Combustion properties of H2/N2/O2/steam mixtures

The present work reports new experimental and numerical results of the combustion properties of hydrogen based mixtures diluted by nitrogen and steam. Spherical expanding flames have been studied in a spherical bomb over a large domain of equivalence ratios, initial temperatures and dilutions at an initial pressure of 100 kPa (T_ini = 296, 363, 413 K; N₂/O₂ = 3.76, 5.67, 9; %Steam = 0, 20, 30). From these experiments, the laminar flame speed $S_L^0$, the Markstein length L’, the activation energy Ea and the Zel'dovich β number have been determined. These parameters were also simulated using COSILAB^® in order to verify the validity of the Mével et al. [1] detailed kinetic mechanism. Other parameters as the laminar flame thickness δ and the effective Lewis number Le_eff were also simulated. These new results aim at providing an extended database that will be very useful in the hydrogen combustion hazard assessment for nuclear reactor power plant new design.     

Experimental determination of counterflow ignition temperatures and laminar flame speeds of C2–C3 hydrocarbons at atmospheric and elevated pressures

Experimental data were acquired for: (1) the ignition temperatures of nitrogen–diluted ethylene and propylene by counterflowing heated air for various strain rates and system pressures up to 7 atm; (2) the laminar flame speeds of mixtures of air with acetylene, ethylene, ethane, propylene, and propane, deduced from an outwardly propagating spherical flame in a constant-pressure chamber, for extensive ranges of lean-to-rich equivalence ratio and system pressure up to 5 atm. These data, respectively, relevant for low- to intermediate-temperature ignition chemistry and high-temperature flame chemistry, were subsequently compared with calculated results using a literature C₁–C₃ mechanism and an ethylene mechanism. Noticeable differences were observed in the comparison for both mechanisms, and sensitivity analyses were conducted to identify the reactions of importance.     

基于Raman与FTIR对掺甲烷乙烯/氢气扩散火焰碳烟有序度和官能团的研究

以甲烷、乙烯、氢气混合扩散火焰碳烟为研究对象,采用激光共聚焦拉曼光谱（Raman）和傅里叶红外光谱（FTIR）研究了不同掺甲烷比例下乙烯、氢气混合火焰碳烟有序度及官能团的分布特性,分析了碳烟石墨化和官能团分布,揭示了掺甲烷对乙烯/氢气（氢气比例30%）层流扩散火焰的碳烟生成影响规律。Raman研究表明在甲烷掺混比为3%和7%时,在火焰高度低于4cm位置生成的碳烟有序程度显著降低,表明在此区域存在明显的碳烟生成协同效应;甲烷掺混比增大超过10%时,协同效应基本消失,碳烟有序度上升。FTIR研究表明掺混甲烷对碳烟官能团组成影响明显。掺混甲烷后脂肪族官能团相对含量整体提高。随着甲烷掺杂比的增大,CH₂相对含量增大到一峰值后减小。碳烟中芳香族官能团含量随着火焰高度的上升含量下降明显。掺混3%和7%甲烷,芳香族官能团在2和3 cm火焰高度时,芳香族官能团的含量明显上升。掺混甲烷比高于10%时,芳香族官能团的含量则有所降低。表明少量甲烷掺混使得CH₃和C₃H₃生成有了新的途径,CH₃和C₃H₃增加,而C₂H₄和C₂H₂减少不明显,从而促进了多环芳香烃(PAHs)的生成。继续增加甲烷因为稀释作用会抑制C₂H₂生成从而减少PAHs的生成,芳香族相对含量降低,因而降低了碳烟的生成。研究揭示了甲烷对乙烯/氢气层流扩散火焰中碳烟形成的相互作用：在低甲烷掺混比时存在协同效应促进碳烟生成,而在高甲烷掺混比时协同效应消失。     

