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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Revealing local order via high energy EELS

Short range order (SRO) is critical in determining the performance of many important engineering materials. However, accurate characterization of SRO with high spatial resolution – which is needed for the study of individual nanoparticles and at material defects and interfaces – is often experimentally inaccessible. Here, we locally quantify SRO via scanning transmission electron microscopy with extended energy loss fine structure analysis. Specifically, we use novel instrumentation to perform electron energy loss spectroscopy out to 12 keV, accessing energies which are conventionally only possible using a synchrotron. Our data is of sufficient energy resolution and signal-to-noise ratio to perform quantitative extended fine structure analysis, which allows determination of local coordination environments. To showcase this technique, we investigate a multicomponent metallic glass nanolaminate and locally quantify the SRO with <10 nm spatial resolution; this measurement would have been impossible with conventional synchrotron or electron microscopy methods. Finally, we discuss the nature of SRO within the metallic glass phase, as well as the wider applicability of our approach for determining processing–SRO–property relationships in complex materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Frustration and Atomic Ordering in a Monolayer Semiconductor Alloy

Frustrated interactions can lead to short-range ordering arising from incompatible interactions of fundamental physical quantities with the underlying lattice. The simplest example is the triangular lattice of spins with antiferromagnetic interactions, where the nearest-neighbor spin-spin interactions cannot simultaneously be energy minimized. In this work, we show that engineering frustrated interactions is a possible route for controlling structural and electronic phenomena in semiconductor alloys. Using aberration-corrected scanning transmission electron microscopy in conjunction with density functional theory calculations, we demonstrate atomic ordering in a two-dimensional semiconductor alloy as a result of the competition between geometrical constraints and nearest-neighbor interactions. Statistical analyses uncover the presence of short-range ordering in the lattice. In addition, we show how the induced ordering can be used as another degree of freedom to considerably modify the band gap of monolayer semiconductor alloys.

2-dimensional systems↗
DOE OSTI2025

Solving disorder in (3D) real space: a comparative study of the three-dimensional difference pair distribution function and atomic resolution holography reconstructions

The quantitative analysis of local ordering principles in disordered crystalline systems has gained much attention over the past few years, as it is often considered crucial for optimizing material functionality. This development has been driven by significant advancements in computational and experimental methods, which have led to the establishment and widespread use of various analytical techniques. In this study, we perform model calculations to compare the effectiveness of atomic resolution holography and three-dimensional difference pair distribution function analysis (3D-ΔPDF). Using Cu 3 Au as a model system, we demonstrate an approach to derive local order parameters quantitatively and show that both techniques are well suited to quantifying chemical short-range order correlations and local bond-distance variations. By evaluating the strengths and limitations of both techniques, we advocate for their combined use to solve complex short-range order problems accurately.

3D-ΔPDF↗
DOE OSTI2026

Disordered hydrogen adsorption at the three-fold site of W(110)

Hydrogen often forms disordered phases on metals; however, deciphering the atomic-scale behavior requires experimental and modeling techniques that directly probe the short-range order between neighboring hydrogen adsorbates. Here, to address this challenge, we applied direct recoil spectroscopy (DRS) to investigate hydrogen adsorption on the W(110) surface. We show that the recoiled hydrogen flux measured during DRS is sensitive to the short range order of the adsorbed hydrogen. Ordered hydrogen neighbors are much more efficient at dechanneling incident ions along low-index surface channels, strongly suppressing the recoiled hydrogen flux along these directions. By modeling the DRS measurements with molecular dynamics for ordered and disordered hydrogen phases, we find that at a hydrogen surface coverage of approximately Θ = 0.6, the hydrogen adsorbates are bound to three-fold sites in a disordered phase at room temperature. This finding is consistent with transfer-matrix scaling model calculations that suggest the transition to an ordered hydrogen phase occurs at a greater surface coverage of Θ = 0.83.

08 HYDROGEN↗
DOE OSTI2021

Designing order–disorder transformation in high-entropy ferritic steels

Order–disorder transformations hold an essential place in chemically complex high-entropy ferritic steels (HEFSs) due to their critical technological application. The chemical inhomogeneity arising from mixing of multi-principal elements of varying chemistry can drive property altering changes at the atomic scale, in particular short-range order. Using density-functional theory-based linear-response theory, we predict the effect of compositional tuning on the order–disorder transformation in ferritic steels—focusing on Cr–Ni–Al–Ti–Fe HEFSs. We show that Ti content in Cr–Ni–Al–Ti–Fe solid solutions can be tuned to modify short-range order that changes the order–disorder path from BCC-B2 (Ti atomic-fraction = 0) to BCC-B2-L2 1 (Ti atomic-fraction > 0) consistent with existing experiments. Our study suggests that tuning degree of SRO through compositional variation can be used as an effective means to optimize phase selection in technologically useful alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Local structural ordering determines the mechanical damage tolerance of amorphous grain boundary complexions

