Aerosol synthesis of silicon nanoparticles with narrow size distribution—Part 1: Experimental investigations

A study on the feasibility of aerosol processing of nearly monodisperse silicon nanoparticles via pyrolysis of monosilane in a hot wall reactor is presented. For optimal conditions silicon nanoparticles with a geometric standard deviation of 1.06 were synthesized at a production rate of 0.7 g/h. The size of the particles could be precisely controlled in the range of 20–40 nm, whilst maintaining a geometric standard deviation in the range of 1.06–1.08, by proper choice of the governing parameters temperature, residence time and precursor concentration. The results show that narrow particle size distributions can only be obtained in the temperature range between 900 and 1100 °C, as long as both the initial silane concentration (1 mbar silane partial pressure) and the reactor total pressure are low (25 mbar). This regime for the production of narrow particle size distributions has not been identified in prior work on the thermal decomposition of silane. Narrowly distributed particles can be obtained under conditions where nucleation and particle growth are separated and the agglomeration rates are negligible.     

Effect of atomization methods on the size and morphology of Gd0.1Ce0.9O2−δ powder synthesized by aerosol flame synthesis

Nano-sized gadolinium doped ceria (GDC) powders were successfully synthesized by aerosol flame deposition (AFD) with two different atomization methods; ultrasonic and electrostatic atomization. The effect of the atomization method on the size and morphology of GDC particles were investigated. It was observed that the diameter range of the GDC small primary particles synthesized by the ultrasonic atomization method was 10–50 nm while with the electrostatic method was 5–25 nm. In addition, the size of primary large particle found to be decreased from 200 nm to 50 nm with increasing electric field up to 15 kV. The GDC powder synthesized by the electrostatic atomization exhibited reduced crystallite size, particle size, and similar electrical conductivity compared to GDC powder synthesized by ultrasonic atomization. This work demonstrated the benefits of the electrostatic atomization for producing smaller-sized GDC nanopowders for the application in intermediate temperature solid oxide fuel cells.     

Performance evaluation of long differential mobility analyzer (LDMA) in measurements of nanoparticles

Performance of a long differential mobility analyzer (LDMA) in measurements of nanoparticles was evaluated experimentally and numerically. In the evaluation of the LDMA measurements, silver particles in a size range of 5–30 nm were used under an increased flow rate. The numerical calculation method was used for calculating the particle trajectory in the LDMA, and the results were used for a comparison with Stolzenburg's transfer function. Using the CFD method, the flow around the aerosol inlet slit was analyzed, and the resulting particle mobility distribution was compared with that for an ideal flow. The resulting flow effect on the penetration efficiency caused by the inlet and exit slits were negligible when a well-designed system was used. The experimental measurements of mobility distributions were in good agreement with the theoretical prediction of particle size ranges over 10 nm, but some discrepancies were observed when particle size ranges were below 10 nm in size. The numerical calculation estimated the discrepancy found below the 10 nm particle size ranges.     

A novel bipolar charger for submicron aerosol particles using carbon fiber ionizers

A simple and novel bipolar charging device using carbon fiber ionizers was developed to neutralize submicron aerosol particles without the generation of ozone. The ion currents of the positive and negative ions generated by carbon fiber ionizers were so chosen as to optimize particle neutralization. The particle penetration, charging probability and charge distribution resulting from the charger were investigated and compared to those from a Kr-85 radioactive neutralizer for the particles in the size range of 20–120 nm. Size distributions for various laboratory-generated aerosols (sodium chloride, ammonium nitrate, ammonium sulfate and glutaric acid) neutralized by the charger were also investigated and compared to those obtained without neutralization. Particle penetration in the charger was over 90% for particles larger than 20 nm. Charging probability and charge distribution for the charger were in good agreement with those from Kr-85 neutralizer and with theoretical estimations. Size distributions observed for the charger and Kr-85 neutralizer were also in good agreement for particles of different concentrations and various chemical compositions. The newly developed bipolar carbon fiber charger can neutralize submicron particles, at least as effectively as currently available radioactive neutralizers and with negligible ozone generation which is its major advantage.     