Comparison of CH4/H2 and C2H6/H2 inductively coupled plasma etching of ZnO

CH₄/H₂-based discharges are attractive for dry etching of single crystal ZnO because of their non-corrosive nature. We show that substitution of C₂H₆ for CH₄ increases the ZnO etch rate by approximately a factor of 2 both with and without any inert gas additive. The C₂H₆/H₂/Ar mixture provides a strong enhancement over pure Ar sputtering, in sharp contrast to the case of CH₄/H₂/Ar. The threshold ion energy for initiating etching is 42.4 eV for C₂H₆/H₂/Ar and 59.8 eV for CH₄/H₂/Ar. The etched surface morphologies were smooth, independent of the chemistry and the Zn/O ratio in the near-surface region was unchanged within experimental error after etching with both chemistries. The plasma etching improved the band-edge photoluminescence intensity and suppressed the deep level emission from the bulk ZnO under our conditions, due possibly to removal of surface contamination layer.     

Second-order conditional moment closure modeling of a turbulent CH4/H2/N2 jet diffusion flame

The second-order CMC model for a detailed chemical mechanism is used to model a turbulent CH₄/H₂/N₂ jet diffusion flame. Second-order corrections are made to the three rate limiting steps of methane–air combustion, while first-order closure is employed for all the other steps. Elementary reaction steps have a wide range of timescales with only a few of them slow enough to interact with turbulent mixing. Those steps with relatively large timescales require higher-order correction to represent the effect of fluctuating scalar dissipation rates. Results show improved prediction of conditional mean temperature and mass fractions of OH and NO. Major species are not much influenced by second-order corrections except near the nozzle exit. A parametric study is performed to evaluate the effects of the variance parameter in log-normal scalar dissipation PDF and the constants for the dissipation term in conditional variance and covariance equations.     

Experimental and kinetic modeling study of C2H4 oxidation at high pressure

A detailed chemical kinetic model for oxidation of C₂H₄ in the intermediate temperature range and high pressure has been developed and validated experimentally. New ab initio calculations and RRKM analysis of the important C₂H₃ + O₂ reaction was used to obtain rate coefficients over a wide range of conditions (0.003-100 bar, 200-3000 K). The results indicate that at 60 bar and medium temperatures vinyl peroxide, rather than CH₂O and HCO, is the dominant product. The experiments, involving C₂H₄/O₂ mixtures diluted in N₂, were carried out in a high pressure flow reactor at 600-900 K and 60 bar, varying the reaction stoichiometry from very lean to fuel-rich conditions. Model predictions are generally satisfactory. The governing reaction mechanisms are outlined based on calculations with the kinetic model. Under the investigated conditions the oxidation pathways for C₂H₄ are more complex than those prevailing at higher temperatures and lower pressures. The major differences are the importance of the hydroxyethyl (CH₂CH₂OH) and 2-hydroperoxyethyl (CH₂CH₂OOH) radicals, formed from addition of OH and HO₂ to C₂H₄, and vinyl peroxide, formed from C₂H₃ + O₂. Hydroxyethyl is oxidized through the peroxide HOCH₂CH₂OO (lean conditions) or through ethenol (low O₂ concentration), while 2-hydroperoxyethyl is converted through oxirane.     

Elucidating surface properties of dry-etched ZnO using H2/CH4 and H2/CH4/Ar plasma

This paper reports a study of reactive ion etching (RIE) of n-ZnO in H₂/CH₄ and H₂/CH₄/Ar gas mixtures. Variables in the experiment were gas flow ratios, radio-frequency (rf) plasma power, and total pressure. Structural and electrical parameters of the etched surfaces and films were determined. Both the highest surface roughness and highest etching rate of ZnO films were obtained with a maximum rf power of 300 W, but at different gas flow ratios and working pressures. These results were expected because increasing the rf power increased the bond-breaking efficiency of ZnO. The highest degree of surface roughness was a result of pure physical etching by H₂ gas without mixed CH₄ gas. The highest etching rate was obtained from physical etching of H₂/Ar species associated with chemical reaction of CH₄ species. Additionally, the H₂/CH₄/Ar plasma treatment drastically decreased the specific contact and sheet resistance of the ZnO films. These results indicated that etching the ZnO film had roughened the surface and reduced its resistivity to ohmic contact, supporting the application of a roughened transparent contact layer (TCL) in light-emitting diodes (LEDs).     