Amorphous grain boundary complexions act as toughening features within a microstructure because they can absorb dislocations more efficiently than traditional grain boundaries. This toughening effect should be a strong function of the local internal structure of the complexion, which has recently been shown to be determined by grain boundary crystallography. To test this hypothesis, molecular dynamics are used here to simulate dislocation absorption and damage nucleation for complexions with different distributions of structural short-range order. Here, the complexion with a more disordered structure away from the dislocation absorption site is actually found to better resist crack nucleation, as damage tolerance requires delocalized deformation and the operation of shear-transformation zones through the complexion thickness. The more damage tolerant complexion accommodates plastic strain efficiently within the entire complexion, providing the key mechanistic insight that local patterning and asymmetry of structural short-range order controls the toughening effect of amorphous complexions.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Chemical order transitions within extended interfacial segregation zones in NbMoTaW

Interfacial segregation and chemical short-range ordering influence the behavior of grain boundaries in complex concentrated alloys. In this study, we use atomistic modeling of a NbMoTaW refractory complex concentrated alloy to provide insight into the interplay between these two phenomena. Hybrid Monte Carlo and molecular dynamics simulations are performed on columnar grain models to identify equilibrium grain boundary structures. Here our results reveal extended near-boundary segregation zones that are much larger than traditional segregation regions, which also exhibit chemical patterning that bridges the interfacial and grain interior regions. Furthermore, structural transitions pertaining to an A2-to-B2 transformation are observed within these extended segregation zones. Both grain size and temperature are found to significantly alter the widths of these regions. An analysis of chemical short-range order indicates that not all pairwise elemental interactions are affected by the presence of a grain boundary equally, as only a subset of elemental clustering types are more likely to reside near certain boundaries. The results emphasize the increased chemical complexity that is associated with near-boundary segregation zones and demonstrate the unique nature of interfacial segregation in complex concentrated alloys.

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

Magnetic anisotropy and two-dimensional short-range chemical ordering in Ba 1−𝑥 ⁢Na 𝑥 ⁢Fe 2 ⁢As 2

A true understanding of the properties of pnictide superconductors requires the development of high-quality materials and performing measurements designed to unravel their intrinsic properties and short-range nematic correlations which are often obscured by extrinsic effects such as poor crystallinity, inhomogeneity, domain formation, and twinning. Here, in this paper, we report the systematic growth of high-quality Na-substituted BaFe 2 As 2 single crystals and their characterization using pulsed magnetic fields x-ray diffraction and x-ray diffuse scattering. Analysis of the properties and compositions of the highest-quality crystals shows that their actual Na stoichiometry is about 50-60% of the nominal content and that the targeted production of crystals with specific compositions is accessible. We derived a reliable equation to estimate the Na stoichiometry based on the measured superconducting T c of these materials. Attempting to force spin reorientation and induce tetragonality, orthorhombic Ba 1-x Na x Fe 2 As 2 single crystals subjected to out-of-plane magnetic fields up to 31.4T are found to exhibit strong in-plane magnetic anisotropy demonstrated by the insufficiency of such high fields in manipulating the relative population of their twinned domains or in suppressing the orthorhombic order. Broad x-ray diffuse-intensity rods observed at temperatures between 30 and 300 K uncover short-range structural correlations. Local structure modeling together with 3D-Δ pair-distribution function mapping of real-space interatomic vectors show that the diffuse scattering arises from in-plane short-range chemical correlations of the Ba and Na atoms coupled with short-range atomic displacements within the same plane due to an effective size difference between the two atomic species.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Metastable solubility and local structure of amorphous calcium carbonate (ACC)

The properties of amorphous calcium carbonate provide the foundation for understanding mineralization of calcified skeletons but inconsistencies between studies suggest the physical picture is incomplete. This study quantifies the metastable solubility and structure of ACC produced under a series of chemical conditions. Using complementary in situ methods that quantify ACC structure (in situ PDF analysis) in parallel with chemical composition (TGA, ICP-OES), we find two short-range structures are produced that also show distinct morphological differences. Conditions with high carbonate ion concentrations stabilize a Ca-rich ACC with short-range order that is independent of Mg content. In contrast, low carbonate solutions favor Mg-rich ACC with mixed Ca- and Mg-short range order. Measurements of solubility product determined from supersaturated and undersaturated conditions find the distinctive structures are related to solution carbonate activity while solubility is primarily determined by the magnesium content of the solid. Bulk solubility is a composite that concurs with established values. The findings demonstrate the type of ACC that forms is tuned by Mg2+ and CO3-2- concentration and suggest ACC structure, not bulk composition, is a reliable indicator of intermediate phase. This chemical framework also provides a basis for interpreting apparent differences between observations of ACC in synthetic and natural systems that reconciles previous structural studies.

