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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Evaluating the effects of structural disorder on the magnetic properties of Nd 2 Zr 2 O 7

Motivated by the variation in reported lattice parameters of floating-zone-grown Nd 2 Zr 2 O 7 crystals, we have performed a detailed study of the relationship between synthesis environment, structural disorder, and magnetic properties. Using a combination of polycrystalline standards, electron-probe microanalysis, and scattering techniques, we show that crystals grown under atmospheric conditions have a reduced lattice parameter relative to pristine polycrystalline powders due to occupation of the Nd site by excess Zr (i.e., negative stuffing). In contrast, crystals grown under high-pressure Ar are nearly stoichiometric with an average lattice parameter approaching the polycrystalline value. While minimal disorder of the oxygen sublattices is observed on the scale of the average structure, neutron pair-distribution function analysis indicates a highly local disorder of the oxygen coordination, which is only weakly dependent on growth environment. Most importantly, our magnetization, heat capacity, and single-crystal neutron scattering data show that the magnetic properties of crystals grown under high-pressure Ar match closely with those of stoichiometric powders. Neutron scattering measurements reveal that the signature of magnetic moment fragmentation—the coexistence of all-in-all-out (AIAO) magnetic Bragg peaks and diffuse pinch-point scattering due to spin-ice correlations–persists in these nearly stoichiometric crystals. However, in addition to an increased AIAO transition temperature, the diffuse signal is seemingly stabilized and remains nearly unchanged upon warming to 800 mK. This behavior indicates that both the AIAO magnetic order and spin-ice correlations are sensitive to deviations of the Nd stoichiometry.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Structural disorder, sublattice melting, and thermo-elastic properties of anti-perovskite Li 3 OBr under high pressure and temperature

Here, in situ synchrotron x-ray diffraction experiments were conducted in the system Li-O-Br at pressures up to 6.5 GPa and temperatures up to the melting points. The thermal equation of state determined from the P–V–T measurements indicates that crystalline anti-perovskite Li 3 OBr exhibits similar thermo-elastic properties to common salts. At temperatures that are 50–75 °C below the crystal melting, a pre-melting behavior was inferred based on weakened Bragg intensity and a substantial increase in the diffuse scattering. Concurrent with the onset of pre-melting, an anomalous increase in the lattice volume was observed and is interpreted as anion sublattice disorder. These findings support previous ab initio molecular dynamics simulations based on a simple anion interchange mechanism, indicating that structural disorder below crystal melting temperature can be a main driving force for Li-sublattice melting and superionic transition in the Li 3 OBr anti-perovskite.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Local Structural Disorder in Metavanadates MV 2 O 6 (M = Zn and Cu) Synthesized by the Deep Eutectic Solvent Route: Photoactive Oxides with Oxygen Vacancies

Metavanadates MV 2 O 6–δ (M = Zn and Cu) are synthesized by using a deep eutectic solvent (DES), a mixture of hydrogen bond donor and acceptor, as a reaction medium. Dissolution of stable binary metal oxides in a DES followed by a heat treatment yields phase-pure vanadates. According to in situ powder X-ray diffraction, ternary phases (α-Zn 2 V 2 O 7 and β-Cu 2–x V 2 O 7 , x ~ 0.27) are intermediates in the reaction pathway taken. Identifying a polymorphic phase transformation temperature for CuV 2 O 6 as well as the narrow temperature range between formation and decomposition for both metavanadates allows for tackling the challenge of the synthesis of these materials. The oxygen vacancy introduced by the DES route is accompanied by the formation of reduced V 4+ and Cu + in the oxide matrix, based on X-ray photoelectron spectroscopy. These oxygen vacancies modify the vibrational modes in the corresponding Raman spectra and are also responsible for broad optical absorptions in the 1.8–1.1 eV range. The optical band gaps of the materials are found at 1.8 eV (CuV 2 O 6 ) and 2.2 eV (ZnV 2 O 6 ), approximately 0.1–0.3 eV below the values reported in the literature. The reduced band gaps and sub-band gap photon absorption are key features of the oxygen-deficient metavanadates. Surface photovoltage spectroscopy reveals that all the synthesized vanadates are n-type materials with electrons as the majority charge carriers, and photoelectrochemical measurements confirm photoanodic currents for methanol oxidation. Furthermore, these results provide insight into the synthesis and structure–property relationship of the metavanadates for their potential use as photoanodes.

