非平衡等离子体有机化学进展

本文综述了非平衡等离子体有机化学几方面的进展, 如反应器以及等离子体在有机反应中的应用,其中包括气体、液体和固体反应。     

Numerical simulation of a nonequilibrium plasma jet in an applied magnetic field using three-fluid model

A three fluid model is applied for the numerical simulation of the axisymmetric flow and temperature fields in a nonequilibrium argon plasma jet which can be controlled by applying art electromagnetic field. The effects of the magnetic field on the characteristics of each plasma species, i.e., electrons, positive ions, and neutral particles, should be accurately clamed. The three-fluid model applied here can clarify the behavior of each plasma species. Equations of conservation for each plasma species coupled witli the generalized Ohm's law, Maxwell's equations, and the equation of state are simultaneously solved taking variable transport properties into account. It is shown that the electron temperature is the highest and the electron velocity is strongly influenced by the magnetic field. Furthermore, the momentum and energy exchanges through electrons can be varied even by a small magnetic flux.Nomenclature B magnetic flux density (T) - c mathematical mean thermal velocity (m/s) - C _p specific heat at constant pressure (J/(kg · K)) d ₀ nozzle diameter (m) - e electron charge (C) - E electric field (V/m) - E effective electric field (V/m) - Ex ^* energy transfer by collision - g relative velocity (m/s) - G partition function - h enthalpy (J/kg) - h _Planck Planck's constant (J · s) - H diffusion enthalpy (J/kg) - j ^* current density (j/en ₀ u ₀ - k Boltzmann constant (J/K) - l mean free path length (m) - L ₀ length of calculation domain along stream (m) - m mass (kg) - M ^* momentum transfer by collision - n number density (m^–3) - production rate of species [/(m³ · 3)] - p pressure (Pa) - collision cross section (m²) - q heat flux (W/m²) - r radial coordinate (m) - r _in inner radius of round tube (m) - R gas constant (J/(kg · K)) - R _in magnetic Reynolds number (=u ₀ d ₀₀µ₀) - s ion slip coefficient [=( _n /gr ₂)² _{e i} ] - S ₁ cross section parameter (m²/J) - T temperature (K) - u axial component of velocity (m/s) - U axial component of diffusion velocity (m/s) - radial component of velocity (m/s) - V radial component of diffusion velocity (m/s) - w peripheral component of velocity (m/s) - W peripheral component of diffusion velocity (m/s) - z axial coordinate (m) - degree of ionization [=n _e /)n _e +n _i +n _n )] - Hall parameter (= ) - ₀ permittivity in vacuum (F/m) - ge ₁ first excitation energy (J) - _ion ionization energy (J) - viscosity (Pa · s) - peripheral coordinate - thermal conductivity [W/(m · K)] - µ₀ permeability in vacuum (H/m) - density (kg/m³) - electrical conductivity (S/m) - mean collision time (s) - cyclotron frequency (Hz) Suffix 0 nozzle exit - e electron - i ion - n neutral particle - r radial component - s plasma species ofs kinds - z axial component - gq peripheral component Originally published inTrans. of the Japan Society of Mechanical Engineers, Ser.B,60, No. 577, 3072–3079 (1994) (in Japanese).     

激光等离子体诱导聚甲基硅氧烷的结构重组

将脉冲激光束在惰性气氛中溅射石墨产生的等离子体,与一维链状聚甲基硅氧烷的蒸气束流反应,在产物中通过真空升华和重结晶分离出了两种单晶,经X射线衍射测定为具有(CH3SiO1.5)n(n=8,10)组成的硅氧烷,它们均具有多面体的三维笼状构型。通过色-质联用还检测到其它硅氧烷化合物,其中某些产物已表征为二维多环的构型,反应结果表明,经由激光等离子体的碰撞和能量传递,反应物的链状结构发生解离和进一步反应,经结构重组形成了多种不同组成和构型的产物。     

Chemical‐surface modification of polymers using atmospheric pressure nonequilibrium plasmas and comparisons with vacuum plasmas

