Multiple charging of ultrafine particles in a corona charger

The charge distribution on ultrafine aerosol particles in the size range below 35 nm has been measured using a corona-based unipolar charger, in which ion generation and aerosol charging take place simultaneously in the region around a sharp-point discharge electrode. The mean number of charges per particle predicted by Fuchs’ diffusion charging theory is in relatively good agreement with the experimental results, and this implies that diffusion charging is the predominant mechanism in spite that the electric field in the charging region is very high. Since a steady state is unattainable in unipolar charging, the charge distribution depends on the geometry and operating conditions of each particular charger. When the present device operates under the conditions (nt-product) which yield the maximum charging efficiency, double charge appears on particles with diameter as small as 15 nm. At larger values of nt, 32 nm particles can acquire up to five charges. The critical particle diameter above which multiple charging occurs is about four times smaller than for bipolar radioactive chargers. In order to use corona charging in aerosol particle size measurement by electrical methods, the required mobility data inversion is thus straightforward for particle diameter below about 15 nm, but becomes quite complex for larger sizes.     

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.     

Estimating aerosol particle charging parameters using a Bayesian inversion technique

A Bayesian inversion routine is described in which data from tandem differential mobility analysis (TDMA) can be used to determine fundamental parameters for charging models as a function of particle size. The measurement and inversion techniques were verified using simulated data for particles in the 50–500 nm range undergoing unipolar diffusion charging as described by Fuchs’ limiting sphere theory, for which the fundamental charging parameter is the product of the unipolar ion concentration and residence time within the charger, the so-called nt product. Under conditions where the average particle charge is greater than one unit charge, the inversion routine is precisely and accurately able to determine the nt value. The inversion routine breaks down, however, when the average number of charges per particle is well below unity, i.e. for low nt values or for small particle sizes. Incorporation of charging efficiency data in addition to TDMA data can allow for use of the inversion routine when the average number of charges per particle is low. With its limitations known, the inversion routine was applied to determine the nt value for the unipolar charger used in the TSI electrical aerosol detector (EAD), model 3070A, for particles in the 50–200 nm size range. The effective nt value within the EAD charger decreased with decreasing particle size, implying that charged particle losses occur within the EAD charger. The described inversion routine is unique in its ability to determine size dependent charge model parameters, and can be utilized with any given charging model. It is expected that this technique will be of use in advancing the understanding of aerosol particle charging models and in future design of unipolar chargers.     

Charging of Ultra-Fine Aerosol Particles by an Ozone-Free Indirect UV Photo-Charger

Particle charging by indirect photoemission may be an alternative to charging methods based on corona discharge or on bipolar charging by radioactive ion sources. An indirect charger using a low energy UV radiation is introduced and characterized in detail. Depending on the carrier gas, photoelectrons or ions formed by electron-attachment charge the particles by diffusion charging. The achieved charging efficiency is in the range of 20–70% for particle sizes of 20 to 100 nm. It can easily be modulated by a small voltage applied to the photoemitter. To achieve stable electron emission, glassy carbon with its very inert surface is used as photoemitter. Particle losses are very small. The charge distribution has been measured by a tandem DMA setup. The experimental results are compared with the theory of unipolar diffusion charging based on the Fuchs’ combination probability of ions with the particles. The charger characterization has been performed by carbon particles in a size range of 20–100 nm, produced by a spark discharge generator.

Copyright 2013 American Association for Aerosol Research     

Ozone-free post-DBD aerosol bipolar diffusion charger: Evaluation as neutralizer for SMPS size distribution measurements

A postplasma neutralizer for submicron particles size measurements by mobility analysis has been evaluated. Bipolar ion currents have been measured downstream a dielectric barrier discharge (DBD) to estimate the ion fluxes at the inlet of charging volume and the n_i·τ product that define the theoretical maximal concentration that can be neutralized. Charge distributions were measured versus DBD voltage, aerosol diameter and concentration for monodisperse aerosols. It is confirmed that the charge distribution of particles depends on the ratio of initial positive and negative ion currents controlled by the DBD voltage leading to a tuneable mean charge of aerosol in this post-DBD bipolar charger. As expected from Gunn's law, the mean charge and the variance are proportional to particle diameter above 50 nm and independent of the aerosol concentration. The size distributions measured with ⁸⁵Kr and post-DBD neutralizer present the same modal diameters and a maximal overestimation of the total concentration of 10%, for aerosol from 15 to 730 nm with concentrations up to 6 × 10¹² m^?3. This post-DBD bipolar charger can be used for submicron aerosol neutralization and thus for scanning mobility particle sizer size distribution measurements in air as well as in nitrogen to suppress ozone downstream DBD.

