Search NASA⌕ Search

SEARCH · Search NASA

Results for “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 595 records · Page 33
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Kinetics Analysis of Boron Removal from Silicon through Reactions with CaO-SiO{sub 2} and CaO-SiO{sub 2}-Al{sub 2}O{sub 3} Slags

Different types of slags have been used to refine silicon, particularly for removing boron impurity from metallurgical grade (MG) silicon. Although a number of slags have been used for silicon refining, there is limited information about boron removal kinetics, particularly during the refining reaction with CaO-SiO{sub 2}-Al{sub 2}O{sub 3} slags. This article investigates the boron removal kinetics using the CaO-SiO{sub 2}-Al{sub 2}O{sub 3} slag systems in the temperature range 1773 K to 1873 K (1500 °C to 1600 °C). All the results obtained in the present study provide a strong indication that the rate limiting step of the slag-silicon reaction kinetics was mass transport in the liquid slag. It was also shown in the study that as the reaction temperature is increased, the mass transfer coefficient is also increased. At any particular reaction temperature, adding alumina in the CaO-SiO{sub 2} slag was shown to decrease the mass transfer coefficient, which is consistent with the substantially higher viscosity of the alumina bearing slags over the CaO-SiO{sub 2} slag. The mass transfer coefficients were determined to be between 1.23 × 10{sup −6} and 2.82 × 10{sup −6} ms{sup −1}, with activation energies between 64 and 109 kJ/mol, respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Investigation of Magnetite Oxidation Kinetics at the Particle Scale

The induration of magnetite pellets is a complex physico-chemical process that involves oxidation, sintering, and heat transfer. The thermal- and gas-composition profile that is experienced by the pellet in an induration reactor could result in the formation of a homogenous or heterogeneous pellet structure, which could affect the pellet quality. The oxidation kinetics of magnetite pellets from sintering studies have been studied at two levels, namely, the pellet scale and at the particle scale, and the findings of the latter are presented here. The rate of oxidation of the magnetite concentrate depends primarily on temperature, oxygen content in the oxidizing gas, and particle size. These factors are investigated in this study. It was found that the oxidation of the magnetite concentrate is comprised of two distinct stages, a primary stage with high rates followed by a secondary stage where rates decrease significantly. The isothermal oxidation behavior as analyzed by the Avrami kinetic model was found to fit better than the shrinking-core model. The partially oxidized particles were examined microstructurally to supplement the experimental and model results. The Avrami kinetic model for isothermal oxidation was extended to non-isothermal profiles using the superposition principle, and the model was validated experimentally.

36 MATERIALS SCIENCE↗
DOE OSTI2019

A Kinetic Model for Dissolution of Zinc Oxide Powder Obtained from Waste Alkaline Batteries in Sodium Hydroxide Solutions

The determination of individual dissolution behaviors of zinc and manganese in waste alkaline battery powders is an important subject from the points of the leaching yield, design of leaching reactor, and separation and recovery steps of hydrometallurgical process. In the current study, we investigated the dissolution kinetics of zinc oxide powder. Zinc oxide was obtained from waste alkaline batteries, and sodium hydroxide solutions were used as solvent. In the experiments, the effects of solution concentration, reaction temperature, stirring speed, solid-to-liquid ratio, and particle size on the dissolution of zinc oxide were investigated. It was demonstrated that the dissolution increased with the increasing concentration, reaction temperature, and stirring speed, and with the decreasing solid-to-liquid ratio and particle size. In consequence of the kinetic analysis performed, it was found that the dissolution kinetics of zinc powder obeyed the Avrami model. Activation energy for the process was determined to be 19.42 kJ/mol. Zinc ions in the resulting solution after dissolution process was recovered in the form of hydroxy-carbonate product by precipitation method. Zinc oxide was produced by isothermal decomposition of hydroxy-carbonate product.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Engineering Nucleation Kinetics of Graphite Nodules in Inoculated Cast Iron for Reducing Porosity

Inoculation of cast iron with spherical graphite (SGI) controls nucleation kinetics of graphite nodules and is used for improving casting performance and eliminating solidification micro-porosity. In this study, thermodynamic simulations were used to design inoculants. Thermal and chemical stability of different potential heterogeneous nuclei formed in the melt above the liquidus temperature and in the mushy zone during solidification was predicted. Several inoculation treatments of SGI were performed in laboratory heats. An automated SEM/EDX analysis was applied to examine the graphite nodule size distribution and the family of the non-metallic inclusions in the experimental castings. The data were used to reconstruct a relative graphite nodule nucleation rate in the castings. It was shown that the graphite nodule nucleation kinetics in the castings were significantly different from those predicted by classical nucleation models. In inoculated SGI, the observed bi-modal distribution of graphite nodules was related to a continuous nucleation that occurred towards the end of solidification. The origin of the continuous nucleation and the possibility of engineering graphite nodules nucleation kinetics to control SGI casting soundness by inoculation are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Development of a Reliable Kinetic Model for Ladle Refining

