不同电离度下大气等离子体粒子行为的数值模拟

利用一个空间零维大气等离子体模型对其中的主要粒子在不同电离度情况下的变化规律进行了研究.得到放电后不同初始电子密度下的电子寿命,同时给出了主要带电粒子和中性粒子密度随时间的演化.结果表明,电子密度随时间快速衰减,电子寿命随电离度的增大而减小.对一些重要的中性粒子(如O,N,O₃和NO)随电离度增大的行为进行了分析. 关键词： 电离度 大气等离子体 数值模拟     

低温等离子体分解N2/O2/NO气氛中NO试验研究

利用自行设计的介质阻挡放电型低温等离子体反应器,研究了NO初始浓度、O₂初始浓度、放电功率、电源频率等因素对NTP转化N₂/O₂/NO气氛中NO的影响规律。研究发现,NO去除率随功率增大而升高,到达一最大值后随功率增大而降低;NO去除率随O₂初始浓度增加而降低,随NO初始浓度增大而减小。相同放电功率下,同一组分中NO去除率随电源频率的增加而降低,因此相同放电功率下降低电源频率可提高NO去除率。O₂初始浓度不高于5%时,NO_x大部分为NO,NO₂和O₃浓度均随放电功率增大而降低,NO₂、O₃生成量随O₂初始浓度升高而增多。     

不同初始温度下H2/O2混合物等离子体的演化

本文对不同初始温度下,H₂/O₂混合物等离子体中主要粒子随时间发展的演化规律进行了数值模拟,得到了放电后等离子体中主要带电粒子和中性粒子密度随时间的变化规律.计算结果表明,H₂/O₂混合物等离子体中主要活性粒子密度随时间的增加减小,化学反应达到平衡所需的时间随初始温度升高逐渐减少. 关键词： 等离子体 化学过程 数值模拟 演化     

介质阻挡均匀大气压氮气放电特性研究

基于一维流体力学模型，对介质阻挡均匀大气压氮气放电特性进行了数值计算研究.模型中考虑了氮气中主要的电离、激发过程，所包含的粒子种类为e，N₂，N⁺₂，N⁺₄，N₂(a¹∑^-_u)，N₂(A³∑⁺_u).模拟结果显示，氮中的放电具有低气压下汤生放电的特性.放电电流幅度较小，放电过程中气体电压变化缓慢，电子密度远低于离子密度，而且最大值出现在阳极，电子不能在放电间隙中被俘获，不存在中性等离子体区，气体中的电场趋于线性变化.亚稳态N₂(A³∑⁺_u)和N₂(a¹∑⁺_u)在整个放电空间都具有非常高的密度，比电子密度高三个量级以上，亚稳态密度的最大值出现在阳极，这样的分布决定了放电的空间结构.放电所需的种子电子主要由亚稳态之间潘宁电离提供，这种机理使放电的电离水平较低，导致氮气中的放电只能是汤生放电.随着放电参数的变化，多电流峰放电也可在氮气中获得. 关键词： 大气压均匀放电 介质阻挡放电 数值模拟 氮气     

脉冲驱动等离子体射流中活性粒子空间分布规律

为探究大气压脉冲驱动等离子体射流中活性粒子空间分布特性,采用同轴双环等离子体射流反应器,在外施脉冲激励驱动下,研究各活性粒子在不同电离段的特征峰相对强度沿轴向空间的变化规律。结果表明：在脉冲激励等离子体射流所有测量点位均能检测到NO、OH、N₂、N ₂⁺、He等活性粒子特征峰,其中以OH、N₂、N ₂⁺粒子所对应的发射光谱谱带及特征峰较为显著;在高压电极和接地电极之间的电场驱动电离段,活性粒子NO、OH、N₂的特征峰相对强度在靠近高压电极和接地电极区域较高,而在两电极中间的区域相对强度较低,不同激发能级He、N ₂⁺特征峰相对强度沿气流方向逐渐降低;在接地电极至反应器管口的半开放离子激发段,活性粒子NO、OH以及不同能级N₂、N ₂⁺、He特征峰的相对强度轴向分布呈现出随着气流方向逐渐降低的趋势;在反应器管口至等离子体射流末端...     

