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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 1,153 records · Page 64
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Multiscale operando X-ray investigations provide insights into electro-chemo-mechanical behavior of lithium intercalation cathodes

The electrochemical performance and cycle life of lithium-ion batteries (LIBs) depend on the electrochemical, chemical, and mechanical behavior of electrodes and electrolytes. Despite extensive studies conducted previously, challenges exist to decouple these behaviors, capture the evolution of electro-chemo-mechanical behavior in realistic conditions, and correlate atomic-scale stress evolution to micro-scale bulk mechanical degradation. Here, we report multiscale operando techniques to investigate polydisperse battery electrodes by integrating volume-averaged quantitative synchrotron X-ray scattering with high-resolution transmission X-ray microscopy (TXM). The former provides us information spanning a wide spatial range, from Angstrom-level atomic structures to micrometer-level particle scales, while the latter provides time-resolved 2D images of the particles during cycling. The complementarity of the two operando techniques is demonstrated by an over-lithiation test of LiCoO 2 electrodes, where particles crack and eventually pulverize. Additionally, the techniques are applied to study LiCoO 2 cycling stability from 3.0 V to 4.5 V. Operando X-ray scattering result shows nanometer-scale features keep forming in LiCoO 2 electrodes during cycling, resulting in an increased projected area observed by the TXM experiment. The formation of such features is inhibited by a polymer coating on the electrode, leading to vastly improved cycling stability. The polymer coating alleviates LiCoO 2 surface deterioration, reduces side product generation, and inhibits LiCoO 2 particles volume expansion during the cycling test. These operando multimodal X-ray techniques presented herein thus offer a novel, multiscale diagnostic modality for studying existing and emerging battery materials, aiding the development of next-generation LIBs.

25 ENERGY STORAGE↗
DOE OSTI2019

Epitaxial Growth and Band Alignment of p-NiO/n-Fe2O3 Heterojunction on Al2O3(0001)

Fe2O3 is one of the promising oxide semiconductors as photoanodes for photoelectrochemical water splitting, but its efficiency is still limited by the short diffusion length of photo-excited carriers. Using the internal electric field formed at a p-n heterojunction (HJ) is an efficient strategy to mitigate such limitation. Accordingly, the interfacial atomic structure and band alignment are the most crucial parameters for efficiency optimization. In this work, we report on the epitaxial growth and determination of the band energy alignment of NiO/Fe2O3 p-n heterojunction grown on Al2O3(0001) substrate by pulsed laser deposition. We show that high crystalline quality NiO(111) thin films can be grown on Fe2O3(0001) with epitaxial relationships of [1 ¯11]NiO||[0001 ¯ ]Fe2O3(out-of-plane), [1 ¯1 ¯0]NiO||[011 ¯0]Fe2O3 and [1 ¯12 ¯ ]NiO||[21 ¯1 ¯0]Fe2O3(in-plane). The rotation of NiO hexagons by 30° can effectively reduce the lattice mismatch from ~17.4% to ~1.58%. High resolution X-ray photoelectron spectroscopy reveals that valence and conduction band offset of NiO/Fe2O3 heterojunction are 0.7 eV and 2.3 eV with an upward band bending potential of 0.23 eV for Fe2O3 and a downward band bending potential of 0.32 eV for NiO, respectively. This kind of interfacial band alignment not only facilitates the charge separation, but lowers the overpotentials for oxygen evolution reaction.

Photoelectrochemical Water Splitting, Oxide Semico↗
DOE OSTI2016

Novel allelic mutations in murine Serca2 induce differential development of squamous cell tumors

