Chemical kinetics and reactive species in atmospheric pressure helium-oxygen plasmas with humid-air impurities

In most applications helium-based plasma jets operate in an open-air environment. The presence of humid air in the plasma jet will influence the plasma chemistry and can lead to the production of a broader range of reactive species. We explore the influence of humid air on the reactive species in radio frequency (rf)-driven atmospheric-pressure helium-oxygen mixture plasmas (He-O, helium with 5000 ppm admixture of oxygen) for wide air impurity levels of 0-500 ppm with relative humidities of from 0% to 100% using a zero-dimensional, time-dependent global model. Comparisons are made with experimental measurements in an rf-driven micro-scale atmospheric pressure plasma jet and with one-dimensional semi-kinetic simulations of the same plasma jet. These suggest that the plausible air impurity level is not more than hundreds of ppm in such systems. The evolution of species concentration is described for reactive oxygen species, metastable species, radical species and positively and negatively charged ions (and their clusters). Effects of the air impurity containing water humidity on electronegativity and overall plasma reactivity are clarified with particular emphasis on reactive oxygen species. © 2013 IOP Publishing Ltd.

Synthesis of surfactant-free electrostatically stabilized gold nanoparticles by plasma-induced liquid chemistry

Plasma-induced non-equilibrium liquid chemistry is used to synthesize gold nanoparticles (AuNPs) without using any reducing or capping agents. The morphology and optical properties of the synthesized AuNPs are characterized by transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy. Plasma processing parameters affect the particle shape and size and the rate of the AuNP synthesis process. Particles of different shapes (e. g. spherical, triangular, hexagonal, pentagonal, etc) are synthesized in aqueous solutions. In particular, the size of the AuNPs can be tuned from 5 nm to several hundred nanometres by varying the initial gold precursor (HAuCl4) concentration from 2.5 mu M to 1 mM. In order to reveal details of the basic plasma-liquid interactions that lead to AuNP synthesis, we have measured the solution pH, conductivity and hydrogen peroxide (H2O2) concentration of the liquid after plasma processing, and conclude that H2O2 plays the role of the reducing agent which converts Au+3 ions to Au-0 atoms, leading to nucleation growth of the AuNPs.

Investigating the dynamics of laser induced sparks in atmospheric helium using Rayleigh and Thomson scattering

We have used optical Rayleigh and Thomson scattering to investigate the expansion dynamics of laser induced plasma in atmospheric helium and to map its electron parameters both in time and space. The plasma is created using 9 ns duration, 140 mJ pulses from a Nd:YAG laser operating at 1064 nm, focused with a 10 cm focal length lens, and probed with 7 ns, 80 mJ, and 532 nm Nd:YAG laser pulses. Between 0.4 μs and 22.5 μs after breakdown, the electron density decreases from 3.3 × 1017 cm−3 to 9 × 1013 cm−3, while the temperature drops from 3.2 eV to 0.1 eV. Spatially resolved Thomson scattering data recorded up to 17.5 μs reveal that during this time the laser induced plasma expands at a rate given by R ∼ t0.4 consistent with a non-radiative spherical blast wave. This data also indicate the development of a toroidal structure in the lateral profile of both electron temperature and density. Rayleigh scattering data show that the gas density decreases in the center of the expanding plasma with a central scattering peak reemerging after about 12 μs. We have utilized a zero dimensional kinetic global model to identify the dominant particle species versus delay time and this indicates that metastable helium and the He2 + molecular ion play an important role.

Evolution of Hot Loops in an Active Region Core Observed with the SDO Atmospheric Image Assembly

