System for <Emphasis Type="Italic">In Situ</Emphasis> Characterization of Nanoparticles Synthesized in a Thermal Plasma Process

We have designed a particle diagnostic system that is able to measure particle size and charge distributions from low stagnation pressure (≥746 Pa) and high temperature (2000–4000 K) environments in near real time. This system utilizes a sampling probe interfaced to an ejector to draw aerosol from the low pressure chamber. Particle size and charge distributions are measured with a scanning mobility particle sizer. A hypersonic impactor is mounted in parallel with the scanning mobility particle sizer to collect particles for off-line microscopic analysis. This diagnostic system has been used to measure size and charge distributions of nanoparticles (Si, Ti, Si–Ti–N, etc.) synthesized with our thermal plasma reactor. We found that the mean particle size increases with operating pressure and reactant flow rates. We also found that most particles from our reactor are neutral for particles smaller than 20 nm, and that the numbers of positively and negatively charged particles are approximately equal.     

Synthesis of amorphous silicon colloids by trisilane thermolysis in high temperature supercritical solvents

Colloidal submicrometer-diameter amorphous silicon (a-Si) particles are synthesized with >90% yield by thermal decomposition of trisilane (Si3H8) in supercritical hexane at temperatures ranging from 400 to 500 degrees C and pressures up to 345 bar. A range of synthetic conditions was explored to optimize the quality of the product. Under the appropriate synthetic conditions, the colloids are spherical and unagglomerated. The colloids can be produced with average diameters ranging from 50 to 500 nm by manipulating the precursor concentration, temperature, and pressure. Relatively narrow particle size distributions, as measured by transmission electron microscopy (TEM), with standard deviations about the mean as low as approximately +/-10% could be obtained in some cases. We explored the thermal annealing of the amorphous silicon particles after isolation from the reactor and found that crystallization to diamond structure silicon occurred at temperatures as low as 650 degrees C. The amorphous and crystalline materials were characterized by X-ray diffraction and high resolution scanning and transmission electron microscopy.     

Effect of pH of aqueous ceramic suspensions on colloidal stability and precision of analytical measurements using slurry nebulization inductively coupled plasma atomic emission spectrometry

Colloidal stability of silicon nitride, silicon carbide and boron carbide aqueous slurries used for slurry nebulization inductively coupled plasma atomic emission spectrometry has been investigated in the pH range 2–10 by electrophoretic mobility and particle size measurements, together with sedimentation tests. The mean particle size of silicon nitride and silicon carbide suspensions change with increasing pH showing a maximum at the isoelectric points (pH 7.5 and 5.5 respectively). The particle size distribution of boron carbide slurries remains practically constant and the zeta potential of suspended boron carbide particles shows a small change in the pH range investigated. The silicon nitride and silicon carbide slurries have good stability at pH below 5 and above 8, respectively. Boron carbide slurries show excellent stability in the whole pH range investigated. The time demand for stabilization of the emission line intensities from the start of nebulization strongly depends on the colloidal stability of slurries. Consequently, it is advantageous to nebulize aqueous suspensions with a pH as far from the isoelectric point of the solid as possible and with the ionic strength of the dispersion medium as low as possible. The RSD values of the line intensity measurements determined after 3 min stabilization time decrease with increasing stability of the aqueous slurries.     

Determination of colloid size by 2-D optical detection of laser induced plasma

A new method is presented for the size determination of aquatic colloids, which is based on the selective plasma generation (breakdown) on individual particles by a focused laser pulse. For this purpose, the breakdown events of particles are monitored by 2-D optical detection instead of commonly used photoacoustic detection. The length of the breakdown volume determined for the 2-D projection of spatially distributed plasma events generated on colloidal particles is proportional to the particle size. Based on this fact, an average diameter of a given colloidal dispersion can be determined. The method is calibrated by well-characterised hard-sphere polystyrene reference particles of different diameters.     

