Size Measurement of Polystyrene Latex Particles Larger than 1 Micrometer using a Long Differential Mobility Analyzer

We describe a newly constructed annular-type differential mobility analyzer (DMA) with an effective electrode length of 60 cm, which is longer than that of our original DMA (40 cm length). This long DMA was developed to extend the classification size of particles measuring up to 1.5 μm. As an application of this DMA, the mean diameters and standard deviations were determined for six samples of monodisperse polystyrene latex (PSL) particles ranging from 0.94 to 1.27 μm in nominal diameter. These PSL particles suspended in double-distilled water were aerosolized by a glass nebulizer and then introduced into the DMA. The mean diameters and standard deviations of these PSL particles were calculated by Ehara's method and compared with the nominal diameters and uncertainties. There was good correlation between the nominal diameters of these samples—particularly for recently certified samples—and the measured diameters. Classification of aerosol particles more than 1 micrometer in diameter using this DMA will be useful for many purposes.     

Sizing of Aerosol in Gases Other Than Air Using a Differential Mobility Analyzer

The differential mobility analyzer (DMA) is a device that sizes aerosol particles based on their electrical mobility. The relationship between particle size and mobility depends, among other factors, on three gas specific parameters, namely, dynamic viscosity, mean free path, and Cunningham slip correction factor C c . Provided these parameters are known, DMA theory is expected to be valid independent of gas type. The present study demonstrates the sizing accuracy of DMAs for gases other than air using monodisperse polystyrene latex (PSL) spheres with nominal diameters of 60 nm, 149 nm, and 343 nm in He, Ar, H 2 , CO 2 , and N 2 O. Eliminating possible systematic errors due to uncertainties in DMA geometry and nominal PSL diameter by normalizing the measured PSL diameters to their respective diameters measured in air, the sheath flow rate Q sh and C c are expected to be the main sources for measurement errors. Since C c data are lacking for PSL spheres in gases other than air, an expression given by Allen and Raabe (1985b) was used to approximate C c . The experimental results of the present study are consistent with a 2% accuracy of this expression for C c , which is considerably better than the 5% accuracy estimated by Rader (1990) for a similar expression for oil drops. Finally, we discuss other aspects of operating a DMA with gases other than air, namely, flow meter calibration and dependence of electrical breakdown voltage on gas type. In the present study a thermal mass flow meter (MFM) was used to measure Q sh . Calibration of this MFM revealed that the gas specific MFM correction factors ( K factors) provided by the technical literature can be highly inaccurate (here between -12% and +31%). More accurate K factors are presented.     

The experimental transfer function of the Couette centrifugal particle mass analyzer

The Couette centrifugal particle mass analyzer (CPMA) classifies particles by their mass-to-charge ratio. Unlike the aerosol particle mass (APM) analyzer, the Couette CPMA uses a stable system of forces to improve the transfer function of the classifier. A prototype Couette CPMA has been built and tested. The experimental results from the prototype agree well with theory and it is found that indeed the transfer function of the Couette CPMA is better than the APM's. Experimental work is shown using a differential mobility analyzer (DMA) and Couette CPMA to classify polystyrene latex (PSL) and di-2-ethylhexyl sebacate (DEHS) particles. By measuring the mass of PSL particles the absolute uncertainty of the Couette CPMA was found to be 6.7–38% higher in terms of mass (or 2.2–11% higher in terms of equivalent diameter) than the expected value. However, when the DMA–CPMA system was calibrated with PSL particles the density of DEHS particles was measured to within approximately 3% of the expected value.     

Particle Classification by the Tandem Differential Mobility Analyzer–Particle Mass Analyzer System

Particle mass analyzers, such as the aerosol particle mass analyzer (APM) and the Couette centrifugal particle mass analyzer (CPMA), are frequently combined with a differential mobility analyzer (DMA) to measure particle mass m_p and effective density ρ_eff distributions of particles with a specific electrical mobility diameter d_m. Combinations of these instruments, which are referred to as the DMA–APM or DMA–CPMA system, are also used to quantify the mass-mobility exponent D_m of non-spherical particles as well as to eliminate multiple charged particles. This study investigates the transfer functions of these setups, focusing especially on the DMA–APM system. The transfer function of the DMA–APM system was derived by multiplying the transfer functions of DMA and APM. The APM transfer function can be calculated using either the uniform or parabolic flow models. The uniform flow model provides an analytical function, while the parabolic flow model is more accurate. The resulting DMA–APM transfer functions were plotted on log(m_p)-log(d_p) space. A theoretical analysis of the DMA–APM transfer function demonstrated that the resolution of the setup is maintained when the rotation speed ω of APM is scanned to measure distribution. In addition, an equation was derived to numerically calculate the minimum values of the APM resolution parameter λ_c for eliminating multiple charged particles.

