Production of Monodisperse Nanoparticles and Application of Discrete-Monodisperse Model in Plasma Reactors

The particle growth in plasma reactor were investigated by using the discrete-monodisperse (D-M) model for various process conditions. The monodisperse large sized particle distribution predicted by the D-M model are in good agreement with the large sized particles by the discrete-sectional model and also in the experiments by Shiratani et al. (1996). Some fractions of the small size particles are in a neutral state or even charged positively, but most of the large sized monodisperse particles are charged negatively. As the mass generation rate of monomers increases, the large sized particles grow more quickly and the production rate of nanoparticles of 100nm by plasma reactor increases. As the initial electron concentration or the monomer diameter increases, it takes longer time for the large sized particles to grow up to 100nm, but the large sized particle concentration of 100nm increases and the resulting production rate of large sized particles of 100nm increases. As the residence time increases, the time for the large sized particles to grow up to 100nm decreases and the large sized particle concentration of 100nm increases and, as a result, the production rate of large sized particles of 100nm increases. We propose that the plasma reactor can be a good candidate to produce monodisperse nanoparticles.     

Industrial-scale experiments of desulfuration of coal flue gas using a pulsed corona discharge plasma

The flow rate of flue gas in the industrial experiments was 3000 Nm/sup 3//h. The flue gas from the boiler burning coal was used. The influences of operating parameters on the efficiency of desulfuration (DeSO/sub 2/) were studied, which include the retention period of flue gas in the reactor, the initial concentration of SO/sub 2/ in flue gas, a mole ratio of NH/sub 3/ to SO/sub 2/ in the gas, the temperature of the gas, as well as the power consumption of pulsed corona discharges. The experimental results shown that the efficiency of DeSO/sub 2/ was above 80%, when the initial concentration of SO/sub 2/ was 1000 /spl sim/ 2000 ppm, the gas temperature was 60 /spl deg/C /spl sim/ 75 /spl deg/C, the retention period was more than 5.8 s, a mole ratio of NH/sub 3/ to SO/sub 2/ was 2 : 1, the water content in flue gas was above 6%, and he consumption was 2.5 /spl sim/ 3.5 Wh/Nm/sup 3/.     

Some insights in the sonochemical preparation of cobalt nano-particles

The preparation of cobalt nano-particles from a solution of Co(CO)₃(NO) in n-decane under ultrasonication with a frequency of 20 kHz yielded cobalt particles of a size of ca. 5 nm. The presence of either silica or oleic acid in the solution reduced the particle size to ca. 3 and 2 nm, respectively. The resulting particle size is independent of the ultrasonication time, initial Co(CO)₃(NO) concentration, ultrasound intensity and solution temperature. It is postulated that bubble collapse generates multiple nucleation sites resulting in the formation of cobalt particles with a rather uniform particle size distribution.     

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。     

Plasma and heat flux characteristics of a supersonic ammonia or nitrogen/hydrogen-mixture direct-current plasma jet impinging on a flat plate

Spectroscopic and electrostatic probe measurements were made to examine plasma characteristics with or without a titanium plate under nitriding for a 10-kW-class direct-current arc plasma jet generator with a supersonic expansion nozzle in a low-pressure environment. Heat fluxes into the plate from the plasma were also evaluated with a Nickel slug and thermocouple arrangement. Ammonia and mixtures of nitrogen and hydrogen were used as a working gas. The NH/sub 3/ and N/sub 2/+3H/sub 2/ plasmas in the nozzle and in the downstream plume without a substrate plate were in thermodynamical nonequilibrium states. As a result, the H-atom electronic excitation temperature and the N/sub 2/ molecule-rotational excitation temperature intensively decreased downstream in the nozzle although the NH molecule-rotational excitation temperature did not show an axial decrease. Each temperature was kept in a small range in the plume without a substrate plate except for the NH rotational temperature for NH/sub 3/ working gas. On the other hand, as approaching the titanium plate, the thermodynamical nonequilibrium plasma came to be a temperature-equilibrium one because the plasma flow tended to stagnate in front of the plate. The electron temperature had a small radial variation near the plate. Both the electron number density and the heat flux decreased radially outward, and an increase in H/sub 2/ mole fraction raised them at a constant radial position. In cases with NH/sub 3/ and N/sub 2/+3H/sub 2/, a radical of NH with a radially wide distribution was considered to contribute to the better nitriding as a chemically active and non heating process.     

Removal of nitrogen oxide in spatially isolated chamber by pulsed intense relativistic electron beam

Nitrogen oxide (NO/sub x/) in a chamber spatially isolated from beam source has been removed by a pulsed, intense, relativistic electron beam (PIREB). The chamber is filled up with dry-air-balanced NO/sub x/, and is irradiated by the PIREB (2 MeV, 2.2 kA, 85 ns) passing through 1.6-m-long atmosphere. The NO/sub x/ concentration decreases from 88 to 25 ppm by ten shots of PIREB.     