N2微空心阴极放电特性及其阴极溅射的PIC/MC模拟

采用两维PIC/MCC模型模拟了氮气微空心阴极放电以及轰击离子 (N₂⁺,N⁺) 的钛阴极溅射. 主要计算了氮气微空心阴极放电离子 (N₂⁺,N⁺) 及溅射原子Ti的行为分布, 并研究了溅射Ti 原子的热化过程. 结果表明: 在模拟条件下, 空心阴极效应是负辉区叠加的电子震荡; 在对应条件下, 微空心较传统空心放电两种离子 (N₂⁺,N⁺) 密度均大两个量级, 两种离子的平均能量的分布及大小几乎相同; 在放电空间N⁺的密度约为N₂⁺的1/6, 最大能量约大2倍; 在不同参数 (P, T, V)下, 轰击阴极内表面的氮离子(N₂⁺,N⁺)的密度近似均匀, 其平均能量几乎相等; 从阴极溅射出的Ti原子的初始平均能量约6.8 eV, 离开阴极约0.15 mm处几乎完全被热化. 模拟结果为N₂微空心阴极放电等离子体特性的认识提供了参考依据. 关键词： 微空心阴极放电 PIC/MC模拟 2等离子体')" href="#">N₂等离子体     

采用详细化学反应机理研究煤富氧燃烧NO_x生成机制

本文采用详细化学反应机理,建立氧煤燃烧气固反应模型,分析煤在富氧燃烧条件下NO_x生成机制,研究不同O₂浓度和分级燃烧对NO_x排放的影响。富氧燃烧时,NO_x生成主要路径为:HCN→CN→NCO→NO和HCN→CN→NCO→HNCO→HN₂→NH→HNO→NO。初始O₂增大,挥发分和HCN析出时间提前,高的O₂初始浓度对燃料N转化率有促进作用;煤富氧分级燃烧时,主燃区还原气氛有利于NO还原为N₂,其主要还原路径如下:NO+CO→N+CO₂、NO+H→N+OH和NO+N→N₂+O,当主燃区过量空气系数SR₁从1.15减小到0.6,N最终转化率（t=1000 ms）只是从0.379减小到0.339,相对于未分级燃烧时变化了10.55%,与煤空气分级燃烧相比,煤富氧分级燃烧对N转化率影响较小。     

氮气辉光放电阴极鞘层重粒子输运过程研究

采用蒙特卡罗模拟对氮气辉光放电等离子体阴极鞘层内离子(N₂⁺,N⁺)和快中性分子(N_2f)的输运过程进行了研究,计算了阴极鞘层中离子(N₂⁺,N⁺)和快中性分子的能量及角分布的空间变化,较好地解释了实验结果.得到了氮气辉光放电等离子体阴极附近主要存在着能量较低的荷能分子、密度较低的高能原子离子及密度和能量居中的分子离子.诸粒子状态随放电条件而变化.模拟结 关键词：     

等离子体金属表面氮化中放电温度对氮原子态粒子的影响

采用快电子和重粒子(N₂⁺,N⁺,N_f)混合的Monte Carlo模型,研究了氮直流辉光放电等离子体金属表面氮化过程中.e-N_2s及N₂⁺-N_2s两种碰撞离解过程产生的原子态粒子(N⁺,N)的产生率和氮化粒子(N⁺,N_f)轰击靶表面的能量、粒子数密度及入射角分布随气体温度的变化规律.结果表明,使阴极靶处活性粒子(N⁺,N_f)的能量高且粒子数密度大,存在一个最佳放电温度;粒子(N⁺,N)的产生率及在靶表面的密度数都随着放电气体温度的升高而减少;有大量中性快原子N_f在工件表面小角入射,且粒子(N⁺,N_f)角分布受温度的影响很小.     

