Sizing of Non-Carbonaceous Nanoparticles by Time-Resolved Laser-Induced Incandescence

Non-carbonaceous nanoparticles represent a growing field in science and technology. Their applications range from medicine to environmental remediation to information technology. As the functionality of nanoparticles in these roles is highly size dependent, it is critical that diagnostics be developed to accurately measure the size of these nanoparticles. Time-resolved laser-induced incandescence (TiRe-LII) is an in situ technique that can measure the size of nanoparticles without physically probing a system. The technique operates using a laser pulse that heats the nanoparticle to incandescent temperatures. The incandescence is then measured from the nanoparticles as they equilibrate with the surrounding gas. As smaller particles will cool more quickly, the size of the nanoparticles can be inferred by modeling the incandescence or, more commonly, the effective temperature decay of the nanoparticles. The present work summarizes attempts to extend the use of TiRe-LII from its original application on soot to non-carbonaceous particles. This will be done by examining experimental data from three non-carbonaceous nanoparticles: molybdenum, silicon, and iron. This includes descriptions of the TiRe-LII models and statistical techniques required to robustly infer parameters and their uncertainties. As one of the major setbacks in extending this technique to other materials is the determination of the thermal accommodation coefficient (TAC), this work also focusses on determining that parameter both from experimental data and molecular dynamics simulations

Advances in the Modeling of Time-Resolved Laser-Induced Incandescence

Aerosolized nanoparticles represent both great potential for the development of emerging technologies and one of the biggest challenges currently facing our planet. In the former case, aerosol-based synthesis techniques represent one of the most cost-effective approaches to generating engineered nanoparticles having applications that range from medicine to energy. In the latter case, aerosolized soot is the second largest forcing factor after carbon dioxide in climate change models and contributes significantly to asthma, bronchitis, and various other respiratory illnesses. The increased predominance of engineered nanoparticles also presents significant environmental and health risks due to various toxicological effects. In any of these cases, robust characterization is critical to the function and regulation of these nanoaerosols. Time-resolved laser-induced incandescence (TiRe-LII) is well-suited to meeting this challenge. Since its inception in the 1980s, TiRe-LII has matured into a standard diagnostic for characterizing soot in combustion applications and, increasingly, engineered nanoparticles synthesized as an aerosol. The in situ nature of the technique makes it well-suited to probe in-flame soot formation and the fundamentals of nanoparticle formation. Moreover, its cost-effectiveness and real-time capabilities make TiRe-LII particularly well-suited as an avenue for online control of nanoparticle synthesis. TiRe-LII involves heating nanoparticles within a sample volume of aerosol to incandescent temperatures using a short laser-pulse. Following the laser pulse, the nanoparticles return to the ambient gas temperature via conductive and evaporative cooling. The magnitude of the peak spectral incandescence signal can be used to derive the particle volume fraction, while the temperature decay of the nanoparticles can be used to infer thermophysical properties, including the nanoparticle size, thermal accommodation coefficient (TAC), and latent heat of vaporization. Data analysis requires the use of spectroscopic models, used to convert the observed incandescence to a volume fraction or nanoparticle temperature, and heat transfer models, used to model the changes in the nanoparticle temperature over the duration of a signal. These models have evolved considerably over the past two decades, increasing the interpretive power of TiRe-LII. Nevertheless, there are several factors that impede further improvements to the reliability of TiRe-LII derived quantities. Several anomalies have been observed in measured signals collected from both engineered nanoparticle and soot, ranging from faster-than-expected temperature decays to inconsistencies in measurements between laboratories and experimental conditions. Resolving these differences is crucial to improving the robustness of TiRe-LII both as a combustion and engineered nanoparticle diagnostic. However, this first requires the development of advanced analysis tools that allow for a better understanding of nanoscale physics and the uncertainties associated with model development. This thesis presents several advances in the modeling and interpretation of TiRe-LII signals. The current state-of-the-art in TiRe-LII models is first established and the process of model inversion is discussed, with particular reference to uncertainty quantification within the Bayesian perspective. This lays the foundation for analysis of the measurement errors associated with TiRe-LII signals, providing practitioners with another source of information to characterize measurement devices and fluctuations in observed processes. Next, a novel approach to describe the relationship between the peak nanoparticle temperature and the laser fluence is derived. This allows the first comparison of fluence curves obtained using different instrumentation and under different measurement conditions. This dissertation proceeds by examining inversion of the spectroscopic model to determine both the nanoparticle temperature decay and the factor that scales emission from the nanoparticles to the observed signal. Unexpected temporal effects in the latter quantity are examined as an additional source of information that TiRe-LII practitioners can use for nanoparticle characterization and for diagnosing problems with measurement devices. Molecular dynamics simulations are employed to calculate the thermal accommodation coefficient, a parameter fundamental to the heat transfer model used in interpreting the inferred nanoparticle temperature decay, using the results are used in an analysis of TiRe-LII collected from iron, silver, and molybdenum nanoparticles. The cross-comparison of these materials highlights the utility of the developed analysis tools and provides fundamental insights into both nanoscale physics and bulk thermophysical properties. This dissertation concludes with a critical discussion of model development, emphasizing the importance of complexity and uncertainty in model selection. This is particularly important in the context of the context of the increasingly divergent set of TiRe-LII models available in the literature, indicative of model tuning. In summary, this dissertation not only presents direct improvements to the spectroscopic and heat transfer models used in traditional TiRe-LII analysis but also presents a set of new approaches by which the remaining challenges in TiRe-LII analysis can be resolved

