Application of Soot Carbonization Kinetics to Deduce Meaningful Soot Formation Rates in Premixed Flat Flames
Explore the source record for details and available documents.
Shaddix, Christopher R. [Sandia National Laborator↗
SEARCH · Engineering Papers
Results for “formation kinetics”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
The interplay of thermodynamics and kinetics: imparting hierarchical control over film formation of self-stratified blends
Neutron reflectivity provide a thorough understanding of the balance of thermodynamic and kinetic factors that influence the stratification of spin cast polymer blend thin films, including blend composition, polymer chain length, and casting speed.
Rinehart, Samantha J.↗
Cations Affect Water Activation on Pt(111) in Alkaline Media
Water activation, oxidatively to produce surface-bound hydroxide (OH*) or reductively to form surface-bound hydrogen (H*) atoms, is ubiquitous in electrocatalysis. We report the impact of cations on the kinetics of the OH* and H* formation from water on single-crystal Pt(111) in alkaline using fast-scan-rate cyclic voltammetry. Isolating the dependence of the electro-adsorption kinetics on pH and ionic strength led to the observation that ion concentrations affected the OH* formation kinetics more strongly than pH. The H* formation exhibited similar behavior, even though the OH* formation rate was observed to be faster by >10x. We attributed the observed ion concentration effect to cations, given that switching cations (from Na + to Li + ) had a bigger impact on the H* and OH* formation rates than switching pH (effectively changing OH – to F – ). We hypothesize the cations softened and allowed the interfacial water layer to more easily reorganize. This result suggests that interfacial water disruption should benefit both H* and OH* electro-adsorption kinetics in alkaline electrolytes.
Lin, Chia-Yi [Cornell Univ., Ithaca, NY (United St↗
Skyrmion lattice formation and destruction mechanisms probed with TR-SANS
Magnetic skyrmions are topologically protected, nanoscale whirls of the spin configuration that tend to form hexagonally ordered arrays. As a topologically non-trivial structure, the nucleation and annihilation of the skyrmion, as well as the interaction between skyrmions, varies from conventional magnetic systems. Recent works have suggested that the ordering kinetics in these materials occur over millisecond or longer timescales, which is unusually slow for magnetic dynamics. The current work investigates the skyrmion ordering kinetics, particularly during lattice formation and destruction, using time-resolved small angle neutron scattering (TR-SANS). Evaluating the time-resolved structure and intensity of the neutron diffraction pattern reveals the evolving real-space structure of the skyrmion lattice and the timeframe of the formation. Measurements were performed on three prototypical skyrmion materials: MnSi, (Fe,Co)Si, and Cu 2 OSeO 3 . To probe lattice formation and destruction kinetics, the systems were prepared in the stable skyrmion state, and then a square-wave magnetic field modulation was applied. The measurements show that the skyrmions quickly form ordered domains, with a significant distribution in lattice parameters, which then converge to the final structure; the results confirm the slow kinetics, with formation times between 10 ms and 99 ms. Comparisons are made between the measured formation times and the fundamental material properties, suggesting the ordering temperature, saturation magnetization and magnetocrystalline anisotropy may be driving the timeframes. Micromagnetic simulations were also performed and support a scaling of the kinetics with sample volume, a behavior which is caused by the reconciling of misaligned domains.
Liyanage, W. L. N. C.↗
The formation and shape transformation mechanism of triangular Au nanoplate revealed by liquid-cell TEM
We report two different fromation mechanisms of triangular Au nanoplate through transformation of truncated octahedron and the direct formation and growth of triangular seed using liquid-cell TEM. This work stresses the great significances of thermodynamics and kinetics in the formation of triangular nanoplate and shape transformation.
Jin, Biao↗
Chemical interactions in the aluminum-carbon and aluminum-silicon carbide systems
XPS was used to investigate the influence of O2 and H2O on the formation of aluminum carbide at Al-C and Al-SiC interfaces. It was determined that dosing the interfaces with H2O catalyzed the formation of aluminum carbide in both systems. This result is consistent with the oxidation model of carbide formation (developed to understand the kinetics of aluminum carbide formation at graphite-aluminum interfaces). These results imply that the formation of aluminum carbide in graphite- and SiC-reinforced metal-matrix composites, which severely degrades the composite mechanical properties by degrading the fiber and interface strength is catalyzed.
Maruyama, Benji↗
Experimental and theoretical studies of NO/x/ formation in a jet-stirred combustor.