Kinetic modeling of ladle refining can be used by steel plants to improve steelmaking and to produce cleaner steels. It can also help researchers to understand the process better. There have been several recent attempts to develop a kinetic model that can predict changes in steel, slag, and inclusion compositions with time. Often the models require parameters that can be difficult to measure under plant conditions, and model limitations have not been discussed in detail. In this study, a two-parameter kinetic model has been developed to predict changes in steel, slag, and inclusion compositions during ladle refining; the two parameters are the mass-transfer coefficient in steel and the inclusion flotation rate constant. The model was based on FactSage macro-processing. Examples of results show that the model can be used to diagnose effects of steel and slag sampling practices and to estimate alloy dissolution time. The model results demonstrate that the presence of solids in slag can significantly reduce the rate of steel–slag reaction while maintaining a high inclusion flotation rate. Some limitations of the model are discussed: the overprediction of calcium transfer to alumina inclusions and the absence of information on inclusions originating from entrained slag.

36 MATERIALS SCIENCE↗
DOE OSTI2019

A Kinetic Study Investigating the Carbothermic Recovery of Chromium from a Stainless-Steel Slag

In 2018, the stainless-steel industry produced > 10 million tons of slag, which for the most part was landfilled because of chromium oxide contamination. Long-term studies indicate a possible formation of soluble hexavalent chromium, which is classified as carcinogenic. Recent research focuses on the development of a treatment technology to recover chromium from the slag into a ferroalloy, producing an oxidic material that can be utilized in the construction industry. To date, there has been no literature dealing with the kinetics of a carbothermic treatment process to result in a model to predict the necessary treatment time. The present article fills this gap by investigating the reduction kinetics of chromium oxide of a process close to practical applications. Based on experimental measurements, a model has been developed to predict the necessary treatment time to reach a specific final chromium concentration as a function of the starting concentration and required process temperature in the range between 1600 °C and 1700 °C. Finally, presented findings can serve as a guideline to develop kinetic models in similar pyrometallurgical recovery processes.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Prediction of Post-deformation Recrystallization Kinetics in AISI 321 Austenitic Stainless Steel Using Double-Stage Hot Compression

In the present research, a series of double-stage hot compression tests were conducted in the temperature range of 950-1150 °C, strain rates in the range of 0.01-1 s{sup −1}, strain in the range of 0.1-0.3, and inter-pass time range of 3-100 s to evaluate the kinetics of the post-deformation recrystallization in AISI 321 austenitic stainless steel. An Avrami-type kinetics equation has been determined based on the obtained experimental data. Results show that the extent of post-deformation recrystallization increases with increase in inter-pass time, deformation temperature, pre-strain, and strain rate. The calculated activation energy for recrystallization (174 kJ/mol) is lower than the activation energy for static recrystallization of austenitic stainless steels. It is concluded that the both static and metadynamic recrystallization occurred during the inter-pass period. Also, the predicted softening fraction using the proposed kinetics equation agreed well with those obtained from experimental results.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Microstructural Coarsening Kinetics and Mechanical Property Changes in Long-Term Aged Sn–Pb–Sb Solder Joints

Tin-lead-antimony (50Sn–47Pb–3Sb wt.%) soldered assemblies were mechanically tested approximately 30 years after initial production and found to have solder joints of reduced strength. The microstructure of this solder alloy exhibits a ternary eutectic structure with Sn-rich, Pb-rich, and SnSb phases. Accelerated aging was performed to evaluate solder microstructural coarsening and associated strength of laboratory solder joints to correlate these properties to the “naturally aged” solder joints. Isothermal aging was conducted at room temperature, 55, 70, 100, and 135 °C and aging times that ranged from 0.1 to 365 days. The coarsening kinetics of the Pb-rich phase were determined through optical microscopy and image analysis methods established in previous studies on binary Sn–Pb solder. A kinetic equation was developed with time exponent n of 0.43 and activation energy of 24000 J/mol, suggesting grain boundary diffusion or other fast diffusion pathways controlling the microstructural evolution. Compression testing and Vickers microhardness showed significant strength loss within the first 20–30 days after soldering; then, the microstructure and mechanical properties changed more slowly over long periods of time. Further, by combining accelerated aging data and the microstructure-based kinetics, strength predictions were made that match well with the properties of the actual soldered assemblies naturally aged for 30 years. However, aging at the highest temperature of 135 °C produced anomalous behavior suggesting that extraneous aging mechanisms are active. Therefore, data obtained at this temperature or higher should not be used. Overall, the combined microstructural and mechanical property methods used in this study confirmed that the observed reduction in strength of ~ 30-year-old solder joints can be accounted for by the microstructural coarsening that takes place during long-term solid-state aging.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Generalized trigonometric Fourier-series method with automatic time step control for non-linear point kinetics equations

