Coating Mass Dependence of Soot Aggregate Restructuring due to Coatings of Oleic Acid and Dioctyl Sebacate

Soot particles in the atmosphere can be coated with organic or nonorganic material, which may affect particle morphology and optical properties. The effect of the mass of coating on the morphology of soot particles was studied using oleic acid and dioctyl sebacate (DOS) coatings. A wide range of coatings were used, with up to 10 times as much coating as the mass of the soot. It is shown that as the coating mass increases the degree of collapsing increases until the coating is so large that the soot particle becomes completely contained within a spherical droplet of the coating material. Higher amounts of coating will not cause further collapse of the particle. The degree of collapse is also a function of the initial size of the soot particle but was independent of the coating materials tested, which have similar surface tensions. A model is presented to predict the change in mobility diameter as a function of coating mass ratio. The effect of coating mass on effective density, shape factor, and fractal dimension is also reported.

Copyright 2013 American Association for Aerosol Research     

Mass,Mobility, Volatility,and Morphology of Soot Particles Generated by a McKenna and Inverted Burner

Particle mass, mobility, volatile mass fraction, effective density, mass concentration, mass–mobility exponent, and particle morphology were measured from soot generated from a premixed flame (McKenna burner) and an inverted diffusion flame over a range of equivalence ratios. It was found that the mass fraction of volatile material on the soot from the McKenna burner could be up to 0.83 at a high equivalence ratio, but there was no measurable volatile material on the soot from the inverted burner. The inverted burner can produce soot at different mass–mobility exponents, ranging from 2.23 to 2.54, over a range of global equivalence ratios of 0.53–0.67, while the mass–mobility exponent ranges from 2.19 to 2.99 for fresh soot and 2.19 to 2.81 for denuded soot for the McKenna burner at equivalence ratios of 2.0–3.75. Transmission electron microscopy analysis of inverted burner soot shows that a range of particle morphologies is present at a given global equivalence ratio, likely due to different local equivalence ratios and flame conditions in the diffusion flame. Primary particle diameter tends to increase with aggregate size, which could contribute to the mass–mobility exponent being well above 2.

Copyright 2013 American Association for Aerosol Research     

Absorption Enhancement of Coated Absorbing Aerosols: Validation of the Photo-Acoustic Technique for Measuring the Enhancement

A photo-acoustic absorption spectrometer (PAS) and a cavity ring down aerosol extinction spectrometer (CRD-AES) were used, in conjunction with Mie Theory, to measure the refractive index (RI) of absorbing polystyrene spheres (APSS). The PAS and CRD-AES were also used to measure the absorption and extinction enhancement after these APSS were coated in oleic acid. The experimental enhancements were then compared to predictions from coated-sphere Mie Theory. The measured absorption and extinction enhancements both agreed with modeled enhancements to within an average of 5%. A filter-based absorption technique (particle soot absorption photometer, PSAP) was also used to measure the absorption by the APSS and showed a significant size-dependent bias, as evidenced by the filter-based method measuring significantly lower absorption for both uncoated and coated APSS compared to the PAS. These results suggest the validity of applying photo-acoustics to measure the absorption enhancement created by semi-volatile atmospheric species coating absorbing particles.     

An Inter-Comparison of Instruments Measuring Black Carbon Content of Soot Particles