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

Effective and asymptotic criticality of structurally disordered magnets

Changes in magnetic critical behaviour of quenched structurally-disordered magnets are usually exemplified in experiments and in MC simulations by diluted systems consisting of magnetic and non-magnetic components. In our study we aim to show that similar effects can be observed not only for diluted magnets with non-magnetic impurities but may be implemented, e.g., by the presence of two (and more) chemically different magnetic components as well. Therefore we consider a model of the structurally-disordered quenched magnet where all lattice sites are occupied by Ising-like spins of different lengths L. In such a random spin length Ising model, the length L of each spin is a random variable governed by the distribution function p (L). We demonstrate that this model belongs to the universality class of the site-diluted Ising model. This proves that both models are described by the same values of asymptotic critical exponents. However, their effective critical behaviour differs. As a case study, we consider a quenched mixture of two different magnets with values of elementary magnetic moments L 1 = 1 and L 2 = s, and of concentration c and 1 - c, correspondingly. We apply field-theoretical renormalization group approach to analyse the renormalization group flow for different initial conditions, triggered by s and c, and to calculate effective critical exponents further away from the fixed points of the renormalization group transformation. We show how the effective exponents are governed by difference in properties of the magnetic components.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Proton, Electron, and Hydrogen-Atom Transfer Thermodynamics of the Metal–Organic Framework, Ti-MIL-125, Are Intrinsically Correlated to the Structural Disorder

Interfacial charge transfer reactions involving protons and/or electrons are fundamental to heterogeneous catalysis and many other reactions relevant to energy, chemical, and biological sectors. Metal–organic frameworks (MOFs) with redox-active metal-oxo nodes have emerged as candidate materials to examine these reactions with near-atomic-level precision, given their crystalline nature. Here, we employed a colloidally stable, Ti-based MOF, Ti-MIL-125, with different crystal sizes to examine catalytically relevant charge transfer thermodynamics. The Ti 8 (μ 2 -O) 8 (μ 2 -OH) 4 nodes structurally mimic TiO 2 , which has shown some PCET reactivity toward reactions of H 2 , O 2 , and others. In this report, we have demonstrated that a change in crystal size induces different amounts of structural disorder to the Ti-oxo node, further changing the thermodynamics of proton/electron/hydrogen-atom transfer reactions. Using electrochemical open-circuit potential (E OCP ) measurements, we have determined that all crystallites undergo a 1H + /1e – redox reaction, which, given the stoichiometry, can be considered as a net H atom transfer (HAT) reaction. The thermodynamics of this HAT reaction, the Ti 3+ O–H bond dissociation free energy (BDFE), was dependent on the crystal size of the MOF, as the decrease in crystal size induced more structural disorder. Our computational calculations have indicated that this difference in BDFE is due to a local change in the geometry of Ti cations, rather than the commonly invoked defects, such as the “missing-linker” defect sites. Individual proton/electron transfer (PT/ET) thermodynamics were also highly dependent on the crystal sizes. These were probed using pK a or band gaps (E g ), respectively. These findings suggest that, particularly when MOFs are nanosized with a large amount of structural disorder, they should no longer be considered “true” single-site catalysts; this is an implicit, but widespread assumption within the MOF-based catalysis field. Implications of these findings will be contrasted with structurally similar metal oxides like TiO 2 and other redox-active MOFs.

Bond dissociation free energy↗
NASA NTRS1988

Crystallography, chemistry and structural disorder in the new high-Tc Bi-Ca-Sr-Cu-O superconductor

Diffraction experiments are reported which indicate that the new Bi-Ca-Sr-Cu-O layer-structure superconductor possesses a primitive orthorhombic unit cell with probable space group Pnnn. The material exhibits severe structural disorder which is primarily related to stacking within the layers. The apparent orthorhombic structure is an average resulting from orthorhombic material mixed with monoclinic domains in two twinned orientations. Two distinct types of structural disorder that are common in materials synthesized to date are also described. This disorder complicates the crystallographic analysis and suggests that X-ray and neutron diffraction methods may yield only an average structure.