Interlaboratory comparison of particle filtration efficiency testing equipment

This work presents the results of two interlaboratory comparisons of particle filtration efficiency measurements performed by a network of laboratories across Canada and Australia. Testing across multiple layers of a common verification material demonstrates a constant size-resolved quality factor when layering uncharged materials. Size-resolved filtration curves also match expectations, with increasingly size-dependent curves and a predictable increase in the PFE. Candidate reference materials with controlled material properties were also tested across multiple laboratories. Each set of materials sharing a common charge level show specific trends with the material basis weight. Respirators showed more consistency between the laboratories than the other filters. However, across a majority of the tests, dark uncertainties, which are otherwise unexplained variability between laboratories, are significant. This leaves room to improve the test method by developing improved verification procedures and additional reference materials.Comment: 14 pages, 8 figure

Systematic experimental comparison of particle filtration efficiency test methods for commercial respirators and face masks

Respirators, medical masks, and barrier face coverings all filter airborne particles using similar physical principles. However, they are tested for certification using a variety of standardized test methods, creating challenges for the comparison of differently certified products. We have performed systematic experiments to quantify and understand the differences between standardized test methods for N95 respirators (NIOSH TEB-APR-STP-0059 under US 42 CFR 84), medical face masks (ASTM F2299/F2100), and COVID-19-related barrier face coverings (ASTM F3502-21). Our experiments demonstrate the role of face velocity, particle properties (mean size, size variability, electric charge, density, and shape), measurement techniques, and environmental preconditioning. The measured filtration efficiency was most sensitive to changes in face velocity and particle charge. Relative to the NIOSH method, users of the ASTM F2299/F2100 method have commonly used non-neutralized (highly charged) aerosols as well as smaller face velocities, each of which may result in approximately 10% higher measured filtration efficiencies. In the NIOSH method, environmental conditioning at elevated humidity increased filtration efficiency in some commercial samples while decreasing it in others, indicating that measurement should be performed both with and without conditioning. More generally, our results provide an experimental basis for the comparison of respirators certified under various international methods, including FFP2, KN95, P2, Korea 1st Class, and DS2.Comment: 34 pages, 8 figures, 3 table

