Cu-Sn binary metal particle generation by spray pyrolysis

Cu-Sn binary particles were generated via spray pyrolysis from metal salt precursors with ethylene glycol as the co-solvent and reducing agent. The morphology, crystallinity, and elemental distribution of particles were tunable by changing the reaction temperature, residence time, and quench gas flow rate. Hollow porous particles were fabricated with a higher Sn concentration on the particle surface when the furnace set point was 500°C, while solid particles with a lower surface Sn concentration were generated when the furnace set point was 1000°C. Particles with spherical morphologies were obtained at long residence time conditions (4.5 s). Cu-Sn binary particles with irregular structures (e.g., pores on the particle surface, fragmented spherical particles, and lamellar fragments) were formed at short residence time conditions (0.92 s). A possible spray pyrolysis mechanism was proposed that incorporates chemical reaction steps and structural progression. By this mechanism, the metal salts are believed to sequentially undergo hydrolysis to metal hydroxides, decomposition to metal oxides, reduction to metals, and finally diffusion of Sn into the Cu matrix to generate the Cu-Sn solid solution.

Copyright © 2017 American Association for Aerosol Research     

Intercomparison of a portable and two stationary mobility particle sizers for nanoscale aerosol measurements

During occupational exposure studies, the use of conventional scanning mobility particle sizers (SMPS) provides high quality data but may convey transport and application limitations. New instruments aiming to overcome these limitations are being currently developed. The purpose of the present study was to compare the performance of the novel portable NanoScan SMPS TSI 3910 with that of two stationary SMPS instruments and one ultrafine condensation particle counter (UCPC) in a controlled atmosphere and for different particle types and concentrations.

The results show that NanoScan tends to overestimate particle number concentrations with regard to the UCPC, particularly for agglomerated particles (ZnO, spark generated soot and diesel soot particles) with relative differences >20%. The best agreements between the internal reference values and measured number concentrations were obtained when measuring compact and spherical particles (NaCl and DEHS particles). With regard to particle diameter (modal size), results from NanoScan were comparable < [± 20%] to those measured by SMPSs for most of the aerosols measured.

The findings of this study show that mobility particle sizers using unipolar and bipolar charging may be affected differently by particle size, morphologies, particle composition and concentration. While the sizing accuracy of the NanoScan SMPS was mostly within ±25%, it may miscount total particle number concentration by more than 50% (especially for agglomerated particles), thus making it unsuitable for occupational exposure assessments where high degree of accuracy is required (e.g., in tier 3). However, can be a useful instrument to obtain an estimate of the aerosol size distribution in indoor and workplace air, e.g., in tier 2.     

Effects of relative humidity and particle and surface properties on particle resuspension rates

Wind tunnel experiments examined the coupled effects of relative humidity (RH) and surface and particle properties on aerodynamically induced resuspension. Hydrophilic glass spheres and hydrophobic polyethylene spheres ～20 μm in diameter, with nanoscale surface features, were resuspended from hydrophilic glass, hydrophobic chemical agent resistant coating (CARC), and gold surfaces. Roughness of the glass and gold surfaces was on the nanoscale, whereas CARC surfaces had microscale roughness. Different particle–surface combinations yielded van der Waals interactions that varied by a factor of 4, but these differences had a relatively minor effect on resuspension. Wind tunnel RH was varied between 7% and 78%. Overall, RH affected the resuspension of hydrophilic particles on hydrophilic surfaces most strongly and that of hydrophobic particles on hydrophobic surfaces the least. For each particle–surface combination there was a threshold RH value below which resuspension rates were essentially constant and in good agreement with a dimensionless model of particle resuspension.

