Challenges of measuring nascent soot in flames as evidenced by high-resolution differential mobility analysis

Nascent soot particles with mobility diameters ≤10 nm were measured in an ethylene/air premixed flame to shed light on the challenges and potential artifacts affecting studies on soot inception by differential mobility analysis (DMA) techniques. The size distribution functions (SDFs) of particles with charge acquired either naturally or diffusively upon ion seeding were measured at several positions in the flame using rapid-dilution probing and a high-resolution DMA for different values of the ratio of dilution ratio to residence time (DR/Δt). The SDFs are roughly bimodal with a sub-3 nm mode and a larger one that appears either downstream in the flame or for low DR/Δts. Soot nuclei smaller than 3 nm preferentially acquire positive charge, which brings into question the assumption of steady-state charging probability of flame sampled soot nuclei in the bipolar diffusion neutralizer. The approximately polarity-symmetric lognormal SDF of larger particles is attributed to nuclei coagulation. Naturally charged particles increase in number when lowering DR/Δt, suggesting either their collisional charging by flame chemi-ions or particle nucleation by condensation of neutral molecules on ions or both. The critical conditions for suppressing particle coagulation and charge redistribution in the sampling system were not achieved under most conditions, despite the fact that values of DR/Δts were more favorable to such a suppression in the present experiment as compared to other studies in the literature. As a result, the identification of this “asymptotic” regime, which is critical to determine the parent SDFs and the charge state of nascent soot in the flame, is still elusive.

© 2016 American Association for Aerosol Research     

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     

Observations of a Correlation Between Primary Particle and Aggregate Size for Soot Particles

For decades, soot has been modeled as fractal-like aggregates of nearly equiaxed spherules. Cluster–cluster aggregation simulations, starting from a population of primary particles, give rise to structures that closely match real aerosols of solid particles produced in flames. In such simulations, primary particle size is uncorrelated with aggregate size, as all aggregates contain primary particles drawn from the same population. Aerosol measurements have been interpreted with this geometric model. Examination of transmission electron micrographs of soot samples from various sources shows that primary particle sizes are not well mixed within an aerosol population. Larger aggregates tend to contain larger primary particles and the variation in size is much larger between aggregates than within aggregates. The soot sources considered here are all substantially not well-mixed (aircraft jet engine, inverted diffusion flame, gasoline direct injection engine, heavy-duty compression ignition engine). The observed variations in primary particle size can be explained if soot aggregates are formed and grew by coagulation in small zones of the combustion chamber, prior to dilution and transport (with minimal coagulation) to the sampling system.

Copyright 2014 American Association for Aerosol Research     

Loss processes affecting submicrometer particles in a house heavily affected by road traffic emissions

The fraction of outdoor aerosol that penetrates into indoor environments plays an important role in determining the contribution of outdoor particles to the total lung dose of particles in human exposure. The objective of this study was to investigate the physical processes affecting migration of outdoor traffic particles into indoor environments. Particle number size distributions were measured by a fast mobility particle sizer system in both indoor and outdoor environments of a house located in close proximity to a busy street in Bologna (Italy) in the period February–April 2012. Indoor to outdoor (I/O) ratios for submicron particle number concentrations showed strong dependence on particle size and meteorological conditions. The loss rates of particles due to deposition, coagulation, and evaporation were determined using dynamic mass balance and coagulation models. Higher loss rates were found for small particles (nucleation and Aitken mode) indoors than for larger particles (accumulation mode). The coagulation and evaporation processes made a significant contribution to the loss of traffic nanoparticles indoors, especially during the day time. Application of positive matrix factorization to the indoor and outdoor particle size distributions showed a substantial loss of traffic-generated nucleation mode particles in the indoor environment, with evaporation playing a major role.

