Gas-phase Crystallization of Titanium Dioxide Nanoparticles

We have investigated the development of crystal morphology and phase in ultrafine titanium dioxide particles. The particles were produced by a droplet-to-particle method starting from propanolic titanium tetraisopropoxide solution, and calcined in a vertical aerosol reactor in air. Mobility size classified 40-nm diameter particles were conveyed to the aerosol reactor to investigate particle size changes at 20–1200°C with 5–1-s residence time. In addition, polydisperse particles were used to study morphology and phase formation by electron microscopy. According to differential mobility analysis, the particle diameter was reduced to 21–23-nm at 600°C and above. Precursor decomposition occurred between 20°C and 500°C. The increased mobility particle size at 700°C and above was observed to coincide with irregular particles at 700°C and 800°C and faceted particles between 900°C and 1200°C, according to transmission electron microscopy. The faceted anatase particles were observed to approach a minimized surface energy by forming {101} and {001} crystallographic surfaces. Anatase phase was observed at 500–1200°C and above 600°C the particles were single crystals. Indications of minor rutile formation were observed at 1200°C. The relatively stable anatase phase vs. temperature is attributed to the defect free structure of the observed particles and a lack of crystal–crystal attachment points.     

Aerosol Synthesis of Fullerene Nanocrystals in Controlled Flow Reactor Conditions

Fullerene nanocrystals in the size range 30–300 nm were produced starting from atomized droplets of C₆₀ in toluene. The experiments were carried out under well-controlled conditions in a laminar flow reactor at temperatures of 20–600°C. Particle transformation and crystallization mechanisms of polydisperse and monodisperse (size classified) fullerene aerosol particles were studied. The results show that fullerene particles are roughly spherical having pores and voids at temperatures of 300°C and below. Particles are already crystalline and likely fine-grained at 20°C and they are polycrystalline at temperatures up to 300°C. At 400°C monodisperse particles evaporate almost completely due to their low mass concentration. Polydisperse particles are crystalline, but sometimes heavily faulted. At 500°C most of the particles are clearly faceted. In certain conditions, almost all particles are hexagonal platelets having planar defects parallel to large (111) faces. We suggest that at 500°C fullerene particles are partially vaporized forming residuals with lamellar defects such as twins and stacking faults, which promote crystal growth during synthesis. Subsequently fullerene vapor is condensed on faces with defects and hexagonal particles are grown by a re-entrant corner growth mechanism. At 600°C particles are single crystals, but they have a less distinct shape due to higher vaporization of fullerene. The final size and shape of the particles are mainly determined at the reactor outlet in the short time when the aerosol cools.     

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.     

Characterization of TiO2 Smoke Prepared Using Gas‐Phase Hydrolysis of TiCl4

The formation of submicron TiO₂ smoke (a gas‐phase suspension) from titanium tetrachloride in a low‐pressure hydrolysis reaction in a simple reactor configuration has been studied. Particle size distribution, particle morphology and degree of crystallinity have been characterized as a function of reaction conditions. Highly crystalline anatase TiO₂ particles with narrow size distribution and smaller particle size were formed at high reactor temperature, while larger, amorphous particles were found at lower reactor temperatures. These results are consistent with literature studies. At 817 °C, small (450 nm), spherical, unagglomerated particles could be produced. A gas‐phase dispersion of these particles is intended for use as seeds in subsequent kinetic studies of titanium dioxide formation reactions involving a rapid compression methodology.     

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.     

A new technique for the measurement of the product CO/CO2 ratio at the surface of char particles burning in a fluidized bed

A new experimental technique is proposed to measure the product CO/CO₂ ratio at the surface of spherical char particles during fluidized bed combustion. It is based on the measurement of the burning rate of a single char particle under low oxygen concentration conditions and on the use of an accurate prediction of the particle Sherwood number. This technique was applied to spherical char particles obtained from a bituminous coal which is characterized by a low attrition and fragmentation propensity. The product CO/CO₂ ratio was measured at a bed temperature of 850 °C and at a fluidization velocity of 0.3 m/s in a lab-scale apparatus operated with a bed of 0.5–0.6 mm sand. The char particle size was varied between 2 and 7 mm and the inlet oxygen concentration between 0.1% and 2.0%. Results showed that under the experimental conditions investigated carbon was mostly oxidized to CO₂ within the particle boundary layer, with a maximum fraction of carbon escaping as CO of 10–20% at the lowest oxygen concentrations and largest particle sizes.     

