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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 1,045 records · Page 58
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Differences in Mechanism and Rate of Zeolite-Catalyzed Cyclohexanol Dehydration in Apolar and Aqueous Phase

The rate of acid-base catalyzed dehydration of alcohols strongly depends on the solvent and the environment of the acid sites. In this work, we find that Brønsted acidic sites in large-pore zeolites, but not in medium-pore zeolites, catalyze cyclohexanol dehydration in decalin at significantly higher rates than hydrated hydronium ions in aqueous phase. Specifically, the difference in turnover rates between the two solvents amounts to two to three orders of magnitude on H-BEA and H-FAU, while being very modest (within a factor of 2) for H-MFI. Combining kinetic, isotopic tracer and 2H NMR measurements, it is established that cyclohexanol dehydration generally follows an E1-elimination pathway in decalin. A notable exception is the monomer dehydration route on H-MFI, which exhibits a much lower activation energy and a substantially negative activation entropy that appear to be associated with an E2-type mechanism. The C-O bond cleavage displays a dominant degree of rate control in decalin, which stands in contrast to deprotonation (C-H cleavage) being rate-limiting in aqueous-phase dehydration.

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

Impact of Stabilizing Cations on Lithium Intercalation in Tunneled Manganese Oxide Cathodes

Stabilizing cations such as K + , Ba 2+ , and Ag + are known to provide charge neutrality and enhance structural stability in low-cost tunneled manganese dioxide (MnO 2 ) cathodes for Li ion batteries. However, a fundamental understanding of the role of these cations in the electrochemical performance of tunneled MnO 2 cathodes remains unclear, especially at low stabilizing cation concentrations. Here, we employ density functional theory (DFT + U) calculations to reveal the impact of stabilizing potassium cation (K + ) concentration on the structural stability, electronic properties, and kinetics of lithium transport in 2 x 2 tunneled manganese oxide (α-K y Mn 8 O 16 , at y = 0, 1, and 2) battery cathodes during lithium intercalation. Specifically, we provide insights into the effect of K + ions on several critical factors governing the electrochemical storage performance of tunneled MnO2 cathodes, including (a) energetically favorable Li+ host sites, (ii) Li + and electron transport capabilities, (iii) optimal intercalation pathways, crystal distortion, microstructural stability, and tunneled-to-layer phase transformation as a function of lithium content, and (iv) cell output voltage profile. Interestingly, we find that low K + concentrations (y ≤ 1) yield partially cation-deficient tunnels in the MnO 2 cathode. Such unique tunnel structures in the cathode enable (a) low kinetic barriers for Li transport, (b) excellent thermodynamic stability of the tunneled structure even at a high Li + loading (up to ~ 0.625 Li/Mn), and (c) good electronic conductivity facilitated by Jahn-Teller distortions; all of which are critical for achieving high capacity batteries with enhanced rate capability. Additionally, these results provide perspectives to design low-cost transition metal oxide cathodes for high-performance Li-ion batteries with excellent cycle life.

25 ENERGY STORAGE↗
DOE OSTI2026

Energy Partition in Collisionless Counterstreaming Plasmas

Fast, counterstreaming plasma outflows drive magnetic field amplification, plasma heating, and particle acceleration in numerous astrophysical environments, from supernova remnant shocks to active galactic nuclei jets. Understanding how, in the absence of Coulomb collisions, energy is redistributed between the different plasma species remains a fundamental open question. We use three-dimensional, fully kinetic simulations to investigate energy partition in weakly magnetized counterpropagating plasmas. Our results reveal a complex interplay between different processes, where at early times the Weibel instability drives a first stage of magnetic field amplification and at late times the kinking of current filaments drives a second amplification stage via a dynamo-type mechanism. Electrons are heated primarily during the latter phase through magnetic pumping. By the time the flows thermalize, we observe that the final temperature ratio T e /T i and energy partition depend on the ion-to-electron mass ratio. For electron–proton flows, the electron thermal energy only reaches up to a few percent of the initial ion kinetic energy.

