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Author: Cornelia Irimiea Publisher: ISBN: Category : Languages : en Pages : 0
Book Description
Combustion impacts many important aspects of our life like the air quality, the local and global climate and the use of energy sources. In the last decades, an outstanding progress towards cleaner combustion has been achieved. However, the reaction pathways leading to the formation of some pollutants, especially particulate matter (soot) resulting from incomplete combustion, are still elusive. In this work, we aim to investigate specific aspects of soot and its precursors formation in laboratory flames for a fundamental understanding of the mechanisms leading from the gas phase up to the mature particulate found in the exhausts. This objective is also pursued in field-campaigns to assess the potential impact of soot surface properties on the environment. Following this approach, experimental techniques like in-situ laser induced incandescence and fluorescence, and ex-situ laser desorption and secondary ion mass spectrometry are used to target specific properties of soot and its precursors. Notably, the evolution of the complex refractive index of soot is measured as a function of soot maturity, and the implications on both the flame physico-chemistry and the analytical techniques applicability are discussed. Additionally, a new detection method for soot and precursors based on simultaneous excitation at one wavelength is developed. In parallel, two campaigns are dedicated to the analysis of the surface chemistry of soot sampled from airplane and car exhausts. Statistical methods as multivariate analysis are used to identify patterns and differences within sets of samples by assessing the influence of the combustion parameters or the role of the fuel.
Author: Cornelia Irimiea Publisher: ISBN: Category : Languages : en Pages : 0
Book Description
Combustion impacts many important aspects of our life like the air quality, the local and global climate and the use of energy sources. In the last decades, an outstanding progress towards cleaner combustion has been achieved. However, the reaction pathways leading to the formation of some pollutants, especially particulate matter (soot) resulting from incomplete combustion, are still elusive. In this work, we aim to investigate specific aspects of soot and its precursors formation in laboratory flames for a fundamental understanding of the mechanisms leading from the gas phase up to the mature particulate found in the exhausts. This objective is also pursued in field-campaigns to assess the potential impact of soot surface properties on the environment. Following this approach, experimental techniques like in-situ laser induced incandescence and fluorescence, and ex-situ laser desorption and secondary ion mass spectrometry are used to target specific properties of soot and its precursors. Notably, the evolution of the complex refractive index of soot is measured as a function of soot maturity, and the implications on both the flame physico-chemistry and the analytical techniques applicability are discussed. Additionally, a new detection method for soot and precursors based on simultaneous excitation at one wavelength is developed. In parallel, two campaigns are dedicated to the analysis of the surface chemistry of soot sampled from airplane and car exhausts. Statistical methods as multivariate analysis are used to identify patterns and differences within sets of samples by assessing the influence of the combustion parameters or the role of the fuel.
Author: Thi Linh Dan Ngo Publisher: ISBN: Category : Languages : en Pages : 0
Book Description
Interest in biofuels has increased significantly in recent years as they could reduce dependence on fossil fuels and contribute to carbon-neutral growth. The influence of using biofuels on their exhaust emissions (CO,CO_2,NO_x,HC, etc.) has been studied widely. However, the effects of the nature of these alternative fuels on the physical and chemical properties of the particles and aromatic species produced are not fully understood. As part of this thesis work, we aim to study the emissions of soot particles and polycyclic aromatic hydrocarbons (PAHs) during the combustion of conventional and alternative fuels (biofuels) relevant to the automotive and aerospace sectors, while trying to highlight their influence on the formation of such pollutants. To achieve this goal, two laboratory combustors, a swirled turbulent jet burner and a Combustion Aerosol STandard (CAST), were used as soot generators. In addition, we have combined various complementary in-situ laser techniques, laser-induced incandescence and fluorescence (LII/LIF), and ex-situ two-step laser mass spectrometry (L2MS) and secondary ion mass spectrometry (SIMS). In a swirled turbulent jet flame for five fuels (Diesel, n-butanol, 50/50 Diesel/n-butanol mixture, Jet A1 and Synthetic Paraffinic Kerosene SPK), the LII and LIF profiles and properties of soot particles and their precursors with the height in the flame as well as their chemical composition were studied. Strong correlations between the results obtained with in-situ and ex-situ techniques have been demonstrated which allowed us to characterize these species spectrally and chemically. In addition, a new calibration method has been developed to directly deduce the soot volume fraction from the LII signal using the absolute radiance emitted from a light source having black body behavior. In parallel, experiments using the CAST device were conducted with aeronautical fuels (Jet A1 and SPK). In addition to the influence of the alternative fuel, the effects of a catalytic stripper (CS) on soot particles and volatile species were examined.
