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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Computational and Experimental Investigation of Thermal-Mechanical- Chemical Mechanisms of High-burnup Spent Nuclear Fuel (SNF) Processes at Elevated Temperatures and Degradation Behavior in Geologic Repositories

The overarching goal of the combined computational and experimental R&D activities proposed in this project is to enhance understanding of the mechanisms and thermal-mechanical-chemical (TMC) parameters controlling the instant release fraction (IRF) and matrix dissolution of high-burnup (HB; burnup) spent nuclear fuels (SNFs) and the subsequent formation, stability, and phase transformations of SNF alteration products under long-term storage and geological disposal conditions. Uranium dioxide may undergo oxidative corrosion/alteration, and the IRF may be increased for HB SNF, both of which may affect environmental systems associated with SNF long-term storage and disposal. The oxidative matrix dissolution may form various complex uranyl-based phases, including a rich variety of oxides, silicates, carbonates and other secondary minerals in varied geological environments (e.g., studtite, metastudtite, amorphous uranyl peroxide, uranium trioxide, triuranium octoxide, schoepite, dehydrated schoepite, metaschoepite, becquerelite, soddyite, rutherfordine,...). These uranyl phases generally have higher mobility UO 2 +2 species than less soluble U 4+ phases. However, limited information on the thermodynamic properties and formation kinetics of these uranyl-bearing phases is available to predict explicitly paragenesis under the conditions relevant to long-term storage or disposal. The proposed project draws on complementary expertise and research backgrounds from the team members: (i) to apply a combined ab initio modeling (UNLV/UTEP and SNL) and experimental (UNLV) strategy investigating the high-temperature TMC mechanisms of alteration of SNF under α-radiolysis conditions; (ii) to investigate the mechanistic of phase transformations in UNF degradation products under various conditions expected in long-term storage systems (e.g. (UO 2 )O 2 (H 2 O) 4 → (UO 2 )O 2 (H 2 O) 2 → U 2 O 7 → UO 3 → U 3 O 8 ); (iii) to determine high-accuracy TMC parameters for complex uranyl-based phases formed in storage or geological disposal environments (e.g. UO 3 (H 2 O) 2 , Ca[(UO 2 ) 6 O 4 (OH) 8 ] 8 H 2 O, (UO 2 ) 2 (SiO 4 ) 3 2H 2 O,…). The unforeseen COVID-19 pandemic led to the laboratory/campus closure since March 2020, that resulted in a significant delay in reaching milestones in a satisfactory manner, due to (i) the statewide recommendation from stop-working to later limited work in the lab and work-from-home (WFH), (ii) no in-person interactions, and (iii) a hiring freeze at UNLV. Therefore, a no cost extension (10/01/2021- 9/30/2022) was requested to help make up the time we lost during the global pandemic in 2020-2021, leading to paradigm shifts in the focus of the project in the following three main tasks: Task 1 (Computational), Task 2 (Experimental), and Task 3 (Final report, due on 12/29/2022).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Diffraction Measurement of Reaction Products in Shock Compressed TATB on the NIF

The shock-induced reaction of high explosives to gaseous and solid reaction products is a rapid, complex process. Understanding solid reaction product structure and formation kinetics is essential in determining the high-pressure equation of state of these multicomponent systems. We use the National Ignition Facility (NIF) to shock compress ~500-µm thick pressed powder high-explosive TATB samples to 70-135 GPa and collect in situ structural data on detonation byproducts using the TARDIS X-ray diffraction diagnostic. Velocimetry is used to record the transmitted compression wave profile, which is well described by Cheetah hydrocode simulations coupled with a reactive flow model, providing strong evidence of reaction in the TATB sample. While an unambiguous determination of the product phases was not possible owing to the low signal-to-noise quality of the diffraction signal, X-ray diffraction data of the product phases formed within the first 50 ns of the reaction is most consistent with a mixture of amorphous products and crystalline hexagonal diamond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

Studies of clusters in the gas phase and application to an understanding of transitions from gaseous to the surface and condensed state

Studies of the structure, stability, electronic properties, and formation kinetics of small clusters were reviewed which provide information useful in furthering understanding of nucleation processes, liquid state properties, and the nature of surfaces. Using mass spectrometric coupled with various high pressure ion clustering and Stark effect-molecular beam techniques, the details of the primary clustering steps leading to the nucleation of bulk liquid from the vapor were and obtained by direct observation results are presented.