Evidence has accumulated of high temperature (> 4 MK) coronal emission in active region cores that corresponds to structures in equilibrium. Other studies have found evidence of evolving loops. We investigate the EUV intensity and temperature variations of short coronal loops observed in the core of NOAA Active Region 11250 on 13 July 2011. The loops, which run directly between the AR opposite polarities, are first detectable in the 94Å band of Fe XVIII, implying an effective temperature ~ 7 MK. The low temperature component of the 94 Å signal is modeled in terms of a linear superposition of the 193 Å and 171 Å signals in order to separate the hot component. After identifying the loops we have used contemporaneous HMI observations to identify the corresponding inter-moss regions, and we have investigated their time evolution in six AIA EUV channels. The results can be separated into two classes. Group 1 (94Å, 335Å, 211Å) is characterized by hotter temperatures (~2-7 MK), and Group 2 (193Å, 171Å, 131Å) by cooler temperatures (0.4 - 1.6 MK). For Group 1 the intensity peaks in the 94Å channel are followed by maxima in the 335 Å channel with a time lag of ~8 min, suggestive of a cooling pattern with an exponential decay. While the 211Å maxima follow those in the 335 Å channel, there is no systematic relation which would indicate a progressive cooling process through the lower temperatures, as has been observed in other investigations. In Group 2 the signals in the 171 and 131Å channels track each other closely, and lag behind the 193Å. In the inter-moss region of the loop the peak temperature and peak emission measure have opposite trends. The hot 94Å brightenings occur in the central part of the loops with maximum temperatures ~7 MK. Subsequently the loops appear to fill with plasma with an emission measure compatible with the 193 Å signal and temperature in the range ~ 1.5-2 MK. Although the exact details of the time evolution are still under investigation, these non static loops show high levels of intermittency in the 94Å signal (please see poster "Intermittent and Scale-Invariant Intensity Fluctuations in Hot Coronal Loops," by Lawrence et al. in this session).

Enhanced Dispersion of TiO2 Nanoparticles in a TiO2/PEDOT:PSS Hybrid Nanocomposite via Plasma-Liquid Interactions

A facile method to synthesize a TiO2/PEDOT:PSS hybrid nanocomposite material in aqueous solution through direct current (DC) plasma processing at atmospheric pressure and room temperature has been demonstrated. The dispersion of the TiO2 nanoparticles is enhanced and TiO2/polymer hybrid nanoparticles with a distinct core shell structure have been obtained. Increased electrical conductivity was observed for the plasma treated TiO2/PEDOT:PSS nanocomposite. The improvement in nanocomposite properties is due to the enhanced dispersion and stability in liquid polymer of microplasma treated TiO2 nanoparticles. Both plasma induced surface charge and nanoparticle surface termination with specific plasma chemical species are proposed to provide an enhanced barrier to nanoparticle agglomeration and promote nanoparticle-polymer binding.

Magnetospheric Structure and Atmospheric Joule Heating of Habitable Planets Orbiting M-dwarf Stars

We study the magnetospheric structure and the ionospheric Joule Heating of planets orbiting M-dwarf stars in the habitable zone using a set of magnetohydrodynamic models. The stellar wind solution is used to drive a model for the planetary magnetosphere, which is coupled with a model for the planetary ionosphere. Our simulations reveal that the space environment around close-in habitable planets is extreme, and the stellar wind plasma conditions change from sub- to super-Alfvénic along the planetary orbit. As a result, the magnetospheric structure changes dramatically with a bow shock forming in the super-Alfvénic sectors, while no bow shock forms in the sub-Alfvénic sectors. The planets reside most of the time in the sub-Alfvénic sectors with poor atmospheric protection. A significant amount of Joule Heating is provided at the top of the atmosphere as a result of the intense stellar wind. For the steady-state solution, the heating is about 0.1%-3% of the total incoming stellar irradiation, and it is enhanced by 50% for the time-dependent case. The significant Joule Heating obtained here should be considered in models for the atmospheres of habitable planets in terms of the thickness of the atmosphere, the top-side temperature and density, the boundary conditions for the atmospheric pressure, and particle radiation and transport. Here we assume constant ionospheric Pedersen conductance similar to that of the Earth. The conductance could be greater due to the intense EUV radiation leading to smaller heating rates. We plan to quantify the ionospheric conductance in future study.

Liquid chromatography-tandem mass spectrometry (LC/APCI-MS/MS) methods for the quantification of captan and folpet phthalimide metabolites in human plasma and urine.