Nanoparticle Formation Mechanism in CVD Reactor with Ionization of Source Vapor

A new chemical vapor deposition (CVD) method, called ionization CVD, was developed, to produce non-agglomerated nanoparticles in which reactant gases are charged. A sonic-jet corona discharger was used as an ionizer in the developed nanoparticle generator. For a tetraethylorthosilicate (TEOS)/O₂ chemical system, SiO₂ nanoparticles were prepared. All particles formed by the ionization CVD were charged unipolarly. SEM micrographs of particles showed that the repulsive Coulombic force between charged particles reduces their coagulation rate and produces non-agglomerated nanoparticles that have a relatively high number concentration and small size. An external field was used to collect the charged particles onto Si wafers. These collected samples indicated that the deposition of charged particles could be controlled by the external electric field. Particle concentration measurement with a condensation nucleus counter at various TEOS concentrations suggested the particle formation mechanism in the ionization CVD was an ion-induced nucleation.     

Size Controlled Synthesis of Gold Nanoparticles using Photochemically Prepared Seed Particles

Gold nanoparticles having prechosen size ranging from 5 to 110 nm have been prepared in two steps. Firstly, small spherical particles (seed) of average diameters between 5 and 20 nm were prepared by varying the ratio of gold ion concentration to stabilizer/reductant, TX-100 concentration and using UV irradiation. Secondly, 20–110 nm particles were formed by a non-iterative seed-mediated growth where small particles produced by the above irradiation technique were exploited as seeds and fresh Au(III) ions were reduced onto the surface on the seed particles by ascorbic acid. The kinetics of particle formation has also been reported. These methods were fast and showed improved monodispersity sphericity and excellent reproducibility.     

Formation of ZnO,MgO and NiO Nanoparticles from Aqueous Droplets in Flame Reactor

Nanoparticles of ZnO, MgO and NiO were produced from droplets of aqueous salt solution in the flame spray pyrolysis reactor. Conventional spray pyrolysis, in which electrical furnace reactor is used, is reported to produce nanoparticles only from acetate precursor. If the reactor pressure is low (60torr), nitrate salt precursor is also known to produce nanoparticles. In this paper, we report that nanoparticles are produced from nitrate as well as acetate salt precursor solution when propane–oxygen diffusion flame is used to decompose aqueous aerosol droplets. At low flame temperature, however, nanoparticles are not formed and the particle morphology is similar to the morphology produced by the conventional spray pyrolysis. At high flame temperature, nanoparticles are formed, regardless of the salt type. Nanoparticles are formed at lower flame temperature from acetate salts than from nitrate salts. All nanoparticle prepared in this work were fully crystallized and the size measured from transmission electron microscopy images was 30nm. This size agreed well with the particle size calculated from X-ray diffraction and specific surface area data.     

Simulation of Nanoparticle Production in Premixed Aerosol Flow Reactors by Interfacing Fluid Mechanics and Particle Dynamics

The interaction of fluid mechanics and particle dynamics at the very early stages of flame synthesis largely affects the characteristics of the product powder. Detailed simulations provide a better understanding of these processes, which take place in a few milliseconds, and offer the possibility to influence the product characteristics by intelligent selection of the process parameters. The present paper reports on the simulation of titania powder formation by TiCl₄ oxidation in an aerosol flow reactor. A commercially available fluid mechanics code is used for the detailed calculation of the fluid flow and the chemical reaction at non-isothermal conditions. This code is then interfaced with a model for aggregate particle dynamics neglecting the spread of the particle size distribution. The simulation shows the onset of the particle formation in the reactor and calculates the dynamic evolution of the aggregate particle size, number of primary particles per aggregate and the specific surface area throughout the reactor. The presented, newly developed calculation technique allows for the first time the simulation of particle formation processes under the authentic, complex conditions as found in actual aerosol reactors.     

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.     

