Similarities and dissimilarities in n-hexane and benzene sooting premixed flames

The flame structure of atmospheric-pressure sooting premixed flames of aliphatic and aromatic hydrocarbons with the same carbon atom number (hexane and benzene) were studied at similar temperatures and C/O ratios by sampling and chemical and spectroscopic analysis. The differences in the oxidation mechanism of hexane and benzene in fuel-rich conditions were found to produce a different chemical environment in the yield of light hydrocarbons and their relative compositions where soot inception occurs. The predominance of acetylene and simple aromatic reactants in the oxidation region of the benzene flame favoured the early appearance and steep rise of soot particles. Large formations of saturated and unsaturated hydrocarbons were observed in the main oxidation region of the hexane flame whereas a delayed formation of aromatics (mainly PAH) was observed at soot inception only after complete oxygen consumption. There are differences in soot inception mechanisms reflected by the soot structure from UV-vis spectral shapes and mass specific absorption coefficients. In the benzene flame, they appeared to be more ordered and aromatic with a narrower size of aromatic systems and/or more curved aromatic structures. By contrast, less ordering with a more complex aliphatic/aromatic structure and a larger variety of aromatic systems were found to characterize soot formed in the hexane flame.     

Influence of oxygen concentration on the sooting behavior of ethanol droplet flames in microgravity conditions

The influence of oxygen (O₂) concentration and inert on the sooting and burning behavior of large ethanol droplets under microgravity conditions was investigated through measurements of burning rate, flame temperature, sootshell diameter, and soot volume fraction. The experiments were performed at the NASA Glenn Research Center (GRC) 2.2 s drop tower in Cleveland, OH. Argon (Ar), helium (He), and nitrogen (N₂) were used as the inerts and the O₂ concentration was varied between 21% and 50% mole fraction at 2.4 atm. The unique configuration of spherically symmetric droplet flames enables effective control of sooting over a wide range of residence time of fuel vapor transport, flame temperature, and regimes of sooting to investigate attendant influences on burning behavior of droplets. For all inert cases, soot volume fraction initially increased as a function of the O₂ concentration. The highest soot volume fractions were measured for experiments in Ar environments and the lowest soot volume fractions were measured for the He environments. These differences were attributed to the changes in the residence time for fuel vapor transport and the flame temperature. For the He inert and N₂ inert cases, the soot volume fraction began to decrease after reaching a maximum value. The competition between the influence of residence time, rate of pyrolysis reactions, and soot oxidation can lead to this interesting behavior in which the soot volume fraction varies non-monotonically with increase in O₂ concentration. These experiments have developed new understanding of the burning and sooting behaviors of ethanol droplets under various O₂ concentrations and inert substitutions.     

Experimental and kinetic modeling study of sooting atmospheric-pressure cyclohexane flame

Experimental data and modelling results of the main products and intermediates from a fuel-rich sooting premixed cyclohexane flame were presented in this work. Model predictions well agree with experimental data both in sooting and non-sooting flames. Major and minor species are properly predicted, together with the soot yield. The initial benzene peak was demonstrated to be due to the fast dehydrogenation reactions of the cycloalkane, which gives rise to cyclohexene and cyclohexadiene both via molecular and radical pathways. Once formed cyclohexadiene quickly forms benzene whereas in the postflame zone, benzene comes from the recombination and addition reactions of small radicals, with C₃H₃ + C₃H₃ playing the most important role in these conditions. An earlier soot inception was detected in the cyclohexane flame with respect to a n-hexane flame and this feature is not reproduced by the model that foresees soot formation significant only in the second part of the flame. The model insensitivity of soot to the reactant hydrocarbon was also observed comparing the predictions of three flames of cyclohexane, 1-hexene and n-hexane with the same temperature profile. A sensitivity analysis revealed that soot primarily comes from the HACA mechanism for the three flames, acetylene being the key species in the nucleation. Experimental data on soot inception seem to indicate the importance of the early formation of benzene, that depends on the fuel structure. It is thus important to further investigate the role of benzene and aromatics in order to explain this discrepancy.     