Captan and folpet are fungicides largely used in agriculture. They have similar chemical structures, except that folpet has an aromatic ring unlike captan. Their half-lives in blood are very short, given that they are readily broken down to tetrahydrophthalimide (THPI) and phthalimide (PI), respectively. Few authors measured these biomarkers in plasma or urine, and analysis was conducted either by gas chromatography coupled to mass spectrometry or liquid chromatography with UV detection. The objective of this study was thus to develop simple, sensitive and specific liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry (LC/APCI-MS/MS) methods to quantify both THPI and PI in human plasma and urine. Briefly, deuterated THPI was added as an internal standard and purification was performed by solid-phase extraction followed by LC/APCI-MS/MS analysis in negative ion mode for both compounds. Validation of the methods was conducted using spiked blank plasma and urine samples at concentrations ranging from 1 to 250 μg/L and 1 to 50 μg/L, respectively, along with samples of volunteers and workers exposed to captan or folpet. The methods showed a good linearity (R (2) > 0.99), recovery (on average 90% for THPI and 75% for PI), intra- and inter-day precision (RSD, <15%) and accuracy (<20%), and stability. The limit of detection was 0.58 μg/L in urine and 1.47 μg/L in plasma for THPI and 1.14 and 2.17 μg/L, respectively, for PI. The described methods proved to be accurate and suitable to determine the toxicokinetics of both metabolites in human plasma and urine.

Etude spectroscopique d’un plasma micro-onde à la pression atmosphérique et son application à la synthèse de nanostructures

L’objectif de ce mémoire de maîtrise est de caractériser la distribution axiale des plasmas tubulaires à la pression atmosphérique créés et entretenus par une onde électromagnétique de surface ainsi que d’explorer le potentiel de ces sources pour la synthèse de matériaux et de nanomatériaux. Un précédent travail de thèse, qui avait pour objectif de déterminer les mécanismes à l’origine de la contraction radiale du plasma créé dans des gaz rares, a mis en lumière un phénomène jusque-là inconnu dans les plasmas d’onde de surface (POS). En effet, la distribution axiale varie différemment selon la puissance incidente ce qui constitue une différence majeure par rapport aux plasmas à pression réduite. Dans ce contexte, nous avons réalisé une étude paramétrique des POS à la pression atmosphérique dans l’Ar. À partir de nos mesures de densité électronique, de température d’excitation et de densité d’atomes d’Ar dans un niveau métastable (Ar 3P2), résolues axialement, nous avons conclu que le comportement axial de l’intensité lumineuse avec la puissance n’est pas lié à un changement de la cinétique de la décharge (qui est dépendante de la température des électrons et de la densité d’atomes d’Ar métastables), mais plutôt à une distribution anormale de dissipation de puissance dans le plasma (reliée à la densité d’électrons). Plus précisément, nos résultats suggèrent que ce dépôt anormal de puissance provient d’une réflexion de l’onde dans le fort gradient de densité de charges en fin de colonne, un effet plus marqué pour de faibles longueurs de colonnes à plasma. Ensuite, nous avons effectué une étude spectroscopique du plasma en présence de précurseurs organiques, en particulier le HMDSO pour la synthèse de matériaux organosiliciés et l’IPT pour la synthèse de matériaux organotitaniques. Les POS à la PA sont caractérisés par des densités de charges très élevées (>10^13 cm^-3), permettant ainsi d’atteindre des degrés de dissociation des précurseurs nettement plus élevés que ceux d'autres plasmas froids à la pression atmosphérique comme les décharges à barrière diélectrique. Dans de tels cas, les matériaux synthétisés prennent la forme de nanopoudres organiques de taille inférieure à 100 nm. En présence de faibles quantités d’oxygène dans le plasma, nous obtenons plutôt des nanopoudres à base d’oxyde de silicium (HMDSO) ou à base de titanate de silicium (IPT), avec très peu de carbone.

Anomalous profile of a self-reversed resonance line from Ba+ in a laser produced plasma from YBa2Cu307

A laser produced plasma from the multielement solid target YBa2Cu3O7 is generated using 1.06 μm, 9 ns pulses from a Q-switched Nd:YAG laser in air at atmospheric pressure. A time resolved analysis of the profile of the 4554.03 Å resonance line emission from Ba II at various laser power densities has been carried out. It has been found that the line has a profile which is strongly self-reversed. It is also observed that at laser power densities equal to or exceeding 1.6×1011 W cm−2, a third peak begins to develop at the centre of the self-reversed profile and this has been interpreted as due to the anisotropic resonance scattering (fluorescence). The number densities of singly ionized barium ions evaluated from the width of the resonance line as a function of time delay with respect to the beginning of the laser pulse give typical values of the order of 1019 cm−3. The higher ion concentrations existing at smaller time delays are seen to decrease rapidly. The Ba II ions in the ground state resonantly absorb the radiation and this absorption is maximum around 120 ns after the laser pulse.

Analysis of incoherent scatter radar data from non-thermal F-region plasma

A procedure is presented for fitting incoherent scatter radar data from non-thermal F-region ionospheric plasma, using theoretical spectra previously predicted. It is found that values of the shape distortion factor D∗, associated with deviations of the ion velocity distribution from a Maxwellian distribution, and ion temperatures can be deduced (the results being independent of the path of iteration) if the angle between the line-of-sight and the geomagnetic field is larger than about 15–20°. The procedure can be used with one or both of two sets of assumptions. These concern the validity of the adopted model for the line-of-sight ion velocity distribution in the one case or for the full three-dimensional ion velocity distribution function in the other. The distribution function employed was developed to describe the line-of-sight velocity distribution for large aspect angles, but both experimental data and Monte Carlo simulations indicate that the form of the field-perpendicular distribution can also describe the distribution at more general aspect angles. The assumption of this form for the line-of-sight velocity distribution at a general aspect angle enables rigorous derivation of values of the one-dimensional, line-of-sight ion temperature. With some additional assumptions (principally that the field-parallel distribution is always Maxwellian and there is a simple relationship between the ion temperature anisotropy and the distortion of the field-perpendicular distribution from a Maxwellian), fits to data for large aspect angles enable determination of line-of-sight temperatures at all aspect angles and hence, of the average ion temperature and the ion temperature anisotropy. For small aspect angles, the analysis is restricted to the determination of the line-of-sight ion temperature because the theoretical spectrum is insensitive to non-thermal effects when the plasma is viewed along directions almost parallel to the magnetic field. This limitation is expected to apply to any realistic model of the ion velocity distribution function and its consequences are discussed. Fit strategies which allow for mixed ion composition are also considered. Examples of fits to data from various EISCAT observing programmes are presented.

Scattered power from non-thermal, F-region plasma observed by EISCAT—evidence for coherent echoes?

Three rapid, poleward bursts of plasma flow, observed by the U.K.-POLAR EISCAT experiment, are studied in detail. In all three cases the large ion velocities (> 1 kms−1) are shown to drive the ion velocity distribution into a non-Maxwellian form, identified by the characteristic shape of the observed spectra and the fact that analysis of the spectra with the assumption of a Maxwellian distribution leads to excessive rises in apparent ion temperature, and an anticorrelation of apparent electron and ion temperatures. For all three periods the total scattered power is shown to rise with apparent ion temperature by up to 6 dB more than is expected for an isotropic Maxwellian plasma of constant density and by an even larger factor than that expected for non-thermal plasma. The anomalous increases in power are only observed at the lower altitudes (< 300 km). At greater altitudes the rise in power is roughly consistent with that simulated numerically for homogeneous, anisotropic, non-Maxwellian plasma of constant density, viewed using the U.K.-POLAR aspect angle. The spectra at times of anomalously high power are found to be asymmetric, showing an enhancement near the downward Doppler-shifted ion-acoustic frequency. Although it is not possible to eliminate completely rapid plasma density fluctuations as a cause of these power increases, such effects cannot explain the observed spectra and the correlation of power and apparent ion temperature without an unlikely set of coincidences. The observations are made along a beam direction which is as much as 16.5° from orthogonality with the geomagnetic field. Nevertheless, some form of coherent-like echo contamination of the incoherent scatter spectrum is the most satisfactory explanation of these data.

EISCAT observations of plasma convection and the high-latitude, winter F-region during substorm activity

A 24 h period of observations by the EISCAT radar and other ground-based instrumentation is used to study the role of plasma convection in determining the morphology of the high-latitude F-region during winter. It is suggested that, in the afternoon sector of the polar convection pattern, rapid zonal (westward) flows caused low F-region electron densities due to an extension of the mid-latitude trough far into the sunlit hemisphere. Low densities on the dawn side prior to 0600 UT may also have been due to a trough-like feature. Although the generation mechanism is unclear, the trough may be the fossil remnant of a substorm. Around midnight, high F-region densities were seen, probably due to plasma flow emerging from the cap through soft particle precipitation in the auroral oval. Two substorms occurred at times when the radar was south of the auroral oval. Both caused enhanced convection speeds, a swing to equatorward flow, enhanced E-region densities and a depleted F-region. The first was seen as a Westward Travelling Surge, and the swing to purely southward flow which followed the surge front did not return to westward flows until 80–110 min later. The Harang discontinuity was observed co-rotating eastwards between the substorms, 65 ± 30 min before the separatrix between the dawn and dusk convection cells.