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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Effect of the ..beta..-Hydroxy Group on Ester Reactivity: Combustion Kinetics of Methyl Hexanoate and Methyl 3-Hydroxyhexanoate

One of the major biofuels used today is biodiesel, composed of fatty acid methyl esters. The fats and oils feedstocks used to make biodiesel are in relatively short supply. To meet increasing global demand, engineered microorganisms have been developed to catalyze conversion of sugar to fatty acid esters that contain unique ..beta..-hydroxy-esters. This study investigated the effect of a hydroxyl group on the combustion characteristics of methyl esters by comparing the chemical behavior of methyl hexanoate (MHx) and methyl 3-hydroxyhexanoate (M3OHHx) - used as surrogates for diesel-boiling-range esters with longer fatty acid chains. The oxidation of these esters was studied experimentally in a flow reactor at 0.84 and 10 bar, 600 to 1,100 K, and stoichiometric conditions; and in a constant volume combustion chamber at 5 and 10 bar, 600 to 900 K, and equivalence ratios of 0.3 and 0.6. MHx was more reactive in the constant volume chamber at temperatures below 800 K at 10 bar and equivalence ratio of 0.6. MHx also exhibited a higher indicated cetane number (16.4) than M3OHHx (8.1). We investigated this reactivity trend using an updated MHx kinetic model and M3OHHx model developed as part of this work. The kinetic models predicted that radicals formed from MHx were consumed by low-temperature chemistry reactions, whereas the M3OHHx reactivity was significantly governed by the ..beta..-radical (on the same carbon as the OH group) chemistry which mainly terminated via the less reactive chain propagation pathway to methyl-3-oxohexanoate + HO2. This study extends our understanding of structural effects on ester reactivity, which will allow for accurate surrogate formulation and performance simulations.

AFIDA↗
DOE OSTI2017

Kinetics and Mechanism of Methanol Conversion over Anatase Titania Nanoshapes

The kinetics and mechanism of methanol dehydration, redox, and oxidative coupling were explored at 300 °C under dilute oxygen concentration over anatase TiO 2 nanoplates and truncated-bipyramidal nanocrystals in order to understand the surface structure effect of TiO 2 . The two TiO 2 nanoshapes displayed both (001) and (101) facets, with a higher fraction of the (001) facet exposed on the nanoplates, while truncated-bipyramidal nanocrystals were dominated by the (101) facet. A kinetic study using in situ titration with ammonia reflects that the active sites for methanol dehydration are acidic and nonequivalent in comparison to redox and oxidative coupling. In situ FTIR spectroscopy reveals that adsorbed methoxy is the dominant surface species for all reactions, while the observed methanol dimer is found to be a spectator species through isotopic methanol exchange, supporting the dissociative mechanism for methanol dehydration via surface methoxy over TiO 2 surfaces. Density functional theory calculations show that the formation of dimethyl ether involves the C–H bond dissociation of an adsorbed methoxy, followed by coupling with another surface methoxy on the 5-fold-coordinated Ti cations on the (101) surface, similar to the mechanism reported on the (001) surface. Kinetic isotope effects are observed for dimethyl ether, formaldehyde, and methyl formate in the presence of deuterated methanol (CD 3 OH and CD 3 OD), confirming that the cleavage of the C–H bond is the rate-limiting step for the formation of these products. A comparison between estimated kinetic parameters for methanol dehydration over various TiO 2 nanocrystals suggests that (001) has a higher dehydration reactivity in comparison to (101), but the surface density of active sites could be limited by the presence of residual fluorine atoms originating from the synthesis. The (001) surface of TiO 2 is also more active than the (101) surface in redox and oxidative coupling of methanol, which is due to the reactive surface oxygen on (001) in comparison to the (101) surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Expanding Lorentz and spectrum corrections to large volumes of reciprocal space for single-crystal time-of-flight neutron diffraction