Copyright © 2016 American Association for Aerosol Research     

Design and Laboratory Evaluation of a Sequential Spot Sampler for Time-Resolved Measurement of Airborne Particle Composition

A new sampling approach has been developed to enable affordable, time-resolved monitoring of particulate chemical composition, and more generally to provide concentrated samples of airborne particles. Using a newly developed, moderated water-based condensational growth technology, individual particle samples are deposited in a 1-mm diameter dry “spot.” The moderated condensation technology enables this collection with minimal temperature rise, providing robust collection for volatile constituents. Measured collection efficiencies are above 95% for particles in the size range from 0.010 μm to 2.5 μm. A set of 20 or more time-resolved samples, plus blanks, may be collected onto a multiwell collection plate. For chemical analysis the plate is returned to the laboratory, and placed directly into a modified autosampler, without extraction or preparation. The autosampler handles the addition of eluent, extraction, and sample injection without user manipulation. This article presents the design and laboratory evaluation of a 1.5 L/min sampling rate version of this system.

Copyright 2014 American Association for Aerosol Research     

An integrative model for the filtration efficiencies in realistic tests with consideration of the filtration velocity profile and challenging particle size distribution

Many well-established models can be applied to calculate the filtration efficiencies. In these models the filtration velocity and challenging particle size are assumed to be known accurately. However, in realistic filtration tests, the filtration velocity has profiles dependent on the filter holder geometry and experimental conditions; the challenging particles have size distributions dependent on the instruments and operation conditions. These factors can potentially affect the measured filtration efficiency and lead to discrepancies with the models.

This study aims to develop an integrative model to predict the filtration efficiencies in realistic tests by incorporating the effects of the filtration velocity profile and challenging particle size distribution classified by a differential mobility analyzer (DMA) into the existing filtration models. Face velocity profile is modeled with fluid mechanics simulations; the initial generated particle size distribution, the particle charging status and the DMA transfer function are modeled to obtain the challenging particle size distribution. These results are then fed into the filtration models. Simulated results are compared with experimental ones to verify the model accuracy. This model can be used to reduce filtration test artifacts and to improve the experimental procedure.

The results reveal that the face velocity upstream the filter exhibits high degree of homogeneity not affecting the filtration efficiency if the filter pressure drop is not very low. The generated particle size distribution and the DMA selection size window could influence the challenging particle size distribution and therefore the measured filtration efficiency.

Copyright © 2017 American Association for Aerosol Research     

Impacts of Aerosol Aging on Laser Desorption/Ionization in Single-Particle Mass Spectrometers

Single-particle mass spectrometry (SPMS) has been widely used for characterizing the chemical mixing state of ambient aerosol particles. However, processes occurring during particle ablation and ionization can influence the mass spectra produced by these instruments. These effects remain poorly characterized for complex atmospheric particles. During the 2005 Study of Organic Aerosols in Riverside (SOAR), a thermodenuder was used to evaporate the more volatile aerosol species in sequential temperature steps up to 230°C; the residual aerosol particles were sampled by an aerosol mass spectrometer (AMS) and a single-particle aerosol time-of-flight mass spectrometer (ATOFMS). Removal of the secondary species (e.g., ammonium nitrate/sulfate) through heating permitted assessment of the change in ionization patterns as the composition changed for a given particle type. It was observed that a coating of secondary species can reduce the ionization efficiency by changing the degree of laser absorption or particle ablation, which significantly impacted the measured ion peak areas. Nonvolatile aerosol components were used as pseudo-internal standards (or “reference components”) to correct for this LDI effect. Such corrected ATOFMS ion peak areas correlated well with the AMS measurements of the same species up to 142°C. This work demonstrates the potential to accurately relate SPMS peak areas to the mass of specific aerosol components.