The trigonometric Fourier-series method (TFS) is generalized to provide approximate solutions for non-linear point kinetics equations with feedback using varying step sizes. This method can provide a very stable solution against the size of the discrete time step allowing much larger step sizes to be used. Systems of the point kinetics equations are solved using Fourier-series expansion over a partition of the total time interval. The approximate solution requires determining the series coefficients over each time step in that partition. These coefficients are determined using the high-order derivatives of the solution vector at the beginning of the time step introducing a system of linear algebraic equations to be solved at each step. This system is similar to the Vandermonde system. Two successive orders of the partial sums are used to estimate the local truncation error. This error and some other constrains are used to produce the largest step size allowable at each step while keeping the error within a specific tolerance. The process of calculating suitable step sizes should be automatic and inexpensive. Convergence and stability of the proposed method are discussed and a new formula is introduced to maintain stability. The proposed method solves the general linear and non-linear kinetics problems. The method has been applied to five different types of reactivities including step/ramp insertions with temperature feedback. The method is seemed to be valid for larger time intervals than those used in the conventional numerical integration, and is thus useful in reducing computing time. Computational results are found to be consistent with the analysis, they demonstrate that the convergence of the iteration scheme can be accelerated and the resulting computing times can be greatly reduced while maintain computational accuracy.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2018

Verification of iterative matrix solutions for multipoint kinetics equations

Multipoint kinetic equation systems have been solved numerically using matrix algebra software and 1st to 4th order implicit schemes based on single-step matrix propagators. These matrix schemes have been validated successfully on demanding point kinetics benchmarks with various prescribed reactivity insertions. Verification tests have also been performed on a simple 3-region fast reactor core model with asymmetric step or ramp reactivity insertions and cross-checked with the multipoint kinetics SACRE code developed at INL and based on existing and validated stiff ODE solver packages. Accurate results can be obtained at a limited time expense. The reason for intriguing results obtained in some transients has been elucidated and linked to the multipoint matrix coefficient interpolation method during the transient.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2018

Solving many-body Schrödinger equations with kinetic energy partition method

We present a general formulation of our previously developed kinetic energy partition (KEP) method for solving many-bodySchrödinger equations. In atomic physics, as well as in general molecular and solid state physics, solving many-electronSchrödinger equations is a very challenging task, often called Dirac’s challenge. The central problem is how to properly handle the electron–electron Coulomb repulsion interactions. Using the KEP solution scheme, in addition to dividing the kinetic energy into partial terms, the electron–electron Coulomb interaction is also separated into parts to be associated with a “negative mass” kinetic energy term. Therefore, the full Hamiltonian can be expressed as a simple sum of subsystem Hamiltonians, each representing an effective one-body problem. Using a Hartree-like product in constructing the wave-function, we achieve fast convergence in the calculations of the ground state energies. First, the model Moshinsky atoms are used to illustrate the solution procedure. We then apply this new KEP method to harmonium atoms and obtain precise energies with an error less than 5% using only two basis functions from each subsystem. It is thus very promising that this methodology, when further extended, can be useful for general many-body systems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Selective oxidation of 3-hydroxypropionic acid to malonic acid over Pd/C: Mechanistic and kinetic study

Malonic acid (MA) is a high-value dicarboxylic acid with strong industrial demand, yet its current production heavily relies on petrochemical feedstocks. Here, we report the first systematic study for sustainable production of MA via oxidation of 3-hydroxypropionic acid (3-HP) with a Pd/Carbon catalyst. The effects of oxidant type (O 2 and H 2 O 2 ), pH, and temperature on the reaction chemistry were comprehensively evaluated. Guided by experimental observation and DFT-calculated thermochemical energetics, reaction networks for 3-HP oxidation with both oxidants are proposed and validated through kinetic modeling. MA was identified as the primary oxidation product, while further oxidation yields acetic acid and oxalic acid. The kinetic model validated the network, displaying excellent agreement (R 2 > 0.95). Kinetic observations also enabled a direct comparison between O 2 and H 2 O 2 and revealed their distinct behaviors. The model was further developed into a temperature-time map, providing insight into conditions that maximize MA production. Malonic acid selectivity of 56.9 % and yield of 50.5 % were achieved at 3 bar oxygen, equimolar NaOH:3-HP ratio, and 50 °C.