Castleman, A. W., Jr.↗
NASA NTRS1989

The role of interfacial dislocation networks in high temperature creep of superalloys

The dislocation networks generated during high-temperature creep of several single-crystal nickel-based superalloys are analyzed. The networks continually evolve during creep at relatively low temperatures or eventually reach a more stable configuration at high temperatures. Specifically, the role of these networks in directional coarsening processes are studied, along with their formation kinetics, characteristics, and stability during creep. The results of this study combined with previous findings suggest that the directional coarsening process is strongly influenced by elastic strain energy. The dislocation networks formed during primary creep are found to be stable during all subsequent creep stages. Aspects of these dislocation networks are determined to be a product of both the applied creep stress and coherency strains.

Gabb, T. P.↗
NASA NTRS1997

Mixing of Pure Air Jets with a Reacting Fuel-Rich Crossflow

Jets in a crossflow play an integral role in practical combustion systems such as can and annular gas turbine combustors in conventional systems, and the Rich-burn/Quick-mix/Lean-burn (RQL) combustor utilized in stationary applications and proposed for advanced subsonic and supersonic transports. The success of the RQL combustor rests with the performance of the quick-mixing section that bridges the rich and lean zones. The mixing of jet air with a rich crossflow to bring the reaction to completion in the lean zone must be performed rapidly and thoroughly in order to decrease the extent of near-stoichiometric fluid pocket formation. Fluid pockets at near-stoichiometric equivalence ratios are undesirable because the high temperatures attained accelerate pollutant formation kinetics associated with nitric oxide (NO). The present study develops a model experiment designed to reveal the processes that occur when jet air is introduced into hot effluent emanating from a fuel-rich reaction zone.

Leong, M. Y.↗
NASA NTRS1999

Thermophysical Property Measurements of Molten Semiconductors in 1-g and Reduced-g Condition

Understanding and controlling the formation kinetics of varieties of crystal imperfections such as point defects, non uniform distribution of doping atoms, and impurity atoms in growing crystals are very important. Theoretical (numerical) modeling of the crystal growth process is an essential step to achieving these objectives. In order to obtain reliable modeling results, input parameters, i.e. various thermophysical parameters, must be accurate. The importance of accurate thermophysical properties of semiconductors in crystal growth cannot be overly emphasized. The total hemispherical emissivity, for instance, has a dramatic impact on the thermal environment. It determines the radiative emission from the surface of the melt which determines to a large extent the profile of the solidified crystal. In order to understand the convection and the turbulence in a melt, viscosity becomes an important parameter. The liquid surface tension determines the shape of the liquid-atmosphere interface near the solid-liquid-atmosphere triple point. Currently used values for these parameters are rather inaccurate, and this program intends to provide more reliable measurements of these thermophysical properties. Thus, the objective of this program is in the accurate measurements of various thermophysical properties which can be reliably used in the modeling of various crystal growth processes. In this program, thermophysical properties of molten semiconductors, such as Si, Ge, Si-Ge, and InSb will be measured as a function of temperature using the High Temperature Electrostatic Levitator at JPL. Each material will be doped by different kinds of impurities at various doping levels. Thermophysical properties which will be measured include: density, thermal expansion coefficient, surface tension, viscosity, specific heat, hemispherical total emissivity, and perhaps electrical and thermal conductivities. Many molten semiconductors are chemically reactive with crucibles. As a result, these dispersed impurities in the melts tend to substantially modify the properties of pure semiconductors. Sample levitation done in a vacuum clearly helps maintain the sample purity. However, in the 1-g environment, all gravity caused effects such as convection, sedimentation and buoyancy are still present in the sample. In addition, large forces needed to levitate a sample in the presence of the gravity can cause additional flows in the melt. The use of the High Temperature Electrostatic Levitator (HTESL) for the present research is a recent development and little is known about the flows induced by the electrostatic forces. In this ground base program, we will define the limits of HTESL technology as various thermophysical properties of molten semiconductors are measured.