Homogeneous nucleation of metals in a plasma-quench reactor

We present a new and general application of the method of moments for modeling the nucleation of condensates in a steady-state supersonic nozzle flora generated in a plasma-quench reactor. A closed set of growth/evaporation rate equations has been employed to propagate the moments of the particle size distribution without invoking the usual coarse-graining or truncation approximations of conventional binning approaches. The method has been employed to calculate the nucleation rates, particle number density, and the particle-size distribution for 11 elemental metals (Ag, Al, Be, Ce, Cr, Fe, Gd, Ti, Th, U, and Zr) condensing in a model argon nozzle flow. We have identified the regions in the nozzle of maximum nucleation rate, and have shown how different particle-size distributions can develop in different regions.     

Surface chemistry of aerosolized silicon nanoparticles: evolution and desorption of hydrogen from 6-nm diameter particles

The surface chemistry of pristine, 6-nm silicon nanoparticles has been investigated. The particles were produced in an RF plasma and studied using a tandem differential mobility analysis apparatus, Fourier transform infrared spectroscopy (FTIR), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and transmission electron microscopy. Particles were extracted from the plasma, which operates at approximately 20 Torr, into an atmospheric pressure aerosol flow tube, and then through a variable-temperature furnace that could be adjusted between room temperature and 1200 degrees C. DMA measurements show that freshly generated silicon particles shrink with heating, with particle diameters decreasing by approximately 0.25 nm between 350 and 400 degrees C. FTIR results indicate that freshly generated particles are primarily covered with SiH2 groups and smaller amounts of SiH and SiH3. Spectra recorded as a function of heating temperature indicate that the amount of surface hydrogen, as measured by the intensity of modes associated with SiH, SiH2, and SiH3, decreases with heating. ToF-SIMS measurements also suggest that hydrogen desorbs from the particles surfaces over the same temperature range that the particles shrink.     

New In-Situ Sampling and Analysis of the Production of CeO<Subscript>2</Subscript> Powders from Liquid Precursors in a rf Thermal Plasma Reactor. Part 2: Analysis of CeO<Subscript>2</Subscript> Powders,Fuel Addition,and Image Analysis

A novel reactor design, sampling probe and wet collection system were used to investigate the combined effects of plasma operating parameters and particle collection mechanisms on the synthesis of CeO₂ particles from liquid precursors. The sampling of particles in-flight and the collection of particles at several reactor regions were used to provide experimental evidence of particle size at different reactor locations at various plasma operating conditions, i.e., power and plasma gas flow rates. This information provided a picture of how CeO₂ particles were formed and how these particles were collected in various locations. The effect of adding water-soluble fuels (alanine and glycine) to the original cerium nitrate solutions was also investigated. Fuel addition decreased the temperature of CeO₂ formation by acting as a local heat source as a result of fuel auto-ignition. Photographs of the particles in-flight were taken using a fast speed CCD camera.     

Heat Generation and Particle Injection in a Thermal Plasma Torch

The operation of plasma guns used for plasma spraying involves a continuous movement of the anode arc root. The resulting fluctuations of voltage and thermal energy input introduce an undesirable element in the spray process. This paper deals with the effects of these arc instabilities on the plasma jet, and the behavior of particles injected in the flow. The first part refers to the formation of the plasma jet. Measurements show that the static behavior of the arc depends strongly upon the plasma-forming gas mixture, especially the mass flow rate, of the heavy gas, injection mode, nozzle diameter, and arc current. These parameters control the electric field in the arc column, the arc length, its stability, and the gas velocity and temperature. The dynamic behavior of the arc is examined to determine how the tempeature and velocity of the plasma gas vary with voltage variations. Relationships between the gas velocity at the nozzle exit and the lifetime of the arc roots, and the independent operating parameters of the gun can be established from a dimensional analysis. The second part discusses the interaction between the plasma jet and the particles injected into the flow. The parameters controlling particle injection and trajectory are examined to determine how injection velocity must vary with particle size and density to achieve a given trajectory. The effect of the transverse injection of the powder carrier gas is investigated using a 3-D computational fluid dynamics code. Finally, the effect of the jet fluctuations on particle trajectory is studied under the assumption that the jet velocity follows the voltage variation. The result is a continuous variation of the particle spray jet position in the flow. Experimental observations confirm the model predictions.     

