大气压介质阻挡辉光放电中放电电流的测量与分析

介质阻挡放电产生的低温等离子体具有广泛的应用前景而成为研究热点。文章利用平行平板介质阻挡放电装置,在流动的氦气中实现了大气压均匀辉光放电,得到了大气压下的均匀等离子体。利用电学方法将放电电流从总电流中分离出来,从而得到了辉光放电的放电电流。通过分析放电电流、外加电压、气隙上电压以及壁电荷电量之间的相互关系,可以研究气体放电过程中壁电荷积累的微观动力学行为。实验结果表明壁电荷主要是在放电电流脉冲持续期间积累的,但电流脉冲结束后,由于气隙电压没有改变极性,壁电荷还会逐渐积累,气隙电压改变极性后,壁电荷量随时间减小。这些结果对壁电荷在介质阻挡辉光放电中作用的深入研究和大气压介质阻挡辉光放电的工业应用具有重要意义。     

Discharge Operation Mode Manipulation of Radio Frequency Atmospheric Pressure Glow Discharges in Argon

Stable operation of radio frequency atmospheric glow discharges is widely desired by most processing applications for their conveniency and feasibility, many of which have been addressed with the noble gas of helium and low discharge current density in stable operation regime of α mode. Here, the operation mode manipulation of rf atmospheric pressure glow discharge in argon is investigated using a one‐dimensional self‐consistent modeling approach. Stable operation regime of α mode is found to expand with rinsing excitation frequency and reducing discharge gap distance. The sheath characteristics in terms of sheath voltage and sheath thickness are given to explain the of α ‐γ mode transition. Furthermore, stable operation of discharge in γ mode is proposed tobe achieved by introducing dielectric barriers, which is indicated by monotonously growing of applied voltage with discharge current density (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

空心针-板电极大气压氩气辉光放电的特性研究

大气压均匀放电等离子体在工业领域具有非常广泛的应用前景,它是利用直流电源激励的空心针-板放电装置,以氩气为工作气体在大气压空气中产生均匀稳定的放电。对氩气流量和气隙间距对辉光放电发光特性的关系进行了研究,结果表明放电所产生的等离子体柱连接两个电极,发光较为均匀(观察不到放电丝)。在板电极附近放电等离子体柱直径最大,最大直径随着电流和气流的增大而增大。放电伏安特性研究发现,与低气压辉光放电相类似,两电极间的电压随着电流的增大而减小,并且随气流和气隙间距的增大而增大。对该大气压直流均匀放电在扫描范围为330～450 nm的光学发射光谱进行分析,获得了放电等离子体的分子振动温度和谱线强度比I_391.4/I_337.1随氩气流量和气隙间距的变化关系。I_391.4/I_337.1均随流量和气隙间距的增大而降低。对等离子体柱的I_391.4/I_337.1沿气流方向(等离子体柱轴向)进行了空间分辨测量,并进行了定性分析,结果表明,振动温度及电子平均能量随着远离空心针口距离的增大而增大。这些结果对大气压辉光放电在工业中的应用具有重要意义。     

大气压介质阻挡放电的光谱研究

使用水电极介质阻挡放电装置,分别在大气压空气和氦气中实现了稳定的高气压放电。通过水电极观察两种气体的放电,发现大气压空气中放电为空间随机分布的微放电丝,等离子体是不均匀的,而在氦气中放电没有微放电丝,空间分布比较均匀。比较而言,这种均匀放电产生的等离子体具有更广泛的工业应用前景。对两种气体中放电的电流波形进行了比较,发现空气中放电的电流脉冲在时间上是随机出现的而氦气中放电的电流脉冲在时间上具有周期性,并且空气中放电脉冲宽度约为几十ns而氦气中放电的电流持续时间较长,脉冲宽度大约为1μs。文章还对两种气体中介质阻挡放电发射光谱进行了研究,结果表明大气压氦气中均匀放电的N+₂(B2Σ+_u→X2Σ+_g)谱线391.4nm很强而在大气压空气放电中此光谱线很弱。这些研究结果对高气压条件下均匀放电的实现和大气压辉光放电的工业应用具有重要意义。     

