A New Thermophoretic Precipitator for Collection of Nanometer-Sized Aerosol Particles

A new thermophoretic precipitator (TP) has been designed and used for the collection of nanosized aerosol particles. NaCl and Fe particles, with mean diameters of 55 nm and 3.6 nm, respectively, were used to determine the thermophoretic deposition efficiency as well as the uniformity of the deposition. When the average temperature gradients applied were 2200 K/cm and 2400 K/cm, a high thermophoretic deposition efficiency, close to 100%, was attained at aerosol flow rates below 15 sccm. A gradual decay in the efficiency was observed as the flow rate was increased. Theoretical calculations of particle deposition efficiency were in good agreement with experimental data. The deposition along the TP was shown to be homogenous on a millimeter scale for both NaCl and Fe particles collected on thin foil substrates and microscope grids, respectively. Finally, the thermophoretic precipitator was used to efficiently deposit Fe nanoparticles on a substrate for the subsequent growth of carbon nanotubes.     

The Development of a New Thermophoretic Precipitator for Scanning Transmission Electron Microscope Analysis of Ultrafine Aerosol Particles

A thermophoretic precipitator specifically for collecting ultrafine aerosol samples onto electron microscope support grids has been designed, and built. The precipitator has been designed to deposit particles of diameter less than 100 nm discretely onto support grids, with uniform deposition velocity across the size range. In addition, it has been designed to be compact, and portable. Preliminary investigations indicate it to give discrete deposits suitable for single particle analysis. Qualitatively, particle deposition velocity appears uniform between 4 and 30 nm, with a slight decrease towards higher diameters, although this is yet to be confirmed by comparison with reference particle size distribution analysis methods. Particle distribution on the microscope grid was shown to be uneven on a millimeter scale, but relatively even on a micrometer scale, enabling good characterization of the deposit.     

Thermophoretic Sampler and its Application in Ultrafine Particle Collection

A thermophoretic sampler is designed for the collection of particles smaller than 10 nm. The sampler is composed of heated and cooled surfaces separated by a gap of 0.1 mm; a bypass flow is introduced in the design to minimize the diffusional loss of nanoparticles in the upstream flow channel. Particles may be directly deposited on a 3 mm diameter TEM grid for chemical analysis or on other substrates for other purposes. Calculations show that at an inlet flow rate of 1.5 lpm and thermal gradient of 5 × 10⁵ K/m, a maximum collection efficiency of 41% can be achieved for a particle diameter of 1 nm. Ag particles with median size of 6 nm are used to characterize the thermophoretic sampler collection efficiency. The TEM images show that a sizeable number of particles less than 10 nm in diameter are collected, although they are not uniformly distributed on the grid, and the collection efficiency deduced from these deposited particles is much less than the theoretical estimation. Despite this, the efficiency is orders of magnitude higher than previous designs and it is easier to build.     

超微颗粒旋风分离与收集器

奈米科技可预期将带动产业革命,奈米粉体制造具有举足轻重的地位,而奈米粉体的分离收集是其中关键步骤.工研院环安中心已研发出超微颗粒旋风分离与收集器,本研究分别以油酸液滴及NaCl固体颗粒为测试微粒,在6 torr及0.455 slpm条件下操作时,100 nm微粒之收集效率＞90%,可有效分离收集奈米粉体以提升制程效率与经济价值.     

Miniature Pipe Bundle Heat Exchanger for Thermophoretic Deposition of Ultrafine Soot Aerosol Particles at High Flow Velocities

The deposition of submicrometer soot aerosol particles in a miniature pipe bundle heat exchanger system has been investigated under conditions characteristic for combustion exhaust from diesel engines and oil or biomass burning processes. The system has been characterized for a wide range of aerosol inlet temperatures (390–510 K) and flow velocities (1–4 m s^?1), and particle deposition efficiencies up to 45% have been achieved over an effective deposition length of 27 cm. Thermophoresis was the dominant deposition mechanism, and its decoupling from isothermal deposition was consistent with the assumption of independently acting processes. The measured deposition efficiencies can be described by simple linear parameterizations based on an approximation formula for thermophoretic plate precipitators. The results of this study support the development of modified heat exchanger systems with enhanced capability for filterless removal of combustion aerosol particles.     

