study is pulsed with a typical duty cycle of 5-10 ms on-off, at 50 mA and 6.7 mbar. A rapid increase of the temperature of the asymmetric stretch vibration (T 3) is observed at the start of the pulse, reaching 1050 K, which is an elevation of 550 K above the rotational temperature () of 500 K. After the plasma pulse, the characteristic relaxation time of T 3 to strongly depends on the rotational temperature. By adjusting the duty cycle, the rotational temperature directly after the discharge is varied from 530 to 860 K, resulting in relaxation times between 0.4 and 0.1 ms. Equivalently, as the gas heats up during the plasma pulse, the elevation of T 3 above decreases strongly.

International audience; The results of the electric field measurements in the capillary of the helium plasma jet are presentedin this article. Distributions of the electric field for the streamers are determined for different gasflow rates. It is found that electric field strength in front of the ionization wave decreases as itapproaches to the exit of the tube. The values obtained under presented experimental conditions arein the range of 5–11 kV/cm. It was found that the increase in gas flow above 1500 SCCM couldinduce substantial changes in the discharge operation. This is reflected through the formation of thebrighter discharge region and appearance of the electric field maxima. Furthermore, using themeasured values of the electric field strength in the streamer head, it was possible to estimateelectron densities in the streamer channel. Maximal density of 41011cm3 is obtained in thevicinity of the grounded ring electrode. Similar behaviors of the electron density distributions to thedistributions of the electric field strength are found under the studied experimental conditions.

International audience; Herein, it is argued that Mars has nearly ideal conditions for CO 2 decomposition by non-equilibrium plasmas. It is shown that the pressure and temperature ranges in the ##IMG## [http://ej.iop.org/images/0963-0252/26/11/11LT01/psstaa8dccieqn1.gif] ∼ 96 % CO 2 Martian atmosphere favour the vibrational excitation and subsequent up-pumping of the asymmetric stretching mode, which is believed to be a key factor for an efficient plasma dissociation, at the expense of the excitation of the other modes. Therefore, gas discharges operating at atmospheric pressure on Mars are extremely strong candidates to produce O 2 efficiently from the locally available resources.

This work explores the effect of nitrogen addition on CO2 dissociation under various non-equilibrium plasma conditions. Experiments are performed in non-thermal plasmas sustained by DC pulsed discharges, for pressure and current ranges of 1 to 5 Torr and 20 to 50 mA, respectively. A self-consistent model, previously validated for pure CO2 discharges, is further extended to take into account e-V, V-T and V-V reactions involving N2. Both model predictions and experimental data reveal a maximum of the asymmetric vibrational temperature T3 at 5 Torr during the discharge around 1 ms, while no such maximum is visible at 1 Torr before the saturation occurs. It is shown that V-T deactivation by O atoms can have a strong influence on the vibrational kinetics, by affecting directly the relaxation of N2 vibrational excited states and, as a consequence, the very important energy transfers between vibrationally excited N2 and CO2 molecules. The experimental results show a twice larger CO2-conversion rate when N2 gas is added to the plasma. The simulations suggest this effect cannot be the result of an increased dissociation by direct electron impact due to modifications in the reduced electric field, but rather of some other contribution to dissociation and/or inhibition of reactions giving back CO2.

International audience; Plasma catalysis, biomedical applications or atomic layer deposition at atmospheric pressure all make use of non-thermal plasmas in contact with a wide variety of surfaces. As the presence of a target (substrate) has been shown to modify the plasma in addition to the plasma modifying the target, it is reasonable to describe and study the plasma-surface as one system. This work shows how the presence of dielectric and metallic targets influences a kHz AC-driven discharge in a He plasma jet. Next to bringing the absolute values of the axial electric field along the plume of the jet, the presence of the surface has been shown to significantly elongate both the plume and the electric field profile. In addition, when a dielectric target is placed closer than the maximum length of the freely expanding jet, the electric field profile is enhanced only in the vicinity of the dielectric, typically between 0.3 and 2 mm above the target surface. The maximum measured relative increase is 31%, for 1000 SCCM flow with the target at 7 mm distance, when the electric field increased from 14.1 kV cm−1 for the freely expanding jet to 32.6 kV cm−1 when the jet was impinging on glass. Finally, a grounded metallic target enhances the electric field compared to the glass target only within a very thin layer just above the surface, typically about 0.2 mm. The highest measured electric field was 40.1 kV cm−1 at a grounded metallic target 12 mm away from the nozzle, for 1000 SCCM of helium flow. The discussion on the effects of the flow on the electric field profile are supported by the visualization of the flow. The discussion brings, among other, the comparison of properties between the 30 kHz AC-driven system and the 5 kHz pulsed jet.