直流大气压辉光放电高能电子密度的空间分布

利用针阴极和水阳极,在6 mm的空气隙产生了大气压空气辉光放电。该大气压辉光放电具有明显的负辉区、正柱区和阳极辉区等明亮的发光区。通过研究放电的电压电流特性,发现该放电处于亚辉光放电到正常辉光放电阶段。由于氮分子第二正带系337.1 nm的光谱强度反映高能电子密度,对337.1 nm谱线的强度进行了空间分辨测量。结果发现高能电子在针尖附近密度最大,而其他区域相差不多。随电压升高,高能电子密度减少。增大限流电阻,高能电子密度也减少。氧原子对杀菌消毒具有重要作用,利用发射光谱法对氧原子谱线强度的空间分布进行了测量,发现氧原子谱线强度与高能电子的空间分布及其随参数的变化关系一致。     

大面积氮气均匀介质阻挡放电发射光谱研究

采用板-板式电极结构在大气压氮气中成功地获得了具有工业应用前景的大面积均匀介质阻挡放电等离子体。利用发射光谱技术测量了N₂(C3Π_u→B3Π_g)和N₂+(B2Σ+_u→X2Σ+_g 0-0 391.4 nm)的发射光谱,并研究了应用电压和驱动频率对N₂(C3Π_u→B3Π_g)和N₂+(B2Σ+_u→X2Σ+_g 0-0 391.4 nm)发射光谱强度的影响。结果表明,当应用电压小于6 kV时,N₂(C3Π_u→B3Π_g)和N₂+(B2Σ+_u→X2Σ+ _g0-0 391.4 nm)的发射光谱强度随应用电压增大变化较小,进一步升高应用电压时,等离子体发射光谱强度陡然增强。本文还讨论了激发态N+₂(B2Σ+_u)离子在纯N₂和He+N₂混合气体中介质阻挡大气压均匀介质阻挡放电下的主要产生机制。     

Free‐Electron Gas Spectrum Uniqueness in the Mixture of Noble Gases

Gas mixtures can reach the Maxwell's specter shape in case of low‐ionized mono‐atomic mixtures in the weak electric field. The parameters pertaining to the Maxwell spectrum of free electrons' gas straightforwardly settle on the insulating characteristics of the examined gas mixture at the fundamental level. In this paper, a condition for breakdown has been accomplished taking as a starting point the ionization coefficients derived accordingly, as well as the conditions for breakdown in keeping with the Townsend mechanism. The dc breakdown voltage value of noble gases mixture has been measured in the experimental part of the paper. The hypothesis that the free‐electron gas spectrum is unique in the noble gas mixture and is of Maxwell's type has been verified. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Determination of N and O‐atoms and N2 (A) Metastable Molecule Densities in the Afterglows of N2‐H2, Ar‐N2‐H2 and Ar‐N2‐O2 Microwave Discharges

Early afterglows of N₂‐H₂, Ar‐N₂‐H₂ and Ar‐N₂‐O₂ flowing microwave discharges are characterized by optical emission spectroscopy. The N and O atoms and the N₂ (A) metastable molecule densities are determined by optical emission spectroscopy after calibration by NO titration for N and O‐atoms and measurements of NO and N₂ band intensities. If an uncertainty of 30% is estimated on N‐atomic density, an inaccuracy of one order of magnitude is obtained on the O and N₂ (A) densities. In N₂‐(0.05‐2.5%)H₂ and Ar‐(1‐50%)N₂‐(0.05‐2.5%) H₂ gas mixtures, the O‐atoms are coming from O₂ impurities in the discharge. Concentrations of N and O‐atoms and of N₂ (A) densities are compared to the ones obtained in Ar‐(5‐50%)N₂‐(0.2‐2.5%) O₂ gas mixtures in which a controlled amount of O₂ is added. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Gas‐phase oxidation of CH2 = C(CH3)CH2Cl initiated by OH radicals and Cl atoms: kinetics and fate of the alcoxy radical formed

Relative kinetics of the reactions of OH radicals and Cl atoms with 3‐chloro‐2‐methyl‐1‐propene has been studied for the first time at 298 K and 1 atm by GC‐FID. Rate coefficients are found to be (in cm³ molecule^?1 s^?1): k₁ (OH + CH₂ = C(CH₃)CH₂Cl) = (3.23 ± 0.35) × 10^?11, k₂ (Cl + CH₂ = C(CH₃)CH₂Cl) = (2.10 ± 0.78) × 10^?10 with uncertainties representing ± 2σ. Product identification under atmospheric conditions was performed by solid phase microextraction/GC‐MS for OH reaction. Chloropropanone was identified as the main degradation product in accordance with the decomposition of the 1,2‐hydroxy alcoxy radical formed. Additionally, reactivity trends and atmospheric implications are discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