宏观放电参数对快原子态氮(N+,Nf)的影响

采用氮直流辉光放电等离子体中快电子和重粒子(N₂⁺,N⁺,N_f)混合的蒙特卡罗方法,模拟研究了快原子态粒子(N⁺,N_f)的产生率及轰击阴极的能量分布随宏观放电参数(P,V)的变化规律.结果表明,存在一最佳放电条件,使阴极壁处粒子(N⁺,N_f)的粒子数密度大且能量高;当电压大于800V时,轰击阴极的活性粒子(N⁺,N_f),主要由N₂⁺-N₂离解过程产生,电压小于300V时,主要由e^--N₂离解过程产生,模拟结果与实验结果相符合.     

Electron spectroscopy using excited atoms and photons IX. Penning ionization of CO2, CS2, COS,N2O,H2S,SO2, and NO2

The electron spectra resulting from thermal collisions of He* (predominantly 2³S) metastable atoms with the seven triatomic molecules, CO₂, COS, CS², N₂O H₂S, SO₂ and NO₂, are compared with their respective 584-Å photoelectron spectra using a transmission-corrected electron spectrometer. The normalised relative electronic-state transition probabilities for production of ionic states in Penning ionization and photoionization are reported together with energy shifts (ΔE values) for He*(2³S) Penning ionization. The cross-section for Penning ionization to lower states of NO₂⁺ is extremely low as has been observed in other open shell molecules such as NO and O₂.     

Fundamental investigation of NOx formation during oxy-fuel combustion of pulverized coal

NO_x formation was measured during combustion of pulverized coals and pulverized coal char in N₂ and CO₂ environments under isothermal and nearly constant oxygen conditions (i.e. using dilute coal loading). Three different oxygen concentrations (12% O₂, 24% O₂, and 36% O₂) and two representative US coals were investigated, at a gas temperature of 1050 °C. To investigate the importance of NO reburn reactions, experiments were also performed with an elevated concentration (550 ppm) of NO in the gases into which the coal was introduced. For low levels of background NO, the fractional fuel-nitrogen conversion to NO_x increases dramatically with increasing bath gas oxygen content, for both N₂ and CO₂ environments, though the fuel conversion is generally lower in CO₂ environments. Char N conversion is lower than volatile N conversion, especially for elevated O₂ concentrations. These results highlight the importance of the volatile flame and char combustion temperatures on NO_x formation. For the high background NO_x condition, net NO_x production is only observed in the 36% O₂ environment. Under these dilute loading conditions, NO reburn is found to be between 20% and 40%, depending on the type of coal, the use of N₂ or CO₂ diluent, the bulk O₂ concentration, and whether or not one considers reburn of volatile-NO_x. This dataset provides a unique opportunity to understand and differentiate the different sources and sinks of NO_x under oxy-fuel combustion conditions.     

Electron spectroscopy using excited atoms and photons: II. Penning ionization of diatomic molecules

A high resolution electrostatic electron analyser has been used to study Penning ionization electron spectra of H₂, HD, D₂, N₂, CO, NO and O₂ using helium metastable atoms (2¹S, 2³S). Results for H₂, N₂ and CO are in good agreement with other work. New data are presented for HD, D₂, NO and O₂. The Penning electron spectra are also compared to the 584 Å photoelectron spectra obtained in the same apparatus. The relative vibrational intensifies for the given electronic bands indicate that in most cases Franck—Condon factors for Penning ionization and photoionization are very similar. However for the O₂⁺(X²Π_g) band, the (2³S) Penning electron and photoelectron spectra show significant differences in the Franck—Condon envelopes This perturbation of the envelope for the Penning ionization may be explained by a competing autoionization process. The relative electronic transition probabilities are in many cases found to be different for Penning ionization and photoionization.     