ArF laser-induced discharge interruption in a mixture of C2H3Cl/CF4/CH4, CF4/CH4, and C2H3Cl/He

The ArF-laser (193-nm)-induced discharge interruption is comparatively described in a mixture of C₂H₃Cl/CF ₄/CH₄, CF₄/CH₄, and C₂ H₃Cl/He using a hollow-cathode-type discharge tube. The unfocused ArF laser (typically 27 mJ/cm² and 10 ns duration) illuminated both the negative glow inside the hollow cathode and the column between the two electrodes. With a 1.8-torr mixture of C₂ H₃Cl/CF₄, the discharge current of 1 mA was decreased rapidly with a current-decay time constant of 1 μs and a current-decay rate of 1 kA/s. With a 1.5-torr mixture of CF₄/CH₄, 2.2 μs and 450 A/s were obtained. With a 1.5-torr mixture of CH₂H₃Cl/He, a time constant of over 3 μs and a rate of less than 300 A/s were obtained. An analysis of the discharge interruption induced by ArF-laser irradiation is given in terms of photon-plasma kinetics. The current peak induced by ArF irradiation is also explained for a mixture of C₂H₃ Cl/He in terms of photoionization and photodetachment processes     

Absolute coverage of C2H2 and C2H4 on Pt(111)

Quantitative XPS measurements have been performed in order to determine the absolute coverage of acetylene and ethylene adsorbed on Pt(111) showing a 2 × 2 LEED pattern. This LEED pattern has so far been attributed to a 2 × 2 superstructure with a coverage of 0.25. A quantitative evaluation of the C(1s) peak intensities for these adsorbed layers in comparison with adsorbed CO shows that the coverage is 0.5 instead of 0.25. Therefore the 2 × 2 LEED pattern should be assigned to a 2 × 1 superstructure in three domains rather than a 2 × 2 superstructure.     

Geometric shielding corrections for total cross section calculations of electron scattering by CH4, C2H6, C2H3F3, C2H4, C2F4, C2Cl4 and C2Cl2F2 from 30–5000?eV

To quantify the changes in the geometric shielding effect in a molecule as the incident electron energy varies, an empirical fraction, which represents the total cross section contributions of shielded atoms in a molecule at different energies, is presented. Using this empirical fraction, the total cross sections for electron scattering by CH₄, C₂H₆, C₂H₃F₃, C₂H₄, C₂F₄, C₂Cl₄ and C₂Cl₂F₂ are calculated over a wide energy range from 30 to 5000 eV by the additivity rule model at the Hartree-Fock level. The quantitative total cross sections are compared with those obtained by experiment and other theories where available. Good agreement is attained above 100 eV.     

Pressure broadening and collisional shift of the Rb D2 absorption line by CH4, C2H6, C3H8, n-C4H10, and He

The pressure broadening and shift rates of the rubidium D2 absorption line 5²S_1/2→5²P_3/2 (780.24 nm) with CH₄, C₂H₆, C₃H₈, n-C₄H₁₀, and He were measured for pressures ≤80 Torr using high-resolution laser spectroscopy. The broadening rates γ_B for CH₄, C₂H₆, C₃H₈, n-C₄H₁₀, and He are 28.0, 28.1, 30.5, 31.3, and 20.3 (MHz/Torr), respectively. The corresponding shift rates γ_S are −8.4, −8.8, −9.7, −10.0, and 0.39 (MHz/Torr), respectively. The measured rates of Rb for the hydrocarbon buffer gas series of this study are also compared to the theoretically calculated rates of a purely attractive van der Waals difference potential. Good agreement is found to exist between measured and theoretical rates.     