Copyright 2014 American Association for Aerosol Research     

Influence of flame-generated ions on the simultaneous charging and coagulation of nanoparticles during combustion

Flames generate a large amount of chemically and thermally ionized species, which are involved in the growth dynamics of particles formed in flames. However, existing models predicting particle formation and growth do not consider particle charging, which may lead to bias in the calculated size distribution of particles. In this study, Fuchs' charging theory was coupled with a monodisperse particle growth model to study the simultaneous charging and coagulation of nanoparticles during combustion. In order to quantify the charging characteristics of nanoparticles, a high-resolution DMA was used to measure the mobilities of ions generated from a premixed flat flame operated at various conditions. The effect of temperature on ion–particle and particle–particle combination coefficients was further examined. The proposed model showed that the influence of charging on particle growth dynamics was more prominent when the ion concentration was comparable to or higher than the particle concentrations, a condition that may be encountered in flame synthesis and solid fuel-burning. Simulated results also showed that unipolar ion environments strongly suppressed the coagulation of particles. In the end, a simplified analysis of the relative importance of particle charging and coagulation was proposed by comparing the characteristic time scales of these two mechanisms.

© 2017 American Association for Aerosol Research     

Differential diffusion analyzer

In this article, a proof of concept of a new measurement instrument, differential diffusion analyzer (DDA), is established. The DDA enables the measurement of the size distribution of sub-10 nm aerosol particles, and it can also be used as a size classifier to separate a certain particle size from a size distribution for subsequent analysis. The developed technique is based on the diffusion separation of different size particles. Thus, the main advantage of the DDA compared to other methods is that particle charging is not required. Simulated and experimentally measured transmission efficiencies show that the diffusion-based differential size classification is a feasible concept, and moreover, shows that particle size is inversely proportional to the square root of the total flow rate.

Copyright © 2017 American Association for Aerosol Research     

Preliminary investigation of a water-based method for fast integrating mobility spectrometry

A water-based condensational growth channel was developed for imaging mobility-separated particles within a parallel plate separation channel of the Fast Integrated Mobility Spectrometer (FIMS). Reported are initial tests of that system, in which the alcohol condenser of the FIMS was replaced by a water-based condensational growth channel. Tests with monodispersed sodium chloride aerosol verify that the water-condensational growth maintained the laminar flow, while providing sufficient growth for particle imaging. Particle positions mapped onto particle mobility, in accordance with theoretical expectations. Particles ranging in size from 12 nm to 100 nm were counted with the same efficiency as with a butanol-based ultrafine particle counter, once inlet and line losses were taken into account.

Copyright © 2017 American Association for Aerosol Research     

Evaporation rate of particles in the vaporizer of the Aerodyne aerosol mass spectrometer

We present calculations for evaporation rates of particles collected on the vaporizer of the Aerodyne aerosol mass spectrometer (AMS). These calculations provide insight on certain observed phenomena associated with the size-resolved mass spectrum (MS), because the time width of the MS signal from a particle can be limited by its evaporation rate upon contact with the vaporizer. We show that the counterintuitive weak dependence of observed MS signal widths (evaporation rates) on particle volatility is due to suppression of evaporation rates induced by latent heat release, which is more prominent at high volatilities. The same physics is responsible for the observed diminishing returns associated with increasing the vaporizer temperature to achieve narrower single particle pulses. We also show that the vaporizer typical operating temperature of 600°C is sufficient to evaporate extremely low volatility organic compounds (ELVOCs) rapidly enough to obtain reliable measurements for particles smaller than approximately 600 nm. However, the sizing resolution is compromised for large (near-micron) sizes regardless of particle volatility. Finally, our calculations indicate that the observed delayed particle signals, which lead to an artificial tail in AMS mass distributions, are not due to slow evaporation of particles deposited on a surface with lower temperature than the vaporizer, but particles bouncing in the ionizer cage and finally depositing on the vaporizer.

Copyright © 2017 American Association for Aerosol Research     

Dependence of CPC cut-off diameter on particle morphology and other factors

In this investigation, we summarize performance parameters of 24 TSI CPCs model 3772 and 9 TSI CPCs model 3790 determined at the World Calibration Aerosol Centre Physics hosted by the Leibniz Institute for Tropospheric Research. Model 3790 CPCs are basically identical to model 3772 laminar continuous flow type butanol-based CPCs with a modified temperature difference between saturator and condenser. The average 50% detection efficiency for silver particles for 3772 and 3790 instruments was found to be 7.52 ± 0.04 nm and 24.34 ± 0.29 nm (average mobility diameter ± standard deviation), respectively. Small changes of the temperature difference between saturator and condenser cause larger shifts of the 50% detection efficiencies of 3790 CPCs compared to 3772 CPCs. In addition to the known calibration material dependence of the 50% detection efficiencies of 3790 CPCs, we found a dependence on the morphology of the particles used for calibration. In our experiments more spherical particles shifted the 50% detection efficiencies towards larger mobility diameters.

