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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 OSTI2021

Synthesis, Electronic Structure, and Reactivity of a Planar Four–Coordinate, Cobalt–Imido Complex

A four-coordinate cobalt imido complex, ( tBu mPNP)Co=NMes ( tBu mPNP = modified PNP pincer ligand) has been synthesized from addition of 2,4,6-trimethylphenylazide (Mes–N 3 ) to the corresponding dinitrogen complex. The solid-state structure determined by X-ray diffraction established a rare, idealized planar geometry with a Co=N bond distance of 1.716(2) Å. Magnetic measurements revealed an S = 1 ground state with CAS-SCF calculations supporting radical character on the imide nitrogen. Here, thermolysis of the cobalt-imido compound induced selective insertion of the imido group into a Co–P bond and yielded a three-coordinate cobalt complex with a distorted T-shaped geometry. Transition state analysis conducted with DFT calculations established the thermodynamic stability of the P–N coupled product and provided insight into the exclusive selectivity.

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

Triel-Defined Helicity in One-Dimensional III–VI–VII van der Waals Crystals

Inorganic extended lattice solids that bear complex helical motifs manifest unusual physical and quantum states that arise due to their noncentrosymmetric or chiral nature. However, the systematic understanding of how elemental composition influences the structure and physical properties in helical inorganic crystals has been precluded by the rarity of these materials and the lack of modular phases that display such motifs. Here, we report the synthesis of AlSeI single crystals, the first aluminum-containing helical crystal in the III-VI-VII 1D van der Waals class. AlSeI completes the experimentally accessible triel series in the helical selene iodides alongside InSeI and GaSeI. Using the Al, Ga, and In triel series in this selene iodide class, we experimentally demonstrate the evolution of the local quasi-tetrahedral building unit geometry, chain packing, helical parameters, and band gaps based primarily on the identity of the triel atom. Our results underscore the chemical modularity of these phases, the broad range of helical parameters, and the spectrum of electronic states from the visible to the ultraviolet range in this emergent class of 1D, exfoliable, and helical extended lattice solids.

Chemical structure↗
DOE OSTI2020

Controlling the corrosion resistance of multi-principal element alloys

Multi-principal element alloys (MPEAs) offer the possibility of many degrees of freedom in the choice of alloying elements to produce either single phase solid solutions or more complex multiphase microstructures. Large ranges of material properties have been observed for MPEAs and mastery of the selection of elements and their compositions can enable novel combinations of properties not possible in traditional alloys. From the aqueous corrosion perspective, optimization of phase stability, control of heterogeneities, passive film identity and its protectiveness, as well as substrate properties such as metal-metal bond strength and activation energy associated with dissolution, can all be controlling factors governed by alloy composition and structure. These factors can mediate the electrochemical reactions controlling spontaneous corrosion. The quest for superior properties based on well-informed element choice is suggested as a path forward guiding MPEA formulations for corrosion performance. However, gaps in fundamental knowledge exist regarding (a) the specific functions of each element, (b) the behavior of elements in unusual combinations, and (c) the formation of complex protective oxides. These issues currently hold back progress in optimization of corrosion properties.

Scully, John R.↗
DOE OSTI2022

Irradiation-induced amorphization of UO 2 films prepared by spraying-assisted combustion synthesis