As an approach to testing kinetic models which couple NO formation to combustion reactions, a jet-stirred combustor was used to study NO(x) formation under kinetically controlled combustion conditions. The experimental data were compared with kinetic calculations for a well-stirred reactor. The agreement between theory and experiment was quite good for the combustion of hydrogen/air and carbon monoxide/air, for which detailed mechanisms were used. A quasi-global mechanism for the combustion of propane/air resulted in substantial underprediction of NO(x) formation.
Engleman, V. S.↗
Storing hydrogen in the form of light alloy hydrides
Different hydrides are investigated to find a system with a sufficiently high storage density (at least 3%). The formation of hydrides with light alloys is examined. Reaction kinetics for hydride formation were defined and applied to the systems Mg-Al-H, Mg-Al-Cu-H, Ti-Al-H, Ti-Al-Cu-H, and Ti-Al-Ni-H. Results indicate that the addition of Al destabilizes MgH2 and TiH2 hydrides while having only a limited effect on the storage density.
Freund, E.↗
Formation of distinctive nanostructured metastable polymorphs mediated by kinetic transition pathways in germanium
High-pressure β -Sn germanium may transform into diverse metastable allotropes with distinctive nanostructures and unique physical properties via multiple pathways under decompression. However, the mechanism and transition kinetics remain poorly understood. Here, we investigate the formation of metastable phases and nanostructures in germanium via controllable transition pathways of β -Sn Ge under rapid decompression at different rates. High-resolution transmission electron microscopy reveals three distinct metastable phases with the distinctive nanostructures: an almost perfect st12 Ge crystal, nanosized bc8/r8 structures with amorphous boundaries, and amorphous Ge with nanosized clusters (0.8–2.5 nm). Fast in situ x-ray diffraction and x-ray absorption measurements indicate that these nanostructured products form in certain pressure regions via distinct kinetic pathways and are strongly correlated with nucleation rates and electronic transitions mediated by compression rate, temperature, and stress. This work provides deep insight into the controllable synthesis of metastable materials with unique crystal symmetries and nanostructures for potential applications.
36 MATERIALS SCIENCE↗
Condensation in CO2 free jet expansions. I - Dimer formation.
A theoretical and experimental investigation of the kinetics of CO2 dimer formation in the adiabatically expanding core of a free jet expansion has been carried out. The theoretical analysis is based on dimer formation by an efficient termolecular process and dimer destruction by bimolecular collisions. Account is taken of the expected variation of the specific heat ratio during the expansion and of the effective increase in the termolecular collision rate at low temperatures due to the presence of loosely bound orbiting pairs. Experimental dimer concentrations were measured mass spectrometrically by forming a molecular beam from the expanded gas mixture after the onset of molecular flow. Observed dimer concentrations, for a range of pre-expansion conditions of 400 to 900 torr pressure and room temperature, are in good agreement with the theoretical analysis, provided that account is taken of the effect of loosely bound orbiting pairs at low temperatures.
Dorfeld, W. G.↗
Rejoining and misrejoining of radiation-induced chromatin breaks. II. Biophysical Model
A biophysical model for the kinetics of the formation of radiation-induced chromosome aberrations is developed to account for the recent experimental results obtained with a combination of the premature chromosome condensation (PCC) and fluorescence in situ hybridization (FISH) techniques. In this model, we consider the broken ends of DNA double-strand breaks (DSBs) to be reactant and make use of the interaction distance hypothesis. The repair/misrepair process between broken ends is suggested to consist of two steps; the first step represents the two break ends approaching each other, and the second step represents the enzymatic processes leading to DNA end-to-end rejoining. Only the second step is reflected in the kinetics observed in experiments using PCC. The model appears to be able to fit existing data for human cells. It is shown that the kinetics of the formation of chromosome aberrations can be explained by a single rate that characterizes both rejoining and misrejoining of DSBs, suggesting that repair and misrepair share the same mechanism. Fast repair (completed in minutes) in a subset of DSBs is suggested as an explanation of the complete exchanges observed with PCC in human lymphocytes immediately after irradiation. The fast repair component seems to be absent in human fibroblasts.
NASA Center JSC↗
Electromagnetic studies of redox systems for energy storage
Both chromium and iron couples were studied on various electrode surfaces in acidic perchlorate solution by using rotating ring-disk techniques. It was found that chloride which forms inner sphere coordination complexes with the redox species enhances the electrode kinetics dramatically. The effects of lead underpotential deposition and surface alloy formation on the kinetics of the chromium couple on gold were studied using both linear sweep voltammetry and potential step techniques. The lad underpotential deposition was found to slow down the kinetics of the reduction of the Cr species on gold surfaces although increase the hydrogen overvoltage. The effect on the chromium kinetics can be explained in terms of principally a double layer effect. The underpotential deposition lead species with its positive charge results in a decrease in the concentration of the Cr species at the electrode surface. Similar phenomena were also observed with bismuth underpotential deposition on gold for the iron couple.
