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Abstract Plasmas interacting with liquid surfaces produce a complex interfacial layer where the local chemistry in the liquid is driven by fluxes from the gas phase of electrons, ions, photons, and neutral radicals. Typically, the liquid surface has at best mild curvature with the fluxes of impinging plasma species and applied electric field being nominally normal to the surface. With liquids such as water having a high dielectric constant, structuring of the liquid surface by producing a wavy surface enables local electric field enhancement due to polarization of the liquid, as well as producing regions of higher and lower advective gas flow across the surface. This structuring (or waviness) can naturally occur or can be achieved by mechanical agitation such as with acoustic transducers. Electric field enhancement at the peaks of the waves of the liquid produces local increases in sources of reactive species and incident plasma fluxes which may be advantageous for plasma driven solution electrochemistry (PDSE) applications. In this paper, results are discussed from a computational investigation of pulsed atmospheric pressure plasma jets onto structured water solutions containing AgNO₃as may be used in PDSE for silver nanoparticle (NP) formation. The solution surface consists of standing wave patterns having wavelength and wave depth of hundreds of microns to 1 mm. The potential for structured liquid surfaces to facilitate spatially differentiated chemical selectivity and enhance NP synthesis in the context of PDSE is discussed. 

Abstract Planar laser-induced fluorescence (LIF) was employed to measure the absolute density of hydroxyl radicals (OH) in the effluent of the COST Reference Microplasma Jet for two feed gas mixtures: He/H₂O and He/O₂. Experiments were conducted with the effluent propagating into air and N₂environments. For the He/H₂O case, measurements were also performed with the effluent impinging on a solid target at varying distances from the jet nozzle. Calibration of the OH-LIF signal from the COST-Jet was achieved by comparing it to a reference signal generated by the photofragmentation of H₂O₂. Results demonstrated that OH densities were sustained longer when the effluent propagates in a nitrogen environment compared to air, particularly with water added to the feed gas. The broader OH distribution in N₂suggests slower consumption due to the absence of oxygen, which accelerates OH depletion in air via reactions involving O₂and HO₂. Even when water was not added to the feed, as in the He/O₂case, appreciable OH densities were observed, due to gas impurities and reactive species interactions with atmospheric humidity, forming reaction fronts that delineate the gas flow. Two-dimensional fluid dynamics simulations elucidated the influence of atmospheric gas entrainment and solid targets on the OH distribution. Experimental trends were further compared with a zero-dimensional chemistry model to explore OH production and consumption mechanisms in air and nitrogen environments. 

Abstract Cold atmospheric plasma devices have shown promise for a variety of plasma medical applications, including wound healing and bacterial inactivation often performed in liquids. In the latter application, plasma-produced reactive oxygen and nitrogen species (RONS) interact with and damage bacterial cells, though the exact mechanism by which cell damage occurs is unclear. Computational models can help elucidate relationships between plasma-produced RONS and cell killing by enabling direct comparison between dissimilar plasma devices and by examining the effects of changing operating parameters in these devices. In biological applications, computational models of plasma-liquid interactions would be most effective in design and optimization of plasma devices if there is a corresponding prediction of the biological outcome. In this work, we propose a hierarchal model for planktonic bacterial cell inactivation by plasma produced RONS in liquid. A previously developed reaction mechanism for plasma induced modification of cysteine was extended to provide a basis for cell killing by plasma-produced RONS. Results from the model are compared to literature values to provide proof of concept. Differences in time to bacterial inactivation as a function of plasma operating parameters including gas composition and plasma source configuration are discussed. Results indicate that optimizing gas-phase reactive nitrogen species production may be key in the design of plasma devices for disinfection. 