Relating the ultrasonic and aerosol filtration properties of filters

Abstract Non-contact methods are useful to improve the quality control of particle filtration media. The purpose of this paper is to investigate the correlation between the filtration efficiency of a porous sheet and its ultrasonic properties obtained using a non-contact technique. An air-coupled ultrasonic technique is used to obtain rapid measurements without affecting the integrity of the material. High frequencies (from 0.1 to 2.5 MHz) are used to improve technique sensitivity, and transmitted waves are measured to probe the internal properties of the material. Measurements of transmission coefficient spectra (amplitude and phase) and the corresponding ultrasound velocity and attenuation coefficient at different frequencies are obtained for a set of filtration media with well-characterized properties. Results show that the ultrasonic properties of filtration media vary as a function of basis weight, and therefore filtration efficiency, for a given charge state. However, the effect of electrostatic charge on ultrasonic propagation is almost negligible, as expected. We conclude that ultrasonic transmission may provide a valuable tool for the continuous online monitoring of material quality during fabrication and as a method to tease apart mechanical and electrostatic contributions to particle filtration

Rapid assessment of jet engine-like soot from combustion of conventional and sustainable aviation fuels using flame spray pyrolysis

Black carbon, or soot, is one of the highest contributors to global warming. The International Civil Aviation Organization (ICAO) has adopted regulatory standards for soot from aircraft engines, also referred to as a nonvolatile particulate matter (nvPM), to limit or reduce the harmful impacts of nvPM on the environment. Sustainable aviation fuels (SAF) offer advantages to reduce soot emissions and overall environmental impact but require extensive testing and evaluation before wider adoption. Typical measurements of soot produced by combustion of aviation fuels require full-sized jet engines and large volumes of fuel, which can be prohibitively expensive. This study investigates flame spray pyrolysis (FSP) as a simple bench-top tool for comparison of soot emissions from the combustion of different liquid jet fuels. A sampling assembly is designed for soot collection and analysis. Morphological analysis follows from transmission electron microscopy (TEM) image analysis and mobility (differential mobility analyzer) classification. Morphologies are compared to previous measurements from aircraft turbines. Soot agglomerate size distributions and elemental to total carbon ratios (EC/TC) are measured for three liquid fuels and flame conditions with Reynolds numbers and burner equivalence ratios ranging from 6100 to 9100 and 7 to 13, respectively. Day-to-day variations in the dilution ratio resulted in up to 20% variability in the measured total agglomerate number-based concentration and mobility diameter. Geometric mean primary particle and mobility diameter values are below 21 and 104 nm, respectively, in excellent agreement with those emitted from jet engines and prior work using FSP. EC/TC remains >0.75 for most flame conditions and fuels and increases with burner equivalence ratio, but values as low as 0.63 are measured from SAF combustion. Copyright © 2024 American Association for Aerosol Research</p

Morphology and size of soot from gas flares as a function of fuel and water addition

A large-scale, laboratory turbulent diffusion flame was used to study the effects of fuel composition on soot size and morphology. The burner and fuels are typical of those used in the upstream oil and gas industry for gas flaring, a practice commonly used to dispose of excess gaseous hydrocarbons. Fuels were characterized by their carbon-to-hydrogen ratio (from 0.264 to 0.369) and their volumetric higher heating value (HHVv) (from 35.8 to 75.2 MJ/m3). Transmission electron microscopy (TEM) was used to assess primary particle and aggregate size, showing that the scaling of primary particle size to aggregate size was roughly the same for all of the considered fuels (dp = 16.3(da,100 [nm]/100)0.35). However, fuels with higher HHVv produced substantially larger soot aggregates. A scanning mobility particle sizer (SMPS) was also used (i) to measure mobility diameter distributions and (ii) in tandem with a centrifugal particle mass analyzer (CPMA) to determine the two-dimensional mass-mobility and effective density-mobility distributions using a new inversion approach. The new approach was shown to improve internal consistency of inferred morphological parameters, though with a shift relative to median-based analysis of the tandem data. Raman spectroscopy was used to quantify the degree of graphitization in the soot nanostructure. The addition of water to the fuel consistently reduced the soot yields but did not affect other morphological parameters. Larger aggregates also tended to have larger primary particles and higher Raman D/G ratios suggesting larger graphitic domains