Measurement and modeling of the sooting propensity of binary fuel mixtures

The sooting behaviour of binary fuel mixtures was evaluated both experimentally and through computer simulations. The soot volume fraction in laminar diffusion flames of mixtures of ethylene/propane, methane/ethylene, methane/propane, methane/ethane, methane/butane, ethane/propane and ethane/ethylene fuels was measured using 2-dimensional line of sight attenuation. A synergistic effect was observed for the ethylene/propane, methane/ethylene, methane/ethane and ethane/ethylene mixtures. The synergistic effect translated into a higher soot concentration for a mixture fraction than could be yielded by the added contribution of both pure fuels. Such an effect was not observed for the methane/propane, methane/butane and ethane/propane mixtures. Through experiments in which the flame temperature was kept constant, it was determined that the synergistic effect in the methane/ethylene mixture is very temperature dependent whereas, that in the ethylene/propane mixture is not. This phenomenon was further studied through the modeling of the ethylene/propane mixture. Numerical simulations were carried out using two different soot models. The simulations confirmed the presence of a synergistic effect. It was found that the effect could be directly correlated to a synergistic effect in the concentration of n-C₄H₅ and n-C₄H₃, which could be traced back to an interaction between ethylene and methyl radical species. These results yield further insight into the pathways to soot formation and highlight the importance of further analyzing binary fuel mixtures as a means of understanding soot formation in practical devices using industrial fuels.     

Simulation on simultaneous estimation of non-uniform temperature and soot volume fraction distributions in axisymmetric sooting flames

For visualizing non-uniform absorbing, emitting, non-scattering, axisymmetric sooting flames, because conventional two-color emission methods are no longer suitable, a three-color emission method for the simultaneous estimation of temperature and soot volume fraction distributions in these flames is studied in this paper. The spectral radiation intensities at wavelengths of red, green, and blue, which may be derived from color flame images, are simulated for the inverse analysis. Then the simultaneous estimation is carried out from the spectral radiation intensities by using a Newton-type iteration algorithm and the least-squares method. In this method, a factor is used to balance the wide variation of spectral radiation intensities due to both the wide ranges of temperature and wavelength of the flame radiation. The results indicate that the three-color method is suited for the reconstruction of flame structures with single or double peaks with small difference between the peak and valley. For a double-peaked flame structure with larger peak and valley difference, reasonable result can be obtained just when the mean square deviations of measurement data are small, for example, not more than 0.01.     

Modeling of radiative heat transfer in 3D complex boiler with non-gray sooting media

The radiative heat transfer problem is solved for 3D complex industrial boiler with five baffles containing a mixture of carbon dioxide and water vapor for non-uniform temperature fields. A numerical formulation using the FTn finite volume method coupled with the bounded high-order resolution CLAM scheme, the blocked-off-region procedure and the narrow-band based weighted-sum-of-gray-gases (WSGG) [Kim OJ, Song T-H. Data base of WSGGM-based spectral model for radiation properties of combustion products, JQSRT 2000; 64: 379-94] model is adapted. The effect of soot volumetric fraction, particle temperature and uniform particle concentration on the radiative heat flux and radiative heat source is investigated and discussed. Also the advantages, in non-gray media, of the FTnFVM compared to the classical FVM are highlighted.     

Validation experiments for spatially resolved one-dimensional emission spectroscopy temperature measurements by dual-pump CARS in a sooting flame

In this work, an emission spectroscopic (ES) technique for the determination of soot temperatures in an axisymmetric flame is validated against coherent anti-Stokes Raman spectroscopy (CARS) as preparation for a zero gravity measurement campaign. In order to reduce valuable measurement times during the parabolic flights, a setup for spatially resolved one-dimensional measurements along a line has been built up using an imaging spectrometer and a CCD-camera for data acquisition.In order to assess the performance of the ES technique, accurate coherent anti-Stokes Raman scattering (CARS) measurements have been performed at the same conditions. Hereby, great care has to be taken to minimize the known interferences in sooting flames. The non-resonant signal contribution was suppressed by a polarization technique and the signal wavelength was shifted to an interference free region. These modifications are discussed in detail. The temperatures obtained by both methods are in good agreement in most regions of the flame. It turned out that the described approach for ES is an appropriate and robust alternative for measuring temperatures in sooting axisymmetric flames, if more accurate techniques cannot be applied, e.g., during investigations in zero-g parabolic flight experiments.     