Abstract Remote plasmas are used in semiconductor device manufacturing as sources of radicals for chamber cleaning and isotropic etching. In these applications, large fluxes of neutral radicals (e.g. F, O, Cl, H) are desired with there being negligible fluxes of potentially damaging ions and photons. One remote plasma source (RPS) design employs toroidal, transformer coupling using ferrite cores to dissociate high flows of moderately high pressure (up to several Torr) electronegative gases. In this paper, results are discussed from a computational investigation of moderate pressure, toroidal transformer coupled RPS sustained in Ar and Ar/NF₃mixtures. Operation of the RPS in 1 Torr (133 Pa) of argon with a power of 1.0 kW at 0.5 MHz and a single core produces a continuous toroidal plasma loop with current continuity being maintained dominantly by conduction current. Operation with dual cores introduces azimuthal asymmetries with local maxima in plasma density. Current continuity is maintained by a mix of conduction and displacement current. Operation in NF₃for the same conditions produces essentially complete NF₃dissociation. Electron depletion as a result of dissociative attachment of NF₃and NF_xfragments significantly alters the discharge topology, confining the electron density to the downstream portion of the source where the NF_xdensity has been lowered by this dissociation. 

Abstract The electric field distribution in the ionization waves propagating over a microchannel array dielectric surface, with the channels either empty or filled with distilled water, is measured by ps Electric Field Induced Second Harmonic (EFISH) generation. The surface ionization wave is initiated by the atmospheric pressure N2-Ar plasma jet impinging on the surface vertically and powered by ns pulse discharge bursts. The results show that the electric field inside the microchannels, specifically its horizontal component, is enhanced by up to a factor of 2. The field enhancement region is localized within the channels. The vertical electric field inside the channels lags in time compared to the field measured at the ridges, indicating the transient reversal of the ionization wave propagation direction across the channels (toward the jet). This is consistent with the phase-locked plasma emission images and confirmed by the kinetic modeling predictions, which show that the ionization wave “jumps” over the empty channels and propagates into the channels only after the jump between the adjacent ridges. When the channels are filled with water, the wave speed increases by up to 50%, due to the higher effective dielectric constant of the surface. No evidence of a significant electric field enhancement near the dielectric surface (ceramic or water) has been detected, within the spatial resolution of the present diagnostic, ~100 μm. 

Abstract Atmospheric pressure plasma jets (APPJs) are increasingly being used to functionalize polymers and dielectric materials for biomedical and biotechnology applications. Once such application is microfluidic labs-on-a-chip consisting of dielectric slabs with microchannel grooves hundreds of microns in width and depth. The periodic channels, an example of a complex surface, present challenges in terms of directly and uniformly exposing the surface to the plasma. In this paper, we discuss results from computational and experimental investigations of negative APPJs sustained in Ar/N₂mixtures flowing into ambient air and incident onto a series of microchannels. Results from two-dimensional plasma hydrodynamics modeling are compared to experimental measurements of electric field and fast-camera imaging. The propagation of the plasma across dry microchannels largely consists of a sequence of surface ionization waves (SIWs) on the top ridges of the channels and bulk ionization waves (IWs) crossing over the channels. The IWs are directed into electric field enhanced vertices of the next ridge. The charging of these ridges produce reverse IWs responsible for the majority of the ionization. The propagation of the plasma across water filled microchannels evolve into hopping SIWs between the leading edges of the water channels, regions of electric enhancement due to polarization of the water. Positive, reverse IWs follow the pre-ionized path of the initial negative waves. 

Abstract Sterilization of skin prior to surgery is challenged by the reservoir of bacteria that resides in hair follicles. Atmospheric pressure plasma jets (APPJs) have been proposed as a method to treat and deactivate these bacteria as atmospheric plasmas are able to penetrate into structures and crevices with dimensions similar to those found in hair follicles. In this paper, we discuss results from a computational investigation of an APPJ sustained in helium flowing into ambient air, and incident onto a layered dielectric similar to human skin in which there are idealized hair follicles. We found that, depending on the location of the follicle, the bulk ionization wave (IW) incident onto the skin, or the surface IW on the skin, are able to launch IWs into the follicle. The uniformity of treatment of the follicle depends on the location of thefirst entryof the plasma into the follicle on the top of the skin. Typically, only one side of the follicle is treated on for a given plasma pulse, with uniform treatment resulting from rastering the plasma jet across the follicle over many pulses. Plasma treatment of the follicle is sensitive to the angle of the follicle with respect to the skin, width of the follicle pocket, conductivity of the dermis and thickness of the underlying subcutaneous fat layer, the latter due to the change in capacitance of the tissue. 

Abstract Mechanisms for the cold atmospheric plasma (CAP) treatment of cells in solution are needed for more optimum design of plasma devices for wound healing, cancer treatment, and bacterial inactivation. However, the complexity of organic molecules on cell membranes makes understanding mechanisms that result in modifications (i.e. oxidation) of such compounds difficult. As a surrogate to these systems, a reaction mechanism for the oxidation of cysteine in CAP activated water was developed and implemented in a 0-dimensional (plug-flow) global plasma chemistry model with the capability of addressing plasma-liquid interactions. Reaction rate coefficients for organic reactions in water were estimated based on available data in the literature or by analogy to gas-phase reactions. The mechanism was validated by comparison to experimental mass-spectrometry data for COST-jets sustained in He/O₂, He/H₂O and He/N₂/O₂mixtures treating cysteine in water. Results from the model were used to determine the consequences of changing COST-jet operating parameters, such as distance from the substrate and inlet gas composition, on cysteine oxidation product formation. Results indicate that operating parameters can be adjusted to select for desired cysteine oxidation products, including nitrosylated products. 

Abstract Ozone, O₃, is a strong oxidizing agent often used for water purification. O₃is typically produced in dielectric barrier discharges (DBDs) by electron-impact dissociation of O₂, followed by three-body association reactions between O and O₂. Previous studies on O₃formation in low-temperature plasma DBDs have shown that O₃concentrations can drop to nearly zero after continued operation, termed the ozone-zero phenomenon (OZP). Including small (<4%) admixtures of N₂can suppress this phenomenon and increase the O₃production relative to using pure O₂in spite of power deposition being diverted from O₂to N₂and the production of nitrogen oxides, N_xO_y. The OZP is hypothesized to occur because O₃is destroyed on the surfaces in contact with the plasma. Including N₂in the gas mixture enables N atoms to occupy surface sites that would otherwise participate in O₃destruction. The effect of N₂in ozone-producing DBDs was computationally investigated using a global plasma chemistry model. A general surface reaction mechanism is proposed to explain the increase in O₃production with N₂admixtures. The mechanism includes O₃formation and destruction on the surfaces, adsorption and recombination of O and N, desorption of O₂and N₂, and NO_xreactions. Without these reactions on the surface, the density of O₃monotonically decreases with increasing N₂admixture due to power absorption by N₂leading to the formation of nitrogen oxides. With N-based surface chemistry, the concentrations of O₃are maximum with a few tenths of percent of N₂depending on the O₃destruction probability on the surface. The consequences of the surface chemistry on ozone production are less than the effect of gas temperature without surface processes. An increase in the O₃density with N-based surface chemistry occurs when the surface destruction probability of O₃or the surface roughness was decreased. 

Abstract Plasmas in contact with liquids can degrade organic molecules in a solution, as reactive oxygen and nitrogen species produced in the plasma solvate into the liquid. Immersing small droplets (tens of microns in diameter) in the plasma can more rapidly activate the liquid compared to treating a large volume of liquid with a smaller surface-to-volume ratio. The interactions between a radio frequency glow discharge sustained in He/H₂O and a water droplet containing formate (HCOO⁻_aq) immersed in and flowing through the plasma were modeled using a zero-dimensional global plasma chemistry model to investigate these activation processes. HCOO⁻_aqinteracts with OH_aq, which is produced from the solvation of OH from the gas phase. The resulting HCOO⁻_aqconcentrations were benchmarked with previously reported experimental measurements. The diameter of the droplet, initial HCOO⁻_aqconcentration, and gas flow rate affect only the HCOO⁻_aqconcentration and OH_aqdensity, leaving the OH density in the gas phase unaffected. Power deposition and gas mixture (e.g. percentage of H₂O) change both the gas and liquid phase chemistry. A general trend was observed: during the first portion of droplet exposure to the plasma, OH_aqprimarily consumes HCOO⁻_aq. However, O₂⁻_aq, a byproduct of HCOO⁻_aqconsumption, consumes OH_aqonce O₂⁻_aqreaches a critically large density. Using HCOO⁻_aqas a surrogate for OH_aq-sensitive contaminants, combinations of residence time, droplet diameter, water vapor density, and power will determine the optimum remediation strategy.