Preparation of porous silver particles using ammonium formate and its formation mechanism

Here we report the preparation of two different types of macroporous silver particles (round and coral) by simple chemical reduction using ammonium formate. We also discuss the chemical mechanism of silver particle and macroporous silver particle formation. The synthesized round type and coral-type porous silver particles were 20–50 μm and 30–150 μm in size and their pores were 100–200 nm and 1–2 μm across, respectively. They were characterized by particle distribution analysis, X-ray diffraction, and scanning electron microscopy.     

Size distribution and sites of origin of droplets expelled from the human respiratory tract during expiratory activities

A new expiratory droplet investigation system (EDIS) was used to conduct the most comprehensive program of study to date, of the dilution corrected droplet size distributions produced during different respiratory activities.Distinct physiological processes were responsible for specific size distribution modes. The majority of particles for all activities were produced in one or more modes, with diameters below 0.8 μm at average concentrations up to 0.75 cm^?3. These particles occurred at varying concentrations, during all respiratory activities, including normal breathing. A second mode at 1.8 μm was produced during all activities, but at lower concentrations of up to 0.14 cm^?3.Speech produced additional particles in modes near 3.5 and 5 μm. These two modes became most pronounced during sustained vocalization, producing average concentrations of 0.04 and 0.16 cm^?3, respectively, suggesting that the aerosolization of secretions lubricating the vocal chords is a major source of droplets in terms of number.For the entire size range examined of 0.3–20 μm, average particle number concentrations produced during exhalation ranged from 0.1 cm^?3 for breathing to 1.1 cm^?3 for sustained vocalization.Non-equilibrium droplet evaporation was not detectable for particles between 0.5 and 20 μm, implying that evaporation to the equilibrium droplet size occurred within 0.8 s.     

Correlation between airborne particle concentrations in seven industrial plants and estimated respiratory tract deposition by number,mass and elemental composition

The number and mass distribution of airborne particles were recorded in several industrial plants. From the data obtained, particle deposition was estimated in three regions of the respiratory tract using the ICRP grand average deposition model based on Hinds' (1999) parameterization. The median diameter was 30–70 nm (number distributions), and >4 μm (mass distributions) near most work activities, resulting in linear relationships between the deposited number/mass concentrations and the number/mass concentrations in the air. Welding and laser cutting produced particles in the 200–500-nm range; total deposition was small, not in accordance with the linear relationship observed for the other work activities. The elemental content varied between particle sizes in some workplaces, causing different elements to deposit in different respiratory regions. Iron was the most abundant element in the particles in many of the workplaces; in an iron foundry, however, Fe was most abundant only in the micron-sized particles whereas the nanoparticles mainly comprised Pb and Sb.     

Penetration of freeway ultrafine particles into indoor environments

High concentrations of ultrafine particles have been reported to exist near major freeways. Many urban residences are located in close proximity to high-density roadways. Consequently, indoor environments near freeways may experience significant concentrations of outdoor ultrafine particles. Given that people spend over 80% of their time indoors, understanding transport of ultrafine particles from outdoor to indoor environments is important for assessing the impact of exposure to outdoor particulate matter on human health. Four two-bedroom apartments within 60 m from the center of the 405 Freeway in Los Angeles, CA were used for this study. Indoor and outdoor ultrafine particle size distributions in the size range of 6–220 nm were measured concurrently under different ventilation conditions without indoor aerosol generation sources. The size distributions of indoor aerosols showed less variability than the adjacent outdoor aerosols. Indoor to outdoor ratios for ultrafine particle number concentrations depended strongly on particle size. Indoor/outdoor (I/O) ratios also showed dependence on the nature of indoor ventilation mechanisms. Under infiltration conditions with air exchange rates ranging from 0.31 to 1.11  ${\mathrm{h}}^{-1}$, the highest I/O ratios (0.6–0.9) were usually found for larger ultrafine particles (70–100 nm), while the lowest I/O ratios (0.1–0.4) were observed for particulate matter of 10–20 nm. Data collected under infiltration conditions were fitted into a dynamic mass balance model. Size-specific penetration factors and deposition rates were determined for all studied residences. Results from this research have implications concerning personal exposure to freeway-related ultrafine particles and possible associated health consequences.     