International audience; This report focuses on the dependence of electric field strength in the effluent of a vertically downwards-operated plasma jet freely expanding into room air as a function of the gas flow speed. A 30 kHz AC-driven He jet was used in a coaxial geometry, with an amplitude of 2 kV and gas flow between 700 sccm and 2000 SCCM. The electric field was measured by means of Stark polarization spectroscopy of the He line at 492.19 nm. While the minimum and the maximum measured electric fields remained unchanged, the effect of the gas flow speed is to cause stretching of the measured profile in space—the higher the flow, the longer and less steep the electric field profile. The portion of the effluent in which the electric field was measured showed an increase of electric field with increasing distance from the capillary, for which the probable cause is the contraction of the plasma bullet as it travels through space away from the capillary. There are strong indications that the stretching of the electric field profile with increase in the flow speed is caused by differences in gas mixing as a function of the gas flow speed. The simulated gas composition shows that the amount of air entrained into the gas flow behaves in a similar way to the observed behaviour of the electric field. In addition we have shown that the visible length of the plasma plume is associated with a 0.027 molar fraction of air in the He flow in this configuration, while the maximum electric field measured was associated with a 0.014 molar fraction of air at gas flow rates up to 1500 SCCM (4.9 m s−1). At higher flows vortices occur in the effluent of the jet, as seen in Schlieren visualization of the gas flow with and without the discharge.

International audience; Atomic oxygen, considered to be a determining reactant in plasma applications at ambient pressure, is routinely detected by two-photon absorption laser induced fluorescence (TALIF). Here, pressure broadening of the (2 p 4 3 P 2 ?????3 p 3 P J =0,1,2 ) two-photon transition in oxygen atoms was investigated using a high-resolution TALIF technique in normal and Doppler-free configurations. The pressure broadening coefficients determined were ##IMG## [http://ej.iop.org/images/0963-0252/25/6/06LT03/psstaa4481ieqn001.gif] γ_\textO_2 ??=??0.40??±??0.08? cm ?1 /bar for oxygen molecules and ##IMG## [http://ej.iop.org/images/0963-0252/25/6/06LT03/psstaa4481ieqn002.gif] γ_\textHe ??=??0.46??±??0.03?cm ?1 /bar for helium atoms. These correspond to pressure broadening rate constants ##IMG## [http://ej.iop.org/images/0963-0252/25/6/06LT03/psstaa4481ieqn003.gif] k_\textPB^\textO_2 ??=??9 · 10 ?9 cm 3 s ?1 and ##IMG## [http://ej.iop.org/images/0963-0252/25/6/06LT03/psstaa4481ieqn004.gif] k_\textPB^\textHe ??=??4 · 10 ?9 cm 3 s ?1 , respectively. The well-known quenching rate constants of O(3 p 3 P J ) by O 2 and He are at least one order of magnitude smaller, which signifies that non-quenching collisions constitute the main line-broadening mechanism. In addition to providing new insights into collisional processes of oxygen atoms in electronically excited 3 p 3 P J state, reported pressure broadening parameters are important for quantification of oxygen TALIF line profiles when both collisional and Doppler broadening mechanisms are important. Thus, the Doppler component (and hence the temperature of oxygen atoms) can be accurately determined from high resolution TALIF measurements in a broad range of conditions.