Design Optimization of a Portable Thermophoretic Precipitator Nanoparticle Sampler

Researchers at the National Institute for Occupational Safety and Health (NIOSH) are developing methods for characterizing diesel particulate matter in mines. Introduction of novel engine and exhaust aftertreatment technologies in underground mines is changing the nature of diesel emissions, and metrics alternative to the traditional mass-based measurements are being investigated with respect to their ability to capture changes in the properties of diesel aerosols. The emphasis is given to metrics based on measurement of number and surface area concentrations, but analysis of collected particles using electron microscopy (EM) is also employed for detailed particle characterization. To collect samples for EM analysis at remote workplaces, including mining and manufacturing facilities, NIOSH is developing portable particle samplers capable of collecting airborne nano-scale particles. This paper describes the design, construction, and testing of a prototype thermophoretic precipitator (TP) particle sampler optimized for collection of particles in the size range of 1–300 nm. The device comprises heated and cooled metal plates separated by a 0.8 mm channel through which aerosol is drawn by a pump. It weighs about 2 kg, has a total footprint of 27 × 22 cm, and the collection plate size is approximately 4 × 8 cm. Low power consumption and enhanced portability were achieved by using moderate flow rates (50–150 cm³/min) and temperature gradients (10–50 K/mm with ΔT between 8 K and 40 K). The collection efficiency of the prototype, measured with a condensation particle counter using laboratory-generated polydisperse submicrometer NaCl aerosols, ranged from 14–99%, depending on temperature gradient and flow rate. Analysis of transmission electron microscopy images of samples collected with the TP confirmed that the size distributions of collected particles determined using EM are in good agreement with those determined using a Fast Mobility Particle Sizer.

Copyright 2012 American Association for Aerosol Research     

Morphological and Elemental Classification of Freshly Emitted Soot Particles and Atmospheric Ultrafine Particles using the TEM/EDS

The Transmission Electron Microscopy (TEM) and Energy Dispersive Spectroscopy (EDS) were used to determine morphology and elemental composition of a variety of freshly emitted soot particles (acetylene flame, candle flame, kerosene flame, diesel exhaust, electric arc, plastic burning, styrofoam burning, wood burning [white oak and pine bark], and rice straw burning), which can be possible candidate soot in the ambient atmosphere, and ultrafine particles sampled in urban, industrial, and coastal sites during ultrafine particle formation events (combustion and photochemical events). By using mobility-classified non-refractory ((NH ₄ ) ₂ SO ₄ ) and refractory (Polystyrene latex (PSL) and salt (NaCl)) particles, limitation of the TEM was tested. Data showed that the TEM method can be used to examine shapes of both volatile particles such as (NH ₄ ) ₂ SO ₄ (100 nm) at low, but not high magnification (refer to low and high beam intensity, respectively), and non-volatile particles like NaCl (100 nm) and PSL (84 nm) at either low or high magnification. Distinct differences in morphological properties such as primary particle diameter, fractal dimension, and microstructure were observed among the different types of fresh soot particles. The atmospheric ultrafine particles were classified as agglomerates, sulfate mixtures (spherical), metallic oxides (spherical and polygonal), C-rich refractory (not agglomerated), C-rich non-refractory (not agglomerated), Si-rich (spherical), Na-rich (porous), or P-containing (non-spherical) particles. At the urban Gwangju site, a higher fraction of fresh and aged agglomerates was observed than at other sites. The C-rich non-refractory and sulfate mixtures were often observed in the photochemical event. The C-rich refractory particles were abundant at the Gwangju and Yeosu sites. The coastal Taean site had few agglomerates due to limited anthropogenic combustion source.     

A Handheld Electrostatic Precipitator for Sampling Airborne Particles and Nanoparticles

Researchers at NIOSH are developing methods for characterizing ultrafine aerosols in workplaces. One method includes the detailed analysis of collected particles using electron microscopy (EM). In order to collect samples for EM at remote workplaces including mining and manufacturing facilities, researchers have developed a handheld electrostatic precipitator (ESP) particle sampler capable of collecting airborne particles including nanoscale materials, for subsequent EM analysis. The handheld ESP has been tested in the laboratory and is currently undergoing beta testing in the field. Gross collection efficiencies were measured with a CPC and net efficiencies by EM analysis of collected samples. Using laboratory-generated NaCl aerosols in the 30–400 nm size range at a flow rate of 55 cc/min and ESP operating voltages between 5.6–6.8 kV, both gross and net efficiencies were measured and showed a similar correlation with voltage, with maximum efficiency of approximately 86% at 6.4 kV. EM images from samples were also used to estimate particle size distributions of the original aerosols and the size-dependent deposition was evaluated for upstream versus downstream locations on the sample media. Results suggest that the number concentration and particle size distribution of sampled aerosols may potentially be estimated from a single ESP sample, but that the accuracy and repeatability of such quantification need to be investigated and refined. NIOSH is planning to license the ESP sampler for commercial manufacturing.     