Atmospheric DBD plasma Deposition of ECO‐Friedly Release Liners for Pressure Sensitive Adhesive Tapes

The presented paper reports on the development of eco‐friendly non‐silicone containing release liners on plastic foils for pressure sensitive adhesive tapes. A solvent free process based on aerosol assisted dielectric barrier discharge (DBD) plasma deposition was used to obtain nano‐sized coatings. Various precursors have been investigated ranging from hydrocarbons and fluorinated hydrocarbons to (meth)acrylates and fluorinated (meth)acrylates. Best results were obtained using 2‐ethylhexyl acrylate. To improved the stability of release properties upon ageing, addition of photo initiators and acrylic cross‐linkers have been evaluated. Tape adhesion tests showed stable release values below 25 cN/20 mm for 2‐ethylhexyl acrylate plasma coatings with acrylic cross‐linkers. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

4‐Phenyl‐1,2,4‐triazoline‐3,5‐dione in the ene reactions with cyclohexene, 1‐hexene and 2,3‐dimethyl‐2‐butene. The heat of reaction and the influence of temperature and pressure on the reaction rate

The values of the enthalpy (53.3; 51.3; 20.0 kJ mol^?1), entropy (?106; ?122; ?144 J mol^?1K^?1), and volume of activation (?29.1; ?31.0; ?cm³ mol^?1), the reaction volume (?25.0; ?26.6; ?cm³ mol^?1) and reaction enthalpy (?155.9; ?158.2; ?150.2 kJ mol^?1) have been obtained for the first time for the ene reactions of 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione 1 , with cyclohexene 4 , 1‐hexene 6 , and with 2,3‐dimethyl‐2‐butene 8 , respectively. The ratio of the values of the activation volume to the reaction volume (?V^≠_corr/ΔV_{r ? n}) in the ene reactions under study, 1 + 4 → 5 and 1 + 6 → 7 , appeared to be the same, namely 1.16. The large negative values of the entropy and the volume of activation of studied reactions 1 + 4 → 5 and 1 + 6 → 7 better correspond to the cyclic structure of the activated complex at the stage determining the reaction rate. The equilibrium constants of these ene reactions can be estimated as exceeding 10¹⁸ L mol^?1, and these reactions can be considered irreversible. Copyright © 2014 John Wiley & Sons, Ltd.     

X‐ray spectroscopy for chemistry in the 2‐4 keV energy regime at the XMaS beamline: ionic liquids,Rh and Pd catalysts in gas and liquid environments,and Cl contamination in γ‐Al2O3

The 2–4 keV energy range provides a rich window into many facets of materials science and chemistry. Within this window, P, S, Cl, K and Ca K‐edges may be found along with the L‐edges of industrially important elements from Y through to Sn. Yet, compared with those that cater for energies above ca. 4–5 keV, there are relatively few resources available for X‐ray spectroscopy below these energies. In addition, in situ or operando studies become to varying degrees more challenging than at higher X‐ray energies due to restrictions imposed by the lower energies of the X‐rays upon the design and construction of appropriate sample environments. The XMaS beamline at the ESRF has recently made efforts to extend its operational energy range to include this softer end of the X‐ray spectrum. In this report the resulting performance of this resource for X‐ray spectroscopy is detailed with specific attention drawn to: understanding electrostatic and charge transfer effects at the S K‐edge in ionic liquids; quantification of dilution limits at the Cl K‐ and Rh L₃‐edges and structural equilibria in solution; in vacuum deposition and reduction of [Rh^I(CO)₂Cl]₂ to γ‐Al₂O₃; contamination of γ‐Al₂O₃ by Cl and its potential role in determining the chemical character of supported Rh catalysts; and the development of chlorinated Pd catalysts in `green' solvent systems. Sample environments thus far developed are also presented, characterized and their overall performance evaluated.     