The influence of structural defects on the adsorption of simple molecules (H2, C2H2, C2H4, C2H6, CO,NO) on rhenium single crystals

Using Thermal Programmed Desorption (TPD), Low Energy Electron Diffraction (LEED) and Auger Electron Spectroscopy (AES) we have studied the adsorption of hydrogen-containing molecules (H₂, C₂H₂, C₂H₄, C₂H₆) and oxygen-containing molecules (CO and NO) on two vicinal planes of the Re(0001) surface. The two surfaces are designated thus: ReS ¦14(0001)(101̄1)¦, ReS |6(0001)(167̄1) | . The structural defects have little effect on the adsorption of hydrogen and the hydrocarbons. They are more influential in the case of the oxygen-containing molecules. This is particularly true for CO; on the kink sites the CO molecules can completely dissociate whereas only a partial dissociation is possible on the steps. These results should be viewed in relation to the strong bond energy between carbon and oxygen in a CO molecule of 256 kcal/mole and the great affinity of oxygen for rhenium; E_Re?O = 127 kcal/mole.     

Ab initio SCF investigation of the core and inner valence electron binding and relaxation energies of the CH4, C2 H2 and C2 H6 molecules

Ab initio ΔSCF values of the electron binding and relaxation energies are presented for the four deepest molecular orbitals of methane, acetylene and the two symmetry forms of ethane. Special attention is paid to the inner valence molecular region with regard to the symmetry-constrained Hartree—Fock calculations. The symmetry-constrained effect for the 1t₂ outer valence orbital of methane has also been investigated. The phenomena due to the broken symmetry are discussed on the basis of the configuration-interaction procedure.     

CO2 addition and pressure effects on laminar and turbulent lean premixed CH4 air flames

An experimental study on CH₄–CO₂–air flames at various pressures is conducted by using both laminar and turbulent Bunsen flame configurations. The aim of this research is to contribute to the characterization of fuel lean methane/carbon dioxide/air premixed laminar and turbulent flames at different pressures, by studying laminar and turbulent flame propagation velocities, the flame surface density and the instantaneous flame front wrinkling parameters. PREMIX computations and experimental results indicate a decrease of the laminar flame propagation velocities with increasing CO₂ dilution rate. Instantaneous flame images are obtained by Mie scattering tomography. The image analysis shows that although the height of the turbulent flame increases with the CO₂ addition rate, the flame structure is quite similar. This implies that the flame wrinkling parameters and flame surface density are indifferent to the CO₂ addition. However, the pressure increase has a drastic effect on both parameters. This is also confirmed by a fractal analysis of instantaneous images. It is also observed that the combustion intensity S_T/S_L increases both with pressure and the CO₂ rate. Finally, the mean fuel consumption rate decreases with the CO₂ addition rate but increases with the pressure.     

工作压强对射频辉光放电H2/C4H8等离子状态的影响

利用辉光放电技术采用等离子体质谱诊断的方法研究了不同工作 压强下H₂/C₄H₈混合气体等离子体中 主要正离子成分及其能量的变化规律, 并分析了压强对H₂/C₄H₈混合气体的离解机理以及主要正离子形成过程的影响. 结果表明: 随着工作压强的增加, 碳氢碎片离子的浓度和能量均逐渐减小. 当工作压强为5 Pa时, H₂/C₄H₈混合气体等离子体中C₃H₅⁺相对浓度最大; 压强为10 Pa时, C₃H₃⁺相对浓度最大; 压强为15, 20 Pa时, C₂H₅⁺相对浓度最大; 压强为25 Pa时, C₄H₉⁺相对浓度最大. 对H₂/C₄H₈等离子体中的主要组分及其能量分布所进行的定性分析, 将为H₂/C₄H₈混合气体辉光放电聚合物涂层的工艺参数优化提供参考技术基础. 关键词： 辉光放电技术 等离子体质谱诊断 工作压强     

Auger spectra of CO,C2H4, C2N2 and C6H6 adsorbed on Pt(111)

Electron excited carbon KVV Auger spectra of CO, C₂H₄, C₂N₂ and C₆H₆ adsorbed on Pt(111) are compared. By estimating the effective Coulomb interaction between the final-state holes it is possible to associate some features with transitions observed in free molecule spectra, but others must involve at least one electron with energy within the conduction band of the metal. Such “cross-transitions” are associated with strong 2π* character of filled states in the presence of a core hole in molecules such as CO.     

