Performance Evaluation of an Improved Particle Size Magnifier (PSM) for Single Nanoparticle Detection

Several modifications of the particle size magnifier (PSM) developed by Okuyama et al. have been introduced recently for detection of particles at diameters of 1 nm and below. However, their evaluation has been incomplete. Here we provide the first direct measurements of counting efficiencies near unity below 2 nm. We use the modified PSM described by Sgro and Fernández de la Mora, which separates thermally the PSM's original vapor generator from the water-cooled growth chamber by means of a narrow and short T where turbulent mixing with the aerosol takes place. The counting efficiency is seen to depend greatly on the aerosol flow, the amount of vapor, and temperature. With ethylene glycol vapor, under optimal conditions, the counting efficiency is 100% down to 1.6 nm (actual diameter of 1.2 nm), and negative particles are more easily activated than positive particles. The improved PSM is applied to the measurement of gold nanoparticle size distributions, and the results show it is a powerful aerosol detector for nanoparticles.     

Heterogeneous Condensation of Water Vapor on Nanoparticles in a Membrane-Based High-Flow Process Monitored by a New In Situ Measuring Cell

This article presents a membrane-based process to improve separation efficiency of airborne particles by heterogeneous condensation of water vapor. A plant was set up in laboratory scale to control the supersaturated state of water vapor in air accurately. Droplet growth due to heterogeneous condensation is investigated experimentally and supersaturation is calculated by solving the differential equations for heat and mass transfer in a laminar gas flow. The apparatus is based on a water condensation particle counter (WCPC). It operates with several growth tubes in parallel thereby allowing higher aerosol throughput. The increase of particle size based on heterogeneous condensation is detected by an in situ measuring system. Therefore a new measuring cell was operated with well-defined test aerosols differing in wetting abilities and initial nuclei size. First results of particle activation and condensational droplet growth are presented.

Copyright 2015 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     

基于分子运动学的水汽在细颗粒表面异质核化的数值模拟

为研究过饱和水汽在细颗粒表面异质核化特性,准确预测成核参数,基于分子运动学异质核化理论建立了过饱和水汽在燃煤细颗粒表面异质核化的运动学模型。数值分析了液滴晶核长大过程中水汽分子和水分子两种扩散凝结机制对晶核长大的促进作用及其相对重要性,数值预测了水汽过饱和度和宏观接触角对成核速率的影响;数值计算了不同温度和宏观接触角下细颗粒的临界过饱和度。结果表明：当液滴晶核尺寸小于临界晶核半径时,颗粒表面吸附水分子扩散凝结速率与水蒸气分子直接扩散凝结速率的比值大于100,颗粒表面吸附水分子的扩散凝结机制对晶核长大起主导作用。提高水汽过饱和度或减小宏观接触角均可显著提高液滴晶核的成核速率;成核速率随水汽过饱和度增大呈指数型增长。提高气相主体中水汽温度或减小细颗粒物的宏观接触角均可显著降低异质成核的临界过饱和度;对于粒径小于0.1 μm的细颗粒物,随着细颗粒粒径的增大,异质核化的临界过饱和度显著减小。     

Effect of Nucleation Temperature on Detecting Molecular Ions and Charged Nanoparticles with a Diethylene Glycol-Based Particle Size Magnifier