The effect of benzo‐annelation on intermolecular hydrogen bond and proton transfer of 2‐methyl‐3‐hydroxy‐4(1H)‐quinolone in methanol: A TD‐DFT study

Excited‐state intermolecular or intramolecular proton transfer (ESIPT) reaction has important potential applications in biological probes. In this paper, the effect of benzo‐annelation on intermolecular hydrogen bond and proton transfer reaction of the 2‐methyl‐3‐hydroxy‐4(1H)‐quinolone (MQ) dye in methanol solvent is investigated by the density functional theory and time‐dependent density functional theory approaches. Both the primary structure parameters and infrared vibrational spectra analysis of MQ and its benzo‐analogue 2‐methyl‐3‐hydroxy‐4(1H)‐benzo‐quinolone (MBQ) show that the intermolecular hydrogen bond O₁―H₂?O₃ significantly strengthens in the excited state, whereas another intermolecular hydrogen bond O₃―H₄?O₅ weakens slightly. Simulated electron absorption and fluorescence spectra are agreement with the experimental data. The noncovalent interaction analysis displays that the intermolecular hydrogen bonds of MQ are obviously stronger than that of MBQ. Additionally, the energy profile analysis via the proton transfer reaction pathway illustrates that the ESIPT reaction of MBQ is relatively harder than that of MQ. Therefore, the effect of benzo‐annelation of the MQ dye weakens the intermolecular hydrogen bond and relatively inhibits the proton transfer reaction.     

A Combined Experimental and Theoretical Study on the Formation of Ag Filaments on β‐Ag2MoO4 Induced by Electron Irradiation

A combined experimental and theoretical study is presented to understand the novel observed nucleation and early evolution of Ag filaments on β‐Ag₂MoO₄ crystals, driven by an accelerated electron beam from an electronic microscope under high vacuum. The growth process, chemical composition, and the element distribution in these filaments are analyzed in depth at the nanoscale level using field‐emission scanning electron microscopy (FE‐SEM) and transmission electron microscopy (TEM) with energy‐dispersive spectroscopy (EDS) characterization. To complement experimental results, chemical stability, structural and electronic aspects have been studied systematically using first‐principles electronic structure theory within a quantum theory of atoms in molecules (QTAIM) framework. The Ag nucleation and formation on β‐Ag₂MoO₄ are a result of structural and electronic changes of the AgO₄ tetrahedral cluster as a constituent building block of β‐Ag₂MoO₄, consistent with Ag metallic formation. The formation of Ag filament transforms the β‐Ag₂MoO₄ semiconductor from n‐ to p‐type concomitant with the appearance of Ag defects.     

Double proton transfer in crystals of 1,3,4,6,7,8‐hexahydro‐2H‐pyrimido[1,2‐a] pyrimidine (hppH): 13C and 15N CPMAS NMR study of (hppH)2

In this paper, we report an example of intermolecular solid‐state proton transfer in the bicyclic guanidine, hppH. A combination of X‐ray crystallography, CPMAS NMR (¹³C and ¹⁵N) and theoretical calculations allows us to determine that a double proton transfer takes place in the (hppH)₂ dimer with an activation energy of about 50 kJ mol^?1. According to the B3LYP/6‐311++G(d,p) calculations, the double proton transfer occurs non‐symmetrically through a zwitterion. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of atomic vibrations in XANES: polarization‐dependent damping of the fine structure at the Cu K‐edge of (creat)2CuCl4

Polarization‐dependent damping of the fine structure in the Cu K‐edge spectrum of creatinium tetrachlorocuprate [(creat)₂CuCl₄] in the X‐ray absorption near‐edge structure (XANES) region is shown to be due to atomic vibrations. These vibrations can be separated into two groups, depending on whether the respective atoms belong to the same molecular block; individual molecular blocks can be treated as semi‐rigid entities while the mutual positions of these blocks are subject to large mean relative displacements. The effect of vibrations can be efficiently included in XANES calculations by using the same formula as for static systems but with a modified free‐electron propagator which accounts for fluctuations in interatomic distances.     

Isentropic Compression of Substances Using Ultra‐High Magnetic Field: Zero Isotherms of Protium and Deuterium in Pressure Range up to ∼5 Mbar

Experiments on isentropic compression of a substance using a high magnetic field pressure are described. Their goal is building of a zero isotherm in a multi‐megabar pressures range. A method of the pressure and density determination of the compressed substance based on radiographic data obtained in the experiment is presented. The results of the experiments with solid (in initial state) protium and deuterium are presented. The densities that correspond to more than seventeen‐fold compression are reached. Obtained experimental points are compared with extrapolation of a curve that is built in the experiments using anvil cells and with the results of several ab‐initio calculations (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)