Copyright © 2017 American Association for Aerosol Research     

Bipolar Charging of Ultrafine Aerosol Particles

The stationary bipolar charging characteristics of aerosol particles in the size range between 4.5 and 40 nm have been studied using a new technique whereby the particles neutralized by a ²⁴¹Am radioactive source are enlarged and directly observed in an electric field. The number ratio of charged particles to total particles obtained in this study was found to deviate from the charge distribution obtained from Boltzmann's law and to agree well with that calculated with the bipolar charging theory of Fuchs using his values for the ion properties. The ratio of positively charged to negatively charged particles was found to be approximately 0.35:0.65.

     

Bipolar Charge Distributions of Aerosol Particles in High-Purity Argon and Nitrogen

The bipolar diffusion charging has been studied for monodisperse sodium chloride and silver particles of 5–100 nm in atmospheric air, argon and nitrogen. The particles were bipolarly charged in a neutralizer by ions, produced by beta-rays from a Kr 85 source. The differently charged particle fractions were separated in a differential mobility analyzer and measured with an aerosol electrometer. The experimentally determined results in atmospheeric air are comparable with earlier measured asymmetric bipolar charge distributions. They show good agreement with the theoretically determined results based on the extended Fuchs model with four-input ion parameters: mobilities and masses of positive and negative ions. The experimentally determined bipolar charge distributions in argon and nitrogen are more asymmetric than in atmospheric air. The theoretically determined distributions, based on the extended Fuchs model, can be fitted to the experimental data. Furthermore, the extended Fuchs model is strongly dependent upon variations of the four input ion parameters. No differences for the experimentally determined bipolar charge distribution could be found between different gas purities and different particle materials.     

Characterization of Aerosol Surface Instruments in Transition Regime

The primary purpose of this study is to measure the size- and composition-dependent responses of aerosol surface instruments designed to measure surface area related properties. Measurements were conducted in the range of 30–150 nm of mobility equivalent diameter, D_p. The responses of a LQ1-DC (a diffusion charger manufactured by Matter Engineering AG) and an EAD (a diffusion charger manufactured by TSI) to singlets (NaCl) particles are proportional to D_p ^1.36 and D_p ^1.13, respectively. The response of LQ1-DC agrees with Fuchs surface area, which is proportional to D_p ^1.39 within 2.4% error. The response of the EAD is almost proportional to diameter, D_p. A PAS2000CE (Photoelectric Aerosol Sensor manufactured by EcoChem) gave both size and composition-dependent responses. For diesel particles produced at high engine loads, the response was nearly proportional to Fuchs surface area. However, at lighter engine loads, the response dropped sharply with decreasing D_p. Light engine loads are associated with high fractions of volatile particles that may suppress the photoemission response. The secondary purpose of this study is to investigate the difference in charging rate between singlets (NaCl particles) and agglomerates (diesel particles) by using diffusion chargers. Agglomerates (diesel particles at engine load 75%) acquire more charge than singlets (NaCl particles) by 15 and 17% for LQ1-DC and EAD, respectively.     

