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Microwave plasma discharges for biomass pretreatment: Degradation of a sodium carboxymethyl cellulose model

2020, Honnorat, B., Brüser, V., Kolb, J.F.

Biogas production is an important component of an environmentally benign renewable energy strategy. However, the cost-effectiveness of biogas production from biomass is limited by the presence of polymeric structures, which are recalcitrant to digestion by bacteria. Therefore, pretreatments must often be applied prior to anaerobic fermentation to increase yields of biogas. Many physico-chemical pretreatments have a high energy demand and are generally costly. An alternative could be the ignition of a plasma directly in the biomass substrate. The reactive species that are generated by plasma-liquid interactions, such as hydroxyl radicals and hydrogen peroxides, could contribute significantly to the disintegration of cell walls and the breakage of poorly digestible polymers. With respect to economic, processing, and other potential benefits, a microwave instigated and sustained plasma was investigated. A microwave circuit transmitted 2-kW pulses into a recirculated sodium carboxymethyl cellulose solution, which mimicked the rheological properties of biomass. Each microwave pulse had a duration of 12.5 ms and caused the ignition of a discharge after a vapor bubble had formed. Microwaves were absorbed in the process with an efficiency of ∼97%. Slow-motion imaging showed the development of the discharge. The plasma discharges provoked a decrease in the viscosity, probably caused by the shortening of polymer chains of the cellulose derivative. The decrease in viscosity by itself could reduce processing costs and promotes bacterial activity in actual biomass. The results demonstrate the potential of microwave in-liquid plasma discharges for the pretreatment of biomass. © 2020 Author(s).

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Plasma medical oncology: Immunological interpretation of head and neck squamous cell carcinoma

2020, Witzke, Katharina, Seebauer, Christian, Jesse, Katja, Kwiatek, Elisa, Berner, Julia, Semmler, Marie‐Luise, Boeckmann, Lars, Emmert, Steffen, Weltmann, Klaus‐Dieter, Metelmann, Hans‐Robert, Bekeschus, Sander

The prognosis of patients suffering from advanced-stage head and neck squamous cell carcinoma (HNSCC) remains poor. Medical gas plasma therapy receives growing attention as a novel anticancer modality. Our recent prospective observational study on HNSCC patients suffering from contaminated tumor ulcerations without lasting remission after first-line anticancer therapy showed remarkable efficacy of gas plasma treatment, with the ulcerated tumor surface decreasing by up to 80%. However, tumor growth relapsed, and this biphasic response may be a consequence of immunological and molecular changes in the tumor microenvironment that could be caused by (a) immunosuppression, (b) tumor cell adaption, (c) loss of microbe-induced immunostimulation, and/or (d) stromal cell adaption. These considerations may be vital for the design of clinical plasma trials in the future.

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Plasma-based VAD process for multiply doped glass powders and high-performance fiber preforms with outstanding homogeneity

2020, Trautvetter, Tom, Schäfer, Jan, Benzine, Omar, Methling, Ralf, Baierl, Hardy, Reichel, Volker, Dellith, Jan, Köpp, Daniel, Hempel, Frank, Stankov, Marjan, Baeva, Margarita, Foest, Rüdiger, Wondraczek, Lothar, Wondraczek, Katrin, Bartelt, Hartmut

An innovative approach using the vapor axial deposition (VAD), for the preparation of silica-based high-power fiber laser preforms, is described in this study. The VAD uses a plasma deposition system operating at atmospheric pressure, fed by a single, chemically adapted solution containing precursors of laser-active dopants (e.g., Yb2O3), glass-modifier species (e.g., Al2O3), and the silica matrix. The approach enables simultaneous doping with multiple optically active species and overcomes some of the current technological limitations encountered with well-established fiber preform technologies in terms of dopant distribution, doping levels, and achievable active core diameter. The deposition of co-doped silica with outstanding homogeneity is proven by Raman spectroscopy and electron probe microanalysis. Yb2O3 concentrations are realized up to 0.3 mol% in SiO2, with simultaneous doping of 3 mol% of Al2O3.

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Positive streamers: inception and propagation along mineral-oil/solid interfaces

2020, Ariza, David, Hollertz, Rebecca, Methling, Ralf, Gortschakow, Sergey

This paper presents an experimental characterization of the prebreakdown phenomena in liquid/solid interfaces. The characterization is devoted to the 2nd mode positive streamers initiated and propagated along interfaces of mineral-oil and solids with different chemical composition and physical properties. Polymers of low density polyethylene (LDPE), polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE) polyvinylidene fluoride (PVDF) and papers made of kraft paper and a kraft fibril paper (made from cellulosic micro and nano fibrils), lignin-free paper and paper with high lignin content (referred to as k107 kraft paper) are used as the solid to study their influence on the streamer inception and propagation. The streamers are initiated at the interface by applying steps of voltage to a point-plane electrode arrangement with a solid (dielectric barrier) into the gap. The solid is placed diagonal to the oil gap and near to the point electrode. Shadowgraphs, charge and light intensity recordings are obtained during the inception and propagation of the streamers. Thus, estimations of the streamer length, velocity, current and average charge, are also presented. A time delay has been observed before the initiation of the streamer. This delay is probably correlated to the initiation process and formation of the gaseous phase of the streamer near to the interface. The threshold propagation voltage of the 2nd mode streamers at mineral-oil/solid interfaces is shown to be independent of the interface. However, the inception voltage is highly influenced by the interface. Additionally, the observed characteristics of streamers propagation (e.g. current, length, velocity, etc) along the tested interfaces cannot be fully explained by a capacitive coupling effect (permittivity mismatch). This open a discussion for the possibility that properties of the solid such as chemical composition, wettability and surface roughness can influence the streamer propagation.

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On the relationship between SiF4plasma species and sample properties in ultra low-k etching processes

2020, Haase, Micha, Melzer, Marcel, Lang, Norbert, Ecke, Ramona, Zimmermann, Sven, van Helden, Jean-Pierre H., Schulz, Stefan E.

The temporal behavior of the molecular etching product SiF4 in fluorocarbon-based plasmas used for the dry etching of ultra low-k (ULK) materials has been brought into connection with the polymer deposition on the surface during plasma treatment within the scope of this work. For this purpose, time-resolved measurements of the density of SiF4 have been performed by quantum cascade laser absorption spectroscopy. A quantification of the non-linear time dependence was achieved by its characterization via a time constant of the decreasing SiF4 density over the process time. The time constant predicts how fast the stationary SiF4 density is reached. The higher the time constant is, the thicker the polymer film on top of the treated ultra low-k surface. A correlation between the time constant and the ULK damage was also found. ULK damage and polymer deposition were proven by Variable Angle Spectroscopic Ellipsometry and X-ray Photoelectron Spectroscopy. In summary, the observed decay of the etching product concentration over process time is caused by the suppressed desorption of the SiF4 molecules due to a more dominant adsorption of polymers. © 2020 Author(s).

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HelixJet: An innovative plasma source for next-generation additive manufacturing (3D printing)

2020, Schäfer, Jan, Quade, Antje, Abrams, Kerry J., Sigeneger, Florian, Becker, Markus M., Majewski, Candice, Rodenburg, Cornelia

A novel plasma source (HelixJet) for use in additive manufacturing (AM)/3D printing is proposed. The HelixJet is a capacitively coupled radio frequency plasma with a double-helix electrode configuration that generates a surprisingly stable and homogeneous glow plasma at low flow rates of argon and its mixtures at atmospheric pressure. The HelixJet was tested on three polyamide powders usually used to produce parts by laser sintering, a powder-based AM process, to form local deposits. The chemical composition of such plasma-printed samples is compared with thermally produced and laser-sintered samples with respect to differences in morphology that result from the different thermal cycles on several length scales. Plasma prints exhibit unique features attributable to the nonequilibrium chemistry and to the high-speed heat exchange.

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Nuclear dynamics in BaZr0.7Ce0.2Y0.1O3−δ proton conductor as observed by neutron diffraction and Compton scattering

2020, Wallis, Jan, Kruth, Angela, da Silva, Ivan, Krzystyniak, Matthew

Concurrent neutron Compton scattering (NCS) and neutron diffraction experiments at temperatures between 70 K and 300 K have been performed on proton-conducting hydrated BaZr0.7Ce0.2Y0.1O3−δ (BZCY72) fabricated by spark plasma sintering. A combined neutron data analysis, augmented with density functional theory modelling of lattice dynamics, has enabled, for the first time, a mass-selective appraisal of the combined thermal and nuclear quantum effect on nuclear dynamics and thermodynamic stability of this technologically important proton conducting perovskite oxide. The analysis suggests that the nuclear dynamics in hydrated BZCY72 is a result of a subtle interplay of harmonic, anharmonic and thermal effects, with the increased anharmonic character of the lattice dynamics above the orthorhombic to rhombohedral phase transition at 85 K. The anharmonic effect seems to be most pronounced in the case of oxygen and cerium. The analysis of the proton momentum distribution reveals that the concentration of the hydrogen in the BZCY72 lattice is constant across the orthorhombic to rhombohedral phase transition and further down to the room temperature. Moreover, the average hydrogen concentration obtained from our analysis of the mass-resolved neutron Compton scattering data seems to be commensurate with the total vacancy concentration in the BZCY72 framework. The calculation of the vibrational enthalpy of both phases allows obtaining the value of the enthalpy of the orthorhombic to the rhombohedral phase transition of −3.1 ± 1 kJ mol−1. Finally, our analysis of the nuclear kinetic energy of the proton obtained from NCS and the oxygen-oxygen distance distributions obtained from ND allows to conclude that BZCY72 in both the orthorhombic and rhombohedral phase at 70 K and 100 K respectively falls into the category of the KDP-type crystals where proton is probably under the influence of a double-well potential and forms hydrogen bonds of moderate strength. The obtained results have important ramifications for this technological important material.

