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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Controlling the structure and ferroic properties of strained epitaxial NiTiO3 thin films on sapphire by post-deposition annealing

Ferroelectrically induced weak ferromagnetism had been predicted earlier in compounds MTiO3 (M = Fe, Mn, Ni) with the LiNbO3-type structure. In order to stabilize this metastable structure by oxide heteroepitaxy, we attempted to grow epitaxial NiTiO3 films on the nonpolar, non-magnetic substrate Al2O3 by pulsed laser deposition. Given the structural imperfections of the as-deposited films arising from the large lattice mismatch, which resulted in weak ferroic ordering, we investigated the effect of post-synthesis annealing on the films’ properties. Our structural data from x-ray diffraction and electron microscopy suggest that the crystalline quality of the NiTiO3 films was greatly improved by annealing the films at 600-1000 oC for 8 hours, with new phase formation along the interface at 1000 oC. Our physical property characterization indicates increased ferromagnetism and polarization after 600 oC, but a change in the magnetic state to likely ferrimagnetism, and a loss of polarization after the 1000 oC treatment. Our results suggest that the ferroic domain properties of the NiTiO3 films can be favorably altered by post-synthesis heat treatment at the proper temperature to manipulate interfacial strain and enhance the multiferroic properties. Improvement in the ferroic properties can be explained by a combination of crystallite growth, interfacial strain relief, and thermodynamic phase stability arguments. At the same time, exceeding temperatures may drive the system to a thermodynamically more favored crystalline order, and eventually to phase segregation and decomposition.

Varga, Tamas↗
DOE OSTI2017

Structural Transformations in High-Capacity Li 2 Cu 0.5 Ni 0.5 O 2 Cathodes

Cathode materials that can cycle > 1 Li+ per transition metal are of substantial interest to increase the overall energy density of lithium-ion batteries. Li2Cu0.5Ni0.5O2 has a very high theoretical capacity of ~ 500 mAh/g assuming both Li+ are cycled reversibly. The Cu2+/3+ and Ni2+/3+/4+ redox couples are also at high voltage, which could further boost the energy density of this system. Despite such promise, Li2Cu0.5Ni0.5O2 undergoes irreversible phase changes during charge (delithiation) that result in large first-cycle irreversible loss and poor long-term cycling stability. Oxygen is evolved before the Cu2+/3+ or Ni3+/4+ transitions are accessed. In this contribution, XRD, TEM, and TXM-XANES are used to follow the chemical and structural changes that occur in Li2Cu0.5Ni0.5O2 during electrochemical cycling. Li2Cu0.5Ni0.5O2 is a solid solution of orthorhombic Li2CuO2 and Li2NiO2, but the structural changes more closely mimic the Li2NiO2 endmember. Li2Cu0.5Ni0.5O2 loses long-range order during charge, but TEM analysis provides clear evidence for particle exfoliation and the transformation from orthorhombic to a partially layered structure. Linear combination fitting and principal component analysis of TXM-XANES are used to map the different phases that emerge during cycling ex situ and in situ. Significant changes in the XANES at the Cu and Ni K-edges correlate with the onset of oxygen evolution.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2018

Hydrogen Bonding Controls the Structural Evolution in Perovskite-Related Hybrid Platinum(IV) Iodides

In this paper, we describe the solid-state structural evolution in four hybrid hexaiodoplatinate(IV) compounds, demonstrating the increasingly important role that extended hydrogen bonding plays in directing the structure across the series. The compounds are A 2 PtI 6 , where A is one of the following amines: ammonium, NH 4 + ; methylammonium, CH 3 NH 3 + ; formamidinium, CH(NH 2 ) 2 + ; guanidinium, C(NH 2 ) 3 + . These are closely related in structure and properties to the hybrid halide perovskites of lead(II) that have recently established their prowess in optoelectronics. The first three of these compounds crystallize in the vacancy-ordered double perovskite A 2 Pt$\square$I 6 ($\square$ indicates a vacant site) structure in the K 2 PtCl 6 archetype, despite the relatively large perovskite tolerance factors involved. The last compound, (GUA) 2 PtI 6 , crystallizes in a vacancy-ordered variant of the hexagonal CsNiCl 3 structure: the K 2 MnF 6 structure. A combination of solid-state 195 Pt and 1 H NMR spectroscopy and detailed density functional theory calculations helps to reveal structural trends and establish the hydrogen-bonding tendencies. Finally, the calculations and measured optical properties support the surprising observation in these iodosalt compounds that, for smaller A cations, the conduction bands are considerably disperse, despite lacking extended I–Pt–I connectivity.