Molecular species adsorbed on soot particles issued from low sooting methane and acetylene laminar flames: A laser-based experiment

Recent advances in the field of laser desorption/laser ionization mass spectrometry (LD/LI/MS) have renewed interest in these separation methods for fast analysis of chemical species adsorbed on soot particles. These techniques provide mass-separation of the desorbed phase with high selectivity and sensitivity and require very small soot samples. Combining LD/LI/MS with in situ measurements of soot and gaseous species is very promising for a better understanding of the early stage of soot growth in flames. In this work, three lightly sooting laminar jet flames (a methane diffusion flame and two premixed acetylene flames of equivalence ratio (?) = 2.9 and 3.5) were investigated by combining prompt and 50 ns-delayed laser-induced incandescence (LII) for spatially resolved measurements of soot volume fraction (f_v) and laser-induced fluorescence (LIF) of polycyclic aromatic hydrocarbons (PAH). Soot and PAH calibration is performed by two-colour cavity ring-down spectroscopy (CRDS) at 1064 and 532 nm. Soot particles were sampled in the flames and analysed by LD/LI/Time-of-flight- MS. Soot samples are cooled to −170 °C to avoid adsorbed phase sublimation (under high vacuum in the TOF-MS). Our set-up is novel because of its ability to measure very low concentration of soot and PAH together with the ability to identify a large mass range of PAHs adsorbed on soot, especially volatile two-rings and three-rings PAHs. Studied flames exhibited a peak f_v ranging from 15 ppb (acetylene, ? = 2.9) to 470 ppb (acetylene, ? = 3.5). Different mass spectra were found in the three flames, each exhibiting one predominant PAH mass; 202 amu (4-rings) in methane, 178 amu (3-rings) in acetylene,? = 2.9 and 128 amu (2-rings) in acetylene, ? = 3.5. These variations with flame condition contrasts with other recent studies and is discussed. The other PAH masses ranged from 102 (C₈H₆) to 424 amu (C₃₄H₁₆) and are well predicted by the stabilomer grid of Stein and Farr.     

A comparative study of nanoparticles in premixed flames by scanning mobility particle sizer, small angle neutron scattering, and transmission electron microscopy

Scanning mobility particle sizer (SMPS) and transmission electron microscopy (TEM) studies were conducted for TiO₂ and soot particles. The TiO₂ particles were produced from a premixed stagnation ethylene-oxygen-argon flame (? = 0.36) doped with titanium tetraisopropoxide. Soot was generated from a burner-stabilized premixed ethylene-oxygen-argon flame (? = 2.5). The close agreement among SMPS, TEM, and X-ray diffraction results for TiO₂ nanoparticles demonstrates that the probe sampling/mobility measurement technique is accurate for on-line analysis of the size distribution of particles as small as 3 nm in diameter. In the case of soot, notable disagreement between the SMPS and TEM sizes was found and attributable to the fact that the soot taken from the flame studied herein is liquid-like and that upon deposition on the TEM grid, the primary particles do not retain their sphericity. This interpretation is supported by measurements with photo ionization aerosol mass spectrometry, small angle neutron scattering, and thermocouple particle densitometry.     

Nuclear electroproduction of negative pions below threshold

We calculate the electroproduction of negative pions into bound atomic states. The effect of the strong π-nucleus interaction is included in the calculation.     

Thermoelectric properties of pressed bismuth nanoparticles

Theory predicts a substantial increase in the dimensionless figure of merit as the dimensionality and characteristic size of a material are decreased. We explore the use of bismuth nanoparticles pressed into pellets as potential increased efficiency thermoelectric materials. The figure of merit of these pellets is determined by independently measuring the electrical conductivity, thermal conductivity and Seebeck coefficient. The results from the nanoparticle sample are compared to microparticle-based samples. Both sample types show a slight reduction in thermal conductivity relative to bulk bismuth and a Seebeck coefficient near or slightly larger in magnitude than bulk bismuth. These changes are dwarfed by a hundred-fold decrease in the electrical conductivity due to porosity and an oxide layer on the particles. The low conductivity leads to figures of merit at least two orders of magnitude smaller than bulk bismuth. Oxide layer removal and reduced pellet porosity will be required to increase the figure of merit.     

Strong-field double ionization of Ar below the recollision threshold

Nonsequential double ionization of Ar by 45 fs laser pulses (800 nm) at (4-7)x10;{13} W/cm;{2} was explored in fully differential measurements. Well below the field-modified recollision threshold we enter the multiphoton regime. Strongly correlated back-to-back emission of the electrons along the polarization direction is observed to dominate in striking contrast to all previous data. No effect of Coulomb repulsion can be found, the predicted cutoff in the sum-energy spectra of two emitted electrons is confirmed, and the potential importance of multiple recollisions is discussed.     

Speculations on the cluster radius below the percolation threshold

We suggest the average radius of percolation clusters withs sites to vary belowp _c ass ⁰, where ₀ is the exponent for the mean radius of self-avoiding walks. This result gives the desired asymptotic behavior of the correlation function for percolation (connectivity) and is consistent with Leath's Monte Carlo data.     

