Engineering Papers⌕ Search

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.

At least 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Kinetic Control via Binding Sites within the Confined Space of Metal Metalloporphyrin-Frameworks for Enhanced Shape-Selectivity Catalysis

One striking feature of enzyme is its controllable ability to trap substrates via synergistic or cooperative binding in the enzymatic pocket, which renders the shape-selectivity of product by the confined spatial environment. The success of shape-selective catalysis relies on the ability of enzyme to tune the thermodynamics and kinetics for chemical reactions. In emulation of enzyme's ability, we showcase herein a targeting strategy with the substrate being anchored on the internal pore wall of metal-organic frameworks (MOFs), taking full advantage of the sterically kinetic control to achieve shape-selectivity for the reactions. For this purpose, a series of binding site-accessible metal metalloporphyrin-frameworks (MMPFs) have been investigated to shed light on the nature of enzyme-mimic catalysis. They exhibit a different density of binding sites that are well arranged into the nanospace with corresponding distances of opposite binding sites. Furthermore, such a structural specificity results in a facile switch in selectivity from an exclusive formation of the thermodynamically stable product to the kinetic product. Thus, the proposed targeting strategy, based on the combination of porous materials and binding events, paves a new way to develop highly efficient heterogeneous catalysts for shifting selectivity.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

Structures of strong shocks in low-density helium and neon gases

Strong shocks are essential components in many high-energy-density environments such as inertial confinement fusion implosions. However, the experimental measurements of the spatial structures of such shocks are sparse. In this paper, the soft x-ray emission of a shock front in a helium gas mixture (90% helium, 10% neon) and a pure neon gas was spatially resolved using an imaging spectrometer. We observe that the shock width in the helium mixture gas is about twice as large as in the pure neon gas. Moreover, they exhibit different precursor layers, where electron temperature greatly exceeds ion temperature, extending for more than ~350 µm with the helium gas mixture but less than 30 µm in the pure neon. At the shock front, calculations show that the electrons are strongly collisional with mean-free path two orders of magnitude shorter than the characteristic length of the shock. However, the helium ions can reach a kinetic regime as a consequence of their mean-free path being comparable to the scale of the shock. A radiation-hydrodynamic simulation demonstrates the impact of thermal conduction on the formation of the precursors with charge state, Z, playing a major role in heat flow and the precursor formation in both the helium mixture and the pure neon gases. Particle-in-cell simulations are also performed to study the ion kinetic effects on the formation of the observed precursors. A group of fast-streaming ions is observed leading the shock only in the helium gas mixture. Additionally, both effects explain the longer precursor layer in the helium shock.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Toward a Unified Kinetic Model of Nitrogenase Catalysis

The microbial enzyme nitrogenase catalyzes the MgATP-dependent reduction of N 2 to 2NH 3 , a transformation central to the global nitrogen cycle. While the canonical Thorneley−Lowe (TL) kinetic model has long served as a mechanistic framework, it does not incorporate several recent insights. Here, we present an updated kinetic model for Monitrogenase that incorporates these new findings. A significant insight is that electron transfer (ET) from the reduced Fe protein to the FeMo-cofactor is gated by MgATP-dependent conformational transitions and can be described as a probabilistic event that is dependent on the ligand bound to the active-site metallocofactor. The updated kinetic model quantitatively reproduces steady-state product formation rates across a broad range of experimental conditions, yielding revised estimates for key rate constants. It is demonstrated that under N 2 turnover, the probability of productive ET to the active site decreases by ∼60%, resulting in a significant fraction of Fe protein cycles that are unproductive for electron delivery. This mechanistic feature explains the observed rate limitation in N 2 reduction and implies a revised minimum energetic cost of approximately 25 MgATP per N 2 reduced. Integrating these new features into the revised kinetic model provides a more complete and usable foundation for understanding nitrogenase catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

Carbon deposition model for oxygen-hydrocarbon combustion. Task 6: Data analysis and formulation of an empirical model

The formation and deposition of carbon (soot) was studied in the Carbon Deposition Model for Oxygen-Hydrocarbon Combustion Program. An empirical, 1-D model for predicting soot formation and deposition in LO2/hydrocarbon gas generators/preburners was derived. The experimental data required to anchor the model were identified and a test program to obtain the data was defined. In support of the model development, cold flow mixing experiments using a high injection density injector were performed. The purpose of this investigation was to advance the state-of-the-art in LO2/hydrocarbon gas generator design by developing a reliable engineering model of gas generator operation. The model was formulated to account for the influences of fluid dynamics, chemical kinetics, and gas generator hardware design on soot formation and deposition.