The classical nucleation theory predicts that a decrease in nucleation temperature under a constant saturation ratio increases the energy barrier for homogeneous nucleation to occur; therefore lower nucleation temperature would allow higher saturation ratio inside a condensation particle counter (CPC) while suppressing homogenous nucleation of working fluid vapor below a threshold value. On the other hand, the classical theory also predicts that a decrease in nucleation temperature increases the energy barrier for heterogeneous nucleation to occur, which potentially increases the minimum detectable size of CPC. Accordingly, it is important to investigate experimentally whether higher super-saturation under lower nucleation temperature decreases the minimum detectable size or not. Minimum detectable sizes of a diethylene glycol (DEG)-based nanoparticle size magnifier (nano-PSM) developed by Ito et al. (Ito, E., Seto, T., Otani, Y., and Sakurai, H. [2011]. Aerosol Sci. Technol. 45:1250–1259) were investigated at three different nucleation temperatures. Mobility standard molecular ions and mobility-classified silver nanoparticles were used as test aerosol particles. The vapor flux exiting from the evaporator in nano-PSM is accurately controlled using a syringe pump. The temperature of the mixing region and condenser in the nano-PSM is controlled at adiabatic mixing temperature, which we call its nucleation temperature. When the nucleation temperature was set at 16.7, 25.0, and 33.3°C, the minimum detectable mobility diameter values, which were defined at 50% value of counting efficiency curve, were 2.2, 2.9, and 3.0 nm, respectively, indicating that lower nucleation temperature is favorable for detecting smaller sized particles using DEG-based PSM or CPCs.

Copyright 2015 American Association for Aerosol Research     

Measurements of Kelvin-Equivalent Size Distributions of Well-Defined Aerosols with Particle Diameters > 13 nm

During the 1979 workshop of the working group on ultrafine aerosols, different experimental techniques for measuring the number concentration and size of ultrafine aerosol particles were compared. In the present paper we report on a comparison of different particle size measuring techniques for ultrafine aerosols. Well-defined monodisperse aerosols with electrical mobility particle diameters ranging from 13 to 100 nm were generated using an electrical aerosol classifier. Kelvin-equivalent size distributions of these aerosols were determined by means of a process-controlled expansion chamber, the size-analyzing nuclei counter (SANC). To this end the considered aerosol was humidified and the number concentration of the droplets growing in the expansion chamber was measured for stepwise increase in supersaturation. At a quite well defined critical supersaturation, a significant increase in the measured droplet concentration, and thus the onset of heterogeneous nucleation, was observed. By means of the Kelvin-Gibbs equation this critical supersaturation is related to the Kelvin-equivalent diameter of the aerosol particles. Measurements were made on NaCl and dioctyl phthalate (DOP) aerosols. For NaCl particles the Kelvin diameter was found to be larger by a factor of about 4 than the electrical mobility diameter, as determined by the electrostatic aerosol classifier. This is explained by the solubility of the NaCl particles. For DOP particles, however, the Kelvin diameter agrees quite well with the electrical mobility diameter. The Kelvin size distributions were found to be quite narrow, indicating a high monodispersity of the generated aerosol as well as a satisfactory size resolution of the SANC. Thus different experimental techniques, based on completely different principles, yielded similar measurement results.     

Water Vapor Depletion in the DMT Continuous-Flow CCN Chamber: Effects on Supersaturation and Droplet Growth

The continuous-flow streamwise thermal-gradient cloud condensation nuclei counter (CFSTGC) is a commercially available instrument that is widely used for laboratory and field measurements of cloud condensation nuclei (CCN). All studies to date assume that the supersaturation profile generated in its growth chamber is not influenced by the condensation of water vapor upon the growing CCN. The validity of this assumption, however, has never been systematically explored. This work examines when water vapor depletion from CCN can have an important impact on supersaturation, measured CCN concentration, and droplet growth. A fully coupled numerical flow model of the instrument is used to simulate the water vapor supersaturation, temperature, velocity profiles, and CCN growth in the CFSTGC for a wide range of operation and CCN concentrations. Laboratory CCN activation experiments of polydisperse calibration aerosol (with a DMT CFSTGC operated in constant flow mode) are used to evaluate the simulations. The simulations and laboratory experiments are then generalized using a scaling analysis of the conditions that lead to supersaturation depletion. We find that CCN concentrations below 5000 cm^?3 (regardless of their activation kinetics or instrument operating conditions) do not decrease supersaturation and outlet droplet diameter by more than 10%. For larger CCN concentrations, a simple correction can be applied that addresses both the depression in supersaturation and droplet size.     

Detection Efficiency of a Water-Based TSI Condensation Particle Counter 3785

In this article we present observations on the detection efficiency of a recently developed TSI 3785 Water Condensation Particle Counter (WCPC). The instrument relies on activation of sampled particles by water condensation. The supersaturation is generated by directing a saturated airflow into a “growth tube,” in which the mass transfer of water vapor is faster than heat transfer. This results in supersaturated conditions with respect to water vapor in the centerline of a “growth tube.” In this study, the cut-off diameter, that is, the size, where 50% of the sampled particles are successfully activated, varied from 4 to 14 nm for silver particles as a function of temperature difference between the saturator and the growth tube. The solubility of the sampled particles to water played an important role in the detection efficiency. Cut-off diameters for ammonium sulphate and sodium chloride particles were 5.1 and 3.6–3.8 nm, respectively at nominal operation conditions. Corresponding cut-off diameter for hydrophobic silver particles was 5.8 nm.     

洗涤塔脱除燃烧源超细颗粒的实验研究

在填料洗涤塔中进行了利用蒸汽相变原理促进燃煤和燃油超细颗粒凝结长大并高效脱除的实验研究;采用电称低压冲击器(ELPI)、SEM及XPS对两种燃烧源细颗粒凝结洗涤前后的数浓度、粒径分布、形貌和元素组分进行了分析测试,考察了洗涤塔进口气液温差、进口烟气含湿量及液气比等对脱除效率的影响。结果表明,燃煤和燃油产生的超细颗粒形貌和组分具有较大的差别,燃煤超细颗粒主要为硅铝矿物质,而燃油超细颗粒主要为含炭物质;在相同条件下,燃煤超细颗粒相变脱除效果优于燃油超细颗粒;脱除效率随洗涤塔进口气液温差的增大而提高,在相同进口气液温差下,增大进口烟气含湿量可显著提高超细颗粒的脱除效率;液气比的影响与填料洗涤塔内是否存在蒸汽相变有关;通过合理调节进口烟气含湿量及进口烟气与洗涤液的温差在填料塔内建立微粒凝结长大所需的过饱和水汽环境可有效脱除燃烧源超细颗粒。     

Modification of Laminar Flow Ultrafine Condensation Particle Counters for the Enhanced Detection of 1 nm Condensation Nuclei

This paper describes simple modifications to thermally diffusive laminar flow ultrafine condensation particle counters (UCPCs) that allow detection of ～1 nm condensation nuclei with much higher efficiencies than have been previously reported. These non-destructive modifications were applied to a commercial butanol-based UCPC (TSI 3025A) and to a diethylene glycol-based UCPC (UMN DEG-UCPC). Size and charge dependent detection efficiencies using the modified UCPCs (BNL 3025A and BNL DEG-UCPC) were measured with high resolution mobility classified aerosols composed of NaCl, W, molecular ion standards of tetra-alkyl ammonium bromide, and neutralizer-generated ions. With negatively charged NaCl aerosol, the BNL 3025A and BNL DEG-UCPC achieved detection efficiencies of 37% (90× increase over TSI 3025A) at 1.68 nm mobility diameter (1.39 nm geometric diameter) and 23% (8× increase over UMN DEG-UCPC) at 1.19 nm mobility diameter (0.89 nm geometric diameter), respectively. Operating conditions for both UCPCs were identified that allowed negatively charged NaCl and W particles, but not negative ions of exactly the same mobility size, to be efficiently detected. This serendipitous material dependence, which is not fundamentally understood, suggests that vapor condensation might sometimes allow for the discrimination between air “ions” and charged “particles.” As a detector in a scanning mobility particle spectrometer (SMPS), a UCPC with this strong material dependence would allow for more accurate measurements of sub-2 nm aerosol size distributions due to the reduced interference from neutralizer-generated ions and atmospheric ions, and provide increased sensitivity for the determination of nucleation rates and initial particle growth rates.