Dominant mutations in the Serca2 gene, which encodes sarco(endo)plasmic reticulum calcium-ATPase, predispose mice to gastrointestinal epithelial carcinoma [1–4] and humans to Darier disease (DD) [14–17]. In this study, we generated mice harboring N-ethyl-N-nitrosourea (ENU)-induced allelic mutations in Serca2: three missense mutations and one nonsense mutation. Mice harboring these Serca2 mutations developed tumors that were categorized as either early onset squamous cell tumors (SCT), with development similar to null-type knockout mice [2,4] (aggressive form; M682, M814), or late onset tumors (mild form; M1049, M1162). Molecular analysis showed no aberration in Serca2 mRNA or protein expression levels in normal esophageal cells of any of the four mutant heterozygotes. There was no loss of heterozygosity at the Serca2 locus in the squamous cell carcinomas in any of the four lines. The effect of each mutation on Ca{sup 2+}-ATPase activity was predicted using atomic-structure models and accumulated mutated protein studies, suggesting that putative complete loss of Serca2 enzymatic activity may lead to early tumor onset, whereas mutations in which Serca2 retains residual enzymatic activity result in late onset. We propose that impaired Serca2 gene product activity has a long-term effect on squamous cell carcinogenesis from onset to the final carcinoma stage through an as-yet unrecognized but common regulatory pathway. -- Highlights: •Novel mutations in murine Serca2 caused early onset or late onset of tumorigenesis. •They also caused higher or lower incidence of Darier Disease phenotype. •3D structure model suggested the former mutations led to severer defect on ATPase. •Driver gene mutations via long-range effect on Ca2+ distributions are suggested.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

Highly insulating ferromagnetic cobaltite heterostructures

Ferromagnetic insulators are rather rare but possess great technological potential in, for example, spintronics. Individual control of ferromagnetic properties and electronic transport provides a useful design concept of multifunctional oxide heterostructures. We studied the close correlation among the magnetism, atomic structure, and electronic structure of oxide heterostructures composed of the ferromagnetic perovskite LaCoO 3 and the antiferromagnetic brownmillerite SrCoO 2.5 epitaxial thin film layers. By reversing the stacking sequence of the two layers, we could individually modify the electric resistance and saturation magnetic moment. Lastly, the ferromagnetic insulating behavior in the heterostructures was understood in terms of the electronic reconstruction at the oxide surface/interfaces and crystalline quality of the constituent layers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Characterization of novel blast-furnace slag cement pastes and mortars activated with a reactive mixture of MgO-NaOH

This paper reports results of strength and reaction products of blast-furnace slag cements activated using a mixture of MgO-NaOH with a ratio 50/50 incorporated at 4, 6 and 8% relative to the slag mass. Pastes and mortars were prepared and cured at 20 °C and 60 °C-24 h-20 °C up to 90 days. The results indicated that the combination of MgO-NaOH acts as an effective alkaline activator of the slag, as samples cured at 20 °C developed 54 MPa at 90 days, while those at 60 °C-24 h-20 °C had a rapid strength gain at early ages but in the long run strengths of ~42 MPa at 90 days were observed. The microstructures consisted of (C-(A)-S-H), third aluminate hydrates and hydrotalcite. The formation of the latter increased at higher MgO:NaOH concentration lowering the Al uptake by C-S-H. MgO and Mg(OH){sub 2} were not detected, indicating an effective incorporation of Mg{sup 2+} ions into the atomic structure of the reaction products.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Characterisation of magnesium silicate hydrate phases (M-S-H): A combined approach using synchrotron-based absorption-spectroscopy and ab initio calculations

The formation of magnesium-silicate-hydrate (M-S-H) phases has been observed at the interface between cement and argillaceous rock formations. In this study the atomic structure of M-S-H and magnesium-calcium-silicate-hydrate (M-C-S-H, a mixing with Ca) was performed by Mg K-edge X-ray absorption spectroscopy combined with ab-initio calculations. The results show that all magnesium containing phases have a TOT phyllosilicate structure with silica defects creating end of silica chains and an interlayer composed of Mg bound to hydroxide groups. Significant differences are observable between the M-S-H and the M-C-S-H. Firstly, the M-C-S-H phases have an enlarged structure compared to the M-S-H phases. Secondly, the results indicate that at least two geometrically distinct Mg octahedral sites are present for all phases. It is concluded that the Mg octahedra are attached to both Si tetrahedra in a manner similarly to that in talc and, to hydroxide groups in a manner similar to that in brucite.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Polymer intercalation synthesis of glycoboehmite nanosheets