Makel, Darby B.↗
DOE OSTI2024

Non-linear MHD modelling of transients in tokamaks: a review of recent advances with the JOREK code

Transient magneto-hydrodynamic (MHD) events like edge localized modes (ELMs) or disruptions are a concern for magnetic confinement fusion power plants. Research with the MHD code JOREK towards understanding control of such instabilities is reviewed here in a concise way to provide a complete overview, while we refer to the original publications for details. Experimental validation for unmitigated vertical displacement events progressed. The mechanism of vertical force mitigation by impurity injection was identified. Two-way eddy current coupling to CARIDDI was completed. Shattered pellet injection was simulated in JET, KSTAR, ASDEX Upgrade (AUG) and ITER. Benign runaway electron beam termination in JET and ITER was studied. Coupling of kinetic REs to the MHD is ongoing and a virtual RE synchrotron radiation diagnostic was developed. Regarding pedestal physics, regimes devoid of large ELMs in AUG were simulated and predictive JT60-SA simulations are ongoing. For ELM suppression by resonant magnetic perturbations (RMPs), AUG, ITER and EAST simulations were performed. A free boundary RMP model was validated against experiments. Evidence for penetrated magnetic islands at the pedestal top based on AUG experiments and simulations was found. Simulations of the naturally ELM-free quiescent H-mode in AUG and HL-3 show external kink mode formation prevents pedestal build-up towards an ELM within windows of the edge safety factor. With kinetic neutral particles, high field side high density formation in ITER was simulated and with kinetic impurities, tungsten transport in AUG RMP plasmas was studied. To capture turbulent transport, electro-static full-f particle in cell models for ion temperature gradient and trapped electron modes were established and benchmarked. Application to RMP plasmas shows enhanced turbulence in comparison to unperturbed states. Energetic particle interactions with MHD were studied. Flux pumping that prevents the safety factor on axis from dropping below unity was simulated. First non-linear stellarator applications include current relaxation in $l$ = 2 stellarators, while verification for advanced stellarators progresses.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Availability and reactivity of N 2 ( v ) for NH 3 synthesis by plasma catalysis

Production of vibrationally excited N 2 (N 2 (v)) in atmospheric pressure nonthermal plasma and loss of N 2 (v) by gas-phase reactions and reactions on catalytic surfaces are analyzed to examine the role of N 2 (v) in NH 3 formation by plasma catalysis. Vibrational state-to-state kinetic models complemented with molecular beam mass spectrometry (MBMS) measurements demonstrate that N 2 (v> 0) is produced with densities 100× greater than the density of N radicals by a radiofrequency atmospheric pressure plasma jet. The experimentally measured loss of N 2 (v) corresponds with a state-to-state kinetic model that describes loss of N 2 (v) by surface-mediated vibrational relaxation without consideration of reactions that convert N 2 (v) to NH 3 over the catalyst surface. Rate constants for vibrational relaxation of N 2 (v) on catalyst surfaces exceed upper bounds on proposed rate constants for NH 3 formation reactions from N 2 (v) over Fe when v < 9, Ni when v < 18, and Ag when v < 39, which indicates that only higher vibrational levels can possibly contribute to catalytic NH 3 formation faster than they undergo vibrational relaxation on the surface. Densities of N 2 (v> 8), vibrational levels that can possibly react over Fe to form NH 3 faster than they undergo vibrational relaxation, are less than or similar to N densities at the inlet of the catalyst bed and measured NH 3 formation for the investigated conditions in this work, while densities of N 2 (v> 17) and N 2 (v> 38) are orders of magnitude below the N density at the inlet of the catalyst bed and the measured NH 3 formation. The loss of N 2 (v) by vibrational relaxation on the surface limits the ability of N 2 (v) to contribute to catalytic NH 3 formation and explains why N 2 (v) does not produce NH 3 in quantities that are comparable to NH 3 formation from N even though N 2 (v > 0) is more abundantly produced by the plasma.