Copyright 2012 American Association for Aerosol Research     

喷淋塔内可吸入颗粒物的脱除与凝结增长特性

引言 可吸入颗粒物是一种重要的大气污染物,其对人类健康和大气环境带来极大危害[1-2].在当前以燃用化石燃料为主的能源结构和与日俱增的能源消耗形势下,燃烧源的排放成为可吸入颗粒物的一个重要来源[3],主要原因是目前电站及工业生产中的除尘设备,如电除尘器、过滤除尘器等虽然已达到很高的水平,但对可吸入颗粒物的脱除效率却较低,使得大量颗粒排放到大气中.     

Generation of Nanoparticles of Lubricating Motor Oil for Inhalation Studies

Recent studies suggest that most 20–30 nm nanoparticles measured at roadsides are composed mainly of organic carbon derived from lubricating motor oil. Therefore, a simple particle generation system has been developed for controlled production of 20–30 nm nanoparticles of lubricating motor oil for inhalation toxicology studies by means of vapor condensation without addition of nuclei. Quasi-monodisperse particles with a modal diameter located at 20 nm and total number concentrations above 10 ⁶ cm ^?3 were generated. Ten 2-h particle generation reproducibility tests were conducted, in which stability and repeatability of particle size and total number concentration were good. Organic carbon is a major component of oil particles, and organic analysis showed that the compositions of oil particles were not subjected to distillation of organic compounds through evaporation to condensation. Using the nose-exposure system connected to the particle generation system, toxicity of 20-nm particle organic compounds of lubricating motor oil can be assessed by inhalation studies of experimental animals.     

A Transition from Heterogeneous to Homogeneous Nucleation in the Turbulent Mixing CNC

A new method for changing the supersaturation in the Turbulent Mixing CNC has been developed and used to examine the transition from heterogeneous nucleation of test particles to homogenous nucleation of working fluid: dibutylphthlate (DBP). Supersaturation was controlled by changing the DBP vapor pressure in the nozzle flow by saturating only a predetermined part of the flow, while the total flow and temperature remain constant. This approach allows for the changing of the initial DBP vapor pressure, while keeping the flow structure and temperature field unchanged. The DBP concentration in the outlet of the vapor generator was measured experimentally for different ratios of saturated and bypass flows and found to be close to estimated values. Experimental results for transitions from heterogeneous nucleation to homogeneous nucleation are presented for NaCl and WO_x particles at various DBP vapor pressures. With an increasing of the DBP vapor pressure, the concentration of enlarged particles increases until it reaches a plateau. At higher initial values of DBP pressure, homogeneous nucleation prevails, and the number concentration of particles follows a curve typical for homogeneous nucleation recorded in the absence of nuclei. Nuclei with different mobility diameters were activated at different values of vapor pressure. There are significant differences in the slopes of particle activation curves for NaCl and WO_x particles. The reasons for such differences are a subject for continuing research.     

A Method for Particle Size Amplification by Water Condensation in a Laminar,Thermally Diffusive Flow

A new method is presented for the enlargement of particle size through condensation of water vapor in a laminar, thermally diffusive flow. The method involves the introduction of an air flow at temperature T _i into a wet-walled tube at a temperature T_w > T_i . This approach yields higher supersaturation values than either mixing or cold-walled condensers when operating between the same temperature extremes. Model results for the saturation profiles within the condensing region show that the peak supersaturations are reached along the centerline of the flow, and that the activation efficiency curves are steeper for large temperature differences when the cutpoint diameter is smaller. Experiments conducted with three types of aerosol, oleic acid (a water-insoluble oil), a mixture of oxalic acid and sulfate, and with ambient laboratory aerosol confirmed that condensational growth is achieved with this approach, although experimental cutpoints are somewhat higher than predicted for wettable particles.     

Untersuchungen zur heterogenen Kondensation von Wasserdampf in Membrankontaktoren

Heterogeneous condensation can contribute to improve the separation efficiency of airborne particles. Submicron particles can be separated due to inertial impaction when particle mass is previously enlarged sufficiently by water vapor condensation. This paper presents a novel, membrane‐based process for creating the requisite supersaturation for condensation. The increase of the particle size based on vapor condensation is detected by a new inline measuring technique.     