Copyright © 2017 American Association for Aerosol Research     

Performance of bipolar diffusion chargers: Experiments with particles in the size range of 100 to 900 nm

Accurate measurement of particle size distribution using electrical-mobility techniques requires knowledge of the charging state of the sampled particles. A consistent particle charge distribution is possible with bipolar diffusion chargers operated under steady-state condition. Theoretical steady-state charge distributions for bipolar charging are well established but recent studies have shown that the performance of particle chargers is a strong function of particle size, particle concentration, ion source, and charger operating conditions. Most of these studies have focused on particles smaller than 100 nm and the applicability of these results for particles larger than 100 nm must be investigated. In this study, experimentally obtained singly-charged and doubly-charged fractions are compared against theoretical predictions for particles in the size range of 100 to 900 nm. The experimental results show that the commercial soft X-ray charger performs as theoretically-predicted over the range of conditions studied while the performance of other commonly used radioactive chargers (⁸⁵Kr and ²¹⁰Po) are dependent on source strengths, flowrates, particle charge polarities, and particle sizes. From measurements of particle residence times and ion concentrations in different test bipolar chargers, prior observations of flowrate-dependent charging fractions can be explained. Additionally, the results from this study are used to determine an acceptable time period for usage of the commercial TSI 3077A ⁸⁵Kr chargers for steady-state charging as a function of flowrate.

Copyright © 2018 American Association for Aerosol Research     

Air Entrainment During Flame Aerosol Synthesis of Nanoparticles

Enclosed flames typically produce substantially larger particles than open flames under identical reactant flows and composition. The enclosure hinders air entrainment to the flame and reduces heat losses by radiation and convection, facilitating particle coagulation and coalescence. Here the effect of natural air entrainment on flame aerosol synthesis is investigated by lifting off the enclosing tube from the burner surface and utilizing tracer gas (Ne) analysis after calibration with forced air entrainment. That way the effect of air entrainment on product primary particle diameter and mobility size distribution dynamics is investigated by microscopy, scanning mobility particle sizing, and N₂ adsorption, while temperature is measured by Fourier-transform infrared spectroscopy. So air entrainment during flame spray pyrolysis is examined here for its versatility in scalable manufacture of an array of material compositions, while copper oxide (CuO) is used for its electro-chemical applications (e.g., battery electrodes). It is shown that natural air entrainment facilitates rapid gas-to-particle conversion and high process yields by minimizing vortex recirculation and particle deposition on the enclosing tube walls and burner surface. For example, the average primary particle diameter of CuO can be controlled from 42 to 10 nm and the yield from 40 to 90% by gradually lifting off the enclosing tube, resulting in up to 250 L/min natural air entrainment at the present CuO synthesis conditions.

Copyright 2014 American Association for Aerosol Research     

Extension of the Smoluchowski Theory to Transitions from Dilute to Dense Regime of Brownian Coagulation: Triple Collisions

In order to study the transition from dilute (controlled by binary collisions) to dense (controlled by multiple collisions) regime of coagulation of colloidal or aerosol suspensions, the Smoluchowski equation is generalized by consideration of triple collisions in the kinetic approach, recently proposed by the authors for coagulation of comparable size particles. A good agreement of the new model predictions with more general results of the direct numerical simulations by Langevin dynamics (from the literature) is attained in a relatively wide range of the fractional volume, corresponding to the transition from dilute to dense regime of coagulation dynamics, in which multiple collisions among more than three particles can be neglected.

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     

A coupled CFD-Monte Carlo method for simulating complex aerosol dynamics in turbulent flows

A coupled computational fluid dynamics (CFD)-Monte Carlo method is presented to simulate complex aerosol dynamics in turbulent flows. A Lagrangian particle method-based probability density function (PDF) transport equation is formulated to solve the population balance equation (PBE) of aerosol particles. The formulated CFD-Monte Carlo method allows investigating the interaction between turbulence and aerosol dynamics and incorporating individual aerosol dynamic kernels as well as obtaining full particle size distribution (PSD). Several typical cases of aerosol dynamic processes including turbulent coagulation, nucleation and growth are studied and compared to the sectional method with excellent agreement. Coagulation in both laminar and turbulent flows is simulated and compared to demonstrate the effect of turbulence on aerosol dynamics. The effect of jet Reynolds (Re_j) number on aerosol dynamics in turbulent flows is fully investigated for each of the studied cases. The results demonstrate that Re_j number has significant impact on a single aerosol dynamic process (e.g., coagulation) and the simultaneous competitive aerosol dynamic processes in turbulent flows. This newly modified CFD-Monte Carlo/PDF method renders an efficient method for simulating complex aerosol dynamics in turbulent flows and provides a better insight into the interactions between turbulence and the full PSD of aerosol particles.