Die Anlagerung radioaktiver Atome an Aerosole (Schwebstoffe) im Größenbereich 0,7–5 μ (Radius)

The attachment of the decay products of thorium emanation to aerosol particles has been studied. The dependence of the attached activity on the particle size was determined for spherical particles with radii ranging from 0,7 to 5 microns. The particles used were solid spheres of paraffin wax. It is found that the attached activity is proportional to theradius of the particles which is in good agreement with theory in this size range.     

有机种子对异戊二烯光氧化反应形成二次有机气溶胶的粒谱演化和形成速率的影响

基于室内烟雾箱实验平台,研究了在有机种子气溶胶下,来自OH启动异戊二烯光氧化反应形成的二次有机气溶胶的动力学. 探究了二次有机气溶胶的粒谱分布分别与来自室内大气中痕量碳氢化合物光氧化反应产生的种子颗粒物浓度以及前体物异戊二烯浓度的依赖关系. 研究结果表明在高浓度种子气溶胶和低浓度异戊二烯条件下(对应于典型城市大气条件),光化学反应形成的二次有机产物凝聚到种子颗粒物表面而造成的颗粒物增长起主导作用;而在低浓度种子气溶胶和相对高浓度异戊二烯条件下(对应于典型偏远地区大气条件),二次有机气溶胶粒谱分布出现双模式结构,分别对应于来自均相成核的新粒子生成和二次有机产物在种子颗粒物上的凝聚增长. 此外,还研究了有机种子颗粒物浓度对二次有机气溶胶形成的影响,评估了在不同种子浓度下二次有机气溶胶粒谱分布的演化和相应新粒子的形成速率.     

随机取向椭球粒子的吸收特性

用Ｔ矩阵方法计算了折射率虚部的范围在０．００１至０．１的几种椭球粒子随机取向时在几种等效尺度参数下的光散射与吸收特性，并与等效的球形粒子的光散射结果进行了比较。分析结果表明：椭球粒子的吸收特性与等效的球形粒子的吸收特性存在着差别，这种差别随粒子的形状、尺度和折射率而改变，考虑到目前气溶胶粒子复折射率虚部的测量精度，以等效的球体粒子处理非球形粒子的吸收不会带来显著的误差。     

Char characteristics and particulate matter formation during Chinese bituminous coal combustion

The characteristics of char particles and their effects on the emission of particulate matter (PM) from the combustion of a Chinese bituminous coal were studied in a laboratory-scale drop tube furnace. The raw coal was pulverized and divided into three sizes, <63, 63–100, and 100–200 μm. These coal samples were subjected to pyrolysis in N₂ and combusted in 20 and 50% O₂ at 1373, 1523, and 1673 K, respectively. Char samples were obtained by glass fiber filters with a pore size of 0.3 μm, and combustion-derived PM was size-segregated by a low pressure impactor (LPI) into different sizes ranging from 10.0 to 0.3 μm. The characteristics of char particles, including particle size distribution, surface area, pore size distribution, swelling behavior and morphology property, were studied. The results show that, coal particle size and pyrolysis temperature have significant influence on the char characteristics. The swelling ratios of char samples increase with temperature increasing from 1373 to 1523 K, then decrease when the temperature further increases to 1623 K. At the same temperature, the swelling ratios of the three size fractions are markedly different. The finer the particle size, the higher the swelling ratio. The decrease of swelling ratio at high temperature is mainly attributed to the high heating rate, but char fragmentation at high temperature may also account for the decrease of swelling ratio. The supermicron particles (1–10 μm) are primarily spherical, and most of them have smooth surfaces. Decreasing coal particle size and increasing the oxygen concentration lead to more supermicron-sized PM formation. The influence of combustion temperature on supermicron-sized PM emission greatly depends on the oxygen concentration.     

Effect of Particle Size and Phase Composition of Titanium Dioxide Nanoparticles on the Photocatalytic Properties

Titanium dioxide (TiO₂) nanoparticles were prepared by the oxidation of titanium tetrachloride (TiCl₄) in a diffusion flame reactor. The average diameter of particles was 15–30 nm and mass fraction of anatase ranged from 40% to 80%. Effects of particle size and phase composition of those TiO₂ nanoparticles on photocatalytic properties such as decomposition of methylene blue, bacteria and ammonia gas were investigated. The degree of decomposition of methylene blue by the TiO₂ nanoparticles under the illumination of the black light was directly proportional to the anatase mass fraction, but inversely to the particle size. The decomposition of bacteria and ammonia gas by the TiO₂ nanoparticles under the illumination of the fluorescent light showed the same trend as in the case of the methylene blue.     