Inter-comparison studies of well-characterized fractal soot particles were conducted using the following four instruments: Aerosol Mass Spectrometer-Scanning Mobility Particle Sizer (AMS-SMPS), Single Particle Soot Photometer (SP2), Multi-Angle Absorption Photometer (MAAP), and Photoacoustic Spectrometer (PAS). These instruments provided measurements of the refractory mass (AMS-SMPS), incandescent mass (SP2) and optically absorbing mass (MAAP and PAS). The particles studied were in the mobility diameter range from 150 nm to 460 nm and were generated by controlled flames with fuel equivalence ratios ranging between 2.3 and 3.5. The effect of organic coatings (oleic acid and anthracene) on the instrument measurements was determined. For uncoated soot particles, the mass measurements by the AMS-SMPS, SP2, and PAS instruments were in agreement to within 15%, while the MAAP measurement of optically-absorbing mass was higher by ～ 50%. Thin organic coatings (～ 10 nm) did not affect the instrument readings. A thicker (～ 50 nm) oleic acid coating likewise did not affect the instrument readings. The thicker (～60 nm) anthracene coating did not affect the readings provided by the AMS-SMPS or SP2 instruments but increased the reading of the MAAP instrument by ～ 20% and the reading of the PAS by ～ 65%. The response of each instrument to the different particle types is discussed in terms of particle morphology and coating material.     

Magnetite core-shell nano-composites with chlorine functionality: preparation by miniemulsion polymerization and characterization

Magnetic composite particles with a magnetic core consisting of superparamagnetic iron oxide and a cover layer of hydrophobic polyvinylbenzylchloride are described. The magnetite was prepared by precipitation starting with mixed iron II and iron III salts and coating of the solid with oleic acid. The coating is conducted via the liquid–liquid phase transfer. Thereby oleic acid adsorbed on the magnetite surface. In a second step the oleic acid treated magnetite was coated with polyvinylbenzylchloride in a miniemulsion polymerization to get a protective layer. The obtained magnetite core-shell nano-composites with chlorine functionality were characterized by different methods: particle size measurement, acid treatment, iron content, morphology and elemental profiles across the composite particles diameter. The test result reveals the binding of the iron oxide inside the composites which can be also recognize in TEM pictures.     

Processing of Soot by Controlled Sulphuric Acid and Water Condensation—Mass and Mobility Relationship

The effects of atmospheric processing on soot particle morphology were studied in the laboratory using the Differential Mobility Analyzer-Aerosol Particle Mass Analyzer (DMA-APM) and the DMA-DMA (Tandem DMA) techniques. To simulate atmospheric processing, combustion soot agglomerates were altered by sulphuric acid vapor condensation, relative humidity (RH) cycling, and evaporation of the sulphuric acid and water by heating. Primary investigated properties were particle mobility size and mass. Secondary properties, derived from these, include effective density, fractal dimension, dynamic shape factor, and the mass fraction of condensed material. A transformation of the soot particles to more compact forms occurs as sulphuric acid and water condense onto fresh soot. The particle mass increases and initially the mobility diameter decreases, indicating restructuring of the soot core, likely due to surface tension forces. For a given soot source and condensing liquid, the degree of compaction depends strongly on the mass (or volume) fraction of condensed material. For water and sulphuric acid condensing on combustion soot, a mass increase of 2–3 times is needed for a transformation to spherical particles. In the limit of spherical particles without voids, the effective density then approaches the inherent material density, the fractal dimension approaches 3 and the dynamic shape factor approaches 1. Our results indicate that under typical atmospheric conditions, soot particles will be fully transformed to spherical droplets on a time scale of several hours. It is expected that the morphology changes and addition of soluble material to soot strongly affect the optical and hygroscopic properties of soot.     

Characterization of Soot Aerosol Produced from Combustion of Propane in a Shock Tube

The knowledge of yields and properties of soot from combustion of hydrocarbon fuels is crucial for accurate evaluation of the impacts of primary aerosols on air quality and climate. This study presents measurements of soot generated from combustion of propane in a shock tube, using independently adjustable fuel equivalence ratio (φ), temperature, and pressure. The characterization of soot yields inside the shock tube by in situ laser extinction is complemented with a set of comprehensive measurements of soot transferred into a fluoropolymer chamber, including particle size distributions, elemental carbon (EC) mass fraction, effective density, mass fractal dimension (Dfm), dynamic shape factor (χ), and optical properties. The properties of soot particles and the soot yield are sensitive to combustion conditions and the duration of the combustion experiment. High-temperature combustion with φ = 2.5 produces small fractal (Dfm = 2) soot particles composed mainly of EC (up to 90%), at a low mass yield. Particles from lower temperature combustion contain a significant fraction of organic material (～50%). Using rich fuel mixtures (φ = 4.0 and 8.0) significantly increases particle size and soot mass yield. At lower temperatures, compact (Dfm = 3) and nearly spherical (χ = 1.1) aggregates with high organic content are formed, whereas at higher temperatures, the particles are fractal and closely resemble those obtained using φ = 2.5. Single scattering albedo (SSA) varies from 0.15 for fractal particles to 0.75 for compact particles. For soot generated at high equivalence ratios, SSA can be used as a proxy for particle morphology and EC content.