Rhim, Won-Kyu↗
NASA NTRS2023

Parameter Dependencies of Early-Stage Tangential Discontinuity-Driven Foreshock Bubbles in Local Hybrid Simulations

Foreshock bubbles (FBs) are significant foreshock transients that can accelerate particles and disturb the magnetosphere-ionosphere system. In the kinetic formation model, foreshock ions interact with the discontinuity by performing partial gyrations to generate currents that change the magnetic field topology around the discontinuity. However, how different foreshock ion properties affect the growth of the field variations is not well understood. Therefore, we use 2-D local hybrid simulations to study the effects of different foreshock ion distributions and properties on the growth of tangential discontinuity (TD)-driven FBs. We discover that for a gyrophase-bunched distribution with an initial phase where the guiding center is on the other side of the TD, the foreshock ions gyrate together across the TD, causing more foreshock ions to cross the TD and leading to a faster expansion of the structure than for a Maxwellian distribution. A ring distribution also yields higher expansion speeds because of the higher projected velocity into the new perpendicular direction. For Maxwellian distributions, there are positive and linear correlations of the FB expansion speeds with the initial foreshock ion densities, thermal speeds, parallel speeds, and sine of the TD magnetic shear angles. These parameter dependencies grow in strength as the structures evolve with time. The foreshock ion distributions and properties that lead to stronger currents produce more significant magnetic field variations and higher expansion speeds. Our study helps quantify the formation and expansion of FBs to forecast their space weather effects and contribution to shock acceleration.

Andrew Vu↗
NASA NTRS1993

The kinetics of composite particle formation during mechanical alloying

The kinetics of composite particle formation during attritor milling of insoluble binary elemental powders have been examined. The effects of processing conditions (i.e., mill power, temperature, and charge ratio) on these kinetics were studied. Particle size distributions and fractions of elemental and composite particles were determined as functions of milling time and processing conditions. This allowed the deduction of phenomenological rate constants describing the propensity for fracture and welding during processing. For the mill-operating conditions investigated, the number of particles in the mill generally decreased with milling time, indicating a greater tendency for particle welding than fracture. Moreover, a bimodal size distribution is often obtained as a result of preferential welding. Copper and chromium 'alloy' primarily by encapsulation of Cr particles within Cu. This form of alloying also occurs in Cu-Nb alloys processed at low mill power and/or for short milling times. For other conditions, however, Cu-Nb alloys develop a lamellar morphology characteristic of mechanically alloyed two-phase ductile metals. Increasing mill power or charge (ball-to-powder weight) ratio (CR) increases the rate of composite particle formation.

Aikin, B. J. M.↗
DOE OSTI2025

Investigating Kinetic Mechanisms of Soot Formation in Plasma Pyrolysis of Methane via Active Learning (Final Technical Report)

Plasma pyrolysis of methane is an effective route for zero-carbon hydrogen production. Yet, soot generated from pyrolysis of hydrocarbons is detrimental to the climate and human health. There is ample experimental and theoretical evidence that suggests polycyclic aromatic hydrocarbons (PAHs) are the molecular precursors to soot particles. The reaction pathways of PAH formation are intricately dependent on a multitude of process parameters, whose kinetic mechanisms are not well-understood in plasma pyrolysis. This project aims to leverage advances in the kinetic modeling of soot formation in combustion, as well as in surrogate modeling and active learning, to systematically investigate the effects of process parameter on the kinetics of PAH formation in plasma pyrolysis of methane. To this end, we propose to use the PAH formation kinetics model developed by the PPPL/PU group based on the well-established ABF and HACA mechanisms, coupled with low-temperature plasma models. We will develop an active learning (AL) framework based on Bayesian optimization to systematically and data-efficiently explore the complex and multivariable parameter space of plasma pyrolysis in order to quantify the effects of plasma and feed parameters on the ABF and HACA kinetic pathways. AL is the branch of machine learning concerned with systematically querying samples from a system (experimental or computational) to train a data-driven model that maps design parameters to a performance criterion. We will use the data generated via AL to perform global sensitivity analysis, combined with uncertainty quantification, to elucidate the impact of different reaction pathways on minimizing formation of soot precursors. This study will result in an improved understanding of kinetics of PAH formation in plasma pyrolysis and can pave the way for more advanced mechanistic studies (e.g., soot nucleation mechanisms). Additionally, the findings will be useful for establishing practical strategies for increasing the pyrolysis efficiency and producing high-grade carbon for synthesis of nanomaterials.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Surface Crust Formation Controls Evaporation Kinetics of Secondary Organic Aerosols