Soot particle size distributions in a well-stirred reactor/plug flow reactor

A well-stirred reactor (WSR) followed by a plug flow reactor (PFR) is being used to study polycyclic aromatic hydrocarbon (PAH) growth and soot inception. Soot size distributions were measured using a dilution probe followed by a nano-differential mobility analyzer (Nano-DMA). A rapid insertion probe was fabricated to thermophoretically collect particles from the reactor for transmission electron microscopy (TEM) imaging. Results are presented on the effect of equivalence ratio on the soot size distributions obtained for fixed dilution ratio, the effect of dilution ratio on the soot size distributions obtained for fixed equivalence ratio, and the effect of temperature on the soot size distributions obtained for fixed equivalence ratio. In addition to particle sizing measurements, gas samples were analyzed by a gas chromatograph to determine the concentration of gaseous species in the PFR thought to be important in soot formation. Our soot size distribution measurements demonstrate that the mixing conditions in the flame zone affect whether or not a nucleation mode was detected in the size distribution.     

Nanoparticle Microreactor: Application to Synthesis Of Titania by Thermal Decomposition of Titanium Tetraisopropoxide

The nanoparticle microreactor (NPMR) is a new concept that we have introduced to describe a very small-scale system capable of converting an aerosol precursor to solid particles. The liquid precursor of about 1 µl is injected by a syringe through a septum into a tubular evaporator of 1.0 cm³ in volume with stopcocks at both ends. The evaporator has been preheated by a heating tape to a temperature sufficiently high for vaporization to occur in half a minute. By opening the stopcocks, the vaporized precursor is transported by a carrier gas stream into a quartz tube which is mounted along the axis of a tubular furnace. The nanoparticle aggregates produced in the reactor are sampled by deposition on an electron micrograph grid at the reactor exit. The NPMR was applied first to the synthesis of TiO₂ particles by thermal decomposition of titanium tetraisopropoxide (TTIP) in a nitrogen carrier gas, with TTIP concentrations varying from 1.0 to 7.0 mol% or 2.35×10^–6 to 1.65×10^–5 in TiO₂ volume loading, and decomposition temperatures from 300°C to 1000°C. Studies were made with a 2 mm reaction tube and a 4 mm tube with sheath gas. With the 2 mm tube, a considerable fraction of the TTIP precursor was consumed at the wall by surface reaction, resulting in very small particles. With the 4 mm tube, the primary particle size was comparable to that reported in the literature for steady flow experiments using a 22.2 mm tube. Primary particle sizes ranged from 200 to 400 nm. Depending on TTIP concentration and reactor temperature, the particles exhibited a bimodal size distribution, probably due to a two-stage nucleation. A fourfold increase in the gas flow rate had little effect on particle size, indicating that particle growth ended early, within one-fourth the tube length. Residence time in the reactor was between 0.35 and 1.4 s, and total run time about 1 min. The NPMR has potential for rapid assembly of large databases and is adaptable to combinatorial discovery of nanoparticles with novel properties. Design requirements for an ideal aerosol microreactor are discussed briefly.     

Magnetic properties of corrosion products investigated by CEMS at low temperatures near 4.2 K

Conversion electron Mössbauer measurements with a proportional counter at 6.3, 78 and 300 K have been done to investigate the magnetic properties of the corrosion products formed on the surface of iron foils, which consist of small particles of γ-Fe₂O₃. The growing period of the corroded layer formed in a solution of low oxygen concentration has insignificant influence on the size of particles composing the layer, however, when the corroded layer is grown in a solution of comparatively high oxygen concentration, the particle size becomes large with growing period of the layer.     

Formation of Si-nanoparticles in a microwave reactor: Comparison between experiments and modelling

The formation and growth of silicon-nanoparticles from silane in a microwave reactor was investigated. Experiments were performed for the following conditions: precursor concentration 380–2530 ppm, pressures of 20–30 mbar, microwave powers 120–300 W. The formed particles were examined in-situ with a particle mass spectrometer. Additionally, particles were collected on grids and analyzed by transmission electron microscopy, X-ray diffraction, and by determining the specific surface area by BET. The particle size was found to be in the range of 5–8 nm in diameter. A simple model was used to simulate the particle formation processes taking place inside the reactor. The microwave energy coupled into the reactor flow was treated as a spatially distributed energy source resulting in a local temperature increase. The particles were assumed to have a monodisperse size distribution. To allow an approximation of their shape they were characterized by their volume and surface area. The model takes nucleation, convection, coagulation, and coalescence into account. The fluid flow inside the microwave reactor was simulated with the commercial CFD-code Fluent.     

