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Non-catalytic oxidation kinetics of diesel engine soot and more than a dozen commercial carbon black samples was investigated using non-isothermal and isothermal thermogravimetric analysis (TGA) experiments. The effect of various operating parameters, such as oxygen flow rate, initial sample mass, oxygen partial pressure, crucible type, and ramp rate, on the oxidation rate was investigated. Three types of TGA experiments (non-isothermal single-ramp rate, non-isothermal multiple-ramp rates, and isothermal) were conducted and analyzed to extract the kinetic parameters for oxidation. Activation energies for oxidation of carbon black samples ranged from 125 to 257 kJ/mol, whereas that for soot oxidation was ∼155 kJ/mol. Furthermore, oxidation rate trends were explained on the basis of structural characteristics, such as scanning electron microscopy (SEM)-based average particle size and Brunauer–Emmett–Teller (BET) surface area. In general, a low particle size and high surface area were associated with a higher oxidation rate and vice versa. A thorough understanding of the non-catalytic oxidation kinetics developed in this work along with the correlation of the oxidation rate with the structural parameters may assist in efficient oxidation of diesel engine soot during the regeneration of diesel particulate filters.

A silica-filled polydimethylsiloxane (PDMS) composite M9787 was investigated for potential outgassing in a vacuum/dry environment with the temperature programmed desorption/reaction method. The outgassing kinetics of 463 K vacuum heat-treated samples, vacuum heat-treated samples which were subsequently re-exposed to moisture, and untreated samples were extracted using the isoconversional and constrained iterative regression methods in a complementary fashion. Density functional theory (DFT) calculations of water interactions with a silica surface were also performed to provide insight into the structural motifs leading to the obtained kinetic parameters. Kinetic analysis/model revealed that no outgassing occurs from the vacuum heat-treated samples in subsequent vacuum/dry environment applications at room temperature (∼300 K). The main effect of re-exposure of the vacuum heat-treated samples to a glove box condition (∼30 ppm by volume of H2O) for even a couple of days was the formation, on the silica surface fillers, of ∼60 ppm by weight of physisorbed and loosely bonded moisture, which subsequently outgasses at room temperature in a vacuum/dry environment in a time span of 10 yr. However, without any vacuum heat treatment and even after 1 h of vacuum pump down, about 300 ppm by weight of H2O would be released from the PDMS in the next few hours. Thereafter the outgassing rate slows down substantially. The presented methodology of using the isoconversional kinetic analysis results and some appropriate nature of the reaction as the constraints for more accurate iterative regression analysis/deconvolution of complex kinetic spectra, and of checking the so-obtained results with first principle calculations such as DFT can serve as a template for treating other complex physical/chemical processes as well.

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Pd is more prone to sulfation compared to Pt. Given the chemical similarity between Pt and Pd, the radical divide in their tendencies for sulfation remains a puzzle. We explain this intriguing difference using an extensive first-principles thermodynamics analysis and computed bulk and surface phase diagrams. In practically relevant temperatures and O2 and SO3 partial pressures, we find that Pt and Pd show significantly different tendencies for oxidation and sulfation. PdO formation is favored even at low oxygen chemical potential; however, PtO2 formation is not favorable in catalytically relevant conditions. Similarly, PdSO4, and adsorbed SO3 and oxygen species on clean and oxidized surfaces are highly favored, whereas PtSO4 formation does not occur at typical temperature and pressure conditions. Finally, several descriptors are identified that correlate to heightened sulfation tendencies, such as the critical O chemical potential for bulk oxide and surface oxide formation, chemical potentials O and SO3 for bulk sulfate formation, and SO3 binding strength on metal surface-oxide layers, which can be used to explore promising sulfur resistant catalysts.

This work focuses on a comprehensive investigation of structure−activity relationships for a diesel engine soot sample (Corning) and 10 commercially available carbon black samples. Particle sizes were determined using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Specific surface area was determined by nitrogen sorption studies, while the microstructure was investigated by X-ray diffraction (XRD) peak profile analysis, Raman spectroscopy, and TEM. Oxidation activity of these samples was studied using thermogravimetric analysis (TGA) under an oxidative (10% O 2 ) environment consistent with the typical oxygen levels in the diesel engine exhaust. Various structural parameters, such as the average particle size, specific surface area, degree of organization, and average crystallite stacking height, were correlated with the TGA oxidation activity data. In general, samples with low particle size, high surface area, highly amorphous nature (low degree of organization), and low crystallite stacking height showed high oxidation activity. A second diesel engine soot sample (Corning), which was collected at different operating conditions, was used to validate the obtained structure−activity correlations. Overall, our rigorous analysis for a large number of samples with multiple techniques indicated unique and novel correlations/trends between soot structure and reactivity.

Moisture uptake and outgassing can be detrimental to a system by altering the chemical and mechanical properties of materials within the system over time. In this work, we conducted isotherm experiments to investigate dynamic moisture sorption and desorption in markedly different materials, i.e., a polymeric material, Sylgard-184 and a ceramic aluminosilicate material, Zircar RS-1200, at different temperatures (30 °C–70 °C) by varying the water activity (0.0–0.90). Sylgard-184 showed a linear sorption and outgassing behavior with no-hysteresis over the entire temperature and water activity range considered here. Whereas, the sorption and outgassing of Zircar RS-1200 was highly non-linear with significant hysteresis, especially at higher water activities, at all temperatures considered here. The type of hysteresis suggested the presence of mesopores in Zircar RS-1200, whereas the lack of hysteresis in Sylgard-184 indicates that it has a nonporous structure. A diffusion model coupled with a dynamic, triple-mode sorption (Langmuir, Henry, and pooling modes) model employed in this study matched our experimental data very well and provides mechanistic insight into the processes. Our triple-mode sorption model was adaptive enough to (1) model these distinctly different materials and (2) predict sorption and outgassing under conditions that are distinctly different from the parameterization experiments.

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