Copyright 2012 American Association for Aerosol Research     

A novel miniature inverted-flame burner for the generation of soot nanoparticles

Lab-scale soot nanoparticle generators are used by the aerosol research community to study the properties of soot over a broad range of particle size distributions, and number and mass concentrations. In this study, a novel miniature inverted-flame burner is presented and its emitted soot particles were characterized. The burner consisted of two co-annular tubes for fuel and co-flow air and the flame was enclosed by the latter. The fuel used was ethylene. A scanning mobility particle sizer (SMPS) and an aerodynamic aerosol classifier (AAC) were used to measure mobility and aerodynamic size distribution of soot particles, respectively. Particle morphology was studied using transmission electron microscopy (TEM). The elemental carbon (EC) and organic carbon (OC) content of the soot were measured using thermal-optical analysis (TOA). The burner produced soot particles with mobility diameter range of 66–270?nm, aerodynamic diameter range of 56–140?nm, and total concentration range of 2?×?10⁵–1?×?10⁷?cm^?3. TEM images showed that most soot particles were sub-micron soot aggregates. Some soot superaggregates, typically larger than 2?µm in length, were observed and their abundance increased with ethylene flow rate. TOA showed that the concentration of EC in the generated soot increased with ethylene flow rate, and the soot was observed to have high EC fraction at high ethylene flow rates. The miniature inverted-flame burner was demonstrated to produce soot nanoparticles over a range of concentrations and sizes with high EC content, making it a practical device to study soot nanoparticle properties in different applications.

Copyright © 2019 American Association for Aerosol Research     

Measurements of Morphology Changes of Fractal Soot Particles using Coating and Denuding Experiments: Implications for Optical Absorption and Atmospheric Lifetime

Mobility-selected fractal and non-fractal soot particles (mobility diameters d _m = 135 to 310 nm) were produced at three controlled fuel equivalence ratios (φ = 2.1, 3.5, and 4.5) by an ethylene/oxygen flame. Oleic acid (liquid) and anthracene (solid) coatings were alternately applied to the particles and removed. Simultaneous measurements with an Aerodyne aerosol mass spectrometer and a scanning mobility particle sizer yielded the particle mass, volume, density, composition, dynamic shape factor, fractal dimension, surface area, and the size and number of the primary spherules forming the fractal aggregate. For a given φ, the diameters of the primary spherules are approximately the same, independent of d _m (15 nm, 35 nm, and 55 nm for φ = 2.1, 3.5, and 4.5, respectively). As the coating thickness on a particle increases, the dynamic shape factor decreases but d _m remains constant until the particle reaches a spherical (for oleic acid) or non-fractal but irregular (for anthracene) shape. Under some conditions, liquid oleic acid coating causes the internal BC framework to rearrange into a more compact configuration. The surface area of fractal particles is up to 2.4 times greater than that of a sphere with the same d _m . Using the surface area determinations, the time for a fractal particle to obtain a monolayer of coating material is compared to that of spheres. If it is assumed that the fractal particle is a sphere with the same d _m as the fractal particle, the monolayer coating time is underestimated by a factor of up to 1.7.     

