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The addition of small amounts of H2 were investigated in a DC glow discharge in N2, at low pressure (~1 mbar) and low power (0.05 to 0.2 W.cm-3). We quantified the electric field, the electron density, the ammonia production and the formation of positive ions for amounts of H2 varying between 0 and 5%, pressure values between 0.5 and 4 mbar, and currents between 10 and 40 mA. The addition of less than 1% H2 has a strong effect on the N2 plasma discharges. Hydrogen quenches the (higher) vibrational levels of N2 and some of its highly energetic metastable states. This leads to the increase of the discharge electric field and consequently of the average electron energy. As a result, higher quantities of radical and excited species are suspected to be produced. The addition of hydrogen also leads to the formation of new species. In particular, ammonia and hydrogen-bearing ions have been observed: N2H+ and NH4+ being the major ones, and also H3+, NH+, NH2+, NH3+, N3H+ and N3H3+. The comparison to a radiofrequency capacitively coupled plasma (RF CCP) discharge in similar experimental conditions shows that both discharges led to similar observations. The study of N2-H2 discharges in the laboratory in the adequate ionization conditions then gives some insights on which plasma species made of nitrogen and hydrogen could be present in the ionosphere of Titan. Here, we identified some protonated ions, which are reactive species that could participate to the erosion of organic aerosols on Titan., Comment: Paper accepted in Plasma Sources Science and Technology in March 2023. The current version on arXiv is the submitted version

Plasma jets are sources of repetitive and stable ionization waves, meant for applications where they interact with surfaces of different characteristics. As such, plasma jets provide an ideal testbed for the study of transient reproducible streamer discharge dynamics, particularly in inhomogeneous gaseous mixtures, and of plasma–surface interactions. This topical review addresses the physics of plasma jets and their interactions with surfaces through a pedagogical approach. The state-of-the-art of numerical models and diagnostic techniques to describe helium jets is presented, along with the benchmarking of different experimental measurements in literature and recent efforts for direct comparisons between simulations and measurements. This exposure is focussed on the most fundamental physical quantities determining discharge dynamics, such as the electric field, the mean electron energy and the electron number density, as well as the charging of targets. The physics of plasma jets is described for jet systems of increasing complexity, showing the effect of the different components (tube, electrodes, gas mixing in the plume, target) of the jet system on discharge dynamics. Focussing on coaxial helium kHz plasma jets powered by rectangular pulses of applied voltage, physical phenomena imposed by different targets on the discharge, such as discharge acceleration, surface spreading, the return stroke and the charge relaxation event, are explained and reviewed. Finally, open questions and perspectives for the physics of plasma jets and interactions with surfaces are outlined.

The debate of whether a glass substrate can be used in Fourier transform infrared spectroscopy is strongly linked to its potential clinical application. Histopathology glass slides of 1 mm thickness absorb the mid-IR spectrum in the rich fingerprint spectral region. Thus, it is important to assess whether emerging IR techniques can be employed to study biological samples placed on glass substrates. For this purpose, we used optical photothermal infrared (O-PTIR) spectroscopy to study for the first time malignant and non-malignant lung cells with the purpose of identifying IR spectral differences between these cells placed on standard pathology glass slides. The data in this feasibility study showed that O-PTIR can be used to obtain good-quality IR spectra from cells from both the lipid region (3000-2700 cm-1) and the fingerprint region between 1770 and 950 cm-1 but with glass contributions from 1350 to 950 cm-1. A new single-unit dual-range (C-H/FP) quantum cascade laser (QCL) IR pump source was applied for the first time, delivering a clear synergistic benefit to the classification results. Furthermore, O-PTIR is able to distinguish between lung cancer cells and non-malignant lung cells both in the lipid and fingerprint regions. However, when these two spectral ranges are combined, classification accuracies are enhanced with Random Forest modeling classification accuracy results ranging from 96 to 99% across all three studied cell lines. The methodology described here for the first time with a single-unit dual-range QCL for O-PTIR on glass is another step toward its clinical application in pathology.

Plasma catalysis is gaining increasing interest for various applications, but the underlying mechanisms are still far from understood. Hence, more fundamental research is needed to understand these mechanisms. This can be obtained by both modelling and experiments. This foundations paper describes the fundamental insights in plasma catalysis, as well as efforts to gain more insights by modelling and experiments. Furthermore, it discusses the state-of-the-art of the major plasma catalysis applications, as well as successes and challenges of technology transfer of these applications.