Veblen, D. R.↗
DOE OSTI2022

Effects of local compositional and structural disorder on vacancy formation in entropy-stabilized oxides from first-principles

Entropic stabilization has evolved into a strategy to create new oxide materials and realize novel functional properties engineered through the alloy composition. Achieving an atomistic understanding of these properties to enable their design, however, has been challenging due to the local compositional and structural disorder that underlies their fundamental structure-property relationships. Here, we combine high-throughput atomistic calculations and linear regression algorithms to investigate the role of local configurational and structural disorder on the thermodynamics of vacancy formation in (MgCoNiCuZn)O-based entropy-stabilized oxides (ESOs) and their influence on the electrical properties. We find that the cation-vacancy formation energies decrease with increasing local tensile strain caused by the deviation of the bond lengths in ESOs from the equilibrium bond length in the binary oxides. The oxygen-vacancy formation strongly depends on structural distortions associated with the local configuration of chemical species. Vacancies in ESOs exhibit deep thermodynamic transition levels that inhibit electrical conduction. By applying the charge-neutrality condition, we determine that the equilibrium concentrations of both oxygen and cation vacancies increase with increasing Cu mole fraction. Our results demonstrate that tuning the local chemistry and associated structural distortions by varying alloy composition acts an engineering principle that enables controlled defect formation in multi-component alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Evidence of a glassy magnetic transition driven by structural disorder in BiFeO 3 nanoparticles

Important effects appear in low and high temperature magnetometry of multiferroic BiFeO 3 (BFO) nanoparticles as sizes are reduced from 105 nm to 18 nm. In these particles, a magnetic transition appears close to 200 K probably associated with a spin reorientation which is absent in bigger particles. At higher temperatures and up to the bulk ferroelectric Curie temperature (1000 K), two additional magnetic transitions can be identified. Around T N 600 K, a size-dependent magnetic transition appears, associated with an antiferromagnetic transition. A model based on atomic vibration instability can describe the variation of T N with nanoparticle size. Furthermore, for certain sizes, the properties are dominated by the glassy state arising from the disorder produced by the formation of a core-shell structure. This implies that the magnetic behavior of nanoparticles is strongly affected by their crystal structure close to the transition temperature. Finally, the structural disorder which couples to the magnetic properties add control to the magnetic and ferroelectric properties of BFO nanoparticles.

36 MATERIALS SCIENCE↗
DOE OSTI2022

On the new universality class in structurally disordered n -vector model with long-range interactions

We study a stability boundary of a region where nontrivial critical behavior of an n-vector model with long-range power-law decaying interactions is induced by the presence of a structural disorder (e.g., weak quenched dilution). This boundary is given by the marginal dimension of the order parameter nc dependent on space dimension, d, and a control parameter of the interaction decay, σ, below which the model belongs to the new dilution-induced universality class. Exploiting the Harris criterion and recent field theoretical renormalization group results for the pure model with long-range interactions, we get nc as a three loop ɛ = 2σ – d-expansion. We provide numerical values for nc applying series resummation methods. Our results show that not only the Ising systems (n = 1) can belong to the new disorder-induced long-range universality class at d = 2 and 3.

Physics↗
DOE OSTI2022

Flexible machine-learning interatomic potential for simulating structural disordering behavior of Li 7 La 3 Zr 2 O 12 solid electrolytes

Batteries based on solid-state electrolytes, including Li 7 La 3 Zr 2 O 12 (LLZO), promise improved safety and increased energy density; however, atomic disorder at grain boundaries and phase boundaries can severely deteriorate their performance. Machine-learning (ML) interatomic potentials offer a uniquely compelling solution for simulating chemical processes, rare events, and phase transitions associated with these complex interfaces by mixing high scalability with quantum-level accuracy, provided that they can be trained to properly address atomic disorder. To this end, we report the construction and validation of an ML potential that is specifically designed to simulate crystalline, disordered, and amorphous LLZO systems across a wide range of conditions. The ML model is based on a neural network algorithm and is trained using ab initio data. Performance tests prove that the developed ML potential can predict accurate structural and vibrational characteristics, elastic properties, and Li diffusivity of LLZO comparable to ab initio simulations. As a demonstration of its applicability to larger systems, we show that the potential can correctly capture grain boundary effects on diffusivity, as well as the thermal transition behavior of LLZO. Here these examples show that the ML potential enables simulations of transitions between well-defined and disordered structures with quantum-level accuracy at speeds thousands of times faster than ab initio methods.