Ultrafast motion of liquids C2H4Cl2 and C2H4Br2 studied with a femtosecond laser

Transient optical Kerr effect of liquids C₂H₄Cl₂ and C₂H₄Br₂ is investigated, for the first time to our knowledge, with a femtosecond (fs) probe laser delayed with respect to a coherent fs pump laser. Coherent coupling and electronic Kerr signals are observed around zero delay when pump and probe overlap. Persisting after the pump-probe overlap are Kerr signals arising from the torsional and other intramolecular vibrations of the trans and gauche conformations; Kerr signals arising from the intermolecular motion are also observed. Vibrational quantum interference is only observed in liquid C₂H₄Br₂ and the related beats data are fitted with the torsional vibrations, 91 cm⁻¹ (gauche) and 132 cm⁻¹ (trans), and the CCBr angle-bending vibrations, 231 cm⁻¹ (gauche) and 190 cm⁻¹ (trans), with dephasing times, 0.45 ps, 0.45 ps, 2 ps, and 1.5 ps, respectively. These vibrational frequencies agree with those obtained in the frequency-domain. That no vibrational mode is observed for C₂H₄Cl₂ might be attributed to ineffective Raman-pumping. Kerr signals observed after the pump-probe overlap are Fourier transformed to give the spectra of the intermolecular motion and the vibrational spectrum, which agrees with the one observed in the infrared absorption and/or Raman scattering heretofore.     

The chemisorption of CO,CO2, C2H2, C2H4, H2 and NH3 on the clean Fe(100) and (111) crystal surfaces

The chemisorption of small molecules (CO, CO₂, C₂H₂, C₂H₄, H₂ and NH₃) has been studied on the clean Fe(110) and (111) crystal faces by low-energy electron diffraction (LEED) and thermal desorption. C₂H₄ and C₂H₂ yield the same sequence of surface structures that change with temperature and crystal orientation. CO and CO₂ chemisorption similarly results in the formation of the same types of surface structures that change with surface temperature and crystal orientation. Ammonia forms several ordered surface structures on both iron crystal faces. All of the molecules decompose as a function of temperature on the iron surfaces as indicated by the Auger and thermal desorption spectra.     

Experimental and Theoretical Study of Hydrogen Atom Abstraction from C2H6 and C4H10 by Zirconium Oxide Clusters Anions

使用配有团簇产生和化学反应源的飞行时间质谱装置,研究了锆氧阴离子团簇Zr_xOy^-与乙烷和丁烷的反应. 在反应中发现了Zr₂O₅H^-和Zr₃O₇H^-产物. 用密度泛函理论研究了乙烷在Zr₂O₅^-上的反应通道,发现乙烷脱氢反应可以发生,从而证明观察到的产物是源于脱氢反应. 该工作揭示了锆氧负离子团簇与烷烃反应中的新通道.     

Experimental study on parameters of dust plasma in SiH4/C2H4/Ar discharges

Measurements of dust plasma parameters were carried out in the discharges of （SiH4/C2H4/Ar） mixtures. Dust particles were formed in the capacitively coupled radio-frequency discharge of these reactive mixtures in a cylindrical chamber. Langmuir probe was employed for diagnosing and measuring the important plasma parameters such as electron density and electron temperature. The results showed that the electron density dropped, and in contrast the electron temperature rose when the dust particles formed. The curves of the electron density and temperature versus the RF power and pressure were presented and analysed. Further, it was found that the wriations of electron temperature and the size of dust void with the RF power followed the similar trends. These trends might be useful for understanding more about the characteristics of dusty voids.