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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.

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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Chemical kinetic studies of atmospheric reactions using tunable diode laser spectroscopy

IR absorption using tunable diode laser spectroscopy provides a sensitive and quantitative detection method for laboratory kinetic studies of atmospheric trace gases. Improvements in multipass cell design, real time signal processing, and computer controlled data acquisition and analysis have extended the applicability of the technique. We have developed several optical systems using off-axis resonator mirror designs which maximize path length while minimizing both the sample volume and the interference fringes inherent in conventional 'White' cells. Computerized signal processing using rapid scan (300 kHz), sweep integration with 100 percent duty cycle allows substantial noise reduction while retaining the advantages of using direct absorption for absolute absorbance measurements and simultaneous detection of multiple species. Peak heights and areas are determined by curve fitting using nonlinear least square methods. We have applied these techniques to measurements of: (1) heterogeneous uptake chemistry of atmospheric trace gases (HCl, H2O2, and N2O5) on aqueous and sulfuric acid droplets; (2) vapor pressure measurements of nitric acid and water over prototypical stratospheric aerosol (nitric acid trihydrate) surfaces; and (3) discharge flow tube kinetic studies of the HO2 radical using isotopic labeling for product channel and mechanistic analysis. Results from each of these areas demonstrate the versatility of TDL absorption spectroscopy for atmospheric chemistry applications.

Worsnop, Douglas R.↗
NASA NTRS1992

The present state and future directions of PDF methods

The objectives of the workshop are presented in viewgraph format, as is this entire article. The objectives are to discuss the present status and the future direction of various levels of engineering turbulence modeling related to Computational Fluid Dynamics (CFD) computations for propulsion; to assure that combustion is an essential part of propulsion; and to discuss Probability Density Function (PDF) methods for turbulent combustion. Essential to the integration of turbulent combustion models is the development of turbulent model, chemical kinetics, and numerical method. Some turbulent combustion models typically used in industry are the k-epsilon turbulent model, the equilibrium/mixing limited combustion, and the finite volume codes.

Pope, S. B.↗
NASA NTRS1968

Fundamental electrode kinetics

Report presents the fundamentals of electrode kinetics and the methods used in evaluating the characteristic parameters of rapid-charge transfer processes at electrode-electrolyte interfaces. The concept of electrode kinetics is outlined, followed by the principles underlying the experimental techniques for the investigation of electrode kinetics.

Elder, J. P.↗
DOE OSTI2025

Dehydroxylation kinetics of kaolinite and montmorillonite examined using isoconversional methods

The use of calcined clays as supplementary cementitious materials (SCMs) in concrete is a promising strategy towards decarbonizing the cement and concrete industry. This is especially relevant considering the ever-increasing demand for concrete. Comprehensive understanding of the kinetics of calcination is essential towards maximizing the potential reactivity of clay minerals while ensuring energy efficiency. In this study, the kinetics of the dehydroxylation of kaolinite and montmorillonite are investigated under non-isothermal conditions at constant heating rate. Activation energies ( E a ) are determined via Friedman differential and advanced Vyazovkin incremental methods over the isoconversional range; these are devoid of computational approximations, thus allowing kinetic analysis without assuming a specific reaction model. Kinetic equations—in the differential form as well as a combination of differential and integral forms are compared against the experimentally determined reaction models to identify the most probable dehydroxylation mechanism for kaolinite and montmorillonite. A reaction order mechanism is established for dehydroxylation of kaolinite, while montmorillonite is noted to undergo dehydroxylation via a single-step reversible diffusion-controlled process. Kinetic triplet—comprising activation energy, reaction model and pre-exponential factor—is used to predict isothermal calcination conditions, which is further verified using analytical techniques. Heat release rates of clay-portlandite blends from isothermal calorimetry are used within a thermodynamic framework to quantify reactivity of the calcined clays. Here, the study demonstrates a general approach based on isoconversional methods to predict calcination conditions for different clays that can be used in efficient and optimized production of blended cements or SCMs.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Synthesis pathways to thin films of stable layered nitrides

Controlled synthesis of metastable materials away from equilibrium is of interest in materials chemistry. Thin-film deposition methods with rapid condensation of vapour precursors can readily synthesize metastable phases but often struggle to yield the thermodynamic ground state. Growing thermodynamically stable structures using kinetically limited synthesis methods is important for practical applications in electronics and energy conversion. Here, in this study, we reveal a synthesis pathway to thermodynamically stable, ordered layered ternary nitride materials, and discuss why disordered metastable intermediate phases tend to form. We show that starting from elemental vapour precursors leads to a 3D long-range-disordered MgMoN 2 thin-film metastable intermediate structure, with a layered short-range order that has a low-energy transformation barrier to the layered 2D-like stable structure. This synthesis approach is extended to ScTaN 2 , MgWN 2 and MgTa 2 N 3 , and may lead to the synthesis of other layered nitride thin films with unique semiconducting and quantum properties.

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

Constraints on Triple Oxygen Isotope Kinetics

Triple oxygen isotope methods (e.g., using δ 18 O, and Δ′ 17 O) have been used to classify meteorites, to constrain atmospheric chemistry, and to estimate primary productivity, among other uses. Such utility relies on the mass dependency of most chemical reactions: δ 17 O is proportional to δ 18 O by roughly a factor of 0.5. However, in detail, mass-dependency factors vary. While constraints on mass dependency are well established for equilibrium isotope effects, similar constraints for kinetic isotope effects are lacking. Using an ab initio Monte Carlo approach (see envelopes in Figure 1), we find the range of kinetic isotope effects (i.e., resulting from unidirectional chemical reactions) contains and exceeds the range of accessible equilibrium isotope effects for the 16 O 17 O 18 O system (Hayles and Killingsworth, 2022). Accessible kinetic isotope effects can yield Δ′ 17 O variations as large 0.8 ‰ from a single kinetic fractionation step. Reactions that yield the largest deviations from equilibrium are those with the largest molecular mass difference between decomposition fragments, typically the two products such as a gas and solid generated from the thermal decomposition of an initial solid. Comparison of DFT transition state model results against previously published experiments on the thermal decomposition of calcite (CaCO 3 ) (Miller et al., 2002) and dehydroxylation of brucite (Mg(OH) 2 ) (Clayton and Mayeda, 2009) show they are matched with mass-dependent kinetic isotope effects. This approach can be applied to any system with more than two isotopes.

Oxygen isotopes↗
NASA NTRS1972

Biological effects of radiation, metabolic and replication kinetics alterations

The biological effects of radiation upon normal and cancerous tissues were studied. A macromolecular precursor of DNA, 3ETdR, was incorporated into the cell nucleus during synthesis and provided intranuclear beta radiation. Tritium labeled cells were studied with autoradiographic methods; cell cycle kinetics were determined and cell functions modified by radiation dosage or by drugs were also evaluated. The long term program has included; (1) effects of radiation on cell replication and the correlation with incorporated dose levels, (2) radiation induced changes in cell function, viz., the response of beta irradiated spleen lymphocytes to antigenic stimulation by sheep red blood cells (SRBC), (3) kinetics of tumor and normal cell replication; and (4) megakaryocyte formation and modification by radiomimetic drugs.

Post, J.↗
DOE OSTI2025

Revisiting a minimally destructive analytic approach for determining electrochemical kinetic parameters: Measuring aluminum corrosion across a wide pH range based on the Butler-Volmer equation

Here, this study revisits the three-point sampling of the simplified Butler-Volmer equation to address the limitations of strong potentiodynamic polarization, which can introduce irreversible damage and uncertainty in corrosion analysis. The method extracts electrochemical kinetic parameters while minimizing polarization effects, evaluates noise sensitivity relative to overpotential, and accounts for errors from signal noise, OCP drift, ohmic resistance, and mass-transfer constraints. Verified against the Tafel extrapolation method for aluminum corrosion across a wide pH range, this low-polarization approach enables accurate evaluations with specific error estimates, offering a robust alternative to linear polarization resistance methods that assume constant Tafel slopes.

36 MATERIALS SCIENCE↗
NASA NTRS1993

Temperature dependence of protein solubility-determination, application to crystallization, and growth kinetics studies

A scintillation method was developed for determinations of the temperature dependence of the solubility, and of nucleation induction times of proteins, in 50-100 mu(l) volumes of solution. Solubility data for lysozyme and horse serum albumin were obtained for various combinations of pH and precipitant concentrations. These data and the nucleation induction information were used for dynamic crystallization control, that is, for the controlled separation of nucleation and growth stages. Individual lysozyme and horse serum albumin crystals were grown in 15-20 mu(l) solution volumes contained in x-ray capillaries. The morphology and kinetics of the growth and dissolution of lysozyme in aqueous solutions with 2.5 percent NaCl and at pH = 4.5 was studied in situ with a depth resolution of 300 A (4 unit cells) by high resolution optical microscopy and digital image processing. The bulk super- or under saturation, sigma, of the solution inside a closed growth cell was controlled by temperature. The growth habit was bound by (110) and (101) faces that grew through layer spreading, although with different growth rate dependencies on supersaturation/temperature. At sigma less than 10 (obtained at higher temperatures) growth was purely kinetic ally controlled, with impurity effects (macrostep formation and kinetic hindrance) becoming significant for sigma less than 2. At sigma greater than 10 (lower temperatures), anisotropies in the interfacial kinetics were more pronounced, with interfacial kinetics and bulk transport becoming equally important to the growth morphology. Growth rates were growth history dependent. The formation of striations (layers of irregularly incorporated solution) was unambiguously correlated with growth temperature variations. Etching exposed dislocations and various high-index faces whose growth morphologies were studied during return to the steady state growth form. Growth steps were observed to originate from two-dimensional nuclei or from outcrops of growth striations, and from dislocations that preferentially formed in growth sector boundaries.

Rosenberger, Franz↗
NASA NTRS1991

Combustion kinetics and sensitivity analysis computations

The stiff ordinary differential equation solution methods more commonly used for chemical kinetics problems are examined, and the efficiency and accuracy of several of the methods are compared by applying them to two combustion kinetics problems. The local sensitivity analysis methods developed to date are outlined, and their advantages and difficulties are briefly discussed. Examples are used to make comparisons among the different techniques.

Radhakrishnan, K.↗
DOE OSTI2024

ELECTRONIC STRUCTURE METHODS AND PROTOCOLS WITH APPLICATION TO DYNAMICS, KINETICS AND THERMOCHEMISTRY

Hydrocarbon combustion involves the reaction dynamics of a tremendous number of species beginning with many-component fuel mixtures and proceeding via a complex system of intermediates to form primary and secondary products. Combustion conditions corresponding to new advanced engines and/or alternative fuels rely increasingly on autoignition and low-temperature-combustion chemistry. In these regimes various transient radical species such as HO2, ROO·, ·QOOH, HCO, NO2, HOCO, and Criegee intermediates play important roles in determining the detailed as well as more general dynamics. A clear understanding and accurate representation of these processes is needed for effective modeling. Given the difficulties associated with making reliable experimental measurements of these systems, computation can play an important role in developing these energy technologies. Accurate calculations have their own challenges since even within the simplest dynamical approximations such as transition state theory, the rates depend exponentially on critical barrier heights and these may be sensitive to the level of quantum chemistry. Moreover, it is well-known that in many cases it is necessary to go beyond statistical theories and consider the dynamics. Quantum tunneling, resonances, radiative transitions, and non-adiabatic effects governed by spin-orbit or derivative coupling can be determining factors in those dynamics. Building upon progress made during a period of prior support through the DOE Early Career Program, this project combines developments in the areas of potential energy surface (PES) fitting and multistate multireference quantum chemistry to allow spectroscopically and dynamically/kinetically accurate investigations of key molecular systems (such as those mentioned above), many of which are radicals with strong multireference character and have the possibility of multiple electronic states contributing to the observed dynamics. An ongoing area of investigation is to develop general strategies for robustly convergent electronic structure theory for global multichannel reactive surfaces including diabatization of energy and other relevant surfaces such as dipole transition. Combining advances in ab initio methods with automated interpolative PES fitting allows the construction of high-quality PESs (incorporating thousands of high-level data) to be done rapidly through parallel processing on high-performance computing (HPC) clusters. In addition, new methods and approaches to electronic structure theory will be developed and tested through applications. This project will explore limitations in traditional multireference calculations (e.g., MRCI) such as those imposed by internal contraction, lack of high-order correlation treatment and poor scaling. Methods such as DMRG-based extended active-space CASSCF and various Quantum Monte Carlo (QMC) methods will be applied (including VMC/DMC and FCIQMC). Insight into the relative significance of different orbital spaces and the robustness of application of these approaches on leadership class computing architectures will be gained. Synergy with other components of this research program such as automated PES fitting and multireference quantum chemistry will be used to address challenges encountered by the standard approaches to computational thermochemistry (those being single-reference quantum chemistry and perturbative treatments of the anharmonic vibrational energy, which break down for some cases of electronic structure or floppy strongly coupled vibrational modes).

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1979

Solution of Boltzmann equation for highly nonequilibrium diatomic gases rotational translational energy relaxation

The direct simulation Monte Carlo method is applied to solve the Boltzmann equation for collisions between internally excited diatomic gases in highly nonequilibrium states. The semiclassical transition probability is incorporated in the simulation for energy exchange between rotational and translational energy. The results provide details on the fundamental mechanisms of gas kinetics where analytical methods are impractical. The validity of the local Maxwellian assumption and relaxation time, rotational-translational energy transition, and a velocity analysis of the inelastic collision are discussed in detail.

Yoshikawa, K. K.↗
DOE OSTI2025

Kinetics of Pyrolysis and Thermal Evolution of Negev Desert Lithologies

The Negev desert in Israel is home to large quantities of organic-rich, shallow marine sedimentary lithologies that could potentially accommodate the disposal of spent nuclear fuel. Previous thermal analyses of Negev carbonates have focused on industrially relevant considerations such as natural gas and oil extraction or pyrolysis for recovering hydrocarbon fuels. Here, this study addresses thermal evolution of the Negev organic-rich carbonate, siliceous, and phosphorite rocks and associated chemical, mineralogical, and microstructural changes that may occur under prolonged thermal loading in the vicinity of spent nuclear fuel disposal systems. Our employed methods include high-temperature X-ray diffraction, high-temperature infrared spectroscopy, and thermal analysis integrating thermogravimetry, differential scanning calorimetry, and mass spectrometry. Further, we apply iterative iso-conversional model-free methods to derive kinetic parameters for thermal decomposition of the Negev organic-rich carbonate rocks from 200 to 550 °C. Our results have provided mechanistic insights into the thermal evolution encompassing water desorption, decomposition of organic matter, and decarbonation of carbonate phases.

58 GEOSCIENCES↗
DOE OSTI2024

Understanding and Tailoring Diffusion and Co-Adsorption Inside the Confined Pores of Metal-Organic Frameworks (Final Scientific/Technical Report for Award DE-SC0019902)

The aim of this program was to gain a fundamental understanding of the behavior of various guest molecules in nano-confined environments, such as metal organic frameworks (MOFs), using a combination of novel synthesis, ab initio modeling, and in situ characterization. Through this project, we developed a concise understanding of the mechanisms that control adsorption/desorption of gaseous molecules and their mixtures, leading to design/synthesis guidelines for MOFs with desired functionality. We further developed methods to disentangle kinetic from thermodynamic effects during adsorption, as well as to characterize the interactions at play. In the first funding cycle, the focus was on the unambiguously characterization of co-adsorption and diffusion of gasses/vapors and their mixtures. In the second funding cycle, the focus was on characterizing the effects of the nano-confinement on the kinetics and thermodynamics of adsorption processes inside MOFs, again with an emphasis on mixtures of gasses and vapors. The nano-confinement can tip the thermodynamic vs. kinetic balance, and current understanding and theory based on single-component analysis can lead to incorrect predictions for mixtures. This is of particular interest in real-world applications, where gasses/vapors are typically mixed, contain impurities, or are often exposed to humid conditions. Our main findings were: (i) within confined environments the adsorption behavior of mixed gasses/vapors can be drastically different from the “sum” of the corresponding single phases; (ii) co-adsorption is often competitive and detrimental to performance, but it can also be cooperative and beneficial; (iii) in some co-adsorbed gasses/vapors, molecules that are strongly bound in the single-component phase can be replaced by molecules that are nominally weaker bound (molecular exchange) due to guest-guest interactions that lower the kinetic barriers and favor the final adsorption state; (iv) kinetic and thermodynamic effects can be precisely controlled through pore-size engineering and synthesis; and, (v) kinetic effects can be identified and disentangled from thermodynamic effects during adsorption through a series of sequential and simultaneous gas loading measurements. The short-term goal of this program was the controlling and understanding of common MOF systems in real-world situations where gasses/vapors are mixed, which will have an important impact on industrial processes and applications from gas storage and sequestration to catalysis and sensors. The long-term goals include the development of theoretical and experimental methods for gaining a fundamental understanding of adsorption/reaction processes within MOFs, as well as new guidelines for synthesizing MOFs with tailored physical and chemical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Mechanism of Catechol Oxidation by the Coupled Bicupric Active Site of Tyrosinase: Completion of the Oxygenase/Oxidase Reaction Cycle

Tyrosinase contains a coupled binuclear copper (CBC) active site, which in its bicuprous form (deoxy-Ty) binds O 2 to form a side-on peroxide [Cu(II) 2 O 2 ] 2+ intermediate (oxy-Ty) that performs the regioselective monooxygenation of monophenols to catechols and their subsequent 2e − oxidation to quinones. Previously, we used spectroscopic, kinetic, and computational methods to elucidate the mechanism of the initial steps in the monooxygenation reaction. Herein, we investigated the final step in catecholate formation and provide experimental and computational results elucidating the catechol oxidation reaction, formally a proton-coupled 2e − process. We employed single-turnover stoppedflow absorption to observe the elusive catecholate-Cu(II) 2 OH intermediate via the anaerobic reaction of resting Cu(II) 2 OH Ty (met-Ty) with the catecholate substrate. This intermediate was cryo-trapped and characterized by electron paramagnetic resonance and X-ray absorption spectroscopies. These experimental results were correlated to quantum mechanics/molecular mechanics (QM/MM) and QM calculations to describe the complete catalytic cycle of tyrosinase, revealing that the 2e − oxidation of catechol to quinone involves two steps: (i) coupled 1H + /1e − transfer from the bound monoanionic catecholate to the bridged hydroxide of the met-Ty active site, followed by (ii) the second 1e − transfer. The latter is calculated to be the rate-limiting step in catechol oxidation, confirmed by experimental solvent kinetic isotope effect studies. Our computational data suggest that quinone release from the protein provides the necessary driving force for this reaction. These results establish a detailed description of this oxidase cycle of the tyrosinase mechanism and more broadly provide molecular-level insights into the diverse reactivity of CBC sites in biology.

QM/MM modeling↗
DOE OSTI2026

Diffusion of NiH on Ni(111) and of Ni with Adsorbed H on Ni(111) in the Context of Ni Coarsening in Solid Oxide Cells

In the Ni-based hydrogen electrode of a solid oxide cell (SOC), Ni coarsening is an important degradation mechanism and could be enhanced by NiH diffusing on the Ni particle surfaces. Here, in this work, the average lifetime and diffusion distance of NiH on Ni(111) are computed using density-functional theory and kinetic Monte Carlo methods. It is found that NiH is extremely short-lived and, thus, cannot promote coarsening in the SOC. Also, the diffusion of Ni on Ni(111) is shown to be at most slightly accelerated by H along NiH dissociation paths involving the movement of Ni with a nearby H. Based on this result, coarsening is not likely to be dramatically accelerated by the diffusion of Ni with H on Ni(111). However, support is provided for the experimental procedure of measuring the product of surface coverage and single-species diffusivity of Ni on Ni(111) in a hydrogen-rich atmosphere.

Ni coarsening↗