In this work, novel materials based on the aluminum oxyhydroxide boehmite phase were prepared using a glycothermal reaction in 1,4-butanediol. Under the synthesis conditions, the atomic structure of the boehmite phase is altered by the glycol solvent in place of the interlayer hydroxyl groups, creating glycoboehmite. The structure of glycoboehmite was examined in detail to determine that glycol molecules are intercalated in a bilayer structure, which would suggest that there is twice the expansion identified previously in the literature. This precursor phase enables synthesis of two new phases that incorporate either polyvinylpyrrolidone or hydroxylpropyl cellulose nonionic polymers. These new materials exhibit changes in morphology, thermal properties, and surface chemistry. All the intercalated phases were investigated using PXRD, HRSTEM, SEM, FT-IR, TGA/DSC, zeta potential titrations, and specific surface area measurement. These intercalation polymers are non-ionic and interact through wetting interactions and hydrogen bonding, rather than by chemisorption or chelation with the aluminum ions in the structure.

36 MATERIALS SCIENCE↗
DOE OSTI2022

BefA, a microbiota-secreted membrane disrupter, disseminates to the pancreas and increases β cell mass

Microbiome dysbiosis is a feature of diabetes, but how microbial products influence insulin production is poorly understood. Here, we report the mechanism of BefA, a microbiome-derived protein that increases proliferation of insulin-producing β cells during development in gnotobiotic zebrafish and mice. BefA disseminates systemically by multiple anatomic routes to act directly on pancreatic islets. We detail BefA’s atomic structure, containing a lipid-binding SYLF domain, and demonstrate that it permeabilizes synthetic liposomes and bacterial membranes. A BefA mutant impaired in membrane disruption fails to expand β cells, whereas the pore-forming host defense protein, Reg3, stimulates β cell proliferation. Our work demonstrates that membrane permeabilization by microbiome-derived and host defense proteins is necessary and sufficient for β cell expansion during pancreas development, potentially connecting microbiome composition with diabetes risk.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Effect of atomic order/disorder on vacancy clustering in concentrated NiFe alloys

Using molecular dynamics simulations, we elucidate in this paper the effect of atomic structure on vacancy clustering in ordered (L1 0 ) and random NiFe. Based on our simulations, we predict the vacancy evolution to be in complete contrast between the two systems. While large vacancy clusters, i.e., stacking fault tetrahedra (SFT) are formed in the random structure, no clustering is observed in the ordered-L1 0 structure. Similar simulations are performed on L1 0 -CuAu and L1 0 -TiAl to understand whether SFT formation is generic in L1 0 structures, or is specific to NiFe. Both materials show SFT formation, thereby highlighting specific defect energetics in L1 0 NiFe that lead to the lack of vacancy clustering. We elucidate that L1 0 -NiFe has unique thermodynamic and kinetic defect energetics, i.e., antisite energies, vacancy sublattice preference, and directional migration energy barriers that collectively lead to the lack of vacancy clustering. Finally, understanding such defect energetics could open avenues to prevent defect clustering in the vision towards development of radiation-tolerant concentrated alloys for nuclear reactor applications.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2021

A microstructure-based modeling approach to predict the mechanical properties of Zr alloy with hydride precipitates

In nuclear reactors, hydrides can form in fuel cladding due to hydrogen absorption in ZIrcaloy and cause embrittlement. This work presents a microstructure-based finite element model to predict the stress-strain response of Zircaloy containing hydrides. Quantitative microstructural details extracted from scanning electron microscopy (SEM) images were used to generate heterogeneous microstructures including the morphology and spatial distribution of hydrides. The constitutive material model for zircaloy in this study is based on crystal plasticity theory which considers the hexagonal close-packed (HCP) atomic structure of Zircaloy material. The hydrides were modeled as brittle material along with a damage model. Hydride formation inside the zircoloy matrix results in residual stress. This phenomenon is also captured in this model. A parametric study has been conducted to understand the effect of volume fraction, orientation, and lamellae thickness of the hydride phase on the mechanical properties of the overall material.