Laboratory Study of Simulated Atmospheric Transformations of Chromium in Ultrafine Combustion Aerosol Particles

While atmospheric particles can have adverse health effects, the reasons for this toxicity are largely unclear. One possible reason is that the particles can contain toxic metals such as chromium. Chromium exists in the environment in two major oxidation states: III, which is an essential nutrient, and VI, which is highly toxic and carcinogenic. Currently little is known about the speciation of chromium in airborne particles or how this speciation is altered by atmospheric reactions. To investigate the potential impacts of atmospheric aging on the speciation and toxicity of chromium-containing particles, we collected chromium and chromium-iron combustion ultrafine particles on Teflon filters and exposed the particles to a combination of light, ozone, water vapor, and, in some cases, basic or acidic conditions. After the aging process, the aged and not-aged samples were analyzed for Cr oxidation state using X-ray Absorption Near Edge Spectroscopy (XANES). We found that the aging process reduced Cr(VI) by as much as 20% in chromium particles that had high initial Cr(VI)/Cr(total) ratios. This reduction of Cr(VI) to Cr(III) appears to be due to reactions primarily with light and hydroperoxyl radical (HO ₂ ) in the chamber. Particles that had low initial Cr(VI)/Cr(total) ratios experienced no significant change in Cr oxidation states after aging. Compared to particles containing only Cr, the addition of Fe to the flame decreased the Cr(VI)/Cr(total) ratio in fresh Cr-Fe particles by ～60%. Aging of these Cr-Fe particles had no additional effects on the Cr(VI)/Cr(total) ratio.     

A Methodology for Measuring Size-Dependent Chemical Composition of Ultrafine Particles

Ultrafine particulate matter (PM) consists of particles mostly emitted by combustion sources but also formed during gas-to-particle formation processes in the atmosphere. Various studies have shown these particles to be toxic. The very small mass of these particles has posed a great challenge in determining their size-dependent chemical composition using conventional aerosol sampling technologies. Implementing 2 technologies in series has made it possible to overcome these 2 problems. The first technology is the USC Ultrafine Concentrator, which concentrates ultrafine particles (i.e., 10-180 nm) by a factor of 20-22. Ultrafine particles are subsequently size fractionated and collected on suitable substrates using the NanoMOUDI, a recently developed cascade impactor that classifies particles in 5 size ranges from 10 to 180 nm. The entire system (concentrator + NanoMOUDI) was employed in the field at 2 different locations in the Los Angeles Basin in order to collect ultrafine particles in 3 consecutive 3 h time intervals (i.e., morning, midday, and afternoon). The results indicate a distinct mode in the 32-56 nm size range that is most pronounced in the morning and decreases throughout the day at Downey, CA (a "source" site), affected primarily by vehicular PM emissions. While the mass concentrations at the source site decrease with time, the levels measured at Riverside, CA (a "receptor" site), are highest in the afternoon with a minimum at midday. In Riverside, ultrafine EC (elemental carbon) and OC (organic carbon) concentrations were highly correlated only during the morning period, whereas these correlations collapsed later in the day. These results indicate that in this area, ultrafine PM is generated by primary emissions during the morning hours, whereas secondary aerosol formation processes become more important as the day progresses.     

Design and Collection Efficiency of a New Electrostatic Precipitator for Bioaerosol Collection

We have developed and tested a new bioaerosol sampler in which airborne microorganisms are collected by electrostatic means. In this sampler, 2 ionizers charge the incoming particles if they carry insufficient electric charge for efficient collection. The organisms are then subjected to a precipitating electric field and are collected onto 2 square agar plates positioned along the flow axis. Tests with nonbiological NaCl particles versus B. subtilis var. niger (BG) spores and vegetative cells have shown that airborne microorganisms are collected more efficiently than nonbiological particles, even when the microorganisms have first passed through an electric charge neutralizer with no additional charging applied. The difference was attributed to the natural charges contained in cell membranes or spore coats of the microorganisms. Charge-neutralized BG spores and vegetative cells were collected at 4 L/min with efficiencies close to 80%, depending on the precipitation voltage, versus 50-60% for NaCl test particles. When incoming BG spores were charged with positive ions and then collected by a precipitating voltage of + 1,300 V, about 80% of the incoming spores were collected and more than 70% of incoming spores formed colonies. These experiments with BG spores have also indicated that there were no significant particle losses inside the sampler. The collection efficiency of biological and nonbiological particles increased to 90-100% when the particles were externally charged and the precipitating voltage was increased to more than - 4,000 V. It has also been shown that the aerosolized BG spores (used as anthrax simulants for bioaerosol sensors) carry a net negative electric charge. Thus the collection efficiency depends on the polarity of the electric field applied across the agar plates. These findings indicate that the collection of airborne microorganisms is possible by electrostatic precipitation without prior electric charging if the microorganisms already carry electric charges. These are usually high immediately after their release into the air.     

