Steven N. Rogak

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

Observations of a Correlation Between Primary Particle and Aggregate Size for Soot Particles

For decades, soot has been modeled as fractal-like aggregates of nearly equiaxed spherules. Cluster–cluster aggregation simulations, starting from a population of primary particles, give rise to structures that closely match real aerosols of solid particles produced in flames. In such simulations, primary particle size is uncorrelated with aggregate size, as all aggregates contain primary particles drawn from the same population. Aerosol measurements have been interpreted with this geometric model. Examination of transmission electron micrographs of soot samples from various sources shows that primary particle sizes are not well mixed within an aerosol population. Larger aggregates tend to contain larger primary particles and the variation in size is much larger between aggregates than within aggregates. The soot sources considered here are all substantially not well-mixed (aircraft jet engine, inverted diffusion flame, gasoline direct injection engine, heavy-duty compression ignition engine). The observed variations in primary particle size can be explained if soot aggregates are formed and grew by coagulation in small zones of the combustion chamber, prior to dilution and transport (with minimal coagulation) to the sampling system. Copyright 2014 American Association for Aerosol Research

Morphology and Raman Spectra of Engine-Emitted Particulates

The morphology and nanostructure of soot from different engines were studied. The soot samples were collected from a 1.9 L Volkswagen light-duty diesel (LDD) engine for two different fuel types [ultralow sulfur diesel (ULSD) and B20] and six speed/load combinations, as well as from a heavy-duty engine using a pilot-ignited high-pressure direct-injection (HPDI) natural-gas combustion system for three different speed/load combinations. Transmission electron microscopy (TEM) was employed to investigate the soot morphology by using alternative fractal measurement methods. The fractal dimensions (Df ) were computed from the scaling of the projected aggregate dimensions with the number of primary particles (“LW” method) and two-dimensional pair correlation functions. For the soot collected from the LDD, it was found that the fractal dimensions are independent of fuel type, while a higher engine load slightly decreased Df . The soot produced by the HPDI exhibited a similar correlation between Df and engine load. The fractal dimension of the engine-emitted soot was measured in a range of 1.70–1.85 and the fractal prefactor kfLW of 1.08–1.39. Raman spectroscopy was used to characterize the soot nanostructure based on the degree of microstructural disorder. The Raman spectral analysis was done using two-band (“G” at ∼1578 and “D” at ∼1340 cm−1) and five-band (G, D1, D2, D3, and D4 at about 1580, 1350, 1500, 1620, and 1200 cm−1 respectively) combinations. For the soot sampled from the LDD, the results from both methods showed that B20 soot exhibited a greater structural disorder. Likewise, the Raman analysis of the soot from both engines also showed that the increase in engine load condition caused increases in the degree of the structural order of soot. The use of either D/G ratio or D1 width cannot distinguish between the HPDI and the LDD soot. However, on a plot of D/G versus D1, the data fall into distinct clusters. This may indicate the importance of using more than two spectral parameters to characterize the soot samples.

Characterization of Particulate Matter Morphology and Volatility from a Compression-Ignition Natural-Gas Direct-Injection Engine

The particulate matter (PM) emitted from a single-cylinder compression-ignition, natural-gas engine fitted with a High-Pressure Direct-Injection (HPDI) system distinctly different from a duel fuel engine was investigated, and characterized by size distribution, morphology, mass-mobility exponent, effective density, volatility, mixing state, and primary particle size using transmission electron microscopy (TEM), and tandem measurements from differential mobility analyzers (DMA) and a centrifugal particle mass analyzer (CPMA). Six engine conditions were selected with varying load, speed, exhaust gas recirculation (EGR) fraction, and fuel delivery strategy. An increase in engine load increased both the number concentration and the geometric mean diameter of the particulate. The fraction of the number of purely volatile particles to total number of particles (number volatile fraction, NVF) was found to decrease as load increased, although at the lower speed, partially premixed mode, the lowest NVF. All size distributions were also found to be unimodal. The size-segregated ratio of the mass of internally mixed volatile material to total particle mass (mass volatile fraction, MVF) decreased with load and with particle mobility-equivalent diameter. A roughly constant amount of volatile material is likely produced at each engine mode, and the decrease in MVF is due to the increase in PM number with load. Effective density and mass-mobility exponent of the non-volatile soot at the different engine loads were the same or slightly higher than soot from traditional diesel engines. Denuded effective density trends were observed to collapse to approximately the same line, although engine modes with higher MVFs had slightly higher effective densities suggesting that the soot structures have collapsed into more dense shapes—a suspicion that is confirmed with TEM images. TEM results also indicated that primary particle size first decreases from low to medium load, then increases from medium to high load. An increase in EGR was also seen to increase primary particle size. Coefficients were determined for a relation that gives primary particle diameter as a function of projected area equivalent diameter. A decrease in load or speed results in a stronger correlation. Copyright 2015 American Association for Aerosol Research

Preventing Airborne Disease Transmission: Review of Methods for Ventilation Design in Health Care Facilities

Health care facility ventilation design greatly affects disease transmission by aerosols. The desire to control infection in hospitals and at the same time to reduce their carbon footprint motivates the use of unconventional solutions for building design and associated control measures. This paper considers indoor sources and types of infectious aerosols, and pathogen viability and infectivity behaviors in response to environmental conditions. Aerosol dispersion, heat and mass transfer, deposition in the respiratory tract, and infection mechanisms are discussed, with an emphasis on experimental and modeling approaches. Key building design parameters are described that include types of ventilation systems (mixing, displacement, natural and hybrid), air exchange rate, temperature and relative humidity, air flow distribution structure, occupancy, engineered disinfection of air (filtration and UV radiation), and architectural programming (source and activity management) for health care facilities. The paper describes major findings and suggests future research needs in methods for ventilation design of health care facilities to prevent airborne infection risk.