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Does the energy transfer from Ar(1s) atoms to N2 lead to dissociation?

2020, Klages, Claus‐Peter, Martinovs, Andris, Bröcker, Lars, Loffhagen, Detlef

Dielectric-barrier discharges (DBDs) in Ar–N2 mixtures, with N2 fractions in 0.1–1% range, would be attractive alternatives to DBDs in pure N2 if energy-transfer reactions between Ar(1s) atoms and N2 molecules were an efficient source of N atoms. Attempts to functionalize polyolefins in flowing postdischarges fed by such DBDs, as well as the search for the First Positive System in the emission spectrum, however, failed. Evidently, the energy-transfer reactions do not produce N atoms. For Ar(1s3) and Ar(1s5) metastable states, this fact has already been reported in the literature. For Ar(1s2) and Ar(1s4) resonant states, a quantitative argument is derived in this paper: energy transfer from Ar(1s) atoms to N2 molecules is not an efficient source of N atoms.

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Inactivation of airborne bacteria by plasma treatment and ionic wind for indoor air cleaning

2020, Prehn, Franziska, Timmermann, Eric, Kettlitz, Manfred, Schaufler, Katharina, Günther, Sebastian, Hahn, Veronika

Airborne bacteria are a general problem in medical or health care facilities with a high risk for nosocomial infections. Rooms with a continuous airflow, such as operation theaters, are of particular importance due to a possible dissemination and circulation of pathogens including multidrug-resistant microorganisms. In this regard, a cold atmospheric-pressure plasma (CAP) may be a possibility to support usual disinfection procedures due to its decontaminating properties. The aim of this study was to determine the antimicrobial efficacy of a plasma decontamination module that included a dielectric barrier discharge for plasma generation. Experimental parameters such as an airflow velocity of 4.5 m/s and microbial contaminations of approximately 6,000 colony-forming units (cfu)/m3 were used to simulate practical conditions of a ventilation system in an operating theater. The apathogenic microorganism Escherichia coli K12 DSM 11250/NCTC 10538 and the multidrug-resistant strains E. coli 21181 and 21182 (isolated from patients) were tested to determine the antimicrobial efficacy. In summary, the number of cfu was reduced by 31–89% for the tested E. coli strains, whereby E. coli K12 was the most susceptible strain toward inactivation by the designed plasma module. A possible correlation between the number or kind of resistances and susceptibility against plasma was discussed. The inactivation of microorganisms was affected by plasma intensity and size of the plasma treatment area. In addition, the differences of the antimicrobial efficacies caused through the nebulization of microorganisms in front (upstream) or behind (downstream) the plasma source were compared. The presence of ionic wind had no influence on the reduction of the number of cfu for E. coli K12, as the airflow velocity was too high for a successful precipitation, which would be a prerequisite for an increased antimicrobial efficacy. The inactivation of the tested microorganisms confirms the potential of CAP for the improvement of air quality. The scale-up of this model system may provide a novel tool for an effective air cleaning process.

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Influence of dielectric thickness and electrode structure on the ion wind generation by micro fabricated plasma actuators

2020, Hink, R., Pipa, A.V., Schäfer, J., Caspari, R., Weichwald, R., Foest, R., Brandenburg, R.

Surface dielectric barrier discharges are investigated in order to explore the combined effects of barrier thickness and microstructure of the exposed electrode on the ion wind generation. Actuators with straight and structured high voltage electrodes with characteristic sizes of 200 and 250 µm and dielectric thicknesses of 0.5, 1 and 2 mm are compared. It is observed that: i) actuator efficiency of ion wind generation strongly depends on the applied voltage amplitude; ii) operation voltage depends on the dielectric thickness logarithmically; iii) electrode microstructure slightly increases the dynamic pressure (few percent in maximum), however the effect decreases with thicker dielectrics and smaller electrode structures; iv) the pattern of the most intensive discharge parts as well as the dielectric erosion repeats the regular structure of the electrodes down to 200 µm. Several identical samples are tested during different days to estimate the impact of the air humidity and the degradation of the dielectric. The microscale precision of the sample manufacture was accomplished by a commercial facility for printed circuit boards. © 2020 The Author(s). Published by IOP Publishing Ltd.