36 MATERIALS SCIENCE↗
DOE OSTI2017

An Efficient Scheme for Crystal Structure Prediction Based on Structural Motifs

An efficient scheme based on structural motifs is proposed for the crystal structure prediction of materials. The key advantage of the present method comes in two fold: first, the degrees of freedom of the system are greatly reduced, since each structural motif, regardless of its size, can always be described by a set of parameters (R, θ, φ) with five degrees of freedom; second, the motifs could always appear in the predicted structures when the energies of the structures are relatively low. Both features make the present scheme a very efficient method for predicting desired materials. The method has been applied to the case of LiFePO 4 , an important cathode material for lithium-ion batteries. Numerous new structures of LiFePO 4 have been found, compared to those currently available, available, demonstrating the reliability of the present methodology and illustrating the promise of the concept of structural motifs.

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

Resolving Atomic-Scale Structure and Chemical Coordination in High-Entropy Alloy Electrocatalysts for Structure–Function Relationship Elucidation

The recent breakthrough in confining five or more atomic species in nanocatalysts, referred to as high-entropy alloy nanocatalysts (HEAs), has revealed the possibilities of multielemental interactions that can surpass the limitations of binary and ternary electrocatalysts. The wide range of potential surface configurations in HEAs, however, presents a significant challenge in resolving active structural motifs, preventing the establishment of structure-function relationships for rational catalyst design and optimization. Here, we present a methodology for creating sub-5 nm HEAs using an aqueous-based peptide-directed route. Using a combination of pair distribution function and X-ray absorption spectroscopy, HEA structure models are constructed from reverse Monte Carlo modeling of experimental data sets and showcase a clear peptide-induced influence on atomic-structure and chemical miscibility. Coordination analysis of our structure models facilitated the construction of structure-function correlations applied to electrochemical methanol oxidation reactions, revealing the complex interplay between multiple metals that leads to improved catalytic properties. Our results showcase a viable strategy for elucidating structure-function relationships in HEAs, prospectively providing a pathway for future materials design.

36 MATERIALS SCIENCE↗
DOE OSTI2018

On the relationship between the structural and volumetric properties of solvated metal ions in O -donor solvents using new structural data in amide solvents

The structures of the N , N -dimethylformamide (dmf), N , N -dimethylacetamide (dma), and N , N -dimethylpropionamide (dmp) solvated strontium and barium ions have been determined in solution using large angle X-ray scattering and EXAFS spectroscopy. The strontium ion has a mean coordination number (CN) between 6.2 and 6.8, and the barium ion has a mean CN between 7.1 and 7.8 in these amide solvents. The non-integer numbers indicates that equilibria between different coordination numbers and geometries exist in these systems. Structural information of the alkali, alkaline earth, and selected transition metal and lanthanoid( III ) ions, and the halide ions in water, methanol, ethanol, dimethylsulfoxide, formamide, dmf and dma has been combined with previously reported standard partial molar volumes, V 0 . The ionic radii and charge densities (charge/ionic volume), and corresponding V 0 values have been used to gain information on the relationship between structural and volumetric properties. For the structure-breaking ions, i.e. the alkali metal and halide ions, there is an almost linear relationship between the ionic radius and V 0 . On the other hand, for the structure-making ions, here the alkaline earth, transition metal and lanthanoid( III ) ions, a linear relationship is observed between the charge density and V 0 . Solvents with a well-defined bulk structure through hydrogen bonding, specifically, water, methanol and ethanol, will be more contracted through solvation than aprotic solvents, as the space between the solvent molecules is lost as a result of the hydrogen bonding. In this respect, methanol stands out as the most compressed solvent participating in solvation compared to its bulk structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Solving the structure of Lgl2, a difficult blind test of unsupervised structure determination

In the companion paper by Ufimtsev and Levitt [Ufimtsev IS, Levitt M (2019) Proc Natl Acad Sci USA , 10.1073/pnas.1821512116], we presented a method for unsupervised solution of protein crystal structures and demonstrated its utility by solving several test cases of known structure in the 2.9- to 3.45-Å resolution range. Here we apply this method to solve the crystal structure of a 966-amino acid construct of human lethal giant larvae protein (Lgl2) that resisted years of structure determination efforts, at 3.2-Å resolution. The structure was determined starting with a molecular replacement (MR) model identified by unsupervised refinement of a pool of 50 candidate MR models. This initial model had 2.8-Å RMSD from the solution. The solved structure was validated by comparison with a model subsequently derived from an alternative crystal form diffracting to higher resolution. This model could phase an anomalous difference Fourier map from an Hg derivative, and a single-wavelength anomalous dispersion phased density map made from these sites aligned with the refined structure.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

SCOPe: classification of large macromolecular structures in the structural classification of proteins—extended database

The SCOPe (Structural Classification of Proteins—extended, https://scop.berkeley.edu) database hierarchically classifies domains from the majority of proteins of known structure according to their structural and evolutionary relationships. SCOPe also incorporates and updates the ASTRAL compendium, which provides multiple databases and tools to aid in the analysis of the sequences and structures of proteins classified in SCOPe. Protein structures are classified using a combination of manual curation and highly precise automated methods. In the current release of SCOPe, 2.07, we have focused our manual curation efforts on larger protein structures, including the spliceosome, proteasome and RNA polymerase I, as well as many other Pfam families that had not previously been classified. Domains from these large protein complexes are distinctive in several ways: novel non-globular folds are more common, and domains from previously observed protein families often have N- or C-terminal extensions that were disordered or not present in previous structures. The current monthly release update, SCOPe 2.07–2018-10–18, classifies 90 992 PDB entries (about two thirds of PDB entries).

Biochemistry & Molecular Biology↗
DOE OSTI2024

The seventh blind test of crystal structure prediction: structure generation methods

A seventh blind test of crystal structure prediction was organized by the Cambridge Crystallographic Data Centre featuring seven target systems of varying complexity: a silicon and iodine-containing molecule, a copper coordination complex, a near-rigid molecule, a cocrystal, a polymorphic small agrochemical, a highly flexible polymorphic drug candidate, and a polymorphic morpholine salt. In this first of two parts focusing on structure generation methods, many crystal structure prediction (CSP) methods performed well for the small but flexible agrochemical compound, successfully reproducing the experimentally observed crystal structures, while few groups were successful for the systems of higher complexity. A powder X-ray diffraction (PXRD) assisted exercise demonstrated the use of CSP in successfully determining a crystal structure from a low-quality PXRD pattern. The use of CSP in the prediction of likely cocrystal stoichiometry was also explored, demonstrating multiple possible approaches. Crystallographic disorder emerged as an important theme throughout the test as both a challenge for analysis and a major achievement where two groups blindly predicted the existence of disorder for the first time. Additionally, large-scale comparisons of the sets of predicted crystal structures also showed that some methods yield sets that largely contain the same crystal structures.

Chemistry↗
DOE OSTI2019

Structural analysis of Gd 6 FeBi 2 from single-crystal X-ray diffraction methods and electronic structure calculations

The crystal structure of the gadolinium iron bis­muthide Gd 6 FeBi 2 has been characterized by single-crystal X-ray diffraction data and analyzed in detail using first-principles calculations. The structure is isotypic with the Zr 6 CoAl 2 structure, which is a variant of the ZrNiAl structure and its binary prototype Fe 2 P (Pearson code hP 9, Wyckoff sequence g f d a ). As such, the structure is best viewed as an array of tricapped trigonal prisms of Gd atoms centered alternately by Fe and Bi. The magnetic-ordering temperature of this compound ( ca 350 K) is much higher than that of other rare-earth metal-rich phases with the same or related structures. It is also higher than the ordering temperature of many other Gd-rich ternary phases, where the magnetic exchange is typically governed by Ruderman–Kittel–Kasuya–Yosida (RKKY) inter­actions. First-principles calculations reveal a larger than expected Gd magnetic moment, with the additional contribution arising from the Gd 5 d electrons. The electronic structure analysis suggests strong Gd 5 d –Fe 3 d hybridization to be the cause of this effect, rather than weak inter­actions between Gd and Bi. These details are of importance for understanding the magnetic response and explaining the high ordering tem­per­ature in this material.