A Wet Electrostatic Precipitator (WESP) for Soft Nanoparticle Collection

Many nanoparticle collection devices have limitations related to retention of particle integrity from bounce, shattering, or aggregation. Suspensions of soft nanoparticles (e.g., proteins, lipids) are required for drug delivery and therapy. To enable direct collection of soft nanoparticles into liquid media, a wet electrostatic precipitator (WESP) was designed and evaluated in this work. Different sections were used for ion generation and particle charging, for minimal contact between the corona wire and particles, which were charged using positive nitrogen ions. WESP dimensions and operating parameters were optimized using charge distribution modeling. The prototype WESP was designed for operation with a continuous flow of liquid over the collection plate, to allow continuous particle collection from the exit stream of an aerosol reactor. The collection efficiency of the WESP, in dry and wet modes, was measured using aerosols of monodisperse polystyrene latex (PSL), polydisperse sucrose, and stearic acid (soft lipid) particles, through SMPS measurements, corrected for diffusional losses, at the entry and exit of the device. Measured collection efficiency was 70%–90% for particles of sizes 80–600 nm diameter in reasonable agreement with theoretical estimates. However, for small particles (20–80 nm diameter) measured collection efficiency ranged 40%–70%, significantly lower than theoretical estimates, possibly from incomplete neutralization of negative charges attained during air-jet atomization. Transmission electron microscopy (TEM) images and dynamic light scattering (DLS) measurements confirm that wet collection produces a suspension of free, unaggregated nanoparticles with sizes similar to their measured mean mobility diameter.

Copyright 2012 American Association for Aerosol Research     

室内大气颗粒物分形结构分析

颗粒物的分形结构能表示颗粒物本身的性质特征,大气颗粒物对人体的危害与其分形结构有关。这里通过制作室内大气悬浮颗粒采集器,采集室内大气颗粒,然后通过数字显微技术和图像处理技术,分析颗粒投影图像的轮廓曲线分形维数值、圆度数值。结果表明：轮廓曲线分形维数值具有近似正态分布特征,圆度值和分形维数值间具有相关关系。通过测算分形维数值和圆度值可以近似判断室内空气的性质,对实现室内大气质量实时监测和计算机处理具有一定意义。     

Preparation of Ultrafine Zirconia Particles

Ultrafine ZrO₂ particles have been prepared via a new sol-gel process. This process involves the addition of excess C₂H₄O into the aqueous ZrOCl₂ solution and reacting the mixture at room temperature; a glassy ZrO(OH)₂ gel is formed moments later. An ultrafine ZrO₂ powder is obtained after the gel is dried and calcined; the powder is monoclinic. The average particle size is ∼12 nm, and its specific surface area is 55.1 m²/g. In addition, partially stabilized ZrO₂ can be prepared in the same manner, yielding a good result.     

Thermophoretic Deposition of Particles in Laminar and Turbulent Tube Flows

Thermophoretic deposition of aerosol particles (particle diameter ranges from 0.038 to 0.498 μm) was measured in a tube (1.18 m long, 0.43 cm inner diameter, stainless steel tube) using monodisperse NaCl test particles under laminar and turbulent flow conditions. In the previous study by Romay et al., theoretical thermophoretic deposition efficiencies in turbulent flow regime do not agree well with the experimental data. In this study, particle deposition efficiencies due to other deposition mechanisms such as electrostatic deposition for particles in Boltzmann charge equilibrium and laminar and turbulent diffusions were carefully assessed so that the deposition due to thermophoresis alone could be measured accurately. As a result, the semiempirical equation developed by Lin and Tsai in laminar flow regime and the theoretical equation of Romay et al. in turbulent flow regime are found to fit the experimental data of thermophoretic deposition efficiency very well with the differences of less than 1.0% in both flow regimes. It is also found that Talbot's formula for the thermophoretic coefficient is accurate while Waldmann's free molecular formula is only applicable when Kn is greater than about 3.0.     

Thermophoretic Deposition of Particles in Laminar Flow in a Concentric Annulus

The thermophoretic deposition efficiency of particles in laminar flow in a concentric annulus is considered. A simple, but formally exact expression for the cumulative deposition efficiency is derived (for PrK = 1). This formula is used to calculate the deposition efficiency, and to demonstrate that 100% collection may be easily realized. The effect of the annulus size and the ratio of inner to outer tube wall temperature on the collection efficiency is explored to some extent.     

A High Volume Apparatus for the Condensational Growth of Ultrafine Particles for Inhalation Toxicological Studies

A high volume (2500 LPM) system for the condensational growth of ultrafine particles was developed and evaluated using indoor air as a test aerosol. The main features of this system are the following: (a) ultrafine particles grow condensationally to supermicron sizes using high purity deionized water as a condensing medium; (b) the supersaturation ratio is adjustable and can be precisely controlled; (c) the system can operate for a wide range of ambient air temperature and relative humidity conditions; and (d) a thermal dryer is used to return the condensationally grown particles back to their original size. Restoring the original ambient size distribution and preserving the composition of the ambient ultrafine particles is very important for inhalation studies. The system is fully automated and has computerized feedback controls. In addition, saturation of the aerosol with water vapor occurs at close to ambient temperatures to minimize particle losses of volatile components. Saturation of sample air is obtained using a direct steam-injecting, fully modulating electric humidifier. The sample air after saturation is drawn through the supersaturator, which is a refrigerant-to-air heat exchanger and is cooled down to obtain the desirable supersaturation ratio. Supersaturation ratios can be precisely adjusted, with the optimum operational level found to be in the range of 2 to 3. The performance of the system was evaluated as a function of critical operation parameters, including the supersaturation ratio as well as the saturation and supersaturation temperatures. A series of virtual and conventional impactors was used to characterize the condensational growth of ultrafine particles. This new high volume apparatus was shown to grow ambient ultrafine particles to supermicron sizes with a particle size growth of approximately 1.8 w m. Particle losses in the system were found to be minimal (about 10%). The thermal dryer was used successfully to restore the grown particles back to their original size distribution. Particle concentration, aerosol temperature, and residence time (aerosol flow) are key parameters shown to affect the performance of the thermal dryer was used successfully to restore the grown particles back to their original size distribution. Particle concentration, aerosol temperature, and residence time (aerosol flow) are key parameters shown to affect the performance of the thermal dryer.     

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.

     

超微粒子的合成及其应用

本文综述了超微粒子的合成方法和应用。着重叙述了超微粒子在催化、生物、医学、记录材料、传感材料等方面的应用。     

Diffusion Sampler for Measurement of Acidic Ultrafine Particles in the Atmosphere

The adverse health effect of acidic ultrafine particles (AUFPs) has been widely recognized in scientific societies. These particles mainly deposit on the surface by diffusion and so far there is no mature method for the measurement of airborne AUFPs. The purpose of this study was to develop a diffusion sampler (DS) with iron nanofilm detectors to effectively measure the number concentration and size distribution of airborne AUFPs in indoor and outdoor environments. The developed DS was made of stainless steel with a flat and rectangular channel with 1.0 mm height, 50 mm width, and 500 mm length. The iron nanofilm detectors were deployed on rectangular recesses inside the sampler at three different locations along the length of the channel to collect the ultrafine particles. The exposed detectors were then scanned using an atomic force microscope (AFM) to numerate and distinguish the AUFPs from the nonacidic UFPs. Prior to sampling, the semi-empirical equations for the diffusive deposition efficiency of particles at the different detector locations in the sampler were obtained on the basis of theoretical diffusive mechanism and modified by the experimental data using polystyrene latex (PSL) standard particles. After calibration, the DS + AFM method and a commercially available online measurement system, i.e., scanning mobility particle sizer (SMPS) incorporated with a condensation particle counter (CPC), were simultaneously used in a 4-week field measurement. Both methods showed very good agreement in terms of total particle number concentration and size distribution. The results indicate that the diffusion sampler is effective for the quantification of ambient acidic ultrafine particles.

Copyright 2014 American Association for Aerosol Research