Copyright 2015 American Association for Aerosol Research     

Design Considerations and Performance Evaluation of a Compact Aerosol Particle Mass Analyzer

A compact aerosol particle mass analyzer (APM) of which the size of the classifier was significantly reduced than that of the first commercial model (Kanomax Model 3600) was developed. Firstly, requirements for desired performance in classifying particle mass were set forth. Secondly, a theoretical framework for the design parameters of an APM that satisfies the requirements was formulated. Thirdly, the design parameters were determined that satisfies the requirements while reducing the instrument size. The requirements include the condition that the classification range covers from 0.001 to 1000 fg (approximately 12 to 1200 nm in size for spherical particles having the density of 1 g/cm³), and the condition that both the classification resolution and particle penetration in this mass range are higher than certain specified values. A prototype having the design parameters determined according to this theoretical framework was constructed, and its performance was evaluated experimentally. The external dimensions of the electrodes of the compact APM are approximately 140 mm in length and 60 mm in diameter. It was confirmed that the performance of the compact APM operated at the aerosol flow rate of 0.3 L/min was comparable to that of the Model 3600 APM operated at 1 L/min. Because of the reduced size and of the resultant improved portability, it is expected that the compact APM is readily applicable to field measurements.

Copyright 2013 American Association for Aerosol Research     

Mass Range and Optimized Operation of the Aerosol Particle Mass Analyzer

We investigated, theoretically, the mass range in which an aerosol particle mass analyzer (APM) can be used for classification, and how the APM classification performance can be optimized. We listed factors that set limits to the APM, which were constraints of the rotation speed and the voltage, as well as requirements on the APM classification performance parameter, λ, that guarantee at least minimal performance in both resolution and penetration. We introduced the APM operation diagram, which is a tool to visualize the limits and mass range. We proposed to operate the APM that was considered in this study with the λ value set within the range from 0.25 to 0.5 for optimum classification performance by balancing both resolution and penetration. The mass range for the APM, with the λ value maintained between 0.25 and 0.5, was calculated to be from 0.003 to 2000 fg, which corresponds to the diameter range from 20 to 1600 nm for the density of 1 g/cm³. To verify the validity of the mass range and the idea of the optimized operation, we carried out experiments on an APM with polystyrene and sodium-chloride particles that were classified by electrical mobility. We found that the APM was able to provide bell-shaped spectra down to 12 nm, and was able to perform mass classification with an accuracy better than 5% down to 50 nm. Underestimation of mass and reduction of resolution and penetration were observed at sizes smaller than about 30 nm.     

Practical limitations of aerosol separation by a tandem differential mobility analyzer–aerosol particle mass analyzer

A cavity ring-down spectrometer and condensation particle counter were used to investigate the limitations in the separation of singly and multiply charged aerosol particles by a tandem differential mobility analyzer (DMA) and aerosol particle mass analyzer (APM). The impact of particle polydispersity and morphology was investigated using three materials: nearly monodisperse polystyrene latex nanospheres (PSL); polydisperse, nearly spherical ammonium sulfate (AS), and polydisperse lacey fractal soot agglomerates. PSL and AS particles were easily resolved as a function of charge. For soot, the presence of multiply charged particles severely affects the isolation of the singly charged particles. In cases where the DMA–APM was unable to fully resolve the singly charged particles of interest, the peak mass deviated by up to 13% leading to errors in the mass specific extinction cross section of over 100%. For measurements of nonspherical particles, nonsymmetrical distributions of concentration as a function of mass were a sign of the presence of multiply charged particles. Under these conditions, the effects of multiply charged particles can be reduced by using a second charge neutralizer after the DMA and prior to the APM. Dilution of the aerosol stream serves to decrease the total number concentration of particles and does not remove the contributions of multiply charged particles.     