Gas-particle partitioning is critical for the evolution of secondary organic aerosols (SOA) in the atmosphere. SOA particles evaporate more slowly than expected at nearly size-independent rates, but the underlying mechanism remains controversial. Here, in this study, we apply kinetic multilayer modeling to simulate evaporation of α-pinene SOA, demonstrating that surface crust formation, emerging from accumulation of low-volatility compounds at the particle surface, leads to slow evaporation and reduced size dependence of the evaporation rate. While evaporation induced by decomposition of oligomers would naturally lead to size-independent evaporation rates, we observe and simulate nearly size-independent slow evaporation of polyethylene glycol mixture particles containing polymeric species that do not decompose, confirming the relevance of composition-dependent diffusivity for size-independent, slow evaporation. Slow evaporation of limonene SOA was also observed in environmental chamber experiments, and model simulations demonstrate strong surface crust formation with bulk diffusivity being depressed by up to 5 orders of magnitude compared to the inner bulk. We present experimental evidence using a surface-based mass spectrometry technique that shows that the particle surface becomes enriched in high molecular weight compounds upon evaporation of monomers. Our findings imply that viscous surface crusts may also limit the growth and chemical transformation of SOA particles, influencing their impacts on air quality and climate.

heterogeneous chemistry↗
NASA NTRS1995

Kinetics of the Formation of Intercalation Compounds in Crystalline Graphite

Crystalline graphite has a structure that can be best described as an ordered stack of flat aromatic layers. It is known to form intercalation compounds with bromine and nitric acid. Their formation was studied using thermal measurements and analytical techniques. Samples of graphite treated with either bromine or nitric acid were prepared by contacting these reagents with powdered graphite.

crystalline graphite intercalation compounds kinet↗
NASA NTRS1989

Solar nebula chemistry - Implications for volatiles in the solar system

Current theoretical models of solar nebula chemistry which take into account the interplay between chemistry and dynamics are presented for the abundant reactive volatile elements including hydrogen, carbon, nitrogen, oxygen, and sulfur. Results of these models indicate that, in the solar nebula, the dominant carbon and nitrogen gases were CO and NO, whereas, in giant planet subnebulae, the dominant carbon and nitrogen gases were CH4 and NH3; in the solar nebula, the Fe metal grains catalyzed the formation of organic compounds from CO and H2 via the Fischer-Tropsch-type reaction. It was also found that, in solar nebula, bulk FeS formation was kinetically favorable, while FeO incorporation into silicates and bulk Fe3O4 formation were kinetically inhibited. Furthermore, clathrate formation was kinetically inhibited in the solar nebula, while it was kinetically favorable in giant planet subnebulae.

Fegley, Bruce, Jr.↗
NASA NTRS2008

Synchrotron Photoionization Mass Spectrometry Measurements of Kinetics and Product Formation in the Allyl Radical (H2CCHCH2)Self Reaction

Product channels for the self-reaction of the resonance-stabilized allyl radical, C3H5 + C3H5, have been studied with isomeric specificity at temperatures from 300-600 K and pressures from 1-6 Torr using time-resolved multiplexed photoionization mass spectrometry. Under these conditions 1,5-hexadiene was the only C6H10 product isomer detected. The lack of isomerization of the C6H10 product is in marked contrast to the C6H6 product in the related C3H3 + C3H3 reaction, and is due to the more saturated electronic structure of the C6H10 system. The disproportionation product channel, yielding allene + propene, was also detected, with an upper limit on the branching fraction relative to recombination of 0.03. Analysis of the allyl radical decay at 298 K yielded a total rate coefficient of (2.7 +/- 0.8) x 10(exp -11) cu cm/molecule/s, in good agreement with pre.vious experimental measurements using ultraviolet kinetic absorption spectroscopy and a recent theoretical determination using variable reaction coordinate transition state theory. This result provides independent indirect support for the literature value of the allyl radical ultraviolet absorption cross-section near 223 nm.