The Effect of Boundary Conditions on Gas-phase Synthesised Silver Nanoparticles

We have prepared spherical non-agglomerated silver nanoparticles by an evaporation–condensation–dilution/cooling technique. Silver was evaporated from a crucible in a tubular flow reactor. A porous tube diluter was used to quench the carrier gas at the outlet of the reactor to enhance the formation of small particles and to suppress agglomeration and other particle growth mechanisms. The number size distribution of the prepared particles was measured with a differential mobility analyser–condensation nucleus counter combination and the size and the shape of the particles were analysed with transmission electron microscope. The system was modelled using a sectional aerosol dynamics computer code to estimate the importance of different aerosol processes. In all conditions the particles obtained were non-agglomerated and spherical. The mean particle diameter varied from 4 to 10-nm depending on boundary conditions. From the modelling studies it can be concluded that the nucleation rate is the most important parameter controlling the final particle size.     

Production of cobalt and nickel particles by hydrogen reduction

Cobalt and nickel nanoparticles were produced by hydrogen reduction reaction from cobalt or nickel chloride precursor vapour in nitrogen carrier gas. This aerosol phase method to produce nanoparticles is a scalable one-step process. Two different setups were introduced in particle production: a batch type reactor and a continuously operated reactor. Common feature in these setups was hydrogen mixing in a vertical flow reactor. The process was monitored on-line for particle mass concentration and for gas phase chemical reactions. Tapered element oscillating microbalance measured the particle mass concentration and Fourier transform infrared spectroscopy was used to monitor relevant gas phase species. The produced cobalt and nickel particles were characterised using transmission electron microscopy and x-ray diffraction. The produced cobalt and nickel particles were crystalline with cubic fcc structure. Twinning was often observed in cobalt particles while nickel particles were mostly single crystals. The cobalt particles formed typically long agglomerates. No significant neck growth between the primary particles was observed. The primary particle size for cobalt and nickel was below 100 nm.     

Particle Sampling and Real Time Size Distribution Measurement in H2/O2/TEOS Diffusion Flame

Growth characteristics of silica particles have been studied experimentally using in situ particle sampling technique from H₂/O₂/Tetraethylorthosilicate (TEOS) diffusion flame with carefully devised sampling probe. The particle morphology and the size comparisons are made between the particles sampled by the local thermophoretic method from the inside of the flame and by the electrostatic collector sampling method after the dilution sampling probe. The Transmission Electron Microscope (TEM) image processed data of these two sampling techniques are compared with Scanning Mobility Particle Sizer (SMPS) measurement. TEM image analysis of two sampling methods showed a good agreement with SMPS measurement. The effects of flame conditions and TEOS flow rates on silica particle size distributions are also investigated using the new particle dilution sampling probe. It is found that the particle size distribution characteristics and morphology are mostly governed by the coagulation process and sintering process in the flame. As the flame temperature increases, the effect of coalescence or sintering becomes an important particle growth mechanism which reduces the coagulation process. However, if the flame temperature is not high enough to sinter the aggregated particles then the coagulation process is a dominant particle growth mechanism. In a certain flame condition a secondary particle formation is observed which results in a bimodal particle size distribution.     

CH4/空气混合物中含N、S组分对生成污染物的影响

本文采用详细的CH4/空气反应机理,在良搅拌反应器的条件下,计算了初始含NH3、HCN和H2S对污染物NO和SOx(SO、SO2)生成规律的影响.结果表明,初始含N、S的组分可使NO和SOx的排放量明显增加.同时还利用敏感性分析对污染物形成的重要反应进行讨论.     

Interaction of ions and electrons with nanoparticles in hydrocarbon combustion plasmas

The interaction of electrons and ions with a polydisperse ensemble of soot nanoparticles during the combustion of hydrocarbon fuels is studied. The dynamics of the particle charging is analyzed. It is shown that, in the initial stage, all the soot particles are charged negatively, the largest particles (100–150 nm) carrying up to 40–50 elementary charges. As time elapses, the negative charge is neutralized and the charge distribution becomes more symmetric. Finally, because of the interaction between ions (electrons) and soot particles, the total concentration of the positive ions becomes higher than that of the negative ones.     