state-to-state kinetic modeling↗
DOE OSTI2021

Mechanisms and kinetics of citrate-promoted dissolution of a uranyl phosphate mineral

The formation of uranyl phosphate precipitates is a remediation strategy to limit the mobility of uranium in contaminated soils. However, exposure to organic ligands, like the plant exudate citrate, can remobilize the uranium. The purpose of this study is to provide a more thorough comprehension of citrate-promoted dissolution of a uranyl phosphate mineral, chernikovite [(H 3 O)(UO 2 )(PO 4 )·3H 2 O], by determining the extent of uranium release from chernikovite at a wide range of citrate concentrations. Here we have quantified the kinetics of dissolution and proposed potential mechanisms of chernikovite dissolution to gain a better understanding of the fate of uranyl phosphate precipitates in the environment. Batch dissolution and continuously stirred tank reactor (CSTR) experiments indicate that increasing citrate concentrations from 0.1 mM to 50 mM increases the concentration of dissolved uranium. However, at citrate concentrations of 10 mM and greater, the effectiveness of the ligand to enhance the dissolution decreases. Density functional theory modeling and Raman spectroscopy indicate a strong interaction between citrate and the uranyl ions at the surface of the uranyl phosphate. The interaction between citrate and uranyl suggests the formation of an alteration layer of uranyl-citrate surface complexes, which could impede uranium release at citrate concentrations of 10 mM or higher. Together, these results indicate that the citrate-promoted dissolution of chernikovite is a fast reaction that is hindered by a combination of surface saturation and a secondary-phase precipitation reaction at higher concentrations of citrate and reaction times greater than or equal to 72 min based on the hydraulic residence time of CSTR experiments. These findings improve our understanding of the stability of uranyl phosphate for use in sequestration of uranium groundwater plumes at contaminated sites.

58 GEOSCIENCES↗
NASA NTRS2014

Diffusivity in Alumina Scales Grown on Al-MAX Phases

Ti3AlC2, Ti2AlC, and Cr2AlC are oxidation resistant MAX phase compounds distinguished by the formation of protective Al2O3 scales with well controlled kinetics. A modified Wagner treatment was used to obtain interfacial grain boundary diffusivity, deltaD(sub gb,O,int.), from scale growth rates and corresponding grain size. It is based on the p(O2)(exp -1/6) dependency of the double charged oxygen vacancy and oxygen diffusivity, coupled with the effective diffusion constant for short circuit grain boundary paths. Data from the literature for MAX phases was analyzed accordingly, and deltaD(sub gb,O,int.) was found to nearly coincide with the Arrhenius line developed for Zr-doped FeCrAl, where: deltaD(sub gb,O,int.) = 1.8x10(exp -10) exp(-375 kJ/RT) cubic meters/s. Furthermore, this oxidation relation suggests the more general format applicable to bulk samples under ambient conditions: deltaD(sub gb,O) = 7.567x10(exp -8) exp(-544 kJ/RT) p(O2)(exp -1/6) cubic meters/[s x Pa(exp -1/6)]. Data from many other FeCrAl(X) studies were similarly assessed to show general agreement with the relation for deltaD(sub gb,O,int.). This analysis reinforces the view that protective alumina scales grow by similar mechanisms for these Al-MAX phases and oxidation resistant FeCrAl alloys.

aluminum oxide↗
NASA NTRS1987

Star formation around active galactic nuclei

Active galactic nuclei (Seyfert nuclei and their relatives) and intense star formation can both deliver substantial amounts of energy to the vicinity of a galactic nucleus. Many luminous nuclei have energetics dominated by one of these mechanisms, but detailed observations show that some have a mixture. Seeing both phenomena at once raises several interesting questions: (1) Is this a general property of some kinds of nuclei? How many AGNs have surround starbursts, and vice versa? (2) As in 1, how many undiscovered AGNs or starbursts are hidden by a more luminous instance of the other? (3) Does one cause the other, and by what means, or do both reflect common influences such as potential well shape or level of gas flow? (4) Can surrounding star formation tell us anything about the central active nuclei, such as lifetimes, kinetic energy output, or mechanical disturbance of the ISM? These are important points in the understanding of activity and star formation in galactic nuclei. Unfortunately, the observational ways of addressing them are as yet not well formulated. Some preliminary studies are reported, aimed at clarifying the issues involved in study of the relationships between stellar and nonstellar excitement in galactic nuclei.