Characterization of LaMnAl11O19 by FT-IR spectroscopy of adsorbed NO and NO/O2

The nature of the NO_x species produced during the adsorption of NO at room temperature and during its coadsorption with oxygen on LaMnAl₁₁O₁₉ sample with magnetoplumbite structure obtained by a sol-gel process has been investigated by means of in situ FT-IR spectroscopy. The adsorption of NO leads to formation of anionic nitrosyls and/or cis-hyponitrite ions and reveals the presence of coordinatively unsaturated Mn³⁺ ions. Upon NO/O₂ adsorption at room temperature various nitro-nitrato structures are observed. The nitro-nitrato species produced with the participation of electrophilic oxygen species decompose at 350 °C directly to N₂ and O₂. No NO decomposition is observed in absence of molecular oxygen. The adsorbed nitro-nitrato species are inert towards the interaction with methane and block the active sites (Mn³⁺ ions) for its oxidation. Noticeable oxidation of the methane on the NOx⁻-precovered sample is observed at temperatures higher than 350 °C due to the liberation of the active sites as a result of decomposition of the surface nitro-nitrato species. Mechanism explaining the promoting effect of the molecular oxygen in the NO decomposition is proposed.     

The role of Sb in the structure of Sb2O3–B2O3 binary glasses—an NMR and Mössbauer spectroscopy study

Glasses of general formula xSb₂O₃ (1−x)B₂O₃ (0x0.8) have been prepared by conventional melt- quenching. Mössbauer spectroscopy shows that a fraction of the Sb³⁺ is converted to Sb⁵⁺ and this fraction increases with x. High-field ¹¹B MAS NMR gives well-resolved resonances from boron atoms which are 3- and 4-coordinated to oxygen. The fraction of 4-coordinated boron, N₄, goes through a maximum value of 0.12±0.01 at x=0.5. The position of the maximum in N₄ is consistent with the cation potential for Sb³⁺, as observed for other systems. However, the low value of N₄ at this maximum is not so readily explained. The values are similar to those predicted if [BO₄]⁻ were stabilised by [SbO₄]⁺ but the trends with composition are different.     

Influence of temperature and humidity on NO x removal by corona discharge

The object of this experimental investigation was the influence of temperature and humidity on the efficiency of removal of NO _x by a pulsed corona discharge from a mixture N₂ : O₂ : CO₂ : H₂O : NO simulating a combustion flue gas. The pulsed corona discharge was generated in a wire-to-cylinder reactor. It was found that removal of NO _x was most efficient when H₂O concentration corresponded with the saturated vapour pressure. In the case of the operating gas containing constant H₂O concentration removal of NO _x decreased with increasing temperature of the operating gas. Dedicated to Prof. Jan Janča on the occasion of his 60^th birthday. This work is devoted to the 60^th birthday of Professor Jan Janca, our good colleague, merited teacher, researcher and famous physicist, discussion with whom stimulated this and other our work during years.     

Simultaneous removal of NO and Hg0 from flue gas over MnSmCo/Ti catalyst at low temperature

The MnSmCo/Ti catalyst was designed for the simultaneous removal of NO and Hg⁰ at low temperature. The MnSmCo/Ti catalyst exhibited 80% NO conversion, almost 100% N₂ selectivity and 100% Hg⁰ removal in the absence of HCl within the temperature range of 150–250 °C with a gas hourly space velocity of 100,000 h^?1. The influence of flue gas components on Hg⁰ oxidation was investigated and the NO and O₂ are mainly responsible for Hg⁰ oxidation. Hg balance analysis revealed that the Hg⁰ removal was achieved through chemisorption and catalytic oxidation. Furthermore, the Hg⁰ oxidation mechanism was explored using transient reaction along with temperature-programmed desorption of mercury and X-ray photoelectron spectroscopy. Hg⁰ oxidation proceeds through Mars–Maessen mechanism in which adsorbed Hg⁰ is bound to MnO_x to form weakly bonded HgMnO_x+1 species and follows Langmuir?Hinshelwood mechanism, where adsorbed Hg⁰ reacts with active NO₂ to generate HgO.     