Charge distribution uncertainty in differential mobility analysis of aerosols

The inference of particle size distributions from differential mobility analyzer (DMA) data requires knowledge of the charge distribution on the particles being measured. The charge distribution produced by a bipolar aerosol charger depends on the properties of the ions produced in the charger, and on the kinetics of charge transfer from molecular ions or ion clusters to the particles. A single parameterization of a theoretically predicted charge distribution is employed in most DMA analyses regardless of the atmospheric conditions being probed. Deviations of the actual charge distribution from that assumed in the data analysis will bias the estimated particle size distribution. We examine these potential biases by modeling measurements and data inversion using charge distributions calculated for a range of atmospheric conditions. Moreover, simulations were performed using the ion-to-particle flux coefficients predicted for a range of properties of both the particles and ions. To probe the biases over the full range of particle sizes, the measurements were simulated through an atmospheric new particle formation event. The differences between the actual charge distribution and that according to the commonly used parametrization resulted in biases as large as a factor of 5 for nucleation-mode particles, and up to 80% for larger particles. Incorrect estimates of the relative permittivity of the particles or not accounting for the temperature and pressure effects for measurements at 10 km altitude produced biases in excess of 50%; three-fold biases result from erroneous estimates of the ion mobility distribution. We further report on the effects of the relative permittivity of the ions, the relative concentrations of negative and positive ions, and truncation of the number of charge states considered in the inversion.

Copyright © 2017 American Association for Aerosol Research     

A Device for Generating Singly Charged Particles in the 0.1–1.0-μm Diameter Range

In this paper an aerosol charger that largely avoids the production of multiply charged particles in the 0.1–1.0 μm diameter range is described. The input aerosol is first passed through an electrostatic condenser to remove all charged particles and ions. The remaining neutral aerosol then flows into a 23-cm-long, 2.1-cm inner diameter cylindrical tube; the inner surface of this tube is uniformly coated with 0.09 μCi⁶³ Ni, a 0.067 MeV β-emitter with a half-life of 92 years. At typical airflow rates of 0.2–1.0 lpm, this low-activity source of ionizing radiation produces bipolar ion concentrations ranging from 1 × 10⁴ to 9 × 10⁴ ion/cm³, which is much lower than levels required to bring the aerosol to Boltzmann charge equilibrium. At a flow rate of 1.0 lpm, particles smaller than about 1.0 μm typically interact with no more than one ion en route through the charger. Therefore, particles at the charger exit are mostly either neutral or singly charged. Charge distributions of initially-neutral mono-disperse polystyrene latex particles were measured at the exit from the charger for particle diameters ranging in size from 0.09 to 1.09 μm. It was found that, at an airflow rate of 1.0 lpm and particle size 1.09 μm, the ratios of singly, doubly, and triply charged to total positively charged concentrations were 0.75, 0.19, and 0.06 respectively; particles with more than three charges were not detected. In contrast, the analogous charge ratio at Boltzmann equilibrium is 0.28 (+ 1), 0.24 (+ 2), 0.19 (+ 3), 0.13 (+ 4), 0.08 (+ 5), 0.05 (+ 6), and 0.7 (+ 02).     

Particle Charging and Transmission Efficiencies of Aerosol Charge Neutralizes

ABSTRACT

Diffusion losses and charging efficiency were measured for three types of charge neutralizers commonly used in aerosol research: two with ⁸⁵Kr and one with ²¹⁰Po as radiation sources. The diffusion losses were characterized at flows of 0.5 -6 1 min^?1 typically used in atmospheric aerosol physics measurements. All of the neutralizers tested exhibited high transmission efficiencies, with losses up to 25% at the smallest tested size of 3 nm, varying with size and flow in general agreement with diffusion loss theory. Charging efficiency was measured for a singly charged, monodisperse aerosol at the same flows and at concentrations of 10³-10⁴ particles cm^?3. Neither of the ⁸⁵Kr chargers brought the charge distribution close to equilibrium at 2 1 min^?1, except at concentrations ≤ 10³ cm^?3. The ²¹⁰Po charger produced the theoretically expected fraction of singly charged particles within the uncertainty of the experiment.     

Ion–Aerosol Flux Coefficients and the Steady-State Charge Distribution of Aerosols in a Bipolar Ion Environment

Fuchs’ theory, as corrected by Hoppel and Frick, is widely used to compute flux coefficients of ions to aerosol particles and the resultant charge distribution. We have identified approximations made in previous works that limit the theory's accuracy. Hoppel and Frick used two characteristic speeds or kinetic energies to calculate the flux coefficients of ions to aerosol particles in lieu of an average of the flux coefficients over the Maxwell–Boltzmann distribution of ion speeds. In the present work, we show that this approximation artificially reduces the number of multiply charged particles. Ion capture may be enhanced by three-body trapping, a process wherein an ion has a collision with a neutral gas molecule and loses sufficient kinetic energy to be captured by the particle. The gas kinetic theory approach to three-body trapping has been refined to better account for the collision between the ion and a neutral gas molecule within the potential presented by the particle. Approximations to the calculation of energy losses and the probability of ion capture have been relaxed. The possibility that an image charge may be induced on the ion as well as on the particle is allowed. While the previous work was limited to electrically conductive particles, both the ion and the particle are allowed to have any dielectric constant in the present work, and the finite size of the ions is taken into account when calculating minimum capture radii for the ion–particle interactions. The resulting ion flux coefficients differ from previous results both in the low nanometer regime and in the continuum regime. We explore the influence of key parameters on the charge distribution, including dielectric constant, temperature, and pressure, to understand how operating conditions may affect the interpretation of differential mobility analyzer measurements of particle size distributions. Finally, an empirical expression for the new charge distribution is given to facilitate rapid calculations.

© 2013 American Association for Aerosol Research     

The Effect of Particle Pre-Existing Charge on Unipolar Charging and Its Implication on Electrical Aerosol Measurements

We investigated the effect of particle pre-existing charges on unipolar charging. Particles carrying a defined number and polarity of pre-existing charges were used to study the unipolar charging process in a unipolar diffusion charger with positive ions. It was found that the particles initially carrying negative charges have almost the same amount of positive charges as the initially uncharged particles after passing the test charger; and the particles initially carrying more positive charges have more final charges. An analytical solution of a model for particle charge distribution of initially charged particles was provided for unipolar charging based on Fuchs' theory and the birth-and-death theory. The N _ion t value used in this model was obtained by fitting the experimental data of average charge on particles for initially uncharged particles. The results from the analytical solution show very good agreements with experimental data regarding the relationship between the pre-existing charge and the final charge on particles (50–200 nm in this study). Experimental tests of the response of Nanoparticle Surface Area Monitor (NSAM) against initially charged particles demonstrated that NSAM could have a large response deviation (more than 20% in the tested charge level) depending on the particle size and the amount of pre-existing positive charges on particles. Modeling of NSAM response showed similar deviation and predicted that when pre-existing charge is high enough, the NSAM response can be as large as 5 and 9 times of the uncharged particle response for alveolar and tracheobronchial surface area concentration, respectively.     

An Improved Method for Charging Submicron and Nano Particles with Uniform Charging Performance

An improved method for charging submicron and nano silver particles with uniform charging performance was developed. Monodisperse silver particles were grown into microdroplets through condensation. The aerodynamic diameter and GSD of the condensed droplets were the same regardless of their original diameter. The diameter of the droplets increased from 1.7μm to 2.5 μm as the temperature of the saturator increased from 45°C to 55°C. They were charged by an indirect corona-based charger, in which the ion-generation zone is followed by a particle-charging zone through which the condensed droplets pass. The charges of the droplets were controlled by varying the droplet size, ion concentration, and strength of electric field in the charger. The solvent of the charged droplets was evaporated in an evaporator. The size distribution of the evaporated particles was measured by SMPS spectrometer and compared with their original size distribution. The particles after evaporation were slightly larger than their original particles, due to recondensation. The total charge and number concentration of the particles were measured by aerosol electrometer and CPC, to calculate the average charge. Their electrical mobility distribution was measured by SMPS spectrometer without a neutralizer, to calculate the charge distribution and average charge of the evaporated particles. The results showed the average charges of the particles were similar, regardless of initial diameter and manner of calculation. The charge distributions of the evaporated particles were identical, except for 16.9 nm particles. Ion evaporation phenomenon of particles smaller than 40 nm in diameter was not detected.     