Wu, C. D.↗
Kinetics and Thermochemistry of Reversible Adduct Formation in the Reaction of Cl((sup 2)P(sub J)) with CS2
Reversible adduct formation in the reaction of Cl((sup 2)P(sub J)) with CS2 has been observed over the temperature range 193-258 K by use of time-resolved resonance fluorescence spectroscopy to follow the decay of pulsed-laser-generated Cl((sup 2)P(sub J)) into equilbrium with CS2Cl. Rate coefficients for CS2Cl formation and decomposition have been determined as a function of temperature and pressure; hence, the equilbrium constant has been determined as a function of temperature. A second-law analysis of the temperature dependence of Kp and heat capacity corrections calculated with use of an assumed CS2Cl structure yields the following thermodynamic parameters for the association reaction: Delta-H(sub 298) = -10.5 +/- 0.5 kcal/mol, Delta-H(sub 0) = -9.5 +/- 0.7 kcal/mol, Delta-S(sub 298) = -26.8 +/- 2.4 cal/mol.deg., and Delta-H(sub f,298)(CS2Cl) = 46.4 +/- 0.6 kcal/mol. The resonance fluorescence detection scheme has been adapted to allow detection of Cl((sup 2)P(sub J)) in the presence of large concentrations of O2, thus allowing the CS2Cl + Cl + O2 reaction to be investigated. We find that the rate coefficient for CS2Cl + O2 reaction via all channels that do not generate Cl((sup 2)P(sub J)) is less than 2.5 x 10(exp-16) cu cm/(molecule.s) at 293 K and 300-Torr total pressure and that the total rate coefficient is less than 2 x 10 (exp -15) cu cm/(molecule.s) at 230 K and 30-Torr total pressure. Evidence for reversible adduct formation in the reaction of Cl((sup 2)P(sub J)) with COS was sought but not observed, even at temperatures as low as 194 K.
Nicovich, J. M.↗
Visualizing the SEI formation between lithium metal and solid-state electrolyte
The solid electrolyte interphase (SEI) is regarded as the most important factor affecting the durability of lithium-metal anode in all-solid-state batteries (ASSBs). Despite its significance, the nucleation and growth mechanism of SEI is not yet well understood. Here, we elucidate the thermodynamics and kinetics governing SEI formation at the Li|β-Li 3 PS 4 interface at the atomic scale via thermodynamic phase equilibrium analysis and machine-learning-potential-assisted molecular dynamics (MD) simulations. An accurate moment tensor potential using the machine-learning method is developed for a reactive model of Li|β-Li 3 PS 4 . This potential enabled us to perform large-scale MD simulations with the model size expanded to the experimental dimensions (~40 nm) while maintaining the same level of accuracy as density functional theory calculations. The results reveal a four-stage evolution process at the Li|β-Li 3 PS 4 interface, namely (i) fast ion diffusion, (ii) nucleation, (iii) Li 2 S growth, and (iv) stabilization. Notably, we demonstrate that the SEI can be categorized into crystalline and amorphous regions. The simulated SEI thickness, structure, and composition closely match experimental findings, validating the accuracy of the MD simulations. We further disclose the significant impact of ion diffusion kinetic limitations on the phase formation and crystallization of interfacial products. Furthermore, we shed light on the detailed potential energy (PE) distribution of lithium along the direction perpendicular to the interface. Finally, this information is crucial for better understanding interfacial ion mobility.
25 ENERGY STORAGE↗
Gas Hydrate Film Growth in Microfluidic Channels for Carbon Dioxide Capture and Sequestration Applications
Gas or clathrate hydrates are a solid, crystalline compound composed of water and guest molecules that typically form at high pressure and low temperature conditions. Carbon dioxide (CO2) hydrates may be involved in several carbon dioxide capture and sequestration (CCS) applications, including CO2 pipeline transportation and CO2 offshore sequestration. Within these applications, the formation mechanism and kinetics must be well understood to manage the CCS processes, either by preventing or promoting hydrate formation. In this work, a high-pressure glass microfluidic reactor is used in tandem with visual microscopy and in-situ Raman spectroscopy to study both the morphological and kinetic behavior of gas hydrate crystals. Subcooling, pressure, and CO2 flow rate are investigated for their impact on the thickening behavior of pure CO2 hydrates, with flow rate being the only parameter to have a significant effect. Visual and Raman spectroscopy evidence show that both a dense hydrate layer and a porous hydrate layer form, and the latter may provide a path for mass transfer to continue hydrate crystallization. A first principles mass transfer model is developed to describe CO2 hydrate crystal thickening at the interface between gas and water. The impacts of gas impurities and channel wettability are also studied. This method is further applied to investigate the conversion of methane hydrate to CO2 hydrate for combined energy recovery and methane hydrate formation. The authors acknowledge the US Department of Energy Basic Energy Science award # DE-SC0022162.