Copyright © 2016 American Association for Aerosol Research     

Characteristics of traffic-induced fugitive dust from unpaved roads

The characteristics of fugitive dust emitted from vehicles traveling on unpaved dirt roads were measured using a suite of instruments including a real-time fugitive dust sampler. The fugitive dust sampler is formed from a combination of a large particle inlet and an optical particle spectrometer that reports particle sizes from 6 to 75 µm. The large particle inlet permits the sampling of particles up to 75 µm with only a moderate dependence of sampling efficiency on wind-speed. Measurements made with the sampler showed that particles as large as ～50 µm were suspended from vehicular movement on the dirt roads, with the mode of the fugitive dust particle number size distribution ～2 µm, while the mass distribution mode was ～7 µm. A comparison of the fugitive dust sampler measurements with those made using standard PM instruments showed that the conventional instruments have a wind-direction bias that can result in under-sampling of large particles. The current measurements suggest that particles suspended from dirt roadways are of importance for local air quality within the near-road environment.

Copyright © 2017 American Association for Aerosol Research     

Size and volatility of particle emissions from an ethanol-fueled HCCI engine

A scanning mobility particle sizer was used to determine the size, number, and mass concentration of particle emissions from an ethanol-fueled homogeneous charge compression ignition (HCCI) engine. Semi-volatile particle composition was characterized using tandem differential mobility analysis (TDMA). Variable temperature thermal conditioning was used to gain insight into particle volatility and a catalytic stripper was used to determine the solid particle distribution. Four engine conditions were evaluated, including low to moderate range loads and motoring (deceleration, coasting). Results indicated that aerosol from a fully premixed HCCI engine under firing conditions is formed almost entirely via nucleation of semi-volatile material originating from the lubricating oil. TDMA analysis indicated 98% of total particle volume evaporated below 100°C. Results pointed towards homogeneous nucleation of precursors derived from the organic species in the lubricating oil, possibly in combination with a sulfur species. The motoring condition, with no fuel injected, exhibited the highest number and mass concentrations. During motoring, there was poor sealing leading to increased atomization of oil and associated ash emissions. Emissions were lower during firing with better sealing and much less atomization, but evaporation of the most volatile fractions of the lubricating oil still led to significant PM emissions consisting of nearly entirely semi-volatile particles containing very little ash.

© 2017 American Association for Aerosol Research     

Clogging of Industrial High Efficiency Particulate Air (HEPA) Filters in Case of Fire: From Analytical to Large-Scale Experiments

The Institute of Radioprotection and Nuclear Safety (IRSN in French) is conducting research on the impact of a fire on the behaviour of containment devices such as high efficiency particulate air (HEPA) pleated filters for radioactive materials. This work aims to study the clogging of HEPA filters in case of fire involving realistic materials (polymers making up gloves boxes, waste treatment solvent, hydraulic oil, solid material mixtures making up a trash bin, electrical cables, and cabinets) used in nuclear facilities, from the medium to large scale. The clogging kinetics of industrial pleated HEPA filters is monitored by measuring the pressure drop of the filters and the filtered air temperature at a given filtration velocity (from 0.23 to 2.1 cm/s). Upstream HEPA filters, combustion aerosols are characterized in terms of size distribution, mass concentration, composition, and particle morphology using, respectively, a DMS500 (Cambustion^LTD), glass fiber filter sampling, and transmission electron microscope analysis of particles deposited on TEM grids. Particles emitted denote well-known fractal morphology, are composed of carbonaceous primary particles with diameters ranging from 31 nm to 48 nm and showing an high clogging efficiency. An empirical relationship has been successfully applied to the obtained results for a larger range of fuels, filtration velocities and fire conditions.