Selby, Talitha M.↗
DOE OSTI2024

Phase transformation mechanism in irradiation-induced superlattice formation

Atomic kinetic Monte Carlo simulations were used to model void superlattice formation under irradiation in molybdenum, driven by anisotropic diffusion of self-interstitial atoms. A change in the phase transformation mechanism from nucleation and growth to spinodal decomposition occurred with increasing dose rate, with both mechanisms leading to superlattice formation. Analysis of a rate-theory based analytical model showed that an observed change in the kinetics of vacancy accumulation, the appearance of a region of positive second derivative in the plot of average vacancy concentration versus time, was caused by the onset of spinodal instability. Further, the analytical model showed that for molybdenum and several other metals where void superlattice formation is commonly observed, the phase transformation likely occurs by nucleation and growth. However, nickel may offer the possibility of experimental observation of the transition between phase transformation mechanisms.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The Kinetics of Aragonite Formation from Solution via Amorphous Calcium Carbonate

Magnesium doped Amorphous Calcium Carbonate was synthesised from precursor solutions containing varying amounts of calcium, magnesium, H2O and D2O. The Mg/Ca ratio in the resultant Amorphous Calcium Carbonate was found to vary linearly with the Mg/Ca ratio in the precursor solution. All samples crystallised as aragonite. No Mg was found in the final aragonite crystals. Changes in the Mg to Ca ratio were found to only marginally effect nucleation rates but strongly effect crystal growth rates. These results are consistent with a dissolution-reprecipitation model for aragonite formation via an Amorphous Calcium Carbonate intermediate.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Product distribution, kinetics, and aerosol formation from the OH oxidation of dimethyl sulfide under different RO 2 regimes

Abstract. The atmospheric oxidation of dimethyl sulfide (DMS) represents a major natural source of atmospheric sulfate aerosols. However, there remain large uncertainties in our understanding of the underlying chemistry that governs the product distribution and sulfate yield from DMS oxidation. Here, chamber experiments were conducted to simulate gas-phase OH-initiated oxidation of DMS under a range of reaction conditions. Most importantly, the bimolecular lifetime (τbi) of the peroxy radical CH3SCH2OO was varied over several orders of magnitude, enabling the examination of the role of peroxy radical isomerization reactions on product formation. An array of analytical instruments was used to measure nearly all sulfur-containing species in the reaction mixture, and results were compared with a near-explicit chemical mechanism. When relative humidity was low, “sulfur closure” was achieved under both high-NO (τbi<0.1 s) and low-NO (τbi>10 s) conditions, though product distributions were substantially different in the two cases. Under high-NO conditions, approximately half the product sulfur was in the particle phase, as methane sulfonic acid (MSA) and sulfate, with most of the remainder as SO2 (which in the atmosphere would eventually oxidize to sulfate or be lost to deposition). Under low-NO conditions, hydroperoxymethyl thioformate (HPMTF, HOOCH2SCHO), formed from CH3SCH2OO isomerization, dominates the sulfur budget over the course of the experiment, suppressing or delaying the formation of SO2 and particulate matter. The isomerization rate constant of CH3SCH2OO at 295 K is found to be 0.13±0.03 s−1, in broad agreement with other recent laboratory measurements. The rate constants for the OH oxidation of key first-generation oxidation products (HPMTF and methyl thioformate, MTF) were also determined (kOH+HPMTF=2.1×10-11 cm3 molec.−1 s−1, kOH+MTF=1.35×10-11 cm3 molec.−1 s−1). Product measurements agree reasonably well with mechanistic predictions in terms of total sulfur distribution and concentrations of most individual species, though the mechanism overpredicts sulfate and underpredicts MSA under high-NO conditions. Lastly, results from high-relative-humidity conditions suggest efficient heterogenous loss of at least some gas-phase products.

Ye, Qing (ORCID:0000000337978988)↗
NASA NTRS1978

Invited papers presented to a workshop on thermodynamics and kinetics of dust formation in the space medium

Abstracts of 25 papers relating to condensation processes in the early solar system are presented. Special emphasis is given to the transition of an initial vapor phase in the space medium, the characterization of condensation environments, and condensation processes in the space medium. The question of whether some fraction of the solar system solids (particularly exemplified by meteoritic solids) may be interstellar grains that gathered in the region of the proto-sun, rather than being products of local condensation is addressed.

Robertson, P. C.↗