Wadsworth, Lindsey [Colorado School of Mines, Gold↗
Measurements and Modeling of Nitric Oxide Formation in Counterflow, Premixed CH4/O2/N2 Flames
Laser-induced fluorescence (LIF) measurements of NO concentration in a variety of CH4/O2/N2 flames are used to evaluate the chemical kinetics of NO formation. The analysis begins with previous measurements in flat, laminar, premixed CH4/O2/N2 flames stabilized on a water-cooled McKenna burner at pressures ranging from 1 to 14.6 atm, equivalence ratios from 0.5 to 1.6, and volumetric nitrogen/oxygen dilution ratios of 2.2, 3.1 and 3.76. These measured results are compared to predictions to determine the capabilities and limitations of the comprehensive kinetic mechanism developed by the Gas Research Institute (GRI), version 2.11. The model is shown to predict well the qualitative trends of NO formation in lean-premixed flames, while quantitatively underpredicting NO concentration by 30-50%. For rich flames, the model is unable to even qualitatively match the experimental results. These flames were found to be limited by low temperatures and an inability to separate the flame from the burner surface. In response to these limitations, a counterflow burner was designed for use in opposed premixed flame studies. A new LIF calibration technique was developed and applied to obtain quantitative measurements of NO concentration in laminar, counterflow premixed, CH4/O2/N2 flames at pressures ranging from 1 to 5.1 atm, equivalence ratios of 0.6 to 1.5, and an N2/O2 dilution ratio of 3.76. The counterflow premixed flame measurements are combined with measurements in burner-stabilized premixed flames and counterflow diffusion flames to build a comprehensive database for analysis of the GRI kinetic mechanism. Pathways, quantitative reaction path and sensitivity analyses are applied to the GRI mechanism for these flame conditions. The prompt NO mechanism is found to severely underpredict the amount of NO formed in rich premixed and nitrogen-diluted diffusion flames. This underprediction is traced to uncertainties in the CH kinetics as well as in the nitrogen oxidation chemistry. Suggestions are made which significantly improve the predictive capability of the GRI mechanism in near-stoichiometric, rich, premixed flames and in atmospheric-pressure, diffusion flames. However, the modified reaction mechanism is unable to model the formation of NO in ultra-rich, premixed or in high-pressure, nonpremixed flames, thus indicating the need for additional study under these conditions.
Thomsen, D. Douglas↗
Theoretical assessments of CO 2 activation and hydrogenation pathways on transition-metal surfaces
Carbon dioxide (CO 2 ) hydrogenation on transition-metal active sites offers a promising carbon utilization route toward mitigating greenhouse gas emissions. C 1 products are often formed in parallel during CO 2 hydrogenation, prompting investigations into the intrinsic properties of transition metals that drive activity and product selectivity. Here, in this work, close-packed surfaces of a selection of transition-metal catalysts (Ni, Co, Rh, Ru, Pd, and Pt) were studied with density functional theory (DFT) calculations to understand their fundamental reactivities for CO 2 transformation reactions. Results indicate that CO 2 conversion proceeds through CO* formation and hydrogenation to form C 1 products (* denotes an adsorbed species). Ni, Co, Rh, and Ru favor CO/CH 4 formation, while Pd and Pt favor CO/CH 3 OH formation. The ability of a metal to dissociate C-O bonds drives selectivity between CH 4 and CH 3 OH, while competition between CO* desorption and surface hydrogenation describes CO selectivities. The C-O bond dissociation steps often impose the highest barrier along CH 4 formation reaction profiles, suggesting their kinetic relevance for CH 4 formation rates. The provided DFT-derived data sets detail a comprehensive reaction network of elementary steps relevant to C 1 chemistries, ultimately offering a benchmark for insights into design strategies for materials that exploit transition-metal active sites in carbon capture or utilization processes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