Author: Chethan Gaddam Publisher: ISBN: Category : Languages : en Pages :
Book Description
Combustion produced soot is highly variable with nanostructure and chemistry dependent upon combustion conditions and fuel. Previous studies have shown soot nanostructure to be dependent upon the source via quantification of high-resolution transmission electron microscopy (HRTEM) images for nanostructural parameters. In principle this permits identification of the soot source and its contribution to any particular receptor site. Yet many structural aspects are subtle, and the chemistry of lamellae is unaddressed for reasons of poorly resolved or differentiated nanostructure and insufficient sample quantity for traditional analytical methods. This characterization gap then leads to the formative question prompting this study: how best to bring out small differences in nanostructure and other seemingly subtle differences in chemistry? A process of pulsed laser annealing is proposed to highlight compositional and structural differences thereby distinctively and uniquely identifying the source of the soot. The operative premise being that small variations in nanostructure and unresolved differences in chemistry exist and are specific to the particular combustion process. The overall goal is then to develop the laser-based heating as an analytical tool by identifying the process conditions and operational parameters for optimal derivatization. Specific objectives directed towards achieving this goal include: 1)Identifying optimal laser operational parameters for derivatization. 2)Defining the dependence upon nanostructure and molecular composition using model soots while also identifying variability and range of outcomes. 3)Demonstrating differentiation upon combustion derived soots from real engines, e.g. diesel, gasoline, gas-turbines, combustors, etc.4)Applying image processing algorithms to the laser heated soots to quantify and differentiate the transformed carbon nanostructures.For laser derivatization, a sample-housing chamber was custom built using a commercial optical grade quartz tube. Depending on the sample quantity, two different sample support systems were designed. Soot was laser-heated while in an inert (Ar) atmosphere using a pulsed Nd:YAG laser operating at 1064 nm. A laser beam dimension of ca 9 mm in diameter ensured that the entire sample area received uniform irradiation. To identify the optimal laser fluence, pulsed laser heating was applied at three different laser fluences to three carbon samples. Laser heating at these short timescales produced partially graphitized structures comprised of extended graphitic layers (>1 nm), and voids as material is rearranged. While laser heating the material with additional pulses did further graphitize the material, multiple pulses were not particularly beneficial for laser derivatization as this repetitive exposure decreased the degree of differentiation between the test samples. Based on visual HRTEM observations and quantified fringe analysis, a single pulse laser fluence of 250 mJ/cm2 (~2800 K, determined from multi-wavelength pyrommetry) produced the best derivatization without causing fragmentation or material ablation. For demonstrating the uniqueness of the laser-derivatized (nano)structure as dependent upon source and combustion conditions, the laser derivatization technique was validated by comparing different synthetic carbons, selected soots from transportation and residential combustion sources, and laboratory flames, each with recognizable nanostructure. After laser heating, the direction of nanostructure evolution of the synthetic carbons (possessing C:H > 10:1) appeared to be governed by their initial nanostructure as shown by HRTEM images. As illustration of chemistry's role, though nascent R250 carbon black showed structural similarity across multiple particles, laser heating led to either hollow shells or particles with internal structures. These differences were attributed to the chemistry of construction, i.e., the sp2/sp3 bonding as quantified by electron energy loss spectroscopy (EELS), showing significant differences between particles as large as 60%. The nanostructure of soots from different transportation sources (such as diesel, jet and gasoline engines) evolved distinctively upon laser annealing. Laser derivatization of soot collected from same platform (engine-type) revealed that fuel commonality leads to similar nanostructure for the same class of combustion source, whereas, fuel dependence and ensuing chemistry differences were prominently illustrated by comparison of laser-annealed soots originating from ultra-low sulfur diesel (ULSD) and an oxygenated fuel blend. The origin for this dependence was identified by X-ray photoelectron spectroscopy (XPS), revealing a significantly lower sp2/sp3 carbon bonding for the oxygenated fuels compared to their pure hydrocarbon fuels. As another example, laser annealing of residential boiler soot produced highly intertwined lamellae; this was attributed to inherent chemistry differences relative to the biodiesel (B100) soot that similarly lacked recognizable nanostructure. These observations suggest that the initial soot nanostructure in conjunction with the chemistry of construction governs the material transformation under pulsed laser annealing. Image processing algorithms were applied to quantify and differentiate the carbon nanostructural changes after laser annealing. A "recognition key" approach using a combination of present quantification algorithms: 1) fringe analysis, 2) stacking distribution, and 3) void dimension was reported for two laser-heated carbons, as examples. A second, method, using the radial intensity profile generated from the Fourier-Transformed bright field image was implemented to identify soot source upon laser derivatization against a reference set of values in a database. This semi-automated analytical method involves conversion of HRTEM images into the frequency domain, band-pass filtering, radial intensity profiling, and identification by least squares comparison with an empirically set limit for the sum of residuals. To illustrate the analytical methodology for source identification, a mixture of three soots was analyzed by laser derivatization. Laser heating led to visual differences; further quantification and comparison to the database identified the respective sources.