Spraying-assisted combustion synthesis with uranyl nitrate – acetylacetone – 2-methoxyethanol solutions was used to prepare UO 2 films on an aluminum alloy substrate. The tuning of the spraying parameters and annealing temperatures allowed the preparation of UO 2 films with thicknesses varying from 10–300 nm and 5–10 nm UO 2 grain size. High-resolution electron microscopy and X-ray photoelectron spectroscopy showed that increasing the annealing temperature promotes Mg diffusion from the substrate into the films. The incorporation of Mg reduced the overall crystallinity of the films. The irradiation with Ar 2+ ions (1.7 MeV energy and a fluence of 2 × 10 16 ions/cm 2 ) did not degrade the quality of the films. However, the Mg content significantly influenced the irradiation-induced restructuring of the UO 2 films. Irradiated films with low or no Mg content exhibit high crystallinity, and the UO 2 /Al interfacial layer becomes highly porous. Films with higher Mg content are mostly amorphized after irradiation. The origin of irradiation-induced amorphization was related to the formation of Mg y U 1-y O 2±x solid solutions. Chemically complex, pore-free, and amorphous Mg-Al-O film/substrate interfacial layers enable continuous Mg diffusion during irradiation. As a result, the gradual increase in Mg amounts triggers irradiation-induced precipitation of a crystalline MgO-rich phase within the amorphous films.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2021

Sulfidation of magnetite with incorporated uranium

Uranium (U) is a radionuclide of key environmental interest due its abundance by mass within radioactive waste and presence in contaminated land scenarios. Ubiquitously present iron (oxyhydr)oxide mineral phases, such as (nano)magnetite, have been identified as candidates for immobilisation of U via incorporation into the mineral structure. Studies of how biogeochemicalprocesses, such as sulfidation from the presence of sulfate-reducing bacteria, may affect iron (oxyhydr)oxides and impact radionuclide mobility are important in order to underpin geological disposal of radioactive waste and manage radioactively contaminated land. Here, this study utilised a highly controlled abiotic method for sulfidation of U(V) incorporated into nanomagnetite to determine the fate and speciation of U. Upon sulfidation, transient release of U into solution occurred (~8.6 % total U) for up to 3 days, despite the highly reducing conditions. As the system evolved, lepidocrocite was observed to form over a period of days to weeks. After 10 months, XAS and geochemical data showed all U was partitioned to the solid phase, as both nanoparticulate uraninite (U(IV)O2) and a percentage of retained U(V). Further EXAFS analysis showed incorporation of the residual U(V) fraction into an iron (oxyhydr)oxide mineral phase, likely nanomagnetite or lepidocrocite. Overall, these results provide new insights into the stability of U(V) incorporated iron (oxyhydr)oxides during sulfidation, confirming the longer term retention of U in the solid phase under complex, environmentally relevant conditions.

Townsend, Luke↗
DOE OSTI2022

In situ feature analysis for large-scale multiphase flow simulations

The study of multiphase flow is essential for designing chemical reactors such as fluidized bed reactors (FBR), as a detailed understanding of hydrodynamics is critical for optimizing reactor performance and stability. An FBR allows scientists to conduct different types of chemical reactions involving multiphase materials, especially interaction between gas and solids. During such complex chemical processes, the formation of void regions in the reactor, generally termed as bubbles, is an important phenomenon. The study of these bubbles has a deep implication in predicting the reactor’s overall efficiency. But physical experiments needed to understand bubble dynamics are costly and non-trivial due to the technical difficulties involved and harsh working conditions of the reactors. Therefore, to study such chemical processes and bubble dynamics, a state-of-the-art computational simulation MFIX-Exa is being developed. Despite the proven accuracy of MFIX-Exa in modeling bubbling phenomena, the large-scale output data prohibits the use of traditional post hoc analysis capabilities in both storage and I/O time. Herein, to address these issues and allow the application scientists to explore the bubble dynamics in an efficient and timely manner, we have developed an end-to-end analytics pipeline that enables in situ detection of bubbles, followed by a flexible post hoc visual exploration methodology of bubble dynamics. The proposed method enables interactive analysis of bubbles, along with quantification of several bubble characteristics, enabling experts to understand the bubble interactions in detail. Positive feedback from the experts has indicated the efficacy of the proposed approach for exploring bubble dynamics in very-large-scale multiphase flow simulations.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2025