Classification of particles in particle-laden stream through a stainless steel fibrous filter

This investigation experimentally explores the penetration curve of particles shot onto a stainless steel fibrous filter or a flat surface. The effect of the pore size of the stainless steel fibrous filter, with or without an oil coating, on the particle penetration was examined at various flow rates, nozzle diameters and dimensionless particle diameters, Sqrt(Stk). The penetration of the flat surface by particles was also determined for comparison. Experimental results demonstrate that oleic acid particles larger than Sqrt(Stk)₅₀ are collected on the stainless steel fibrous filter with a low penetration, while smaller particles stay in the particle-laden stream with high penetration. The penetration of potassium chloride particles exceeds that of oleic acid particles, because potassium chloride particles bounce off the stainless steel fibrous filter and the flat surface. Particles bounce off the metal filter less easily than the flat surface. Coating the stainless steel fibrous filter with oil effectively reduces problems of particle bounce. The potassium chloride particles sucked the coated oil forming a small mountain on the surface. When the loaded particle mass on the coated stainless steel fibrous filter ranges between 0.4 and 2.3 mg, Sqrt(Stk)₅₀ is a constant 0.35.     

An improved low-flow thermodenuder

Thermodenuders are used to remove the volatile fraction of an aerosol. All designs until now have a cooled adsorption section where the volatile material is trapped, but theoretical considerations suggest that the adsorption section should be heated. Therefore, we built a thermodenuder with a heated adsorption section. We tested its performance with respect to particle penetration and its ability to remove DEHS coated onto NaCl nuclei. The measured losses are lower than in previously published designs and the DEHS removal appears to be satisfactory. Additionally, the new thermodenuder is practical for field use thanks to its small size. It should therefore be a good alternative to previous designs.     

纳米四氧化三铁磁性微粒的表面有机改性

通过液相共沉淀法制备了纳米四氧化三铁溶胶，利用油酸对纳米粒子体进行表面改性和萃取实验，获得油酸包覆的四氧化三铁微粒。采用FT—IR和高分辨透射电镜对改性后的纳米粉体进行结构和形貌的表征。研究结果表明油酸与四氧化三铁纳米粒子间存在化学键结合。油酸对纳米四氧化三铁微粒进行改性，并且对纳米粒子进行包覆，使外表面形成保护层阻止粒子团聚，改性后的四氧化三铁微粒与有机物具有良好的相溶性，采用表面改性显著改善了纳米四氧化三铁微粒的性能指标。     

The Detection Efficiency of the Single Particle Soot Photometer

A single particle soot photometer (SP2) uses an intense laser to heat individual aerosol particles of refractory black carbon (rBC) to vaporization, causing them to emit detectable amounts of thermal radiation that are used to quantify rBC mass. This approach is well suited for the detection of the majority of rBC mass loading in the ambient atmosphere, which occurs primarily in the accumulation mode (～ 1–300 fg-rBC/particle). In addition to operator choices about instrument parameters, SP2 detection of rBC number and/or mass can be limited by the physical process inherent in the SP2 detection technique — namely at small rBC mass or low laser intensities, particles fail to heat to vaporization, a requirement for proper detection. In this study, the SP2's ability to correctly detect and count individual flame-generated soot particles was measured at different laser intensities for different rBC particle masses. The flame-generated soot aerosol used for testing was optionally prepared with coatings of organic and non-organic material and/or thermally denuded. These data are used to identify a minimum laser intensity for accurate detection at sea level of total rBC mass in the accumulation mode (300 nW/(220-nm PSL)), a minimum rBC mass (～ 0.7-fg rBC-mass corresponding to 90 nm volume-equivalent diameter) for near-unity number detection efficiency with a typical operating laser intensity (450 nW/(220-nm PSL)), and a methodology using observed color temperature to recognize laser intensity insufficient for accurate rBC mass detection. Additionally, methods for measurement of laser intensity using either laboratory or ambient aerosol are presented.     