Finally, experiments have been performed on a large-scale facility, using full-scale fire scenarios (electrical cabinet, constant, and variable filtration velocity) and a reasonable agreement was observed with our empirical relationship. At this scale, particles appear to be compact, with a complex composition and diameters close to 220 nm with a lower clogging efficiency.

Copyright 2014 American Association for Aerosol Research     

SEM and AFM characterization of surface of two RMGICs for degradation before and after modification with bioactive glass ceramic

Objectives: The aim of this study was to evaluate the effect of bioactive glass–ceramic particles (Biosilicate®) addition on surface nanoroughness and topography of Resin-modified glass ionomer cements (RMGICs).

Methods: Experimental materials were made by incorporating 2 wt% of Biosilicate® into Fuji II LC® (FL) and Vitremer® (VT) powders. Disks of RMGICs (with and without Biosilicate®) measuring 0.5 cm (diameter) × 0.5 mm (thickness) were fabricated and polished. Samples were stored at 37 °C in dry or immersed in distilled water for 30 days. Digital images (20 × 20 μm) from the surfaces were obtained by means of an atomic force microscopy. Three images were acquired for each sample, and four nanoroughness measurements were performed in each image. Nanoroughness (Ra, nm) was assessed by Nanoscope Software V7. Data were analyzed with ANOVA and Student–Newman–Keuls multiple comparisons (p < 0.05). SEM images were obtained for surface topography analysis.

Results: FL was significantly rougher than VT (p < 0.05) in wet and dry conditions. The addition of Biosilicate® increased the surface roughness in VT and decreased in FL, regardless of the storage media (p ≤ 0.05). No differences existed between materials and storage conditions after Biosilicate® addition. Significance: The Biosilicate® particles addition produced changes on the surface nanoroughness of the RMGICs. These changes depended on the particles size of the original cements in dry conditions. In water storage, dissolution of the Biosilicate® particles, a silica-rich gel formation, and a hydroxyl carbonate apatite precipitation on the surface of the materials changed the nanoroughness surface. FL was the roughest in both conditions.

Significance: The Biosilicate® particles addition produced changes on the surface nanoroughness of the RMGICs. These changes depended on the particles size of the original cements in dry conditions. In water storage, dissolution of the Biosilicate® particles, a silica-rich gel formation, and a hydroxyl carbonate apatite precipitation on the surface of the materials changed the nanoroughness surface. FL was the roughest in both conditions.     

Measuring ultrafine aerosols by direct photoionization and charge capture in continuous flow

Direct ultraviolet (UV) photoionization enables electrical charging of aerosol nanoparticles without relying on the collision of particles and ions. In this work, a low-strength electric field is applied during particle photoionization to capture charge as it is photoemitted from the particles in continuous flow, yielding a novel electrical current measurement. As in conventional photocharging-based measurement devices, a distinct electrical current from the remaining photocharged particles is also measured downstream. The two distinct measured currents are proportional to the total photoelectrically active area of the particles. A three-dimensional numerical model for particle and ion (dis)charging and transport is evaluated by comparing simulations of integrated electric currents with those from charged soot particles and ions in an experimental photoionization chamber. The model and experiment show good quantitative agreement for a single empirical constant, K_cI, over a range of particle sizes and concentrations providing confidence in the theoretical equations and numerical method used.