Mergelsberg, Sebastian T.↗
DOE OSTI2026

From high-entropy ceramics to compositionally complex ceramics and beyond

Over the past decade, the field of high-entropy ceramics (HECs) has expanded rapidly to encompass a broad range of oxides, borides, silicides, and other ceramic solid solutions. In 2020, we proposed extending HECs to compositionally complex ceramics (CCCs), where non-equimolar compositions and the presence of long- or short-range order, although reducing configurational entropy, create new opportunities to tailor and enhance properties, often surpassing those of higher-entropy counterparts. Along these lines, several fundamental scientific questions arise. Is the entropy in HECs truly high? Is maximizing entropy always desirable? In this perspective article, I revisit key concepts and terminologies and highlight emerging directions, including dual-phase CCCs, ultrahigh-entropy phases, and novel processing routes such as ultrafast reactive sintering. I propose that exploring compositional complexity across vast non-equimolar spaces, together with exploiting correlated disorder (coupled chemical and structural short-range order), represents a transformative strategy for designing ceramics with superior performance.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Phonon gas model for thermal conductivity of dense, strongly interacting liquids

Developing predictive thermal property models for liquids based on microscopic principles has been elusive. The difficulty is that liquids have gas-like and solid-like attributes that are at odds when considering the frameworks of microscopic models: Models for gases are simple due to randomness and low density, whereas models for crystalline solids rely on symmetry and long-range order for easier calculation. The short-range order in liquids does, however, provide structure to neighboring molecules similar to amorphous solids, and there have been recent advances indicating that collective vibrational modes store heat in liquids. Models combining Debye approximations from solid-state physics and Frenkel’s theory of liquids can accurately predict the heat capacity of liquids. Phonon-like dispersions in liquids have also been widely observed in neutron scattering experiments. These developments motivate us to propose a model where high-frequency vibrational modes, which travel at the speed of sound and have a mean free path on the order of the average intermolecular distance, conduct heat in liquids. We use this liquid phonon gas model to calculate the thermal conductivity of liquids with varying intermolecular interaction energies from strongest to weakest—Coulomb, hydrogen-bonding, Keesom, and London dispersion energy. Generally, the model is more accurate as the intermolecular interaction energy and density of liquids increase. The calculated thermal conductivity of Coulombic-bound molten sodium nitrate and hydrogen-bonded water is within 1.46% and 2.98% of the experimentally measured values, respectively, across their entire temperature ranges. Further modal analysis of the velocity and the mean free path of collective vibrations could establish the liquid phonon gas model as an accurate model for weakly interacting liquids as well.

36 MATERIALS SCIENCE↗
NASA NTRS1973

Debye-Scherrer investigations of experimentally shocked silicates.

Small ballistic ranges were used to perform controlled laboratory shock experiments on 12 selected silicates. Debye-Scherrer investigations of shocked materials revealed a gradual lattice breakdown of crystalline matter under shock. Individual mineral species behave selectively. Sheet silicates break down very easily, followed by tecto-silicates. Chain-, ino- and ortho-silicates are of considerably higher shock resistance. Depending on the mineral species, the first sign of shock damage is evidenced in the long range order at 20-70 kb. At intermediate pressures (100-200 kb) the long range order is essentially destroyed with the short range order heavily disturbed. At pressures exceeding 300 kb tecto-silicates are completely collapsed.

Hoerz, F.↗
NASA NTRS1994

Formation Energy of Disordered Alloys form the Energetics of Ordered Compounds

The cluster expansion technique is used in combination with first-principles calculations of the total energy of ordered compounds to study the energetics of the disordered phase for a number of alloy systems. The effect of short-range order, as seen in the energy differences between an alloy with the configuration corresponding to finite temperature and the perfectly random one is studied. The role of relaxation due to large size mismatch is discussed in terms of an effective cluster volume approximation. Very good agreement with measured energies of formation is obtained when short-range order and relaxation effects are taken into account.