3-hydroxypropionic acid↗
DOE OSTI2022

Addition of transient kinetics capabilities to an infrared reflection absorption spectroscopy system through synchronized gas pulsing and data acquisition

Surface science methodologies for understanding thermodynamic aspects of surface processes are at an advanced level. However, instrumentation and approaches for extracting kinetic parameters from elementary steps are far less accessible. In this work, we present an approach combining the use of a fast gas pulsing valve synchronized with data acquisition to enable surface transient kinetics studies using infrared reflection absorption spectroscopy. This methodology applies to the study of reversible processes and borrows concepts and ideas from molecular beam scattering and temporal analysis of products. Here, a temporal resolution of ~67 ms is achieved, and this is illustrated through the study of CO adsorption and desorption on a Pd(111) crystal in the presence and absence of background O 2 . The same approach can be extended to other surface spectroscopies, such as X-ray photoelectron spectroscopy, to obtain spectra with high temporal resolution and signal-to-noise ratio and enable future multimodal surface transient kinetic studies aiming at elucidating reaction mechanisms.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Optimizing complexity in the kinetic modelling of integrated flue gas purification for pressurized oxy-combustion

A 5-step mechanism and a corresponding kinetic model are presented for integrated flue gas purification, where SOx and NOx are removed during pressurized oxy-coal combustion. Three coupled subsystems (‘blocks”) of gas–liquid transformations are considered: 1) oxidation of NO to NO 2 and dissolution of NO 2 in water; 2) dissolution of SO 2 in the water; and 3) interactions between S- and N- containing substances in the liquid phase. The model has been formulated in terms of only species that can be experimentally measured (model of optimal complexity). Subsystem I is limiting regarding NO removal. Subsystem II is very fast in comparison with the other subsystems and can be treated separately. Analytical expressions for all independent subsystems have been found and compared with computational results for the whole system. The temporal domain of validity of all these subsystems is presented. Finally, the validity of the NO 2 quasi-steady-state assumption is verified, and it is reported that variables such as NO, NO 2 and HNO 3 can be considered decoupled from the whole system since they appear in only Subsystem I, while HSO 3 - and HNO 2 are coupled. The presented kinetic model was verified experimentally by determining the 1:1 ratio of HNO 2 and HNO 3 , in gas–liquid NO-O 2 interaction. Additionally, new experimental facts on kinetic orders and stoichiometry between HNO 2 and HSO 3 - have been used to optimize the model. It is concluded that all NO x - SO x interactions can be essentially grasped by a sequence of only 4 irreversible reactions considering, in addition, the 5th reaction, i.e. the fast ‘SO 2 -water’ equilibrium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Reduction kinetics of hercynite redox materials for solar thermochemical water splitting

Solar thermochemical water splitting (STWS) using a hercynite redox cycle is a promising technology for producing renewable H 2 . Here, the reduction kinetics of hercynite (FeAl 2 O 4 ) is evaluated using thermogravimetric and XRD analyses. The results indicate that as-prepared hercynite materials undergo reduction via two different reaction mechanisms. The reaction first proceeds by a nucleation and growth mechanism (AE1), followed by a third-order kinetic model (F3). XRD analyses show the occurrence of superstoichiometric oxygen in the spinel structure of FeAl 2 O 4+δ in the second reaction mechanism, which indicates the formation of cationic vacancies. TGA and XRD analyses confirm that hercynite maintains its spinel structure when the materials are thermally reduced and oxidized with steam. Differential scanning calorimetry (DSC) performed on FeAl 2 O 4 particles shows two heats of reaction in agreement with the two observed mechanisms. This is the first kinetics study to report on the thermal reduction of hercynite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A Transient-Response methodology based on experiments and modeling for Cu-Redox Half-Cycle kinetic analysis on a Cu-SSZ-13 SCR catalyst

In this report the Standard SCR reaction catalyzed by Cu-SSZ-13 is a redox process consisting of a reduction half cycle (RHC) and an oxidation half cycle (OHC) that cycle the active Cu sites between the Cu(II) and Cu(I) states. In the current work, a transient-response methodology consisting of experimental transient response Cu-redox (TRCR) measurements and kinetic modeling was developed for detailed study of individual SCR Cu-redox half cycles. The TRCR protocol allows quantification of the reducible Cu density, Cu(II)-Cu(I) partitioning, relative native RHC and OHC rates, and limiting half cycle during SCR. The half-cycle kinetics are studied over a wide (170–450 °C) temperature, and in differential segments along the catalyst length using spatially resolved capillary inlet mass-spectrometry (SpaciMS). The protocol alone provides two independent measures indicating that OHC increases faster than RHC with temperature, and that at all but the lowest temperature SCR is RHC limited. Introducing the transient kinetic models allows half-cycle reaction pathways, orders and activation energies to be studied and determined; e.g., RHC involves surface and gas-phase NH 3 routes, and OHC with O 2 involves dimer formation. Application of the full methodology provides further confirmation and quantification of the protocol conclusions, and specifically the first measurements of RHC and OHC activation energies; specifically for parallel RHC surface and gas-phase routes, and experimentally obtained OHC activation energy vs. first-principle calculations in the literature. Beyond insights related to the degreened catalyst studied here, the methodology provides a broadly available approach for quantifying how aging processes selectively impact RHC and OHC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Insights into co-pyrolysis of polyethylene terephthalate and polyamide 6 mixture through experiments, kinetic modeling and machine learning

The non-isothermal pyrolysis of polyethylene terephthalate (PET), polyamide 6 (PA6), and their mixtures was studied in a thermogravimetric analyzer at different heating rates. Temperature of maximum decomposition (T max ) decreased by 25–45 °C and 35–55 °C for the PET:PA6 mixtures (3:1, 1:1, 1:3) compared to PET and PA6, respectively. The kinetic analysis was initially carried out using isoconversional method. However, the dependency of activation energy on conversion was observed for the co-pyrolysis of PET and PA6 that suggested the occurrence of multi-step reactions in the mixtures. Distributed activation energy model (DAEM) was used in this study to describe the multistep reactions occurring during pyrolysis of PET:PA6 mixtures. Here, in this work, a four-parallel reaction DAEM was developed to describe the pyrolysis kinetics of PET:PA6 mixtures. The apparent mean activation energies (E o ) for PET, PA6, and mixtures varied in the range of 244–255, 140–215, and 138–255 kJ mol –1 , respectively. The mass loss profiles of PET and PA6 mixtures were also modeled using artificial neural network (ANN). Out of 155 ANN models, the best prediction was made by ANN511 with R 2 greater than 0.997 for both test and unseen data. The interaction effects observed through TGA experiments and subsequent kinetic analysis were further assessed in terms of product composition using analytical pyrolysis coupled with gas chromatograph/mass spectrometer (Py-GC/MS). Co-pyrolysis of PET and PA6 resulted in the formation of new aromatic compounds with nitrogen-containing functional groups, which were not detected when PET or PA6 were pyrolyzed individually.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Theoretical and kinetic modeling study of hydrazine oxidation

The present work constitutes the first theoretical and kinetic modeling study of hydrazine oxidation, which may be important for burnout in ammonia-fueled combustion. The kinetics of the oxidation of N 2 H 4 , N 2 H 3 and tHNNH by molecular oxygen were investigated via a quantum chemistry/canonical transition state theory approach. Geometries and anharmonic frequencies were obtained with density functional theory, and energies from coupled cluster calculations (CCSD(T)) extrapolated to the infinite basis set limit, with corrections for core-valence electron correlation, scalar relativistic effects, and higher level correlation up to lambda coupled cluster, CCSDT(Q) Λ . The key reactions occurred on the N 2 H 4 O 2 potential energy surface, where the results indicated a fast reaction of N 2 H 3 with HO 2 via singlet adducts to yield tHNNH + H 2 O 2 and HNN(H)O + H 2 O, while reaction on the triplet surface proceeds via a bound complex followed by a tight, submerged barrier to yield N 2 H 4 + O 2 . The results were incorporated in a detailed reaction mechanism, which was used to interpret the shock tube results from Michel and Wagner (1965) on the effect of O 2 on hydrazine conversion at 1100–1400 K. The kinetic model captured qualitatively the observed behavior, but underestimated the reaction rate under oxidizing conditions. The hydrazine pyrolysis chemistry dominated conversion at reducing conditions and/or high temperature. At oxidizing conditions and intermediate temperatures (≲ 1400 K), reactions of N 2 -amines with HO 2 and O 2 were important for the oxidation rate.

Ab initio calculations↗