25 ENERGY STORAGE↗
DOE OSTI2022

Reversible motions and disordered structure of soft particles in amorphous solids

In amorphous solids, soft vibrational modes derived from normal mode analysis can be utilized to identify the soft particles that are prone to irreversible rearrangements. However, the normal mode analysis approach cannot explain why the spatial distributions of clustered soft particles do not change over time. We define a softness parameter based on the vibrational density of states calculated directly from molecular dynamics simulations with both the harmonic vibrations and anharmonic relaxations being properly captured at finite temperatures. This parameter spontaneously correlates with the real space atomic motions and the dynamics heterogeneity. Using the softness parameter, we show that the softest particles are confined within rigid cages. These particles keep rearranging reversibly without long-range diffusion. The moderately soft particles rearrange irreversibly, and the hard particles mainly participate in vibrations without rearrangement. Here, we also show that the soft particles form locally disordered structures, while the hard particles present strong ordering. These findings confirm the defective nature of soft particles, and provide insights on the nature of softness as the ability to rearrange, but not necessarily irreversibly.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Coexisting structural disorder and robust spin-polarization in half-metallic FeMnVAl

We report half-metallic ferromagnets (HMFs) are one of the most promising materials in the field of spintronics due to their unique band structure, consisting of one spin subband having metallic characteristics along with another subband with semiconductor-like behavior. In this work, we report the synthesis of a novel quaternary Heusler alloy—FeMnVAl—and we have studied the structural, magnetic, transport, and electronic properties complemented with first-principles calculations. Among different possible structurally ordered arrangements, the optimal structure is identified by theoretical energy minimization. The corresponding spin-polarized band-structure calculations indicate the presence of a half-metallic ferromagnetic ground state. A detailed and careful investigation of the x-ray diffraction data, Mössbauer spectra, and nuclear magnetic resonance spectra suggests the presence of site disorder between the Fe and Mn atoms in the stable ordered structure of the system. The magnetic susceptibility measurement clearly establishes a ferromagnetic-like transition below ~213 K. The Fe Mössbauer spectrometry measurements suggest that only the Mn spins could be responsible for the magnetic order, which is consistent with our theoretical calculation. Surprisingly, the density-functional-theory calculations reveal that the spin-polarization value is almost immunized (92.4% → 90.4%) from the Mn-Fe structural disorder, even when nonmagnetic Fe and moment-carrying Mn sites are entangled inseparably. The robustness of spin polarization and half-metallicity in the studied FeMnVAl compound comprising structural disorder is thus quite interesting and could provide a new direction to investigate and understand the exact role of disorders on spin polarization in this class of materials, beyond the available knowledge.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Irradiation-Induced Structural Disorder and Its Influence on the Mechanical Response of Polycrystalline MoS2

Molybdenum disulfide (MoS2) thin films are widely used as dry-film lubricants and protective coatings in aerospace and other radiation-exposed environments. Conventional synthesis routes produce polycrystalline films whose grain boundaries and other native defects cause their mechanical and tribological behavior to differ substantially from that of ideal single crystals. Under irradiation, these films progressively evolve from polycrystalline structures, composed of layered MoS2 grains, into highly disordered and eventually amorphous structures, altering both their tribological performance and mechanical integrity. Here, we employ reactive atomistic simulations to investigate irradiation-driven structural evolution in bulk polycrystalline MoS2. Using controlled primary knock-on atom (PKA) events, we characterize the progressive transition from a polycrystalline microstructure to an amorphous network by tracking defect accumulation and structural disorder. We then establish how this transition modifies the dominant deformation mechanisms and the temperature-dependent tensile response. Specifically, irradiation suppresses interlayer sliding and delamination, mechanisms which facilitate the deformation of the pristine polycrystal, resulting in defect-induced hardening. Broadly, our results establish direct process–structure–property relationships linking irradiation-induced defect accumulation, microstructural evolution, deformation mechanisms, and mechanical behavior, providing an atomistic framework for understanding the structural integrity and long-term reliability of irradiated MoS2 coatings.

Moore, Daniel [Sandia National Laboratories (SNL)]↗
DOE OSTI2023

Ab initio study of short-range ordering in vanadium-based disordered rocksalt structures

Disordered rocksalt Li-excess (DRX) compounds are attractive new cathode materials for Li-ion batteries as they contain resource-abundant metals and do not require the use of cobalt or nickel. Understanding the delithiation process and cation short-range ordering (SRO) in DRX compounds is essential to improve these promising cathode materials. Herein, we use first-principles calculations along with the cluster-expansion approach to model the disorder in DRX Li 2-x VO 3 , 0 < x < 1. We discuss the SRO of Li in tetrahedral and octahedral sites, and the order in which Li delithiates and V oxidizes with respect to local environments. We reveal that the number of nearest-neighbor V dictates the order of delithiation from octahedral sites and that V is oxidized in a manner that minimizes the electrostatic interactions among V. In conclusion, our results provide valuable insight for tailoring the performance of V-based DRX cathode materials in general by controlling the SRO features that reduce energy density.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Elucidating Structural Disorder in Ultra‐Thin Bi‐Rich Bismuth Oxyhalide Photocatalysts