International audience; The kinetics of the formation of NO in pulsed air-like dc plasmas at a pressure of 1.33 mbar and mean currents between 50 and 150 mA of discharge pulses with 5 ms duration has been investigated both experimentally and by self-consistent numerical modelling. Using time-resolved quantum cascade laser absorption spectroscopy, the densities of NO, NO2 and N2O have been measured in synthetic air as well as in air with 0.8% of NO2 and N2O, respectively. The temporal evolution of the NO density shows four distinct phases during the plasma pulse and the early afterglow in the three gas mixtures that were used. In particular, a steep density increase during the ignition phase and after termination of the discharge current pulse has been detected. The NO concentration has been found to reach a constant value of , , and for mean plasma currents of 50 mA, 100 mA and 150 mA, respectively, in the afterglow. The measured densities of NO2 and N2O in the respective mixture decrease exponentially during the plasma pulse and remain almost constant in the afterglow, especially where the admixture of NO2 has a remarkable impact on the NO production during the ignition. The numerical results of the coupled solution of a set of rate equations for the various heavy particles and the time-dependent Boltzmann equation of the electrons agree quite well with the experimental findings for the different air-like plasmas. The main reaction processes have been analysed on the basis of the model calculations and the remaining differences between the experiment and modelling especially during the afterglow are discussed.

This paper deals with generation of diaphragm discharge in water solutions of sodium chloride with fixed conductivity of 275 mu S. The photos were recorded by high-speed iCCD camera at defined times synchronized by the current passing through the system. Three different phases in the current-voltage curve were recognized under all conditions. Only electrolysis proceeds during the first phase at the lowest applied voltage (300 - 1200 V depending on the orifice dimensions), while bubbles were created thanks to the intense Joule heating inside the orifice during the second phase. Finally, the discharge was ignited at applied voltages over 1600 V. These facts were confirmed by iCCD images taken during all three phases. We concluded, by comparing current-voltage characteristics of different orifice diameter sizes, that this parameter had an important influence on the bubbles generation phase. On the contrary, the diaphragm thickness played an important role at the discharge breakdown. Příspěvek pojednává o generaci diafragmového výboje v roztoku chloridu sodného s vodivostí 275 microS/cm. Fotografie průběhu zapálení byly pořizovány vysokorychlostní iCCD kamerou, která byla nastavena na spínání pomocí procházejícího proudu. Byly sledovány tři fáze buzení výboje – elektrolýza, generace bublin a samotné zapálení výboje. Výboj byl zapalován v oblasti nad 1 600 V. Na fázi generace bublin měla velký vliv zejména velikost otvoru dírky. Na samotné zapálení výboje měla hlavní vliv zejména tloušťka přepážky.

International audience; Time-resolved quantum cascade laser absorption spectroscopy at 1897 cm−1 (5.27 µm) has been applied to study the NO(X) kinetics on the micro- and millisecond time scale in pulsed low-pressure N2/NO dc discharges. Experiments have been performed under flowing and static gas conditions to infer the gas temperature increase and the consequences for the NO line strength. A relatively small increase of ~20 K is observed during the early plasma phase of a few milliseconds. After some 10 ms gas temperatures up to 500 K can be deduced. The experimental data for the NO mixing ratio were compared with the results from a recently developed time-dependent model for pulsed N2–O2 plasmas which are well in accord. The early plasma pulse is determined by vibrational heating of N2 while the excitation of NO(X) by N2 metastables is almost completely balanced. Efficient NO depletion occurs after several milliseconds by N atom impact.

International audience; Thomson scattering using a Bragg grating notch filter is used to determine the electron properties of a pulsed, kHz-driven, non-thermal atmospheric pressure plasma jet in helium expanding in air. The plasma jet is allowed to freely expand or interact with targets with different electrical properties, i.e. glass, copper and water. With the same setup, Raman scattering is used to determine spatially- and time-resolved the densities and rotational temperatures of oxygen and nitrogen molecules entrained into the jet. Fast imaging is used to determine the development of the discharge in the plasma jet as well as its behavior in the plasma-target interaction zone. As the discharge approaches the target, the rise of electron density was followed by the fall of electron temperature. The discharge is influenced only over a few millimeters before it hits the target. The electron density and temperature during the spreading of the discharge on the low-permittivity target are measured to be resp. 2 × 1019 m−3 and ≈1 eV. During the return stroke on the high-permittivity and the metallic target the densities rise with a factor 1.5 resp. 2.2, and the temperature with a factor 2.5 for both cases. The discharges on the high- and low-permittivity targets extinguished soon after the initial impact of the ionization front, while the diffuse discharge on the metallic target extinguished only after the end of the voltage pulse (with a duration of 1 μs). In the diffuse discharge the electron temperature reaches 3.4 eV, the gas temperature increases by approximately 100 K and the electron density increases by approximately a factor three with respect to before its formation.

Thevenet, F. Guaitella, O. Puzenat, E. Guillard, C. Rousseau, A.; Non-thermal plasma as well as photocatalysis is intensively investigated for volatile organic compounds (VOCs) oxidation. Their association exhibits high performances for air pollutant removal and mineralization. Nevertheless, numerous experimental investigations are performed under dry conditions, or on very short range of water vapour amounts. This article aims at determining the influence of water vapour on the oxidation efficiency of (i) photocatalysis, (ii) non-thermal plasma, and (iii) their association. The amount of water vapour investigated in dry conditions ranges from 0 ppm to 23,000 ppm. Acetylene has been selected as a model pollutant. The presence of watervapour in the gas stream induces a strong decrease in the photocatalytic oxidation of acetylene. The mineralization process is modified. The efficiency of acetylene removal by non-thermal plasma decreases regularly with the water vapour amount. Nevertheless, the presence of water vapour improves significantly the selectivity of carbon dioxide. The same tendency is reported for plasma/photocatalysis association. Those results are interpreted in terms of oxidative species modification due to the presence of water. Moreover, the investigation of water vapour contribution into oxidative processes improves the understanding of plasma/photocatalytic association mechanisms. (C) 2008 Elsevier B.V. All rights reserved.

International audience; Plasma/catalyst combination is an active solution to reach high conversion rates at low energetic cost. TiO2 is one of the catalysts frequently used in dielectric barrier discharges. Plasma/TiO2 synergy was already exhibited but the mechanisms still have to be understood. This work distinguishes three main effects involved in the synergy: (a) effect of catalyst on the injected power, (b) the effect of porosity on C2H2 oxidation, and (c) the photocatalytic degradation of C2H2 on TiO2 under plasma exposure. Different glass fibres-based catalytic materials coated with SiO2 and/or TiO2 nano-particles are used to separate these three contributions regarding to C2H2 conversion. It is reported that at constant voltage the injected power is mainly increased by the presence of glass fibres. C2H2 oxidation is mainly enhanced by the macroporosity of glass fibres and in a minor way by the nano-particles. The production of O atoms close to the surface is probably responsible for the higher C2H2 removal efficiency with porous material. The photocatalytic activity of TiO2 is negligible in the plasma except if additional UV lamps are used to activate TiO2.With external UV, photocatalytic activity is more efficient in the plasma phase than in a neutral gas phase. This plasma/photocatalysis synergy is due to the use of O atoms in photocatalytic mechanisms.

International audience; The formation of NO 2 molecules on a Pyrex surface, as a result of NO oxidation by adsorbed O atoms on the wall, is experimentally demonstrated and quantified. The measurements reveal that the characteristic times of heterogeneous NO 2 production and NO gas phase decay change from ?60 to ?1500 s as the gas phase concentration of NO introduced in a tube pretreated with an oxygen radiofrequency discharge increases from 10 13 to 10 15 cm ?3 . Moreover, a clear variation of the characteristic loss frequency of NO molecules when small amounts of NO are successively injected in the tube is detected, between ?7 × 10 ?2 and ?5 × 10 ?3 s ?1 . The complex surface kinetics observed is studied and interpreted with the help of a mesoscopic surface model accounting for Eley?Rideal NO oxidation and slow NO 2 adsorption, confirming the existence of adsorption sites possessing a distribution of reactivity on the surface.

International audience; The first part of the review summarizes the problem of air pollution and related air-cleaning technologies. Volatile organic compounds in particular have various effects on health and their abatement is a key issue. Different ways to couple non-thermal plasmas with catalytic or adsorbing materials are listed. In particular, a comparison between in-plasma and post-plasma coupling is made. Studies dealing with plasma-induced heterogeneous reactivity are analysed, as well as the possible modifications of the catalyst surface under plasma exposure. As an alternative to the conventional and widely studied plasma–catalyst coupling, a sequential approach has been recently proposed whereby pollutants are first adsorbed onto the material, then oxidized by switching on the plasma. Such a sequential approach is reviewed in detail.

International audience; A self-consistent model is developed to study the temporal variation of the gas temperature in millisecond single dc pulsed discharges and their afterglows in air-like mixtures (N2–20%O2) at low pressures. The model is based on the solutions to the time-dependent gas thermal balance equation, under the assumption of a parabolic gas temperature profile across the discharge tube, coupled to the electron, vibrational and chemical kinetics. Modelling results provide a satisfactory explanation for recently published time-resolved experimental data for the gas temperature in a 5 ms pulsed air plasma with a current of 150mA and the corresponding afterglow at a pressure of 133 Pa (1 Torr). It is shown that the main heating mechanisms during the first millisecond of the pulse come predominantly from O2 dissociation by electron impact through the pre-dissociative excited state O2(B 3− u ) and the quenching of nitrogen electronically excited states N2(A 3 u , B 3 g, a 1− u , a 1 g, w 1u) by O2, agreeing with other studies on fast gas heating in air plasmas. As the pulse duration increases, other gas heating sources become important, namely V–T N2–O energy exchanges, recombination of oxygen atoms at the wall, N2(A) quenching by O(3P) and reaction N(4S) NO(X) → N2(X, v ∼3) O, contributing altogether to an additional smooth increase in the gas temperature until the end of the pulse. In the first instants of the early afterglow, the gas temperature decreases very rapidly as a consequence of the minor role played by electronic collisions and due to a fast decay of N2 electronic states. For afterglow times up to 10 ms, the gas temperature continues to decrease, following the time-dependent kinetics of [N2(X,v)], [N(4S)], [O(3P)] and [NO(X)]. Sensitivity of the model to different input parameters such as thermal accommodation coefficient and probabilities for atomic recombination at the wall are reported.

International audience; An extensive electrical study was performed on a coaxial geometry atmospheric pressure plasma jet source in helium, driven by 30 kHz sine voltage. Two modes of operation were observed, a highly reproducible low-power mode that features the emission of one plasma bullet per voltage period and an erratic high-power mode in which micro-discharges appear around the grounded electrode. The minimum of power transfer efficiency corresponds to the transition between the two modes. Effective capacitance was identified as a varying property influenced by the discharge and the dissipated power. The charge carried by plasma bullets was found to be a small fraction of charge produced in the source irrespective of input power and configuration of the grounded electrode. The biggest part of the produced charge stays localized in the plasma source and below the grounded electrode, in the range 1.2–3.3 nC for ground length of 3–8 mm.

International audience; The wall de-excitation probability of vibrationally excited nitrogen molecules was determined using infrared (IR) titration with CO, CO 2 and N 2 O. Gas mixtures of N 2 with 0.05?0.5% of CO (CO 2 or N 2 O) were excited by a pulsed dc discharge at p = 133 Pa in a cylindrical discharge tube. During the afterglow, the vibrational relaxation of titrating molecules was monitored in situ with quantum cascade laser absorption spectroscopy. The value of was deduced from measured vibrational relaxation times using a model of vibrational kinetics in N 2 . It was found that adsorption of IR tracers on the surface may increase the value of by a factor up to two, depending on the molecule and the surface material. It was demonstrated that N 2 O is the most inert and reliable tracer and it was used for the determination of on silica, Pyrex, TiO 2 , Al 2 O 3 and anodized aluminum. Pretreatment of the silica surface by low-pressure plasma was found to have a strong effect on the vibrational de-excitation. Values of measured after O 2 , Ar and N 2 plasma pretreatment of the same silica discharge tube were 5.7 × 10 ?4 , 8.2 × 10 ?4 and 11 × 10 ?4 , respectively. This study clearly demonstrates that the presence of adsorbed atoms and molecules on the surface may significantly alter the value of .