Amador, Carlos↗
DOE OSTI2022

Structural Principles in Liquids and Glasses: Bottom-Up or Top-Down

The conventional approach to elucidate the atomic structure of liquid and glass is to start with local structural units made of several atoms, and to use them as building blocks to form a global structure, the bottom-up approach. We propose to add an alternative top-down approach in which we start with a global high-temperature gas state and then apply interatomic potentials to all atoms at once. This causes collective density wave instability in all directions with the same wavelength. These two driving forces, local and global, are in competition and are mutually frustrated. The final structure is determined through the compromise of frustration between these two, which creates the medium-range-order. This even-handed approach on global and local potential energy landscapes explains the distinct natures of short-range order and medium-range order, and strong temperature dependence of various properties of liquid.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Polytypism in semi-disordered lizardite and amesite by low-dose HAADF-STEM

Serpentine minerals exert important controls on the physical properties of ultramafic rocks and have the potential to influence deformation phenomena in fault zones and to control the release of water in subducted slabs. Sheet serpentine generally, and lizardite and amesite specifically, can adopt alternative crystallographic stacking arrangements called polytypes. Polytypism has been extensively studied in fully ordered crystals, but it remains largely enigmatic in the more common semi-disordered crystals that in long-range analyses such as X-ray diffraction only exhibit random combinations of 0b and ±1/3b interlayer shifts. To date, atomic-resolution imaging to identify locally ordered polytypes has been precluded by the beam-sensitive nature of this hydrous magnesium silicate mineral. Here, in this study, we employed low-dose high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) to study the polytypic structure of semi-disordered lizardite and amesite. Because the electron dose was as low as ~6000 e–/Å 2 , it was possible to directly resolve oxygen atomic columns and all the cations with a resolution of ~1 Å and reveal the short-range order. For lizardite, we identified long-period non-standard polytypes, including examples with 3, 4, 8, and 9 layers stemming from the ordering of the octahedral tilt along the a-axis. For amesite, we found short-range ordered polytypes with periodicities of up to 42 Å stemming from the ordering of interlayer shifts along the b-axis. The resolution was sufficient to determine the relative abundance of 6R 2 , 6R 1 , 2H 1 , and 2H 2 polytypes in amesite to be 46.1, 29.6, 7.7, and 1.9%, respectively. This is contrary to the expectation that the most common form of amesite is the 2H 2 polytype, which may be more likely to form macroscopic crystals suitable for conventional X-ray diffraction-based studies. We conclude that HAADF-STEM methods open the way for the characterization of beam-sensitive minerals and to resolve the structural details of less well-ordered (but possibly more abundant) minerals at a unit-cell scale.

58 GEOSCIENCES↗
DOE OSTI2022

Local cation order and ferrimagnetism in compositionally complex spinel ferrites

We present an exploration of a family of compositionally complex cubic spinel ferrites featuring combinations of Mg, Fe, Co, Ni, Cu, Mn, and Zn cations, systematically investigating the average and local atomic structures, chemical short-range order, magnetic spin configurations, and magnetic properties. All compositions result in ferrimagnetic average structures with extremely similar local bonding environments; however, the samples display varying degrees of cation inversion and, therefore, differing apparent bulk magnetization. Additionally, first-order reversal curve analysis of the magnetic reversal behavior indicates varying degrees of magnetic ordering and interactions, including potentially local frustration. Finally, reverse Monte Carlo modeling of the spin orientation demonstrates a relationship between the degree of cation inversion and the spin collinearity. Collectively, these observations correlate with differences in synthesis procedures. This work provides a framework for understanding magnetic behavior reported for “high-entropy spinels,” revealing many are likely compositionally complex oxides with differing degrees of chemical short-range order—not meeting the community established criteria for high or medium entropy compounds. Moreover, this work highlights the importance of reporting complete sample processing histories and investigating local to long-range atomic arrangements when evaluating potential entropic mixing effects and assumed property correlations in high entropy materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Assembling PNIPAM-Capped Gold Nanoparticles in Aqueous Solutions

Employing small-angle X-ray scattering (SAXS), we explore the conditions under which assembly of gold nanoparticles (AuNPs) grafted with the thermosensitive polymer poly(N-isopropylacrylamide) (PNIPAM) emerges. We find that short-range order assembly emerges by combining the addition of electrolytes or polyelectrolytes with raising the temperature of the suspensions above the lower-critical solution temperature (LCST) of PNIPAM. Our results show that the longer the PNIPAM chain is, the better organization in the assembled clusters. Interestingly, without added electrolytes, there is no evidence of AuNPs assembly as a function of temperature, although untethered PNIPAM is known to undergo a coil-to-globule transition above its LCST. This study demonstrates another approach to assembling potential thermosensitive nanostructures for devices by leveraging the unique properties of PNIPAM.

Nayak, Binay P↗