Author: Madhu Singh Publisher: ISBN: Category : Languages : en Pages :
Book Description
The negative health implications associated with combustion produced soot demand identification of contributing sources, quantification and characterization of their emissions to assess its impact, and control to minimize the imposed hazard. Distinguishing different sources of soot from engines and combustors is challenging, given the morphological and chemical similarity of the emitted soot. Leaner combustion conditions and tighter emission limits challenge traditional filter-based measurements for soot mass. Meanwhile, current after-treatment particulate control strategies are based on regeneration, i.e., soot oxidation which in turn depends upon soot nanostructure and composition (such as in a diesel particulate filter). Presently, effects on human health associated with soot exposure are largely correlative, while controlled lab studies predominantly use varied washings or extracts of soot, but rarely the actual particulate. Given the intertwined nature of these topics this dissertation addresses each in an integrated approach. Laser-induced incandescence (LII) is used to determine soot concentration while Time-resolved LII (TiRe-LII) can be used to estimate soot primary particle size largely by using available and appropriate models. The use of laser diagnostics has been used to experimentally demonstrate prevailing inconsistencies between experimentally measured and model-derived particle diameter values. Discrepancies have been attributed (a) to the empiricism associated with evaluating modeling variables and (b) to the lack of proper accountability of the changes in soot nanostructure upon heating with a pulsed laser. This work uses an experimental approach coupled with microscopy to (a) test the robustness of existing LII models and (b) inform existing models of experimental observations so that these can be accounted for in future models. Specifically, the contribution of changing soot nanostructure on laser heating is known and is shown here again with transmission electron microscopy (TEM). However, the change in soots optical properties because of an altered nanostructure remains unclear. Optical properties change when soot is laser-heated, and this alteration of optical properties upon laser heat treatment has been shown in this work experimentally, by using UV-Vis spectroscopy. Also, the effect of the degree of aggregation on the soots cooling profile is highlighted. This work demonstrates that different degrees of aggregation results in a shift of the time-temperature-history (TTH), thereby resulting in erroneous particle size predictions, which are calculated from the materials TTH. Unfortunately, most models assume point-contacting spheres and aggregation remains unaccounted for. The effect of the thermal accommodation coefficient is similar in that a small change in the value of this mathematical parameter significantly alters particle cooling as simulated here by an open-access simulator, indicating the need to exercise caution when assigning a value to this parameter in the model. While the change in soot nanostructure as a consequence of laser annealing complicates the interpretation from LII measurements, laser heating of soot can reciprocally be used to purposefully study the evolution in soot nanostructure as a function of its chemistry. Soot chemistry varies with its combustion environment, with fuel and combustion conditions specific to each source. Thus, by association, the evolution of soot nanostructure observed upon laser heat treatment can be correlated to its fuel origins and combustion origins, potentially identifying its formation source. Fundamentally, the presence of oxygen in nascent soot is identified here as a key compositional parameter. The increase in oxygen content of the fuel, as diesel is blended with increased proportions of biofuel, is correlated to increased oxygen content in the soot that is generated by the respective fuel. In other words, fuel with a higher oxygen content generates soot which also has oxygen content relatively higher than soot generated by fuel with low oxygen content. This work shows that oxygen dictates the evolution of soot nanostructure when it escapes the material upon laser heat treatment. When laser heated, the nanostructure of soot with a higher oxygen content evolves as hollow-shell like structures while nanostructure of soot with a low oxygen content evolves to show a ribbon-like interior. This divergence in soot nanostructure based on the oxygen content of nascent soot, which in turn is shown to be a function of the fuel composition, could be used to identify the source that generated the soot sample studied. Given the lack of availability of authentic soot samples, the combination of laser heat treatment and TEM of soot to identify fuel or source is powerful when sample quantities are in the range of less than a few nanograms. Being able to identify sources and their contributions using laser derivatization of soot as a diagnostic can help optimize new or existing control measures to reduce the concentration of atmospheric soot. For instance, diesel particulate filters (DPFs) are used to reduce diesel soot emissions. Effective protocols for DPF operation can be developed by understanding soot nanostructure changes as captured soot is oxidized during passive and active DPF regeneration. Typically, O2, NO2 or a combination of the two