Chemistry↗
DOE OSTI2016

Structural health monitoring of engineered structures using a space-borne synthetic aperture radar multi-temporal approach: from cultural heritage sites to war zones

Typically, structural health monitoring (SHM) of engineered structures consists of an automated or semi-automated survey system that seeks to assess the structural condition of an anthropogenic structure. The aim of an SHM system is to provide insights into possible induced damage or any inherent signals of deformation affecting the structure in terms of detection, localization, assessment, and prediction. During the last decade there has been a growing interest in using several remote sensing techniques, such as synthetic aperture radar (SAR), for SHM. Constellations of SAR satellites with short repeat time acquisitions permit detailed surveys temporal resolution and millimetric sensitivity to deformation that are at the scales relevant to monitoring large structures. The all-weather multi-temporal characteristics of SAR make its products suitable for SHM systems, especially in areas where in situ measurements are not feasible or not cost effective. To illustrate this capability, we present results from COSMO-SkyMed (CSK) and TerraSAR-X SAR observations applied to the remote sensing of engineered structures. We show how by using multiple-geometry SAR-based products which exploit both phase and amplitude of the SAR signal we can address the main objectives of an SHM system including detection and localization. We highlight that, when external data such as rain or temperature records are available or simple elastic models can be assumed, the SAR-based SHM capability can also provide an interpretation in terms of assessment and prediction. We highlight examples of the potential for such imaging capabilities to enable advances in SHM from space, focusing on dams and cultural heritage areas.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

In Situ ATR-FTIR Study of the Cathode–Electrolyte Interphase: Electrolyte Solution Structure, Transition Metal Redox, and Surface Layer Evolution

We present a study of the lithium nickel manganese cobalt oxide (LiNi 0.6 Mn 0.2 Co 0.2 O 2 , NMC622) cathode-electrolyte interphase (CEI) during galvanostatic charging and discharging using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) methods to investigate the voltage dependent electrolyte solution structure changes at the interface, transition metal (TM) redox chemistry, and cathode/electrolyte interfacial layer evolution. Furthermore, our in situ cell design provides both reliable electrochemical device testing and strong FTIR vibrational absorption signals near the cathode surface. Specifically, advanced spectral analysis elucidates changes of near-surface Li+ ion (de)solvation by solvent molecules during galvanostatic cycling. Moreover, cathode metal-oxygen vibrational absorptions, sensitive to TM redox behaviors and subsequent local structural variations, were correlated to cathode de-lithiation (and lithiation) and electrolyte solution structure changes. In addition, we have detected the formation and evolution of a CEI surface layer on the NMC622 cathode that contributes to the cell's capacity fade.

25 ENERGY STORAGE↗
DOE OSTI2026

Improved Accuracy in Semi-Experimental Structure Determination by Resolving Problems Associated with Rotation of Principal Inertial Axes of Isotopologues: Structures of 1,3-Oxazole ( c -C 3 H 3 NO)

The rotational spectrum of the normal isotopologue of 1,3-oxazole (c-C 3 H 3 NO) was observed from 43 to 750 GHz. Over 3900 transitions for the ground vibrational state are measured, assigned, and least-squares fit to sextic centrifugally distorted-rotor Hamiltonians. The measured frequencies and resulting spectroscopic constants from this extended spectral range, combined with previous measurements of the nuclear quadrupole coupling constants, will facilitate astronomical searches for oxazole across the majority of the range of modern radiotelescopes. Spectra for a set of 30 oxazole isotopologues, which include multiple isotopic substitutions of each atom, are used to determine the first semi-experimental equilibrium ($r$$^{SE}_{e}$) structure and semi-experimental substitution structure ($r$$^{SE}_{e}$), each using CCSD(T) computed values for the vibration–rotation interaction and electron-mass corrections. The large number of isotopologues, including 21 isotopologues observed for the first time, and the redundant substitutions of each atom provide sufficient spectroscopic information to determine the $r$$^{SE}_{e}$ structure with the expected high level of accuracy and precision (0.0001 or 0.0002 Å in bond distances and 0.013 to 0.025° in bond angles). In the course of this study, we analyzed a known issue for some $r$$^{SE}_{e}$ structure determinations of near-oblate asymmetric tops in which inclusion of individual isotopologues degrades the structure determination. We demonstrate that this problem primarily arises from the difference in the values of the computed vibration–rotation interaction corrections as evaluated at the computed re geometry vs the $r$$^{SE}_{e}$ geometry of the “real” molecule. Our solution to this problem substantially improves the $r$$^{SE}_{e}$ structure of oxazole and likely can be generalized to many other molecules.

Chemical structure↗