Abstract Advancing the field of photocatalysis requires the elucidation of structural properties that underpin the photocatalytic properties of promising materials. The focus of the present study is layered, Bi‐rich bismuth oxyhalides, which are widely studied for photocatalytic applications yet poorly structurally understood, due to high levels of disorder, nano‐sized domains, and the large number of structurally similar compounds. By connecting insights from multiple scattering techniques, utilizing electron‐, X‐ray‐ and neutron probes, the crystal phase of the synthesized materials is allocated as layered Bi 24 O 31 X 10 (X = Cl, Br), albeit with significant deviation from the reported 3D crystalline model. The materials comprise anisotropic platelet‐shaped crystalline domains, exhibiting significant in‐plane ordering in two dimensions but disorder and an ultra‐thin morphology in the layer stacking direction. Increased synthesis pH tailored larger, more ordered crystalline domains, leading to longer excited state lifetimes determined via femtosecond transient absorption spectroscopy (fs‐TAS). Although this likely contributes to improved photocatalytic properties, assessed via the photooxidation of benzylamine, increasing the overall surface area facilitated the most significant improvement in photocatalytic performance. This study, therefore, enabled both phase allocation and a nuanced discussion of the structure‐property relationship for complicated, ultra‐thin photocatalysts.

Chemistry↗
DOE OSTI2026

Thermoelectric Behavior of Structurally Disordered Lanthanide and Actinide Silicides

Lanthanide and actinide intermetallic materials exhibit intriguing electronic, structural, and magnetic properties arising from their partially filled f orbitals. Strong f-electron correlations can significantly modify the electronic density of states, carrier scattering, and transport behavior, making these systems promising candidates for unconventional thermoelectric materials. In previous studies, single crystals of A1.33T4Al8Si2 (A = Ce, Th, U, Np; T = Co, Ni) were synthesized. This structure consists of ordered TAl2 corrugated double layers separated by disordered An–Si monolayers. The inherent disorder within the An–Si layers has been linked to unusual magnetic behavior, such as spin-glass phenomena, and is expected to strongly influence phonon scattering and charge-carrier transport relevant to thermoelectric performance. However, the thermoelectric properties of this material family have not previously been explored. In this work, DFT calculations were performed to evaluate the electronic density of states, band structures, and thermoelectric properties, including the effects of doping. To validate these predictions, Ce1.33Co4Al8Si2 single crystals were grown and experimentally characterized. Additionally, a new Yb1.33Co4Al8Si2 phase was synthesized and characterized using single-crystal XRD, SEM-EDS, magnetization measurements, and thermoelectric measurements. These results provide insight into structure–property relationships governing thermoelectric behavior in f-electron intermetallics and offer guidance for future thermoelectric materials.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2021

Complex Structural Disorder in a Polar Orthorhombic Perovskite Observed through the Maximum Entropy Method/Rietveld Technique

Ambient pressure stable perovskite oxides with all Bi3+ on the A-site are rare, with only four examples known. Due to the lone pair on Bi 3+ , these materials are seen as the best alternative to Pb-based piezoelectrics, which are used widely in society. The industry standard piezoelectric, Pb (Zr 1 – x Ti x )O 3 , relies on the [001] polarization of PbTiO 3 , but there are currently no ambient pressure stable Bi-based perovskites with this polarization vector, preventing the creation of an analogous system. We present the full structural analysis of the orthorhombic phase of (1 – x)Bi (Ti 3/8 Fe 2/8 Mg 3/8 )O 3 – x CaTiO 3 , which crystallizes in Pna2 1 symmetry with [001] polarization. This symmetry is rare and has only been reported twice for perovskites at ambient conditions. Analysis of maximum entropy method (MEM) models using synchrotron radiation powder X-ray diffraction reveals a disordered A-site configuration, and the MEM/Rietveld technique generates a structural model of this extreme disorder. Combined Rietveld analysis of X-ray and neutron diffraction data yields an accurate description of the local A-site configuration, which we use to understand our dielectric, ferroelectric, and piezoelectric measurements. These results give insight into how to stabilize this unique symmetry and inspire new design principles for Bi-based piezoelectrics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