Transient Spark Discharge Generated in Various N2/O2 Gas Mixtures: Reactive Species in the Gas and Water and Their Antibacterial Effects

Reactive species generated in the gas and in water by cold air plasma of the transient spark discharge in various N₂/O₂ gas mixtures (including pure N₂ and pure O₂) have been examined. The discharge was operated without/with circulated water driven down the inclined grounded electrode. Without water, NO and NO₂ are typically produced with maximum concentrations at 50% O₂. N₂O was also present for low O₂ contents (up to 20%), while O₃ was generated only in pure O₂. With water, gaseous NO and NO₂ concentrations were lower, N₂O was completely suppressed and HNO₂ increased; and O₃ was lowered in O₂ gas. All species production decreased with the gas flow rate increasing from 0.5 to 2.2 L/min. Liquid phase species (H₂O₂, NO₂￣, NO₃￣, ^·OH) were detected in plasma treated water. H₂O₂ reached the highest concentrations in pure N₂ and O₂. On the other hand, nitrites NO₂￣ and nitrates NO₃￣ peaked between 20 and 80% O₂ and were associated with pH reduction. The concentrations of all species increased with the plasma treatment time. Aqueous ^·OH radicals were analyzed by terephthalic acid fluorescence and their concentration correlated with H₂O₂. The antibacterial efficacy of the transient spark on bacteria in water increased with water treatment time and was found the strongest in the air-like mixture thanks to the peroxynitrite formation. Yet, significant antibacterial effects were found even in pure N₂ and in pure O₂ most likely due to high ^·OH radical concentrations. Controlling the N₂/O₂ ratio in the gas mixture, gas flow rate, and water treatment time enables tuning the antibacterial efficacy.

     

Chlorination reaction behavior of Zircaloy-4 hulls: experimental and theoretical approaches

Chlorination reaction behavior of Zircaloy-4 (Zry-4) cladding hulls was demonstrated by using a quartz reactor system. By reacting at 380 °C for 3 h, mass of the Zry-4 hulls decreased by 65.8 wt% with Cl₂ utilization of 87.1 mol%. Composition of collected product was analyzed and it was revealed that concentration of Zr was higher than 99.97 wt%. The purity of Zr in the experimental result was higher than expectation when considering Sn (1.31 wt%) and Fe (0.25 wt%) contents which can produce gaseous SnCl₄ and FeCl₃ at the experimental condition. Theoretical calculations were performed to clarify the high purity of Zr by using the HSC code. The simulation results revealed that formation of ZrCl₄ is more preferred than SnCl₄, FeCl₃, and CrCl₃. The preference of chloride formation was confirmed by the theoretical calculation, and it was suggested that the major constituents of Zry-4 might react with Cl₂ to produce chlorides in an order of ZrCl₄ > CrCl₃ > SnCl₄ > FeCl₃. It was also suggested that continuous removal of ZrCl₄ and sufficient supply of Zr source during the chlorination reaction might have contributed to the high purity of Zr.     

Photoinitiated RAFT polymerization of vinyl acetate

A photoinitiation process was investigated to develop a rapid and well‐controlled RAFT polymerization method applied to vinyl acetate (VAc) using methyl (ethoxycarbonothioyl)sulfanyl acetate (MESA) and bis(2,4,6‐trimethylbenzoyl)phenylphosphine oxide as the RAFT agent and photoinitiator, respectively. MESA was selected as the photochemically inert RAFT agent to minimize photolysis of the thiocarbonylthio groups during polymerization. Poly(vinyl acetate) with a prespecified well‐controlled molecular weight (MW) and a narrow MW distribution was successfully synthesized. The polymerization reaction proceeded as a living polymerization and was remarkably rapid compared with approaches that use thermally initiated processes with a very short induction period. A detailed kinetic study of the mechanism underlying the polymerization reaction, however, revealed that the chain ends containing xanthate moieties were not perfectly stable upon UV‐irradiation, and they generated radicals via homolytic cleavage. This reaction appeared to proceed by a combination of a degenerative transfer RAFT mechanism and a dissociation‐combination mechanism. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

The dispersion of pigment slurries via incorporation with water-soluble sulfonate poly(ethylene terephthalate)

A water-soluble sulfonate poly(ethylene terephthalate) copolymer has been synthesized and identified as a high-temperature endurable surfactant. The glass-transition temperature and the storage modulus increase in correlation to the increase in sulfonate content. Various characterization studies were performed, including light scattering, zeta-potential measurement and a sedimentation test. The results suggest that at equal numbers of sulfonate units in a solution, a low concentration of a dispersant of high sulfonate content is more effective than a high concentration of a dispersant of low sulfonate content. Received: 6 April 2000 Accepted: 23 September 2000     

Bifurcation of periodic solutions to variational inequalities in R κ based on Alexander-Yorke theorem

Variational inequalities are studied, where K is a closed convex cone in , 3, B is a × matrix, G is a small perturbation, a real parameter. The assumptions guaranteeing a Hopf bifurcation at some ₀ for the corresponding equation are considered and it is proved that then, in some situations, also a bifurcation of periodic solutions to our inequality occurs at some _{I 0}. Bifurcating solutions are obtained by the limiting process along branches of solutions to penalty problems starting at ₀ constructed on the basis of the Alexander-Yorke theorem as global bifurcation branches of a certain enlarged system.     

Optical constants of thin oxide films on titanium

Thin oxide films on titanium formed by heating were studied by the ellipsometric method. To obtain the complex refractive index and film thicknesses, the ellipsometric measurements were performed by means of the immersing method: each sample was measured first in air and then in a liquid of known refractive index (in our case CCl₄). The optical constants and the oxide film thickness were computed by means of a computer from two pairs of ellipsometric values. To state the optical constants of clean titanium surface the graphic-computational method was proposed and applied. The measurements were carried out at two wavelengths on oxide films grown in air and dry oxygen by thermal oxidation at temperatures from 150 to 700 °C. It has been shown that when increasing the film thickness the refractive index of the film decreases, whereas the absorption coefficient is independent on the film thickness. Optical constants of oxide films growing in dry oxygen are smaller than those growing in air.