Terahertz-field activation of polar skyrons

Unraveling collective modes arising from coupled degrees of freedom is crucial for understanding complex interactions in solids and developing new functionalities. Unique collective behaviors emerge when two degrees of freedom, ordered on distinct length scales, interact. Polar skyrmions, three-dimensional electric polarization textures in ferroelectric superlattices, disrupt the lattice continuity at the nanometer scale with nontrivial topology, leading to previously unexplored collective modes. Here, using terahertz-field excitation and femtosecond x-ray diffraction, we discover subterahertz collective modes, dubbed “skyrons”, which appear as swirling patterns of atomic displacements functioning as atomic-scale gearsets. The key to activating skyrons is the use of the THz field that couples primarily to skyrmion domain walls. Momentum-resolved time-domain measurements of diffuse scattering reveal an avoided crossing in the dispersion relation of skyrons. Atomistic simulations and dynamical phase-field modeling provide microscopic insights into the three-dimensional crystallographic and polarization dynamics. The amplitude and dispersion of skyrons are demonstrated to be controlled by sample temperature and electric-field bias. The discovery of skyrons and their coupling with terahertz fields opens avenues for ultrafast control of topological polar structures.

ferroelectrics↗
DOE OSTI2020

The chemical and physical properties of tetravalent lanthanides: Pr, Nd, Tb, and Dy

The fundamental redox chemistry and valence electronic structure of the lanthanides in molecular complexes and extended solids continues to be a fertile area of research. The contemporary understanding of the accessible oxidation states of the lanthanide elements and the variability in their electronic structure is the result of several paradigm shifts. While the lanthanide elements have already found widespread use in technical and consumer applications, the continued reevaluation of basic redox properties is a central chemical concern to establish a more complete description of periodic properties. This fundamental understanding of valence electronic structure as it is derived from oxidation state and coordination environment is essential for the continued development of lanthanides in quantum information science and quantum materials research. This review presents the chemical and physical properties of tetravalent lanthanide ions in extended solids and molecules with a focus on the elements apart from cerium: praseodymium, neodymium, terbium, and dysprosium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

High-Pressure Apparatus for Monitoring Solid–Liquid Phase Transitions

This work presents a new technique for observing the solid–liquid phase transformations in complex diesel fuel blends and diesel surrogates under high-pressure conditions intended to simulate those occurring in vehicle fuel injectors. A high-pressure apparatus based on a visual identification of freezing and thawing has been designed and built to monitor phase behavior and determine the crystallization temperature of complex fuels to predict wax precipitation. The proposed methodology was validated using pure substances—n-hexadecane (C16H34), cyclohexane (C6H12), and a binary cyclohexane/n-hexadecane mixture—all of which have been well-characterized previously. The crystallization temperatures of these compounds were measured from atmospheric pressure to 400 MPa for temperatures varying from 290 to 363 K and compared to those reported in the literature. The standard error of the estimated temperatures, based on a given pressure, between the experimental data obtained in this work was compared to data in the literature from Domanska et al. This methodology is being extended to investigate the properties of more complex fuel mixtures.

High-Pressure, phase change, diesel, solidificatio↗
DOE OSTI2023

Prediction of hemiwicking dynamics in micropillar arrays

Dynamic hemiwicking behavior is observable in both nature and a wide range of industrial applications ranging from biomedical devices to thermal management. We present a semi-analytical modeling framework (without empirical fitting coefficients) to predict transient capillary-driven hemiwicking behavior of a liquid through a nano/microstructured surface, specifically a micropillar array. In our model framework, the liquid domain is discretized into micropillar unit cells to enable the time marching of the hemiwicking front. A simplified linear pressure drop is assumed along the hemiwicking length such that the local meniscus curvature, contact angle, and effective liquid height are determined at each time step in our transient model. This semi-analytical model is validated with experimental data from our own experiments and from published literature for different fluids. Our model predicts hemiwicking dynamics with <20% error over a broad range of micropillar geometries with height-to-pitch ratio ranging between ≈0.34 and 6.7 and diameter-to-pitch ratio in the range of ≈0.25–0.7 and without any fitting parameters. For lower diameter-to-pitch ratio data points related to sparse micropillar array arrangements, we suggest modifications to the semi-analytical model. This work sheds light on complex and dynamic solid–liquid–vapor interfacial interactions which could serve as a guide for the design of textured surfaces for wicking enhancement in multi-phase thermal and mass transport technologies and applications.