Formation and stabilization of submicron particles via rapid expansion processes

Submicron particles were produced by rapid expansion of supercritical solution into air (RESS) or an aqueous surfactant solution (RESSAS) to minimize particle growth and to prevent particle agglomeration. Thereby the effect of process conditions on the size of the particles precipitated was investigated. The obtained product was evaluated by measuring particle size by 3-wavelength extinction measurements, dynamic light scattering, specific surface areas by nitrogen gas adsorption, melting behaviour by differential scanning calorimetry, particle morphology by X-ray diffraction, scanning electron micrographs (SEM), and drug loading by high performance liquid chromatography.Prior to the particle formation experiments, the melting temperature of Salicylic acid under CO₂ pressure and the solubility of Salicylic acid in CO₂ were measured. The size of Salicylic acid particles produced via RESS decreased from 230 to 130 nm as the pre-expansion temperature decreased from 388 to 328 K and the specific surface area of the micronized particles was found to be up to 60 times higher than that of the unprocessed material. RESSAS experiments demonstrate that in 1 wt.% Tween 80 solutions Salicylic acid concentrations of 4.6 g/dm³ could be stabilized with particle diameters in the range of 180 nm. Additional experiments show that Ibuprofen nanoparticles with an average size of 80 nm and a drug concentration of 2.4 g/dm³ could be stabilized in 1 wt.% Tween^® 80 solutions. The use of a SDS solution instead of Tween^® 80 results in a stable aqueous suspension of phytosterol nanoparticles, where the average particle size is 50 nm at a drug concentration of 5.6 g/dm³.     

Synthesis of 5-Fluorouracil nanoparticles via supercritical gas antisolvent process

The micronization of an anticancer compound (5-Fluorouracil) by supercritical gas antisolvent (GAS) process was investigated. 5-Fluorouracil was dissolved in dimethyl sulfoxide (DMSO) and subsequently carbon dioxide as an antisolvent was injected into this solution thus, the solution was supersaturated and nanoparticles were precipitated. The influence of antisolvent flow rate (1.6, 2 and 2.4 mL/min), temperature (34, 40 and 46), solute concentration (20, 60 and 100 mg/mL) and pressure (9, 12 and 15 MPa) on particle size and particle size distribution were studied. Particle analyses were performed by scanning electron microscopy (SEM) and Zetasizer Nano ZS. The mean particle size of 5-Fluorouracil was obtained in the range of 260–600 nm by varying the GAS effective parameters. The High performance liquid chromatography (HPLC) and Fourier transforms infrared spectroscopy (FTIR) analyses indicated that the 5-Fluorouracil nanoparticles were pure and the nature of the component did not change. The experimental results indicated that increasing the antisolvent flow rate and pressure, while decreasing the temperature and initial solute concentration, led to a decrease in 5-Fluorouracil particle size.     

Precipitation kinetics of PMMA sub-micrometric particles with a supercritical assisted-atomization process

Sub-micrometric particles of PMMA were successfully prepared via a supercritical assisted-atomization (SAA) process using acetone as a solvent and supercritical carbon dioxide as a spraying medium. The effects of several key factors on the particle size were investigated. These factors included the concentration of polymer solution, temperature in saturator and volumetric flow rate ratio of carbon dioxide to polymer solution. The shape of the polymer's primary particles is spherical with the arithmetic mean size ranging from 82 nm to 176 nm and the mass-weighted mean size ranging from 127 nm to 300 nm. As evidenced from the experimental results, the lower concentrations of polymer solution, optimized volumetric flow rate ratios, and higher temperatures in saturator can effectively reduce the mean particle size. The precipitation kinetic parameters were determined from the particle size distributions with the aid of the population balance theory. This study found the primary nucleation to be dominant in the precipitation and diffusion may govern particle growth.     

Computational fluid dynamics simulations of submicrometer and micrometer particle deposition in the nasal passages of a Sprague-Dawley rat