Homogeneous Nucleation by Continuous Mixing of High Temperature Vapor with Room Temperature Gas

The formation of aerosol particles by homogeneous nucleation in a supersaturated vapor has been studied experimentally and theoretically. In the laboratory, a particle-free gas at room temperature is continuously mixed with a high-temperature gas containing dibutylphthalate vapor in a new device for the study of aerosol nucleation called a particle size magnifier. A highly supersaturated vapor is rapidly formed in the mixing zone of the particle size magnifier, and the resulting number concentrations of aerosol particles are measured under various temperatures, mixing ratios, and mixing methods. Measured number concentrations are compared with those predicted by the classical and Lothe-Pound nucleation theories. The measured concentrations lie between the predictions of the two theories, and the trends with temperature and saturation ratio are consistent with either nucleation theory, provided vapor depletion is considered.     

Laboratory Verification of PH-CPC's Ability to Monitor Atmospheric Sub-3 nm Clusters

Gas-to-particle conversion takes readily place in the atmosphere. Detecting the initial clusters, which act as embryos for the newly formed particles, is beyond traditional aerosol instrumentation. Charged atmospheric clusters can be measured with air ion spectrometers, but typical state-of-the-art condensation particle counters, which detect both neutral and charged clusters, only see particles larger than 2.5 nm in diameter. In this study we present a modified pulse-height condensation particle counter (PH-CPC) and confirm by laboratory verification that it is capable of detecting charged clusters with electrical mobility equivalent diameter down to ～1 nm. We show how the detection efficiency and the pulse heights depend on the calibration particle size, polarity and composition. The effect of butanol supersaturation on the PH-CPC counting efficiency is also discussed. Furthermore, we developed an inversion method for the data to obtain true particle size distribution from the measurement signal.     

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.     

Minimizing Concentration Effects in Water-Based,Laminar-Flow Condensation Particle Counters

Concentration effects in water condensation systems, such as used in the water-based condensation particle counter, are explored through numeric modeling and direct measurements. Modeling shows that the condensation heat release and vapor depletion associated with particle activation and growth lowers the peak supersaturation. At higher number concentrations, the diameter of the droplets formed is smaller, and the threshold particle size for activation is higher. This occurs in both cylindrical and parallel plate geometries. For water-based systems, we find that condensational heat release is more important than vapor depletion. We also find that concentration effects can be minimized through use of smaller tube diameters, or more closely spaced parallel plates. Experimental measurements of droplet diameter confirm modeling results.

© 2013 American Association for Aerosol Research     

On Measuring the Critical Diameter of Cloud Condensation Nuclei Using Mobility Selected Aerosol

Cloud condensation nuclei (CCN) instruments determine the so-called “critical diameter” for activation of particles into cloud droplets at a fixed water supersaturation. A differential mobility analyzer is often used to size-select particles for purposes of scanning for the critical diameter. Usually the diameter where 50% of the particles have activated to cloud droplets is assumed to be equal to the critical diameter. We introduce a model that describes the transfer of polydisperse charge-equilibrated particles through an ideal differential mobility analyzer followed by transit through an ideal CCN instrument. We show that if the mode diameter of the polydisperse size distribution exceeds the critical diameter of the particles, multiply-charged particles may lead to nonmonotonic CCN counter response curves (plots of CCN-active fraction vs. mobility diameter) that exhibit multiple peaks, rather than a simple sigmoidally-shaped curve. Hence, determination of the 50% activation diameter is ambiguous. Multiply-charged particles significantly skew the CCNc response curves when sampling particles with critical diameters exceeding 0.1 μ m from particle size distributions with mode diameters also larger than the critical diameter. We present a method for inversion of CCN counter data that takes multiple-charging effects into account, and demonstrate its application to laboratory data. Our calculated CCN counter response curves are in good agreement with observations, and can be used to infer the critical activation diameter for a specified supersaturation.