Mechanics↗
DOE OSTI2023

Effect of local chemical order on the irradiation-induced defect evolution in CrCoNi medium-entropy alloy

High- (and medium-) entropy alloys have emerged as potentially suitable structural materials for nuclear applications, particularly as they appear to show promising irradiation resistance. Recent studies have provided evidence of the presence of local chemical order (LCO) as a salient feature of these complex concentrated solid-solution alloys. However, the influence of such LCO on their irradiation response has remained uncertain thus far. Here, in this work, we combine ion irradiation experiments with large-scale atomistic simulations to reveal that the presence of chemical short-range order, developed as an early stage of LCO, slows down the formation and evolution of point defects in the equiatomic medium-entropy alloy CrCoNi during irradiation. In particular, the irradiation-induced vacancies and interstitials exhibit a smaller difference in their mobility, arising from a stronger effect of LCO in localizing interstitial diffusion. This effect promotes their recombination as the LCO serves to tune the migration energy barriers of these point defects, thereby delaying the initiation of damage. These findings imply that local chemical ordering may provide a variable in the design space to enhance the resistance of multi-principal element alloys to irradiation damage.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Near-surface modification of defective KTaO 3 by ionizing ion irradiation

The synergistic effect of nuclear (S n ) and electronic (S e ) energy loss observed in some ABO 3 perovskites has attracted considerable attention due to the real possibility to modify various near-surface properties, such as the electronic and optical properties, by patterning ion tracks in the defective near-surface regions. In this study, we show that low-energy ion-induced disordering in conjunction with ionizing ion irradiation (18 MeV Si, 21 MeV Ni and 91.6 MeV Xe) is a promising approach for tailoring ion tracks in the near-surface of defective KTaO 3 . Experimental characterization and computer simulations reveal that the size of these latent ion tracks increases with S e and level of pre-existing damage. These results further reveal that the threshold S e value (S e th ) for track creation increases with decreasing pre-damage level. The values of S e th increase from 5.02 keV nm -1 , for a pre-existing fractional disorder of 0.53 in KTaO 3 , to 10.81 keV nm -1 for pristine KTaO 3 . Above these thresholds, amorphous latent tracks are produced due local melting and rapid quenching. Below a disorder fraction of 0.08 and S e ≤ 6.68 keV nm -1 , the synergistic effect is not active, and damage accumulation is suppressed due to a competing ionization-induced damage annealing process. These results indicate that, depending on S e and the amount of pre-existing damage, highly ionizing ions can either enhance or suppress damage accumulation in KTaO 3 , thus providing a pathway to tailoring defects states. Comprehending the conflicting roles of highly ionizing ions in defective ABO 3 oxides is vital for understanding and predictive modeling of ion-solid interactions in complex oxides, as well as for achieving control over ion track size in the near-surface of defective KTaO 3 .

36 MATERIALS SCIENCE↗
DOE OSTI2021

Numerically exact generalized Green's function cluster expansions for electron-phonon problems

We generalize the family of approximate momentum average methods to formulate a numerically exact, convergent hierarchy of equations whose solution provides an efficient algorithm to compute the Green's function of a particle dressed by bosons suitable in the entire parameter regime. We use this approach to extract ground-state properties and spectral functions. Our approximation-free framework, dubbed the generalized Green's function cluster expansion (GGCE), allows access to exact numerical results in the extreme adiabatic limit, where many standard methods struggle or completely fail. We showcase the performance of the method, specializing three important models of charge-boson coupling in solids and molecular complexes: the molecular Holstein model, which describes coupling between charge density and local distortions, the Peierls model, which describes modulation of charge hopping due to intersite distortions, and a more complex Holstein + Peierls system with couplings to two different phonon modes, paradigmatic of charge-lattice interactions in organic crystals. Furthermore, the GGCE serves as an efficient approach that can be systematically extended to different physical scenarios, thus providing a tool to model the frequency dependence of dressed particles in realistic settings.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Additive Manufacturing of Controlled Porous Elastomeric Nanocomposites for Enhanced Sensing Function

Sensors manufactured using piezoresistive elastomeric nanocomposites have a wide range of applications in many fields such as structural health monitoring, robotics, and biomedical industries. Additive manufacturing of these sensors, achieved using Direct Ink Writing (DIW), has provided numerous advantages including increased sensitivity and the fabrication of complex geometry. However, solid sensors manufactured either additively or using conventional methods, display a greater level of hysteresis, especially at strains higher than 10%, which limits their sensitivity. The solid sensors also display a greater level of piezoresistive relaxation where the resistance change with time either in a static or dynamic loading environment. Porosity can be introduced in the form of varying infill patterns and densities to reduce bulk material effects. In this paper, a lattice structure with four infill densities are investigated, and the samples are printed using a grid infill pattern. The fabricated samples are characterized using a scanning electron microscope (SEM) to validate the microstructural features and layer bonding. The pressure-sensing capability of each sensor is investigated using cyclic compression loading at various strain levels. Sensing results show that an increase in sensitivity, as well as a decrease in hysteresis with an increase in porosity, compared to solid samples (100% in-fill). The highest porosity was measured to be 62.3% with a corresponding 112% increase in the gauge factor compared to the solid bulk. These results indicate that introducing porosity using DIW is a sensible strategy to improve the piezoresistive performance of nanocomposites and to allow for the tunability of sensing capacity in pressure sensors

Sukati, Musa↗
DOE OSTI2020

Radiation Damage in Materials—Helium Effects

Despite its scarcity in terrestrial life, helium effects on microstructure evolution and thermo-mechanical properties can have a significant impact on the operation and lifetime of applications, including: advanced structural steels in fast fission reactors, plasma facing and structural materials in fusion devices, spallation neutron target designs, energetic alpha emissions in actinides, helium precipitation in tritium-containing materials, and nuclear waste materials. The small size of a helium atom combined with its near insolubility in almost every solid makes the helium–solid interaction extremely complex over multiple length and time scales. This Special Issue, “Radiation Damage in Materials—Helium Effects”, contains review articles and full-length papers on new irradiation material research activities and novel material ideas using experimental and/or modeling approaches. These studies elucidate the interactions of helium with various extreme environments and tailored nanostructures, as well as their impact on microstructural evolution and material properties.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Uranyl Naphthylsalophen and Pyrasal Complexes: Oxo Ligands Acting as Hydrogen Bond Acceptors in the Solid State

Uranium is most stable when it is exposed to oxygen or water in its +6 oxidation state as the uranyl (UO 2 2+ ) ion. This ion is subsequently particularly stable and very resistant to functionalization due to the inverse trans effect. Uranyl oxo ligands are typically not considered good hydrogen bond acceptors due to their weak Lewis basicity; however, the ligands bound in the equatorial plane greatly affect the strength of the oxo ligands’ hydrogen bonding. Here, in this work, new naphthylsalophen and pyrasal complexes of uranium were synthesized and crystallized for characterization in the solid state. The bond lengths and angles of the uranyl ion and the ligand conformation are compared. In the solid state, one of the pyrasal complexes showed a hydrogen bond directly from a water molecule to the uranyl oxo ligand, which resulted in an asymmetric lengthening of the U–O yl bonds from 1.789 to 1.862 Å and 1.784 to 1.844 Å.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