Pump-dependent luminescence in the Ag nanoparticles doped by Erbium

A substantial spectral shift of the UV-laser induced luminescence in the Ag nanoparticles (NP) doped by Er³⁺ ions attached to ITO substrates was observed at T = 4.2 K. We have established high energy spectral shift of principal luminescent maxima (from wavelength equal to about 1.45 up to 1.15 μm) with increasing of the pumping nanosecond nitrogen laser power density up to 1.1 GW/cm² operating at λ = 337 nm. With increasing Erbium content with respect to Ag the spectral shift and spectral line broadening increase. It may be caused by specific features of trapping level occupation kinetics on interfaces NP/ITO substrate. The observed process is fully reversible. The luminescence is observed only during excitation by the 337 nm laser pulses and is absent for laser pulses operating at other wavelengths (like excimer laser at 218 nm and nitrogen laser at 371 nm).     

Combustion-formed nanoparticles

The processes by which carbonaceous nanoparticles are produced from combustion of liquid and gaseous fuels are reviewed. The focus of the paper is on the formation and properties of nanoparticles in laboratory laminar, premixed and diffusion flames and on the most popular methods of sampling and detection of these particles. Particle chemical nature is analyzed from data obtained by several measurement techniques. Measurements characterizing nanoparticles in the exhausts of practical combustion systems such as engines and commercial burners are also reported. Two classes of carbonaceous material are mainly formed in combustion: nanoparticles with sizes in the range 1-5 nm, and soot particles, with sizes from 10 to 100 nm. Nanoparticles show unique chemical composition and morphology; they maintain molecular characteristics in terms of chemical reactivity, but at the same time exhibit transport and surface related phenomena typical of particles. The emission of these particles contributes to atmospheric pollution and constitutes a serious health concern. A simplified modeling analysis is used to show how the growth of aromatics and the chemical nature of the particles depend on temperature and radical concentration distributions encountered in flames.     

Dynamics below the depinning threshold in disordered elastic systems

We study the steady-state low-temperature dynamics of an elastic line in a disordered medium below the depinning threshold. Analogously to the equilibrium dynamics, in the limit T-->0, the steady state is dominated by a single configuration which is occupied with probability 1. We develop an exact algorithm to target this dominant configuration and to analyze its geometrical properties as a function of the driving force. The roughness exponent of the line at large scales is identical to the one at depinning. No length scale diverges in the steady-state regime as the depinning threshold is approached from below. We do find a divergent length, but it is associated only with the transient relaxation between metastable states.     

碰撞阈值下氩原子非次序双电离

利用三维经典系综模型研究了碰撞阈值下氩原子的非次序双电离.计算结果表明,关联电子末态纵向动量主要分布在二、四象限,且在原点附近几乎没有分布;Ar²⁺离子末态纵向动量谱在零动量附近呈单峰结构.上述结果与实验结果 定量一致.轨迹分析表明,在碰撞阈值下,氩原子非次序双电离的微观物理机理在不同激光强度下是不相同的.当激光强度I=0.7×10¹⁴ W/cm²时,一次碰撞主导重碰撞过程.而当I=0.4×10^{14关键词： 非次序双电离 库仑引力 碰撞阈值 电子关联}     

Cavity ring-down spectroscopy of metallic gold nanoparticles

The optical properties of supported gold nanoparticles with sizes of 1.3 nm, 1.6 nm, 2.5 nm, and 2.9 nm have been studies by using cavity ring-down spectroscopy in the photon energy range between 1.8 eV and 3.0 eV. The obtained results show the possibility to obtain optical information of nanoassembled materials with high sensitivity. The experimental findings are compared to calculations using Mie-Drude theory. Whereas the broadening of the surface plasmon resonance with decreasing size is well described by this model, the observed blue-shift of the surface plasmon resonance contradicts the predictions of the Mie-Drude theory. The latter effect can be explained by the presence of a skin region with decreased polarizability typical for coinage metal particles. Furthermore, it is found that the supported gold nanoparticles are robust under ambient conditions, an important issue when using these materials for optical applications.     

Directly writing with nanoparticles at the nanoscale using dip-pen nanolithography

Well-defined nanostructures were written with quantum dots and magnetic nanoparticles on gold and mica surfaces using dip-pen nanolithography at room temperature. The structures with both the nanoparticles were characterised by in situ topography measurements, and the quantum dot structures were mapped by fluorescence mapping. It is demonstrated that structures of various kinds such as dots and lines can be prepared using such nanoparticles on suitably prepared surfaces.