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.

International audience; 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., n.d.) 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°), 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.

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.

Pockels-based Mueller polarimetry is presented as a novel diagnostic technique for studying time and space-resolved and in-situ the interaction between an organic sample (a layer of onion cells) and non-thermal atmospheric pressure plasma. The effect of plasma is complex, as it delivers electric field, radicals, (UV) radiation, non-uniform in time nor in space. This work shows for the first time that the plasma-surface interaction can be characterized through the induced electric field in an electro-optic crystal (birefringence caused by the Pockels effect) while at the same moment the surface evolution of the targeted sample is monitored (depolarization) which is attached to the crystal. As Mueller polarimetry allows for separate detection of depolarization and birefringence, it is possible to decouple the entangled effects of the plasma. In the sample three spatial regions are identified where the surface evolution of the sample differs. This directly relates to the spatial in-homogeneity of the plasma at the surface characterized through the detected electric field. The method can be applied in the future to investigate plasma-surface interactions for various targets ranging from bio-films, to catalytic surfaces and plastics/polymers.

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.

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.

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

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; Organic aerosols formed in Titan's upper atmosphere are surrounded by very reactive plasma species. The present work aims to study the potential interactions between aerosols and plasma species. The exposure of aerosols to plasma is simulated in a cold plasma reactor. IR transmission spectroscopy gives clues about the chemical modifications of the aerosols. Mass spectrometry simultaneously measures the neutral species and positive ions in the gas phase. We observe the formation of HCN and carbocations while ammonia density is decreased by the addition of organic aerosols in the N2-H2 plasma.

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 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.

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; 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.

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.

Low temperature plasmas at atmospheric pressure are usable on materials sensitive to high temperatures, (bio)materials that are not resistant to vacuuming or even fully drying, (bio)targets that are sensitive to significant current transfer. A great number of scientific publications has followed this rise in interest for atmospheric pressure plasmas and they most commonly address the discharge dynamics, densities of heavy species, at times gas temperature measurements, imaging of flow fields and rarely electron densities and electric field but very few on electric field measurements. This paper will give an overview of the recent work in the electric field measurements in atmospheric pressure plasma jets that operate in the ’bullet mode’ when in contact with various surfaces. The results focus on the comparison between the jets driven by 30 kHz sine voltage and jets driven by short high voltage pulses. Two measurement methods have been used that allow for comparison between the electric field in the gas phase and on the treated targets, which vary from dielectrics to liquids. Acknowledgement European Cooperation in Science and Technology Action COST TD1208 for financial support for a short-term scientific mission.

Low temperature plasmas at atmospheric pressure offers possibilities that were not accessible to plasma-based technologies for a long time, such as usage on materials sensitive to high temperatures, (bio)materials that are not resistant to vacuuming or even fully drying, (bio)targets that are sensitive to significant current transfer. In addition to the simplicity with which the plasma sources can be built and the ease with which they can be operated, lot temperature plasmas have become very popular in the recent years. A great number of scientific publications has followed this rise in interest for atmospheric pressure plasmas, covering different geometries of mostly dielectric barrier discharges (DBDs), used with or without gas flow and a wide range of excitation frequencies from Hz to MHz. Most commonly reports address the discharge dynamics, densities of heavy species, at times gas temperature measurements, imaging of flow fields and rarely electron densities and electric field but very few on electric field measurements. This paper will give an overview of the recent work in the electric field measurements in atmospheric pressure plasma jets that operate in the ’bullet mode’. A Helium jet with flow rates up to 2 SLM, in a low-power mode (up to 1 W dissipated in the discharge). The jet is run in the bullet mode where one plasma bullet is emitted per voltage period. The results fill focus on the comparison between the jets driven by 30 kHz sine voltage and jets driven by short high voltage pulses. Two measurement methods have been used that allow for comparison between the electric field in the gas phase and on the treated targets, which vary from dielectrics to liquids.

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; 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; 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.

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; 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.

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.