Adsorption of pairs of NOx molecules on single-walled carbon nanotubes and formation of NO + NO3 from NO2

The adsorption of NO_x(x = 1, 2, 3) molecules on single-walled carbon nanotubes (SWCNTs) is investigated using first-principle calculations. Single NO, NO₂ and NO₃ molecules are found to physisorb on SWCNTs, but molecules can be chemisorbed in pairs on the top of carbon atoms at close sites of SWCNTs. The adsorption energy for pairs of NO or NO₃ molecules is larger than for pairs of NO₂ molecules. The local curvature is found to have a sizable effect on adsorption energies. The possibility of a surface reaction NO₂ + NO₂ → NO + NO₃ is examined and the relative pathway and barrier is calculated. The results are discussed with reference to available experimental results.     

DC discharge experiment in an Ar/N2/CO2 ternary mixture: A laboratory simulation of the Martian ionosphere's plasma environment

A low-pressure DC plasma discharge sustained in a 1.6%Ar–2.7%N₂–95.3%CO₂ ternary mixture is studied. This plasma was generated in a total pressure range from 1.0 to 4.0 Torr, a power of 6.3 W and a 12 l/min flow rate of gases. The electron temperature was found to be 8.41 eV and the ion density, in the order of 10⁹ cm⁻³. The species observed in the plasma mixture were CO₂, CO₂⁺, CN, CO, CO⁺, O₂, O₂⁺, N₂, N₂⁺, NO, C⁺, Ar and Ar⁺. At the pressure range in the present study, the species observed do not change their intensity due to an increase in the pressure and they separate in two groups according to their emission intensity: the band of the first group (CO₂, CO₂⁺ and CN) is approximately a factor of 3 more intense than that of the second group (CO, CO⁺, O₂, O₂⁺, N₂, N₂⁺, NO, C⁺, Ar and Ar⁺). The behavior of the emission intensities may be correlated to the constant ion density and electron temperature measured. Also, we observed the same constant behavior in the ratios of the neutral and positive species intensities to that of the N₂ intensity, as a function of pressure. This may suggest that the different rate coefficients and cross sections of elastic collision, excitation and de-excitation of electronic or vibrational levels, inelastic and superelastic collisions of electrons with the gas phase and products, neutral–neutral interactions, resonant charged transfer processes, recombination, to mention some, to produce these species change in the same proportion, as a function of the pressure to keep the relative ratios of the species almost constant.     

Computational study of the perhalogenated methyl nitrates CX3ONO2, CX x Y3−x ONO2 (X,Y = F,Cl)

Ab initio and density functional theory methods are employed to study the structures, harmonic frequencies, energetics and thermodynamic properties of the perhalogenated methyl nitrates, CX₃ONO₂, CX _x Y_3?x ONO₂ (X, Y =?F, Cl), which may be formed as secondary reactive intermediates in the coupling of the halogenated methylperoxy radicals with NO. Reaction energies are computed with respect to CX₃O₂ +?NO, CX _x Y_3?x O₂ +?NO and CX₃O +?NO₂, CX _x Y_3?x O +?NO₂ radical pair decomposition species. The large heat of formation values calculated indicate the high stabilization achieved upon halogenation of the methyl radical, particularly for the fluorinated compounds. Thus, the halogenated methyl nitrates which appear in the oxidation chain of halomethanes can be thermally deactivated under suitable temperature and pressure conditions and act as reservoir compounds for the halogenated methylperoxy radicals, CX₃O₂, CX _x Y_3?x O₂ and NO, in the troposphere. The computational investigation also demonstrates the significant structural changes caused by the halogen electron withdrawing effect, compared with the methyl analogue, CH₃ONO₂.