We demonstrate that stable microwave‐coupled atmospheric pressure nonequilibrium plasmas (APNEPs) can be formed under a wide variety of gas and flow‐rate conditions. Furthermore, these plasmas can be effectively used to remove surface contamination and chemically modify polymer surfaces. These chemical changes, generally oxidation and crosslinking, enhance the surface properties of the materials such as surface energy. Comparisons between vacuum plasma and atmospheric plasma treatment strongly indicate that much of the vacuum‐plasma literature is pertinent to APNEP, thereby providing assistance with understanding the nature of APNEP‐induced reactions. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 95–109, 2002     

Two-temperature modeling of an arc plasma reactor

In this paper a two-temperature plasma model is established and applied to the injection of cold gases into an atmospheric-pressure, high-intensity argon arc. The required nonequilibrium plasma composition and the non-equilibrium transport properties are also calculated. The results show that the arc becomes constricted at the location of gas injection due to thermal and fluid dynamic effects of the injected cold flow. Enhanced Joule heating in the constricted arc path raises the electron as well as the heavy-particle temperatures. This temperature increase resists, via secondary effects, the penetration of the cold gas into the hot arc core which behaves more or less as a solid body as far as the injected flow is concerned. The temperature discrepancy between electrons and heavy particles is most severe at the location of cold flow injection, a finding which may have important consequences on chemical reactions in an arc plasma reactor.     

Numerical computations of molecular reactions in associated systems caused by the formation of fractal structures

The interaction between particles in a system containing fractal clusters has been computationally simulated. The fractal structure of the system has been demonstrated to determine the kinetic characteristics of particle interaction. If a system in an N-dimensional space (N = 2, 3, 4) contains fractal clusters with the fractal dimension D > N-1, the rate of interaction of a free particle with particles belonging to clusters depends on their concentration according to the power law. The exponent gamma of this power law formally corresponds to the kinetic order of the reaction with respect to the concentration of particles belonging to the clusters. Its value is determined by the free surface of the clusters and depends on its fractal dimension D. The results of simulation qualitatively agree with the data on high, non-integral orders of many liquid phase molecular reactions characterized by self-organization of the medium via weak intermolecular interactions, such as hydrogen bonds.     

Imaging of metals in biological tissue by laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS): state of the art and future developments

Laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) is well established as a sensitive trace and ultratrace analytical technique with multielement capability for bioimaging of metals and studying metallomics in biological and medical tissue. Metals and metalloproteins play a key role in the metabolism and formation of metal‐containing deposits in the brain but also in the liver. In various diseases, analysis of metals and metalloproteins is essential for understanding the underlying cellular processes. LA–ICP–MS imaging (LA–ICP–MSI) combined with other complementary imaging techniques is a sophisticated tool for investigating the regional and cellular distribution of metals and related metal‐containing biomolecules. On the basis of successful routine techniques for the elemental bioimaging of cryosections by LA–ICP–MSI with a spatial resolution between 200 and ~10 µm, the further development used online laser microdissection ICP–MSI to study the metal distribution in small biological sample sections (at the cellular level from 10 µm to the submicrometer range). The use of mass spectrometric imaging of metals and also nonmetals is demonstrated on a series of biological specimens. This article discusses the state of the art of bioimaging of metals in thin biological tissue sections by LA–ICP–MSI with spatial resolution at the micrometer scale, future developments and prospects for quantitative imaging techniques of metals in the nanometer range. In addition, combining quantitative elemental imaging by LA/laser microdissection–ICP–MSI with biomolecular imaging by matrix‐assisted laser desorption/ionization–MSI will be challenging for future life science research. Copyright © 2013 John Wiley & Sons, Ltd.     

Temporally resolved laser diagnostic measurements of atomic hydrogen concentrations in RF plasma discharges

Ground-state atomic hydrogen produced in radio-frequency plasma discharges (20 KHz-5 MHz) has been detectedin situ using two-photon absorption laser-induced fluorescence (TALIF). Atomic ground-state concentration measurements have demonstrated excellent spatial resolution in the interelectrode gap of a planar discharge configuration with 10 nsec temporal resolution at all phases of the RF driving voltage waveform. Concentrations were measured in gas mixtures of helium and hydrogen down to 2×10¹³ H atoms/cm³.     