The photodegradation of acetylene (C 2 H 2 ) was investigated over various powders or supported titanium dioxide (TiO 2 ) photocatalysts in air into static conditions. It was found that UV-irradiated TiO 2 is effective in order to lead to the complete mineralization of the pollutant containing a triple carbon carbon bonding without deactivating. No organic intermediates were detected in the gas phase, implying that oxidation mechanisms take place in the adsorbed phase. The efficiency of P25-Degussa and PC500-Millennium photocatalysts were compared; the mixed anatase/rutile P25-Degussa is reported as the most efficient photocatalytical material in our conditions. The topology of the photocatalyst support is reported as a significant parameter in TiO 2 efficiency. Fibre-deposited photocatalysts lead to the highest activity, and the chemical nature of the fibre did not influence the photodegradation. The influence of TiO 2 amonut, silica binder and adsorbing additives such as zeolite, and activated carbon coupled with TiO 2 photocatalyst were investigated.

International audience; The regeneration of isopropanol (IPA) and/or acetone saturated TiO2 surface by ozone is investigated. TiO2 catalyst is placed downstream a dielectric barrier discharge and is subsequently exposed to ozone considered as the main oxidative species generated by non-thermal plasma and able to interact with the material surface at room temperature. The oxidation of isopropanol and/or acetone is monitored using two parallel and complementary infrared diagnostics: (1) Fourier Transform Infrared Spectroscopy for the analysis of the gas phase composition; and (2) Diffuse Reflectance Infrared Fourier Transform Spectroscopy for the in situ analysis of the adsorbent/catalyst surface. In this study, the pollutant is first adsorbed on the TiO2 surface, the plasma being switched off. The irreversibly adsorbed amounts of isopropanol and acetone have been respectively quantified as 5.3 μmol/m2 and 1.9 μmol/m2. In a second step, the plasma is switched on to regenerate the surface by mineralization of the adsorbed organic species. A 70-min plasma phase, with approximately 20 ppm of ozone constantly flowing through the adsorbent bed yields 8.5 nmol and 8.9 nmol of CO2 per injected joule of energy for isopropanol and acetone saturated surfaces, respectively. Acetone has been evidenced as the main oxidation intermediate of isopropanol on TiO2 surface. It has been proven that the complete oxidation of isopropanol and acetone is mainly limited by the acetone oxidation rate. Competitive adsorption on the surface of the catalyst between both compounds has been studied. Results obtained are compared with those observed in the photocatalytic oxidation of the same species.

International audience; Successive discharges of alternating polarities in distilled water have been studied. Cathode-initiated discharges develop in two possible configurations: slow and weakly luminescent bushlike mode or fast and luminous treelike mode with well-pronounced branching. Under our experimental conditions, the two modes originate with approximately equal probability. Positive discharge demonstrates only one discharge morphology with two hemispherical weakly luminescent structures. Successive negative pulse results in the formation of one of the negative modes, bushlike or treelike.

International audience; A compact and transportable three channel quantum cascade laser system (TRIPLE Q) based on mid-infrared absorption spectroscopy has been developed for time-resolved plasma diagnostics. The TRIPLE Q spectrometer encompasses three independently controlled quantum cascade lasers (QCLs), which can be used for chemical sensing, particularly for gas phase analysis of plasmas. All three QCLs are operated in the intra-pulse mode with typical pulse lengths of the order of 150 ns. Using a multiplexed detection, a time resolution shorter than 1 μs can be achieved. Hence, the spectrometer is well suited to study kinetic processes of multiple infrared active compounds in reactive plasmas. A special data processing and analysis technique has been established to account for time jitter effects of the infrared emission of the QCLs. The performance of the TRIPLE Q system has been validated in pulsed direct current plasmas containing N2O/air and NO2/air.

This paper is an experimental study of a pulsed filamentary plasma discharge inside liquid water in pin-to-plane electrode configuration. Time-resolved electrical and imaging diagnostics have been performed. The initiation and the propagation of the discharge have been studied for several experimental parameters. The propagation is continuous and is followed by reilluminations at low water conductivity. The measured propagation velocity of the plasma discharge is 30 km s−1for the secondary positive mode. This velocity was found to be surprisingly constant whatever the experimental parameters and especially as a function of the water conductivity.

International audience; Analysis of available data on electric field measurements in surface dielectric barrier discharges (DBDs) was carried out. Experimental measurements of emission spectra in triggered and non–triggered sinusoidal surface DBD were performed. The obtained results were used for the calculation of electric field value. The comparison of data obtained and the results published by other authors is presented.