Measurement, Characterization, Identification and Control of Combustion Produced Soot

Open Access
Singh, Madhu
Graduate Program:
Energy and Mineral Engineering
Doctor of Philosophy
Document Type:
Date of Defense:
March 01, 2019
Committee Members:
  • Randy Lee Vander Wal, Dissertation Advisor
  • Randy Lee Vander Wal, Committee Chair
  • Chunshan Song, Committee Member
  • Ramakrishnan Rajagopalan, Committee Member
  • Patricia Silveyra, Outside Member
  • Carbon
  • Soot
  • Nanostructure
  • Microscopy
  • Spectroscopy
  • TEM
  • Carbon Black Functionalization
  • Laser-induced Incandescence
  • LII
  • Soot Source Identification
  • Laser Derivatization
  • Time-resolved LII
  • Carbon Characterization
  • Health effects of combustion soot
  • Cytotoxicity
  • Diesel Particulate Filter
  • DPF
  • Cell viability
  • BEAS-2B male lung cells
  • XPS
  • XRD
  • TGA
  • Soot oxidation
  • NO2 Oxidation
  • TiRe-LII
  • Carbonizaton
  • graphitization
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 soot’s 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 soot’s 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 material’s 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.