Simultaneous Elemental Composition and Size Distributions of Submicron Particles in Real Time Using Laser Atomization Ionization Mass Spectrometry

Composition and size of individual submicron particles have been measured using a laser atomization ionization mass spectrometry technique, the Particle Blaster. Individual particles are quantitatively converted to atomic cations, providing information on both their complete elemental composition and particle size. Measured average atomic ratios for 100 nm particles of sodium chloride is 1.12 +- 0.36 (Cl:Na), for 50 nm particles of silica is 1.93 +- 0.52 (O:Si), and for 64 nm polystyrene latex spheres (PSL) is 1.13 +- 0.19 (H:C), in excellent agreement with the empirical formulae. Calculated particle sizes agree well with electrostatic classifier or TEM measurements in the size range of 17-900 nm diameter for particles of sodium chloride, silicon, and PSL. Size distributions are also obtain able, giving narrower distributions than are measured with an electrostatic classifier, for particles of alumina, silica, sodium chloride, and PSL spheres. Comparison with TEM data shows comparable primary particle sizes, but numerous particle aggregates are detected by the Particle Blaster which are unreported by the TEM measurements.     

A High Resolution Study of the Effect of Morphology On the Mass Spectra of Single PSL Particles with Na-containing Layers and Nodules

The interpretation and quantification of measurements of particle composition by laser ablation based single particle mass spectrometry is complex. Among the most difficult systems to quantify are internally mixed particles containing alkali metals and organics. The alkali atoms in such particles tend to suppress the formation of other ions sometimes to below the detection limit. Here we present a study of the behavior of single particle mass spectral peak intensities as a function of the amount of the sodium containing compounds deposited on the surface of 240 nm polystyrene latex (PSL) spheres. We generate three morphologically distinct and well defined coating types: uniform layers, cubic nodules and rounded nodules, and measure the individual particle mass spectra as a function of the vacuum aerodynamic diameter with nanometer resolution. The data show that the probability of detecting the PSL spheres depends on the amount of the alkali metal on the PSL sphere surface, its morphological distribution and the ablation laser power. The data suggest that PSL spheres with localized Na-containing nodules are easier to detect than those which are completely encapsulated. We show, for example, that at low laser power, PSL particles that are completely encapsulated with Na-containing compounds, whose weight fraction is close to 50%, cannot be detected, while 35% of PSL spheres with same amount of coating can be detected if coating is localized in nodules on a fraction of the particle surface.     

Development of a Pulsed-Field Differential Mobility Analyzer: A Method for Measuring Shape Parameters for Nonspherical Particles

For a nonspherical particle, a standard differential mobility analyzer (DMA) measurement yields a mobility-equivalent spherical diameter, but provides no information about the degree of sphericity. However, given that the electrical mobility for nonspheres is orientation-dependent, and that orientation can be manipulated using electric fields of varying strength, one can, in principle, extract some type of shape information through a systematic measurement of mobility as a function of particle orientation. Here, we describe the development of a pulsed-field differential mobility analyzer (PFDMA) which enables one to change the peak E-field experienced by the particle to induce orientation, while still maintaining the same time-averaged field strength as a standard DMA experiment. The instrument is validated with polystyrene latex (PSL) spheres with accurately known size, and gold rods with dimensions accurately determined by transmission electron microscopy (TEM). We demonstrate how the instrument can be used for particle separation and extraction of shape information. In particular, we show how one can extract both length and diameter information for rod-like particles. This generic approach can be used to obtain dynamic shape factors or other multivariate dimensional information (e.g., length and diameter).

Copyright 2014 American Association for Aerosol Research     

Radial Differential Mobility Analyzer

A differential mobility analyzer in which particles are classified in a radial flow toward the center of parallel disk electrodes, termed the Radial Differential Mobility Analyzer (RDMA), has been developed. Its classifying characteristics have been determined experimentally using both standard polystyrene latex spheres and mobility-classified aerosol particles over the size range of 3–200 nm. The idealized transfer function for the RDMA differs from that of the conventional cylindrical DMA only by a group of geometrical constants. The RDMA is designed specifically for the measurement of ultrafine aerosol particles, achieving a transmission efficiency of 0.85 to 0.90 in the 3–10-nm size range and having a short residence time to limit diffusional broadening of the transfer function. The simple design of the RDMA reduces the number of precision parts that must be fabricated below that for cylindrical DMAs, resulting in a compact, relatively lightweight, and low-cost instrument.     

Evaluation of a Method to Measure Black Carbon Particles Suspended in Rainwater and Snow Samples

We conducted a detailed evaluation of a method for measuring the mass concentrations and size distributions of black carbon (BC) particles in rainwater and snow. The method uses an ultrasonic nebulizer (USN) and a single particle soot photometer (SP2). The USN disperses sample water into micron-size droplets at a constant rate and then dries them to release BC particles into the air. The masses of individual BC particles are measured by the SP2, using the laser-induced incandescence technique. The loss of BC particles during the extraction from liquid water to air depends on their sizes. We determined the size-dependent extraction efficiency using polystyrene latex (PSL) spheres with 12 different diameters between 107 and 1025 nm. The PSL concentrations in water were measured by the light extinction at 532 nm. The extraction efficiency of the USN showed a broad maximum of about 10% in the diameter range 200–500 nm and decreased substantially at larger sizes. The accuracy and reproducibility of the measured mass concentration of BC in sample water after long-term storage were about ±25% and ±35%, respectively. We tested the method by analyzing rainwater and surface snow samples collected in Okinawa and Sapporo, respectively. The measured number size distributions of BC in these samples showed negligible contributions of BC particles larger than 300 nm to the total number of BC particles. A dominant fraction of BC mass in these samples was observed in the diameter range 100–500 nm.

Copyright 2013 American Association for Aerosol Research     

Performance of Vienna Type Differential Mobility Analyzer at 1.2–20 Nanometer

ABSTRACT

The transfer functions of the so called “Vienna type” differential mobility analyzer (DMA) were studied experimentally at the size range of 1.2–20 nm following the procedure suggested by Stolzenburg (1988) Ph.D. Thesis. For the study, two identical DMAs were used as a tandem DMA (TDMA) arrangement to measure nanoparticles from a hot wire WO_x generator. The approximate analytical formulae by Stolzenburg describing diffusion broadening of the DMA transfer function were observed to be valid with high accuracy from 20 nm down to ～ 2 nm. In the size range of 1.2–2 nm nominal mobility equivalent diameter small deviations of the shape of the TDMA output signal predicted by Stolzenburg were found.     

A Numerical Calculation of the Transfer Function of the Fluted Centrifugal Particle Mass Analyzer

A new particle mass classifier called the Fluted Centrifugal Particle Mass Analyzer (CPMA) is presented and compared to the Aerosol Particle Mass (APM) Analyzer and the Couette CPMA. These particle mass classifiers use electrostatic and centrifugal forces to classify particles by their mass-to-charge ratio. The Fluted CPMA uses reversed ‘scooped’ sections to create a stable system of forces in the radial direction but not in the angular direction. The stable forces in the radial direction improve the transfer function of the classifier. A Lagrangian model (neglecting diffusion) of the Fluted CPMA is derived from which the transfer function of the classifier is found. The model shows that, like the APM and Couette CPMA, a single non-dimensional number determines the shape of the transfer function. The comparison of the classifiers shows that the Couette CPMA outperforms the Fluted CPMA and APM. However, the Fluted CPMA outperforms the APM over a wide range of operating conditions and may be easier to manufacture than the Couette CPMA.     

Influence of Sampling Artefacts on Measured PM,OC, and EC Levels in Carbonaceous Aerosols in an Urban Area

The registration efficiency of the TSI model 3025 ultra-fine condensation particle counter for Ag and NaCl particles of between 2 and 20 nm in diameter was determined. Taking into account the different shapes of the input aerosol size distributions entering the differential mobility analyzer (DMA) and the transfer function of the DMA, the counting efficiencies of condensation nucleus counters (CNC) for monodisperse Ag and NaCl particles were estimated. In addition, the dependence of the CNC registration efficiency on the particle concentration was investigated.     

The Effect of Nanoparticle Convection-Diffusion Loss on the Transfer Function of an Aerosol Particle Mass Analyzer

The existing theoretical response spectra of APM-3600 agree well with the experimental data for submicron particles larger than 100 nm in the electrical mobility diameter but not for nanoparticles. In this study, a 2-D numerical model was developed to predict the transfer function and response spectra of APM-3600 based on the detailed simulation of flow and particle concentration fields. It was found that recirculation flows existed in the annular classifying region and APM's inlet and outlet regions, which led to enhanced convection-diffusion loss of nanoparticles compared to that without considering flow recirculation. As a result, the APM underestimates the mass of naonoparticles due to the shift of the peak position of the transfer function to a larger diameter than the targeted diameter. The response spectra calculated with the simulated transfer function agree well both in shapes and peak values with the experimental data present in a previous study for both nanoparticles and submicron particles larger than 100 nm. The predicted particle masses also agree well with the PSL's experimental data of the article.