International audience; Using a three-stage dielectric packed-bed plasma reactor at atmospheric pressure, the destruction of ethylene, a typical volatile organic compound, and the generation of major by-products have been studied by means of Fourier Transform Infrared Spectroscopy. A test gas mixture air at a gas flow of 1 slm containing 0.12% humidity with 0.1% ethylene has been used. In addition to the fragmentation of the precursor gas, the evolution of the concentration of ten stable reaction products, CO, CO2, O3, NO2, N2O, HCN, H2O, HNO3, CH2O, and CH2O2 has been monitored. The concentrations of the by-products range between 5 ppm, in the case of NO2, and 1200 ppm, for H2O. By the application of three sequentially working discharge cells at a frequency of f = 4 kHz and voltage values between 9 and 12 kV, a nearly complete decomposition of C2H4 could be achieved. Furthermore, the influence of the specific energy deposition (SED) on the destruction process has been studied and the maximum value of SED was about 900 J l−1. The value of the characteristic energy β, characterizing the energy efficiency of the ethylene destruction in the reactor, was found to be 330 J l−1. It was proven that the application of three reactor stages suppresses essentially the production of harmful by-products as formaldehyde, formic acid, and NO2 compared to the use of only one or two stages. Based on the multi-component detection, the carbon balance of the plasma chemical conversion of ethylene has been analyzed. The dependence of the fragmentation efficiencies of ethylene (RF(C2H4) = 5.5 × 1019 molecules J−1) and conversion efficiencies to the produced molecular species (RC = (0.1–3) × 1016 molecules J−1) on the discharge conditions could be estimated in the multistage plasma reactor.

International audience; We report on experimentally obtained values of the electric field magnitude on a dielectric surface induced by an impinging atmospheric pressure plasma jet. The plasma plume was striking the dielectric surface at an angle of 45◦, at 5mm from the surface measured at the axis of the jet. The results were obtained using Pockels technique on a BSO (Bi12SiO20) crystal. A coaxial configuration of the plasma jet was used, operating in a stable mode with one bullet per voltage period, at 30 kHz and amplitude of 2 kV. The electric field was shown to be a function of the gas flow (He, at 300, 500 and 700 SCCM) and the manner in which the discharge spreads over the dielectric surface. The maximum value of 11.6 × 105Vm−1 was obtained at the negative half-period of the discharge current measured at the grounded electrode, at the flow of 300 SCCM. The largest electric field averaged over the area of the spreading of the discharge (3.6 × 105Vm−1) was found in the same conditions.

International audience; The objective of this study is to understand fundamental aspects of interactions of plasmas with catalytic surfaces. Based on this approach the reactivity of plasma treated and stimulated catalytic surfaces of TiO2 is studied by analysing the oxidation (i) of C2H2 to CO and CO2 and (ii) of CO to CO2. The inner surface of a Pyrex discharge tube is coated with TiO2 films impregnated with TiO2 nanoparticles, which provides a surface area of about 4 m2. In addition to the exposure of the TiO2 surface by low-pressure radio-frequency plasmas using O2, Ar or N2 (f = 13.56 MHz, p = 0.53 mbar, P = 17 W) the surfaces are stimulated by heating and UV radiation treatment. The temporal development of the concentrations of the precursor gases C2H2 or CO and of the reaction products is monitored using quantum cascade laser absorption spectroscopy, which provides multi-component detection in the mid-infrared spectral range. The C2H2 concentration was found to be nearly constant over time after a pre-treatment with Ar or N2 discharges using an initial gas mixture of 1% C2H2 in Ar. However, a strong decay of the concentration of C2H2 is observed for pure O2 plasma pre-treatment. In general, the decay is found to be nearly exponential with time constant in the order of about 10 min. The reactive adsorption of C2H2 molecules on the inner surface of the tube reactor showed a density of about 7.5 × 1012 C2H2 molecules cm−2. This behaviour demonstrates that the reaction (\rm O_\rm ads \rm C_2 \rm H_2)_\rm TiO_2 produces some adsorbed intermediates, which can be thermally or photo-catalytically oxidized to CO2. In contrast, when 1% CO in Ar is used as an initial gas mixture no adsorption processes on the TiO2 surface could be detected. An effective destruction of CO took part via photo-catalytic oxidation.