Generation,analysis, and deposition of silicon nanocrystals up to 10 nm in diameter

Silicon clusters have been generated by CO₂- laser-induced decomposition of SiH₄ in a flow reactor. By introducing a conical nozzle into the reaction zone, the clusters are extracted into a molecular beam apparatus and analyzed with a time-of-flight mass spectrometer. Besides small clusters, the mass spectra show also very large aggregates containing a few thousand of silicon atoms. A velocity analysis of the neutral cluster beam reveals that the particle velocity decreases with increasing mass. Thus it is possible to perform a size selection of the neutrals by introducing a velocity selector into the cluster beam. The silicon clusters have been deposited at low energy, and TEM micrographs of size-selectively prepared films are presented. A quantitative analysis of two different deposits reveals mean particle diameters of 3.5 and 6.5 nm. The results demonstrate the possibility of fabricating thin films of nanostructured materials with a mean particle diameter controlled by combining the cluster beam deposition technique with a velocity selector.     

Application of atomic force microscopy to particle sizing

AFM has been applied for studying morphology and size distribution of nanometer-sized particles adsorbed on flat surfaces. For the quantitative evaluation of the images an algorithm for automatical particle detection and volume calculation has been developed. In this way a large number of particles can be automatically evaluated in order to derive size distributions or surface coverages. The method has been successfully applied to determine size distributions of environmental aerosol particles collected with an 11-stage low pressure impactor. The first four stages with average aerodynamic equivalent diameters (aed) ranging from 21 to 170 nm were investigated. The calculated aed values were in good agreement with the predicted aed for each stage. Additionally, it could be shown that sampling conditions and storage time affect the derived size distributions. Furthermore, AFM has been applied as reference method for conventional particle sizing techniques. For this purpose technologically relevant powders as titanium oxide powder and tungsten carbide powder were investigated using AFM and the results were compared with conventional techniques such as high resolution SEM and a light scattering method. The derived cumulative size distributions were in good agreement. The results clearly show that AFM constitutes a convenient tool for size determination, not only for ultrafine particles exploiting the high resolving power, but also in the case of larger particles. Received: 2 September 1998 / Revised: 19 October 1998 / Accepted: 22 October 1998     

Size-controlled, one-pot synthesis, characterization, and biological applications of epoxy-organosilica particles possessing positive zeta potential

Epoxy-organosilica particles made from 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (EpoMS) as a single silica source were synthesized by means of a one-pot method. We evaluated three sets of synthesis conditions, including traditional Stober conditions and two variations. Although the traditional conditions did not afford EpoMS particles, the variations did. The size distributions of the particles were evaluated by means of transmission electron microscopy. The mean diameters and size distributions of the particles depended on the EpoMS concentration, and the best coefficient of variation for the size distribution was 5.9%. The surface of the particles had unique properties, such as a positive zeta potential. The particles bound strongly to proteins as well as to DNA. The particles made from EpoMS, allowing particles internally functionalized with fluorescent dye to be prepared by means of a one-pot synthesis. EpoMS particles doped and tuned with fluorescent dye showed strong fluorescence signals and distinct peaks on flow cytometry, and the fluorescent particles could be used to label cells. The labeled cells showed clear fluorescence under a fluorescence microscope, and electron microscopy showed many particles in the cytoplasm. This is the first report describing the synthesis of epoxy-organosilica particles with a positive zeta potential and describing differences in the characteristics of particle formations due to changes in synthesis conditions. We also discuss the advantages of EpoMS particles, as well as the potential biological applications of these particles.     

Characterization of silicon nitride particles synthesized in an atmospheric-pressure convection-stabilized arc

Silicon nitride powders were synthesized in an atmospheric-pressure convection-stabilized arc using silicon and ammonia as reactants. The morphology and particle size distributions of the silicon nitride particles were characterized by SEM, TEM, and electron diffraction analyses. The silicon nitride particles collected in the plasma reactor were formed by either gas-condensed phase reactions or chemical vapor reactions. The morphologies of the particles formed by gas-condensed phase reactions consisted of -Si₃N₄ prisms, -Si₃N₄ matte, -Si₃N₄ needles, and spaghetti-like whiskers. For the homogeneously nucleated particles, the morphologies included dendrites, needles, platelets, and amorphous particles. Most of the particles formed were aggregates with particle size distributions ranging from 500 to 1500 Å depending on the location of injection of the reactants.     