oxidants are encountered during DPF regeneration. In this work, soot nanostructure has been shown to vary with the order of oxidants to which it is exposed, a significant finding towards optimizing DPF filter regeneration protocols. The study has been performed on authentic diesel soot in a thermogravimetric analyzer under conditions mimicking active and passive regeneration in a DPF. To validate observations with diesel soot, three carbon blacks with varying nanostructure are also subjected to oxidation by O2 and NO2. The intriguing result is that order of oxidation matters, i.e., the oxidation rates are dependent upon nanostructure changes in response to oxidation by O2 alone, or O2 with NO2.Prolonged exposure to particulate matter causes unwanted ill-health, lung dysfunctions, and breathing problems. Most toxicity studies are done using a washing, or an extract of the organic fraction of soot and cells are exposed to this extract. This work tests the adverse effect of soot on human (male) lung cells when these are exposed to surrogate soot as is, i.e., structure and chemistry intact to mimic real-time exposure conditions. The impact of soot chemistry and the presence of acidic functional groups on lung epithelial cells for varying exposure times is demonstrated in our collaborative work with the College of Medicine at Penn State, Hershey, PA. Soot chemistry is shown to directly and adversely impact cell viability and mRNA expressions of the IL-1B and IL-6 cytokines as well as mRNA expression of the TLR4 protein. Specifically, cell viability was shown to reduce significantly after 6- and 24-hours of exposure to carboxylic groups on the soot, thereby demonstrating the health impact of soot surface chemistry in comparison to extracts.In summary, soot measurement, its extensive characterization to identify source contributions and develop practically applicable control strategies has a direct implication on our health and surroundings and can aid in promoting a healthy living environment.
Author: Sandra Török Publisher: ISBN: 9789178959716 Category : Languages : en Pages :
Book Description
The formation path from small poorly absorbing incipient soot to larger fractal-like strongly absorbing black soot is extensive, and along this path the optical and physicochemical properties of the soot evolve. Soot emitted into the atmosphere may originate from some stage of this process, which will result in a wide spectrum of carbonaceous aerosols in the atmosphere which may interact with the sun and influence the radiative balance of the earth.?In this work, differently matured soot from a mini-CAST soot generator was studied in terms of optical properties and the relation to its physicochemical properties. Various optical diagnostic tools, mainly multi-wavelength extinction, elastic light scattering (ELS), and laser-induced incandescence (LII), but also complementary aerosol instrumentation, were used for these purposes. These tools have provided generic information about soot properties, and additionally the applicability of the methods for soot analysis has been evaluated.?Soot from the mini-CAST was found to have properties which range from nm-sized soot with optical properties of brown carbon (BrC) to larger soot aggregates of black carbon (BC) type. It was shown that the BrC type of soot had a refractory soot core with properties similar to young soot. Hence, it was shown to not consist of a BC core with a BrC like coating. Also it was shown that upon heating during thermo-optical analysis in an inert atmosphere that the BrC soot transformed and became more absorbing.?LII was used to study the optical properties of soot, and it was shown that the optical properties of mature soot agreed well with results from extinction measurements, but for young soot LII results indicated absorption of slightly more mature soot character. Further analysis of the temperature evolution of the soot in the low fluence regime allowed for estimation of the soot absorption efficiency. Results showed large differences in absorption efficiencies for the differently matured soot and values for the mature soot agreed well with values presented in the literature.?Double-pulse LII experiments showed how rapid laser heating induced changes in soot of different maturity. It was shown that the absorption properties were enhanced as a result of thermal annealing for all soot with the strongest effect for young soot. Another effect for young soot (using LII at 532 nm excitation) was an increased fluorescence from vaporized fragments that potentially can interfere with the detection of LII signals.?A nephelometer was used to study the elastic scattering by soot particles, and it was investigated if scattering theory could be used to solve the inverse problem and obtain information on the morphological properties. The method appeared feasible as tests revealed good results when compared to results based on micrograph image analysis. The method may be useful for estimation of morphological properties of fractal-like soot, as it provides a faster and less elaborate estimation than microscopy analysis.?The findings of this work contribute to the understanding of how differently matured soot interact with electromagnetic radiation, especially for the laser-induced incandescence method. Hence information has been gained on how to optimise the diagnostic potential of LII as well as on limitations in the diagnostics of soot of different maturity.?