Modeling refraction characteristics of silicon nitride film deposited in a SiH/sub 4/-NH/sub 3/-N/sub 2/ plasma using neural network

Silicon nitride has been deposited using plasma-enhanced chemical deposition (PECVD) equipment. The PECVD process was characterized by conducting a 2/sup 6-1/ fractional factorial experiment on six experimental factors, including substrate temperature, pressure, radio frequency (RF) power, ammonia NH/sub 3/, silane SiH/sub 4/, and nitrogen N/sub 2/ flow rates. Refractive characteristics of the deposited film were examined by modeling the refractive index as a function of experimental factors. A helium-neon laser with a wavelength 6328 /spl Aring/ was used to measure the refractive index. To evaluate the appropriateness of the model, the network trained with 32 experiments was then tested with 12 experiments not pertaining to the training data. Several learning factors involved in training neural networks were optimized and an accurate prediction model with the root mean-squared error of 0.018 was achieved. Compared to statistical regression model, the neural network model demonstrated an improvement of more than 65%. Using various three-dimensional plots, underlying deposition mechanisms were qualitatively estimated. For the limited experimental ranges, the index increased with increasing SiH/sub 4/ flow rate. With an increase in either NH/sub 3/ or N/sub 2/, meanwhile, the index decreased consistently. The index also increased with increasing substrate temperature or pressure. The effects of the temperature were very complex as it interacted with other factors.     

透过率起伏光谱分析法测粒技术

提出的透过率起伏光谱分析法是一种新的颗粒测量方法。采用一细小光束照射匀速流动的颗粒系统,通过采集透射光起伏信号,经统计处理得到透过率的平均值与起伏谱。通过求解逆问题,从透过率的起伏谱中得到颗粒粒径分布信息,再结合透过率的平均值得到颗粒的体积分数信息。给出了关于单层颗粒透过率的平均值与起伏谱的理论表达式,并推广到三维单分散和多分散的颗粒系统。对粒径在32~425μm内的稀薄颗粒系进行了部分实验测试和模拟计算,结果表明该方法可同时对颗粒粒径分布和体积分数进行有效测量。     

The Measurement of Particles Suspended in a stirred vessel using microphotography and digital image analysis

A novel technique to determine the size of particles suspended in a stirred vessel is investigated. The method uses microphotography to obtain a still image of the particles in situ. The equivalent circular diameter of the particles is obtained from the photographs using digital image analysis. The particles used for the test were certified particle size standards of a very small tolerance in diameter deviation. The size comparison was determined as a percent error between the measured particle diameter (equivalent circular diameter) and the diameter established by the particle manufacturer. To determine the limiting ranges of particle size and concentrations, spherical particles in a size range of approximately 1 to 10.0 μm (microns) in diameter were employed in the test. Concentrations varied from 0.00005% to 0.1% (mass basis). For each particle size, an aqueous solution of the particles was prepared at the desired concentration and placed in a stirred vessel. Photographs of the solutions were made at 25.5x, 40x, 60x and 80x magnification. For all sizes of particles, the entire range of concentration was examined. The results indicate a minimum size resolution of approximately 3μm, in a corresponding concentration range of 0.0001% to 0.05%. Similar limits on concentration were found for the larger diameter particles, although a true upper limit for the largest particle sizes was not established. The functional concentration range appears to shift towards higher mass concentrations with increasing particle size. For 2.92 μm diameter particles, the error in size measurement was found to be below 10% for a concentration range of 0.0005% to 0.05%. Additionally, a relationship between turbidity and the error was seen at low particle concentration levels where decreasing levels of turbidity generated increasing levels of error.     

Space-time structure near particles and its influence on particle behavior

An interrelation between the properties of the space-time structure near moving particles and their dynamics is discussed. It is suggested that the space-time metric near particles becomes a curved one depending on a random vectorb _E =(b ₄,b) with a distributionw(b _E ² /l ²); the averaged space-time metric over this distribution gives the general effect on particle behavior. As a result the particle motion in our scheme is described by a nonlinear equation. It turns out that the nonrelativistic limit of this equation gives a simple connection between the space-time structure at small distances and the dynamical behavior of particles. Different types of particle motion (nearly rectilinear, stochastic, and solitonlike) caused by some concrete forms of the averaged conformally flat space-time metric are considered.     

Optical properties of hybrid plasmonic nanofluid based on core/shell nanoparticles

The plasmonic effect is used in nanofluid to help capture and absorb sunlight. The optical absorption is significantly enhanced as plasmonic effect excited. To obtain an enhanced absorption in a broad band, the hybrid plasmonic nanofluid is developed. It is composed of core/shell nanoparticles of different sizes. The overall absorption of hybrid nanofluid is examined. Compared to the nanofluid of single particle size, the hybrid nanofluid exhibits a broadband absorption. As particle size increases, the plasmon resonance peak is shifted to longer wavelength. The variation in the sizes of core/shell nanoparticles can broaden the absorption spectrum. In the near-infrared region, the proportion of different size particles has an obvious influence. With the increase of proportion of larger particles, the absorption band is broadened. Since the suspended nanoparticles have different sizes, the particle distribution in base fluid also has an effect on absorption of light. The large particle in upper has a broadband absorption, however, less energy can be transmitted to lower after the absorption of upper particles. The contribution from the particles in lower is relatively weak.