Evidence is mounting that potentially exploitable properties of technologically and chemically interesting crystalline materials are often attributable to local structure effects, which can be observed as modulated diffuse scattering (mDS) next to Bragg diffraction (BD). BD forms a regular sparse grid of intense discrete points in reciprocal space. Traditionally, the intensity of each Bragg peak is extracted by integration of each individual reflection first, followed by application of the required corrections. In contrast, mDS is weak and covers expansive volumes of reciprocal space close to, or between, Bragg reflections. For a representative measurement of the diffuse scattering, multiple sample orientations are generally required, where many points in reciprocal space are measured multiple times and the resulting data are combined. The common post-integration data reduction method is not optimal with regard to counting statistics. A general and inclusive data processing method is needed. In this contribution, a comprehensive data analysis approach is introduced to correct and merge the full volume of scattering data in a single step, while correctly accounting for the statistical weight of the individual measurements. Development of this new approach required the exploration of a data treatment and correction protocol that includes the entire collected reciprocal space volume, using neutron time-of-flight or wavelength-resolved data collected at TOPAZ at the Spallation Neutron Source at Oak Ridge National Laboratory.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

MgADP Promotes Myosin Head Movement toward Actin at Low [Ca 2+ ] to Increase Force Production and Ca 2+ -Sensitivity of Contraction in Permeabilized Porcine Myocardial Strips

Myosin cross-bridges dissociate from actin following Mg 2+ -adenosine triphosphate (MgATP) binding. Myosin hydrolyses MgATP into inorganic phosphate (P i ) and Mg 2+ -adenosine diphosphate (ADP), and release of these hydrolysis products drives chemo-mechanical energy transitions within the cross-bridge cycle to power muscle contraction. Some forms of heart disease are associated with metabolic or enzymatic dysregulation of the MgATP-MgADP nucleotide pool, resulting in elevated cytosolic [MgADP] and impaired muscle relaxation. We investigated the mechanical and structural effects of increasing [MgADP] in permeabilized myocardial strips from porcine left ventricle samples. Sarcomere length was set to 2.0 µm at 28 °C, and all solutions contained 3% dextran T-500 to compress myofilament lattice spacing to near-physiological values. Under relaxing low [Ca 2+ ] conditions (pCa 8.0, where pCa = -log 10 [Ca 2+ ]), tension increased as [MgADP] increased from 0-5 mM. Complementary small-angle X-ray diffraction measurements show that the equatorial intensity ratio, I 1,1 /I 1,0 , also increased as [MgADP] increased from 0 to 5 mM, indicating myosin head movement away from the thick-filament backbone towards the thin-filament. Ca 2+ -activated force-pCa measurements show that Ca 2+ -sensitivity of contraction increased with 5 mM MgADP, compared to 0 mM MgADP. These data show that MgADP augments tension at low [Ca 2+ ] and Ca 2+ -sensitivity of contraction, suggesting that MgADP destabilizes the quasi-helically ordered myosin OFF state, thereby shifting the cross-bridge population towards the disordered myosin ON state. Together, these results indicate that MgADP enhances the probability of cross-bridge binding to actin due to enhancement of both thick and thin filament-based activation mechanisms.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

Structure-Sensitive Scaling Relations: Adsorption Energies from Surface Site Stability

Here, the design of heterogeneous catalysts is accelerated by the identification of thermochemical reactivity descriptors, which enable the prediction of promising materials through efficient screening. Motivated by previous discoveries of linear scaling relations between the adsorption energies of related atoms and molecules, we present a new scaling between the adsorption energies of metal atoms and metal–adsorbate complexes, which can be used to directly predict catalytically relevant molecular adsorption energies. In contrast to existing models based on the coordination number of surface atoms alone, our model can predict adsorption energies with site–by–site resolution considering local structural effects and also has potential extensions to include contributions of neighboring metal identity in alloy systems. Integration of this scaling with a previously identified model for metal–metal interactions enables the accurate prediction of molecular adsorption energies on nanoparticles by performing only a small set of slab–based calculations.

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

Computational study of Fermi kinetics transport applied to large-signal RF device simulations

Here, a detailed description and analysis of the Fermi kinetics transport (FKT) equations for simulating charge transport in semiconductor devices is presented. The fully coupled nonlinear discrete FKT equations are elaborated, as well as solution methods and work-flow for the simulation of RF electronic devices under large-signal conditions. The importance of full-wave electromagnetics is discussed in the context of high-speed device simulation, and the meshing requirements to integrate the full-wave solver with the transport equations are given in detail. The method includes full semiconductor band structure effects to capture the scattering details for the Boltzmann transport equation. The method is applied to high-speed gallium nitride devices. Finally, numerical convergence and stability examples provide insight into the mesh convergence behavior of the deterministic solver.

42 ENGINEERING↗
DOE OSTI2019

Development of a High-Strength Low-Carbon Steel with Reasonable Ductility through Thermal Cycling

In this research work, cost-effective structural material synthesis routes have been adopted in the form of thermal cycling designed and applied on a low-cost material (AISI 1010 steel). The main synthesis route consists of two-step thermal cycling (designed with respect to iron–carbon phase diagram) combining short-duration holding in upper critical and intercritical temperature regimes and different cooling conditions (forced air cooling and ice-brine quenching). Accordingly, the adopted hierarchical design approach (from nanoscale onwards) with a combination of hard and soft phases (to attain an adequate balance between mutually exclusive strength and ductility properties) results in origin of a novel microstructure. The microstructure consists of dislocation-enriched martensite regions (possessing plate and lath morphologies in 1:4 ratio) containing nanosized cementite particles and α-ferrite regions containing submicroscopic cementite particles. As a consequence, an excellent combination of strength (UTS = 905 MPa) and ductility (%Elongation = 17) is achieved in the synthesized material.

36 MATERIALS SCIENCE↗
DOE OSTI2023

First-principles study of grain-boundary wetting in Fe-Σ5(013)[100] tilt boundary

Here, we report an ab-initio study of grain-boundary wetting (GBW) in three systems (Fe/Zn, Fe/Pb & Fe/Bi) on a Σ5(013)[100] tilt grain boundary. An energy-based approach is pursued and adapted to the study of liquid-metal/solid-metal interfaces. We provide a sound calculation of the wettability parameter S (i.e., defined as the minimum energy difference between the unbroken initial state and final state with liquid-metal/solid-metal interfaces). Solid/liquid interfaces are modelled by ab-initio molecular dynamics, also allowing a study of structural effects in the liquid phase near the solid interface. We show how surface energies for solid-metal/liquid-metal interfaces need a special treatment for the liquid-metal chemical potential due to the change in crystallinity near the interface. The computation of the wettability criterion for the three systems correctly predicts the GBW trend known experimentally for these systems. The computations are compared with small-scale TEM experiments on GBW of two systems (Fe/Pb and Fe/Bi) and it is shown to provide reasonable results. This approach offers new perspectives in predicting GBW trends across various systems.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Calculating electronic stopping power in materials from first principles

From the early models of electronic stopping power to the current first principles simulations, the techniques evolved to increase the range of validity and to reduce empiricism. Thanks to a combination of theoretical advances provided by Time Dependent Density Functional Theory and the development of numerical codes, it is currently possible to predict electronic stopping power for realistic materials by performing direct simulations of the electron excitation processes beyond linear response, and including electronic band structure effects. Electronic stopping power is an important quantity used to predict and understand the effects of particle radiation in matter. First principles calculations of electronic stopping power can be applied to any atomistic system, solids, liquids and alloys. This review aims here to help graduate level students and researchers immerse themselves into state-of-the-art techniques to computationally model and calculate electronic stopping power.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Economic competitiveness of pultruded fiber composites for wind turbine applications

Pultrusion manufacturing of fiber reinforced polymers has been shown to yield some of the highest mechanical properties for unidirectional composites, having a high degree of fiber alignment with consistent performance. Pultrusions offer a low-cost manufacturing approach for producing unidirectional composites with a constant cross-section and are used in many applications, including spar caps of wind turbine blades. However, as an intermediate processing step for wind blades, the additional cost of manufacturing pultrusions must be accompanied by sufficient increases in mechanical performance and system benefits. Wind turbine blades are manufactured using vacuum-assisted resin transfer molding with infused unidirectional fiberglass or carbon pultrusions for the spar cap. Infused fiberglass composites are among the most cost-effective structural materials available and replacing this material in the cost-driven wind industry has proven challenging, where infused fiberglass spar caps are still the predominant material system in use. To evaluate alternative material systems in a pultruded composite form, it is necessary to understand the costs for this additional manufacturing step which are shown to add 33%–55% on top of the material costs. A pultrusion cost model has been developed and used to quantify cost sensitivities to various processing parameters. The mechanical performance for pultruded composites is improved versus resin-infusion manufacturing with a 17% increase in design strength at a constant fiber volume fraction, but also enables higher achievable fiber volume fractions. The cost-specific mechanical performance is compared as a function of processing parameters for pultruded composites to identify the opportunities for alternative material and manufacturing approaches for wind turbine spar caps. Finally, four materials are compared in a representative wind turbine blade model to assess the performance of pultruded carbon fiber systems and pultruded fiberglass relative to infused fiberglass, where the pultruded systems produce lower weight blades with various cost distinctions.

42 ENGINEERING↗
DOE OSTI2020

Activation and surface reactions of CO and H 2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions

Here, activation and surface reactions of CO and H 2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions were (quasi) in situ studied using temperature programmed surface reaction spectra, diffuse reflectance Fourier transform infrared spectroscopy, inelastic neutron scattering spectroscopy and electron paramagnetic resonance. CO undergoes disproportion reaction to produce gaseous CO 2 and surface carbon adatoms, and adsorbs to form surface formate species. H 2 adsorption forms dominant irreversibly-adsorbed surface hydroxyl groups and interstitial H species and very minor surface Zn-H species. Surface formate species and hydroxyl groups react to produce CO 2 and H 2 , while surface carbon adatoms are hydrogenated by surface Zn-H species sequentially to produce CH(a), CH 2 (a), CH 3 (a) and eventually gaseous CH 4 . The ZnO nanoplates, exposing a higher fraction of Zn-ZnO(0001) and O-ZnO(000–1) polar facets, are more active than the ZnO powders to catalyze CO hydrogenation to CH 4 . These results provide fundamental understanding of the reaction mechanisms and structural effects of CO hydrogenation reaction catalyzed by ZnO-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Expanding the interlayer spacing of MXene through nanoarchitecture design

MXenes, a diverse class of two-dimensional transition metal carbides and nitrides with distinct surface chem istries, offer remarkable electrochemical and physicochemical properties. Yet, their performance can be hindered by the intrinsic restacking of layers, which restricts surface activity. This review outlines recent advances in interlayer spacing modulation strategies designed to overcome this limitation. A wide range of guest spe cies–including mono- and polyatomic ions, small molecules, low-dimensional nanomaterials, and polymers–are discussed with respect to their intercalation mechanisms, structural effects, and capacity to introduce functional enhancements. These intercalating species interact with MXene via electrostatic forces, hydrogen bonding, redox reactions, or covalent linkages, resulting in stable, expanded nanoarchitectures. The influence of expanded spacing on capacitive behavior is briefly highlighted to illustrate its practical relevance. Although Ti 3 C 2 T x is currently the most extensively investigated MXene, applying these interlayer engineering strategies to other MXene compositions will be essential for accessing a wider range of properties and functionalities.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Electrochemo-mechanics unlocks hidden dynamics of lithium plating under stacking pressure

Understanding and mitigating lithium plating remains one of the most pressing challenges in advancing the safety and longevity of lithium-ion batteries (LIBs). Here, we present a novel integrative framework that combines in-operando swelling force measurements with a physics-based electro-chemo-mechanical model to uncover previously inaccessible insights into lithium plating dynamics under mechanical constraints. Unlike existing approaches that focus primarily on electrochemical signatures, our approach captures the coupled mechanical responses of commercial pouch cells during cycling, revealing how mechanical constraints fundamentally alter degradation pathways. We demonstrate that the use of a moderate stacking pressure suppresses lithium plating and enhances lithium stripping. This mechanically driven structural effect, coupled with the electrochemical process, significantly extends the linear aging regime in LIBs. Intriguingly, intermittent capacity recovery events that were observed during the battery cycling suggest dynamic lithium reactivation, a phenomenon rarely captured in real-time. This study pioneers a stress-aware methodology for diagnosing and managing lithium plating, establishing a new paradigm for real-time battery health monitoring. The findings offer transformative implications for the design of durable, high-performance LIB systems, opening new avenues for intelligent control strategies in battery management systems.

Bhowmick, Amit↗
DOE OSTI2017

Revisiting Grodzins systematics of B(E2) values

Using Grodzins formalism, we analyze systematics of our latest evaluated B(E2) data for all the even–even nuclei in Z=2–104. The analysis indicates a low predictive power of systematics for a large number of cases, and a strong correlation between B(E2) fit values and nuclear structure effects. These findings provide a strong rationale for introduction of individual or elemental (grouped by Z) fit parameters. The current estimates of quadrupole collectivities for systematics of even–even nuclei yield complementary values for comparison with experimental results and theoretical calculations. Furthermore, the lists of fit parameters and predicted B(E2) values are given and possible implications are discussed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Probing the limits of statistical neutron capture for the r process: Experimental constraints on 141 Cs nuclear level densities

The r-process abundance peaks, particularly near mass number A ∼ 130, reflect underlying nuclear structure effects such as closed neutron shells, yet modeling the nucleosynthesis in this region remains hindered by uncertain neutron-capture rates. These rates are especially sensitive to nuclear level densities (NLDs) and γ-ray strength functions of neutron-rich nuclei, where experimental data are scarce. We present the first experimental constraint on the NLD of 141 Cs using the β-Oslo method, extending sensitivity to the neutron-rich regime near the N = 82 closed shell. Our data allow for critical calibration of microscopic NLD models and reveal that 141 Cs lies near the limit of statistical model applicability. Using this experimental input, we evaluate radiative neutron-capture rates across neighboring isotones using both Hauser–Feshbach (HF) and High Fidelity Resonance (HFR) models. Our results show order-of-magnitude rate increases for nuclei along the N = 86 line, signaling a transition to resonance-dominated capture in this region. These findings underscore the importance of constraining NLDs to improve r-process reaction network predictions, particularly in environments where the validity of statistical models breaks down.

Nuclear level density↗
DOE OSTI2016

Competing Structural Instabilities in the Ruddlesden–Popper Derivatives HRTiO 4 (R = Rare Earths): Oxygen Octahedral Rotations Inducing Noncentrosymmetricity and Layer Sliding Retaining Centrosymmetricity

We report the discovery of noncentrosymmetry in the family of HRTiO 4 (R = Eu, Gd, Dy) layered oxides possessing a Ruddlesden-Popper derivative structure, by second harmonic generation and synchrotron x-ray diffraction with the support of density functional theory calculations. These oxides were previously thought to possess inversion symmetry. Here, inversion symmetry is broken by oxygen octahedral rotations, a mechanism that is not active in simple perovskites. We discover a competition between oxygen octahedral rotations and sliding of the octahedral perovskite blocks at the OH layers. For the smaller rare earth ions, R = Eu, Gd, Dy, which favor the octahedral rotations, noncentrosymmetry is present but the sliding at the OH layer is absent. For the larger rare earth ions, R = Nd and Sm, the octahe-dral rotations are absent, but sliding of the octahedral blocks at the OH layer is present, likely to optimize the hydrogen bond length arising from the directional nature of these bonds in the crystal structure. The study reveals a new mechanism for inducing noncentrosymmetry in layered oxides, and chemical-structural effects related to rare earth ion size and hydrogen bonding that can turn this mechanism on and off. In conclusion, we construct a complete phase diagram of temperature versus rare earth ionic radius for the HRTiO 4 family.

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

Defect Engineering of Earth-Abundant Solar Absorbers BiSI and BiSeI

Bismuth-based solar absorbers have recently garnered attention due to their promise as cheap, nontoxic, and efficient photovoltaics. To date, however, most show poor efficiencies far below those seen in commercial technologies. In this work, we investigate two such promising materials, BiSI and BiSeI, using relativistic first-principles methods with the aim of identifying their suitability for photovoltaic applications. Both compounds show excellent optoelectronic properties with ideal band gaps and strong optical absorption, leading to high predicted device performance. Using defect analysis, we reveal the electronic and structural effects that can lead to the presence of deep trap states, which may help explain the prior poor performance of these materials. Crucially, detailed mapping of the range of experimentally accessible synthesis conditions allows us to provide strategies to avoid the formation of killer defects in the future.

14 SOLAR ENERGY↗
DOE OSTI2026

Cation Site Occupancy in Natural Ferroan Double Carbonates via Mössbauer and Fe K-Edge X-ray Absorption Spectroscopy

Double carbonates are minerals with a calcite type structure with alternating cation layers composed of Ca and Mg/Fe coordinated by carbonate groups. While the perfectly ordered AB-stacked crystal is the thermodynamically most stable configuration, natural mineral formation pathways can leave signatures through kinetically trapped disorder such as AB antisite cation substitutions. This study probes the degree of cation ordering in naturally occurring double carbonate samples.in particular, the distribution of Fe A and B crystallographic sites (A site is Ca layer and B site is Mg/Fe layer). Mössbauer, X-ray diffraction, X-ray absorption fine structure (both X-ray absorption near edge structure, XANES, and extended x-ray absorption fine structure, EXAFS), and energy dispersive X-ray spectroscopies were used to collect a comprehensive experimental data set, which we interpret using density functional theory to elucidate the structural effects of cation disorder. Our results show that the A (nominally Ca) site can host a relatively high Fe fraction. We discuss the implications in terms of mineral formation.

Boglaienko, Daria (ORCID:0000000160943877)↗