Keel, William C.↗
NASA NTRS1999

Sources and sinks for ammonia and nitrite on the early Earth and the reaction of nitrite with ammonia

An analysis of sources and sinks for ammonia and nitrite on the early Earth was conducted. Rates of formation and destruction, and steady state concentrations of both species were determined by steady state kinetics. The importance of the reaction of nitrite with ammonia on the feasibility of ammonia formation from nitrite was evaluated. The analysis considered conditions such as temperature, ferrous iron concentration, and pH. For sinks we considered the reduction of nitrite to ammonia, reaction between nitrite and ammonia, photochemical destruction of both species, and destruction at hydrothermal vents. Under most environmental conditions, the primary sink for nitrite is reduction to ammonia. The reaction between ammonia and nitrite is not an important sink for either nitrite or ammonia. Destruction at hydrothermal vents is important at acidic pH's and at low ferrous iron concentrations. Photochemical destruction, even in a worst case scenario, is unimportant under many conditions except possibly under acidic, low iron concentration, or low temperature conditions. The primary sink for ammonia is photochemical destruction in the atmosphere. Under acidic conditions, more of the ammonia is tied up as ammonium (reducing its vapor pressure and keeping it in solution) and hydrothermal destruction becomes more important.

NASA Discipline Exobiology↗
NASA NTRS1974

Theoretical study of production of unique glasses in space

Analytical functional relationships describing homogeneous nucleation and crystallization in various supercooled liquids were developed. The time and temperature dependent relationships of nucleation and crystallization (intrinsic properties) are being used to relate glass forming tendency to extrinsic parameters such as cooling rate through computer simulation. Single oxide systems are being studied initially to aid in developing workable kinetic models and to indicate the primary materials parameters affecting glass formation. The theory and analytical expressions developed for simple systems is then extended to complex oxide systems. A thorough understanding of nucleation and crystallization kinetics of glass forming systems provides a priori knowledge of the ability of a given system to form a glass.

Larsen, D. C.↗
DOE OSTI2020

Conversion kinetics of container glass batch melting

Abstract Understanding the batch‐to‐glass conversion process is fundamental to optimizing the performance of glass‐melting furnaces and ensuring that furnace modeling can correctly predict the observed outcome when batch materials or furnace conditions change. To investigate the kinetics of silica dissolution, gas evolution, and primary foam formation and collapse, we performed X‐ray diffraction, thermal gravimetry, feed expansion tests, and evolved gas analysis of batch samples heated at several constant heating rates. We found that gas evolving reactions, foaming, and silica dissolution depend on the thermal history of the batch in a similar manner: the kinetic parameters of each process were linear functions of the square root of the heating rate. This kinetic similarity reflects the stronger‐than‐expected interdependence of these processes. On the basis of our results, we suggest that changes in furnace operating conditions, such as firing or boosting, influence the melting rate less than what one would expect without consideration of batch conversion kinetics.

Ueda, Nanako↗
NASA NTRS1950

The Effect of Ice Formations on Propeller Performance

Measurements of propeller efficiency loss due to ice formation are supplemented by an analysis to establish the magnitude of efficiency losses to be anticipated during flight in icing conditions. The measurements were made during flight in natural icing conditions; whereas the analysis consisted of an investIgation of changes in blade-section aerodynamic characteristics caused by ice formation and the resulting propeller efficiency changes. Agreement in the order of magnitude of eff 1- ciency losses to be expected is obtained between measured and analytical results. The results indicate that, in general, efficiency losses can be expected to be less than 10 percent; whereas maximum losses, which will be encountered only rarely, may be as high as 15 or 20 percent. Reported. losses larger than 15 or 20 percent, based on reductions in airplane performance, probably are due to ice accretions on other parts of the airplane. Blade-element theory is used in the analytical treatment, and calculations are made to show the degree to which the aerodynamic characteristics of a blade section. must be altered to produce various propeller efficiency losses. The effects of ice accretions on airfoil-section characteristics at subcritical speeds and their influence on drag-divergence Mach number are examined, and. the attendant maximum efficiency losses are computed. The effect of kinetic heating on the radial extent of ice formation is considered, and its influence on required length of blade heating shoes is discussed. It is demonstrated how the efficiency loss resulting from an icing encounter is influenced by the decisions of the pilot in adjusting the engine and propeller controls.