Kulkarni, Shank S.↗
DOE OSTI2023

A sensitivity analysis of twinning crystal plasticity finite element model using single crystal and poly crystal Zircaloy

The popularity of crystal plasticity finite element method (CPFEM) models is increasing due to their ability to predict the mechanical response of crystalline materials such as metals and metal alloys more accurately than traditional continuum mechanics models. This is since the crystal plasticity models consider the effect of atomic structure, microstructural morphology, and properties of individual grains. These CPFEM models use a large number of material parameters in order to capture the mesoscale physics which comes with the downside of the tedious calibration process. In this paper, a CPFEM code was developed to include the twinning induced grain reorientation and subsequent crystallographic slip for HPC material. The developed code is incorporated in a large-scale, parallelized nonlinear solver WARP3D. Further, a sensitivity analysis with respect to 22 material parameters was then conducted using single crystal and polycrystal representative volume element (RVE) of Zircaloy material. Loading was applied along five different crystallographic orientations for single crystal RVE and along three directions namely, rolling (RD), transverse (TD), and normal (ND) direction for polycrystal RVE. Results obtained from the sensitivity analysis were used for the calibration of material parameters for Zircaloy. Finally, developed code along with calibrated material parameters was used to investigate the effect of the hydride phase formation in Zircaloy which is a typical case observed for nuclear applications. It was found that the volume fraction of the hydride phase has a significant impact on the mechanical properties of Zircaloy.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Advanced techniques for characterization of ion beam modified materials

Understanding the mechanisms of damage formation in materials irradiated with energetic ions is essential for the field of ion-beam materials modification and engineering. Utilizing incident ions, electrons, photons, and positrons, various analysis techniques, including Rutherford backscattering spectrometry (RBS), electron RBS, Raman spectroscopy, high-resolution X-ray diffraction, small-angle X-ray scattering, and positron annihilation spectroscopy, are routinely used or gaining increasing attention in characterizing ion beam modified materials. The distinctive information, recent developments, and some perspectives in these techniques are reviewed in this paper. Applications of these techniques are discussed to demonstrate their unique ability for studying ion-solid interactions and the corresponding radiation effects in modified depths ranging from a few nm to a few tens of μm, and to provide information on electronic and atomic structure of the materials, defect configuration and concentration, as well as phase stability, amorphization and recrystallization processes. Finally, such knowledge contributes to our fundamental understanding over a wide range of extreme conditions essential for enhancing material performance and also for design and synthesis of new materials to address a broad variety of future energy applications.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Thermodynamics of concentrated solid solution alloys

This study reviews the three main approaches for predicting the formation of concentrated solid solution alloys (CSSA) and for modeling their thermodynamic properties, in particular, utilizing the methodologies of empirical thermo-physical parameters, CALPHAD method, and first-principles calculations combined with hybrid Monte Carlo/Molecular Dynamics (MC/MD) simulations. In order to speed up CSSA development, a variety of empirical parameters based on Hume-Rothery rules have been developed. Herein, these parameters have been systematically and critically evaluated for their efficiency in predicting solid solution formation. The phase stability of representative CSSA systems is then illustrated from the perspectives of phase diagrams and nucleation driving force plots of the σ phase using CALPHAD method. The temperature-dependent total entropies of the FCC, BCC, HCP, and σ phases in equimolar compositions of various systems are presented next, followed by the thermodynamic properties of mixing of the BCC phase in Al-containing and Ti-containing refractory metal systems. First-principles calculations on model FCC, BCC and HCP CSSA reveal the presence of both positive and negative vibrational entropies of mixing, while the calculated electronic entropies of mixing are negligible. Temperature dependent configurational entropy is determined from the atomic structures obtained from MC/MD simulations. Current status and challenges in using these methodologies as they pertain to thermodynamic property analysis and CSSA design are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Pseudoatom molecular dynamics plasma microfields

Spectral lines are powerful diagnostic tools for both laboratory and astrophysical plasmas, as their shape is sensitive to the plasma environment. The low-frequency component of the electric microfield is an important input for semi-analytic line broadening codes. Here, in this paper, we detail a new method of calculating plasma microfields using configuration-resolved pseudoatom molecular dynamics. This approach accounts for both quantum atomic structure and N-body effects, similar to density functional theory molecular dynamics, but with less computational cost. We present pseudoatom microfields at plasma conditions relevant for recent high energy density laboratory astrophysics experiments conducted at the Sandia Z-Machine, National Ignition Facility, and Linac Coherent Light Source. Compared to established microfield codes we find moderate deviations at solid density conditions and strong agreement at lower plasma densities.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2013

Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O₂ lattice in an irradiated (60 MW d kg⁻¹) MOX sample was performed employing micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (~0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am³⁺ species within an [AmO₈]¹³⁻ coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix. - Graphical abstract: Americium LIII XAFS spectra recorded for the irradiated MOX sub-sample in the rim zone for a 300 μm×300 μm beam size area investigated over six scans of 4 h. The records remain constant during multi-scan. The analysis of the XAFS signal shows that Am is found as trivalent in the UO₂ matrix. This analytical work shall open the door of very challenging analysis (speciation of fission product and actinides) in irradiated nuclear fuels. - Highlights: • Americium was characterized by microX-ray absorption spectroscopy in irradiated MOX fuel. • The americium redox state as determined from XAS data of irradiated fuel material was Am(III). • In the sample, the Am³⁺ face an AmO₈¹³⁻coordination environment in the (Pu,U)O₂ matrix. • The americium dioxide is reduced by the uranium dioxide matrix.

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

Study of the Al-T-Si (T = Fe, Co, Ni) alloys in the solid, liquid and as-quenched states

Highlights: • Analysis of the formation and evolution of crystalline phases during heat-treatment of as-quenched alloys using in-situ high-temperature XRD. • XRD study and MD simulations of SRO in liquid and amorphous Al-T-Si (T = Fe, Co, Ni) alloys. • Similarity between the CSRO in amorphous Al{sub 65}T{sub 15}Si{sub 20} (T = Fe, Ni) alloys and crystalline Al{sub 9}Fe{sub 2}Si{sub 2} and Al{sub 3}Ni phases. - Abstract: Local atomic structure of liquid and amorphous Al{sub 80 − x}T{sub x}Si{sub 20} (where T = Fe, Co, Ni and x = 10, 15) alloys has been studied by X-ray diffraction (XRD) and molecular dynamics simulations. Chemical short-range order in the liquid and amorphous alloys has been found to be similar to that in the corresponding crystalline counterparts. Formation and evolution of crystalline phases during heat-treatment of the as-quenched ternary alloys up to liquid state were shown using in-situ XRD. Analysis of the morphology of the as-quenched and annealed Al-T-Si ribbons has been performed by transmission electron microscopy.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Synthesis of crystalline carbon nanofern-like structure by dc-PECVD and study of its electrical and field emission properties

Graphical abstract: Display Omitted Highlights: ► Branched, carbon nanofern like structure have been synthesized on glass substrate via PECVD. ► Ni catalyst played important role in growing such structure. ► The as prepared sample shows good field emission property with turn on field as low as 4.8 V/mm. ► Temperature dependent conductivity of the sample showed non-linearity. -- Abstract: Carbon nanofern-like structure was synthesized by direct current plasma enhanced chemical vapor deposition at 400 °C using acetylene as carbon precursor and nickel particle as seed. High resolution transmission electron microscopy (HRTEM) study confirmed the fern-like structure of the as-synthesized sample. It was seen that when nickel was not used a cluster deposition took place without forming any structure. Atomic force microscopy study showed the surface topology of the as-prepared samples. X-ray photoelectron spectroscopy as well as HRTEM studies confirmed the presence of nickel in the carbon matrix. Current (I)–voltage (V) characteristics have been taken for three different temperatures. A non-linear I–V characteristic was obtained for the fern like sample. Field emission study showed that carbon nanofern showed efficient field emission with a turn-on field as low as 4.8 V/μm. Also, the field emission has been studied for different inter-electrode distances.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Tribology of two-dimensional materials: From mechanisms to modulating strategies

Two-dimensional (2D) materials are crystalline materials made of a single or a few layers of atoms. They have been an active research subject in recent years because of their unique physical and chemical properties. In particular, 2D materials such as graphene, hexagonal BN, and MoS 2 exhibit some of the lowest friction coefficients and wear rates, making them attractive for enhancing the efficiency, durability, and environmental compatibility of future mechanical systems. This review will focus on recent advances in the tribology of 2D materials. Starting from general physical characteristics, the essential friction and wear behavior of 2D materials together with the associated mechanisms are reviewed for both interlayer and surface sliding. Influences of the atomic structures of the slip interfaces and environmental factors are discussed, with special attention given to various strategies for achieving friction modulation and superlubricity. Finally, the emerging engineering applications of 2D materials, as well as future prospects, are summarized.

36 MATERIALS SCIENCE↗