Copyright © 2018 American Association for Aerosol Research     

On the Feasibility of a Number Concentration Calibration Using a Wafer Surface Scanner

A new primary standard method for calibrating optical particle counters (OPC) has been developed based on quantitative gravitational deposition on a silicon wafer and accurate counting of the particles by a wafer surface scanner (WSS). The test aerosol consists of 3-μm diameter monodisperse polystyrene latex (PSL) spheres at concentrations in the range of 0.1 cm^?3 to 1 cm^?3. A key element to the calibration is the ability to generate monodisperse PSL spheres without residue particles by use of a virtual impactor and differential mobility analyzer. The use of these devices reduced the percentage of residue particles from more than 99.98% to about 5%. The expanded relative uncertainty (95% confidence level) in the number concentration determined with a WSS for a deposition of 200 particles is 17.8%. The major uncertainty component arises from the Poisson fluctuations in the aerosol concentration because of the low concentration. This methodology has advantages of a fast scanning time by the WSS of minutes compared to hours or days by microscopy and of counting every particle deposited compared to often only a small fraction via microscopy.

The WSS was used in the calibration of an OPC based on 12 depositions with concentrations ranging from 0.1 cm^?3 to 1 cm^?3 for each deposition. Make-up air was added to the aerosol entering the OPC so that the lowest achievable concentration for the OPC measurement is about 0.01 cm^?3 in this study. The detection efficiency of the OPC was measured to be 0.984 with an expanded uncertainty of 13.4%.

Copyright 2014 American Association for Aerosol Research     

Modeling the thermodynamics and kinetics of sulfuric acid-dimethylamine-water nanoparticle growth in the CLOUD chamber

Dimethylamine (DMA) has a stabilizing effect on sulfuric acid (SA) clusters, and the SA and DMA molecules and clusters likely play important roles in both aerosol particle formation and growth in the atmosphere. We use the monodisperse particle growth model for acid-base chemistry in nanoparticle growth (MABNAG) together with direct and indirect observations from the CLOUD4 and CLOUD7 experiments in the cosmics leaving outdoor droplets (CLOUD) chamber at CERN to investigate the size and composition evolution of freshly formed particles consisting of SA, DMA, and water as they grow to 20 nm in dry diameter. Hygroscopic growth factors are measured using a nano-hygroscopicity tandem differential mobility analyzer (nano-HTDMA), which combined with simulations of particle water uptake using the thermodynamic extended-aerosol inorganics model (E-AIM) constrain the chemical composition. MABNAG predicts a particle-phase ratio between DMA and SA molecules of 1.1–1.3 for a 2 nm particle and DMA gas-phase mixing ratios between 3.5 and 80 pptv. These ratios agree well with observations by an atmospheric-pressure interface time-of-flight (APi-TOF) mass spectrometer. Simulations with MABNAG, direct observations of the composition of clusters <2 nm, and indirect observations of the particle composition indicate that the acidity of the nucleated particles decreases as they grow from ～1 to 20 nm. However, MABNAG predicts less acidic particles than suggested by the indirect estimates at 10 nm diameter using the nano-HTDMA measurements, and less acidic particles than observed by a thermal desorption chemical ionization mass spectrometer (TDCIMS) at 10–30 nm. Possible explanations for these discrepancies are discussed.

Copyright © 2016 American Association for Aerosol Research     

Water-based single-flow mixing condensation particle counter

A novel water-based condensation particle counter has been developed using a patented, single-flow mixing (SFM) condenser that permits a conventional thermal approach of using a hot saturator followed by a cold condenser to activate and grow particles for counting with an optical detector. A computational fluid dynamics (CFD) model of the internal flow, temperature, and vapor profiles was used to predict the effectiveness of the SFM condenser. Using the results from the CFD model, the counting efficiency was numerically calculated for pure water droplets, and the CPC cut-point (i.e., 50% counting efficiency) was predicted to be 8.3 nm. The experimental performance of the new CPC was measured with differential mobility analyzer-classified, monodisperse particles. The measured cut-points were 8.2 nm for Ag particles and 3.9 nm for NaCl particles. The reduction in the cut-point for NaCl is the result of a compound effect: water uptake by NaCl particles, which increases their size before entering into the growth section (condenser), and the reduction of the equilibrium vapor pressure of water over NaCl-water droplets, resulting in a decrease of the activation diameter.

Copyright © 2016 American Association for Aerosol Research