Computational fluid dynamics (CFD) simulations were conducted in a model of the complete nasal passages of an adult male Sprague-Dawley rat to predict regional deposition patterns of inhaled particles in the size range of 1 nm to 10 μm. Steady-state inspiratory airflow rates of 185, 369, and 738 ml/min (equal to 50%, 100%, and 200% of the estimated minute volume during resting breathing) were simulated using Fluent?. The Lagrangian particle tracking method was used to calculate trajectories of individual particles that were passively released from the nostrils. Computational predictions of total nasal deposition compared well with experimental data from the literature when deposition fractions were plotted against the Stokes and Peclet numbers for micro- and nanoparticles, respectively. Regional deposition was assessed by computing deposition efficiency curves for major nasal epithelial cell types. For micrometer particles, maximum olfactory deposition was 27% and occurred at the lowest flow rate with a particle diameter of 7 μm. Maximum deposition on mucus-coated non-olfactory epithelium was 27% for 3.25 μm particles at the highest flow rate. For submicrometer particles, olfactory deposition reached a maximum of 20% with a particle size of 5 nm at the highest flow rate, whereas deposition on mucus-coated non-olfactory epithelium reached a peak of approximately 60% for 1–4 nm particles at all flow rates. These simulations show that regional particle deposition patterns are highly dependent on particle size and flow rate, indicating the importance of accurate quantification of deposition in the rat for extrapolation of results to humans.     

On-road and laboratory evaluation of combustion aerosols—Part1: Summary of diesel engine results

The objective was to characterize diesel exhaust aerosols on road and to duplicate the results in the laboratory without altering the physical characteristics of the nuclei mode. On-road emissions from four, heavy-duty diesel truck engines were measured. The same engines were reevaluated in the manufacturers’ laboratories. For highway cruise and acceleration conditions, all engines produced bimodal size distributions with the nuclei mode ranging in size from 6 to 11 nm and the accumulation mode from 52 to 62 nm. On-road size distribution measurements nearly always showed a nuclei mode while laboratory measurements showed a nuclei mode under many, but not all conditions. Laboratory studies showed that nuclei mode particles consisted mainly of heavy hydrocarbons. More than 97% of the volume of 12 and 30 nm particles disappeared on heating to 400 °C. The volatility resembled that of C24–C32 n-alkanes implying a significant contribution from lubricating oil.     

AEROSOL CHARACTERISATION IN MEDIUM-SPEED DIESEL ENGINES OPERATING WITH HEAVY FUEL OILS

Aerosol measurements were carried out in medium-speed diesel engines to determine the aerosol characteristics and formation in four-stroke diesel engines equipped with turbocharger(s) burning heavy fuel and high ash-content heavy fuel oil. The mass size distributions are bimodal with a main mode at 60–90 nm and a second mode at 7–10 μm. The small mode particles are formed by nucleation of volatilized fuel oil ash species, which further grow by condensation and agglomeration. The large mode particles are mainly agglomerates of different sizes consisting of the small particles. The number size distributions peak at 40–60 nm, as also observed in the SEM micrographs. Agglomerates consisting of these primary spherical particles are also found. The TEM micrographs reveal that these particles consist of even smaller structures. Based on the mass and elemental size distributions evidence of high volatility of the fuel oil ash was found. The main effect on the aerosol size distributions was caused by the engine type and fuel oil properties.     

Effect of Cu particle size on hydrogenation of dimethyl succinate over Cu–SiO2 nanocomposite

Copper–silica nanocomposite with different Cu particle size was synthesized by changing the concentration of Cu nitrate solution by precipitation-deposition method. In this preparation method, the average Cu particle size was estimated to be 11 nm, 23 nm and 33 nm for 0.05 M, 0.8 M, and 2.0 M of Cu nitrate solution, respectively, which was confirmed by XRD and TEM. When the catalytic activities of these materials, Cu(76)/SiO₂, were compared in hydrogenation of dimethyl succinate (DMS) at 265 °C and 25 bar, the product distribution as well as DMS conversion was highly dependent on Cu particle size. At WHSV 0.4 h^− 1, Cu(76)/SiO₂ with Cu particle size of 11 nm gave much higher tetrahydrofuran (THF) selectivity (93%) than that of 33 nm (20%) for the same DMS conversion (100%). The smaller Cu particles size was more advantageous to higher DMS conversion and higher THF selectivity, while the larger Cu particle size was more advantageous to higher γ-butyrolactone (GBL) selectivity. It is concluded that THF could be produced selectively by controlling only Cu particle size without adding the acidic promoters such as alumina to Cu metallic sites.     