包覆油酸的Fe_3O_4纳米粒子的制备

用FeSO4和FeCl3在氨水和油酸作用下,共沉淀制备了包覆油酸的Fe3O4纳米粒子,考察了沉淀温度、油酸加入前反应时间及总铁离子浓度对其粒径的影响。结果显示,沉淀温度的升高和油酸加入前反应时间的延长,均可使Fe3O4粒径增大。沉淀温度从20℃增加到80℃,粒径从大约5 nm增加到8 nm;油酸加入前反应时间从10 min延长到30 min,粒径从大约3 nm增加到8 nm。c(总铁离子)=0.1~1.1 mol/L时对粒径没有显著影响,Fe3O4粒径均为8 nm左右,c(总铁离子)>1.1 mol/L时,粒径明显减小。     

TEM study on volatility and potential presence of solid cores in nucleation mode particles from diesel powered passenger cars

Nucleation mode particles were investigated for their morphology using TEM and the presence or absence of solid cores was addressed. At cold start idle nucleation particles were observed in the exhaust of a diesel passenger car. These particles occurred with both low and high S fuel and were only partly volatile in a thermodenuder, which indicates that the composition was not sulfate and as derived from TEM/EDX (transmission electron microscopy/energy dispersive X-ray analysis) probably not ash. It could be high boiling hydrocarbons, or primary soot particles. With all fuels at warm idle no nucleation particles and only soot particles were observed in the SMPS and the TEM. With 3.0×10¹¹ s^?1 the total soot particle number during idle was much less than during driving, e.g. at 120 km h^?1 the emission rate was 6.7×10¹² s^?1.At high load and high S fuel 10–20 nm nucleation particles were observed by SMPS and TEM. A thermodenuder at 280 °C and TEM showed that all nucleation particles were volatile. EDX gave a weak S-signal only. Some nucleation particles contained smaller spots (1–3 nm) with a very high contrast, which might be due to heavy elements. However, under the electron beam of the TEM these spots disappeared and EDX analysis was not possible. With low S fuel at 120 km h^?1 only soot particles and no nucleation particles were observed.     

粉煤灰微珠-Ag复合颗粒的制备工艺和分析

采用化学镀的方法,以银氨溶液为镀液,甲醛为还原剂,按照一定的工艺过程对粉煤灰微珠进行表面镀银处理,得到了粉煤灰微珠-Ag复合颗粒。同时借助激光粒径分析仪、X射线衍射仪、场发射扫描电子显微镜、X射线能谱仪等检测设备对复合颗粒的粒径分布、化学成分、镀层表面形貌和结构进行了分析。对复合微珠进行保温隔热性能测试,掺镀银微珠的涂料比原微珠的涂料温度低约4℃。结果表明,按照设定的工艺过程,可以成功制备出具有保温隔热低辐射功能的粉煤灰微珠-Ag复合颗粒,作为一种功能性骨料有望用于建筑物外围护结构表面的砂浆或涂料中以降低对远红外热的辐射能力。     

Effects of Mixing State on Black Carbon Measurements by Laser-Induced Incandescence

Laboratory experiments and theoretical calculations were made to characterize the performance of a Single Particle Soot Photometer (SP2) manufactured by Droplet Measurement Technologies (DMT), which was designed to measure the mass and the mixing state of individual black carbon (BC) or elemental carbon (EC) particles, based on the laser-induced incandescence (LII) technique. In this study, graphite was used as a surrogate of EC. Graphite particles with mass equivalent diameters of 110–200 nm were layered with organic liquids (glycerol and oleic acid) to produce coated graphite with diameters up to 650–800 nm. These were sampled by the SP2 to measure the waveforms (i.e., time development) of the LII and scattering signals. The peak temperature and the peak LII signal of graphite particles were independent of the coating thickness or the coating material to within experimental errors. These results indicate that the mass of EC can be measured by using peak LII signal without interference by the coating conditions. It was also shown that the difference between the times of the scattering and LII peaks can be used as an indicator of coating on EC with thicknesses larger than about 100–200 nm. LII and scattering waveforms were calculated using a newly developed theoretical model that takes into account the physical processes controlling the temperature and evaporation rate of the coated graphite particle in the laser beam. The calculations reproduced the general features of observed waveforms of LII and scattering signals, providing a firm theoretical basis for the interpretation of the SP2 data.     