Neel, C. B., Jr.↗
DOE OSTI2026

Unraveling In-Situ Formation of Surface Nickel Nitride Structures in Plasma-Assisted Catalytic Ammonia Synthesis

We report the in situ formation of Ni nitride for plasma-assisted ammonia synthesis. Both the surface nitrogen concentration and the ammonia formation rate exhibit dependence on the N 2 :H 2 feed ratio. The maximum surface nitrogen concentration occurs at a N 2 :H 2 ratio of 4:1, and the maximum catalytic activity occurs at 2:1. In contrast, the formation of gas phase radicals is less sensitive to feed composition, indicating that Ni nitride is more kinetically relevant to ammonia production than gas-phase radicals. The plasma-induced formation of Ni nitride is therefore proposed to be a critical contributor to the synergistic effects in plasma-assisted catalytic ammonia synthesis. Additionally, Ni nitride alters the surface reaction mechanism of plasma-assisted ammonia synthesis, with the rate-determining-step (RDS) shifting to surface-bound NH 3 formation rather than N 2 activation at temperatures below 373 K. These findings provide mechanistic insight that opens opportunities for optimizing the performance of plasma-assisted catalytic ammonia synthesis

Ammonia↗
DOE OSTI2025

Ab initio prediction of rapid kinetics of Fe impurities in δ -Pu

Here, we study the formation energies of iron impurities in δ-Pu within spin–orbital-polarized density functional theory (SOP-DFT). The thermodynamic solubility limit of iron in δ-Pu is calculated, indicating low miscibility. We show that surprisingly, Fe impurities at equilibrium are almost equally likely to occupy octahedral interstitial sites or substitutional sites, with slight preference for the former. In contrast, we find the energy of the tetrahedral interstitial Fe to be nearly 1 eV higher than the octahedral one. We explore the energy landscape for Fe impurity hopping diffusion and conclude that Fe impurities in δ-Pu are divided into two populations: (i) Immobile substitutional Fe impurities and (ii) highly mobile interstitial Fe impurities. The latter, (ii), migrate between octahedral interstitial sites with an energy barrier of around 0.2 eV. The energy barrier for exchange between the two populations is calculated to exceed 0.7 eV. Finally, we discuss the role of magnetic order on the impurity energetics.

Atomic structure↗
DOE OSTI2023

Understanding the Polymorphism of Cobalt Nanoparticles Formed in Electrodeposition–An In Situ XRD Study

An advanced synchrotron-based in situ X-ray diffraction (XRD) technique is successfully developed and employed to track and monitor the formation and phase selection of cobalt (Co) in electrodeposition in real time and verify DFT computational results. The impacts of a number of controlling factors including the pH of the electrolyte and deposition overpotential are systematically studied. The results show that the yielded phase of the electrodeposited Co is controlled by both thermodynamics and kinetics. The low pH low overpotential condition favors the formation of the thermodynamically stable fcc phase. While the high pH high overpotential condition promotes the formation of the metastable hcp phase. The experimental results agree well with the nanometric phase diagram computed with DFT. Layer-by-layer alternative stacking of fcc-hcp polymorphic phases can be facilely fabricated by just varying the overpotential. This work not only offers an effective means to control the phase of electroplating of Co but also presents a new approach to reveal the fundamental insights of the formation of metals under electrochemical reduction driving force.

36 MATERIALS SCIENCE↗
NASA NTRS1989

Interstellar SiO as a tracer of high-temperature chemistry

A search for the J = 2-1 transition toward both hot and cold molecular gas is reported. SiO was observed toward all sources with kinetic temperatures greater than or equal to 30 K. No SiO was detected toward the dark clouds TMC-1, L134 N, and B335. The abundances of SiO relative to HCN and the SiO/H2 ratios are determined. A linear relation between the natural log of the SiO concentration and 1/Tk is found, suggesting that species formation involves a chemically specific process with an activation barrier of about 90 K. It is concluded that the formation of SiO is linked to the local gas kinetic temperature, rather than the oxygen abundance.

Ziurys, L. M.↗