Determination of volume,scaling exponents,and particle alignment of nanoparticle agglomerates using tandem differential mobility analyzers

Tandem Differential Mobility Analyzers (TDMA) were used along with TEM analysis to determine agglomerate volume, scaling exponents for both mass-mobility diameter (D_fm) and friction coefficient-number of primary particles (η) for the mobility diameter in the range 30–300 nm. The larger agglomerates with d_m=250 and 300 nm require a temperature of 800 °C and a sintering time of 0.7 s to form a spherical shape compared to 600 °C for a mobility diameter of 150 nm. It is shown that the 3% decrease in mobility size of the 250 and 300 nm agglomerates with increasing sintering temperature (600–800 °C) is a result of a morphology change from an ellipsoid to a sphere during the sintering process. The effect of sublimation on the sintered particle size is negligible with less than a 0.5% decrease in diameter for a 300 nm mobility diameter agglomerate at 800 °C. The TDMA results show that D_fm is not dependent on mobility size range and that η is dependent on the size range. Both results are counter to predictions based on free molecular models. These results confirm previous results obtained using a DMA together with an aerosol particle mass analyzer (APM) and are shown to have about a factor of two smaller uncertainty. It is also experimentally demonstrated that the agglomerate particles with d_m=300 nm are partially aligned in the electric field of DMA. The correction for a random orientation results in a significant decrease in D_fm by 3.5% and a significant increase in η by 3%.     

Monodisperse biopolymer nanoparticles by Continuous Supercritical Emulsion Extraction

In this work Continuous Supercritical Emulsions Extraction (SEE-C) has been tested to produce monodisperse biopolymer nanoparticles. The SEE-C technology allows an improved control of particle size distribution by reducing the emulsion processing times and preventing any droplet/particle aggregation. Biopolymers as, poly-lactic acid (PLA), poly-caprolactone (PCL) and poly-lactic-co-glycolic acid (PLGA) in different emulsion formulations were tested using acetone as oily-phase solvent. Emulsion formulation parameters, such as surfactant and/or polymer concentration and emulsification techniques (ultrasound or high speed emulsification) were analyzed in connection to SEE-C, to produce monodisperse nanoparticles. Operating at 38 °C and 80 bar, with an L/G ratio of 0.1, particles of PLA, PCL and PLGA with mean size of 233 nm, 342 nm and 212 nm, respectively, were produced. Poly-dispersity indexes lower to 0.1 nm were also obtained, confirming the possibility to obtain sharp distributions with monodisperse characteristics. Solvent residues as low as 500 ppm were also observed.     

Self-oscillations of methane oxidation rate over Pd/Al2O3 catalysts: Role of Pd particle size

Oscillations of the methane oxidation rate were studied under methane-rich conditions on Pd/Al₂O₃ catalysts differing in Pd particle size. It was demonstrated that the temperature interval where oscillations occur narrows from 300–360 °C for the catalyst with Pd particle aggregates from 50–100 nm to 345–355 °C for the catalyst with isolated Pd particles of ~ 5 nm in size. At the same time, the period of oscillations showed ~ 6-fold increase. Structural transformations of Pd in the oscillation cycle were similar to those observed on bulk Pd used as a catalyst in the same reaction.     

Micronization of salicylic acid and taxol (paclitaxel) by rapid expansion of supercritical fluids (RESS)

The particle sizes of the pharmaceutical substances are important for their bioavailability. The bioavailability can be improved by reducing the particle size of the drug. In this study, salicylic acid and taxol were micronized by the rapid expansion of supercritical fluids (RESS). Supercritical CO₂ and CO₂ + ethanol mixture were used as solvent. Experiments were carried out to investigate the effect of extraction temperature (318–333 K) and pressure (15–25 MPa), pre-expansion temperature (353–413 K), expansion chamber temperature (273–293 K), spray distance (6–13 cm), co-solvent concentration (ethanol, 1, 2, 3, v/v, %) and nozzle configuration (capillary and orifice nozzle) on the size and morphology of the precipitated salicylic acid particles. For taxol, the effects of extraction pressure (25, 30, 35 MPa) and co-solvent concentration (ethanol, 2, 5, 7, v/v, %) were investigated. The characterization of the particles was determined by scanning electron microscopy (SEM), optical microscopy, and LC–MS analysis.The particle size of the original salicylic acid particles was L/D: 171/29–34/14 μm/μm. Depending upon the different experimental conditions, smaller particles (L/D: 15.73/4.06 μm/μm) were obtained. The particle size of taxol like white crystal powders was reduced from 0.6–17 μm to 0.3–1.7 μm The results showed that the size of the precipitated salicylic acid and taxol particles were smaller than that of original particles and RESS parameters affect the particle size.