In-Flight Spheroidization of Alumina Powders in Ar–H<Subscript>2</Subscript> and Ar–N<Subscript>2</Subscript> Induction Plasmas

In-flight spheroidization of alumina powders in Ar–H₂ (H₂–7.6%, vol/vol) and Ar–N₂ (N₂–13.0%, vol/vol) RF induction plasmas was investigated numerically and experimentally. The mathematical model for the plasma flows incorporates the k– turbulence model, and that for particles is the Particle-Source-in-Cell (PSI-Cell) model. Experimental results demonstrate that spheroidized alumina particles are produced in both Ar–H₂ and Ar–N₂ RF plasmas, with different particle size distributions and crystal phases. Agreement between the predicted and measured particle size distributions is satisfactory under high particle feed rate conditions, while the results obtained for the Ar–H₂ plasma are better than those for the Ar–N₂ plasma. The discrepancy occurring in low feed rate conditions suggests that particle evaporation is an important factor affecting the plasma–particle heat transfer.     

Synthesis of platinum nanoparticles on substrates of various chemical natures using supercritical carbon dioxide

A method for synthesizing platinum nanoparticles on a dispersed substrate using supercritical carbon dioxide was applied on substrates of various chemical natures: silicon carbide, titanium nitride, and tin dioxide. On all the substrates, materials with narrow uniform platinum nanoparticle size distributions were obtained. The platinum nanoparticle size distribution on each of the substrates was studied. It was shown that the platinum particle sizes are within a narrow range with an average particle size of about 3 nm and scarcely dependent on the chemical nature of the substrate.     

Preparation of Silicon Nanopowder by Recycling Silicon Wafer Waste in Radio-Frequency Thermal Plasma Process

Silicon nanopowders were prepared from silicon waste by using radio-frequency thermal plasma. Silicon waste, generated from the manufacturing process of silicon wafers, was pulverized to form micrometer-sized silicon starting powder. In order to obtain as much silicon nanopowder as possible from thermal plasma processing, the enhancement of vaporization and the quenching rate of the silicon starting powder were considered as major factors. A counter-flow injection apparatus (CFIA) was introduced for improved vaporization and homogeneous nanoparticles. It was designed to inject argon as a quenching gas in the direction opposite the thermal plasma flame flow. The controlled location of the CFIA injection nozzle and the flow rate of the quenching gas affect the residence time of the injected staring powder by recirculating flow and the vapor density by gas mixing. The variation of the flow pattern inside the reactor and the characteristics of the products were investigated to determine the optimal processing environment to prepare uniform and small silicon nanopowder particles. The environment was defined by two parameters: the flow rate of the counter quenching gas and the distance between the torch and CFIA nozzles. The flow rate of the quenching gas was controlled from 30 to 70 L/min. The distance between the torch and CFIA nozzles was adjusted from 150 to 350 mm. When the quenching gas flow rate of 70 L/min and the distance of 350 mm were applied, the uniform and smallest silicon nanopowders were obtained.     

The self-preserving size distribution theory. II. Comparison with experimental results for Si and Si3N4 aerosols

The gas to particle synthesis route is a relatively clean and efficient manner for the production of high-quality ceramic powders. These powders can be subsequently sintered in any wanted shape. The modeling of these production systems is difficult because several mechanisms occur in parallel. From theoretical considerations it can be determined, however, that coagulation and sintering are dominant mechanisms as far as shape and size of the particles are considered. In part I of this article an extensive theoretical analysis was given on the self-preserving size distribution theory for power law particles. In this second part, cumulative particle size distributions of silicon and silicon nitride agglomerates, produced in a laser reactor, were determined from TEM pictures and compared to the distributions calculated from this self-preserving theory for power law particles. The calculated distributions were in fair agreement with the measured results, especially at the high end of the distributions. Calculated and measured particle growth rates were also in fair agreement. Using the self-preserving theory an analysis was made on the distribution of annealed silicon agglomerates, of interest in applications to nanoparticle technology.     