Quantitative images of metals in plant tissues measured by laser ablation inductively coupled plasma mass spectrometry

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for quantitative imaging of toxic and essential elements in thin sections (thickness of 30 or 40 μm) of tobacco plant tissues. Two-dimensional images of Mg, Fe, Mn, Zn, Cu, Cd, Rh, Pt and Pb in leaves, shoots and roots of tobacco were produced. Sections of the plant tissues (fixed onto glass slides) were scanned by a focused beam of a Nd:YAG laser in a laser ablation chamber. The ablated material was transported with argon as carrier gas to the ICP ion source at a quadrupole ICP-MS instrument. Ion intensities of the investigated elements were measured together with ¹³C⁺, ³³S⁺ and ³⁴S⁺ within the entire plant tissue section. Matrix matching standards (prepared using powder of dried tobacco leaves) were used to constitute calibration curves, whereas the regression coefficient of the attained calibration curves was typically 0.99. The variability of LA-ICP-MS process, sample heterogeneity and water content in the sample were corrected by using ¹³C⁺ as internal standard. Quantitative imaging of the selected elements revealed their inhomogeneous distribution in leaves, shoots and roots.     

Rapid survey analysis of polymeric materials by laser ablation-inductively coupled plasma spectrometry. An analytical note

An Nd-Yag laser (1064 nm) in combination with a multichannel emission spectrometer was used for rapid survey analysis of polymers and paints. A novel design feature of the ablation chamber was the incorporation of a graphite furnace to effect electrothermal pretreatments of samples. Transient emission signals were studied as a function of laser operating mode, laser duration and flashlamp energy.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria     

Detection efficiencies in nano- and femtosecond laser ablation inductively coupled plasma mass spectrometry

Detection efficiencies of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), defined as the ratio of ions reaching the detector and atoms released by LA were measured. For this purpose, LA of silicate glasses, zircon, and pure silicon was performed using nanosecond (ns) as well as femtosecond (fs) LA. For instance, ns-LA of silicate glass using helium as in-cell carrier gas resulted in detection efficiencies between approximately 1E-7 for low and 3E-5 for high mass range elements which were, in addition, almost independent on the laser wavelength and pulse duration chosen. In contrast, the application of argon as carrier gas was found to suppress the detection efficiencies systematically by a factor of up to 5 mainly due to a less efficient aerosol-to-ion conversion and ion transmission inside the ICP-MS.     

Review of oxide formation in a plasma

The physical processes occurring at the surface and in the bulk of an oxide during plasma oxidation or anodization are discussed. It is shown that (i) the majority of oxygen ions used in the growth are formed by electron-assisted surface processes, (ii) the nature of the oxide surface and especially the presence of electrode contamination can have a determinant role in the oxygen exchange between the plasma and the oxide, and (iii) ion space charge can control the anodization kinetics. Two applications (formation of the insulating barrier of Josephson junctions, and GaAs MOSFET devices) are presented.     

Nonequilibrium modeling of low-pressure argon plasma jets; Part I: Laminar flow

This paper presents a modeling attempt related to low-pressure plasma spraying processes which find increasing applications for materials processing. After a review of the various models for ionization and recombination processes, a two-temperature model for argon plasmas in chemical (ionization) nonequilibrium is established using finite rate chemistry. Results of sample calculations manifest departures from kinetic as well as chemical equilibrium, demonstrating that the conventional models based on the LTE (local thermodynamic equilibrium) assumption cannot provide proper prediction for low-pressure plasma jets.     

The role of continuum radiation in laser induced plasma spectroscopy

This paper focuses on the interpretation of the origin of the continuum radiation in Laser Induced Plasma (LIP) emission spectra, a subject that has received little consideration in the literature when compared to the analysis of the line emission spectrum. The understanding of the spectral peculiarities observed immediately after the laser pulse, when the continuum radiation prevails on discrete emission lines, can be extremely important to retrieve the initial conditions of LIP and to correlate the produced plasma to the ablation mechanism. In this work, in addition to a qualitative interpretation of the LIP continuum in the initial stage of expansion, a methodology is proposed for a better measurement of the atomic temperature in the expansion stage of the LIP. Such methodology is based on the analysis of the combined Boltzmann and Planck plots. The results obtained stress once again the importance of considering non equilibrium effects in the initial stage of LIP expansion.     