Copyright 2014 American Association for Aerosol Research     

Equations Governing Single and Tandem DMA Configurations and a New Lognormal Approximation to the Transfer Function

The basic equations governing the responses of single and tandem differential mobility analyzer (DMA) systems are summarized. Particle diffusion within the DMA resulting in broadening of the transfer function is included in this analysis. For tandem DMA (TDMA) work, a given particle diameter exiting the first DMA is modeled in the following conditioner as growing into a multi-modal lognormal distribution before entering the second DMA. Approximations and solution techniques for both single and tandem DMA systems are discussed. A new lognormal approximation to the DMA transfer function is introduced leading to a simple lognormal form for the TDMA response function. The maximum absolute error of the transfer function is 0.10 at 200 nm in the range plus or minus one and a half standard deviations of the lognormal fit. It is 0.035 at 3 nm in the range plus or minus two standard deviations of the lognormal fit. The maximum fractional error in the calculated TDMA response is no more than 0.08 at 200 nm and 3 nm in the range plus or minus one standard deviation of the lognormal fit.     

Using ATOFMS to Determine OC/EC Mass Fractions in Particles

Historically, obtaining quantitative chemical information using laser desorption ionization mass spectrometry for analyzing individual aerosol particles has been quite challenging. This is due in large part to fluctuations in the absolute ion signals resulting from inhomogeneities in the laser beam profile, as well as chemical matrix effects. Progress has been made in quantifying atomic species using high laser powers, but very few studies have been performed quantifying molecular species. In this study, promising results are obtained using a new approach to measure the fraction of organic carbon (OC) associated with elemental carbon (EC) in aerosol particles using single particle laser desorption ionization. A tandem differential mobility analyzer (TDMA) is used to generate OC/EC particles by size selecting EC particles of a given mobility diameter and then coating them with known thicknesses of OC measured using a second DMA. The mass spectra of the OC/EC particles exiting the second DMA are measured using an ultrafine aerosol time-of-flight mass spectrometer (UF-ATOFMS). A calibration curve is produced with a linear correlation (R² = 0.98) over the range of OC/EC ion intensity ratios observed in source and ambient studies. Importantly, the OC/EC values measured in ambient field tests with the UF-ATOFMS show a linear correlation (R² = 0.69) with OC/EC mass ratios obtained using semi-continuous filter based thermo-optical measurements. The calibration procedure established herein represents a significant step toward quantification of OC and EC in sub-micron ambient particles using laser desorption ionization mass spectrometry.     

A Cylindrical Thermal Precipitator with a Particle Size-Selective Inlet

We designed a thermal precipitator in a cylindrical configuration with a size-selective inlet, and investigated its performance in experiments using differential mobility analyzer (DMA)-classified particles of sodium chloride (NaCl) and polystyrene latex (PSL). Our investigation was performed in two parts: (1) using the size-selective inlet to determine the best inlet-to-wall distance for optimal impaction of 1 μm particles; (2) using a simple inlet tube to measure particle collection via thermophoresis over a size range from 40 nm to 1000 nm. The results showed that the inlet had a particle cut-off curve, with a 50% particle cut-off Stokes number of 0.238, resulting in removing particles with sizes larger than 1 μm at an aerosol flow rate of 1.5 lpm. The thermophoretic particle collection efficiency in the prototype was measured without the size-selective inlet installed. The size dependence of the collection efficiency was negligible for particles with diameters ≤300 nm and became noticeable for those with diameters >300 nm. An analytical model was further developed to estimate the particle collection efficiency due to thermophoresis of the prototype under various aerosol flow rates and temperature gradients. For particles with diameters less than 400 nm, reasonable agreement was obtained between the measured data and the collection efficiency calculated from the developed analytical model. It was further concluded that the derived formula for the calculation of thermophoretic particle collection efficiency could serve as the backbone for future design of thermal precipitators in any configuration, when combined with the proper formula for the dimensionless thermophoretic particle velocity.

Copyright 2012 American Association for Aerosol Research     

Relaxed step functions for evaluation of CCN counter data on size-separated aerosol particles

Atmospherically important data are gained from cloud condensation nucleus counter (CCNC) analysis of aerosols that are particle mobility separated using differential mobility analysers (DMA). We present relaxed step functions that can be fitted to these data to obtain critical diameters or critical supersaturations. The step functions are based on the DMA transfer function. We treat the case with fixed supersaturation and varied particle diameter as well as fixed particle size and varied supersaturation. Comparison with experimental data shows that the width of the DMA transfer function controls the steepness of the relaxed step function. The less steep slope in the activation curve caused by the presence of a slightly soluble compound in the particle is discussed. Also in this case, the DMA transfer function width influences the steepness of the activation curve. Finally we demonstrate the errors made if doubly charged particles are not accounted for and a wide DMA transfer function is used.