基于平均质量的悬浮颗粒物的质量密度算法

基于米氏(Mie)散射理论得到了粒子计数器测量球形颗粒物质量密度的计算公式。考虑非球形颗粒,从颗粒群粒度分布概念出发,提出了统计意义上的平均质量概念,推导了非球形颗粒物质量密度的理论公式。运用理论公式证明了粒子计数器测量非球形颗粒物质量密度计算公式的合理性,进而给出了基于平均质量的悬浮颗粒物的质量密度算法,该算法只需对两个系数进行标定。实验表明,该算法的质量密度计算值与实际值十分吻合,两者拟合直线的斜率为0.9713,相关系数为0.9998。该算法为实现粒子计数器在线测量悬浮颗粒物的质量密度提供了一种可行途径。     

Measurements of Silica Aggregate Particle Growth Using Light Scattering and Thermophoretic Sampling in a Coflow Diffusion Flame

The evolution of silica aggregate particles in a coflow diffusion flame has been studied experimentally using light scattering and thermophoretic sampling techniques. An attempt has been made to calculate the aggregate number density and volume fraction using the measurements of scattering cross section from 90° light scattering with combination of measuring the particle size and morphology from the localized sampling and a TEM image analysis. Aggregate or particle number densities and volume fractions were calculated using Rayleigh–Debye–Gans and Mie theory for fractal aggregates and spherical particles, respectively. Using this technique, the effects of H₂ flow rates on the evolution of silica aggregate particles have been studied in a coflow diffusion flame burner. As the flow rate of H₂ increases, the primary particle diameters of silica aggregates have been first decreased, but, further increase of H₂ flow rate causes the diameter of primary particles to increase and for sufficiently larger flow rates, the fractal aggregates finally become spherical particles. For the cases of high flame temperatures, the particle sizes become larger and the number densities decrease by coagulation as the particles move up within the flame. For cases of low flame temperatures, the primary particle diameters of aggregates vary a little following the centerline of burner and for the case of the lowest flame temperature in the present experiments, the sizes of primary particles even decrease as particles move upward.     

Nanoparticle production by UV irradiation of combustion generated soot particles

Laser ablation of surfaces normally produce high temperature plasmas that are difficult to control. By irradiating small particles in the gas phase, we can better control the size and concentration of the resulting particles when different materials are photofragmented. Here, we irradiate soot with 193 nm light from an ArF excimer laser. Irradiating the original agglomerated particles at fluences ranging from 0.07 to 0.26 J/cm² with repetition rates of 20 and 100 Hz produces a large number of small, unagglomerated particles, and a smaller number of spherical agglomerated particles. Mean particle diameters from 20 to 50 nm are produced from soot originally having a mean electric mobility diameter of 265 nm. We use a non-dimensional parameter, called the photon–atom ratio (PAR), to aid in understanding the photofragmentation process. This parameter is the ratio of the number of photons striking the soot particles to the number of the carbon atoms contained in the soot particles, and is a better metric than the laser fluence for analyzing laser–particle interactions. These results suggest that UV photofragmentation can be effective in controlling particle size and morphology, and can be a useful diagnostic for studying elements of the laser ablation process.     

Effects of Preparation Parameters on the Characteristics of NiPxBY Nanomaterials

A series of NiP _x B _y nanomaterials were prepared by a chemical reduction method under various preparation parameters. Experiment results show that the different preparation parameters affected the morphology, particle size, surface area and the composition of the sample. However, they did not influence the electronic state of nickel. The type of solution showed significant influence on the properties of the sample, whereas, the type of nickel salt did not. The particle size of NiPB, NiB, and NiP were 10–30 nm. The NiP sample prepared in the aqueous solution had the largest particle size 50–150 nm. If the solvent was 50% ethanol in water, the surface area of the sample significantly increased nine fold for NiP and four fold for NiPB powders. In contrast, the surface area of NiB did not increase. The NiPB, NiB, and NiP powders had a spherical morphology if they were prepared with aqueous solution. The NiPB prepared in 50% ethanol solution showed floss morphology and had a very high surface area.