Experimental study of a new corona-based unipolar aerosol charger

A corona-based unipolar aerosol charger has been constructed, and its performance has been systematically evaluated. The prototype consists of completely separated corona ionization and charging chambers. With this configuration the electrostatic loss of charged particles is eliminated, and particle loss by diffusion and the space charge effect is minimized by the angular injection of the ionizer flow and the rapid exit of charged particles. The charger performance was optimized by varying different operational parameters, i.e., total and ionizer flowrates, and ion concentration. It was found that operation with one corona ionizer gave higher extrinsic charging efficiency than operation with two ionizers. The corona-discharge current has negligible effect on the charging performance. Operating the charger at a total flowrate of 5 lpm, with 1.0 lpm flow in each of the two ionizers, gave the highest extrinsic charging efficiency. Further, the performance of prototype charger was not compromised even at a total flowrate of 10 lpm. The charger provides higher extrinsic charging efficiency than other corona-based unipolar chargers. Extrinsic charge distributions for particles of different sizes were at last measured by the tandem-DMA technique.     

Detection and Analysis of Aerosol Particles by Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) was evaluated as a means for quantitative analysis of the size, mass, and composition of individual micron-to submicron-sized aerosol particles over a range of well-characterized experimental conditions. Conditional data analysis was used to identify LIBS spectra that correspond to discrete aerosol particles under low aerosol particle loadings. The size distributions of monodisperse particle source flows were measured using the LIBS technique for calcium- and magnesium-based aerosols. The resulting size distributions were in good agreement with independently measured size distribution data. A lower size detection limit of 175 nm was determined for the calcium- and magnesium-based particles, which corresponds to a detectable mass of approximately 3 femtograms. In addition, the accuracy of the LIBS technique for the interference-free analysis of different particle types was verified using a binary aerosol system of calcium-based and chromium particles.     

Bipolar Diffusion Charging of Aggregates

In this paper, the effect of particle morphology on bipolar diffusion charging is studied. A modified tandem differential mobility analyzer (TDMA) method used to measure the charge distribution of submicron particles in the range of 70–300 nm is described in detail. The method requires an independent measurement of the neutral fraction, followed by the measurement of the size-dependent charge distribution, which requires the knowledge of the neutral fraction. The method was validated experimentally using dioctyl sebacate and ammonium sulfate spherical particles and compared with Fuchs’ theory. Diesel particles and silver aggregates were used to evaluate the impact of morphology on charging. The results show that aggregates have a slightly lower (about 7%) neutral fraction than spheres. These results are in agreement with the predictions of Lall and Friedlander's theory and previous studies. However, results from charge distribution indicate that more (about 46%) particles are negatively charged than predicted by Lall and Friedlander's theory, while 32% fewer particles are positively charged. This relatively large asymmetry between the negative and the positive charge fraction is not fully predicted by either Fuchs' or aggregate charging theories. Our results suggest that the current inversion method of scanning mobility particle sizer (SMPS) data, based on Fuchs’ or Lall and Friedlander's distribution, would underestimate the total number concentration by about 15% or 27% if applied to diesel aggregates.

Copyright 2012 American Association for Aerosol Research     

Free electron charging of ultrafine aerosol particles

Experiments of free electron charging of aerosol particles in the free molecule regime are reported. Monodisperse ultrafine silver particles of 5–30 nm were exposed to known concentrations of low energy electrons produced by ionization by -particles in a unipolar aerosol charger. The kinetic energy of the electrons was varied by changing the electric field intensity in the charger (i.e. between 93 and 279 V cm⁻¹). The range of Knudsen number for aerosol charging (i.e. the ratio of the electron mean free path to the particle radius) was from 30 to 261. The charged fraction was measured as a function of particle size in high-purity helium and nitrogen under different charging conditions. The experimental results for the combination coefficient between neutral particles and electrons suggested a free-molecule diffusion charging mechanism which was dependent on the electron mobility, transverse diffusion coefficient, mean free path, and mean kinetic energy (i.e. electron temperature). The functional dependence was similar to that given by the ionic charging theories of Natanson (1960, Sov. Phys. 5, 538–551), and Fuchs (1963, Geofis. Pura Appl. 56, 185–193) when the appropriate electron properties were used. The electron charging models of O'Hara et al. (1989, J. Aerosol Sci. 20, 313–330), and Zagnit'ko et al. (1989, Russ. J. Phys. Chem. 63, 883–888) did not fit the experimental results because they were not derived for the free-molecule regime. A modified Fuchs charging theory that uses an empirical accommodation coefficient for the electrons at the surface of the particle was used to fit the experimental results. Good agreement was found by using an accommodation coefficient of 0.4 for both helium and nitrogen.