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.     

Mobility of nanofiber,nanorod, and straight-chain nanoparticles in gases

With the fast development of nanotechnology, accurate measurement and classification of nanoparticles are in great need. Nanoparticles frequently appear in non-spherical forms such as long aspect ratio nanofibers, nanotubes, and irregular nano-agglomerates. While the well-developed classical studies were mainly in continuum regime with spherical particles, dynamics of the non-spherical nanoparticles is not fully understood. In this study, orientation-averaged mobility of nanofiber and nanorod (with no preferred alignment) is examined by the methods of Brownian diffusion theory, a combination of collision limited reaction rate theory and the bipolar diffusion charging analysis. Comparisons to empirical predictions from the experimental measurements are also made. The study leads to the discovery of a surface-dominated mobility for high aspect ratio nanoparticles with characteristic Knudsen number greater than 5. In view of the extreme relative length scales between particle size and the gas mean free path, particles of all morphologies can be viewed as point collisions; therefore, the equivalent surface mobility diameter is reasonably justified. This finding has been verified in the current study with high aspect ratio particles. For non-spherical particles of more general forms, further investigation is needed. As expected, accuracy of this approximation reduces as the characteristic Knudsen number decreases. When Kn(d_L) < 0.1, the study shows that particle morphology starts to play an important role. A review of particle mobility for all Knudsen number flows is also provided.

© 2017 American Association for Aerosol Research     

Real-time measurement of size-resolved elemental composition ratio for flame synthesized composite nanoparticle aggregates using a tandem SMPS-ICP-OES

Composite nanoparticles find application in catalysis, drug delivery, and energy storage and require increasingly fine control of their physical properties and composition. While composite nanoparticles have been widely synthesized and characterized, little work has systematically correlated the initial concentration of precursors and the final composition of flame synthesized composite nanoparticles. This relationship is explored in a diffusion flame aerosol reactor by coupling a scanning mobility particle sizer (SMPS) with an inductively coupled plasma optical emission spectrometer (ICP-OES). A framework for studying the relationship between the initial precursor concentrations of different elements and the final nanoparticle composition is explored. The size-resolved elemental composition was measured by directly injecting size-selected fractions of aggregated magnetite and silicon dioxide composite nanoparticles into the ICP-OES plasma. This work showed a correlation between precursor molar ratio and the measured elemental ratio in the mobility size range of 50 to 140 nm. Building on previous work studying size resolved elemental composition of engineered nanoparticles, the analysis is extended to flame synthesized composite nanoparticle aggregates in this work.

Copyright © 2017 American Association for Aerosol Research     

Charge Transfer to Metal Nanoparticles Bouncing from Conductive Surfaces

The charging behavior of metal nanoparticles bouncing from conductive surfaces was investigated in a single-stage-low-pressure-impactor. Ag and Pt particles of a fixed particle size between 20 nm and 100 nm were impacted on targets of bulk Au and Pt, respectively, and the resulting contact charge was measured as a function of impact velocity. The influence of target hardness was revealed by the comparison to measurements with soft nanostructured layers obtained by direct current sputtering of Au and Pt on mica discs. From the dataset, regions of elastic, elastoplastic, and fully plastic particle deformation were identified, and the size-dependent effective yield stress for the respective particle materials was calculated. The influence of electron back-tunneling in the separation phase of the collision on the effective contact charge is discussed.

Copyright 2014 American Association for Aerosol Research     

Characterization and Response Model of the PPS-M Aerosol Sensor

The Pegasor PPS-M sensor is an electrical aerosol sensor based on diffusion charging and current measurement without particle collection. In this study, the role and effect of each component in the instrument is discussed shortly and the results from a thorough calibration measurements are presented. A comprehensive response model for the operation of the PPS-M sensor was developed based on the calibration results and computational fluid dynamics (CFD) modeling results. The obtained response model, covering the effects of the particle charger, the mobility analyzer, and both diffusion and inertial losses, was tested in the laboratory measurements with polydisperse test aerosols, where a good correlation between the model and the measured results was found.