悬浮液进样电感藕合等离子体发射光谱中颗粒的输运和蒸发行为

以碳化硼为例,研究了悬浮液雾化进样中的粒子在传输和蒸发过程中的行为,并对分析结果出现负偏离的原因进行了详细探讨.对比悬浮液颗粒的原始粒径分布和经过传输过程后的粒径分布,获得到达等离子体的颗粒粒径上限小于10 Am.样品中存在的部分超大粒径的颗粒(d>>10 μm)会严重影响可传输区域颗粒(d<10 μm)的质量运输效率...     

Surface chemistry of aerosolized nanoparticles:thermal oxidation of silicon

The kinetics of reaction between silicon nanoparticles and molecular oxygen were studied by tandem differential mobility analysis. Aerosolized silicon nanoparticles were extracted from a low-pressure silane plasma into an atmospheric pressure aerosol flow tube reactor. Particles were initially passed through a differential mobility analyzer that was set to transmit only those particles having mobility diameters of approximately 10 nm. The monodisperse particle streams were mixed with oxygen/nitrogen mixtures of different oxygen volume fractions and allowed to react over a broad temperature range (600-1100 degrees C) for approximately one second. Particles were size-classified after reaction with a second differential mobility analyzer. The particle mobility diameters increased upon oxidation by up to 1.3 nm, depending on the oxygen volume fraction and the reaction temperature. Oxidation is described by a kinetic model that considers both oxygen diffusion and surface reaction, with diffusion becoming important after formation of a 0.5 nm thick oxide monolayer.     

PARTICLE SIZE DISTRIBUTION OF POLYMER POWDERS BY ANALYSIS OF SORPTION KINETICS

A method has been proposed for determination of particle size distributions of polymer powders via analysis of the Fickian sorption and desorption kinetics of organic vapors. The basis for this method is a model describing the kinetics of sorption in homogeneous spherical particles having diameters distributed a-mong a finite set of diameters. A computation procedure has been developed for determining the weight fractions of each particle diameter which optimize the fit between the model and experimental sorption data. This procedure has been applied to gravimetric sorption data for several organic vapors in PVC powders ranging in diameter from 0.2 to 80 μm. For samples whose particle structure meets the assumptions of the model, the procedure yields histographic distributions closely approximating the particle size distributions determined by conventional microscopic and sedimentation methods. For porous or agglomerated particles, the method yields an “equivalent spherical size distribution” which adequately describes the sorption kinetics, but may differ significantly from size distributions measured by other methods.     

Flow field-flow fractionation-inductively coupled plasma mass spectrometry of chemical mechanical polishing slurries

Alumina- and silica-based chemical mechanical polishing slurries were analyzed to demonstrate the feasibility of field-flow fractionation-inductively coupled plasma mass spectrometry (FFF-ICP-MS). After FFF separation ²⁷Al and ²⁹Si were measured by ICP-MS to obtain size distributions, mean particle size, number average-, mass average-, Z average- diameters, minimum and maximum particle sizes, dominant particle size, and particle size ranges (breadth of size distribution, and polydispersity) characteristics. Five commercial alumina and 13 silica slurry samples were characterized. Broad distributions were detected and two polydispersity calculations were compared. Most silica samples and one alumina sample show monomodal normal distributions. Asymmetric distributions were observed for a few silica and most alumina slurries. The degree of deviation from normal distribution was assessed. Mean particle sizes of alumina slurries varied between 150 and 350 nm with the maximum detected particle of less than 680 nm. Silica slurries exhibited maximum particle sizes of less than approximately 400 nm with the mean particle sizes ranging from 110 to 220 nm. Trace metals (Fe, Ti and Zr) coeluted with Al, Si; whereas, Pb appeared to be present as colloidal fractions.