Marret, Alexis [SLAC National Accelerator Laborato↗
DOE OSTI2020

Unraveling the Crystallization Kinetics of 2D Perovskites with Sandwich-Type Structure for High-Performance Photovoltaics

2D perovskite solar cells with high stability and high efficiency have attracted significant attention. A systematical static and dynamic structure investigation is carried out to show the details of 2D morphology evolution. A dual additive approach is used, where the synergy between an alkali metal cation and a polar solvent leads to high-quality 2D perovskite films with sandwich-type structures and vertical phase segregation. Such novel structure can induce high-quality 2D slab growth and reduce internal and surface defects, resulting in a high device efficiency of 16.48% with enhanced continuous illumination stability and improved moisture (55-60%) and thermal (85°C) tolerances. Transient absorption spectra reveal the carrier migration from low n to high n species with different kinetics. An [PbI 6 ] 4- octagon coalescence transformation mechanism coupled with metal and organic cations wrapped is proposed. By solvent vapor annealing, a recrystallization and reorientation of the 2D perovskite slabs occurs to form an ideal structure with improved device performance and stability.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Effect of synthesis temperature on the phase formation of NiTiAlFeCr compositionally complex alloy thin films

Here, the synthesis temperature dependent phase formation of Ni 10 Ti 10 Al 25 Fe 35 Cr 20 thin films is compared to a bulk processed sample of identical composition. The as-cast alloy exhibits a dual-phase microstructure which is composed of a disordered BCC phase and AlNiTi-based B2- and/or L2 1 -ordered phase(s). Formation of the BCC phase as well as an ordered AlNi-based B2 phase is observed for a thin film synthesised at 500 °C (ratio of synthesis temperature of thin film to melting temperature of bulk alloy: T/T m = 0.49), which is attributed to both surface and bulk diffusion mediated growth. Post deposition annealing at 900 °C (T/T m = 0.75) of a thin film deposited without intentional heating results in the formation of NiAlTi-based B2 and/or L2 1 -phase(s) similar to the bulk sample, which is attributed to bulk diffusion. Depositions conducted at room temperature without intentional substrate heating (T/T m = 0.20) resulted in the formation of an X-ray amorphous phase, while a substrate temperature increase to 175 °C (T/T m = 0.28) causes the formation of a BCC phase. Atom probe tomography of the thin films deposited without intentional substrate heating and at 175 °C indicates the formation of ~5 nm and ~10 nm FeAl-rich domains, respectively. This can be rationalized based on the activation energy for surface diffusion, as Ti and Ni exhibt 2.5 to 4 times larger activation energy barriers than Al, Fe and Cr. It is evident from the homologous temperature that the phase formation observed at 500 °C (T/T m = 0.49) is a result of both surface and bulk diffusion. As the temperature is reduced, the formation of FeAl-rich domains can be understood based on the differences in activation energy for surface diffusion and is consistent with kinetically limited thin film growth.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Direct Monitoring of Conical Intersection Passage via Electronic Coherences in Twisted X-Ray Diffraction

Quantum coherences in electronic motions play a critical role in determining the pathways and outcomes of virtually all photophysical and photochemical molecular processes. However, the direct observation of electronic coherences in the vicinity of conical intersections remains a formidable challenge. Here we propose a novel time-resolved twisted x-ray diffraction technique that can directly monitor the electronic coherences created as the molecule passes through a conical intersection. We show that the contribution of electronic populations to this signal is canceled out when using twisted x-ray beams that carry a light orbital angular momentum, providing a direct measurement of transient electronic coherences in gas-phase molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Exploring the Origin of Anionic Redox Activity in Super Li-Rich Iron Oxide-Based High-Energy-Density Cathode Materials

Super alkali-rich materials (alkali:transition metal ratio of ≥2:1), such as Li 5 FeO 4 , exhibit the potential to realize anionic redox upon deep delithiation. Li 5 FeO 4 was shown to undergo reversible cycling between Li 4 FeO 3.5 and Li 3 FeO 3.5 with combined cation/anion redox, a remarkable capacity of 189 mAh/g, and no O 2 release. However, the impact of phase transformations on the reaction thermodynamics and the correlation between the structural changes and reaction reversibility remain unclear. In this study, we use first-principles calculations to examine the delithiation and (re)lithiation reactions of Li 5 FeO 4 . We show that the experimentally observed charge and discharge processes go through non-equilibrium pathways. Upon delithiation, the compound undergoes a phase transformation from Li 5 FeO 4 , with tetrahedrally coordinated (T d ) Fe ions, to a delithiated disordered rocksalt structure, with octahedral (O h ) Fe ions. Fe-ion migration has an asymmetric kinetic barrier that makes T d → O h migration facile, whereas the reverse process has a much larger barrier, explaining the difficulties in reaction reversibility. We further elucidate the transition metal and O redox sequences during the charge cycle and identify the complex electrochemistry associated with the dual participation of cationic redox (Fe 3+ /Fe 4+ ) and anionic redox (O 2– /O – /O o ). Armed with this knowledge, we conduct high-throughput screening of known alkali-rich transition metal oxides by evaluating their potential to enable reversible anionic redox, with multiple candidates proposed for further experimental trials. Furthermore, our work provides a useful guide for the further development of super alkali-rich anionic-redox-active electrodes for high-energy-density batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Replicating HCCI-like autoignition behavior: What gasoline surrogate fidelity is needed?

This work seeks to characterize the fidelity needed in a gasoline surrogate with the intent to replicate the complex autoignition behavior exhibited within advanced combustion engines, and specifically Homogeneous Charge Compression Ignition (HCCI). A low-temperature gasoline combustion (LGTC) engine operating in HCCI mode and a rapid compression machine (RCM) are utilized to experimentally quantify fuel reactivity, through autoignition and preliminary heat release characteristics. Fuels considered include a research grade E10 U.S. gasoline (RD5-87), three multi-component surrogates (PACE-1, PACE-8, PACE-20), and a binary surrogate (PRF88.4). Each fuel was studied at lean/HCCI-like conditions covering a wide range of temperatures and pressures that are representative of naturally aspirated to high boost engine operation. Detailed chemical kinetic modeling is also undertaken using a recently updated gasoline surrogate kinetic model to simulate the RCM experiments and to provide chemical insight into surrogate-to-surrogate differences. The LGTC engine experiments demonstrate nearly identical reactivity between PACE-20 and RD5-87 across studied conditions, while faster phasing is seen for both PACE-1 and PACE-8 due to their stronger intermediate- and low-temperature heat release (ITHR/LTHR) at naturally aspirated and boosted conditions, respectively. The RCM experiments reveal typical low-temperature, negative temperature coefficient (NTC) and intermediate-temperature autoignition behaviors at all pressure conditions for RD5-87, which are qualitatively reproduced by all surrogates. Quantitative discrepancies in both autoignition and preliminary heat release are observed for all surrogates, while their ability to replicate RD5-87 autoignition behavior follows the order of PACE-20 > PACE-1 > PACE-8 > PRF88.4. Excellent mapping is obtained between the LGTC engine and the RCM, where the engine pressure-time trajectories can be characterized by the regimes represented by the RCM autoignition isopleths. The kinetic model performs commendably when simulating both autoignition and preliminary heat release of PACE-20, while typically overpredicting ignition delay times for PACE-1, PACE-8 and PRF88.4 at high-pressure and low-temperature/NTC conditions. Sensitivity and rate of production (ROP) analyses highlight surrogate-to-surrogate differences in the governing chemical kinetics where n-pentane initiates rapid OH branching at a faster rate and an earlier timing for PACE-20 than iso-pentane does for PACE-1 and PACE-8, making it computationally more reactive than the other surrogates. The current study highlights the need to include non-standardized properties, such as the lean/HCCI-like autoignition characteristics, in addition to ASTM properties (e.g., RON, MON) as metrics of fuel reactivity and targets to be matched when formulating high-fidelity surrogates that fully capture gasoline advanced combustion behavior such as HCCI-like autoignition.

42 ENGINEERING↗
DOE OSTI2021

A Mechanism for Carbon Depletion at Bondline of High-Frequency Electric-Resistance-Welded X70 Pipeline Steel

The bondline of electric-resistance-welded (ERW) linepipe steel, often etched white (i.e., ferrite) in optical microscopy, is generally believed to be carbon depleted. The mechanism for the carbon depletion, however, is not fully understood by researchers. To this end, here we used atom probe tomography (APT) to measure elemental segregation of the as-welded and post-weld heat-treated bondline regions of X70 linepipe welds. The thin vertical features at the bondline in the as-welded condition were identified as carbon-rich martensite-austenite (M-A) constituents, and the majority ferrite phase in the bondline was identified as carbon-depleted ferrite. Following the post-weld normalization, all alloying elements, except Nb and Mo, are homogenized across the bondline and heat-affected zone. The carbon depletion in the ERW bondline was accurately measured. A new mechanism for carbon depletion has been proposed using Scheil calculations of elemental partitioning during weld formation. Segregation of elements in the heat-affected zone was shown to follow the negligible partitioning local equilibrium (NPLE) kinetics for bainite transformation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Oxidation of ultrahigh temperature ceramics: kinetics, mechanisms, and applications

Materials capable of oxidizing in a protective manner at ultrahigh (>1700 °C) temperatures are needed to push beyond this barrier defined by SiC. Although possessing attractive mechanical properties and oxidation resistance, SiC-based materials are ultimately temperature limited by the melting point of SiO 2 . The vast array of ultra-high and high temperature ceramic literature indicates the majority of these materials, like borides, carbides, MAX-phases, and high-entropy ceramics, fall woefully short regarding oxidation resistance. However, for specific applications, like low-orbit aeropropulsion, high ballistics coefficient atmospheric re-entry, and hypersonic cruise, there are a few promising materials. Here, oxidation criteria are gathered to build application specific heuristics and are then applied to a multitude of ultra-high temperature ceramics to gauge material efficacy. Discussion of oxidation kinetics, mechanisms and reaction products is offered for each material, identifying strengths, weaknesses, and the remaining gaps in our knowledge.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Nanoscale Design of Pd-Based Electrocatalysts for Oxygen Reduction Reaction Enhancement in Alkaline Media

Palladium (Pd)-based electrocatalysts have recently emerged as one class of the foremost promising candidates for the oxygen reduction reaction (ORR) in alkaline media due to their excellent ORR activity and durability and lower costs compared with platinum. Insightful design of Pd-based nano-architectures with optimized active surface sites and maximal intrinsic performance is central to promoting the ORR applications. To further accelerate the sluggish ORR kinetics at the cathode of fuel cells and substantially decrease the overall cost of the electrocatalysts, various strategies, including controlled sizes and shapes with selected crystallographic facets, crystal-phase engineering, heteroatom doping, tailored surface strains, and surface engineering by de-alloying, have been extensively developed in the past decade. Here in this review, a brief introduction to the fundamental ORR mechanisms of Pd-based electrocatalysts in alkaline media is presented, followed by a thorough discussion on various strategies for delicately designing high-performance Pd-based catalysts with corresponding examples. Thereafter, the perspectives and new insights into the challenges are outlined, and some emerging research directions related to the rational design and controlled synthesis of Pd-based ORR electrocatalysts are also proposed.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Driving rapid atomic order in MnAl via low-magnitude magnetic field annealing

Application of a mild (60 mT), uniform magnetic field during short-term thermal treatment of kinetically retained, atomically disordered (paramagnetic) ε-MnAl was found to deliver a significant ~50 % increase in the formation of L1 0 atomically ordered (ferromagnetic) τ-MnAl product phase, compared to that produced by conventional (i.e., zero-field) annealing under identical thermal conditions. The magnetic field, applied in a passive closed-circuit configuration during annealing, induced significant changes in the structural, magnetic, and phase evolution of the material. Computational results based on electronic structure calculations demonstrate that the effective magnetic susceptibility of τ-MnAl is sensitive to the orientation, rather than the magnitude, of an applied magnetic field in the vicinity of the Curie temperature. The uniaxial magnetocrystalline anisotropy of the L1 0 structure is proposed to act as a filter for selective propagation of the population of τ-MnAl variants that are favorably aligned with the applied field. In this manner, crystallographic “gridlock” is alleviated that would otherwise arise from the coexistence of multiple, energetically equivalent τ-phase variants within the parent ε-phase matrix. These results confirm that static, low-magnitude magnetic field annealing is able to accelerate L1 0 atomic ordering in the MnAl system and likely can exert similar influences in relevant magnetic systems, facilitating efficient tailoring of structure-sensitive magnetic properties for the manufacture of magnetic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Evolution of elastic and thermal properties of cementitious composites containing micro-size lightweight fillers after exposure to elevated temperature

This work studies the evolution of elastic and thermal properties of cementitious composites containing micro-size lightweight fillers after exposure to elevated temperatures (up to 800 °C). A multiscale investigation is carried out to study the thermal degradation of cementitious composite materials at multiple scale levels: at cement past level, the dehydration kinetics of cement hydrates (i.e., C–S–H, CH and aluminate hydrates) and development of microcracks are studied as functions of exposure temperatures. The damage mechanism of the inclusion phases and damages within the interfacial transition zone (ITZ) under elevated temperature are also investigated. In addition, the change of mechanical (i.e., elastic moduli, compressive strengths) and thermal (thermal conductivities) properties are measured as functions of the exposure temperature. Based on the experimental studies, a multiscale thermal degradation model is developed where the thermal degradations of cement paste (including water composition, porosity, and solid phase changes), inclusion phases, and the interfaces are captured through a multiscale sub-stepping homogenization scheme. The thermal degradation model is validated through multiple sets of experimental data. Finally, the influence of key parameters including the particle size distribution of the inclusions, the chemical composition, as well as the effects of ITZ damage are studied.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Advantages of tandem versus simultaneous operation: The case of isomerization/hydrogenation of terpinolene epoxide to Terpinen-4-ol using a Ni/TiO 2 -SiO 2 bifunctional catalyst

The conversion of terpinolene epoxide to terpinen-4-ol is a desirable chemical transformation for the production of a valuable intermediate. Here this report describes a one-pot, two-step system for the reaction that uses a bifunctional Ni/TiO 2 -SiO 2 catalyst with isomerization and hydrogenation capabilities. The TiO 2 -SiO 2 serves to isomerize the starting epoxide. The Ni component works to hydrogenate the allylic double bond. The tandem system achieves a high 64% yield of terpinen-4-ol. X-ray diffraction analysis showed that TiO 2 -SiO 2 was a mixed binary oxide, and Fourier transform infrared spectroscopy of adsorbed pyridine suggested that acid sites were mainly Lewis acid sites. Electron microscopy showed that the Ni/TiO 2 -SiO 2 catalyst consisted of spherical particles comprising a titanosilicate phase with highly dispersed zero-valent Ni or anatase on the surface. Additionally, there was strong interaction between Ni and the TiO 2 -SiO 2 mixed oxides. Control kinetic experiments demonstrated that the tandem use of the catalysts was more effective than simultaneous operation.

42 ENGINEERING↗
DOE OSTI2020

High susceptibility to adiabatic shear banding and high dynamic strength in tungsten heavy alloys with a high-entropy alloy matrix

The susceptibility to adiabatic shear banding (ASB) of tungsten heavy alloys (WHAs) is a key factor to determine their penetration performance for kinetic energy penetrators (KEPs). This work reports a novel WHA with strong susceptibility to ASB that uses a precipitation-hardening high-entropy alloy (HEA) as the binding phase of W particles. The results find that nanoscale L12 precipitates and high dislocation density in the matrix contribute a high dynamic yield strength of ~2300 MPa. Also, a narrow ASB with a width of ~12 μm forms in the novel WHA, which is only 6% of the width of ASB in traditional WHAs like W-NiFe, exhibiting a great susceptibility to ASB. The redissolution of precipitates into the matrix because of temperature rise during shearing could sharply soften the shearing location, which is suggested to be a very important factor of destabilizing mechanism to promote the development of ASB.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Probing Early-Time Dynamics and Quark-Gluon Plasma Transport Properties with Photons and Hadrons

In this work, we use a hybrid model which relies on QCD effective kinetic theory - KøMPøST - to dynamically bridge the gap between IP-Glasma initial states and viscous hydrodynamics, for the theoretical interpretation of heavy-ion collision results. The hydrodynamic phase is then followed by dynamical freeze-out handled by UrQMD. It is observed that the new pre-equilibrium/pre-hydro phase does influence the extraction of transport coefficients. We also show how the early dynamics is reflected in photon observables.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

Role of fast ions in spontaneous neoclassical tearing mode instabilities in NSTX

Spontaneous neoclassical tearing modes (spontaneous NTMs) have been observed in the National Spherical Torus Experiment (NSTX). Recently, a TRANSP based model for the modified Rutherford equation analysis was developed to accurately predict the effect of fast ions on the growth of magnetic islands. The goal of this paper is to utilize the TRANSP NTM model to understand the role of fast ions in NSTX spontaneous NTMs. Our analysis shows that when the passing fast ion driven kinetic neoclassical polarization current term is larger than 1% of the bootstrap current term in the modified Rutherford equation, fast ions play a decisive role in the early growth phase of spontaneous NTM. This result is applicable to any tokamak plasmas with a fast ion drift orbit width, or the fast ion poloidal Larmor radius, comparable to the magnetic island width.

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↗