Copyright 2014 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     

Recent Advances in Flame Retardancy of Polymeric Materials (Materials,Applications, Industry Developments,Markets)

The Fifth Annual Conference on Flame Retardancy was held May 24–26, 1994, at the Ramada Plaza Hotel, Stamford, Connecticut, USA. The conference was organized by Business Communications Company, Inc., Norwalk, Connecticut (Company President, Mr. Louis Naturman; Conference Coordinator, Mrs. Sharon D. Faust). New materials (polymers, blends, composites), their applications, industry developments, and markets were considered. Specifically, the most important topics were:

Introduction of new technological achievements and development in the field of flame retardancy (FR)

Review of the current state of science and technology in FR

Review of applications and markets for FR products

Presentation of recent developments in local and global standardization and in testing technology

Discussion of toxicity and environmental issues

Provision of a unique opportunity for newcomers to FR research technology and marketing to become acquainted with the FR field in all its aspects

Discussion of halogen-based and non-halogen-based flame retardant chemicals, syngergism, intumescence, FR mechanisms, modeling, flame parameters, inherently FR polymers, and polymer blends     

Aerosol Measurement by Induced Currents

We introduce a new electrical measurement technique for aerosol detection, based on pulsed unipolar charging followed by a non-contact measurement of the rate of change of the aerosol space charge in a Faraday cage. This technique, which we call “aerosol measurement with induced currents,” has some advantages compared to the traditional method of collecting the charged particles on either an electrode or with a particle filter. We describe the method and illustrate it with a simple and miniature (shirt-pocket-sized) instrument to measure lung-deposited surface area. Aerosol measurement by induced currents can also be applied to more complex devices.

Copyright 2014 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     

Laboratory study of the generation of nanoparticles from tire tread

An experimental study was carried out to investigate the formation process of airborne nanoparticles from tire tread. The formation of nanoparticles by volatilization of the tire tread was simulated in a reaction chamber. The number concentration of nanoparticles in the reaction chamber suddenly increased when the tire tread surface temperature reached above 160°C. The generated nanoparticles have a unimodal distribution and the number of nanoparticles increased as the heating rate increased. The geometric mean diameter and size distribution of the generated particles can be controlled by adjusting the cooling rate since the cooling rate is directly related to the growth of particles. From the morphological and elemental analyses, the main components of the tire nanoparticles were C, O, S, and Si and the particles had an irregular shape. Based on these observations, we concluded that the formation mechanism of nanoparticles from the tire tread was volatilization and condensation of the organic materials in the tire tread.

Copyright © 2017 American Association for Aerosol Research     

Development and Evaluation of a Nanoparticle Generator for Human Inhalation Studies with Airborne Zinc Oxide

In the EU there is an increasing need for regulatory agencies to derive health based threshold limits based on human inhalation studies with airborne particles. A necessary prerequisite for such projects is the development of a suitable generator system to produce nanoparticle test aerosols for human whole-body inhalation studies. We decided to use a generator with flame-based heating of aqueous precursor solutions. Validation of the test system was done by generating zinc oxide (ZnO) nanoparticles with minimal contamination of trace gases, i.e., nitric oxides or carbon monoxide that could confound the effects seen in exposed subjects. ZnO was selected based on the uncertainties surrounding its health effects after exposure at the workplace. The generation process of the developed flame generator yields ZnO nanoparticles with monomodal size distribution and very good temporal stability. The maximum target exposure mass concentration of 2 mg/m³ ZnO, with a resulting median particle diameter of 57 nm, is attainable in our human exposure laboratory. The morphological examination shows typical agglomerates and aggregates formed by high temperature processes. Overall, the performed experiments confirm that a constant exposure can be provided for all subjects at all times.

Copyright 2014 American Association for Aerosol Research