Modeling Small Cluster Deposition on the Primary Particles of Aerosol Agglomerates

ABSTRACT Dense particles, such as the primary particles in aerosol agglomerates, are formed by coagulation with rapid coalescence, or by condensation-like growth. This latter mechanism is explored in a new model. It uses the discrete-sectional model to describe the evolution of the particle mass distribution. In addition, new equations are used to describe the formation of primary particles. Primary particles are “born” when a new particle is formed above a critical size D melt. Particles smaller than D melt are assumed to be liquid-like, sintering rapidly in the available time. Changes in the final primary particle size Dp can be attributed to growth from small particle deposition. This growth increases as the monomer source rate decreases. For conditions representative of TiO2 formation from chloride in a tube reactor, Dp /D melt ranges from 1.5 to 3. When D meit decreases, as would be expected if temperature decreases, Dp /D melt increases. The result is that Dp is much less sensitive to temperature th...

Carbon Nanotube and Fullerene Emissions from Spark-Ignited Engines

Particles were collected from the exhaust of Indian autorickshaws with natural gas and gasoline-fueled spark-ignited engines. Transmission electron microscopy was used to determine the size and shape of 2121 systematically selected particles. Particles were largely soot agglomerates and other types documented in the literature, but approximately 10% of the nonvolatile particles were multiwalled carbon nanotubes and fullerenes, forms of crystalline carbon distinct from soot. Autorickshaw fullerenic particle number emissions can be above 1011 per kg of fuel consumed. The nanotubes identified from the exhaust of autorickshaws average 168 nm in length. This is shorter than those nanotubes of greatest health concern, but given the paucity of toxicological data on carbon nanotubes and fullerenes, the potential environmental abundance from engine sources warrants closer attention. In particular, a broader range of engine types should be considered. [Supplemental materials are available for this article. Please go to the publishers online edition of Aerosol Science & Technology to view the online files.] Copyright 2012 American Association for Aerosol Research

Effective density and mass-mobility exponent of aircraft turbine particulate matter

A centrifugal particle mass analyzer and a modified differential mobility spectrometer were used to measure the mass and mobility of particulate matter emitted by CFM56-5B4/2P, CFM56-7B26/3, and PW4000-100 gas turbine engine sources. The mass-mobility exponent of the particulate matter from the CFM56-5B4/2P engine ranged from 2.68 to 2.82, whereas the effective particle densities varied from 600 to 1250  kg/m3, depending on the static engine thrust and sampling methodology used. The effective particle densities from the CFM56-7B26/3 and PW4000-100 engines also fell within this range. The sample was conditioned with or without a catalytic stripper and with or without dilution, which caused the effective density to change, indicating the presence of condensed semivolatile material on the particles. Variability of the determined effective densities across different engine thrusts, based on the scattering about the line of best fit, was lowest for the diluted samples and highest for the undiluted sample without a catalytic stripper. This variability indicates that the relative amount of semivolatile material produced was engine thrust dependent. It was found that the nonvolatile particulate matter, effective particle density (in kilograms per cubic meter) of the CFM56-5B4/2P engine at relative thrusts below 30% could be approximated using the particle mobility diameter (dme in meters) with 11.92d(2.76−3)me.

Effect of Oxygen on the Corrosion Behavior of Alloy 625 from 25 to 200 ° C

Electrochemical polarization and impedance experiments were conducted on alloy 625 in ammoniacal solution between 298 and 473 K and at various oxygen partial pressures. Increased oxygen concentrations (as a result of higher temperatures or autoclave oxygen loading) resulted in increased corrosion potentials and corrosion rates. The inversion temperature (onset transpassive corrosion) was found to be ∼ 373 K at P TOTAL > 40 bar. A binary barrier layer/ outer layer film configuration was assumed and it was found that the outer layer dominated the corrosion process as temperatures and pressures were increased such that oxygen diffusion control was rate limiting. An oxygen solubility model for supercritical water oxidation (SCWO) conditions was generated using the Redlich-Kwong-Soave equation of state. Results of the model experimental work confirm many of the observations from SCWO reactors which suggest that corrosion reaches a maximum at temperatures just short of the critical point. Exchange current densities for oxygen reduction and effective diffusion layer thicknesses have also been calculated.

Use of tracer gas for direct calibration of emission-factor measurements in a traffic tunnel

Pollutant measurements in traffic tunnels have been used to estimate motor-vehicle emissions for several decades. The objective in this type of study is to use the traffic tunnel as a tool for characterizing motor vehicles rather than seeking a tunnel design with acceptably low pollutant concentrations. In the past, very simple aerodynamic models have been used to relate measured concentrations to vehicle emissions. Typically, it is assumed that velocities and concentrations are uniform across the tunnel cross section. In the present work, a vehicle emitting a known amount of sulfur hexafluoride (SF6) was driven repeatedly through a 730-m-long traffic tunnel in Vancouver, Canada. Comparing the measured SF6 concentrations to the known emission rates, it is possible to directly assess the accuracy of the simple tunnel aerodynamic models typically used to interpret tunnel data. Correction factors derived from this procedure were then applied to measurements of carbon monoxide and other pollutants to obtain gram-per-kilometer emission factors for vehicles. Although the specific correction factors measured here are valid only for the tunnel tested, the magnitude of the factors (up to two or more) suggests that the phenomena observed here should be considered when interpreting data from other tunnels.