Transport efficiency in femtosecond laser ablation inductively coupled plasma mass spectrometry applying ablation cells with short and long washout times

Relative mass transport efficiencies of near infrared (λ = 795 nm) femtosecond laser generated brass aerosols in helium were measured by ICP-MS applying different ablation cells with short and long washout times. It was found that the transport efficiencies are independent of the cell used within the mutual experimental uncertainties. This finding was confirmed by additional measurements providing the absolute particle mass transport efficiencies of femtosecond laser ablation in He. Here, the transport efficiencies were determined by weighing the samples before and after ablation with a micro-balance, collecting the particles by low-pressure impaction, and evaluating the impacted masses quantitatively by total reflection X-ray fluorescence. Within the experimental uncertainties (± 9–19%) the same absolute transport efficiency (about 77%) was found for all cells applied. This efficiency value can be regarded as a lower limit of the absolute mass transport efficiency since mass losses in the impactor are difficult to quantify.     

Calculation of diffusion impedance in the terms of locally nonequilibrium diffusion

An equation for diffusion impedance is derived in the terms of the lattice diffusion model based on the assumption as to the local nonequilibrium distribution of diffusing particles across the sites of different types. This equation is valid at low lattice occupation. Unlike the multiple trapping model, all site types are interpreted symmetrically. In the boundary condition, it is assumed that there is a unique relationship between the electric potential variation, on one side of the interface and variation of the generalized particle activity on the other side.     

Electrode potentials of electrochemical cells with oxide-conducting solid electrolyte in chemically nonequilibrium gas mixtures

A wide range of electrodes for solid oxide electrolyte cells in chemically nonequilibrium gas media simultaneously containing oxygen and combustible gases is systematically studied. The concentration dependences are investigated for the potential response of electrodes made of conducting oxides, noble metals (platinum, gold, silver), and also composite electrodes containing dispersed oxide semiconductor phases, apart from the main conducting material. Besides, dynamic characteristics of these electrodes are investigated. The studies are performed in the temperature range from 450 to 800°C. The content of combustible gases in the mixture was varied from 10 ppm to 2%. The research results are of interest for development of sensors for combustible gases and for studying kinetics and mechanisms of catalytic oxidation reactions.     

Time evolution of the pulsed HF chemical laser system. I. Kinetic modeling - rotational nonequilibrium

A detailed model of a pulsed F + H₂ → HF + II laser is used to investigate the kinetic behaviour of the system and to provide input data for a thermodynamic analysis of its time evolution. The rate equations for all relevant vib-rotational level populations and photon densities are solved for various initial conditions without using the rotational equilibrium assumption. The results of the kinetic model are in good agreement with the experimental results of Berry in which high inert gas pressure was used to enhance rotational relaxation. The effects of specific kinetic processes on the time evolution of the molecular populations and the laser output are evaluated by varying the inert gas pressure and by “switching on and off” the influence of various kinetic factors. The laser efficiency ranges between ≈ 1 to 2 photons per molecule. The major rate process enhancing the efficiency is rotational relaxation. The reduction in laser efficiency due to vibrational relaxation is ≈ 20%.     

Multiple steady states in a CSTR with total condenser: Comparison of equilibrium and nonequilibrium models

Comparison of equilibrium and nonequilibrium models of a CSTR with total condenser focused on the multiple steady states and dynamic behaviour was carried out. The steady-state behaviour of the model system, MTBE synthesis from methanol and isobutene in a reactive distillation column, was studied in terms of the input parameters, i. e. feed flow rate of methanol or butenes, reflux ratio, and mass of catalyst. The dynamic behaviour of the system during the start-up was investigated and perturbations of manipulated variables were found to cause transitions between the parallel steady states. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

Basic investigations for laser microanalysis: IV. The dependence on the laser wavelength in laser ablation

The fourth harmonic wavelength at 266 nm as well as the fundamental radiation at 1.06 m of a pulsed Nd: YAG laser has been used for ablation of solid samples. Using different buffer gases and different samples, the ablated masses and plasma temperatures obtained with the two different laser wavelengths are compared. The analytical application of 266-nm laser pulses is studied by the measurement of aluminium and manganese in steel and boraxglass (Na₂B₄O₇) samples.