Author: Kenneth Brezinsky Publisher: Elsevier ISBN: 0323993109 Category : Science Languages : en Pages : 666
Book Description
As the demands for cleaner, more efficient, reduced and zero carbon emitting transportation increase, the traditional focus of Combustion Chemistry research is stretching and adapting to help provide solutions to these contemporary issues. Combustion Chemistry and the Carbon Neutral Future: What will the Next 25 Years of Research Require? presents a guide to current research in the field and an exploration of possible future steps as we move towards cleaner, greener and reduced carbon combustion chemistry. Beginning with a discussion of engine emissions and soot, the book goes on to discuss a range of alternative fuels, including hydrogen, ammonia, small alcohols and other bio-oxygenates, natural gas, syngas and synthesized hydrocarbon fuels. Methods for predicting and improving efficiency and sustainability, such as low temperature and catalytic combustion, chemical looping, supercritical fluid combustion, and diagnostic monitoring even at high pressure, are then explored. Some novel aspects of biomass derived aviation fuels and combustion synthesis are also covered. Combining the knowledge and experience of an interdisciplinary team of experts in the field, Combustion Chemistry and the Carbon Neutral Future: What will the Next 25 Years of Research Require? is an insightful guide to current and future focus areas for combustion chemistry researchers in line with the transition to greener, cleaner technologies. Provides insight on current developments in combustion chemistry as a tool for supporting a reduced-carbon future Reviews modeling and diagnostic tools, in addition to key approaches and alternative fuels Includes projections for the future from leaders in the field, pointing current and prospective researchers to potentially fruitful areas for exploration
Author: Publisher: ISBN: Category : Carbonization Languages : en Pages : 0
Book Description
This research has provided an understanding of the formation of earliest soot particles (soot precursor particles) in combustion processes, and thus indicates strategies to intervene in their formation in various types of combustion devices. Major progress was achieved in characterizing the chemical composition and the carbonization of soot precursor particles that have been found in laboratory flames. The use of TEN has permitted the observation of precursor particles in flames fueled by CH4, C2H4 and C2H2. The transformation of the liquid-like precursor particles into solid clustered aggregates by the carbonization process was displayed. The conversion kinetics of carbonization ere studied because this process converts the young more easily oxidized young particles into the more inert carbonaceous aggregates that are likely to be released to the surroundings. A major effort was in the area of chemical analysis of the precursor particles as studied by use of the LANMA-500 instrument at the NIST. These studies revealed the precursor particles to consist of PAHs and that these compounds are embers of the stabilomer classes predicted by Stein and Fahr to be the most chemically stable. Our last task has related to the development of crystallinity in precursor particles and in carbonaceous aggregates formed in hydrocarbon combustion.
Author: Cornelia Irimiea
Author: Cornelia Irimiea
Author: Thi Linh Dan Ngo
Author: Chethan Gaddam
Author: K. R. McManus
Author: Madhu Singh
Author: 
Author: Sandra Török
Author: Kenneth Brezinsky
Author: Alexandre Dias Flügel
Author: