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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 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Fast Oxygen Redox Kinetics Induced by CoO 6 Octahedron With π –Interaction in P2–Type Sodium Oxides

Enhancing the kinetics of lattice oxygen redox (LOR) in P2-type layered sodium oxide cathodes is crucial for the advancement of sodium-ion batteries (SIBs) with superior energy and power densities. Electronic structure regulation stands out as a highly effective approach to address the inherent limitations of P2-type layered oxides with LOR, including sluggish kinetics, phase transitions, voltage hysteresis, and local structural distortion. In this work, a strategy involving the introduction of CoO 6 octahedra with π-interaction into Na 0.6 Li 0.1 Fe 0.3–x Co x Mn 0.6 O 2 (x = 0, 0.15, 0.3) cathodes to facilitate Na-ion transport is proposed. Furthermore, the impact of FeO 6 octahedra with σ-interaction in P2-type cathodes on electrochemical performance is comprehensively investigated. Through multimodal in-situ and ex-situ characterization techniques, it is revealed that Co–O with π-interaction effectively mitigates P2-OP4 phase transitions by strengthening Na–O, reduces voltage hysteresis, and stabilizes the local structure. Consequently, Na 0.6 Li 0.1 Co 0.3 Mn 0.6 O 2 demonstrates enhanced Na-ion diffusion kinetics, leading to improved rate performance and a reversible capacity of 55 mAh g –1 at 10 C, significantly outperforming cathodes with Fe–O σ-interaction. Moreover, when coupled with hard carbon, the full cell achieves a remarkable energy density of 395 Wh kg –1 (on cathode) at 0.1 C, with a capacity retention of 75% over 100 cycles at 1 C.

25 ENERGY STORAGE↗
DOE OSTI2023

A Nanoscale Ternary Amide‐rGO Composite with Boosted Kinetics for Reversible H 2 Storage

Abstract Metal amides are attractive candidates for hydrogen storage due to their high volumetric and gravimetric hydrogen densities. However, the sluggish kinetics and competing side reactions during hydrogen uptake and release limit their practical use. Here, a novel nanoconfined Li 2 Mg(NH) 2 @reduced graphene oxide (rGO) composite is presented, which is fabricated using a melt‐infiltration method with a minimum weight penalty of only 2 wt.%. The presence of rGO ensures close contact between the active phases, effectively preventing aggregation during cycling process. As a result, the reversible capacity of Li 2 Mg(NH) 2 @rGO reaches 4.42 wt.%, with no capacity degradation observed after multiple cycling. Theoretical calculations show that rGO catalyzes the hydrogen bond cleavage at the Mg‐amide/Li hydride interface, leading to local dehydrogenation hotspots and significantly improves kinetics of dehydrogenation compared to the bulk counterpart. This study provides a promising strategy for designing metal imide‐based composites to overcome the kinetic limitations and improve their reversible hydrogen storage performance.

08 HYDROGEN↗
DOE OSTI2023

Non‐Linear Kinetics of The Lithium Metal Anode on Li 6 PS 5 Cl at High Current Density: Dendrite Growth and the Role of Lithium Microstructure on Creep

Abstract Interfacial instability, viz., pore formation in the lithium metal anode (LMA) during discharge leading to high impedance, current focusing induced solid–electrolyte (SE) fracture during charging, and formation/behaviour of the solid–electrolyte interphase (SEI), at the anode, is one of the major hurdles in the development of solid‐state batteries (SSBs). Also, understanding cell polarization behaviour at high current density is critical to achieving the goal of fast‐charging battery and electric vehicle. Herein, via in situ electrochemical scanning electron microscopy (SEM) measurements, performed with freshly deposited lithium microelectrodes on transgranularly fractured fresh Li6PS5Cl (LPSCl), the LiǀLPSCl interface kinetics are investigated beyond the linear regime. Even at relatively small overvoltages of a few mV, the LiǀLPSCl interface shows non‐linear kinetics. The interface kinetics possibly involve multiple rate‐limiting processes, i.e., ion transport across the SEI and SE|SEI interfaces, as well as charge transfer across the LiǀSEI interface. The total polarization resistance R P of the microelectrode interface is determined to be ≈ 0.8 Ω cm 2 . It is further shown that the nanocrystalline lithium microstructure can lead to a stable LiǀSE interface via Coble creep along with uniform stripping. Also, spatially resolved lithium deposition, i.e., at grain surface flaws, grain boundaries, and flaw‐free surfaces, indicates exceptionally high mechanical endurance of flaw‐free surfaces toward cathodic load (>150 mA cm −2 ). This highlights the prominent role of surface defects in dendrite growth.

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

Leveraging Exchange Kinetics for the Synthesis of Atomically Precise Porous Catalysts

Metal-organic frameworks (MOFs) have attracted significant attention as porous catalyst platforms due to the synthetic modularity of these materials and the diversity of lattice-confined catalytic active sites that are readily embedded within periodic crystalline frameworks. MOFs offer platforms to heterogenize molecular catalysts, stabilize novel coordination motifs, and leverage confinement effects in catalysis. Crystallinity allows diffraction-based methods to be employed in the characterization of these catalysts. Access to crystalline MOFs typically requires reversible construction of the metal-ligand (M-L) bonds that connect the SBUs, which provides a mechanism to anneal defects during crystallization. While the required M-L bond reversibility is often promoted by synthesis at elevated temperature, access to crystalline materials based on either transition metals with characteristic slow exchange kinetics or highly basic donor ligands remains a synthetic challenge. Here in this paper, we highlight synthetic strategies that leverage M-L exchange kinetics to access MOFs based on kinetically inert ions and extensions of these strategies to the assembly of atomically precise multimetallic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Verification of 5D continuum gyrokinetic code COGENT: Studies of kinetic drift wave instability

COGENT (Continuum Gyrokinetic Edge New Technology) is a kinetic plasma simulation code that is being developed by the edge simulation laboratory (ESL) collaboration. The original version of the code has been developed in a 4D phase space (2D configuration space and 2D velocity space) to address kinetic plasma phenomena in a complex magnetic field geometry including the core, magnetic separatrix, and scrape-off layer regions. This paper is focused on extending the original 4D phase space to a 5D phase space (3D2V) to address full kinetic turbulences in a tokamak edge region. Here, we report on the current status of 5D COGENT, which presently operates in a shear-less, simple slab geometry. As a verification study, we use the problems of collision-less drift wave instability (universal instability) including its modification in the presence of collisional effects. The simulation model includes the gyrokinetic equations for ion and electron species coupled to the long-wavelength limit of the gyro-Poisson equation. Collisional effects are represented by the Krook collision model. Linear analytical results for the drift mode growth rate and real frequency are recovered, and the non-linear stage is modelled and analysed as well. In addition, extensive 5D runs have been performed to address the effects of the drift wave instability on blob/filamentary structures characteristic of a tokamak edge. Finally, a helical-shaped potential perturbation is observed to grow exponentially in time while spinning around the filament axis with electron drift frequency.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Kinetic Study of the OH + Ethylene Reaction using Frequency Modulated Laser Absorption Spectroscopy

The pressure dependence of the OH + C 2 H 4 addition reaction has been investigated using frequency modulated laser absorption spectroscopy to monitor OH kinetics. Bimolecular rate coefficients for the title reaction are reported in argon bath gas at room temperature and total pressures ranging from 2–361Torr. The pressure dependent rate coefficients measured here agree well with the majority of published kinetic studies under similar conditions. Previous high-level ab initio calculations have identified a pre-reaction complex on the OH + C 2 H 4 potential energy surface. In conclusion, the influence of this complex on the OH + C 2 H 4 kinetics has been investigated using one-dimensional master equation analyses of the current and previous experimental measurements

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

Experimental Investigation of the Thermal Decomposition Pathways and Kinetics of TATB by Isotopic Substitution

Real-time measurements of the product gases arising from the thermal decomposition of triamino-trinitro benzene (TATB), its deuterated analogue, and plastically bonded TATB (LX-17) are presented in this study. Gas-phase decomposition products are identified by IR absorption spectroscopy. The frequency shifts in rovibrational spectra due to isotopic substitution and the change in rate of formation of decomposition products due to the kinetic-isotope-effect (KIE) help elucidate the decomposition pathways. The formation of H 2 O precedes other molecules (e.g., HCN, HNCO) during decomposition. After the concentrations of HCN and HNCO molecules reach a peak, their amounts gradually decrease. The concentrations of the other decomposition products (e.g., NH 3 and CO 2 ) rapidly rise after an induction period, which is attributed to the presence of autocatalytic reactions. The trends of chemical evolution are similar for all the samples, but their kinetic behaviors are different. This indicates the rates of consistent pathways are changed during thermal decomposition. Additionally, the kinetics of deuterated TATB decomposition is slower than that of unsubstituted TATB due to the KIE (kH/kD~1.41). The rate of LX-17 decomposition is slightly lower than unsubstituted TATB (k TATB /k LX-17 ~1.15). The KIE is more pronounced during the early stage of decomposition, which is attributed to the first steps of TATB decomposition involving water formation (i.e., H vs D transfer). The KIE slows down the formation of all gases, including those lacking hydrogen (e.g., CO 2 ). These results suggest the TATB thermal decomposition mechanism might involve a series of pathways rather than a set of independent and parallel reactions.

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

Thermal Decomposition Kinetics of 4,6‐Diamino‐5,7‐dinitro‐benzo‐furazan

This experimental study investigated the thermal decomposition kinetics of 4,6-diamino-5,7-dinitro-benzo-furazan (referred to as F1 hereafter)—an important decomposition product of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB—a prototypical insensitive high explosive). Simultaneous differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and mass spectrometry (MS) measurements were employed to determine the decomposition kinetics of F1 and to track the evolution of product gases. The DSC profiles were measured at 10 different heating rates between 0.025°C/min and 10°C/min. The measured exotherms were influenced by F1 melting at heating rates above 0.25°C/min, and corresponding changes in decomposition enthalpy and TGA mass-loss-rate profiles indicated a transition from solid-to-gas decomposition to an increasing contribution from liquid-to-gas decomposition. Analysis of low-heating-rate DSC data between 0.025°C/min and 0.17°C/min with the extended Prout–Tompkins model yielded an activation energy of 305 kJ/mol for solid-to-gas F1 decomposition, higher than previous values inferred from TATB decomposition models involving F1. This study provides the first direct experimental determination of the energy barrier for F1 decomposition. MS measurements showed that the major gaseous products matched species previously reported for TATB decomposition (e.g., CO 2 , HCN, C 2 N 2 , etc.), with water identified as the dominant product. Furthermore, these results provide important experimental constraints for improving chemical kinetics models of TATB decomposition and for predicting the reactivity, stability, and safety of TATB-based high explosives under long-term aging conditions and abnormal thermal environments.

4,6-Diamino-5,7-dinitro-benzo-furazan↗
DOE OSTI2018

Adsorption Studies of Dimetridazole and Metronidazole onto Biochar Derived from Sugarcane Bagasse: Kinetic, Equilibrium, and Mechanisms

Biochar derived from sugarcane bagasse was prepared at different pyrolysis temperatures and holding times for adsorption of dimetridazole and metronidazole from aqueous solution. The optimal pyrolysis temperature and holding time were 500 °C and 120 min, respectively. The removal efficiencies of dimetridazole and metronidazole were 98.0% and 88.8%, respectively, at biochar dosage of 4.0 g L{sup −1} and solution temperature of 30 °C. Kinetics data were fitted by four kinetics models, and results indicated that adsorption was governed by pseudo-second-order kinetics. Adsorption is a multi-step process that involves film diffusion and pore filling. In addition, five isotherm models were employed to describe the adsorption equilibrium. Brunauer–Emmett–Teller model presented better fitting for the adsorption equilibrium, and the maximum adsorption capacities were 72.17 and 23.61 mg g{sup − 1} for dimetridazole and metronidazole, respectively. The calculated values of ΔG{sup 0} and ΔH{sup 0} indicated the non-spontaneous and exothermic nature of the adsorption process at the range of temperature studied. Thermodynamic studies also revealed that physical and chemical adsorptions were co-action. The adsorption mechanisms of dimetridazole and metronidazole onto biochar were mainly hydrogen bonding and π–π interaction. All the results revealed that sugarcane bagasse biochar can be used as alternative to costly adsorbents for the removal of dimetridazole and metronidazole from aqueous solution.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Photochemical Kinetic Modeling of Degradation of Aqueous Polyvinyl Alcohol in a UV/H{sub 2}O{sub 2} Photoreactor

This study presents a photochemical kinetics model to describe the degradation of water-soluble PVA (Polyvinyl Alcohol) polymer in a UV/H{sub 2}O{sub 2} batch reactor. Under the effect of UV light, the photolysis of hydrogen peroxide into hydroxyl radicals can generate a series of polymer scission reactions. For a better understanding and analysis of the UV/H{sub 2}O{sub 2} process in the cracking of the PVA macromolecules, a chemical reaction mechanism of the degradation process and a relevant photochemical kinetics model are developed to describe the disintegration of the polymer chains. Taking into account the probabilistic fragmentation of the polymer, the statistical moment approach is used to model the molar population balance of live and dead polymer chains. The model predicts the PVA molecular weight reduction, the acidity of the solution, and hydrogen peroxide residual. In addition to previously published data collected in this laboratory, a new set of experiments were conducted using a 500 mg/L PVA aqueous for different hydrogen peroxide/PVA ratios for model validation. Measurements of average molecular weights of the polymer, hydrogen peroxide concentrations and pH of the PVA solution were determinant factors in constructing a reliable photochemical model of the UV/H{sub 2}O{sub 2} process. Experimental data showed a decrease in the PVA molecular weight and a buildup of the solution acidity. The experimental data also served to determine the kinetics rate constants of the PVA photochemical degradation and validate the model whose predictions are in good agreement with data. The model can provide a comprehensive understanding of the impact of the design and operational variables.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Lessons Learned in Employing Data Analytics to Predict Oxidation Kinetics and Spallation Behavior of High-Temperature NiCr-Based Alloys

Machine learning (ML) can offer many advantages in predicting material properties over traditional materials development methods based solely on limited experimental investigations or physical-based simulations with the capability to reduce development cost, risk, and time. However, so far, limited efforts have been made to predict alloy oxidation kinetics and spallation behavior via ML due to the lack of consistently measured and sufficient experimental data and the inherent complexity in oxidation behavior of multicomponent high-temperature alloys. A previous study reported the ability of ML to predict oxidation kinetics of NiCr-based alloys as a function of alloy composition and operating conditions. Here, the performance of a ML model in predicting rate constants and spallation probability was evaluated in light of the roles of the data distribution of the experimental dataset (data analytics), the alloy composition, the exposure environment and the chosen oxidation approach to extracting kinetic values from the measured mass changes (but using either a simple parabolic law or a statistical cyclic oxidation model). Potential strategies to improve the predictions and enhance the extrapolative capability of the previously trained model will be discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Equilibrium, kinetic, and thermodynamic studies on the sorption of some heavy metal ions by the phosphorus-containing polymer sorbent

The sorption of Cu+{sup 2}, Ni+{sup 2}, Co+{sup 2}, and Zn+{sup 2} ions onto the phosphorus-containing sorbent were studied as a function of the contact time, temperature, and concentration of the initial metal ions. The equilibrium studies are presented by the Langmuir, Freundlich, and Temkin isotherm models. The sorption data are well described by the Langmuir isotherm model, and they also can be simulated by the Freundlich isotherm model. The pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were applied to test the experimental data of the kinetic studies. The pseudo-second-order kinetic model provided the best correlation of the experimental data compared to the other kinetic models. The sorption capacity of the metal ions increased with temperature increasing. The positive value of enthalpy (ΔH°) and the negative value of Gibbs free energy (ΔG°) indicated that the sorption process was endothermic and spontaneous.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Theory of a High-Voltage Pulse Discharge in a High-Pressure Gas: Hydrodynamic and Kinetic Approaches

Comparative results of modeling of the phenomenon of a high-voltage discharge in nitrogen at atmospheric pressure based on two theoretical approaches: hydrodynamic and kinetic descriptions of electrons in discharge plasma are presented. The detailed spatiotemporal pattern of the development of coaxial gas-filled diode breakdown with formation of runaway electrons in it is described. It is demonstrated that the switching characteristics of the subnanosecond discharge are reliably modeled within the limits of both hydrodynamic and kinetic descriptions of electron components, whereas the parameters of runaway electrons can reliably be calculated only using the kinetic description.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2018

Effect of Slag Composition on the Crystallization Kinetics of Synthetic CaO-SiO{sub 2}-Al{sub 2}O{sub 3}-MgO Slags

The crystallization kinetics of CaO-SiO{sub 2}-Al{sub 2}O{sub 3}-MgO (CSAM) slags was studied with the aid of single hot thermocouple technique (SHTT). Kinetic parameters such as the Avrami exponent (n), rate coefficient (K), and effective activation energy of crystallization (E{sub A}) were obtained by kinetic analysis of data obtained from in situ observation of glassy to crystalline transformation and image analysis. Also, the dependence of nucleation and growth rates of crystalline phases were quantified as a function of time, temperature, and slag basicity. Together with the observations of crystallization front, they facilitated establishing the dominant mechanisms of crystallization. In an attempt to predict crystallization rate under non-isothermal conditions, a mathematical model was developed that employs the rate data of isothermal transformation. The model was validated by reproducing an experimental continuous cooling transformation diagram purely from isothermal data.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Numerical Investigation of Desulfurization Kinetics in Gas-Stirred Ladles by a Quick Modeling Analysis Approach

A quick modeling analysis approach for predicting the slag-steel reaction and desulfurization kinetics in argon gas-stirred ladles has been developed in this study. The model consists of two uncoupled components: (i) a computational fluid dynamics (CFD) model for predicting the fluid flow and the characteristics of slag-steel interface, and (ii) a multicomponent reaction kinetics model for calculating the desulfurization evolution. The steel-slag interfacial area and mass transfer coefficients predicted by the CFD simulation are used as the processing data for the reaction model. Since the desulfurization predictions are uncoupled from the CFD simulation, the computational time of this uncoupled predictive approach is decreased by at least 100 times for each case study when compared with the CFD-reaction kinetics fully coupled model. The uncoupled modeling approach was validated by comparing the evolution of steel and slag compositions with the experimentally measured data during ladle metallurgical furnace (LMF) processing at Nucor Steel Tuscaloosa, Inc. Then, the validated approach was applied to investigate the effects of the initial steel and slag compositions, as well as different types of additions during the refining process on the desulfurization efficiency. The results revealed that the sulfur distribution ratio and the desulfurization reaction can be promoted by making Al and CaO additions during the refining process. It was also shown that by increasing the initial Al content in liquid steel, both Al oxidation and desulfurization rates rapidly increase. In addition, it was found that the variation of the initial Si content in steel has no significant influence on the desulfurization rate. Lastly, if the initial CaO content in slag is increased or the initial Al{sub 2}O{sub 3} content is decreased in the fluid-slag compositional range, the desulfurization rate can be improved significantly during the LMF process.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Kinetic Modeling of a Silicon Refining Process in a Moist Hydrogen Atmosphere

We developed a kinetic model that considers both silicon loss and boron removal in a metallurgical grade silicon refining process. This model was based on the hypotheses of reversible reactions. The reaction rate coefficient kept the same form but error of terminal boron concentration could be introduced when relating irreversible reactions. Experimental data from published studies were used to develop a model that fit the existing data. At 1500 °C, our kinetic analysis suggested that refining silicon in a moist hydrogen atmosphere generates several primary volatile species, including SiO, SiH, HBO, and HBO{sub 2}. Using the experimental data and the kinetic analysis of volatile species, we developed a model that predicts a linear relationship between the reaction rate coefficient k and both the quadratic function of p(H{sub 2}O) and the square root of p(H{sub 2}). Moreover, the model predicted the partial pressure values for the predominant volatile species and the prediction was confirmed by the thermodynamic calculations, indicating the reliability of the model. We believe this model provides a foundation for designing a silicon refining process with a fast boron removal rate and low silicon loss.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Developing the Oxidation Kinetic Model for Magnetite Pellet

Oxidation is a vital phenomenon for magnetite pellets in their excursion through the furnace during induration. One of the pre-requisites for magnetite pellets to achieve homogeneously structured good quality pellets is to have complete oxidation before sintering begins. Partially oxidized magnetite pellets, upon sintering, might result in inhomogeneous structured pellets which could be detrimental to pellet quality. It is necessary to understand the mechanisms responsible for magnetite oxidation, and hence, it is intended in this study to investigate experimentally as well as develop a mathematical model based on oxidation kinetics. Oxidation of pellets is largely influenced by the oxidation kinetics of particles and hence should be studied at particle as well as at pellet scale. The principles of the Grain Model have been adopted to develop the Oxidation Model at pellet scale, whereas the particles’ oxidation follows the Avrami Kinetic Model. Isothermal oxidation experiments performed Thermogravimetric Analyzer showed that oxidation rate of magnetite at pellet scale contained two peaks. They were complemented well by oxidation rates predicted from the model. Further, the pellet was investigated microstructurally at pellet and particle scale to substantiate the findings from the experiments and the model. The oxidation model developed is used to predict the progression of oxidation in the magnetite pellet with respect to the reaction time at three different temperatures (873 K, 973 K, and 1073 K (600 °C, 700 °C, and 800 °C)) and at four levels of oxygen (0.21, 0.30, 0.60, and 1.00 atm) in the oxidizing gas.

36 MATERIALS SCIENCE↗