Fe3O4水基磁流体的制备及其分散性能研究

采用共沉淀法制备了纯Fe3O4纳米粒子,分别用高氯酸、四甲基羟胺和油酸/十二烷基苯磺酸钠为表面活性剂对其进行表面处理后分散在水中,得到了3种水基磁流体,对这3种磁流体的浓度及稳定性进行了测定。实验结果显示:酸性、碱性和中性水基磁流体中Fe3O4的浓度分别为4.8%、5.8%和8.1%,其中中性水基磁流体中粒子的分散性能最佳;经过离心后,3种水基磁流体中的粒子均产生了沉降,且酸性和碱性磁流体中的粒子比中性磁流体中的粒子沉降的多。在此基础上,对影响粒子分散稳定性的机理进行了初步探讨。     

Soot Particle Studies—Instrument Inter-Comparison—Project Overview

An inter-comparison study of instruments designed to measure the microphysical and optical properties of soot particles was completed. The following mass-based instruments were tested: Couette Centrifugal Particle Mass Analyzer (CPMA), Time-of-Flight Aerosol Mass Spectrometer—Scanning Mobility Particle Sizer (AMS-SMPS), Single Particle Soot Photometer (SP2), Soot Particle-Aerosol Mass Spectrometer (SP-AMS) and Photoelectric Aerosol Sensor (PAS2000CE). Optical instruments measured absorption (photoacoustic, interferometric, and filter-based), scattering (in situ), and extinction (light attenuation within an optical cavity). The study covered an experimental matrix consisting of 318 runs that systematically tested the performance of instruments across a range of parameters including: fuel equivalence ratio (1.8 ≤ φ ≤ 5), particle shape (mass-mobility exponent ( D _fm ), 2.0 ≤ D _fm ≤ 3.0), particle mobility size (30 ≤ d _m ≤ 300 nm), black carbon mass (0.07 ≤ m _BC ≤ 4.2 fg) and particle chemical composition. In selected runs, particles were coated with sulfuric acid or dioctyl sebacate (DOS) (0.5 ≤ Δ r _ve ≤ 201 nm) where Δ r _ve is the change in the volume equivalent radius due to the coating material. The effect of non-absorbing coatings on instrument response was determined. Changes in the morphology of fractal soot particles were monitored during coating and denuding processes and the effect of particle shape on instrument response was determined. The combination of optical and mass based measurements was used to determine the mass specific absorption coefficient for denuded soot particles. The single scattering albedo of the particles was also measured. An overview of the experiments and sample results are presented.     

Investigation of soot nanoparticles during combustion of liquid hydrocarbons with injection of a superheated steam jet into the reaction zone

The characteristics of soot particles formed during combustion of liquid hydrocarbons in a laboratory model of an original burner with injection of a superheated steam jet into the reaction zone are experimentally studied. The concentration and size distribution of soot particles formed in the burner flame are measured by a diffusion aerosol spectrometer. It is shown that the majority of the primary particles have sizes ranging from 20 to 60 nm. The particle concentration in the external flame rapidly decreases with distance from the burner exit from 10⁸ to 5 · 10⁶ cm^?3. The images obtained by transmission electron microscopy demonstrate a chain-branched (fractallike) structure of aggregates. The primary particles composing these aggregates have a union-like structure with the interplane distance between the layers smaller than 1 nm. Compact aggregates with sizes up to 500 nm are observed in cooled combustion products. The content of soot in combustion products is 35 mg/m³, and the mean particle mass is 7 · 10^?12 mg. Results obtained in the combustion modes with injection of a superheated steam jet and with injection of an air jet are compared.